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
  • C09D5/027—Dispersing agents
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • 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
  • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/66—Additives characterised by particle size
  • C09D7/67—Particle size smaller than 100 nm
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2237—Oxides; Hydroxides of metals of titanium
  • C08K2003/2241—Titanium dioxide

Definitions

• the present invention relates to colors containing nanoparticles as a component.
• Paints also called paints, consist of liquid to paste-like substances or mixtures which, when applied to surfaces, give a physically or chemically drying coat.
• a paint is a "liquid to paste-like coating material, which is mainly applied by brushing or rolling.”
• a coating material is basically composed of: binders, colorants, solvents and usually also fillers and any additives such as thickeners, dispersants and preservatives. Paints are classified according to their film-forming binders, which in turn can be subdivided into organic and inorganic binders and the product classes:
• the organic binders include, for. As the oils of oil paints, acrylic resins or epoxy resins, which typically give paints or varnishes. Other organic binders are, above all, acrylate polymers or vinyl acetate copolymers which are part of the commercial emulsion paints. Natural colors also use natural binders such as casein.
• the inorganic binders include, for. As calcined lime, cement, anhydrite, ettringite and potash water, which are used in construction and mural painting. In silicate colors, water glass serves as a binder.
• Emulsion paints are high-viscosity paints which consist of a chemical dispersion (usually an emulsion) of binders and solvents, Colorants (mostly pigments) and additives exist. In this general sense, most of the liquid paints (paints, paints) are dispersions.
• a film preservation that is, a biocidal coating equipment, which is effective in the cured and dried state.
• the active ingredients such as fungicides, algicides and bactericides have limited water solubility, so they are not washed out by weathering. Nevertheless, they often lose their effect after a few years. In the event of a discoloration of the surface due to microbial attack, the paint usually has to be renewed.
• the emulsion paints also include the silicone resin paints, in which organic polymers serve as binders and, in addition, contain silicate particles.
• silicone resin paints are highly permeable to water vapor combined with the benefits of organically bound emulsion paints.
• nanoparticles are solid particles with particle sizes below 1 ⁇ , often to understand 100 nm and below.
• NanoHybrid technology polymer silicate binders are used for facade paints which contain chemically crosslinked nanoparticles, eg silica sol particles, in a polymeric binder, for example in an acrylate binder.
• the nanoparticles are finely distributed in the polymer matrix and thus form a reinforcement of this matrix in the form of a network. The result is a seal of the surface against contamination and ingress of water.
• NanoHybrid binders are commercially available, eg under the name Mowilith Nano from Celanese and SilaClean from Carparol, see eg "* technikforum", issue 01/2007 of Caparol Maschinen Lacke Bautenschutz GmbH, p. 7-9.
• the facade paints with these binders have a nanostructured surface and show good durability, weatherability and vapor permeability as well as a reduced soiling tendency.
• lithium polyacrylate as a dispersant can significantly reduce the cracking of paints with NanoHybrid binder systems.
• the above object is therefore achieved by the use of fully neutralized lithium polyacrylate as a dispersant for paints containing silicate particles having a mean particle size below 100 nm, which are chemically crosslinked with a polymeric binder, and by paints, in particular emulsion paints, containing chemically with a polymeric binder crosslinked silicate particles with a mean particle size below 100 nm and lithium polyacrylate.
• a further advantage of the dispersants and of the paints according to the invention is an improved theological stability of the dispersions in comparison with the paints stabilized with commonly used dispersants such as polyphosphates and polyacrylates or other polymers in the form of the sodium, potassium or ammonium salt. Therefore, paints according to the invention also have improved storage stability.
• the applied dispersion films also show better wall adhesion.
• the invention has proven itself in all paints formulated with a NanoHybrid binder system, but especially in emulsion paints and most preferably in facade paints.
• the paints according to the invention contain, in aqueous dispersion / emulsion, at least the silicate particles crosslinked with the polymeric binder, colorants, usually pigments but also dyes, as well as the dispersant. Usually also fillers and additives such as thickening agents, and preservatives are included. With regard to colorants, fillers and additives, the substances known per se are suitable in the usual amounts.
• the chemically crosslinked with polymeric binder silicate is known per se.
• the polymer is generally an acrylate, for example a homo- or copolymer of acrylic acid and / or methacrylic acid and / or esters thereof and, in the case of copolymers, optionally further olefinically unsaturated monomers, eg vinyl acetate.
• Acrylic acid homopolymers are currently preferred.
• the silicate particles are silica sol particles.
• the average particle size is below 100 nm, usually at 80 nm, in particular in the range from 10 to 50 nm, preferably from 20 to 30 nm.
• the solids content is usually from 30 to 50% by weight, of which, for example about 40 wt .-% silicate particles.
• binder dispersion is used.
• lithium polyacrylates used according to the invention as dispersants are also known per se, see, for example, WO 2010/070407,
• WO 2009/124871 and US 5,424,259. They are usually offered as aqueous solutions.
• the solids content is usually from 20 to 60 wt .-%, preferably 30 to 45 wt .-%.
• According to the invention completely neutralized with lithium acrylic acid homopolymers are used. Amounts of 0.1 to 5 wt .-%, preferably 0.2 to 1 wt .-% lithium polyacrylate have been proven.
• the usual siliceous and carbonatic fillers are suitable, typically at least one filler is included, usually several.
• the paints according to the invention also contain customary colorants. Most are pigments, and depending on the color, also combinations of pigments. As a colorant titanium dioxide is particularly widespread, since almost all paints are made with the base color white. If other shades are desired, further pigments and / or dyes are added. Titanium dioxide provides not only the white color but also the opacity, if necessary in combination with the filler (s). The colorant is usually contained in amounts ranging from 10 to 20 wt .-%.
• Contain paints On the one hand they ensure the preservation of the Paints until their processing. Thus, it is required that the paint can be stored both for processing for a long time and the opened containers. For this container preservation, the usual preservatives in the amounts known per se are suitable. In addition, thickeners, emulsifiers, pH regulators, defoamers, complexing agents and other conventional additives may be present individually or as mixtures in the amounts known per se.
• a standard facade color formulation according to the invention consists, for example, of the following components: 100 to 120 parts of water, 250 to 300 parts of nanoparticulate dispersion, e.g. based on copolymers of acrylic acid and
• Methacrylic acid 0.1 to 10 parts of fully neutralized lithium polyacrylate, 100-150 parts of titanium dioxide / white pigment, 250-400 parts of silicate and carbonaceous fillers, 1-5 parts of thickener, 2-4 parts of defoamer, 3-5 parts of nonionic dispersant, 10 to 15 parts of hydrophobing agent and 10-15 parts of film-forming agent. Preservatives and biocidal agents may also be present.
• the preparation and processing of the paint is done in a conventional manner and need not be explained in detail here.
• the paints are obtained by mixing the solid and liquid components in suitable mixing equipment.
• Inventive paint can be applied with a brush or rollers, spraying, etc. and are adapted as usual in the consistency.
• the effect of the dispersion according to the invention was compared with that of conventional dispersants.
• the following standard facade paint formulation was used: 110.5 parts water, 1.5 parts thickener, 2.0 parts defoamer, 3.0 parts non-ionic dispersant, 120 parts titanium dioxide, 460 parts mixture of siliceous and carbonated fillers, 275 Parts with copolymer of acrylic acid and methacrylic acid chemically crosslinked silica sol, 15 parts of water repellent and 13 parts of film-forming agent.
• the inks according to the invention have a better storage stability even with a smaller amount of dispersant, the viscosity has not increased so much.
• test panels consisting of fiber cement boards were coated with the emulsion paints prepared according to the above formulation and subjected to a weathering test. The colors were applied with the doctor blade with a layer thickness of 400 ⁇ .
• the paints contained 1 part of fully neutralized lithium polyacrylate or 4 parts of nonionic dispersant.
• Figures 1 (invention, with 1 part Li-polyacrylate) and 2 (prior art, with 4 parts non-ionic dispersant) show the photos of the walls with the color films after 4 weeks storage in 30-fold magnification.

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

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• 2012
  • 2012-05-05 DE DE102012009320A patent/DE102012009320A1/de not_active Ceased
• 2013
  • 2013-04-26 EP EP13721260.1A patent/EP2844709A1/de not_active Withdrawn
  • 2013-04-26 JP JP2015509328A patent/JP2015520784A/ja active Pending
  • 2013-04-26 MX MX2014012047A patent/MX2014012047A/es unknown
  • 2013-04-26 US US14/398,258 patent/US20150133596A1/en not_active Abandoned
  • 2013-04-26 WO PCT/EP2013/001268 patent/WO2013167243A1/de not_active Ceased

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