WO2008049679A1 - Liant contenant des particules nanométriques présentant une meilleure résistance aux éraflures et une meilleure flexibilité, son procédé de fabrication et peinture d'une grande transparence le contenant - Google Patents

Liant contenant des particules nanométriques présentant une meilleure résistance aux éraflures et une meilleure flexibilité, son procédé de fabrication et peinture d'une grande transparence le contenant Download PDF

Info

Publication number
WO2008049679A1
WO2008049679A1 PCT/EP2007/059114 EP2007059114W WO2008049679A1 WO 2008049679 A1 WO2008049679 A1 WO 2008049679A1 EP 2007059114 W EP2007059114 W EP 2007059114W WO 2008049679 A1 WO2008049679 A1 WO 2008049679A1
Authority
WO
WIPO (PCT)
Prior art keywords
particles
paint
compounds
nanoscale
binder according
Prior art date
Application number
PCT/EP2007/059114
Other languages
German (de)
English (en)
Inventor
Martin Bartmann
Thorsten Brand
Pedro Cavaleiro
Thomas Hasskerl
Lothar Hayen
René Koschabek
Wolfgang Lortz
Bernd Mueller
Original Assignee
Evonik Degussa Gmbh
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 Evonik Degussa Gmbh filed Critical Evonik Degussa Gmbh
Publication of WO2008049679A1 publication Critical patent/WO2008049679A1/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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/80—Processes for incorporating ingredients
    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other 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
    • 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
    • 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
    • C09D7/68—Particle size between 100-1000 nm
    • 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
    • C09D7/69—Particle size larger than 1000 nm
    • 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
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Definitions

  • Polyester coatings which are used, for example, for strip coating, are characterized by high flexibility and moderate scratch resistance.
  • the flexibility is demonstrated in particular by the T-bend test, in which a coated sheet is bent by 180 °. Sheets coated with isocyanate-cured polyester lacquers withstand this test without tearing or delamination of the lacquer layer.
  • increasingly scratch resistant coatings but no or only small losses in their flexibility, required.
  • the degree of crosslinking can be increased, but the flexibility is significantly reduced.
  • an improvement in the scratch resistance is also achieved, but this measure, depending on the particle size of the fillers in clearcoats, leads to haze, matting and / or roughening of the paint surface.
  • the incorporation of particles into the paint formulation is also associated with a loss of extensibility of the coating and manifests itself, for example, by loss of gloss or matting effects during stretching or bending of coated substrates at the stretched locations.
  • cured coatings having a plurality of particles wherein a concentration of the particles within a surface region of the coating is greater than a concentration within the volume range, are more scratch resistant than unmodified coatings.
  • the nanoparticles used are organosols with monodisperse silica particles. These paints are characterized by special binders and hardeners, which cause migration of the nanoparticles to the paint surface.
  • the patentee documents the migration of the particles to the surface up to the phase boundary between paint and air by transmission electron micrographs (TEM images) and attributes the experimentally proven improvement in scratch resistance to the accumulation of nanoparticles on the surface.
  • the patent also describes an embodiment in which there is still a thin particle-free binder layer over the particle-enriched layer.
  • Both surface-modified and untreated particles can be used become. (Page 6, paragraph 0047). However, if untreated particles are used, the varnish must contain a polysiloxane compound which, together with the nanoparticles, causes the scratch resistance to be improved. If no siloxanes are used, the particles agglomerate and do not produce the desired effect. (P.33, line 11).
  • a siloxane-containing formulation is used, which favors the separation of binders and nanoparticles.
  • organosols are used which, in combination with the polysiloxanes, improve the scratch resistance.
  • the amount of siloxane required to stabilize the monodisperse nanoparticles is comparatively high.
  • Example 2A requires 10.3 parts by weight of polysiloxane for 6.7 parts by weight of SiO 2 (values based on solids).
  • Example 1C even 15.3 parts by weight of polysiloxane are needed for 6.7 parts by weight of SiO 2 .
  • Organosols are prepared by complex processes via the sol-gel process or via solvent exchange and surface modification of silica sols. The costs of organosols and polysiloxanes are very high in terms of paint costs for large-scale products and limit the range of application.
  • inorganic nanoparticles are modified with silanes and can be used in radiation-curable highly crosslinked paints to improve the scratch resistance.
  • the modified nanoparticles are better compatible with the coatings and can be coupled by reactive groups to the paint. If a tetrafunctional crosslinker is used, improved abrasion values are found. With soft monofunctional reactive diluents you will find an improvement only at high fill levels.
  • DE 10326538 describes abrasion-resistant coatings based on surface-modified nanoparticles and blocked isocyanates.
  • the coatings have excellent abrasion resistance with high filler content.
  • silanes containing protic groups or precursors of such silanes are used.
  • DE 19920801 describes a two-stage coating which is cured both thermally and photochemically.
  • the coating contains monodispersed nanoparticles of the type Highlink OG 103-31. After the first particle-free layer was only partially cured, is coated with the second particle-containing layer and then cured again.
  • pyrogenic silica (Aerosil) is used instead of the monodisperse particles.
  • Aerosil type was used.
  • US 5,853,809 describes a nanoparticle-containing coating comprising a carbamate functional silica obtained by reacting colloidal silica with a previously prepared carbamate functional silane.
  • the coatings contain very high filler contents and show in the scratch test with a Crockmeter lower percentage loss of gloss than unfilled paints or coatings in which the silica filler was not reacted with the coupling reagent.
  • US Pat. No. 6,916,368 describes aluminosilicate-containing coatings having largely spherical particles which are substantially unmodified and an improved percentage gloss retention after the Crockmeter test.
  • the coatings with 5 or 40% nanofiller are significantly cloudier than unfilled coatings due to the difference in refractive index in the scratched state.
  • WO 0245129 (nanophase) describes abrasion-resistant films with surface-modified nanocrystalline particles which are produced by depositing one or more species of polysiloxanes, preferably star polymers, on the particle surface. Abrasion-resistant films or films with increased pencil hardness are obtained, which have better transparency than films with microparticles.
  • WO 03040223 (nanophase) describes compositions containing micro- and nanoparticles. Non-linear effects are found, but due to the content of microparticles, they do not have clear transparent films.
  • WO 03084871 (nanophase) describes nonaqueous dispersions with nanoparticles wherein polymeric dispersing additives having repeating units and anchor groups, such. As polyvinylpyrrolidone be used for stabilization.
  • WO 0400916A2 (nanophase) describes long-term stable aqueous dispersions with metal oxide nanoparticles, water-soluble polymeric dispersing additives having pigment affinities and water-soluble groups being used. In some cases cyclic phosphates can also be used.
  • WO 2005119359 (nanophase) describes scratch-resistant articles having a substantially transparent coating, wherein a dispersion of predominantly non-agglomerated nanocrystalline primary particles, polymeric dispersant and surface-active material is used (page 5, 2nd paragraph).
  • An object of the cited document is the migration of the nanoparticles to the phase interface and thereby the use of small amounts of nanoadditive to achieve increased scratch resistance.
  • the substantially spherical nanoparticles have a non-porous structure. The stabilization and migration of the nanoparticles are significantly controlled by the nature of the polymeric dispersing additives having a molecular weight above 1000 used.
  • EP-A-0766997 describes a jet-blasting method for comminuting agglomerates and aggregates of nanoscale primary particles, in which two liquid jets are shot at pressures of up to 200 bar in several passes and in which the particles dispersed in the liquids are ground.
  • EP 943664B1 describes a process for the production of scratch-resistant coatings using agglomerates of nanoscale particles ground by the jet-blast method.
  • the invention relates to nanoparticle-containing transparent paint binders containing based on the paint solids 0.5 to 25 wt .-% incorporated as a solid primary nanoscale particles prepared by jet jet dispersion of the nanoscale particles in the binder. (EP 943664B1, 0016). It is disclosed that it may be advantageous to use also surface-modified particles or z.
  • Particularly preferred resins include polyester polyols.
  • Blocked polyisocyanates come under consideration as hardeners.
  • the compositions described allow improved scratch resistance with constant transparency and gloss.
  • the subject of EP 943664B1 is also a process for the preparation of transparent nanoparticle-containing paint binders, characterized in that the preparation consisting of nanoparticles and paint binders is passed in at least one passage through a device having at least one nozzle or a slot gap, wherein the region for the dimensions and the constructional arrangement (ebda. 0034).
  • a pressure of 5 to 50 MPa, preferably 7 to 30 MPa is used.
  • the significant "destructuring and milling effects" occurring only at significantly higher grinding pressures can not be achieved.
  • the dispersants are more preferably oligomeric or polymeric organic compounds, such as. B. resins and binders commonly used in paint and coating technology as further substances.
  • the addition of resins and binders increases the viscosity of the formulations, which limits the maximum manageable concentration of nanoscale particles.
  • the powdery, primarily nanoscale particles are introduced into the solvent and diluted to less than 2000 mPas polyol component in a dissolver and deagglomerated.
  • fumed silicas produced only by flame pyrolysis are referred to as nanoscale particles.
  • Silicas have a low refractive index, which does not deviate so much from the refractive indices of conventional coating resins. In the case of silicas, therefore, a content of non-nanoscale fractions is not as noticeable as with high-index metal oxides.
  • the haze of the paints in the most effective scratch-resistant additives based on high-index metal oxides, especially alumina is too high for use in clear transparent clearcoats.
  • the use of small amounts of nanocrystalline primary particles (WO 2005119359) also does not allow the production of clear, low haze paints.
  • the dispersing process described in EP 766 997 and EP 943 664 B1 operates at a pressure of 230 bar to possibly 500 bar, which does not allow grinding.
  • the apparatus described in EP 766 997 with the specified geometry of the grinding chamber and the specified arrangement of the nozzles is not suitable to be operated at a higher pressure, since the liquid jets destroy the opposite nozzles after a short period of operation.
  • a paint binder which comprises a matrix based on one or a plurality of polymers and 100% by weight of the total binder, a stabilized suspension of nanoscale particles, in a Solids antei I the suspension measured amount of 0.5 to 25 wt -.%, And is characterized in that the suspension of the particles is obtainable by a) grinding of the particles with the addition of a solvent in a high-pressure mill, which decomposes under a pressure in the range of> 500 - about 10,000 bar agglomerates and / or aggregates of the particles into nanoscale fragments; and b) adding one or more dispersing additives to stabilize the surface of the milled particles, wherein the dispersing additive (s) is present in an amount of 1 to 25 parts by weight based on 100 parts by weight of the particles.
  • lacquers resulting from the formulation using the lacquer binder of the invention consist of a) a resin system, b) a hardener system, c) a filler system, d) optionally solvents and e) optionally further additives customary in lacquers and coatings, wherein at least the components a) and c) originate from the paint binder, meet the requirement for transparent coatings with improved scratch resistance and / or improved abrasion resistance when the components are selected from the product systems described below and the inorganic fillers by means of a high-pressure milling process as nanoscale particles to be provided.
  • a suitable high-pressure milling process operates according to the procedures described in DE 10360766 of 23.12.2003, "Method and apparatus for the preparation of dispersions” or DE 102 04 470 C1 of 5.02.2002 (US Pat. No. 6,991,190) "Method for the production of dispersions”.
  • a special feature of the paint binder / paint system according to the invention consists in the use of nanoscale particles obtained in a special way, which are expediently used in stabilized suspension in the present case.
  • nanoscale particles refers to those particles whose size is determined as aggregates of primary particles on a scale in the nanometer range, which is the range of 1, 0 to about 500 nm Particle size d50 determined by Horiba LA 920 particle size analyzer
  • the nanoscale particle aggregates can not agglomerate (agglomerate / form agglomerates) in coating systems according to the invention to form larger structures.
  • paint binders of particular interest are those in which the nanoscale particles present in stabilized suspension have an average particle size d50 in the range from 0.05 to 10 ⁇ m determined by means of light scattering according to Mie.
  • paint binders which are distinguished by the fact that the nanoscale particles have a d50 value in the range from 0.05 to 0.5 ⁇ m, preferably from 0.1 to 0.5 ⁇ m.
  • a distinction must be made between the size of the primary particles, the size of the primary particle aggregates (“nanoscale”) and the size of the particle aggregates in stabilized suspension / dispersion.
  • a particular embodiment of the paint binder of the invention is characterized in that the nanoscale particles consist of primary particles that are globular, have a size in the range of 5 to 30 nm, and have a fracture ⁇ 3, measured by N 2 adsorption in the pressure range p / p ⁇ of 0.5 to 0.8.
  • Particles with the aforementioned properties can be recruited from a whole range of substance groups.
  • interesting lacquer binders have nanoscale particles selected from the group consisting of oxidic, nitridic and carbidic metal and semimetal compounds and mixtures of two or more of the above.
  • paint binders are particularly preferred in which the nanoscale particles are selected from the group consisting of alpha-alumina, gamma-alumina, delta-alumina, theta-alumina, zirconia, yttrium-doped zirconia, titania, rutile, anatase, brookite, silica , Antimony oxide, zinc oxide, cerium oxide, iron oxides, palladium dioxide, indium tin oxide, antimony tin oxide, spinel type compounds, aluminum spinels, iron spinels, chromium spinels, titanium spinels, cobalt spinels, ceramic particles, boron nitride, boron carbide, silicon carbide, silicon nitride, mixed compounds and mixed oxides of the above-mentioned elements, and mixtures having two or more of the above substances.
  • an expedient embodiment of the paint binder of the invention is characterized in that the surface of the nanoscale particles is modified by post-oxidation, adsorption, reactions on the surface or complexing of or with inorganic and / or organic reagents.
  • surprisingly positive properties can be achieved in the finished coatings.
  • those modifications of the paint binder are particularly preferred in which the surface of the nanoscale particles is modified with two or more different types of functional groups. This assists in stabilizing the suspension of the particles at each stage of the processing.
  • the paint binders of the invention are admixed with dispersing additives for stabilizing the suspension of the nanoscale primary particle aggregates.
  • dispersing additives for this purpose in question.
  • Particularly preferred paint binders of the invention are characterized in that the added dispersing additive is selected from the group consisting of a) alkyltrialkoxysilanes of the general formula R-Si-O-R'3 , where R can be an aliphatic or mixed aliphatic / aromatic radical and heteroatoms selected from the group N, O, S, Cl may be included, which may also interrupt the main chain; and wherein R 'is an aliphatic radical; b) hexamethyldisilazane and its derivatives; c) silicone-based compounds having a backbone of [SiR 2 -O] building blocks and end groups differing therefrom, and [SiRR'-O] building blocks in which R 'is an aliphatic radical grafted onto the main chain; d) vinyl
  • polyglycerols i) star polymers; j) Compounds having a polyethyleneimine backbone and grafted thereon
  • Side chains selected from the group: polyethers, polyesters; k) phosphorus-containing oligomers, such as. B. tego dispers 655; and
  • paint binder comprises aluminum oxide as nanoscale particles and phosphorus-containing oligomers as dispersing additive.
  • tego dispers 655 is very particularly preferred as the phosphate-containing oligomer.
  • a particular paint binder of the invention is therefore characterized in that the suspension of the particles is obtainable by pre-dispersing the particles in a liquid phase in a rotor-stator-run aggregate prior to the step of grinding in a high energy mill. This leads to a further unexpected improvement in the stability of the suspension.
  • the grinding process can also be supported by further measures.
  • the addition of a solvent is essential.
  • the solvent added for grinding is selected from the group consisting of aliphatic and cycloaliphatic compounds, aromatic and substituted aromatic compounds, petroleum and gasoline fractions usable in paints, esters, lactones, ethers, glycol ethers, ketones, alcohols, mixtures of two or more of the abovementioned compounds and mixtures comprising at least one compound of the abovementioned substances.
  • the solvent comprises a combination of solvents of different boiling points and / or evaporation rate and / or different polarity.
  • Special embodiments are characterized in that the solvent combination Solvesso 150 / butylglycol and / or Solvesso 150 / methoxypropylacetate and / or Solvesso 150 / dibasic ester mixture DBE used and / or solvent combinations with xylene or butyl acetate.
  • the matrix is selected from the group consisting of organic oligomers having free hydroxyl groups, which are available for reaction with a curing agent, organic polymers having free hydroxyl groups, which are suitable for a curing reaction, combinations of the above Oligomers and polymers, as well as blends having oligomers and / or polymers with free hydroxyl groups available for reaction with a hardener.
  • paint binders are characterized in that the matrix comprises polyacrylate, polyester, polycaprolactone, polyether, polycarbonate, polyurethane polyol resins, any mixtures of the above substances, or mixtures comprising at least one of the above polymeric substances.
  • the matrix comprises polyester resins and / or polyacrylate resins.
  • the paint binders of the invention have a high transparency and allow highly transparent coatings.
  • the paint binders preferably have a high transparency of more than 70% transmission, more preferably more as 85% transmission, more preferably greater than 88%.
  • the invention also relates to a process for the preparation of
  • Lacquer binders in which process i) provides a matrix based on one or a plurality of polymers; ii) mixing the provided matrix with a stabilized suspension of nanoscale particles; and iii) optionally adding to the mixture of ii) other conventional additives; with 100% by weight of the total binder, nanoscale particles in an as
  • Solid particles of the suspension of from 0.5 to 25% by weight incorporated; wherein the method is characterized in that the suspension of the particles is obtainable by a) grinding of the particles with the addition of a solvent in a high pressure mill under a pressure in the range of> 500 - about 10,000 bar agglomerates and / or aggregates of the particles in nanoscale Fragments decomposed; and b) adding one or more dispersing additives to stabilize the surface of the milled particles, wherein the dispersing additive (s) is present in an amount of 1 to 25 parts by weight based on 100 parts by weight of the particles.
  • the paint binders of the invention and paint binders obtainable by the process of the invention can be used extremely expedient together with aliphatic polyisocyanates in two-component clearcoats.
  • Another preferred use of the paint binders relates to the combination with curing agents which can be reacted with hydroxyl groups for the preparation of coatings and coatings.
  • curing agents selected from the group consisting of polyisocyanates, capped polyisocyanates, Isocyanatprepolymeren, melamines, silanes, silyl phenomenon termen compounds, mixtures of one or more of the above compounds and mixtures comprising at least one of the above compounds is particularly preferred.
  • the invention also includes a paint comprising a paint binder as described herein. Also included in the invention are painted articles comprising a coating of a cured lacquer containing / containing a lacquer binder as described herein.
  • the paints according to the invention consist of: a) an oligomeric or polymeric resin or a mixture of oligomeric and / or polymeric resins which may contain functional groups useful for paint curing, b c) a filler system consisting essentially of a nanoscale particulate filler or a mixture of substantially nanoscale particulate fillers, wherein the fillers are selected from the group of inorganic amorphous or crystalline materials or the surface of organically modified inorganic materials and wherein the filler or the mixture of fillers are ground in a solvent and for grinding a high-pressure mill is used, the agglomerates and / or aggregates of the Fül under very high pressure lstoffs can decompose into nanoscale fragments and the reaggregation or reagglomeration of the particles by stabilizing the particle surface with silanes and / or phosphorus-containing compounds; Silanes and / or oligo
  • flow aids wetting agents, dispersants, antioxidants, curing catalysts, drying agents, reactive diluents, pigments, release agents, slip additives, adhesion promoters, silanes, Phosphorus compounds, alkylphosphonates.
  • the coating system of the invention is further distinguished by the fact that the silanes used for surface stabilization, phosphorus compounds or oligomeric dispersing additives are selected from the group of a) Alkyltrialkoxysilanes of the general formula R-Si-O-R'3 , where R may be an aliphatic or mixed aliphatic / aromatic radical and may contain heteroatoms selected from the group N, O, S, Cl, which may also interrupt the main chain ; and wherein R 'is an aliphatic radical. b) hexamethyldisilazane.
  • Silicone-based dispersing additives having a backbone of [SiR 2 -O] - building blocks and other end groups and [SiRR'-O] - blocks in which R 'stands for a grafted onto the main chain aliphatic radical.
  • block copolymers containing polar protic or polar aprotic functional groups in at least one of the blocks f) polycondensates, such as. B.
  • Essential for the invention is the grinding of the nanoscale fillers which takes place under very high pressure, so that even particle aggregates which are not destroyed under conventional dispersing processes can be broken down into their constituents. Description of the grinding system according to the invention
  • a process has proven particularly suitable in which the dispersion is first carried out with an energy input of less than 1000 kJ / m 3 to form a predispersion (eg dissolver or rotor-stator machines), the predispersion in at least two Divide sub-streams, these sub-streams in a high-energy mill under a pressure of at least 500 bar sets, relaxed via a nozzle and meet in a gas- or liquid-filled reaction space and optionally repeated high energy milling one or more times.
  • a predispersion eg dissolver or rotor-stator machines
  • the paint system consists of:
  • Resins of the present invention are organic polymers having free hydroxyl groups available for reaction with a hardener; z.
  • polyester resins and polyacrylates Saturated polyester resins are usually by condensation of saturated polycarboxylic acids, such as. As dicarboxylic acids, or their anhydrides or other esterifiable derivatives with polyols, eg. As diols or triols produced. Their properties largely depend on the nature and proportions of the starting materials.
  • acids or acid derivatives for the preparation of the polyesters are phthalic acid, isophthalic acid, terephthalic acid, 1, 4-cyclohexanedicarboxylic acid, succinic acid, sebacic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, pyromellitic acid, dimer fatty acids, and / or trimellitic acid, their acid anhydrides and / or lower alkyl esters such.
  • polystyrene resin examples include: ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1, 4-butanediol, 1, 3-butylethylpropanediol, 2-methyl-1, 3-propanediol, 1, 5-pentanediol, cyclohexanedimethanol, glycerol, 1, 6-hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, 1, 2,6-trihydroxyhexaerythritol, trishydroxyethyl isocyanurate, pentaerythritol, sorbitol, mannitol, XyNt, 1, 4-benzyldimethanol, 1, 4- Benzyl diethanol, 2,4-dimethyl-2-ethylhexane
  • polyesters of the present invention are prepared by known methods (see Dr. P. Oldring, Resins for Surface Coatings, Volume III, published by Sita Technology, 203 Gardiness House, Bromhill Road, London SW 184JQ, England 1987) by condensation.
  • the saturated polyesters according to the invention can have an acid number between 0 and 10 mg KOH / g, preferably 0 to 5 mg KOH / g and particularly preferably 0 to 3 mg KOH / g; a hydroxyl number between 3 and 80 mg KOH / g, preferably 10 to 50 mg KOH / g and more preferably 15 to 30 mg KOH / g.
  • the number average molecular weights Mn of the linear or branched, preferably linear or weakly branched polyesters are between 2000 and 20,000; the glass transition temperature (Tg) between -20 0 C and + 60 0 C, preferably between -10 0 C and + 40 0 C,
  • Suitable compounds are polyisocyanates, capped polyisocyanates, isocyanate prepolymers, melamines, silanes and silyl-containing compounds, other compounds which undergo a reaction with chain extension or crosslinking at room temperature or elevated temperature, if appropriate with the aid of a catalyst having hydroxyl groups.
  • Suitable compounds are z. B. in: Bodo Müller / Ulrich Poth: paint formulation and paint formulation, Vi ncentz- Verlag Hannover, 2003, Part II, Chapter 2: stoving enamels and specified in the literature cited therein.
  • the filler system which consists essentially of a nanoscale particulate filler or a mixture of substantially nanoscale particulate fillers, wherein the fillers are selected from the group of inorganic amorphous or crystalline materials or on the surface of organically modified inorganic materials is an essential component of the coatings of the invention and coatings, and is provided by careful dispersion and / or milling in combination with suitable nanoscale surfactants.
  • Suitable inorganic particles of a certain size and a specific structure This is achieved by adding to the polymers ceramic particles with non-spherical morphology. These particles may consist of aggregates of globular primary particles (size of the primary particles: 5 to 30 nm), which are to achieve the high surface has a fractality of less than 3, preferably less than 2.8, more preferably less than 2.5.
  • the fractality is determined by the method described in DE1976840 by N2 adsorption in the pressure range p / p ⁇ of 0.5 to 0.8.
  • the evaluation of the measurement results is carried out according to the fractal BET theory for the multi-charge adsorption according to the method specified by Pfeifer, Obert and CoIe (Proc. R. Soc., London, A423, 169 (1989)
  • the particles are added in such a way that a Once set particle distribution, only such changes undergoes that changes the desired improvement of the property profile only insignificantly.
  • the quantities vary from 0.1 to 20 wt .-%, preferably 0.2 to 10 wt .-% and particularly preferably 0.5 to 3 wt .-%, based on solid resin.
  • a suitable production process for particles with fractal structures is the flame pyrolysis process of Degussa AG for the production of pyrogenic oxides.
  • Fractal structures can, for. B. be formed by aggregation of spherical, ellipsoidal, crystalline or irregularly shaped particles in the manufacturing process, for example, in the flame pyrolysis in a hot flame or immediately behind the hot flame.
  • Particles having a fractal structure can, for. Example, consist of aggregates of at least two and up to several hundred spherical, ellipsoidal, crystalline or irregularly shaped primary particles.
  • particles having fractal structures prepared by another method are also suitable. Examples of other suitable methods are precipitation methods, hydrothermal methods or plasma methods.
  • the particles of the invention are made compatible by surface modification with the polymer matrix.
  • surface modification includes post-oxidation, adsorption, reactions on the surface or complexing of or with inorganic and / or organic reagents.
  • the particles are modified in such a way that they carry functional groups which have a positive van der Waals type and / or hydrogen bond and / or electrostatic bond and / or ionic bonding and / or coordinate bonding and / or covalent bonding between the particle and the polymer.
  • the particles contain at least two, particularly preferably at least three, functional groups of different reactivity, in order to achieve good binding of the particles to the polymer matrix in all phases of the production and processing process.
  • oxidic, nitridic and carbidic metal and metalloid compounds are preferred:
  • Alumina alpha, beta, delta, theta
  • zirconia zirconia, yttria-doped zirconia, titania, (rutile, anatase and brookite), silica, antimony oxide, zinc oxide, ceria, iron oxides, palladium dioxide, mixed oxides of the above elements.
  • indium tin oxide antimony tin oxide.
  • spinel type materials such as aluminum, iron, chromium, titanium and cobalt spinels.
  • the following ceramic particles such as boron nitride, boron carbide, silicon carbide, silicon nitride.
  • the oxidic particles also have free hydroxyl groups in different proportions in addition to the oxidic groups. The hydroxyl groups may preferably be reacted in a subsequent surface modification.
  • the particles are surface-modified in order to ensure adaptation to the polymer matrix.
  • the surface modification can take place in several stages and take place already during the synthesis.
  • a preferred method is the post-oxidation whereby the number of hydroxyl groups on the surface can be reduced. By this modification, one obtains particles with reduced aggregation behavior, which are characterized by good dispersibility.
  • the particles are surface-modified only in one step.
  • the surface modification with two or more different functional groups is particularly preferred.
  • the first surface modification of the Particles can, following the particle synthesis z. B. by reaction of the pyrogenic oxides with reactive low molecular weight; functional oligomeric or reactive oligomeric substances.
  • suitable modifiers are silicon-containing compounds, such as.
  • silanes substituted silanes, silicone oil, hexamethyldisilazane, alkyltrialkoxysilanes, alkyltrihalogenosilanes, dialkyldialkoxysilanes, dialkyldihalosilanes, trialkylalkoxysilanes, trialkylhalosilanes, glycidyloxypropyltrialkoxysilanes, aminopropyltrialkoxysilanes, methacryloxypropyltrialkoxysilanes, perfluorinated and partially fluorinated alkyltrialkoxysilanes, silanes with further functional groups.
  • Suitable compounds are phosphorus-containing substances, such as. As organically modified phosphates, phosphonates, di- or polyphosphorus, alkyl phosphonates, phosphorus compounds with mixed organic radicals, mixtures of phosphorus compounds or oligomers and polymers with phosphate-containing radicals, such as. B. tego dispers 655 from Degussa, Essen. Phosphorus compounds are particularly effective for surface modification of aluminas but may be used on other pyrogenic oxides. For the surface modification of alumina according to the invention, a modification step is usually sufficient. In a preferred embodiment, aluminum oxide particles are surface-modified in a process step with a plurality of modifiers.
  • dispersants are used for the modification.
  • dispersants are used for the second modification.
  • Dispersants are understood to mean agents which facilitate the dispersion of particles in a dispersion medium, the liquid phase of a dispersion, by lowering the interfacial tension. The property of the dispersant to facilitate dispersing the particles by lowering the interfacial tension between the solid and liquid phases is exhibited when the particles of the present invention are dispersed in an organic liquid.
  • the dispersants assist in the breakup of agglomerates, wet as surface-active materials Surface of the particles to be dispersed and stabilize them against unwanted reagglomeration.
  • the optional second functionalization of the particles can be carried out together with the first functionalization, following the first functionalization or preferably before, during or after the dispersing process, before, during or after the milling process according to the invention.
  • the substances required for the second surface modification are added before the dispersing process to a solvent-containing dispersion of the nanoscale fillers or their precursors or to a binder-containing dispersion of the fillers or precursors in organic solvents.
  • the modifiers for the second surface modification may be the same as or different from those of the first modification.
  • Suitable modifiers for the second modification are the silicon compounds mentioned in the first modification, phosphorus compounds and, in addition, oligomeric dispersing aids having suitable functional groups.
  • the choice of functional groups must be such that they do not or only to a minor extent intervene in the hardening process. Apart from the chemical nature of the functional groups, the accessibility and position in the molecule also play a role.
  • Preferred oligomeric dispersing aids contain aprotic polar groups, more preferably ether, ester and amide groups. Protic or ionic functional groups are favorable for the dispersion process, but may be reactive with the cure system.
  • the silanes, phosphorus compounds or oligomeric dispersing additives used for surface stabilization are selected from the group of a) alkyltrialkoxysilanes of the general formula R-Si-O-R'3 , where R can be an aliphatic or mixed aliphatic / aromatic radical and heteroatoms selected from the group N. , O, S, Cl may be included, which may also interrupt the main chain; and wherein R 'is an aliphatic radical.
  • block copolymers containing polar protic or polar aprotic functional groups in at least one of the blocks f) polycondensates, such as. B.
  • Suitable wetting and dispersing agents are, for. Available from Degussa AG, Essen under the trade name tego dispers, from EFKA (now Ciba) or from Byk Chemie, Wesel.
  • Suitable silanes are available from Degussa AG, Aerosil & Silane business unit, Rheinfelden.
  • Suitable particulate fillers are, for. B. under the trade names Aerosil, Aeroxide ® , AdNano ® or under the chemical name of the metal oxides at Degussa AG, Aerosil & Silane division available.
  • the nanoscale fillers are pressed through a nozzle under very high pressure in solvents containing at least one low molecular weight, oligomeric or polymeric dispersing additive.
  • solvents containing at least one low molecular weight, oligomeric or polymeric dispersing additive When passing through the nozzle very high shear forces occur and the material is accelerated to high speeds during this relaxation.
  • at least one partial stream is expanded by a second nozzle and the generated accelerated liquid jets are focused on a common point in order to mash larger aggregates by impacting action. It is advantageous if the liquid jets collide from opposite direction to each other.
  • the kinetic energy is used for grinding the particles or converted into heat, thereby avoiding excessive abrasive damage to the grinding chamber walls.
  • a grinding unit for grinding, which can disassemble agglomerates and / or aggregates of the filler into nanoscale fragments under high pressure.
  • the reaggregation or reagglomeration of the particles is achieved by stabilizing the particle surface with silanes and / or phosphorus-containing Links; Silanes and / or oligomeric dispersing additives; Combinations of phosphorus-containing compounds with oligomeric dispersing additives prevented.
  • a suitable two-stage process is the predispersion of the nanomaterials in the liquid phase in a rotor-stator-continuous-unit type Ystral Conti TDS and the subsequent milling of the predispersion in a high-energy mill at a pressure above 500 bar, preferably between 500 and 5000 bar and from Z. B. 2500 bar.
  • the process according to the invention gives fractal nanoscale particles which on the one hand are small enough to make no appreciable contribution to the light scattering and thus clouding of the varnish produced therewith and, on the other hand, have not yet lost their fractal character.
  • the aim of the milling is therefore not the production of primary particles, wherein the composition of the dispersion after the wet-grinding can also have a content of primary particles.
  • the wetting and dispersing additives described above are used. Further explanations about the use and combination of suitable surfactants are given in the examples.
  • a single solvent or a combination of solvents can be used.
  • the solvent for the preparation of the nanoparticle dispersion should be compatible with the solvents in the paint.
  • Suitable solvents are selected from the group: aliphatic and cycloaliphatic solvents, aromatic and substituted aromatic solvents, oil and gasoline fractions customary in coatings, esters, lactones, ethers, glycol ethers, ketones, alcohols and other solvents common in paints.
  • solvent combinations are Solvesso 150 / butyl glycol; Solvesso 150 / methoxypropyl acetate and Solvesso 150 / dibasic ester mixture DBE; Solvent combinations with xylene or butyl acetate.
  • additives customary in coatings and coatings can be used, selected from the group of flow control agents, wetting agents and dispersants, antioxidants, curing catalysts, drying agents, reactive diluents, pigments, release agents, slip additives, skin preventatives, adhesion promoters, silanes, phosphorus compounds, alkyl phosphonates, corrosion inhibitors, defoamers.
  • Foam problems are suitable for deaerators, which are also used in diesel fuel:
  • Antifoam systems are used with amounts between 6 ppm and 0.5% (flow).
  • the coating can be done on a laboratory scale according to the usual methods. Examples of metal coating on a production scale are the coating of strip sheets by the coil coating method and the can coating method for metal can coating.
  • the curing of the paints can be done for economic reasons at very short times and high temperatures.
  • the paints according to the invention are intended to develop their required properties under production conditions.
  • a suitable method for the laboratory is doctoring. With a doctor blade, a groove doctor blade or a wire bar to wear, the paint layer, allowed to flash, short and cures the layer in a drying cabinet, depending on the curing agent system is between 130 0 C and 310 0 C.
  • the wet film thickness is selected so that a dry film between 5 and 100 microns, preferably 30 and 60 microns thickness results.
  • the curing time can be between 60 minutes at low temperature and 30 seconds at the highest temperature. It will depending on the reactivity of hydroxy-functional component and the hardener component selected according to the recommendations of the raw material manufacturers. Information on suitable time / temperature combinations can be found in: Bodo Müller / Ulrich Poth: paint formulation and paint formulation, Vincentz-Verlag Hannover, 2003, Part II, Chapter 2: stoving enamels
  • An essential feature of the coating according to the invention is that clear transparent or substantially clear transparent coatings are obtained. Nanoscale fillers with a high refractive index naturally lead to greater haze for the same particle size than fillers with a refractive index close to the refractive index of the resin hardener system. After curing of the coating is left to stand for 24 h. Thereafter, the test of the paint properties. All paint properties are compared with the unmodified blank.
  • the following coating properties were tested: MEK resistance, adhesion (cross-hatch), layer thickness, pendulum hardness according to König, Erichsen indentation, ball hardness, abrasion resistance (Taber Abraser, friction wheels CS 10, 1000 revolutions (standard), if necessary up to 5000 revolutions), wet rubbing test according to internal Method, gloss before and after wet rub test, reflow after 2 h 60 0 C or 2 d RT, pencil hardness, Erichsen scratch hardness.
  • the paints of the invention are flexible and scratch-resistant, abrasion-resistant and / or abrasion-resistant than the unmodified paints.
  • the prerequisite for increased scratch resistance and / or abrasion resistance is the grinding, dispersion and stabilization of the fractal, particulate fillers according to the invention.
  • the fractal particulate fillers are not distributed uniformly or may agglomerate.
  • the viscosity of the coating may also be too high for optimum processing.
  • the corresponding paints show turbidity and the scratch resistance, scuff resistance and / or abrasion resistance is reduced compared to the unmodified paints.
  • an important feature of the invention is also the stabilization of the nanoscale particles produced by high energy milling in the dispersion by the abovementioned surface-active agents.
  • the paints according to the invention have the same or improved flexibility compared with unmodified paints in the Erichsen recess.
  • the dispersions are dispersed for 15 minutes with a dissolver or for 30 minutes with a rotor-stator continuous shear unit (Ystral).
  • the particle size and particle size distribution of the nanoparticle dispersions were determined by means of light scattering analysis according to Mie theory using a Horiba LA 920 laser scattered light spectrometer. Further suspensions S6 to S10 were prepared by the same procedure in butyl acetate. Instead of the abovementioned surface-active compounds, only a polymeric dispersing additive based on a polyethyleneimine with polyether and polyester side chains grafted onto it (test product, Degussa AG, Essen) is used. The following dispersions are used:
  • Nanoparticle dispersions in butyl acetate with polymeric dispersing additive are described in detail below.
  • dispersions are prepared: c) dispersions without dispersing additive and without grinding on the high-energy mill d) dispersions with dispersing additive without grinding on the high-energy mill
  • the dispersions are dispersed for 15 minutes with a Pendulol LD 50 dissolvers with 35 mm disc and 930 rpm. Without a dispersing additive, viscous pastes are sometimes obtained so that it is not possible to achieve the same amount of filler as with dispersing additive.
  • the maximum settable solids content is 25% with a content of 4.5% polymeric dispersing additive absolute. Above this concentration, pudding-like thickening occurs.
  • the nanoparticle suspensions are mixed with resins and hardeners as well as other additives, if necessary dispersed again with a dissolver, allowed to stand for degassing, coated on sheets and thermally cured.
  • the cure temperature / time combination is chosen to pass the MEK test but no yellowing due to over cure.
  • the addition of nanoparticles may make it necessary to slightly increase the curing time compared to unmodified coatings. Usually it is cured at 160 ° C. and curing times between 10 and 30 minutes.
  • An inventive paint consists z. B.
  • lacquers of polyester and phenol-formaldehyde resin examples include polyester and phenol-formaldehyde resin:
  • the paint formulations were applied as topcoats on a primer.
  • the layer thickness is 20 microns
  • the oven temperature was 310 0 C at a residence time of 30 sec.
  • the paint formulations were applied as topcoats on a primer.
  • the layer thickness is 20 microns
  • the oven temperature was 310 0 C at a residence time of 30 sec.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un liant comprenant une matrice à base d'un ou de plusieurs polymères et pour 100 % en poids de l'ensemble du liant une suspension stabilisée de particules nanométriques, en une quantité de 0,5 à 25 % en poids mesurée en tant que proportion de solides de la suspension, ledit liant étant caractérisé en ce que la suspension de particules peut être obtenue par a) broyage des particules avec ajout d'un solvant dans un broyeur haute pression qui, sous une pression comprise entre > 500 et environ 10 000 bars, atomise les agglomérats et/ou les agrégats des particules en fragments nanométriques ; et b) ajout d'un ou de plusieurs additifs de dispersion pour stabiliser la surface des particules broyées, le ou les additifs de dispersion étant introduits en une quantité de 1 à 25 parties en poids pour 100 parties en poids des particules. L'invention concerne également un procédé de fabrication du liant et son utilisation dans des peintures. Les peintures contenant le liant permettent d'obtenir des revêtements transparents présentant une grande résistance aux éraflures et une grande flexibilité.
PCT/EP2007/059114 2006-10-27 2007-08-31 Liant contenant des particules nanométriques présentant une meilleure résistance aux éraflures et une meilleure flexibilité, son procédé de fabrication et peinture d'une grande transparence le contenant WO2008049679A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006050748.7 2006-10-27
DE102006050748A DE102006050748A1 (de) 2006-10-27 2006-10-27 Nanoskalige Partikel enthaltende Lackbindemittel mit verbesserter Kratzfestigkeit und Flexibilität, Verfahren zu deren Herstellung sowie diese enthaltende hochtransparente Lacke

Publications (1)

Publication Number Publication Date
WO2008049679A1 true WO2008049679A1 (fr) 2008-05-02

Family

ID=38747977

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2007/059114 WO2008049679A1 (fr) 2006-10-27 2007-08-31 Liant contenant des particules nanométriques présentant une meilleure résistance aux éraflures et une meilleure flexibilité, son procédé de fabrication et peinture d'une grande transparence le contenant

Country Status (3)

Country Link
CN (1) CN101168631A (fr)
DE (1) DE102006050748A1 (fr)
WO (1) WO2008049679A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2213706A1 (fr) 2009-02-03 2010-08-04 Bühler PARTEC GmbH Additif destiné à l'amélioration de la résistance aux solvants et à d'autres propriétés de systèmes de liant à base d'eau
WO2010089295A1 (fr) 2009-02-03 2010-08-12 Bühler PARTEC GmbH Particules d'oxyde de zinc modifiées par de l'acide phosphonocarboxylique et utilisation de particules d'oxyde de zinc
EP2241602A1 (fr) 2009-04-17 2010-10-20 Bühler PARTEC GmbH Particules d'oxyde de zinc modifiées à l'aide d'acide de carbone phosphonique et utilisation de particules d'oxyde de zinc
CN102971384A (zh) * 2010-07-09 2013-03-13 赢创罗姆有限公司 含热稳定分散添加剂的用于聚（甲基）丙烯酸酯着色的水基液体色料
WO2013100836A1 (fr) * 2011-12-29 2013-07-04 Perstorp Ab Composition de résine alkyde comprenant de la silice
US10745580B2 (en) 2014-09-11 2020-08-18 Evonik Operations Gmbh Surface-finishing on the basis of cross-linkable, saturated polyester resins and fluoropolymers
CN112394029A (zh) * 2019-08-13 2021-02-23 宝山钢铁股份有限公司 用于评价覆膜铁表面薄膜结合力的模拟液及其评价方法

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009040488A1 (de) 2009-09-08 2011-03-10 Cetelon Lackfabrik Gmbh Verfahren zur Herstellung von Dispersionen mit nanoskaligen Siliziumdioxid-Partikeln aus pyrogenen Kieselsäuren
CN101914319B (zh) * 2010-08-09 2014-04-02 南开大学 一种高硬度、抗划伤性纳米汽车油漆的制备技术
CN101985541B (zh) * 2010-10-25 2013-03-20 江苏考普乐新材料股份有限公司 聚氨酯涂料及其制备方法
CN102867557B (zh) * 2012-10-09 2015-08-05 哈尔滨工业大学 一种氮化硼-聚乙烯空间辐射防护复合材料的制备方法
CN103146243B (zh) * 2013-03-25 2015-09-16 新疆红山涂料有限公司 涂料用无苯稀释剂及其制备方法
CN103351701A (zh) * 2013-07-24 2013-10-16 舟山市新龙电子设备有限公司 提高着墨牢度的涂料
CN103589311B (zh) * 2013-10-16 2016-06-29 国家电网公司 一种钛酸酯改性纳米氧化铈/聚氨酯复合涂料的制备方法
CN105295788A (zh) * 2014-01-09 2016-02-03 苏州斯迪克新材料科技股份有限公司 耐气候丙烯酸胶粘剂的制造方法
CN105176435A (zh) * 2014-01-09 2015-12-23 苏州斯迪克新材料科技股份有限公司 强粘接压敏胶带的制备方法
WO2017110670A1 (fr) * 2015-12-24 2017-06-29 Sintokogio, Ltd. Système de dispersion et procédé de dispersion
CN106590363A (zh) * 2016-12-08 2017-04-26 苏州纳贝通环境科技有限公司 一种耐酸碱金属包装涂料及其制备方法
CN110072929B (zh) * 2016-12-20 2022-02-11 宝洁公司 用于从再生产品中分离和纯化聚合物的方法
DE102017101978B4 (de) 2017-02-01 2023-02-02 Fachhochschule Kiel Transparente, kratzfeste Schicht mit Antifouling-Eigenschaften und Verfahren zur Herstellung derselben
CN110066581A (zh) * 2017-11-01 2019-07-30 丹阳西联生物技术有限公司 一种耐磨搅拌桨叶涂层
CN108219653B (zh) * 2018-01-02 2020-04-03 海洋化工研究院有限公司 一种耐油罩光清漆及其制备方法
DE102019102083A1 (de) * 2019-01-28 2020-07-30 Ludwig Schletter Nanopartikuläres Siliziumcarbid und Elektrode umfassend nanopartikuläres Siliziumcarbid
CN110845944A (zh) * 2019-11-07 2020-02-28 广东四方威凯新材料有限公司 一种有机无机杂化耐磨涂料及其制备方法
CN112076762B (zh) * 2020-10-09 2023-04-25 上海翼湍科技有限责任公司 制备新戊二醇用催化剂

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19536845A1 (de) * 1995-10-02 1997-04-03 Bayer Ag Verfahren und Vorrichtung zur Herstellung von feinteiligen Feststoffdispersionen
EP0943664A2 (fr) * 1998-03-18 1999-09-22 Bayer Ag Liant de revêtement transparent contenant des nanoparticules ayant une résistance améliorée au rayage, procédé pour leur préparation et leur utilisation

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6318649B1 (en) * 1999-10-06 2001-11-20 Cornerstone Technologies, Llc Method of creating ultra-fine particles of materials using a high-pressure mill
DE10007816A1 (de) * 2000-02-21 2001-09-06 Bayer Ag Verfahren zur Herstellung von Nanosuspensionen
DE10124952A1 (de) * 2001-05-21 2002-12-12 Bayer Ag Verfahren zur Herstellung von Nanodispersionen
WO2002094443A2 (fr) * 2001-05-23 2002-11-28 E.I. Du Pont De Nemours And Company Broyeur a charge broyante sous haute pression
EP1484050A3 (fr) * 2003-06-02 2006-05-10 STS TENSID SERVICE GmbH Composition pour la préparation de produits de soins corporels et cosmétiques et compléments nutritionels

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19536845A1 (de) * 1995-10-02 1997-04-03 Bayer Ag Verfahren und Vorrichtung zur Herstellung von feinteiligen Feststoffdispersionen
EP0943664A2 (fr) * 1998-03-18 1999-09-22 Bayer Ag Liant de revêtement transparent contenant des nanoparticules ayant une résistance améliorée au rayage, procédé pour leur préparation et leur utilisation

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2213706A1 (fr) 2009-02-03 2010-08-04 Bühler PARTEC GmbH Additif destiné à l'amélioration de la résistance aux solvants et à d'autres propriétés de systèmes de liant à base d'eau
WO2010089295A1 (fr) 2009-02-03 2010-08-12 Bühler PARTEC GmbH Particules d'oxyde de zinc modifiées par de l'acide phosphonocarboxylique et utilisation de particules d'oxyde de zinc
US8791191B2 (en) 2009-02-03 2014-07-29 Buehler Partec Gmbh Zinc oxide particles which have been modified with phosphonocarboxylic acid and use of zinc oxide particles
US8865818B2 (en) 2009-02-03 2014-10-21 Buehler Partec Gmbh Additive for improving the solvent resistance and other properties of water-based binder systems
EP2241602A1 (fr) 2009-04-17 2010-10-20 Bühler PARTEC GmbH Particules d'oxyde de zinc modifiées à l'aide d'acide de carbone phosphonique et utilisation de particules d'oxyde de zinc
CN102971384A (zh) * 2010-07-09 2013-03-13 赢创罗姆有限公司 含热稳定分散添加剂的用于聚（甲基）丙烯酸酯着色的水基液体色料
CN102971384B (zh) * 2010-07-09 2016-01-20 赢创罗姆有限公司 含热稳定分散添加剂的用于聚（甲基）丙烯酸酯着色的水基液体色料
WO2013100836A1 (fr) * 2011-12-29 2013-07-04 Perstorp Ab Composition de résine alkyde comprenant de la silice
US10745580B2 (en) 2014-09-11 2020-08-18 Evonik Operations Gmbh Surface-finishing on the basis of cross-linkable, saturated polyester resins and fluoropolymers
CN112394029A (zh) * 2019-08-13 2021-02-23 宝山钢铁股份有限公司 用于评价覆膜铁表面薄膜结合力的模拟液及其评价方法

Also Published As

Publication number Publication date
CN101168631A (zh) 2008-04-30
DE102006050748A1 (de) 2008-04-30

Similar Documents

Publication Publication Date Title
WO2008049679A1 (fr) Liant contenant des particules nanométriques présentant une meilleure résistance aux éraflures et une meilleure flexibilité, son procédé de fabrication et peinture d'une grande transparence le contenant
EP0943664B1 (fr) Liant de revêtement transparent contenant des nanoparticules ayant une résistance améliorée au rayage, procédé pour leur préparation et leur utilisation
EP2049603B1 (fr) Particule à surface modifiée et procédé de fabrication
EP1690902B1 (fr) particules nanométriques à surfaces modifiées, procédé de fabrication et utilisation
EP2421924B1 (fr) Laques de base à teneur élevée en matières solides et exemptes d'eau, leur fabrication et leur utilisation pour l'enduction de laques en plusieurs couches ainsi que des laques en plusieurs couches contenant une laque de base à teneur élevée en matières solides et exempte d'eau
EP2092001B1 (fr) Agent de revêtement pigmenté et contenant un solvant, son utilisation pour la fabrication de revêtements multicouches et procédé d'amélioration du flop de revêtements à effet
US7780777B2 (en) Dispersion containing titanium dioxide
EP1922368B1 (fr) Matieres d'enduction contenant des nanoparticules d'oxyde mixte
EP2668240B1 (fr) Agent mouillant et dispersant, procédé de production et utilisation
EP2107086B1 (fr) Dispersion comprenant des particules de dioxyde de silicium hydrophobes
DE10212121A1 (de) Verfahren zur Herstellung von nano-Zinkoxid-Dispersionen stabilisiert durch hydroxylgruppenhaltige anorganische Polymere
EP1692078A1 (fr) Sulfate de baryum desagglomere
EP2072554B1 (fr) Liant contenant des nanoparticules
WO2010121799A1 (fr) Vernis multi-couches, procédé de production et utilisation associés
EP2665784B1 (fr) Utilisation de polyhydroxyalkanoates en tant qu'additifs dans des compositions de revêtement
EP2638114B1 (fr) Dispersion et préparation pour laque contenant des particules hydrofugées de dioxyde de silicium
WO2007020064A1 (fr) Nanoparticules a surface modifiee, constituees par un oxyde d'aluminium et des oxydes d'elements du i. ou ii. groupe principal de la classification periodique des elements et realisation associee
DE102007030285A1 (de) Oberflächenmodifizierte Partikel und Herstellungsverfahren
EP1947141B1 (fr) Suspensions stabilisées de particules inorganiques
JPH09169925A (ja) 表面改質重質炭酸カルシウムとその製造方法及び水系塗料組成物
WO2008022760A1 (fr) Encres d'impression contenant des nanoparticules d'oxyde mixte
EP3663365A1 (fr) Dispersion et préparation pour laque aqueuse contenant du dioxyde de silicium hydrophile et du silanol
DE102006021705B3 (de) Verwendung von Mischoxid-Nanopartikeln in Beschichtungsmassen
DE102006054013A1 (de) Beschichtungsmassen enthaltend reaktive Esterwachse und Mischoxid-Nanopartikel
DE102007014872A1 (de) Stabilisierte Suspensionen von anorganischen Nano-Partikeln

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: 07820005

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: 07820005

Country of ref document: EP

Kind code of ref document: A1