WO2015065164A1 - Composition de peinture non toxique contenant des nanostructures d'oxydation organiques et inorganiques et son procédé de préparation - Google Patents

Composition de peinture non toxique contenant des nanostructures d'oxydation organiques et inorganiques et son procédé de préparation Download PDF

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WO2015065164A1
WO2015065164A1 PCT/KR2014/010531 KR2014010531W WO2015065164A1 WO 2015065164 A1 WO2015065164 A1 WO 2015065164A1 KR 2014010531 W KR2014010531 W KR 2014010531W WO 2015065164 A1 WO2015065164 A1 WO 2015065164A1
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weight
parts
oxide
graphene oxide
paint composition
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Korean (ko)
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김상재
케이카티케얀
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제주대학교 산학협력단
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Priority to EP14858569.8A priority Critical patent/EP3067394B1/fr
Priority to EP18176146.1A priority patent/EP3392316B1/fr
Priority claimed from KR1020140152156A external-priority patent/KR101678279B1/ko
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • 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
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • 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
    • C09D7/43—Thickening 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/45—Anti-settling 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • 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
    • 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
    • C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
    • 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
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc

Definitions

  • the present invention relates to a paint composition, more specifically, containing graphene oxide nanosheets (GO nanosheets), zinc oxide particles (ZnO nanoparticles) and molybdenum oxide nanoplates (MoO 3 nanoplates) (hereinafter referred to as oxide nanostructures) (hereinafter referred to as oxide nanostructures) It relates to a non-toxic paint composition and a method for producing the same.
  • GO nanosheets graphene oxide nanosheets
  • ZnO nanoparticles zinc oxide particles
  • MoO 3 nanoplates molybdenum oxide nanoplates
  • Paint is a kind of material used to decorate and / or protect surfaces. They are used in a variety of applications, including home appliances, biomedical devices, and industrial processes (particularly corrosion protection coatings).
  • Corrosion of steel structures means that rust or red blue (Fe (OH) 3 and Fe 2 O 3 ) are generated.Their causes are oxygen (O 2 ) and moisture (H 2 O) in the air. can see. This corrosion tends to be accelerated by polluted atmospheres, soot, salts in sea water, acid rain, chemicals (acids, alkalis and salts), and the like.
  • a corrosion inhibitor such as photo-list, zinc chromate, passivation when water comes into contact with the metal by the reaction suppression function, or inflow of water or air that causes corrosion
  • Sacrificial anodes such as aluminum or mica-like oxidized iron oxides, which act as barriers, or metal pigments, such as zinc, which tend to ionize more than iron in the cathode. have.
  • Republic of Korea Patent No. 503,561 is a coating composition for preventing corrosion and improving durability of the steel structure and aluminum oxide film adhesion method using the same, by applying a coating using zinc, chromium, nickel, aluminum oxide, etc.
  • the formation method is disclosed.
  • heavy metals such as chromium and lead are contained to improve the rust prevention function of the paint, they may be absorbed by the human body through the respiratory organ or the skin, which may cause serious problems.
  • marine vessels and marine steel structures, etc. play a major role in causing corrosion of marine organisms that cause macrofouling, such as silk tuna shells and scallop shells, as well as corrosion caused by marine salts.
  • Arthropod barnacles, algae brown algae, red algae, green algae, etc. are also placed on the steel, which serves to corrode and inhibit the operation of the ship.
  • the organic poison type TBT (Tributyltin) is an antifouling paint prepared by mixing TBT with self-polishing acrylic resin or synthetic resin, and its longest antifouling life is about 3 to 5 years, but this material is used for shellfish in shellfish. As a deadly environmental hormone that causes a problem, it has a problem that adversely affects the environment as recently called sea herbicides.
  • the inorganic poisonous copper dioxide is an antifouling paint prepared by mixing copper dioxide with an inorganic resin, which has a short antifouling life and has a severe problem of releasing copper oxide in the early stages, and also causes environmental hormones in shellfish. There is a problem.
  • Arsenic antifouling paints are manufactured by mixing arsenic materials with self-polishing acrylic resins or synthetic paints, and have good antifouling properties, but have serious problems of causing serious side effects in marine ecosystems.
  • the conventional technology is excellent in antifouling performance itself, but has a disadvantage of causing serious environmentally adverse side effects, while maintaining antifouling performance, development of an environmentally friendly antifouling paint is required without toxicity.
  • An object of the present invention is to prepare a paint composition by blending graphene oxide nanosheets (GO nanosheets), zinc oxide particles (ZnO nanoparticles) and molybdenum oxide nanoplates (MoO 3 nanoplates) in an optimal ratio of alkyd resin as a pigment, Compared to the conventional paint, it is not only excellent in corrosion resistance, but also free of toxic substances such as chromates or biocides, and to provide an environmentally friendly paint composition.
  • Another object of the present invention to provide a method for producing the paint composition.
  • oxide nanostructures as pigments 15-20 parts by weight of oxide nanostructures as pigments, 60-70 parts by weight of alkyd synthetic resins as binders, 0.5-1.0 parts by weight of stabilizers, 0.3-0.7 parts by weight of precipitation inhibitors, 0.05-0.15 parts by weight of thickeners, 0.5-1.0 parts by weight of wetting agents , 1.0-2.0 parts by weight of a desiccant and 15-20 parts by weight of a diluent are provided.
  • the paint composition comprising the oxide nanostructures according to the present invention is economical, has a high solids content compared to conventional paints, and dries quickly and is free of toxic substances such as chromates or biocides.
  • paint compositions comprising oxide nanostructures according to the present invention exhibited good corrosion resistance behavior in acidic and high salt content solutions, in particular oxide nanopaint coatings measured in saline, as measured from linear polarization studies. A corrosion protection efficiency of% was shown.
  • the paint composition comprising oxide nanostructures according to the present invention inhibits the growth of bacterial strains (E.
  • HR-TEM high-resolution transmission electron microscope
  • SAED selective area electron diffraction
  • FIG. 2 is a photograph of a graphene oxide nanopaint according to an embodiment of the present invention, (b) an embodiment of the present invention painted on a drawdown card for measurement of gloss level and hiding power. According to graphene oxide nanopaint.
  • FIG. 3 is a Fourier transform infrared spectrum of an alkyd synthetic resin and graphene oxide nanopaint according to an embodiment of the present invention, and (b) a Raman spectrum of an alkyd synthetic resin and graphene oxide nanopaint according to an embodiment of the present invention. Indicates.
  • Figure 4 is (a) the X-ray photoelectron spectrum of the alkyd synthetic resin and graphene oxide nanopaint according to an embodiment of the present invention, (b) of the graphene oxide nanopaint showing the presence of CC, COC and C-OO groups C 1s unwound spectrum (c) Low magnification (scale-10 ⁇ m) and d) high magnification (scale-1 ⁇ m) FE-SEM images of graphene oxide nanopaint coatings.
  • FIG. 5 is an optical image of uncoated (left) and graphene oxide-painted (right) GI substrates ((a) before exposure to acid and (b) after impregnation for 24 hours in 0.1 M HCl solution).
  • FIG. 8 shows (a) graphene oxide-nanopaint-coated and uncoated substrates impregnated in a lagoon with tide directly connected to Jeju sea, (b) uncoated substrate and painting before and after 3 weeks Of the substrate.
  • FIG. 9 is a result of XRD analysis of coating zinc oxide nanopaint on a glass material in order to measure the binding relationship between zinc oxide and alkyd resin.
  • FIG. 10 is a result of measuring Raman spectra by coating zinc oxide nanopaint on a glass material to measure a binding relationship between zinc oxide and alkyd resin.
  • Figure 12 shows the bacterial survival rate by coating with molybdenum oxide nanopaint, (a) the reduction rate of Escherichia coli (b) the reduction rate of Pseudomonas aeruginosa (c) the reduction rate of Staphylococcus aureus (d) the reduction rate of pneumococci.
  • 'oxide nano paint' means a paint composition containing oxide nanostructures such as graphene oxide nanosheets (GO nanosheets), zinc oxide particles (ZnO nanoparticles), and molybdenum oxide nanoplates (MoO 3 nanoplates). Oxide nanopaints and paint compositions containing oxide nanostructures are used interchangeably.
  • 'paint' and 'paint' have the same meaning and are used interchangeably within the specification.
  • the present invention is 15-20 parts by weight of oxide nanostructures as a pigment, 60-70 parts by weight of alkyd synthetic resin as a binder, 0.5-1.0 parts by weight of stabilizer, 0.3-0.7 parts by weight of precipitation inhibitor, 0.05-0.15 parts by weight of thickener, 0.5-wetting agent.
  • a paint composition comprising 1.0 part by weight, 0.5-1.0 part by weight of the internal coating desiccant, 0.5-1.0 part by weight of the top coating desiccant and 15-20 parts by weight of the diluent.
  • the oxide may use graphene oxide, zinc oxide (zinc oxide) or molybdenum oxide.
  • Graphene is a combination of graphite, which means graphite, and the suffix -ene, which means a molecule with a carbon double bond in chemistry.
  • graphene is the substance observed in graphite, an allotrope of carbon. Magnifying a pencil lead with an electron microscope reveals a stack of thin plates. It is a three-dimensional structure of numerous carbon atoms stacked in a hexagonal honeycomb.
  • Graphene is the thinnest layer here. That is, it is a thin film structure of the two-dimensional planar form of thickness 0.35 nm which consists of one layer of carbon atoms.
  • Such graphene compounds are called fullerenes, which are graphite when stacked in three dimensions, carbon nanotubes when dried in one dimension, and zero-dimensional structures when they become balls.
  • Graphene was first produced at room temperature in 2004 by a team at the University of Manchester, England.
  • Graphene oxide is a compound in which the graphene is oxidized and has various functional groups such as epoxyl, hydroxyl, and canonyl.
  • the graphene oxide nanosheets are harmless to the human body due to biocompatibility and non-toxic properties, and have environmentally friendly advantages.
  • the zinc oxide is a compound of oxygen and zinc, which is a light white powder, also referred to as zinc or zinc bag, and is used as a raw material for medicines, pigments and cosmetics.
  • Zinc oxide is a light white powder, melting point 1,975 °C (pressurization), 1,720 °C (atmospheric pressure), specific gravity 5.47 (non-crystalline), 5.78 (crystalline), when heated to about 300 °C turns yellow, but when cooled to its original color. Dilute acids and concentrated alkalis are soluble amphoteric oxides.
  • the molybdenum since the molybdenum is easily converted into an oxidized form, the molybdenum may act as an electron transport material in the oxidation-reduction reaction, and the molybdenum oxide refers to the oxidized molybdenum.
  • the oxide nanostructures according to the present invention may also be prepared by methods known in the art, for example, Krishnamoorthy K, et al., Carbon 2012, 53: 38-49; Krishnamoorthy K, et al., Appl. Phys. Lett. 2011,98: 244101 (1-3)] and the like can be prepared using, but is not limited thereto.
  • the graphene oxide nanosheets exhibited a sheet-like morphology with the presence of folded regions at the corners, as shown in FIG. 1.
  • the corresponding selective area electron diffraction (SAED) pattern shows a clear diffraction point with six-fold symmetry, which coincides with the hexagonal lattice.
  • the Raman spectra of the graphene oxide nanosheets show the presence of wide D bands (1350 cm ⁇ 1 ) and G bands (1597 cm ⁇ 1 ) since graphite oxidizes to form graphene oxide.
  • the content of the oxide nanosheets is preferably 15-20 parts by weight.
  • the alkyd synthetic resin serves as a binder and occupies most of the paint composition.
  • the content of the alkyd synthetic resin is preferably 60 to 70 parts by weight.
  • soybean lecithin can be used as the humectant, wherein the soybean lecithin is preferably used 0.5-1.0 parts by weight. The absence of the humectant can cause non-uniform surface finish due to the aggregation of graphene oxide nanosheets.
  • the desiccant is used for the formulation, whereby an external desiccant and an internal desiccant can be used.
  • the external desiccant is an active catalyst for the lipid oxidation process, which results in faster drying times and more homogeneous coatings on the surface.
  • the internal desiccant is a chemical cross-linker for unsaturated fatty acids, which improves the rate of cross-linking during drying.
  • the external desiccant preferably uses cobalt naphthenate, but is not limited thereto, and its content is preferably 0.5-1.0 parts by weight.
  • the internal desiccant preferably uses nano-sized zirconia, but is not limited thereto, and its content is preferably 0.5-1.0 parts by weight.
  • thickeners and precipitation inhibitors may be used to adjust the viscosity and prevent solidification, the content of which is 0.05-0.15 parts by weight and 0.3-0.7 parts by weight of precipitation inhibitor, respectively. It is preferable.
  • commercially available thickener A may be used as the thickener, and aluminum stearate may be used as the precipitation inhibitor, but is not limited thereto.
  • a stabilizer may be used to inhibit the separation of graphene oxide nanosheets in the alkyd synthetic resin and also to reduce the color fading when stored for a long period of time.
  • Nano-sized ZnO may be used, but is not limited thereto.
  • the stabilizer is preferably used 0.5 to 1.0 parts by weight based on the total weight of the paint composition.
  • the diluent serves to effectively and evenly mix the synthetic resin and graphene oxide nanosheets, thereby improving antifouling performance and coating work, mineral solvent, ether solvent, glycidyl It is preferably at least one of an ether solvent, an alcohol solvent, an ether solvent, an ester solvent, a ketone solvent, a hydrocarbon solvent or a nitrogen solvent, more preferably a mineral solvent and even more preferably a mineral terebin oil. effective.
  • the content of the diluent may vary depending on the viscosity, but generally it is preferable to use 15-20 parts by weight.
  • the present invention also provides a method for producing the paint composition.
  • the method for producing a paint composition according to the present invention is characterized in that the paint composition is homogeneously mixed by a ball-milling process, and the common contents of both inventions are described in order to avoid excessive complexity of the specification according to the repeated description. Omit.
  • the ball milling is characterized by maintaining for 4-6 hours at a milling speed of approximately 300 rpm, then adding a diluent and maintaining milling for an additional 20 minutes-1 hour.
  • the drying mechanism of the oxide nanopaints according to the invention relies on lipid autooxidation of alkyd synthetic resins, which is a well-known free-radical mechanism present in atmospheric oxygen [Muizebelt WJ, et al., Prog. Org. Coat. 2000, 40: 121-30; Bieleman, JH., Wiley-VCH, Weinheim, 2000].
  • Polyunsaturated fatty acids in alkyd resins undergo cross-linking by free radical-mediated chain reactions, resulting in a uniform film coating dried on the surface [Schaich KM. Baileys Industrial Oil and Fat Products. 6th ed. Edited by Fereidoon Shahidi. John Wiley & Sons, Inc; 2005].
  • graphene oxide pigments in paints can facilitate lipid auto-oxidation reactions due to the carbocatalytic properties of graphene oxide for the oxidation, polymerization and ionization of long chain fatty acids [Liu Y, et al. , Rapid Commun. Mass Spectrom. 2011; 25: 3223-34.
  • Graphene oxide can easily cross-link with macromolecules during oxidative polymerization, which acts as a template for the growth of macromolecules [Park S, et al., ACS Nano. 2008; 4: 572-78.
  • graphene oxide nanosheets are cross-linked through electrostatic interaction and hydrogen bonding with lipid molecules present in the alkyd resin, which leads to the formation of a homogeneous black paint.
  • graphene oxide nanosheets will catalyze the lipid autooxidation process by providing a sufficient amount of oxygen during the drying process.
  • partial reduction of graphene oxide can occur due to free radicals occurring during the autooxidation process, which has been reported previously for graphene oxide reduction via bacterial respiration, free radical reduction, and during chemical functionalization [Akhavan O, et al., Carbon 2012, 50: 1853-60; Vinodgopal K, et al., J. Phys. Chem. Lett. 2010; 1: 1987-93.
  • the oxide nanopaint prepared by the above method is economical because it has a higher solids content than conventional paints, is fast drying, and is environmentally friendly since there is no toxic substance such as chromate or biocide.
  • the oxide nanopaints exhibited good corrosion resistance behavior in acidic and high salt content solutions, and in particular, as shown in FIG. 6, about 76% corrosion protection in saline in linear polarization studies. Efficiency was shown.
  • the oxide nanopaints inhibit growth against bacterial strains (E. coli ( Esherichia coli ), Staphylococcus aureus , and Pseudomonas aeruginosa ) on the painted surface, as shown in FIG. As shown in FIG. 8, the effect of suppressing the attachment of marine organisms was excellent. Therefore, the oxide nanopaint according to the present invention may be usefully used in place of paint used in general steel structures and ships or marine steel structures.
  • the graphene oxide nanosheets are described in Krishnamoorthy K, et al., J. Phys. Chem. C 2012; 116: 17280-87, according to the modified Hummers method.
  • Raman spectra of graphene oxide nanosheets indicate the presence of wide D bands (1350 cm -1 ) and G bands (1597 cm -1 ), from which graphite was oxidized to form graphene oxide [Krishnamoorthy K , et al., Carbon 2012; 53: 38-49. Freshly synthesized graphene oxide nanosheets were used to prepare graphene oxide nanopaints.
  • Alkyd paints incorporating graphene oxide nanosheets were prepared using a ball-milling approach.
  • the paint used graphene oxide as pigment, and other additional additives for binders, thickeners, wetting agents, internal coating desiccants, external coating desiccants, diluents, and stabilizers are listed in Table 1.
  • Alkyd paints bound with zinc oxide (ZnO) were prepared using a ball-milling approach.
  • the paint used zinc oxide as pigment, and other additional additives for binders, thickeners, wetting agents, internal coating desiccants, external coating desiccants, diluents, and stabilizers are listed in Table 2.
  • Pigment ZnO Nanoparticles Provide color of paint 20.0 Binder Alkyd resin Film-forming composition of paint 60.0 Stabilizer Nano-sized ZnO Reduced the color fading effect of paint 0.6
  • Precipitation inhibitor Aluminum stearate Prevention of precipitation of pigments and binders 0.5 Thickener Polyvinyl alcohol Improve viscosity and prevent solidification 0.1 Humectant Soy lecithin Wetting on the pigments in the binder for homogeneous dispersion 0.6
  • Exterior coating desiccant Cobalt naphthenate Active Catalysts for Lipid Autooxidation 0.6 Thinner (solvent) toluene Dispersion 17.0
  • Molybdenum Oxide (MoO) 3 Preparation of Paint Composition Comprising Nanoplates
  • Alkyd paints bonded with molybdenum oxide nanoplates were prepared using a ball-milling approach.
  • the paint used molybdenum as pigment, and other additional additives for binders, thickeners, wetting agents, internal coating desiccants, external coating desiccants, diluents, and stabilizers are listed in Table 3.
  • the hiding power and gloss levels of graphene oxide nanopaints were tested by applying a certain amount of paint on a drawdown card with a controlled thickness of about 150 ⁇ m using a multifunctional film applicator.
  • 1 g of paint was placed on a drop-down card, cut using a multifunctional film applicator, and then dried at room temperature.
  • the hiding power of the paint was then visually observed by testing whether the background color (black or white) was covered by the paint.
  • Gloss measurement was performed using a Rajdhani digital gloss meter (RSPT-200 model, India).
  • the graphene oxide nanopaint completely concealed both the black and white background of the voltage drop card.
  • the gloss level of graphene oxide nanopaints was 60 to 75 GU. According to ASTM (American Standard for Testing and Materials) standards, 60 to at least 60 GU coatings are classified as high-gloss surfaces, which demonstrates the excellent surface finish of graphene oxide nanopaints according to the present invention.
  • the solids content of the paint is the ratio of the solid phase components to the weight of the total components in the paint.
  • the amount of solids present in the paint was determined by drying 1 g of paint on a clean, dried watch glass. Based on the initial and final weight measurements, the solids content of graphene oxide and commercial paints was evaluated using the following formula.
  • W 1 is the initial weight of the paint and W 2 is the weight of the paint after drying.
  • the solids content of graphene oxide nanopaint was 64.24%, but only 39.21% of commercial paints. This means that graphene oxide nanopaints can be more economical than commercial paints.
  • surface drying time, drying time to hardening and drying time to coating were observed as 1, 3, and 6 hours, respectively. Drying times for graphene oxide nanopaints were faster than commercial paints.
  • FT-IR Fourier transform infrared
  • XPS X-ray photoelectron spectroscopy
  • Figure 3a shows the FT-IR spectrum of the uncoated alkyd synthetic resin and the final graphene oxide nanopaints.
  • the FT-IR spectra of the uncoated alkyd resins are CO bonds (1070 cm -1 ), as well as planar CH vibrations (1121 cm -1 ), COC groups (1261 cm -1 ), pyrrole rings (1459 cm -1 , 1579 cm ⁇ 1 ), CC stretching (1600 cm ⁇ 1 ), carboxyl group (1730 cm ⁇ 1 ), and CH vibrations (2800-3000 cm ⁇ 1 ) in the methyl and methylene groups. All these functional groups are conserved in the FT-IR spectrum of graphene oxide nanopaints, as well as the oxygen-containing functional groups present in the graphene oxide nanosheets.
  • the spectral characteristics of the epoxy, hydroxyl, carbonyl, and carboxyl groups add to the spectrum of the alkyd synthetic resin.
  • the strength of the CH groups in the alkyd synthetic resin was significantly reduced in (2800-3000 cm ⁇ 1 ) graphene oxide nanopaints, and the peaks were blue-shifted due to CC oscillation.
  • the change in carbonyl groups is due to the chemical cross-linking process that occurs in graphene oxide nanopaints. This experiment suggests that structural changes occur in graphene oxide nanopaints as a result of electrostatic interactions and / or hydrogen bonding between graphene oxide and alkyd resins.
  • Raman spectroscopy is one of the nondestructive analyzes used to study the binding properties, crystallinity, defects, and displacement of nanomaterials and also functional coatings.
  • the Raman spectra of the alkyd synthetic resin and the graphene oxide nanopaint were examined as shown in FIG. 3B to study the binding interactions between the graphene oxide and the alkyd synthetic resin in the nanopaint.
  • Raman spectra of alkyd synthetic resins exhibit characteristic bands at 1265 cm ⁇ 1 , 1443 cm ⁇ 1 , 1675 cm ⁇ 1 , 2900 cm ⁇ 1 , and 3100 cm ⁇ 1 , respectively.
  • the surface state and composition of graphene oxide nanopaints were investigated by XPS analysis.
  • 4A shows XPS measurement spectra of alkyd resin and graphene oxide nanopaints.
  • the graphene oxide nanopaints from Figure 4a showed an increase in oxygen content compared to alkyd synthetic resins, due to the presence of oxygen-containing functional groups in graphene oxide.
  • the C / O ratios calculated from the XPS spectra of the uncoated alkyd resin and the graphene oxide nanopaint were respectively 3.75 and 3.29.
  • the C-1s unwinded spectrum is shown in FIG.
  • the surface morphology of the painted surface was investigated using field emission scanning electron microscopy (FE-SEM) studies.
  • 4C and 4D show low- and high-magnification images of the paint coating, respectively. Both images showed a uniform coating of the pate on the substrate and no porosity was observed in the FE-SEM data.
  • the presence of graphene oxide nanosheets in the paint was not distinguished from these images due to the effectiveness of the ball-milling process in preparing a homogeneous mixture of paints.
  • Corrosion inhibition properties (in acidic environment) of graphene oxide nanopaints were determined by weight-loss method.
  • graphene oxide nanopaint was coated onto a zinc iron (GI) substrate using brush coating.
  • the uncoated GI substrate (control) and the painted GI substrate were immersed in 0.1 N HCl for 24 hours at room temperature. Thereafter, the substrate was removed from the beaker and immersed in distilled water to remove acidic impurities and dried at room temperature. The weight of each substrate before and after the reaction was measured and used to calculate the degree of corrosion inhibition of the coating. The experiment was repeated three times and the average value was recorded.
  • Inhibition Efficiency% [(W uncoated -W coated ) / W uncoated ] ⁇ 100,... ... ... ... ... ... (2)
  • W uncoated is the weight loss of the uncoated substrate
  • W coated is the weight loss of the substrate coated with graphene oxide nanopaint
  • the corrosion-inhibition efficiency of the graphene oxide nanopaint coating was about 88.70%, indicating the potential usefulness of graphene oxide nanopaint in acid resistant coatings.
  • the upper and lower potential limits of linear sweep voltammetry were set to +200 and -200 mV, respectively, for the OCP.
  • the cleaning speed was 1 mV ⁇ s ⁇ 1 .
  • Corrosion potential E corr and corrosion current I corr were determined by Tafel extrapolation.
  • Tafel electrochemical analysis is one of the standard methods used for the study of corrosion in metals. Corrosion behavior of metals can be explained by combining anodic oxidation of the metal to metal ions and cathodic reduction utilizing electrons that disappear during the oxidation reaction. Both reactions occur at the same time, so the limitation of these reactions leads to the inhibition of corrosion.
  • the potential mechanical polarization curves measured in 3.5% NaCl solution for both the uncoated GI substrate and the GI substrate coated with graphene oxide nanopaint are shown in FIG. 6.
  • the corrosion potentials E corr , and the corrosion current density I corr for uncoated GI substrates and painted substrates were calculated from the polarization curves by the Tafel equation. It is clear from FIG. 6 that the anode current density of the painted substrate was at least one order of magnitude lower than that of the uncoated substrate. This explains that the graphene oxide nanopaint coating significantly reduced the dissolution of metal ions from the substrate.
  • the measured E corr of the GI substrate was -1047 mV and the painted substrate was -995 mV.
  • the movement of the painted substrate in the E corr was about +52 mV, accompanied by a significant decrease in the I corr , which corroded the uncoated substrate by acting as graphene oxide nanopaint as a protective layer between the substrate and the corrosive environment. It suggests that the resistance is significantly improved.
  • the protective efficiency P i of the graphene oxide nanopaint coating was obtained from the polarization curve calculated from the following equation:
  • I corr and I ' corr are the corrosion current densities of substrates coated with graphene oxide nanopaint and uncoated keys, respectively.
  • Microbial Escherichia coli (MTCC739), Staphylococcus aureus (MTCC96), and Pseudomonas aeruginosa (MTCC1688) were collected from bacterial strains and from the Gene Bank (IMTECH, Chandigarh, India). Were obtained and maintained in an incubator (Sigma Aldrich, India).
  • the microbial activity of the graphene oxide nanosheets was determined by microdilution and the corresponding minimum inhibitory concentration (MIC) was determined.
  • the MIC values of the graphene oxide nanosheets for Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa were 0.5, 0.5, and 1 ⁇ g / mL, respectively. From this, the antimicrobial properties of the graphene oxide nanosheets can be seen.
  • the coated and uncoated (ie, control) surfaces were exposed to 200 ⁇ L of microorganisms, respectively, in culture at an initial concentration of 10 5 CFU / mL. They were then air dried and kept at room temperature. After the exposure period (24 and 48 hours), the material surface was washed three times with 2 mL of culture. The washed culture was used for colony counting by agar dilution and to count fractions of dead cells.
  • a 10-fold serial dilution was prepared using the culture, sprinkled onto nutrient agar plates and incubated at 37 ° C. for 24 hours. All experiments were performed three times. The number of colonies in each sample was recorded and the percentage of bacterial reduction was calculated as follows.
  • A is the number of live bacteria on the uncoated surface and B is the number of live bacteria on the painted surface.
  • FIG. 7C shows the percentage loss of bacterial populations in the phase of graphene oxide nanopaints after 24 and 48 hours.
  • the antimicrobial test was repeated three times to ensure reproducibility and at least two different times were used.
  • the distribution of viable cells on the painted surface was reduced by 76, 73, and 69% for E. coli, Staphylococcus aureus, and Pseudomonas aeruginosa, respectively.
  • the painted surface inhibited 94, 88, and 85% of living cells, respectively, against E. coli, Staphylococcus aureus, and Pseudomonas aeruginosa. From this it can be seen that the graphene oxide nanopaint according to the present invention inhibited the growth of all tested bacterial strains and increased the rate of death upon prolonged exposure.
  • the washed nutrient solution was centrifuged and the pellets stained using the live / dead BacLight kit (Molecular Probes, Invitrogen, Carlsbad, Calif.) According to the manufacturer's protocol. Colors comprising a mixture of SYTO 9 and propidium iodide were dissolved in a mixture of 3% dimethylsulfoxide and double-distilled water and incubated for 15 minutes. In this process, living bacteria with intact cell membranes were colored green, while dead bacteria with damaged membranes were colored red. Excitation and emission peaks for these two dyes were 480 and 500 nm for SYTO 9 colorants and 490 and 635 nm for propidium iodide, respectively.
  • Bacterial colonies are the first step in the formation of biofilms, which induce colony of biofouling on the surface of the main part of the hull.
  • Marine biofouling is estimated at $ 260 million annually in the US Navy fleet alone, and is a significant problem for the marine industry.
  • the current problem with marine antimicrobial paints is the release of toxic biocides that are harmful to nature. Thus, a non-pollution approach to inhibit colonies is highly desirable.
  • an uncoated and graphene oxide nanopaint coated GI substrate (2 ⁇ 2 cm) was immersed in seawater in a tide lagoon connected to Jeju sea for a period of 3 weeks, as shown in FIG. 8A. Thereafter, the substrate was recovered, and biofouling was observed.
  • XRD of the zinc oxide nanopaint coated glass material showed a diffraction peak corresponding to the zincite of zinc oxide. Peaks at 2 ⁇ 31.77, 34.42, 36.25, 47.54, 56.59, 62.85, 66.32, 67.95, 69.02 and 72.79 Temperatures are (100), (002), (110), (103), (200), (112), ( 201) and (004) hexagonal zinc oxide zinc oxide particles were assigned to the reflection line and coincided with the zinc oxide in the hexagonal zinc oxide state (see FIG. 9).
  • Raman spectra of alkyd synthetic resin and zinc oxide nanopaints were examined as provided in FIG. 3B.
  • Raman spectra of the alkyd synthetic resin show characteristic bands at 439 cm ⁇ 1 , respectively (see FIG. 10).
  • Zinc oxide nanoparticles are antibacterial materials that have been shown in previous studies that zinc oxide nanopaints inhibit the growth of bacteria on the surface, which is why anti-fouling of zinc oxide nanopaints in the lagoon of Jeju sea. The antifouling properties were tested.
  • Escherichia coli ATCC 25922
  • Staphylococcus aureus ATCC 25923
  • Pseudomonas aeruginosa ATCC 27853
  • klebsiella pneumoniae ATCC 10031
  • the antimicrobial activity of molybdenum (MoO 3 ) nanoplates was determined by microdilution method and the corresponding minimum inhibitory concentration (MIC) was determined.
  • the MIC values of the molybdenum (MoO 3 ) nanoplates for Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa and Pneumococcus were 8, 8, 16, and 32 ⁇ g / mL ⁇ 1 , respectively. From this, the antibacterial properties of the molybdenum nanoplates can be seen.
  • the coated and uncoated (ie, control) surfaces were exposed to 200 ⁇ L of microorganisms, respectively, in culture at an initial concentration of 10 5 CFU / mL. They were then air dried and kept at room temperature. After the exposure period (24 and 48 hours), the material surface was washed three times with 2 mL of culture. The washed culture was used for colony counting by agar dilution and to count fractions of dead cells.
  • a 10-fold serial dilution was prepared using the culture, sprinkled onto nutrient agar plates and incubated at 37 ° C. for 24 hours. All experiments were performed three times. The number of colonies in each sample was recorded and the percentage of bacterial reduction was calculated as follows.
  • A is the number of live bacteria on the uncoated surface and B is the number of live bacteria on the painted surface.

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Abstract

Cette invention concerne une composition de peinture et, plus spécifiquement, une composition de peinture non toxique contenant des nanofeuillets d'oxyde de graphène (GO), des nanoparticules de ZnO, et des nanoplaquettes de MoO3, et son procédé de préparation. Plus spécifiquement, la composition de peinture contenant des nanofeuillets de GO selon l'invention est économique et sèche rapidement compte tenu sa teneur élevée en solides comparativement aux peintures classiques ; elle est respectueuse de l'environnement et manifeste une excellente résistance à la corrosion dans une solution acide et à teneur élevée en sel étant donné que les substances toxiques, telles que l'acide chromique ou les biocides sont absents ; a d'excellents effets d'inhibition de la croissance des souches bactériennes (Escherichia coli, Staphylococcus aureus, et Pseudomonas aeruginosa) et de suppression de l'adhérence des organismes marins, et peut par conséquent être utile en tant que substitut aux peintures utilisées dans les structures et les bateaux en acier à caractère général ou les structures maritimes en acier.
PCT/KR2014/010531 2013-11-04 2014-11-04 Composition de peinture non toxique contenant des nanostructures d'oxydation organiques et inorganiques et son procédé de préparation WO2015065164A1 (fr)

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EP18176146.1A EP3392316B1 (fr) 2013-11-04 2014-11-04 Composition de peinture non toxique contenant des nanostructures d'oxydation organiques et inorganiques et leur procédé de préparation

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CN105944522A (zh) * 2016-05-21 2016-09-21 杨勇 一种有干燥功能的防霉剂
CN105976941A (zh) * 2016-06-13 2016-09-28 天津宝兴威科技有限公司 一种柔性铝掺杂氧化锌/石墨烯复合材料的制备工艺
CN107556852A (zh) * 2017-10-17 2018-01-09 三河市安霸生物技术有限公司 一种单组份抗菌涂料
CN110157288A (zh) * 2018-03-28 2019-08-23 山东佳星环保科技有限公司 一种石墨烯增强的防腐涂料
CN111729664A (zh) * 2020-06-05 2020-10-02 吉林大学 一种负载型纳米氧化锌及其制备和应用
CN114836122A (zh) * 2022-06-29 2022-08-02 佛山市高明区首邦化工有限公司 一种具有快干高耐候性能的家具涂料及制备方法

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CN105944522A (zh) * 2016-05-21 2016-09-21 杨勇 一种有干燥功能的防霉剂
CN105976941A (zh) * 2016-06-13 2016-09-28 天津宝兴威科技有限公司 一种柔性铝掺杂氧化锌/石墨烯复合材料的制备工艺
CN107556852A (zh) * 2017-10-17 2018-01-09 三河市安霸生物技术有限公司 一种单组份抗菌涂料
CN110157288A (zh) * 2018-03-28 2019-08-23 山东佳星环保科技有限公司 一种石墨烯增强的防腐涂料
CN111729664A (zh) * 2020-06-05 2020-10-02 吉林大学 一种负载型纳米氧化锌及其制备和应用
CN111729664B (zh) * 2020-06-05 2022-11-11 吉林大学 一种负载型纳米氧化锌及其制备和应用
CN114836122A (zh) * 2022-06-29 2022-08-02 佛山市高明区首邦化工有限公司 一种具有快干高耐候性能的家具涂料及制备方法

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