Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/02—Making microcapsules or microballoons
• • 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
  • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G7/00—Compounds of gold
• • 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
  • C08K3/02—Elements
  • C08K3/08—Metals
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/0078—Pigments consisting of flaky, non-metallic substrates, characterised by a surface-region containing free metal
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/62—Metallic pigments or fillers
  • C09C1/64—Aluminium
  • C09C1/642—Aluminium treated with inorganic compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
  • C09C3/06—Treatment with inorganic compounds
  • C09C3/063—Coating
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
  • C09C3/06—Treatment with inorganic compounds
  • C09C3/066—Treatment or coating resulting in a free metal containing surface-region
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/01—Particle morphology depicted by an image
  • C01P2004/03—Particle morphology depicted by an image obtained by SEM
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/01—Particle morphology depicted by an image
  • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
  • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
  • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
• • 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
  • C08K3/02—Elements
  • C08K3/08—Metals
  • C08K2003/0806—Silver
• • 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
  • C08K3/02—Elements
  • C08K3/08—Metals
  • C08K2003/0831—Gold
• • 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
  • C08K3/02—Elements
  • C08K3/08—Metals
  • C08K2003/085—Copper
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/005—Additives being defined by their particle size in general
• • 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
  • C08K9/02—Ingredients treated with inorganic substances
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
  • C09C2200/10—Interference pigments characterized by the core material
  • C09C2200/1004—Interference pigments characterized by the core material the core comprising at least one inorganic oxide, e.g. Al2O3, TiO2 or SiO2
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
  • C09C2200/10—Interference pigments characterized by the core material
  • C09C2200/102—Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
  • C09C2200/10—Interference pigments characterized by the core material
  • C09C2200/1054—Interference pigments characterized by the core material the core consisting of a metal
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
  • C09C2200/10—Interference pigments characterized by the core material
  • C09C2200/1054—Interference pigments characterized by the core material the core consisting of a metal
  • C09C2200/1058—Interference pigments characterized by the core material the core consisting of a metal comprising a protective coating on the metallic layer
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
  • C09C2200/50—Interference pigments comprising a layer or a core consisting of or comprising discrete particles, e.g. nanometric or submicrometer-sized particles
  • C09C2200/502—Metal particles

Definitions

• the present invention relates to methods of preparing colored materials using metallic nanoparticles of gold, copper or silver, said colored materials, and their uses in various applications.
• a metal in the form of nanoparticles can make it possible to confer on a suspension or on a solid substrate comprising said nanoparticles a color different from the original color of the solid metal (ie not being in the form of nanoparticles).
• a metal particle is subjected to an electromagnetic field whose wave length is much larger than the particle size: l >> 0 pa rticuies, all the free electrons of the conduction band undergo the same field and oscillate collectively and in phase.
• plasmon resonance a resonance phenomenon occurs, called plasmon resonance. This resonance takes place in the visible domain, only for gold, copper and silver, hence the particular coloration of the nanoparticles of these metals.
• 20nm gold nanoparticles typically have a plasmon resonance band at 520nm (green absorption) and are red.
• the plasmon resonance frequency depends on the nature of the metal, on the size of the particle and on its shape, as well as on the dielectric properties of the substrate or of the surrounding medium (eg suspension) and on inter-particle interactions. It is possible to play on these different parameters to vary the color of the gold nanoparticles throughout the visible range, or even to shift the plasmon resonance frequency in the near infrared.
• International application WO2011035446 A1 describes the manufacture of a colored material comprising the mixture of an organo-mineral matrix based on a thermosetting or photopolymerizable resin with a suspension or dispersion of metallic nanoparticles of noble metal coated by a shell. (in particular based on oxide), the deposition of the mixture in a cavity of a substrate, and the polymerization of the mixture. This process provides access to a colored material in pink or red shades in the cavity. The colors obtained are limited and localized in a specific place on the substrate.
• the aim of the present invention is therefore to overcome the aforementioned drawbacks, and in particular to provide a method of manufacturing a colored material, possibly capable of changing color under the influence of at least one stimulus, said method being simple. , economical, guaranteeing optimum color stability, making it possible to obtain an extremely well defined color spectrum, having an important modularity in that it allows access to a large palette of colors and types of colored substrates, and avoiding transfers of solvents as much as possible.
• the first subject of the invention is a process for preparing a colored material, characterized in that it comprises at least the following steps:
• said colored material being in the form of gold nanoparticles supported by said micrometric particulate support.
• the manufacturing process for the colored material is simple, economical, it guarantees optimum color stability, enables an extremely well-defined color spectrum to be obtained, exhibits significant modularity, and avoids solvent transfers as much as possible.
• nanoparticles means particles having at least one dimension less than or equal to 500 nm, of preferably less than or equal to 250 nm, and particularly preferably less than or equal to approximately 100 nm.
• the term “dimension” means the number-average dimension of all the particles of a given population, this dimension being conventionally determined by methods well known to those skilled in the art.
• the size of the particle (s) according to the invention can for example be determined by microscopy, in particular by scanning electron microscope (SEM) or by transmission electron microscope (TEM).
• the gold salt (+ III) is a salt in which the gold is in the oxidation state (+ III).
• the gold (+ III) salt is chosen from tetrachloroauric acid HAuCU, potassium tetrachloroaurate KAuCU and their mixture, and preferably KAuCU.
• Gold nanoparticles are gold nanoparticles in which gold is at zero oxidation state.
• the aqueous suspension may comprise one or more solvents, the one or more solvents containing at least 50% by volume approximately of water, preferably at least 80% by volume approximately of water, and particularly preferably 100% by volume approximately of water, relative to the total volume of solvent (s) in the aqueous suspension.
• the heating of step i) can be carried out by heating to temperature, in particular using a heating plate, or by microwave heating.
• the temperature heating can be carried out at a temperature ranging from 30 to 200 ° C approximately, and particularly preferably from 50 to 110 ° C approximately.
• the microwave heating can be carried out at a frequency ranging from approximately 25 to 65 Hz, and preferably of the order of 45 kHz.
• Step i) can be carried out with stirring, for example with mechanical or magnetic stirring.
• the aqueous suspension used in step i) may comprise from 0.005 to 1.0% by mass approximately of gold (+ III) salt, and preferably from 0.01 to 0.5% by mass approximately of salt d. 'gold (+ III), relative to the total mass of said aqueous suspension.
• the aqueous suspension used in step i) may comprise from 0.05 to 1.0% by mass approximately of reducing agent, and preferably from 0.08 to 0.5% by mass approximately of reducing agent, by relative to the total mass of said aqueous suspension.
• the mass ratio in the aqueous suspension used in step i): mass of gold salt (+ III) / mass of reducing agent varies from 0.1 to 1, About 5, and preferably about 0.1 to 1.0.
• the aqueous suspension used in step i) can comprise from 0.002 to 0.6% by mass approximately of gold nanoparticles, and preferably from 0.04 to 0.3% by mass approximately of gold nanoparticles, by relative to the total mass of said aqueous suspension.
• the mass ratio in the aqueous suspension of step i): mass of gold nanoparticles / mass of reducing agent varies from approximately 0.05 to 0.55, and from preferably from 0.1 to 0.5 approximately.
• the reducing agent can be chosen from alkali metal citrates, citrates of zwitterionic derivatives of amino acids, borohydrides, hydrazine, hydroquinone, and one of their mixtures, and preferably chosen from metal citrates. alkaline, citrates of zwitterionic amino acids, and their mixture.
• borohydrides mention may be made of sodium borohydride.
• alkali metal citrates mention may be made of potassium or sodium citrate.
• citrates of zwitterionic amino acid derivatives mention may be made of citrates of derivatives comprising at least one carboxylate function and at least one quaternary ammonium function, such as betaine citrate.
• the aqueous suspension used in step i) can also comprise a stabilizing agent, in particular when the reducing agent has no stabilizing or surfactant properties.
• a stabilizing agent in particular when the reducing agent has no stabilizing or surfactant properties.
• citrates exhibit, in addition to their reducing power, stabilizing properties.
• the stabilizing agent can be chosen from polymers such as polyvinyl alcohol or polyacrylic acid, poly (ethylene glycol) (PEG), sulfur derivatives such as thiols, ligands based on triphenylphosphine, dendrimers, and surfactants such as cetyltrimethylammonium bromide (CTAB), sodium dodecylsulfate (SDS) or amine surfactants.
• polymers such as polyvinyl alcohol or polyacrylic acid, poly (ethylene glycol) (PEG), sulfur derivatives such as thiols, ligands based on triphenylphosphine, dendrimers, and surfactants such as cetyltrimethylammonium bromide (CTAB), sodium dodecylsulfate (SDS) or amine surfactants.
• CTAB cetyltrimethylammonium bromide
• SDS sodium dodecylsulfate
• micrometric particulate support means that the support is in the form of micrometric particles.
• the micrometric particles acting as a support for the gold nanoparticles may have at least one dimension less than approximately 300 ⁇ m, preferably ranging from 50 nm to 150 ⁇ m approximately, and particularly preferably ranging from 1 to 100 ⁇ m approximately. .
• the micrometric particulate support can be organic or inorganic.
• Said support can comprise or consist of an inorganic material chosen from silicates such as, for example, micas, borosilicates, or talc; glasses such as silica; metal oxides, such as for example zinc oxide; rare earth oxides such as cerium oxide; metals such as for example aluminum; and one of their mixtures; or can include or be made up of an organic material chosen from materials derived from natural compounds such as oyster powders or oyster shells, and derivatives of materials from the forest and wood industry such as cellulose or its derivatives.
• An inorganic particulate carrier is preferred.
• the particulate support can be in the form of flakes, platelets, polyhedra, balls, in particular solid or hollow, particles, for example spherical, or a powder.
• the support comprises at the surface a layer containing at least one metal oxide.
• the support material can be coated with a layer containing at least one metal oxide. This thus makes it possible to facilitate the attachment of the gold nanoparticles to said support.
• the support is preferably inorganic.
• the layer containing at least one metal oxide can be of hydrophilic or hydrophobic nature. Depending on the nature of the layer, different colors can be obtained.
• the layer containing at least one metal oxide may have a thickness ranging from 5 to 200 nm approximately, preferably ranging from 30 to 160 nm approximately, and particularly preferably ranging from 50 to 145 nm approximately. Depending on the thickness of the layer, different colors can be obtained. These thickness ranges allow better control of the final color of the pigment, while ensuring access to a large palette of different colors.
• the layer containing at least one metal oxide can be a layer of silica, for example of amorphous silica.
• the support is chosen from aluminum flakes, preferably comprising a layer of silica; borosilicate flakes, preferably comprising a metal oxide layer; silica beads; mica particles; zinc oxide particles; particles of calcium oxide; cerium oxide particles; talc particles; flakes and beads of cellulose; and a powder of oyster shells.
• Aluminum flakes coated with a layer of silica are, for example, marketed under the reference Frost, Crystal or Velvet by the company Toyal Europe.
• the borosilicate flakes coated with a metal oxide layer are for example sold under the reference KT700 by the company Kolortek.
• the silica beads are, for example, sold under the reference CL-Silica-900 by the company Maprecos.
• the mica particles are for example sold under the reference C86-6105 Satin Mica by the company Maprecos.
• the zinc oxide particles are for example sold by the company Sigma Aldrich.
• the calcium oxide particles are for example sold by the company Sigma Aldrich.
• the aqueous suspension used in step i) can comprise from 0.005 to 60% by mass approximately, preferably from 0.01 to 50% by mass approximately, and particularly preferably from 0.1 to 10% by mass approximately, of micrometric particulate support, relative to the total mass of said aqueous suspension.
• Step i) can last from 0.5 to 120 minutes approximately, and preferably from 2 to 45 minutes approximately.
• the process further comprises, before step i), a step iO) of preparing the aqueous suspension.
• step i) uses at least one gold salt (+ III).
• the gold nanoparticles are prepared in situ.
• step iO) for preparing the aqueous suspension can in particular comprise the following sub-steps:
• Sub-step iO-1) prepare an aqueous solution comprising the gold (+ III) salt, iO-2) prepare an aqueous solution comprising the reducing agent, and iO-3) add the micrometric particulate support and the aqueous solution obtained to the sub-step iO-1), to the aqueous solution of sub-step iO-2).
• Sub-step iO-1) can be carried out at room temperature (ie 18-
• Sub-step iO-2) can be carried out at room temperature (i.e. 18-
• Step iO) for preparing the aqueous suspension can further comprise, after sub-step iO-2) and before sub-step iO-3), a sub-step iO-2 ′) consisting in heating the aqueous solution obtained in the sub-step iO-2).
• the heating during the sub-step iO-2 ′) can be carried out by heating to temperature, in particular using a hot plate, or by microwave heating.
• the temperature heating can be carried out at a temperature ranging from 80 to 200 ° C approximately, and particularly preferably from 80 to 110 ° C approximately.
• the microwave heating can be carried out at a frequency ranging from approximately 25 to 65 Hz, and preferably of the order of 45 kHz.
• the proportion of aqueous solution of gold (+ III) salt added is such that the volume ratio: volume of the aqueous solution comprising the gold (+ III) salt obtained at the sub-step iO-1) / volume of the aqueous solution comprising the reducing agent obtained in the sub-step iO-2), preferably ranges from 0.1 to 2.5 approximately, and particularly preferably from 0 , 5 to 2.0.
• Sub-step iO-3 can be carried out all at once (i.e. the whole quantity of gold salt solution (+ III) is added at once) or in several times.
• step iO) comprises substep iO-2 ′
• heating is maintained during substeps iO-3) and i).
• step i) uses at least gold nanoparticles.
• This second variant makes it possible to prepare the gold nanoparticles beforehand and then to bring them into contact with the micrometric support. particulate matter, which leaves more latitude in the choice of support, the shape of gold nanoparticles, and the possibilities for recycling raw materials.
• the gold nanoparticles can be obtained beforehand according to any method well known from the state of the art, such as the Turkevich method.
• step iO) of preparing the aqueous suspension can in particular comprise the following sub-steps: iO-A) preparing an aqueous suspension comprising the gold nanoparticles,
• iO-C add the micrometric particulate support.
• the aqueous suspension of substep iO-A) can be obtained according to any method well known from the state of the art, such as the Turkevich method.
• Step ii) of recovering said colored material can be carried out by filtration, decantation, or centrifugation.
• the method may further comprise a step iii) of drying, in particular by steaming.
• the method can further comprise a step iv) of implementing a stimulus, in order to modify the color of the colored material.
• the stimulus can be an external stimulus such as heating or annealing the colored material obtained in step ii) or iii), exposure to UV radiation, use of a laser, or its spontaneous or induced rehydration.
• the gold nanoparticles of the colored material obtained according to the process in accordance with the first subject of the invention have at least one dimension ranging from approximately 5 to 100 nm.
• the second subject of the invention is a colored material obtained according to a process in accordance with the first subject of the invention, characterized in that it is in the form of gold nanoparticles supported on a micrometric particulate support.
• the gold nanoparticles and the micrometric particulate support can be as defined in the first subject of the invention.
• the colored material may comprise from 1 to 20% by mass approximately gold, and from 99 to 80% by mass approximately of micrometric particulate support, relative to the total mass of the colored material.
• the colored material is preferably in the form of a powder or a powdery material.
• the gold nanoparticles in the colored material obtained according to the process in accordance with the second subject of the invention have at least one dimension ranging from approximately 2 to 100 nm.
• the third subject of the invention is a colored composition comprising at least one colored material in accordance with the second subject of the invention or obtained according to a process in accordance with the first subject of the invention, and at least one solvent in which said colored material is dispersed. .
• the solvent can be an organic solvent, such as a solvent chosen from alcohols such as ethanol, and esters such as ethyl acetate; or an aqueous solvent.
• the colored composition may further comprise any additive suitable for forming a nail varnish base, in particular translucent or transparent.
• Such additives can be chosen from a film-forming agent, a plasticizer, a thixotropic agent, a resin, and one of their mixtures. These additives are well known to those skilled in the art.
• the expression “translucent” means having an optical transmission coefficient ranging from approximately 10% to approximately 80%, measured by a conventional UV-visible spectrometer.
• the expression “transparent” means having an optical transmission coefficient greater than approximately 80%, measured by a conventional UV-visible spectrometer.
• the colored composition can be obtained by mixing the colored material with at least one organic solvent, and optionally the aforementioned additive (s).
• the colored composition can be applied to a support, for example a flexible or rigid support, and dried, so as to form a support comprising a continuous colored layer.
• the support can be chosen from a leather, fabric, polymeric material, or metal surface.
• the application can be done with an airbrush, or with a brush.
• the fourth subject of the invention is a process for preparing a colored material, characterized in that it comprises at least the following steps:
• step b) a step of mixing the crosslinkable composition of step a) with a suspension in a polar protic solvent of metallic nanoparticles of a metal chosen from gold, copper, silver, and one of their mixtures, in order to obtain a colored composition, and
• said colored material is in the form of metallic nanoparticles of a metal chosen from gold, copper, silver, and a mixture thereof, dispersed in a crosslinked epoxy polymer material.
• the manufacturing process for the colored material is simple, economical, it guarantees optimum color stability, enables an extremely well-defined color spectrum to be obtained, exhibits significant modularity, and avoids solvent transfers as much as possible.
• Step a) can be carried out with stirring, in particular in the presence of ultrasound. This thus makes it possible to form a homogeneous mixture while avoiding the presence of air bubbles.
• Step a) is preferably carried out at ambient temperature (i.e. approximately 18-25 ° C.).
• the epoxy precursor comprises one or more epoxy groups (or oxyran rings).
• the epoxy precursor of the crosslinkable composition can be chosen from cycloaliphatic epoxy resins, epoxy resins of glycidyl ethers, in particular (poly) phenolic and / or aliphatic, epoxy resins of glycidyl esters, epoxy resins obtained by copolymerization with glycidyl methacrylate, and epoxy resins obtained from glycerides of unsaturated fatty acids.
• epoxy resins of glycidyl ethers in particular (poly) phenolic and / or aliphatic, such as the condensation reaction products of epichlorohydrin with polyalcohols or polyphenols. (eg bisphenol A, bisphenol F), epoxy aliphatic resins of glycidyl ethers, or a mixture thereof.
• Step b) is preferably carried out by adding the suspension of metal nanoparticles in the crosslinkable composition, in particular in several times and / or gradually.
• Step b) can be carried out with stirring, in particular in the presence of ultrasound. This thus makes it possible to form a homogeneous mixture while avoiding the presence of air bubbles.
• the polar protic solvent can be chosen from lower alcohols (ie C 1 -C 5 )
• the polar protic solvent is preferably ethanol.
• the molar concentration of the metal nanoparticles in the suspension preferably ranges from approximately 1 ⁇ 10 9 to 1 ⁇ 10 7 mol / l, and particularly preferably from 5 ⁇ 10 9 to 5 ⁇ 10 8 mol / l approximately.
• the mass ratio: mass of the metallic nanoparticles / mass of the crosslinkable epoxy precursors ranges from approximately 3 ⁇ 10 9 to 3 ⁇ 10 7 and preferably from 1.5 ⁇ 10 8 to 1.5 ⁇ 10 7 .
• Step b) is preferably carried out at room temperature.
• Step c) is preferably carried out at room temperature. Step c) can last from 5 minutes to approximately 24 hours.
• Steps b) and c) can be concomitant, or step c) can take place before or after step b).
• Step c) can be a photopolymerization step or a step using at least one crosslinking agent.
• the crosslinking agent is preferably introduced into the crosslinkable composition during step a).
• the crosslinked epoxy polymer material is obtained by polymerization of at least epoxy precursor as defined in the invention and of the crosslinking agent (also called hardener), in particular by polycondensation or by polyaddition.
• the crosslinking agent also called hardener
• the crosslinking agent can be based on at least one acid anhydride, on at least one polyamine (eg (cyclo) aliphatic amines, aromatic amines), on at least one polyamide, on at least one amidoamine , or one of their mixtures.
• polyamine eg (cyclo) aliphatic amines, aromatic amines
• acid anhydrides examples include methyltetrahydrophthalic (MTHPA), methylnadic anhydride (NMA) or methylhexahydrophthalic anhydride (MHHPA).
• MTHPA methyltetrahydrophthalic
• NMA methylnadic anhydride
• MHHPA methylhexahydrophthalic anhydride
• polyamines of the aliphatic or cycloaliphatic amine type mention may be made of those comprising two primary amines such as diethylene triamine (DETA), tetraethylene tetramine (TETA), polyetheramines such as polyoxypropylene diamine or the compounds marketed under the Jeffamine® reference, or isophorone diamine (IPDA).
• DETA diethylene triamine
• TETA tetraethylene tetramine
• IPDA isophorone diamine
• polyamines of the aromatic amine type mention may be made of those comprising two primary amines such as 4,4′-diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), methylene-bis (diisopropylaniline) (MPDA) or bis (amino-chloro-diethylphenyl) methane (MCDEA).
• DDM 4,4′-diaminodiphenylmethane
• DDS diaminodiphenylsulfone
• MPDA methylene-bis (diisopropylaniline)
• MCDEA bis (amino-chloro-diethylphenyl) methane
• polyamides mention may be made of the condensation products of polyamines with acid or fatty acid dimers.
• amidoamines there may be mentioned the reaction products of carboxylic acids (derivatives of C 6 -C 9 fatty acids) with aliphatic polyamines (TETA).
• the method may further comprise between steps b) and c), a step b ′) during which the colored composition is cast in a mold, in particular in a silicone mold.
• Step c) can be concomitant with step b ′).
• step c) can be followed by a step d) during which the colored material obtained is demolded.
• the suspension of metal nanoparticles as used in step b) can be obtained by techniques well known to those skilled in the art.
• the suspension of metal nanoparticles can for example be obtained by preparing an aqueous suspension of gold nanoparticles according to the Turkevich method, then a transfer of solvent inducing the replacement of the water with a polar protic solvent as defined in the invention.
• the metallic nanoparticles in the colored material obtained according to the process in accordance with the fourth subject of the invention have at least one dimension ranging from approximately 2 to 100 nm.
• the metallic nanoparticles are preferably nanoparticles of a metal chosen from copper, silver, a mixture of copper and silver or a mixture of copper, silver and gold.
• the metal nanoparticles can be coated with an organic or inorganic layer.
• they can be free of an organic or inorganic layer, and in particular free of an organic layer, in particular when the metal nanoparticles are gold particles.
• the organic layer can comprise a material chosen from polymers such as polyvinyl alcohol or polyacrylic acid, poly (ethylene glycol) (PEG), sulfur derivatives such as thiols, ligands based on triphenylphosphine, dendrimers, surfactants such as cetyltrimethylammonium bromide (CTAB), sodium dodecylsulfate (SDS) or amino surfactants, and preferably such as polyvinyl alcohol or polyacrylic acid, poly (ethylene glycol) (PEG), ligands made of triphenylphosphine, dendrimers, surfactants such as cetyltrimethylammonium bromide (CTAB), sodium dodecylsulphate (SDS) or amino surfactants.
• polymers such as polyvinyl alcohol or polyacrylic acid, poly (ethylene glycol) (PEG), sulfur derivatives such as thiols, ligands based on triphenylphosphine, dendrimers, surfactants
• the organic layer is preferably different from a layer comprising a polyvinylpyrrolidone such as poly-N-vinyl-2-pyrrolidone, or a thiol such as dodecanethiol, in particular when the metal nanoparticles are gold particles.
• a polyvinylpyrrolidone such as poly-N-vinyl-2-pyrrolidone
• a thiol such as dodecanethiol
• the inorganic layer may comprise a metal or metalloid oxide such as, for example, a layer of silicon oxide.
• An inorganic silica layer is particularly suitable for gold or silver nanoparticles.
• the method may further comprise, before step b), a step a ′) of coating the nanoparticles.
• the method may further comprise, during step b) or between steps b) and c), the addition to the colored composition of a color modifying agent.
• This agent makes it possible to modify the color of the colored composition.
• the method may further comprise a step e) of implementing a stimulus in order to modify the color of the colored material.
• This step e) can make it possible to switch from a material having a homogeneous distribution of metallic nanoparticles to a heterogeneous distribution of metallic nanoparticles within said material, then inducing a change in color.
• Step e) is particularly suitable when the metal nanoparticles are gold and silver nanoparticles.
• the stimulus can be an external stimulus such as heating or annealing the colored material obtained in step c), exposure to UV radiation, or the use of a laser.
• the stimulus can be an internal stimulus such as step c) of polymerization “proper”, or the pH of the crosslinkable composition, and in particular of the crosslinking or hardening agent.
• the crosslinked epoxy polymer material of the colored material is obtained from the crosslinkable composition as defined in the invention.
• the fifth subject of the invention is a colored material obtained according to a process in accordance with the fourth subject of the invention, characterized in that it is in the form of metallic nanoparticles of a metal chosen from gold, copper, l silver, and a mixture thereof, dispersed in a crosslinked epoxy polymeric material.
• the colored material obtained according to a process in accordance with the fourth object of the invention is preferably different from a colored material in the form of gold nanoparticles dispersed in a crosslinked epoxy polymer material, said gold nanoparticles comprising an organic layer comprising a polyvinylpyrrolidone such as poly-N-vinyl-2-pyrrolidone, or a thiol such as dodecanethiol.
• the metallic nanoparticles and the crosslinked epoxy polymer material can be as defined in the fourth subject of the invention.
• the colored material may comprise from 0.5 to 10% by mass approximately of metallic nanoparticles, and from 90 to 99.5% by mass approximately of crosslinked epoxy polymer material, relative to the total mass of the colored material.
• the colored material is preferably in the form of a solid mass, i.e. in the form of a non-pulverulent material.
• all of the primary colors of the visible light spectrum are obtained using only one or more metals, as well as an infinite range of secondary colors by simply mixing two or more.
• three types of metal nanoparticles in particular in the case of the process in accordance with the fourth subject of the invention.
• the methods also make it possible to modulate the hue of a coloration, to confer irreversible and / or photosensitive thermochromic properties to certain micrometric particulate supports or crosslinked polymer materials, and to offer a range of micrometric-sized pigments whose optical properties are provided. by the nanometric entities that compose them.
• the sixth object of the invention is the use of a colored material conforming to the second object (or obtained according to a process conforming to the first object) or conforming to the fifth object of the invention (or obtained according to a process conforming to the fourth object) , in cosmetic or perfume applications, in the field of fashion articles such as buttons, in packaging, in jewelery, in printing, in a paint or varnish, or as a means of authentication, in particular of counterfeiting, or decoration.
• Example 1 process for preparing a colored material in the form of gold nanoparticles on aluminum flakes coated with a layer of amorphous silica
• a 1.5 g / L aqueous solution of KAuCU was prepared.
• the aqueous solution of betaine citrate was heated using a hotplate with magnetic stirring at 100 ° C. Then, the aluminum flakes were added and the aqueous solution of KAuCU was added in 3 batches over a period of 15 minutes, while maintaining the heating.
• the colored material obtained was recovered by centrifugation and then dried in an oven at 120 ° C.
• the colored material obtained is in the form of gold nanoparticles of average size approximately 20 nm supported.
• Example 2 process for preparing a colored material in the form of gold nanoparticles on aluminum flakes coated with a layer of amorphous silica
• a 1.5 g / L aqueous solution of KAuCU was prepared.
• the aqueous solution of betaine citrate was heated using a hotplate with magnetic stirring at 100 ° C. Then, the aluminum flakes were added and the aqueous solution of KAuCU was added in 3 batches over a period of 15 minutes, while maintaining the heating.
• the colored material obtained was recovered by centrifugation and then dried in an oven at 120 ° C.
• the colored material obtained is in the form of gold nanoparticles of average size approximately 20 nm supported.
• the colored material obtained has a pale pink color (pantone color: 5245).
• the colored material obtained is in the form of gold nanoparticles with an average size of approximately 30 nm supported, forming a semi-continuous layer on the surface of the particles of the micrometric support.
• the colored material obtained has a midnight blue color (pantone color: 2705).
• Example 3 process for preparing a colored material in the form of gold nanoparticles on aluminum flakes coated with a layer of amorphous silica
• a 1.5 g / L aqueous solution of KAuCU was prepared.
• the aqueous solution of betaine citrate was heated using a hotplate with magnetic stirring at 100 ° C. Then, the aluminum flakes were added and the aqueous solution of KAuCU was added in 3 batches over a period of 15 minutes, while maintaining the heating.
• the colored material obtained was recovered by centrifugation and then dried in an oven at 120 ° C.
• the colored material obtained is in the form of gold nanoparticles of average size approximately 30 nm supported.
• the colored material obtained exhibits a fuchsia color in normal incidence, and a golden color in grazing incidence (pantone colors: 17-2034 (fuchsia) and 871-C (gold)).
• FIG. 1 represents a scanning electron microscopy image of the aluminum flakes used as a particulate micrometric support in the process of Example 3.
• FIG. 2 represents images by STEM-EDX of the colored material obtained in example 3.
• FIG. 2 [a) and b)] shows in particular a deposit of gold particles on an aluminum flake.
• the support represents an aluminum flake and appears in blue
• layer 1 represents a layer of amorphous silica and appears in green
• layer 3 represents the gold particles and appears in red.
• Example 4 process for preparing a colored material in the form of gold nanoparticles dispersed in an epoxy polymer material
• aqueous solution comprising 20 ml of ultrapure water (water resistivity of at least about 10 MQ.cm) and 0.25 mM HAuCU gold salt was prepared and stirred vigorously. It was heated to reflux, then 1 ml of a 1.7 x 10 -2 M sodium citrate solution was added. The resulting solution was stirred for 20 min while maintaining heating at reflux. The solution turns gray, then purple and finally ruby red in the first few minutes. Then, the resulting solution was allowed to cool to room temperature. Gold nanoparticles 15 nm in diameter in aqueous suspension were thus obtained. The aqueous suspension obtained comprises 2.0 x 10 -9 mol / l of gold nanoparticles.
• An epoxy resin was prepared as follows: 10 ml of resin and 5 ml of hardener, sold under the name Crystal Resin marketed by the company PEBEO, are mixed.
• Example 5 process for preparing a colored material in the form of copper nanoparticles dispersed in an epoxy polymer material
• a suspension of copper nanoparticles is obtained according to the solvothermal synthesis route assisted by microwave heating.
• 0.1178 g of CuCl 2 , 0.4 g of PVP 10000 sold under the trade name PVP-10 by the company Sigma Aldrich, and 40 ml of ethanol are introduced into a Teflon reactor, and the reactor is inserted in a microwave oven. It then undergoes heating according to the following schedule: temperature rise from room temperature to 140 ° C in 5 minutes / no temperature maintenance / microwave heating off / and drop to room temperature by inertia. Microwave heating is carried out at a frequency of 45 Hz. An alcoholic suspension of bright yellow-orange color is then obtained.
• An epoxy resin is prepared as follows: 10 ml of resin and 5 ml of hardener, sold under the name Crystal Resin marketed by the company PEBEO, are mixed.
• the solid obtained is in the form of a translucent material of blue color (Pantone color 18-3949).
• Example 6 process for preparing a colored material in the form of silver nanoparticles dispersed in an epoxy polymer material
• a solution of silver nanoparticles is obtained according to the solvothermal synthesis route assisted by microwave heating.
• a mixture comprising 0.1578 g of silver nitrate AgN0 3 , and 12 ml of a solution of PVP 10000 sold under the trade name PVP-10 by the company Sigma Aldrich in ethanol at 33.3 g / L, is subjected to ultrasound using an ultrasonic bath, in order to dissolve all of the silver salt in the ethanoic solution of PVP, then the resulting mixture is introduced into a Teflon reactor. The reactor is inserted into a microwave oven. It then undergoes heating according to the following schedule: temperature rise from room temperature to 150 ° C in 2 minutes / temperature maintenance for 30 seconds at 150 ° C / microwave heating off / and drop to room temperature by inertia. Microwave heating was carried out at a frequency of 45 Hz. An alcoholic suspension of bright yellow-orange color is then obtained.
• An epoxy resin is prepared as follows: 10 ml of resin and 5 ml of hardener, sold under the name Crystal Resin marketed by the company PEBEO, are mixed.
• the solid obtained is in the form of a translucent material of yellow color (Pantone PMS color 109).

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Dispersion Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Manufacture Of Metal Powder And Suspensions Thereof (AREA)
• Powder Metallurgy (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=68138348

Family Applications (1)

Country Status (5)

Family Cites Families (2)

• 2019
  • 2019-05-28 FR FR1905635A patent/FR3096685B1/fr active Active
• 2020
  • 2020-05-27 WO PCT/FR2020/050895 patent/WO2020240137A1/fr unknown
  • 2020-05-27 US US17/614,634 patent/US20220227967A1/en active Pending
  • 2020-05-27 EP EP20743192.5A patent/EP3976716A1/de active Pending
  • 2020-05-27 JP JP2021570434A patent/JP2022534580A/ja active Pending

Also Published As

Similar Documents

Legal Events