EP3374436A1 - Mit färbemitteln gefüllte sphärische partikel - Google Patents

Mit färbemitteln gefüllte sphärische partikel

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Publication number
EP3374436A1
EP3374436A1 EP16809982.8A EP16809982A EP3374436A1 EP 3374436 A1 EP3374436 A1 EP 3374436A1 EP 16809982 A EP16809982 A EP 16809982A EP 3374436 A1 EP3374436 A1 EP 3374436A1
Authority
EP
European Patent Office
Prior art keywords
particles
matrix
coloring agents
seconds
temperature
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP16809982.8A
Other languages
English (en)
French (fr)
Inventor
Loïc MARCHIN
Marie-Laure DESSE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Pylote SA
Original Assignee
Pylote SA
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 Pylote SA filed Critical Pylote SA
Publication of EP3374436A1 publication Critical patent/EP3374436A1/de
Pending legal-status Critical Current

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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
    • 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
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3045—Treatment 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
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3045—Treatment with inorganic compounds
    • C09C1/3054—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
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3063—Treatment with low-molecular organic 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
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
    • 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
    • C09C1/40—Compounds of aluminium
    • C09C1/407—Aluminium oxides or hydroxides
    • 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
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • 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
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • 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
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
    • 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
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • 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
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon 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
    • C09C3/12—Treatment with organosilicon compounds

Definitions

  • the coloring agent is compatible with the medium of the precursor solution and / or is chosen so that it does not degrade at the temperatures to be applied during the particle preparation process, which can be generally between 100 and 300 ° C.
  • brilliant blue E133; CI 42090
  • tartrazine E102, Cl, 18140
  • azorubine El 12, Cl, 14720
  • EXT. D & C Green No. 1 CI 10020
  • azo-acid type dyes in particular such as those described in COLOR INDEX INTERNATIONAL, 3rd edition under the name ACID, for example: Disperse Red 17, Acid Yellow 9, Acid Black 1, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 35, Acid Yellow 23, Acid Orange 24, Acid Violet 43, Acid Blue 62, Acid Blue 9 -Acid Violet 49, Acid Blue 7.
  • Agents may also be mentioned Naturally occurring dyes, such as grape extracts, safflower extracts, cochineal extracts, beet extracts, turmeric, riboflavin, xanthophyll, carotenoids, carmine, carminic acid, anthocyanins, chlorophylls, etc.
  • the dye may be cationic, anionic, neutral, amphoteric, zwitterionic or amphiphilic.
  • the particles according to the invention can be loaded with one or more organic coloring agents.
  • organic coloring agents When there are several coloring agents in the same particle, it may be a mixture of organic coloring agents, a mixture of inorganic coloring agents or a mixture of organic and inorganic coloring agents.
  • the process according to the invention makes it possible to obtain a higher content of dyestuffs in the particles than conventional processes.
  • the process according to the invention has the advantage of having a low loss of the reagents used. initially (high utilization rate of the reagents used), and in particular a low loss of the coloring agents used.
  • the matrix is a flexible, rigid, or solid matrix used as a coating, for example a ceramic or polymeric matrix, in particular a polymeric matrix of the paint type, sol-gel layers, varnish or one of their mixture.
  • the material according to the invention may be intended for use in stationery, painting, food processing, cosmetics or pharmaceuticals.
  • the material is an ink formulation, in particular that can be used for writing or printing.
  • the inclusion of the particles according to the invention in a matrix makes it possible to confer the coloring property on the matrix.
  • the inclusion of the particles in the matrix can be carried out by the techniques conventionally used in the art, in particular by mechanical stirring when the matrix is liquid.
  • the material according to the invention may especially be in the form of liquid, powder, beads, pellets, granules, films, foam, the shaping or preparation operations of these materials being carried out by known conventional techniques. of the skilled person.
  • the particles according to the invention have the particularity of being dispersed substantially homogeneously in volume in the matrix, whatever their chemical nature, their morphology and the nature of the matrix. This means that the particle density per unit volume is the same at every point of the matrix. In the case of a solid matrix, the density of particles per unit area is preferably the same whatever the surface of the matrix considered, whether it is an end surface of the matrix, or a "core" surface obtained by cutting the material for example. Thus, the coloring property imparted to the matrix by inclusion of the particles according to the invention is distributed substantially homogeneously throughout the matrix volume.
  • the sphericity of the particles according to the invention also makes it possible, for the same charge rate in a liquid matrix, to obtain a lower viscosity than with nonspherical particles.
  • Another object of the present invention is a method for preparing a set of particles according to the invention.
  • the process according to the invention is a so-called "aerosol pyrolysis" process (or pyrolysis spray) which is carried out at drying and not pyrolysis temperatures.
  • This process is an improved process compared to the aerosol pyrolysis process described in particular in application FR 2 973 260. More specifically, the process according to the invention is generally carried out in a reactor. This process comprises the non-dissociable and continuous stages in the same reactor, as follows:
  • the liquid solution also comprises at least one coloring agent, as defined above,
  • the heating step (2) (drying) is preferably carried out at a temperature of 40 to 120 ° C, and / or preferably for a duration of less than or equal to 10 seconds, in particular between 1 and 10 seconds.
  • the advantage of the process according to the invention is that it can be achieved in a relatively short time.
  • the duration of the process implementing the successive steps specified above may for example be less than a few minutes (for example 2 or 3 minutes, or even a minute).
  • the temperatures of each of the steps may be outside the range of temperatures provided above. Indeed, for the same particles, the temperature to be applied may depend on the speed at which the droplets, then the particles circulate in the reactor. The more the droplets and then the particles circulate quickly in the reactor, the higher the set temperature must be high to obtain the same result. Of course, the maximum temperature applied in the reactor depends on the coloring agent chosen so as not to degrade the latter.
  • steps (2), (3) and optionally (4) are carried out in the same reactor. All the steps of the process, in particular steps (2), (3) and optionally (4), are carried out in continuity with one another.
  • the temperature profile applied in the reactor is adapted according to the particles that it is desired to form so that these two or three steps take place one after the other.
  • the temperature in the reactor is adjusted via at least one, preferably 2 or 3, heating elements whose temperatures can be set independently.
  • the temperatures of the sequential steps (2), (3) and optionally (4) are increasing.
  • Such an embodiment makes it possible to use a reactor without gas entry in its lower part, thus limiting process disturbances and losses, and thus optimizing the process efficiency and the size distribution of the particles obtained.
  • the reactor in which the process is implemented also includes a gas inlet at the level where the mist is formed.
  • the gas entering the reactor at this level is preferably air.
  • these may comprise any constituent chemical that it is possible to to densify, especially to crystallize, even the metastable phases.
  • the particular conditions used in the process make it possible to preserve compounds whose degradation temperature is lower than the temperature actually applied, because the time spent at high temperature is very short.
  • the term "high temperature” preferably denotes a temperature greater than 40 ° C.
  • “Time spent at high temperature” generally refers to the time spent on the drying, pyrolysis and densification steps.
  • the time spent at high temperature does not exceed 70 seconds, in particular it is between 30 and 70 seconds.
  • quenching is characterized by a cooling rate greater than or equal to 100 ° C per second.
  • the precursor or the precursors of the three-dimensional network of the particles may be or may be of any origin, it (they) is (are) introduced in step (1) of the process in the form of a liquid solution, in particular an aqueous or hydroalcoholic solution containing the metal ions (such as an organic or inorganic salt of the metal in question) or the precursor molecules (such as organosilanes) or in the form of a colloidal sol (such as a colloidal dispersion of nanoparticles of the metal or of the oxide of the metal in question).
  • the precursor (s) of the three-dimensional network is or are chosen according to the particles that it is desired to form. In a particular embodiment, this precursor is at least partly derived from plant or food waste, which represents biosources. Examples of such precursors of inorganic material include sodium silicate from rice husks.
  • hydrolyzable group is meant a group capable of reacting with water to give a group -OH, which will undergo itself a polycondensation.
  • Said metal precursor (s) containing one or more hydrolyzable groups is chosen from an alkoxide or a metal halide, preferably a metal alkoxide, or an alkynylmetal, of formula (1), (2) , (3) or (4) below: L m xMZn-mx (2),
  • M represents Si (IV), the number in parenthesis being the valency of the atom M;
  • n the valence of the atom M
  • x is an integer from 1 to n-1;
  • x ' is an integer from 1 to 3;
  • R represents an alkyl group preferably comprising 1 to 4 carbon atoms, such as a methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl or t-butyl group, preferably methyl, ethyl or i-propyl, more preferably ethyl;
  • Each R ' represents, independently of one another, a non-hydrolyzable group chosen from alkyl groups, especially C 1 -C 4 groups, for example methyl, ethyl, propyl or butyl; alkenyl groups, especially C 2 -C 4, such as vinyl, 1-propenyl, 2-propenyl and butenyl; alkynyl groups, especially C 2 -C 4, such as acetylenyl and propargyl; aryl groups, in particular C 6-10, such as phenyl and naphthyl; methacryl or methacryloxy (C1-10 al
  • L represents a monodentate or polydentate complexing ligand, preferably polydentate, for example a carboxylic acid, preferably a C 1 -C 18 carboxylic acid, such as acetic acid, a C 5-20 ⁇ -diketone, for example acetylacetone, a ⁇ -diketone, preferably a C5-20 ketoester, such as methyl acetoacetate, a C5-20 ⁇ -ketoamide preferably, such as an N-methylacetoacetamide, preferably a C3-20 a- or ⁇ -hydroxyacid, such as lactic acid or salicylic acid, an amino acid such as alanine, a polyamine such as diethylenetriamine (or DETA), or a phosphonic acid or a phosphonate;
  • a monodentate or polydentate complexing ligand for example a carboxylic acid, preferably a C 1 -C 18 carboxylic acid, such as acetic acid, a C 5-20 ⁇
  • n represents the hydroxylation number of ligand L
  • R represents a non-hydrolyzable function chosen from alkylene groups, preferably C 1 -C 12, for example methylene, ethylene, propylene, butylene, hexylene, octylene, decylene and dodecylene, and alkynylene groups, preferably C 2 -C 12, by acetylenylene (-OC-), -C ⁇ CC ⁇ C-, and -C ⁇ CC 6 H 4 -C ⁇ C-; N, N-di (C 2 -C 10) alkylene amino groups such that ⁇ , ⁇ - diethyleneamino; bis [N, N-di (C2-10 alkylene) amino] groups such as bis [N- (3-propylene) -N-methyleneamino]; C 2 -C 10 mercaptoalkylene such as mercaptopropylene; C2 io) polysulfide such as propylene disulfide or propylene tetrasulf
  • organosilane types such as
  • organoalkoxysilane of formula (3) there may be mentioned 3-aminopropyltrialkoxysilane (RO) 3Si - (CH 2 ) 3 -NH 2, 3- (2-aminoethyl) aminopropyltrialkoxysilane (RO) 3 Si ( CH 2 ) 3-NH- (CH 2 ) 2 -NH 2, 3- (trialkoxysilyl) propyldiethylenetriamine (RO) 3Si- (CH 2 ) 3 -NH- (CH 2) 2 -NH- (CH 2 ) 2 -NH 2; organosilyl azoles of the N- (3-trialkoxysilylpropyl) -4,5-dihydroimidazole type, R having the same meaning as above.
  • bis-alkoxysilane of formula (4) a bis [trialkoxysilyl] methane (RO) 3 Si-CH 2 -Si (OR) 3, a bis (trialkoxysilyl) ethane (RO) 3 Si (preferably CH 2) 2 -Si (OR) 3, a bis- [trialkoxysilyl] octane (RO) 3 Si- (CH 2) 8 Si (OR) 3, bis [trialcoxysilyHpropyl] amine (RO) 3 Si- (CH 2 ) 3-NH- (CH 2 ) 3 -Si (OR) 3, a bis- [trialkoxysilylpropyl] ethylenediamine (RO) 3Si- (CH 2) 3 -NH- (CH 2 ) 2 -NH- (CH 2 ) 3 Si (OR) 3; bis- [trialkoxysilylpropyl] disulfide (RO) 3Si- (CH 2 ) 3S 2 - (CH 2 ) 3S
  • an organic-inorganic hybrid is understood to mean a network consisting of molecules corresponding to formulas (2), (3) or (4).
  • the coloring agents may be introduced into the liquid solution in step (1) either in dry form or in the form of a liquid solution.
  • the coloring agents are nanoparticles, they can be introduced into the liquid solution of step (1) in the form of an aqueous or aqueous-alcoholic suspension comprising nanoparticles or else in dry form to be dispersed in the liquid solution of the step (1) of the process according to the invention.
  • the coloring agents are salts, they may be introduced into the liquid solution of step (1) in dry form or in dissolved form in an aqueous or aqueous-alcoholic solution.
  • the amount of coloring agents introduced during the process according to the invention can vary to a large extent, this amount depends in particular on the size and nature of the desired particles. This quantity also depends on the rate of desired coloration and the nature of the coloring agents used.
  • the process according to the invention makes it possible to obtain a higher content of dyestuffs in the particles than conventional processes.
  • the process according to the invention has the advantage of having a low loss of the reagents used initially (high utilization rate of the reagents used), and in particular a low loss of the coloring agents used. artwork.
  • at least the amount of coloring agents introduced may be substantially the same as that desired in the particles obtained.
  • the amount of coloring agents introduced in the process according to the invention, and in particular in step (1) can be from 0 to 20% greater than the quantity finally obtained in the particles of the invention.
  • the quantity of organic coloring agents introduced into step (1) of the process according to the invention is such that the quantity of coloring agents present in the particles of the invention is from 5 to 35%, preferably from 5 to 30%, and more particularly from 10 to 30%, by weight relative to the weight of the particles obtained.
  • the process according to the invention makes it possible to obtain particles having a high degree of purity. These particles do not necessarily require the implementation of subsequent processing steps, such as washing, heat treatment, milling, etc., prior to use.
  • the process according to the invention may optionally comprise at least one post-treatment stage of the particles.
  • it may be a wash step with a suitable solvent, a particle heating step, and / or a coating step particles, in particular for "sealing" said particles, as described above.
  • a post-treatment step by heating the particles may be necessary to optimize the properties of the particles such as their composition or their crystalline structure.
  • a post-treatment step by heating the particles will generally be all the less necessary as the speed of the drops then particles in the weak reactor.
  • the method according to the invention makes it possible to precisely control the size of the particles at the output of the process. Indeed, there is a constant ratio, which is around 5, between the diameter of the drops of the mist used and the diameter of the particles at the output of the process.
  • the person skilled in the art knows how to determine, according to the concentration of precursor, the ratio between these two diameters. For example, if the precursor concentration is decreased by a factor of 10, then the size of the particles obtained is reduced by a cubic root factor of 10, or about 3.
  • the diameter of the drops may also be controlled in particular by the parameters the nebulization mode, for example the frequency of the piezoelectric elements used to form the fog.
  • the process according to the invention also makes it possible to precisely control the pore size at the output of the process.
  • the size of the pores is controlled by the choice of the precursor compounds of the solution, their concentrations, the pH and the presence of the coloring agents. In the present invention, it will be advantageous to limit the pore size and the specific surface area for values of less than 5 m 2 / g.
  • Another subject of the invention is a set of particles capable of being prepared according to the process defined above.
  • the particles thus prepared have the characteristics described above. This process makes it possible in particular to obtain spherical particles and in particular without aggregates. Preferably, it also allows that each particle is not constituted by the aggregation of several smaller particles.
  • a final subject of the invention is a method for preparing a material according to the invention, comprising contacting a matrix as defined above with at least one set of particles according to the invention. This process then preferably comprises a step of shaping the material as described above.
  • Preparation of the solution In a beaker, the following compounds are added in order and with magnetic stirring: 70.7 g of an aqueous acetic acid solution, 14 g of TEOS (ie 4.04 g of silica, 75% of the particles obtained) with 14.0 g of ethanol. The solution is then stirred for at least 1 hour to allow hydrolysis-condensation of TEOS. A mass of 1.35 g of organic dye (25% of the particles obtained) is added to the soil.
  • TEOS ie 4.04 g of silica, 75% of the particles obtained
  • the precursor solution is nebulized by the pyrolysis spray method according to the invention in step (1).
  • step (2) and (3) the maximum temperature of the oven in which the drying and pyrolysis steps take place is set at 250 ° C in order to preserve the coloring agent.
  • the particles are recovered directly in step (5) on the filter and optionally dried under air.
  • the particles are spherical and have a mean diameter of 1.0 micron, with a particle size distribution in the range of 0.3 to 4 microns (electron microscopy at scan), and a sphericity calculated from the microscopy images of 0.9.
  • the BJH surface area is 1.8 m 2 / g and a pore diameter of 2.4 nm.
  • the particles are spherical and have an average diameter of 1.0 ⁇ 0.5 microns, with a particle size distribution in the range of 0.3 to 4 microns (scanning electron microscopy) and a sphericity calculated from the 0 microscopy images.
  • Figure 1 shows an image of Scanning Electron Microscopy of the particles of Example 2. The particles are well unaggregated.
  • a mass of 0.25 g of microparticles of Example 2 (with 24% dye) is dispersed in ethanol at a concentration of 20 g / L microparticles.
  • the solution is centrifuged.
  • the sediments are dried and the supernatant is analyzed by UV-Visible spectrometry.
  • the supernatant contains 0.1 g / l of dye, ie a release of 2% by weight.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Cosmetics (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Silicon Compounds (AREA)
  • Coloring Foods And Improving Nutritive Qualities (AREA)
  • General Preparation And Processing Of Foods (AREA)
  • Glanulating (AREA)
EP16809982.8A 2015-11-12 2016-11-10 Mit färbemitteln gefüllte sphärische partikel Pending EP3374436A1 (de)

Applications Claiming Priority (2)

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FR1560840A FR3043683B1 (fr) 2015-11-12 2015-11-12 Particules spheriques et chargees en agents colorants
PCT/FR2016/052936 WO2017081427A1 (fr) 2015-11-12 2016-11-10 Particules sphériques et chargées en agents colorants

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EP3374436A1 true EP3374436A1 (de) 2018-09-19

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EP (1) EP3374436A1 (de)
JP (2) JP7382715B2 (de)
CN (1) CN108779343A (de)
CA (1) CA3004343A1 (de)
FR (1) FR3043683B1 (de)
WO (1) WO2017081427A1 (de)

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FR3043683B1 (fr) * 2015-11-12 2019-04-12 Pylote Particules spheriques et chargees en agents colorants
KR20240073391A (ko) 2022-11-18 2024-05-27 경희대학교 산학협력단 약물 관련 주입 반응 탐지를 위한 웨어러블 디바이스용 모니터링 시스템

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JP2019503405A (ja) 2019-02-07
JP7382715B2 (ja) 2023-11-17
WO2017081427A1 (fr) 2017-05-18
FR3043683A1 (fr) 2017-05-19
US11208560B2 (en) 2021-12-28
JP2021185248A (ja) 2021-12-09
US20190100657A1 (en) 2019-04-04
CA3004343A1 (fr) 2017-05-18
FR3043683B1 (fr) 2019-04-12
CN108779343A (zh) 2018-11-09

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