WO2012107622A1 - A method for obtaining a ceramic toner and ceramic toner obtained - Google Patents

A method for obtaining a ceramic toner and ceramic toner obtained Download PDF

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Publication number
WO2012107622A1
WO2012107622A1 PCT/ES2012/070078 ES2012070078W WO2012107622A1 WO 2012107622 A1 WO2012107622 A1 WO 2012107622A1 ES 2012070078 W ES2012070078 W ES 2012070078W WO 2012107622 A1 WO2012107622 A1 WO 2012107622A1
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WO
WIPO (PCT)
Prior art keywords
toner
ceramic
obtaining
monomers
inorganic
Prior art date
Application number
PCT/ES2012/070078
Other languages
Spanish (es)
French (fr)
Inventor
Juan Vicente BONO SALES
Vicente Sanz Solana
Yolanda Bautista Rabanal
Celia RIBES VIDAL
Original Assignee
Asociación De Investigación De Las Industrias Cerámicas A.I.C.E.
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Application filed by Asociación De Investigación De Las Industrias Cerámicas A.I.C.E. filed Critical Asociación De Investigación De Las Industrias Cerámicas A.I.C.E.
Publication of WO2012107622A1 publication Critical patent/WO2012107622A1/en

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0819—Developers with toner particles characterised by the dimensions of the particles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0802—Preparation methods
    • G03G9/0804—Preparation methods whereby the components are brought together in a liquid dispersing medium
    • G03G9/0806—Preparation methods whereby the components are brought together in a liquid dispersing medium whereby chemical synthesis of at least one of the toner components takes place
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/097—Plasticisers; Charge controlling agents
    • G03G9/09708—Inorganic compounds

Definitions

  • the present invention falls within the sector of decoration of ceramic materials, glass and metals, by electrostatic techniques. It refers to the composition and preparation of ceramic inks, ceramic, glass or metal pieces decorated with them and the process of fixing the inks.
  • the xerographic printing technique consists of selectively depositing a powder ink (toner) on a support to be decorated.
  • a photoconductor roller is used, where the latent image is formed in the form of electrostatic charges.
  • the developer roller in the case of two component toner, contains a mixture of toner and developer. During mixing of both, the toner develops an electric tribocharge by friction. Due to this load and the application of a potential difference between the rollers, a transfer of the loaded toner to the photoconductor roller occurs.
  • the transfer of the toner from the photoconductor roller to the transfer roller is made by the existence of a potential difference.
  • the transfer roller deposits the toner particles on the surface to be decorated. During this process, exposure to heat and pressure causes the image to be fixed to the support. In the case of decoration of ceramic pieces, glass, or metal, these supports have to be subjected to a subsequent heat treatment, at temperatures above 400 ° C, which eliminates the organic components of the toner and allows the integration of the component inorganic on the surface to decorate.
  • the ceramic toner must therefore contain an inorganic fraction active in decoration, capable of aesthetically modifying the surface to be coated (for example: inorganic pigments, inorganic opacifiers, phosphates, wolfram, etc.) ... and an inorganic fraction that It confers fundence, which facilitates the integration of the inorganic fraction into the surface at high temperature.
  • an inorganic fraction active in decoration capable of aesthetically modifying the surface to be coated (for example: inorganic pigments, inorganic opacifiers, phosphates, wolfram, etc.) ... and an inorganic fraction that It confers fundence, which facilitates the integration of the inorganic fraction into the surface at high temperature.
  • it should include in its composition a polymeric material with a suitable glass transition temperature that allows it to be fixed to the support, with little energy input.
  • the surface of the toner particles must be electrostatically charged with some ease.
  • toner particles There are different techniques for preparing toner particles. These can be grouped into two families, the traditional, spray-based method, and polymerization methods.
  • the traditional method is to mix all components at a temperature higher than the melting of the resin used. The melt is cooled and cut, then pulverized, to obtain small particles of the desired size.
  • Kawase in US Pat. No. 5,976,736 claims a ceramic toner prepared by the traditional method, and formed by a binder resin and a coloring agent. This colored agent is obtained by sintering the inorganic pigment together with a fluxing agent. This toner is transferred to the ceramic piece indirectly using a transfer sheet.
  • the preparation of ceramic toner by the traditional method has a number of drawbacks.
  • the inorganic component has different Fracture resistance than the plastic organic component, so that during the process of generating the toner powder, the particles are broken by the interface between the inorganic particles and the polymer matrix. This generates irregularly shaped toner particles and with inorganic particles only partially covered by the plastic organic matrix, causing problems of electrical conductivity and fluidity of the particles.
  • the high specific weight of ceramic toner makes it very difficult to obtain a narrow particle size distribution by the traditional method. These inconveniences can cause printing problems such as white holes in the images.
  • Kmiecik-Lawrynowicz in European patent application EP-1975728 claims a ceramic toner prepared by an emulsion polymerization method from ceramic pigments with hydrophilic surface modification, and polymeric resins. These toner particles have ceramic pigment percentages between 2 and 18% by weight.
  • the emulsion polymerization process has certain disadvantages, such as the difficulty of eliminating the surfactants and emulsifying agents used, the difficulty of controlling the particle size distribution, obtaining wide distributions, therefore the quality control of the same.
  • the presence of particles of a nanometric size can be detrimental to human health.
  • the use of a method of synthesis of the toner by suspension polymerization avoids the inconveniences presented by the traditional synthesis, in addition to those presented by the emulsion polymerization.
  • the present invention therefore describes a suspension polymerization method for the preparation of ceramic toner, which includes a high percentage of inorganic component in its composition.
  • the inorganic component includes an inorganic fraction active in decoration, capable of modifying the aesthetic appearance of the surface to be coated and an inorganic fraction that facilitates fundence and integration with the support.
  • the present invention relates firstly to a process of preparing a toner from a suspension polymerization.
  • This procedure is particularly suitable for obtaining a toner for decoration of ceramic materials, glass and metal, and comprises the following steps:
  • Polymerization of one or more monomers occurs in the presence of particles of the inorganic component.
  • the inorganic component comprises at least one inorganic fraction for fundency and at least one inorganic fraction active in decoration, all inorganic components having a hydrophobic surface behavior.
  • the ceramic toner particles obtained are preferably spherical.
  • the materials of the organic component are always the initiators, and optionally, the load control agents and the waxes
  • toner additives which will remain in the material to sell (load control agents, initiators, waxes, and external fluidizing additives) and process additives, which are necessary for the polymerization process but are removed once synthesized (stabilizing additives, surfactants).
  • the other components such as hydrophobic inorganic components, charge control agents, initiators and waxes, are added to the monomers.
  • the oleophilic mixture is dispersed in an aqueous medium (where a stabilizing agent and, optionally, an ionic surfactant have been previously dissolved or dispersed to obtain a droplet suspension, forming a discontinuous phase.
  • the dispersion and drop formation treatment is obtained using high-speed emulsifying-dispersing equipment
  • the suspension of the drops is thermodynamically unstable, so that the coalescence is controlled by a balance between the agitation and the stabilizing agent of the suspension and the surfactant used.
  • initiator that has previously dissolved in the monomers and is therefore inside the droplets in suspension.
  • the particles of the inorganic component must be mostly surrounded by the polymer, so before starting the polymerization, these particles must be dispersed inside the monomer drops.
  • the polymerization is started by increasing the temperature of the system.
  • the initiators present in the drops decompose and initiate polymerization of the monomers.
  • Said polymer particles contain inorganic particles, charge control agents and waxes.
  • the present invention also relates to a toner for the decoration of ceramic materials, glass and metal, - hereafter referred to as "ceramic toner" - obtained by the described process.
  • Said toner comprises at least:
  • an inorganic component that is present between 5 and 90% by weight, and which comprises:
  • an organic polymer component that is present between 95 and 10% by weight and which comprises one or more organic polymers.
  • the weight of the inorganic component is preferably between 40 and 80%.
  • the inorganic fraction active in decoration has the function of modifying the aesthetic appearance of the surface to be decorated.
  • aesthetic effects we can include the color, the metallic aspect, the luster or the iridescent effect.
  • the inorganic fraction that confers fundence It will provide the necessary functionality for the integration of the inorganic fraction responsible for the aesthetic change, during the last stage of high temperature cooking ensuring a good adhesion of the decoration.
  • the polymer is synthesized during the process of preparing the toner and acts as a carrier of the electric charge, carrier of the inorganic materials and ensures the first fixation to the support before the cooking stage.
  • the inorganic component may be present in the toner between 5 and 90% by weight Preferably the inorganic component is present between 7 and 85% by weight, more preferably it is present between 9 and 82% in weight and even more preferably between 10 and 80% by weight. This component is what will remain in the decoration after the cooking process at high temperatures.
  • the organic component comprises the polymer, the charge control agent, the initiator and the waxes, the assembly being generally 20%, the inorganic component is the pigments and the frit and / or the melting materials being generally 80% .
  • the frit for ceramic toner can be obtained by melting raw materials with subsequent cooling in water and / or air, from raw materials such as metal oxides, silicates, carbonates, aluminosilicates, borates, nitrates, sulfates, oxalates, chlorides or oxides mixed.
  • raw materials such as metal oxides, silicates, carbonates, aluminosilicates, borates, nitrates, sulfates, oxalates, chlorides or oxides mixed.
  • the low organic polymer content favors that there are no calcination residues that could modify the desired aesthetic effect.
  • toner can be prepared with a high ratio of active inorganic fraction in decoration / inorganic fraction that confers fundence, which allows to obtain greater color saturations, or a greater aesthetic effect, with smaller amounts of material, without losing adhesion to ceramic, vitreous or metallic support.
  • the values of the ratio inorganic active fraction in decoration / inorganic fraction that confers fundancy can range between 10 and 0.1, and preferably are between 9 and 0.2, more preferably between 8 and 0.7, and more preferably even between 7 and 1.
  • the organic polymer component of the toner is prepared from monomers with functional groups capable of polymerizing.
  • the polymer formed has to meet certain characteristics, among which are: that they admit the highest possible inorganic component content; certain ability to electrostatically charge; the glass transition temperature suitable for the provisional fixation of the toner particles after deposition and burn easily during the cooking process without leaving ashes that can modify the desired color or aesthetic effect.
  • the monomers that can be employed are aromatic vinyl monomers, unsaturated ethylenic monomers, acrylated monomers, methacrylated monomers, and dienyl monomers, or mixtures of the foregoing.
  • aromatic vinyl monomers are: styrene, methylstyrene, monochlorostyrene, dimethylstyrene, and the like.
  • unsaturated ethylenic monomers are: vinyl acetate, vinyl formate, alkyl vinyl ethers, ethylene, propylene, butylene, vinylidene chloride, alkyl acrylates and ketacrylates, alkyl maleates and alkyl fumarates.
  • acrylated monomers are: acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, dimethylaminoethyl acrylate, and similar acrylate.
  • methacrylated monomers are: methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, dimethylaminoethyl methacrylate, methacrylamide and the like.
  • crosslinking of the chains can be favored by using crosslinking monomers.
  • crosslinker dienyl monomers are: butadiene, allyl methacrylate, ethylene dimethacrylate, 1, 6-hexamethylene diacrylate, 1,1,1-trimethyl propane triacrylate, triallyl amine, isoprene, divinyl benzene, divinyl naphthalene, and derivatives, dimethacrylate, diethylene glycol dimethacrylate, ⁇ , ⁇ -divinyl aniline and the like.
  • an active inorganic fraction is used in decoration, depending on the aesthetic effect that is desired to be obtained.
  • the inorganic fraction active in decoration may contain at least one of the following components: metal oxides, mixtures of metal oxides, mixtures of oxides, mixed oxides, solid solutions of colored compounds, solid solutions of non-colored compounds, solid solutions of metal oxides, colloidal metals, sulphides, pigments protected from inclusion or mordants , metal oxides with metal phosphates, melting raw materials comprising cerium or metal tungsten, vitreous materials comprising cerium or tungsten, vitreous materials comprising titanium.
  • the vitreous materials comprising cerium or tungsten are frits comprising these metals.
  • the vitreous materials that comprise titanium are frits that comprise a high content of titanium.
  • an inorganic pigment will be used depending on the aesthetic effect that is desired to be obtained.
  • any of the inorganic chromophores pigments present in the state of the art can be used, which withstand the cooking temperatures of the decoration.
  • Some of the types of pigments that can be used are, for example, metal oxides, transition element oxides, oxide mixtures, solid solutions of colored, or non-colored compounds, colloidal metals (Cu, Au, Ag, Pt), non-oxidized systems such as sulfides (Se, Au and Pt), protected inclusion pigments or mordants, and mixtures of any of the above.
  • metal oxides such as iron oxide together with metal phosphates can be used as an inorganic active fraction in decoration, for example aluminum phosphate.
  • frits with high titanium oxide contents can be used as an active inorganic fraction in decoration.
  • the compounds that are part of the active inorganic fraction in decoration are usually refractory compounds which makes it difficult to integrate into the surface to be decorated.
  • an inorganic fraction is used for fundence, which at the maximum cooking temperature of the decoration is very softened around the most refractory inorganic fraction.
  • the viscosity of the inorganic fraction for flux increases considerably while retaining the refractory components and remaining adhered to the surface to be decorated.
  • the inorganic fraction for flux can be formed by fried type materials or melting materials.
  • the frits are vitreous compounds, insoluble in water, which are obtained by melting and subsequent rapid cooling of controlled mixtures of raw materials and with a softening temperature lower than the melting of the original raw materials.
  • Raw materials contain oxides such as, among others, silicon oxide, aluminum oxide, boron oxide, alkaline oxides, alkaline earth oxides, zinc oxide, etc., which give them their properties.
  • the melting materials that can be used are those inorganic materials that generate low temperature eutectic with the ceramic materials.
  • the active inorganic fraction in decoration into the support can be ensured, after the cooking process, when a ratio of 0.1 ⁇ inorganic fraction active in decoration / inorganic fraction for funcy ⁇ 10 is used.
  • the particle size of any of the inorganic components may range between 1 and 10 ⁇ , preferably between 2 and 8 ⁇ , more preferably between 3 and 7 ⁇ , and more preferably even between 4 and 6 ⁇
  • the inorganic particles be placed inside the monomer droplets.
  • the hydrophilic nature of the surface of the inorganic particles causes them to show a greater tendency to be in the aqueous phase. Therefore it is necessary to have particles with a hydrophobic surface or subject these particles to a surface treatment that converts them into hydrophobic
  • the functionalization of the inorganic particles can be carried out by a hydrolysis and condensation reaction between the surface hydroxyl groups of the inorganic solids (inorganic fraction active in decoration and inorganic fraction for fundence) and functionalized alkoxysilanes with organic groups compatible with the functional groups of the monomers.
  • a charge control agent can be incorporated into the composition of the polymer formed.
  • This charge control agent can be selected from different types of compounds, taking into account the load that you want to contribute to the toner particles.
  • Some of the compounds of the following families can be used as charge control agents: nigrosines, triphenylmethane complexes, cationic dyes, dioxacins, benzimidazolones, copper phthalocyanines, perilenes, quinacridones, azo pigments, azo pigment metal salts, azo complexes copper, salicylic acid metal complexes, tetraphenyl borate derivatives, derivatives of an aromatic hydroxycarboxylic acid, derivatives of an aliphatic hydroxycarboxylic acid, calixarene derivatives, quaternary ammonium salts, quaternary alkylammonium salts, quaternary pyridinium salts, bisulfates, chlorinated paraffin , chlorinated polyester, polyesters with acid groups, polymers containing sulfonic acid groups, carbon black, iron black
  • These compounds can be used alone or in combination, in percentages between 0.01 and 20 percent by weight with respect to the total weight of monomers, preferably between 0.1 and 18% by weight, more preferably between 0.4 and 16 % by weight, and more preferably even between 0.8 and 14% by weight.
  • an additive can be used to avoid sticking the toner particles onto the hot transfer roller.
  • This additive avoids having to feed the transfer roller regularly of oil that fulfills this function.
  • this type of additive may include polyolefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight polybutylene, natural waxes such as candelilla, carnauba, jojoba, rice wax, petroleum waxes, such as paraffins, microcrystalline, petrolatum, mineral waxes such as montan, ceresin, ozoquerite, and synthetic waxes such as Fischer-Tropsch waxes, fatty amides, silicone oils.
  • polyolefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight polybutylene, natural waxes such as candelilla, carnauba, jojoba, rice wax, petroleum waxes, such as paraffins, microcrystalline, petrolatum, mineral wax
  • These compounds can be used alone or combinations of two or more of them, in percentages between 0.1 and 20 percent by weight with respect to the total weight of monomers, preferably between 0.1 and 18% by weight, more preferably between 0.4 and 16% by weight, and more preferably even between 0.8 and 14% by weight.
  • initiators that may be employed in the present invention, peroxide type initiators such as benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, stearoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, methyl ethyl ketone peroxide, may be mentioned, cyclohexanone peroxide, eumene hydroperoxide, t-butyl hydroperoxide, tert-butyl peroxy pivalerate, isopropyl diperoxide carbonate, hydrogen peroxide, di-1- peroxide naphthoyl, and azo compounds such as azobisisobutyronitrile, azobisdimethylvaleronitrile, or peroxide-disulfuric acid salts, these include potassium peroxide type initiators such as benzoyl peroxide, lauroyl peroxide, octanoyl peroxid
  • These compounds can be used alone or in combination, in percentages between 0.01 and 10 percent by weight with respect to the total weight of monomers, preferably between 0.04 and 8% by weight, more preferably between 0.08 and 6 % by weight, and more preferably even between 0.2 and 5% by weight.
  • stabilizing agents can be of different nature.
  • inorganic additives such as calcium or barium sulfates, calcium, barium or magnesium carbonates, calcium phosphate, hydrophobic or hydrophilic silica, colloidal silica, aluminum oxide, titanium oxide, aluminum hydroxides, magnesium or iron
  • Organic compounds such as polyvinyl alcohol, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium carboxymethyl cellulose, gelatin, or starch may also be included.
  • These compounds can be used alone or in combination, in percentages between 0.01 and 20 percent by weight with respect to the amount of water in the continuous phase, preferably between 0.04 and 18% by weight, more preferably between 0 , 08 and 16% by weight, and more preferably even between 0.25 and 15% by weight.
  • At least one surfactant can also be used. How Surfactants in the present invention can be used different types of compounds selected from at least one of the following families: fatty acid salts, alkyl sulfate ester salts, aryl sulfate ester salts, dialkyl sulfosuccinates, alkyl phosphates. Some exemplary compounds are included below: sodium dodecylbenzenesulfonate, sodium dodecyl sulfonate, sodium tetradecyl sulfonate, sodium pentadecyl sulfonate, sodium octyl sulfonate, sodium oleate, sodium laureate, potassium stearate, sodium oleate. These compounds can be used alone or in combination, in percentages between 0.001 and 5 percent by weight with respect to the amount of water in the continuous phase.
  • the use of external fluidizing agents is recommended.
  • this type of additive include very fine particles of inorganic materials such as silica, aluminum oxide and titanium oxide.
  • the particles selected as fluidizing agents of the claimed toner must have a surface treatment that provides hydrophobic behavior to their surface.
  • the toner particles have average particle diameters between ⁇ and 30 ⁇ , preferably between 2 ⁇ and 25 ⁇ , more preferably between 5 ⁇ and 23 ⁇ and more preferably even between 7 ⁇ and 20 ⁇ .
  • the present invention also relates to a use of the ceramic toner of the invention as decoration ink.
  • the toner manufactured as previously described can be mixed with magnetic developer particles and used as ink in the decoration of ceramic, glass or metal materials, using, for example, xerographic application equipment.
  • the printed image is fixed to the ceramic support, glass or metal, by subjecting the piece to a cooking cycle.
  • the synthesis method claimed in the present invention allows the use of high percentages of inorganic components.
  • Figure 1 Photograph taken with a scanning electron microscope of a synthesized toner particle as described in example 1 herein. The image has been obtained by bombardment with a beam of secondary electrons and the image observed corresponds to the topography of the particle. In the foreground, a whitish area corresponding to a prominence of the surface of the particle is observed. In the outline of the particle other prominences are observed that cause a slight loss of sphericity. On the surface of the particle, the nanometric silica particles used as a fluidizer are observed.
  • Figure 2 Photograph of the same particle as Figure 1, taken in a scanning electron microscope using a beam of backscattered electrons.
  • the gray scale seen in the photograph is directly related to the atomic weight of the atoms that make up the particle.
  • the lighter grays correspond to the atoms of higher atomic weights.
  • the darkest grays correspond to the lowest atoms of atomic weight. It is therefore an image of compositions, unlike Figure 1 which is a topographic image.
  • the prominence observed in Figure 1 corresponds to a pigment particle with atoms of high atomic weight (whitish area) that is inside the toner particle as seen in the topographic image of Figure 1.
  • Other lighter areas are observed inside the particle showing other inorganic particles present inside.
  • the outer part of the particle has a darker gray corresponding to the polymerized organic part formed by carbon, oxygen and hydrogen atoms of lower atomic weights.
  • the inorganic components For the functionalization of the inorganic components, 80 g of a pink tin and chromium sphene pigment are weighed, and 20 g of a ceramic frit whose chemical composition is included in Table 1. These components are dispersed in 300 ml of hydrochloric acid at 0.01M, and 30 g of methacryloxy propyl trimethoxysilane are added. The mixture is kept under stirring for 30 minutes, subsequently filtering, washing and drying the functionalized solids.
  • the continuous phase (aqueous phase) and the discontinuous phase (organic phase) are prepared separately:
  • the discontinuous phase is stirred at 3000 rpm for 5 minutes. Subsequently, the continuous phase is added. The mixture is kept under stirring at 4000 rpm for an additional 30 minutes. After this time, the assembly is introduced into a 2-liter reactor under a stream of nitrogen and heated at 80 ° C for 10 hours, maintaining a constant stirring of 500 rpm. The product obtained from the polymerization is washed with water, It is filtered and allowed to dry obtaining the particles of toner.
  • the inorganic components 80 g of a yellow pigment are weighed Zirconium and praseodymium silicate, and 20 g of a ceramic frit whose chemical composition is included in Table 1. These components are dispersed in 300 ml of 0.01M hydrochloric acid, and 30 g of methacryloxy propyl trimethoxysilane are added. The mixture is kept under stirring for 30 minutes, subsequently filtering, washing and drying the functionalized solids.
  • the continuous phase (aqueous phase) and the discontinuous phase (organic phase) are prepared separately:
  • the discontinuous phase is stirred at 3000 rpm for 5 minutes. Subsequently, the continuous phase is added. The mixture is kept under stirring at 4000 rpm for an additional 30 minutes. After this time, the assembly is introduced into a 2-liter reactor under a stream of nitrogen and heated at 80 ° C for 10 hours, maintaining a constant stirring of 500 rpm. The product obtained from the polymerization is washed with water, filtered and allowed to dry to obtain the toner particles.
  • a blue pigment of zirconium and vanadium silicate are weighed, and 20 g of a ceramic frit whose chemical composition is included in table 1. These components are dispersed in 300 ml of hydrochloric acid at 0.01M, and 30 g of methacryloxy propyl trimethoxysilane are added. The mixture is kept under stirring for 30 minutes, subsequently filtering, washing and drying the functionalized solids.
  • the continuous phase (aqueous phase) and the discontinuous phase (organic phase) are prepared separately:
  • the discontinuous phase is stirred at 3000 rpm for 5 minutes. Subsequently, the continuous phase is added. The mixture is kept under stirring at 4000 rpm for an additional 30 minutes. After this time, the set is it enters a reactor of 2 liters of capacity under a stream of nitrogen and is heated at 80 ° C for 10 hours, maintaining a constant stirring of 500 rpm. The product obtained from the polymerization is washed with water, filtered and allowed to dry to obtain the toner particles.
  • the inorganic components 80 g of a black pigment of iron, chromium, cobalt, nickel and manganese sphene and 20 g of a ceramic frit whose chemical composition is included in table 1 are weighed. These components are dispersed in 300 ml of 0.01M hydrochloric acid, and 30 g of methacryloxy propyl trimethoxysilane are added. The mixture is kept under stirring for 30 minutes, subsequently filtering, washing and drying the functionalized solids.
  • the continuous phase (aqueous phase) and the discontinuous phase (organic phase) are prepared separately:
  • the discontinuous phase is stirred at 3000 rpm for 5 minutes. Subsequently, the continuous phase is added. The mixture is kept under stirring at 4000 rpm for an additional 30 minutes. After this time, the assembly is introduced into a 2-liter reactor under a stream of nitrogen and heated at 80 ° C for 10 hours, maintaining a constant stirring of 500 rpm. The product obtained from the polymerization is washed with water, filtered and allowed to dry to obtain the toner particles.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Developing Agents For Electrophotography (AREA)

Abstract

The present invention relates to a method for obtaining a toner, more specifically for decorating ceramic materials, glass and metal, characterized in that the method comprises: -dispersing the particles of the inorganic component of the toner, which have a hydrophobic surface, in a mixture comprising at least: one or more organic monomers and one or more initiators, -dispersing the oleophilic mixture obtained in the previous step in an aqueous medium comprising one or more dissolved stabilizing agents, obtaining suspended beads, -polymerizing the suspended beads obtained in the previous step by increasing the temperature in a stirred vessel, obtaining particles of ceramic toner, -washing and subsequently drying the synthesized particles, -incorporating and mechanically mixing external additives.

Description

UN PROCEDIMIENTO PARA OBTENER UN TÓNER CERÁMICO Y TÓNER  A PROCEDURE TO OBTAIN A CERAMIC TONER AND TONER
CERÁMICO OBTENIDO CERAMIC OBTAINED
SECTOR DE LA TÉCNICA SECTOR OF THE TECHNIQUE
La presente invención se encuadra en el sector de decoración de materiales cerámicos, vidrios y metales, por técnicas electrostáticas. Se refiere a la composición y preparación de las tintas cerámicas, a las piezas cerámicas, de vidrio o de metal decoradas con ellas y al proceso de fijación de las tintas.  The present invention falls within the sector of decoration of ceramic materials, glass and metals, by electrostatic techniques. It refers to the composition and preparation of ceramic inks, ceramic, glass or metal pieces decorated with them and the process of fixing the inks.
ESTADO DE LA TÉCNICA ANTERIOR A LA INVENCIÓN STATE OF THE PRIOR ART OF THE INVENTION
La técnica de impresión xerográfica consiste en depositar selectivamente una tinta en polvo (tóner) sobre un soporte a decorar. Para ello se emplea un rodillo fotoconductor, en donde se forma la imagen latente en forma de cargas electrostáticas. El rodillo revelador (en el caso del tóner de dos componentes) , contiene una mezcla de tóner y revelador. Durante el mezclado de ambos, el tóner desarrolla una tribocarga eléctrica por fricción. Debido a esta carga y a la aplicación de una diferencia de potencial entre los rodillos, se produce una transferencia del tóner cargado hacia el rodillo fotoconductor . Habitualmente existe un rodillo intermedio acondicionador entre el rodillo revelador y el rodillo fotoconductor . Las propiedades magnéticas del revelador, hacen que éste permanezca en el rodillo revelador. La transferencia del tóner desde el rodillo fotoconductor hasta el rodillo de transferencia se realiza por la existencia de una diferencia de potencial. El rodillo de transferencia deposita las partículas de tóner sobre la superficie a decorar. Durante este proceso, la exposición al calor y la presión hacen fijar la imagen al soporte. En el caso de decoración de piezas cerámicas, vidrio, o metal, estos soportes tienen que ser sometidos a un tratamiento térmico posterior, a temperaturas superiores a los 400 °C, que elimina los componentes orgánicos del tóner y que permite la integración de la componente inorgánica en la superficie a decorar. The xerographic printing technique consists of selectively depositing a powder ink (toner) on a support to be decorated. For this, a photoconductor roller is used, where the latent image is formed in the form of electrostatic charges. The developer roller (in the case of two component toner), contains a mixture of toner and developer. During mixing of both, the toner develops an electric tribocharge by friction. Due to this load and the application of a potential difference between the rollers, a transfer of the loaded toner to the photoconductor roller occurs. There is usually an intermediate conditioning roller between the developer roller and the photoconductor roller. The magnetic properties of the developer make it remain in the developer roller. The transfer of the toner from the photoconductor roller to the transfer roller is made by the existence of a potential difference. The transfer roller deposits the toner particles on the surface to be decorated. During this process, exposure to heat and pressure causes the image to be fixed to the support. In the case of decoration of ceramic pieces, glass, or metal, these supports have to be subjected to a subsequent heat treatment, at temperatures above 400 ° C, which eliminates the organic components of the toner and allows the integration of the component inorganic on the surface to decorate.
El tóner cerámico debe contener, por tanto, una fracción inorgánica activa en decoración, capaz de modificar estéticamente la superficie a recubrir (por ejemplo: pigmentos inorgánicos, opacificantes inorgánicos, fosfatos, wolframatos, etc.,...) y una fracción inorgánica que confiere fundencia, la cual facilite la integración de la fracción inorgánica en la superficie a alta temperatura. Además, debe incluir en su composición un material polimérico con una temperatura de transición vitrea adecuada que le permita fijarse al soporte, con poco aporte de energía. La superficie de las partículas de tóner debe cargarse electrostáticamente con cierta facilidad.  The ceramic toner must therefore contain an inorganic fraction active in decoration, capable of aesthetically modifying the surface to be coated (for example: inorganic pigments, inorganic opacifiers, phosphates, wolfram, etc.) ... and an inorganic fraction that It confers fundence, which facilitates the integration of the inorganic fraction into the surface at high temperature. In addition, it should include in its composition a polymeric material with a suitable glass transition temperature that allows it to be fixed to the support, with little energy input. The surface of the toner particles must be electrostatically charged with some ease.
Existen diferentes técnicas para la preparación de las partículas de tóner. Estas pueden agruparse en dos familias, el método tradicional, basado en pulverización, y los métodos de polimerización. El método denominado tradicional consiste en mezclar todos los componentes a una temperatura superior a la de fusión de la resina empleada. La masa fundida se enfría y se corta, pulverizándola posteriormente, para obtener pequeñas partículas del tamaño deseado.  There are different techniques for preparing toner particles. These can be grouped into two families, the traditional, spray-based method, and polymerization methods. The traditional method is to mix all components at a temperature higher than the melting of the resin used. The melt is cooled and cut, then pulverized, to obtain small particles of the desired size.
La fabricación del tóner cerámico por el método tradicional se encuentra descrita en diferentes patentes. Zimmer en la patente alemana DE-19709011, reivindica un tóner cerámico fabricado por el método tradicional, con pigmentos inorgánicos, fundente y una resina aglutinante. Este tóner puede aplicarse de forma directa o también indirectamente sobre un medio de transferencia. The manufacture of ceramic toner by the traditional method is described in different patents. Zimmer in the German patent DE-19709011, claims a ceramic toner manufactured by the traditional method, with inorganic pigments, flux and a binder resin. This toner can be applied directly or indirectly on a transfer medium.
Schultheis en la patente alemana DE-10200412, reivindica un tóner preparado por el método tradicional a partir de pigmentos inorgánicos, frita y una resina termoplástica de base acrilada. Además se incluyen en la composición compuestos azo o peróxidos que facilitan la descomposición de los polímeros evitando la presencia de residuos tras el proceso de cocción.  Schultheis in the German patent DE-10200412, claims a toner prepared by the traditional method from inorganic pigments, fried and a thermoplastic resin of acrylated base. Also included in the composition are azo compounds or peroxides that facilitate the decomposition of polymers avoiding the presence of residues after the cooking process.
Tavernier en la patente europea EP-0851306 Bl reivindica la posibilidad de aplicar separadamente un tóner que contiene el pigmento inorgánico y un tóner que contiene el material fundente. Ambos tipos de tóner los prepara por el método tradicional descrito previamente.  Tavernier in European Patent EP-0851306 Bl claims the possibility of separately applying a toner containing the inorganic pigment and a toner containing the melting material. Both types of toner prepare them by the traditional method described previously.
Kawase en la patente estadounidense US-5.976.736 reivindica un tóner cerámico preparado por el método tradicional, y formado por una resina ligante y un agente de coloreado. Este agente coloreado se obtiene por la sinterización del pigmento inorgánico junto con un agente fundente. Este tóner se transfiere a la pieza cerámica de forma indirecta empleando una hoja de trasferencia .  Kawase in US Pat. No. 5,976,736 claims a ceramic toner prepared by the traditional method, and formed by a binder resin and a coloring agent. This colored agent is obtained by sintering the inorganic pigment together with a fluxing agent. This toner is transferred to the ceramic piece indirectly using a transfer sheet.
Okahata en la solicitud de patente estadounidense US20080254268, reivindica un tóner cerámico preparado por el método tradicional a partir de pigmento cerámico, frita y una resina ligante que selecciona para que tenga una buena descomposición en el intervalo de cocción sin que genere restos que puedan impedir una buena adherencia a la pieza cerámica o vidrio.  Okahata in US patent application US20080254268, claims a ceramic toner prepared by the traditional method from ceramic pigment, fried and a binding resin that selects to have a good decomposition in the cooking range without generating debris that can prevent a Good adhesion to the ceramic or glass piece.
En todos los casos, la preparación del tóner cerámico por el método tradicional presenta una serie de inconvenientes. La componente inorgánica, tiene diferente resistencia a la fractura que la componente orgánica plástica, por lo que durante el proceso de generación del polvo de tóner, las partículas se rompen por la interfase entre las partículas inorgánicas y la matriz polimérica. Esto genera partículas de tóner con formas irregulares y con partículas inorgánicas solo parcialmente recubiertas por la matriz orgánica plástica, pudiendo causar problemas de conductividad eléctrica y fluidez de las partículas. Además, el elevado peso específico del tóner cerámico, hace muy difícil obtener por el método tradicional, una distribución estrecha de tamaños de partícula. Estos inconvenientes pueden generar problemas de impresión como huecos blancos en las imágenes. In all cases, the preparation of ceramic toner by the traditional method has a number of drawbacks. The inorganic component has different Fracture resistance than the plastic organic component, so that during the process of generating the toner powder, the particles are broken by the interface between the inorganic particles and the polymer matrix. This generates irregularly shaped toner particles and with inorganic particles only partially covered by the plastic organic matrix, causing problems of electrical conductivity and fluidity of the particles. In addition, the high specific weight of ceramic toner makes it very difficult to obtain a narrow particle size distribution by the traditional method. These inconveniences can cause printing problems such as white holes in the images.
Tomiaki en la solicitud de patente estadounidense US20010031415 Al, manteniendo el método tradicional de preparación intenta aminorar el problema, haciendo que el porcentaje de partículas de tóner con un diámetro igual o superior a 16 μιη no supere el 20%.  Tomiaki in US patent application US20010031415 Al, while maintaining the traditional method of preparation tries to reduce the problem, causing the percentage of toner particles with a diameter equal to or greater than 16 μιη not to exceed 20%.
En la preparación del tóner que hace uso de colorantes orgánicos (que no son adecuados para la decoración de cerámica, vidrio o metal, ya que los colorantes empleados descomponen durante la cocción) , para evitar los problemas comentados previamente se han buscado vías de síntesis alternativas. Estas hacen uso de una polimerización in situ de los monómeros orgánicos, obteniendo partículas de tóner más redondeadas. Estos métodos de polimerización, que se encuentran muy desarrollados para el tóner orgánico no se han extendido para el tóner cerámico debido a la complejidad de la presencia de partículas inorgánicas durante el proceso de polimerización .  In the preparation of the toner that makes use of organic dyes (which are not suitable for decorating ceramics, glass or metal, since the dyes used decompose during cooking), in order to avoid the problems mentioned previously, alternative synthesis routes have been sought . These make use of an in situ polymerization of the organic monomers, obtaining more rounded toner particles. These polymerization methods, which are highly developed for organic toner, have not been extended for ceramic toner due to the complexity of the presence of inorganic particles during the polymerization process.
Durford en la patente estadounidense US6110632, reivindica un tóner cerámico preparado por un método consistente en la floculación de un material polimérico orgánico a partir de una suspensión acuosa de dicho material y de las partículas de pigmento inorgánico y frita. La fracción inorgánica alcanza valores entre el 60 y el 90% en peso. Dicha fracción inorgánica está formada por pigmento inorgánico y frita. Durford in US Patent US6110632, claims a ceramic toner prepared by a method consisting of the flocculation of an organic polymeric material from an aqueous suspension of said material and the particles of inorganic and fried pigment. The inorganic fraction reaches values between 60 and 90% by weight. Said inorganic fraction is formed by inorganic and fried pigment.
Kmiecik-Lawrynowicz en la solicitud de patente europea EP-1975728 reivindica un tóner cerámico preparado por un método de polimerización en emulsión a partir de pigmentos cerámicos con modificación superficial hidrófila, y de resinas poliméricas. Estas partículas de tóner tienen porcentajes de pigmento cerámico entre un 2 y un 18% en peso.  Kmiecik-Lawrynowicz in European patent application EP-1975728 claims a ceramic toner prepared by an emulsion polymerization method from ceramic pigments with hydrophilic surface modification, and polymeric resins. These toner particles have ceramic pigment percentages between 2 and 18% by weight.
Es conocido que el proceso de polimerización por emulsión presenta ciertas desventajas, como la dificultad de eliminar los surfactantes y agentes emulsificantes utilizados, la dificultad de controlar la distribución de tamaño de partícula, obteniéndose distribuciones amplias, siendo por tanto difícil el control de calidad de los mismos. Además, la presencia de partículas de un tamaño nanométrico puede ser perjudicial para la salud humana.  It is known that the emulsion polymerization process has certain disadvantages, such as the difficulty of eliminating the surfactants and emulsifying agents used, the difficulty of controlling the particle size distribution, obtaining wide distributions, therefore the quality control of the same. In addition, the presence of particles of a nanometric size can be detrimental to human health.
Existen numerosas solicitudes de patentes, y patentes publicadas sobre la preparación de tóner por el método de polimerización en suspensión (EP2124107, US6458502, US5605992, EP90313023, US2009004594) aunque ninguna de ellas emplea este método de preparación, para el tóner destinado a la decoración de vidrio, de metal o de cerámica. Algunas de estas patentes, como Lee en la solicitud de patente WO2009054624, Maeda en la patente estadounidense US3634251, o Wakimoto en la patente estadounidense US4314932 reivindican el empleo de pigmentos inorgánicos en la preparación de un tóner elaborado por polimerización en suspensión, pero sin reivindicar su empleo para la decoración de este tipo de materiales. El tóner descrito en las anteriores patentes, a pesar de emplear pigmentos inorgánicos, no podría emplearse para la decoración de cerámica, metal o vidrio, ya que no se integraría fácilmente en la superficie a decorar, debido a la refractariedad de los pigmentos inorgánicos . There are numerous patent applications, and published patents on the preparation of toner by the suspension polymerization method (EP2124107, US6458502, US5605992, EP90313023, US2009004594) although none of them uses this method of preparation, for the toner destined for the decoration of glass, metal or ceramic. Some of these patents, such as Lee in patent application WO2009054624, Maeda in US patent US3634251, or Wakimoto in US patent US4314932 claim the use of Inorganic pigments in the preparation of a toner made by suspension polymerization, but without claiming its use for the decoration of such materials. The toner described in the previous patents, despite using inorganic pigments, could not be used for the decoration of ceramic, metal or glass, since it would not be easily integrated into the surface to be decorated, due to the refractoriness of inorganic pigments.
El empleo de un método de síntesis del tóner por polimerización en suspensión, permite evitar los inconvenientes presentados por la síntesis tradicional, además de los presentados por la polimerización en emulsión. La presente invención describe por tanto, un método de polimerización en suspensión para la preparación de tóner cerámico, que incluye un elevado porcentaje de componente inorgánica en su composición. La componente inorgánica incluye una fracción inorgánica activa en decoración, capaz de modificar el aspecto estético de la superficie a recubrir y una fracción inorgánica que facilita la fundencia y la integración con el soporte.  The use of a method of synthesis of the toner by suspension polymerization, avoids the inconveniences presented by the traditional synthesis, in addition to those presented by the emulsion polymerization. The present invention therefore describes a suspension polymerization method for the preparation of ceramic toner, which includes a high percentage of inorganic component in its composition. The inorganic component includes an inorganic fraction active in decoration, capable of modifying the aesthetic appearance of the surface to be coated and an inorganic fraction that facilitates fundence and integration with the support.
DESCRIPCIÓN DE LA INVENCIÓN DESCRIPTION OF THE INVENTION
La presente invención se refiere en primer lugar a un procedimiento de preparación de un tóner a partir de una polimerización por suspensión.  The present invention relates firstly to a process of preparing a toner from a suspension polymerization.
Este procedimiento es particularmente apropiado para obtener un tóner para decoración de materiales cerámicos, vidrio y metal, y comprende las siguientes etapas:  This procedure is particularly suitable for obtaining a toner for decoration of ceramic materials, glass and metal, and comprises the following steps:
dispersar las partículas de una componente inorgánica del tóner, las cuales tienen una superficie hidrófoba, en una mezcla que comprende al menos: uno o más monómeros orgánicos y uno o más iniciadores, obteniendo una mezcla oleofilica, disperse the particles of an inorganic component of the toner, which have a surface hydrophobic, in a mixture comprising at least: one or more organic monomers and one or more initiators, obtaining an oleophilic mixture,
- dispersión de la mezcla oleofilica obtenida en la etapa anterior en un medio acuoso que comprende uno o más agentes estabilizantes disueltos, y opcionalmente uno o más surfactantes , obteniendo gotas suspendidas, - dispersion of the oleophilic mixture obtained in the previous stage in an aqueous medium comprising one or more dissolved stabilizing agents, and optionally one or more surfactants, obtaining suspended drops,
- polimerización de las gotas suspendidas obtenidas en la etapa anterior por aumento de la temperatura en un recipiente en agitación, obteniendo partículas, preferentemente esféricas, de tóner cerámico, - polymerization of the suspended drops obtained in the previous stage by increasing the temperature in a stirring vessel, obtaining particles, preferably spherical, of ceramic toner,
- lavado y posterior secado de las partículas de tóner cerámico sintetizadas,  - washing and subsequent drying of the synthesized ceramic toner particles,
incorporación y mezclado mecánico, de aditivos externos que favorecen la fluidez del tóner sintetizado .  incorporation and mechanical mixing of external additives that favor the fluidity of the synthesized toner.
La polimerización de uno o varios monómeros se produce en presencia de las partículas de la componente inorgánica . Polymerization of one or more monomers occurs in the presence of particles of the inorganic component.
La componente inorgánica comprende al menos una fracción inorgánica para fundencia y al menos una fracción inorgánica activa en decoración, presentando todos los componentes inorgánicos un comportamiento superficial hidrófobo.  The inorganic component comprises at least one inorganic fraction for fundency and at least one inorganic fraction active in decoration, all inorganic components having a hydrophobic surface behavior.
Las partículas de tóner cerámico obtenidas son preferentemente esféricas.  The ceramic toner particles obtained are preferably spherical.
Entre los materiales del componente orgánico se encuentran siempre los iniciadores, y opcionalmente, los agentes de control de carga y las ceras  Among the materials of the organic component are always the initiators, and optionally, the load control agents and the waxes
Hay dos tipos de aditivos:  There are two types of additives:
los aditivos del tóner, que van a permanecer en el material para vender (agentes de control de carga, iniciadores, ceras, y aditivos externos fluidificantes) y los aditivos de proceso, que son los necesarios para el proceso de polimerización pero que se eliminan una vez sintetizado (aditivos estabilizadores, surfactantes ) . toner additives, which will remain in the material to sell (load control agents, initiators, waxes, and external fluidizing additives) and process additives, which are necessary for the polymerization process but are removed once synthesized (stabilizing additives, surfactants).
Para llevar a cabo la polimerización por suspensión es necesario emplear uno o varios monómeros relativamente insolubles en agua. A los monómeros se les adicionan los demás componentes, como los componentes inorgánicos hidrófobos, los agentes de control de carga, los iniciadores y las ceras. La mezcla oleofilica, se dispersa en un medio acuoso (donde se ha disuelto o dispersado previamente un agente estabilizante y, opcionalmente, un surfactante iónico para obtener una suspensión de gotas, formando una fase discontinua. El tratamiento de dispersión y formación de las gotas se obtiene empleando equipos emulsionantes-dispersantes de alta velocidad. La suspensión de las gotas es termodinámicamente inestable por lo que la coalescencia se controla por un balance entre la agitación y el agente estabilizante de la suspensión y el surfactante empleado. Para iniciar la polimerización se emplea un iniciador que se ha disuelto previamente en los monómeros y que se encuentra por tanto en el interior de las gotas en suspensión. Las partículas de la componente inorgánica deben quedar mayoritariamente rodeadas del polímero, por lo que antes de iniciarse la polimerización, estas partículas deben estar dispersas en el interior de las gotas de monómero. To carry out the suspension polymerization it is necessary to use one or more relatively water-insoluble monomers. The other components, such as hydrophobic inorganic components, charge control agents, initiators and waxes, are added to the monomers. The oleophilic mixture is dispersed in an aqueous medium (where a stabilizing agent and, optionally, an ionic surfactant have been previously dissolved or dispersed to obtain a droplet suspension, forming a discontinuous phase. The dispersion and drop formation treatment is obtained using high-speed emulsifying-dispersing equipment The suspension of the drops is thermodynamically unstable, so that the coalescence is controlled by a balance between the agitation and the stabilizing agent of the suspension and the surfactant used. initiator that has previously dissolved in the monomers and is therefore inside the droplets in suspension.The particles of the inorganic component must be mostly surrounded by the polymer, so before starting the polymerization, these particles must be dispersed inside the monomer drops.
La polimerización se inicia aumentando la temperatura del sistema. Los iniciadores presentes en las gotas se descomponen e inician la polimerización de los monómeros.The polymerization is started by increasing the temperature of the system. The initiators present in the drops decompose and initiate polymerization of the monomers.
Al final del proceso de polimerización dispondremos de una suspensión en agua de partículas de polímero. At the end of the polymerization process we will have a suspension in water of polymer particles.
Dichas partículas de polímero contienen en su interior las partículas inorgánicas, los agentes de control de carga y las ceras.  Said polymer particles contain inorganic particles, charge control agents and waxes.
Estas partículas se lavan y secan para obtener las partículas de tóner. Para aportar fluidez al producto, es aconsejable emplear fluidificantes externos.  These particles are washed and dried to obtain the toner particles. To provide fluidity to the product, it is advisable to use external fluidizers.
La presente invención se refiere también a un tóner para la decoración de materiales cerámicos, vidrio y metal, - de ahora en adelante llamado "tóner cerámico" - obtenido por el procedimiento descrito.  The present invention also relates to a toner for the decoration of ceramic materials, glass and metal, - hereafter referred to as "ceramic toner" - obtained by the described process.
Dicho tóner comprende al menos:  Said toner comprises at least:
- una componente inorgánica que está presente entre un 5 y un 90 % en peso, y que comprende:  - an inorganic component that is present between 5 and 90% by weight, and which comprises:
o una fracción inorgánica activa en decoración Y  or an inorganic fraction active in decoration Y
o una fracción inorgánica que confiere fundencia, y  or an inorganic fraction that confers fundence, and
- un componente polimérico orgánico que está presente entre un 95 y un 10 % en peso y que comprende uno o más polímeros orgánicos.  - an organic polymer component that is present between 95 and 10% by weight and which comprises one or more organic polymers.
El peso de la componente inorgánica está comprendido preferentemente entre un 40 y un 80 %. La fracción inorgánica activa en decoración tiene como función modificar el aspecto estético de la superficie a decorar. Entre los efectos estéticos que pueden obtenerse podemos incluir el color, el aspecto metálico, el lustre o el efecto iridiscente.  The weight of the inorganic component is preferably between 40 and 80%. The inorganic fraction active in decoration has the function of modifying the aesthetic appearance of the surface to be decorated. Among the aesthetic effects that can be obtained we can include the color, the metallic aspect, the luster or the iridescent effect.
La fracción inorgánica que confiere fundencia aportará la fundencia necesaria para que se produzca la integración de la fracción inorgánica responsable del cambio estético, durante la última etapa de cocción a alta temperatura asegurando una buena adherencia de la decoración. The inorganic fraction that confers fundence It will provide the necessary functionality for the integration of the inorganic fraction responsible for the aesthetic change, during the last stage of high temperature cooking ensuring a good adhesion of the decoration.
El polímero se sintetiza durante el proceso de preparación del tóner y actúa como portador de la carga eléctrica, portador de los materiales inorgánicos y asegura la primera fijación al soporte antes de la etapa de cocción.  The polymer is synthesized during the process of preparing the toner and acts as a carrier of the electric charge, carrier of the inorganic materials and ensures the first fixation to the support before the cooking stage.
Entre los materiales de la componente orgánica se encuentran opcionalmente los agentes de control de carga y las ceras. Los iniciadores son siempre necesarios.  Among the materials of the organic component there are optionally load control agents and waxes. Initiators are always necessary.
El componente inorgánico puede estar presente en el tóner entre un 5 y un 90 % en peso De modo preferente la componente inorgánica está presente entre un 7 y un 85% en peso, de modo más preferente está presente entre un 9 y un 82 % en peso y de modo aún más preferente está presente entre un 10 y un 80% en peso. Esta componente es la que permanecerá en la decoración tras el proceso de cocción a altas temperaturas.  The inorganic component may be present in the toner between 5 and 90% by weight Preferably the inorganic component is present between 7 and 85% by weight, more preferably it is present between 9 and 82% in weight and even more preferably between 10 and 80% by weight. This component is what will remain in the decoration after the cooking process at high temperatures.
El componente orgánico comprende el polímero, el agente de control de carga, el iniciador y las ceras, estando el conjunto generalmente en un 20%, el componente inorgánico son los pigmentos y la frita y/o los materiales fundentes estando generalmente en un 80%.  The organic component comprises the polymer, the charge control agent, the initiator and the waxes, the assembly being generally 20%, the inorganic component is the pigments and the frit and / or the melting materials being generally 80% .
La frita para el tóner cerámico puede obtenerse por fusión de las materias primas con posterior enfriamiento en agua y/o aire, a partir de materias primas como óxidos metálicos, silicatos, carbonatos, aluminosilicatos , boratos, nitratos, sulfatos, oxalatos, cloruros u óxidos mixtos . El bajo contenido en polímero orgánico favorece que no queden restos de calcinación que podrían modificar el efecto estético deseado. The frit for ceramic toner can be obtained by melting raw materials with subsequent cooling in water and / or air, from raw materials such as metal oxides, silicates, carbonates, aluminosilicates, borates, nitrates, sulfates, oxalates, chlorides or oxides mixed. The low organic polymer content favors that there are no calcination residues that could modify the desired aesthetic effect.
Según la presente invención, se puede preparar tóner con una elevada razón de fracción inorgánica activa en decoración/fracción inorgánica que confiere fundencia, lo que permite obtener mayores saturaciones de color, o un mayor efecto estético, con menores cantidades de material, sin perder adherencia al soporte cerámico, vitreo o metálico. Los valores de la razón fracción inorgánica activa en decoración/fracción inorgánica que confiere fundencia, pueden oscilar entre 10 y 0,1, y preferentemente están entre 9 y 0,2, más preferentemente entre 8 y 0,7, y más preferentemente aún entre 7 y 1.  According to the present invention, toner can be prepared with a high ratio of active inorganic fraction in decoration / inorganic fraction that confers fundence, which allows to obtain greater color saturations, or a greater aesthetic effect, with smaller amounts of material, without losing adhesion to ceramic, vitreous or metallic support. The values of the ratio inorganic active fraction in decoration / inorganic fraction that confers fundancy can range between 10 and 0.1, and preferably are between 9 and 0.2, more preferably between 8 and 0.7, and more preferably even between 7 and 1.
El componente polimérico orgánico del tóner se prepara a partir de monómeros con grupos funcionales capaces de polimerizar. El polímero formado tiene que cumplir ciertas características entre las que se encuentran: que admitan el mayor contenido en componente inorgánica posible; cierta capacidad para cargarse electrostáticamente; la temperatura de transición vitrea adecuada para el fijado provisional de las partículas del tóner tras la deposición y quemarse fácilmente durante el proceso de cocción sin dejar cenizas que puedan modificar el color o el efecto estético deseado.  The organic polymer component of the toner is prepared from monomers with functional groups capable of polymerizing. The polymer formed has to meet certain characteristics, among which are: that they admit the highest possible inorganic component content; certain ability to electrostatically charge; the glass transition temperature suitable for the provisional fixation of the toner particles after deposition and burn easily during the cooking process without leaving ashes that can modify the desired color or aesthetic effect.
Los monómeros que pueden emplearse se encuentran monómeros vinílicos aromáticos, monómeros etilénicos insaturados, monómeros acrilados, monómeros metacrilados , y monómeros dienilos, o mezclas de los anteriores.  The monomers that can be employed are aromatic vinyl monomers, unsaturated ethylenic monomers, acrylated monomers, methacrylated monomers, and dienyl monomers, or mixtures of the foregoing.
Entre los monómeros vinílicos aromáticos se encuentran: estireno, metilestireno, monocloroestireno, dimetilestireno, y similares. Entre los monómeros etilénicos insaturados se encuentran: acetato de vinilo, formiato de vinilo, éteres alquil vinílicos, etileno, propileno, butileno, cloruro de vinilideno, acrilatos alquílicos y cetacrilatos , maleatos alquílicos y fumaratos alquílicos. Among the aromatic vinyl monomers are: styrene, methylstyrene, monochlorostyrene, dimethylstyrene, and the like. Among the unsaturated ethylenic monomers are: vinyl acetate, vinyl formate, alkyl vinyl ethers, ethylene, propylene, butylene, vinylidene chloride, alkyl acrylates and ketacrylates, alkyl maleates and alkyl fumarates.
Entre los monómeros acrilados se encuentran: ácido acrílico, acrilato de metilo, acrilato de etilo, acrilato de propilo, acrilato de n-butilo, acrilato de isobutilo, acrilato de dodecilo, 2-etilhexil acrilato, acrilato de dimetilaminoetilo, acrilamida y similares.  Among the acrylated monomers are: acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, dimethylaminoethyl acrylate, and similar acrylate.
Entre los monómeros metacrilados se encuentran: ácido metacrílico, metacrilato de metilo, metacrilato de etilo, metacrilato de propilo, metacrilato de butilo, metacrilato de dodecilo, 2-etilhexil metacrilato, metacrilato de dimetilaminoetilo, metacrilamida y similares .  Among the methacrylated monomers are: methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, dimethylaminoethyl methacrylate, methacrylamide and the like.
Para incrementar la temperatura de transición vitrea del polímero sintetizado puede favorecerse el entrecruzamiento de las cadenas empleando monómeros entrecruzadores . Entre los monómeros dienilos entrecruzadores se encuentran: butadieno, alil metacrilato, dimetacrilato de etileno, 1 , 6-hexametilen diacrilato, 1 , 1 , 1-trimetil propano triacrilato, trialil amina, isopreno, divinil benceno, divinil naftaleno, y derivados, etilen glicol dimetacrilato, dietilen glicol dimetacrilato, Ν,Ν-divinil anilina y similares.  In order to increase the glass transition temperature of the synthesized polymer, the crosslinking of the chains can be favored by using crosslinking monomers. Among the crosslinker dienyl monomers are: butadiene, allyl methacrylate, ethylene dimethacrylate, 1, 6-hexamethylene diacrylate, 1,1,1-trimethyl propane triacrylate, triallyl amine, isoprene, divinyl benzene, divinyl naphthalene, and derivatives, dimethacrylate, diethylene glycol dimethacrylate, Ν, Ν-divinyl aniline and the like.
Para la preparación del tóner cerámico según la presente invención se emplea una fracción inorgánica activa en decoración, en función del efecto estético que se desea obtener.  For the preparation of the ceramic toner according to the present invention an active inorganic fraction is used in decoration, depending on the aesthetic effect that is desired to be obtained.
La fracción inorgánica activa en decoración puede contener al menos uno de los siguientes componentes: óxidos de metales, mezclas de óxidos de metales, mezclas de óxidos, óxidos mixtos, soluciones sólidas de compuestos coloreados, soluciones sólidas de compuestos no coloreados, soluciones sólidas de óxidos de metales, metales en estado coloidal, sulfuros, pigmentos protegidos de inclusión o mordientes, óxidos metálicos con fosfatos metálicos, materias primas fundentes que comprenden cerio o wolframio metálico, materiales vitreos que comprenden cerio o wolframio, materiales vitreos que comprenden titanio. Entre los materiales vitreos que comprenden cerio o wolframio se encuentran fritas que comprenden estos metales. Entre los materiales vitreos que comprenden titanio se encuentran fritas que comprenden un alto contenido en titanio. The inorganic fraction active in decoration may contain at least one of the following components: metal oxides, mixtures of metal oxides, mixtures of oxides, mixed oxides, solid solutions of colored compounds, solid solutions of non-colored compounds, solid solutions of metal oxides, colloidal metals, sulphides, pigments protected from inclusion or mordants , metal oxides with metal phosphates, melting raw materials comprising cerium or metal tungsten, vitreous materials comprising cerium or tungsten, vitreous materials comprising titanium. Among the vitreous materials comprising cerium or tungsten are frits comprising these metals. Among the vitreous materials that comprise titanium are frits that comprise a high content of titanium.
Para la preparación del tóner cerámico según la presente invención se empleará un pigmento inorgánico en función del efecto estético que se desea obtener. Para obtener un aspecto coloreado, puede emplearse cualquiera de los pigmentos cromóforos inorgánicos presentes en el estado del arte, que soporten las temperaturas de cocción de la decoración. Algunos de los tipos de pigmentos que pueden emplearse son por ejemplo, óxidos metálicos, óxidos de elementos de transición, mezclas de óxidos, soluciones sólidas de compuestos coloreados, o no coloreados, los metales coloidales (Cu, Au, Ag, Pt) , los sistemas no óxidos como los sulfuros (Se, Au y Pt) , los pigmentos protegidos de inclusión o mordientes, y mezclas de cualquiera de los anteriores.  For the preparation of the ceramic toner according to the present invention an inorganic pigment will be used depending on the aesthetic effect that is desired to be obtained. To obtain a colored appearance, any of the inorganic chromophores pigments present in the state of the art can be used, which withstand the cooking temperatures of the decoration. Some of the types of pigments that can be used are, for example, metal oxides, transition element oxides, oxide mixtures, solid solutions of colored, or non-colored compounds, colloidal metals (Cu, Au, Ag, Pt), non-oxidized systems such as sulfides (Se, Au and Pt), protected inclusion pigments or mordants, and mixtures of any of the above.
Es conveniente evitar los pigmentos que presenten un comportamiento magnético, en la preparación de las partículas de tóner, cuando se emplea un revelador bicomponente . Para obtener un efecto metálico, pueden emplearse, como fracción inorgánica activa en decoración, óxidos metálicos como por ejemplo el óxido de hierro junto con fosfatos metálicos siendo un ejemplo el fosfato de aluminio. It is convenient to avoid pigments that exhibit a magnetic behavior, in the preparation of the toner particles, when using a two-component developer. In order to obtain a metallic effect, metal oxides such as iron oxide together with metal phosphates can be used as an inorganic active fraction in decoration, for example aluminum phosphate.
Para obtener un aspecto de lustre, pueden emplearse como fracción inorgánica activa en decoración, fritas de cerio o wolframio metálico.  To obtain a luster look, they can be used as an active inorganic fraction in decoration, cerium frits or metallic tungsten.
Para obtener un efecto iridiscente, pueden emplearse como fracción inorgánica activa en decoración, fritas con altos contenidos de óxido de titanio.  To obtain an iridescent effect, frits with high titanium oxide contents can be used as an active inorganic fraction in decoration.
Los compuestos que forman parte de la fracción inorgánica activa en decoración, tales como los pigmentos inorgánicos, suelen ser compuestos refractarios lo que dificulta su integración en la superficie que se desea decorar. Para facilitar este proceso de integración se emplea una fracción inorgánica para fundencia, que a la máxima temperatura de cocción de la decoración se encuentra muy reblandecida en torno a la fracción inorgánica más refractaria. Al enfriar la pieza, la viscosidad de la fracción inorgánica para fundencia aumenta considerablemente reteniendo en su interior los componentes refractarios y permaneciendo adherida a la superficie a decorar.  The compounds that are part of the active inorganic fraction in decoration, such as inorganic pigments, are usually refractory compounds which makes it difficult to integrate into the surface to be decorated. In order to facilitate this integration process, an inorganic fraction is used for fundence, which at the maximum cooking temperature of the decoration is very softened around the most refractory inorganic fraction. When the piece cools, the viscosity of the inorganic fraction for flux increases considerably while retaining the refractory components and remaining adhered to the surface to be decorated.
La fracción inorgánica para fundencia, puede estar formada por materiales de tipo frita o materiales fundentes .  The inorganic fraction for flux, can be formed by fried type materials or melting materials.
Las fritas son compuestos vitreos, insolubles en agua, que se obtienen por fusión y posterior enfriamiento rápido de mezclas controladas de materias primas y con una temperatura de reblandecimiento inferior a la de fusión de las materias primas originales. Estas materias primas contienen óxidos como pueden ser, entre otros, óxido de silicio, óxido de aluminio, óxido de boro, óxidos alcalinos, óxidos alcalinotérreos , óxido de cinc, etc, que les confieren sus propiedades. Los materiales fundentes que pueden emplearse son aquellos materiales inorgánicos que generen eutécticos a baja temperatura con los materiales cerámicos. The frits are vitreous compounds, insoluble in water, which are obtained by melting and subsequent rapid cooling of controlled mixtures of raw materials and with a softening temperature lower than the melting of the original raw materials. These matters Raw materials contain oxides such as, among others, silicon oxide, aluminum oxide, boron oxide, alkaline oxides, alkaline earth oxides, zinc oxide, etc., which give them their properties. The melting materials that can be used are those inorganic materials that generate low temperature eutectic with the ceramic materials.
Según esta invención puede asegurarse una buena integración de la fracción inorgánica activa en decoración en el soporte, tras el proceso de cocción, cuando se emplea una razón 0,1 < fracción inorgánica activa en decoración / fracción inorgánica para fundencia <10. El tamaño de partícula de cualquiera de los componentes inorgánicos, puede oscilar entre 1 y 10 μιη, preferentemente entre 2 y 8 μιη, más preferentemente entre 3 y 7 μτα, y más preferentemente aún entre 4 y 6 μη  According to this invention, a good integration of the active inorganic fraction in decoration into the support can be ensured, after the cooking process, when a ratio of 0.1 <inorganic fraction active in decoration / inorganic fraction for funcy <10 is used. The particle size of any of the inorganic components may range between 1 and 10 μιη, preferably between 2 and 8 μιη, more preferably between 3 and 7 μτα, and more preferably even between 4 and 6 μη
Para conseguir que las partículas de cualquiera de los componentes inorgánicos queden retenidas en el interior de la partícula polimérica de tóner, es necesario que, en la suspensión, las partículas inorgánicas se sitúen en el interior de las gotas de monómero. La naturaleza hidrófila de la superficie de las partículas inorgánicas hace que muestren una mayor tendencia a situarse en la fase acuosa. Por lo tanto es necesario disponer de partículas con una superficie hidrófoba o someter a estas partículas a un tratamiento superficial que las convierta en hidrófobas  In order to ensure that the particles of any of the inorganic components are retained inside the polymeric toner particle, it is necessary that, in the suspension, the inorganic particles be placed inside the monomer droplets. The hydrophilic nature of the surface of the inorganic particles causes them to show a greater tendency to be in the aqueous phase. Therefore it is necessary to have particles with a hydrophobic surface or subject these particles to a surface treatment that converts them into hydrophobic
La funcionalización de las partículas inorgánicas puede realizarse por una reacción de hidrólisis y condensación entre los grupos hidroxilos superficiales de los sólidos inorgánicos (fracción inorgánica activa en decoración y fracción inorgánica para fundencia) y alcoxisilanos funcionalizados con grupos orgánicos compatibles con los grupos funcionales de los monómeros. The functionalization of the inorganic particles can be carried out by a hydrolysis and condensation reaction between the surface hydroxyl groups of the inorganic solids (inorganic fraction active in decoration and inorganic fraction for fundence) and functionalized alkoxysilanes with organic groups compatible with the functional groups of the monomers.
Dado que la transferencia de las partículas de tóner se realiza mediante cargas electrostáticas, es necesario favorecer la presencia de estas cargas en la superficie de las partículas de tóner. Para ello se puede incorporar a la composición del polímero formado, un agente de control de carga.  Since the transfer of the toner particles is done by electrostatic charges, it is necessary to favor the presence of these charges on the surface of the toner particles. For this, a charge control agent can be incorporated into the composition of the polymer formed.
Este agente de control de carga puede ser seleccionado entre diferentes tipos de compuestos, teniendo en cuenta la carga que desea aportarse a las partículas de tóner. Pueden emplearse como agentes de control de carga algunos de los compuestos de las siguientes familias: nigrosinas, complejos de trifenilmetano, colorantes catiónicos, dioxacinas, bencimidazolonas , ftalocianinas de cobre, perilenos, quinacridonas , pigmentos azo, sales metálicas de pigmentos azo, complejos azo de cobre, complejos metálicos de ácido salicílico, derivados de tetrafenil borato, derivados de un ácido hidroxicarboxílico aromático, derivados de un ácido hidroxicarboxilico alifático, derivados del calixareno, sales de amonio cuaternario, sales de alquilamonio cuaternario, sales de piridinio cuaternarias, bisulfatos, parafina clorada, poliéster clorado, poliésteres con grupos ácidos, polímeros conteniendo grupos de ácido sulfónico, negro de humo, óxido negro de hierro, grafito, amarillo hansa, amarillo de bencidina. Estos compuestos pueden ser utilizados solos o combinados, en porcentajes entre el 0, 01 y el 20 por ciento en peso con respecto al peso total de monómeros, preferentemente entre 0,1 y 18% en peso, más preferentemente entre 0,4 y 16% en peso, y más preferentemente aún entre 0,8 y 14 % en peso. This charge control agent can be selected from different types of compounds, taking into account the load that you want to contribute to the toner particles. Some of the compounds of the following families can be used as charge control agents: nigrosines, triphenylmethane complexes, cationic dyes, dioxacins, benzimidazolones, copper phthalocyanines, perilenes, quinacridones, azo pigments, azo pigment metal salts, azo complexes copper, salicylic acid metal complexes, tetraphenyl borate derivatives, derivatives of an aromatic hydroxycarboxylic acid, derivatives of an aliphatic hydroxycarboxylic acid, calixarene derivatives, quaternary ammonium salts, quaternary alkylammonium salts, quaternary pyridinium salts, bisulfates, chlorinated paraffin , chlorinated polyester, polyesters with acid groups, polymers containing sulfonic acid groups, carbon black, iron black oxide, graphite, hansa yellow, benzidine yellow. These compounds can be used alone or in combination, in percentages between 0.01 and 20 percent by weight with respect to the total weight of monomers, preferably between 0.1 and 18% by weight, more preferably between 0.4 and 16 % by weight, and more preferably even between 0.8 and 14% by weight.
En la preparación del tóner puede emplearse un aditivo que evite el pegado de las partículas de tóner sobre el rodillo de transferencia caliente. Este aditivo evita tener que alimentar el rodillo de transferencia regularmente de aceite que cumpla esta función. Ejemplos de este tipo de aditivo pueden incluir las ceras poliolefínicas como polietileno de bajo peso molecular, polipropileno de bajo peso molecular, polibutileno de bajo peso molecular, ceras naturales como candelilla, carnauba, jojoba, cera de arroz, ceras de petróleo, como parafinas, microcristalinas , vaselina, ceras minerales como montan, ceresina, ozoquerita, y ceras sintéticas como ceras de Fischer-Tropsch, amidas grasas, aceites de silicona. Estos compuestos pueden utilizarse solos o combinaciones de dos o más de ellos, en porcentajes entre el 0,1 y el 20 por ciento en peso con respecto al peso total de monómeros, preferentemente entre 0,1 y 18% en peso, más preferentemente entre 0,4 y 16% en peso, y más preferentemente aún entre 0,8 y 14 % en peso.  In the preparation of the toner, an additive can be used to avoid sticking the toner particles onto the hot transfer roller. This additive avoids having to feed the transfer roller regularly of oil that fulfills this function. Examples of this type of additive may include polyolefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight polybutylene, natural waxes such as candelilla, carnauba, jojoba, rice wax, petroleum waxes, such as paraffins, microcrystalline, petrolatum, mineral waxes such as montan, ceresin, ozoquerite, and synthetic waxes such as Fischer-Tropsch waxes, fatty amides, silicone oils. These compounds can be used alone or combinations of two or more of them, in percentages between 0.1 and 20 percent by weight with respect to the total weight of monomers, preferably between 0.1 and 18% by weight, more preferably between 0.4 and 16% by weight, and more preferably even between 0.8 and 14% by weight.
Para provocar la polimerización de los monómeros es preferible emplear un iniciador soluble en los propios monómeros e insoluble en agua. Como ejemplos de iniciadores que pueden emplearse en la presente invención pueden mencionarse, iniciadores de tipo peróxido como el peróxido de benzoilo, peróxido de lauroilo, peróxido de octanoilo, peróxido de estearoilo, peróxido de ortoclorobenzoilo, peróxido de ortometoxibenzoilo, peróxido de metil etil cetona, peróxido de ciclohexanona, hidroperóxido de eumeno, hidroperóxido de t-butilo, tert- butil peroxi pivalerato, carbonato de isopropilo diperoxido, peróxido de hidrógeno, peróxido de di-1- naftoilo, e iniciadores de tipo compuestos azo como azobisisobutironitrilo, azobisdimetilvaleronitrilo, o las sales de peróxido-ácido de disulfúrico, estos incluyen persulfato potásico, persulfato amónico o persulfato sódico. To cause polymerization of the monomers it is preferable to employ an initiator soluble in the monomers themselves and insoluble in water. As examples of initiators that may be employed in the present invention, peroxide type initiators such as benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, stearoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, methyl ethyl ketone peroxide, may be mentioned, cyclohexanone peroxide, eumene hydroperoxide, t-butyl hydroperoxide, tert-butyl peroxy pivalerate, isopropyl diperoxide carbonate, hydrogen peroxide, di-1- peroxide naphthoyl, and azo compounds such as azobisisobutyronitrile, azobisdimethylvaleronitrile, or peroxide-disulfuric acid salts, these include potassium persulfate, ammonium persulfate or sodium persulfate.
Estos compuestos pueden ser utilizados solos o combinados, en porcentajes entre el 0,01 y el 10 por ciento en peso con respecto al peso total de monómeros, preferentemente entre 0,04 y 8% en peso, más preferentemente entre 0,08 y 6% en peso, y más preferentemente aún entre 0,2 y 5 % en peso.  These compounds can be used alone or in combination, in percentages between 0.01 and 10 percent by weight with respect to the total weight of monomers, preferably between 0.04 and 8% by weight, more preferably between 0.08 and 6 % by weight, and more preferably even between 0.2 and 5% by weight.
Para evitar la coalescencia de las gotas oleófilas en la suspensión acuosa es necesario usar agentes estabilizantes de la suspensión. Los agentes estabilizantes que pueden emplearse en la presente invención pueden ser de diferente naturaleza. Como ejemplos, pueden mostrarse los siguientes, aditivos inorgánicos como sulfatos de calcio o bario, carbonatos de calcio, bario o magnesio, fosfato de calcio, sílice hidrófoba o hidrófila, sílice coloidal, óxido de aluminio, óxido de titanio, hidróxidos de aluminio, de magnesio o de hierro. También pueden incluirse compuestos orgánicos como alcohol polivinílico, metilcelulosa, metil hidroxipropil celulosa, etil celulosa, carboximetil celulosa sódica, gelatina, o almidón. Estos compuestos pueden ser utilizados solos o combinados, en porcentajes entre el 0,01 y el 20 por ciento en peso con respecto a la cantidad de agua en la fase continua, preferentemente entre 0,04 y 18% en peso, más preferentemente entre 0,08 y 16% en peso, y más preferentemente aún entre 0,25 y 15 % en peso ..  To avoid coalescence of the oleophilic drops in the aqueous suspension it is necessary to use stabilizing agents of the suspension. The stabilizing agents that can be used in the present invention can be of different nature. As examples, the following may be shown, inorganic additives such as calcium or barium sulfates, calcium, barium or magnesium carbonates, calcium phosphate, hydrophobic or hydrophilic silica, colloidal silica, aluminum oxide, titanium oxide, aluminum hydroxides, magnesium or iron Organic compounds such as polyvinyl alcohol, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium carboxymethyl cellulose, gelatin, or starch may also be included. These compounds can be used alone or in combination, in percentages between 0.01 and 20 percent by weight with respect to the amount of water in the continuous phase, preferably between 0.04 and 18% by weight, more preferably between 0 , 08 and 16% by weight, and more preferably even between 0.25 and 15% by weight.
Se puede usar también al menos un surfactante. Como surfactantes en la presente invención pueden emplearse diferentes tipos de compuestos seleccionados entre al menos una de las siguientes familias: sales de ácidos grasos, sales de éster de sulfatos alquilicos, sales de éster de sulfatos arilicos, dialquil sulfosucinatos , fosfatos alquilicos. A continuación se incluyen algunos compuestos a modo de ejemplo: dodecilbencenesulfonato sódico, dodecilsulfonato sódico, tetradecil sulfonato sódico, pentadecil sulfonato sódico, octil sulfonato sódico, oleato sódico, laureato sódico, estearato potásico, oleato sódico. Estos compuestos pueden ser utilizados solos o combinados, en porcentajes entre el 0,001 y el 5 por ciento en peso con respecto a la cantidad de agua en la fase continua. At least one surfactant can also be used. How Surfactants in the present invention can be used different types of compounds selected from at least one of the following families: fatty acid salts, alkyl sulfate ester salts, aryl sulfate ester salts, dialkyl sulfosuccinates, alkyl phosphates. Some exemplary compounds are included below: sodium dodecylbenzenesulfonate, sodium dodecyl sulfonate, sodium tetradecyl sulfonate, sodium pentadecyl sulfonate, sodium octyl sulfonate, sodium oleate, sodium laureate, potassium stearate, sodium oleate. These compounds can be used alone or in combination, in percentages between 0.001 and 5 percent by weight with respect to the amount of water in the continuous phase.
Para mejorar la fluidez de las partículas de tóner en la presente invención, es recomendable el empleo de agentes fluidificantes externos. Ejemplos de este tipo de aditivo incluye partículas muy finas de materiales inorgánicos como la sílice, el óxido de aluminio y el óxido de titanio. Las partículas seleccionadas como agentes fluidificantes del tóner reivindicado, deben tener un tratamiento superficial que le aporte comportamiento hidrófobo a su superficie.  To improve the fluidity of the toner particles in the present invention, the use of external fluidizing agents is recommended. Examples of this type of additive include very fine particles of inorganic materials such as silica, aluminum oxide and titanium oxide. The particles selected as fluidizing agents of the claimed toner must have a surface treatment that provides hydrophobic behavior to their surface.
Las partículas de tóner tienen diámetros medios de partícula comprendidos entre Ιμιη y 30 μιη, preferentemente entre 2μη y 25 ιη, más preferentemente entre 5μη y 23μη y más preferentemente aún entre 7μη y 20μη .  The toner particles have average particle diameters between Ιμιη and 30 μιη, preferably between 2μη and 25 ιη, more preferably between 5μη and 23μη and more preferably even between 7μη and 20μη.
La presente invención se refiere también a un uso del tóner cerámico de la invención como tinta en decoración. Para dicho uso, el tóner fabricado como se ha descrito previamente, se puede mezclar con partículas magnéticas de revelador y se emplea como tinta en la decoración de materiales de cerámica, vidrio o metal, empleando, por ejemplo, un equipo de aplicación xerográfica. La imagen impresa se fija al soporte cerámico, al vidrio o al metal, al someter a la pieza a un ciclo de cocción. The present invention also relates to a use of the ceramic toner of the invention as decoration ink. For such use, the toner manufactured as previously described, can be mixed with magnetic developer particles and used as ink in the decoration of ceramic, glass or metal materials, using, for example, xerographic application equipment. The printed image is fixed to the ceramic support, glass or metal, by subjecting the piece to a cooking cycle.
El método de síntesis reivindicado en la presente invención permite el empleo de elevados porcentajes de componentes inorgánicos.  The synthesis method claimed in the present invention allows the use of high percentages of inorganic components.
DESCRIPCIÓN DE LAS FIGURAS DESCRIPTION OF THE FIGURES
Para completar la descripción que se está realizando y con objeto de mejorar la comprensión de lo que aquí se describe, se acompaña a la presente memoria descriptiva y como parte integrante de la misma, varias figuras, en las cuales, con carácter ilustrativo y no limitativo se muestra lo siguiente:  To complete the description that is being made and in order to improve the understanding of what is described here, several figures are attached to this descriptive report and, as an integral part thereof, in which, with an illustrative and non-limiting nature the following is displayed:
Figura 1.- Fotografía tomada con un microscopio electrónico de barrido, de una partícula de tóner sintetizada según se describe en el ejemplo 1 de la presente memoria. La imagen ha sido obtenida mediante bombardeo con un haz de electrones secundarios y la imagen observada corresponde a la topografía de la partícula. Se observa en primer plano, una zona más blanquecina correspondiente a una prominencia de la superficie de la partícula. En el contorno de la partícula se observan otras prominencias que originan una ligera pérdida de la esfericidad. En la superficie de la partícula, se observan las partículas de sílice nanométrica empleada como fluidificante.  Figure 1.- Photograph taken with a scanning electron microscope of a synthesized toner particle as described in example 1 herein. The image has been obtained by bombardment with a beam of secondary electrons and the image observed corresponds to the topography of the particle. In the foreground, a whitish area corresponding to a prominence of the surface of the particle is observed. In the outline of the particle other prominences are observed that cause a slight loss of sphericity. On the surface of the particle, the nanometric silica particles used as a fluidizer are observed.
Figura 2.- Fotografía de la misma partícula que la figura 1, tomada en un microscopio electrónico de barrido empleando un haz de electrones retrodispersados . La escala de grises que se observa en la fotografía está directamente relacionada con el peso atómico de los átomos que forman la partícula. Los grises más claros corresponden a los átomos de pesos atómicos más altos. Los grises más oscuros corresponden a los átomos de peso atómico más bajos. Es por tanto una imagen de composiciones, a diferencia de la figura 1 que es una imagen topográfica. En el primer plano de la partícula, la prominencia observada en la figura 1 corresponde a una partícula de pigmento con átomos de elevado peso atómico (zona blanquecina) que se encuentra en el interior de la partícula de tóner según se observa en la imagen topográfica de la figura 1. Otras zonas más claras se observan en el interior de la partícula mostrando otras partículas inorgánicas presentes en el interior. La zona exterior de la partícula tiene un gris más oscuro correspondiente a la parte orgánica polimerizada formada por átomos de carbono, oxígeno e hidrógeno de menores pesos atómicos. Figure 2.- Photograph of the same particle as Figure 1, taken in a scanning electron microscope using a beam of backscattered electrons. The gray scale seen in the photograph is directly related to the atomic weight of the atoms that make up the particle. The lighter grays correspond to the atoms of higher atomic weights. The darkest grays correspond to the lowest atoms of atomic weight. It is therefore an image of compositions, unlike Figure 1 which is a topographic image. In the foreground of the particle, the prominence observed in Figure 1 corresponds to a pigment particle with atoms of high atomic weight (whitish area) that is inside the toner particle as seen in the topographic image of Figure 1. Other lighter areas are observed inside the particle showing other inorganic particles present inside. The outer part of the particle has a darker gray corresponding to the polymerized organic part formed by carbon, oxygen and hydrogen atoms of lower atomic weights.
Figura 3. -Gráfico mostrando la distribución de tamaños de partícula para las partículas de tóner sintetizadas según se describe en el ejemplo 1 de la presente memoria. Esta distribución de tamaños de partícula se ha obtenido por difracción láser vía húmeda. A partir de esta distribución de tamaños de partícula se han determinado los parámetros
Figure imgf000022_0001
μιτι, d5o=8,63 μιη y μιη, correspondientes a los diámetros por debajo de los cuales queda respectivamente el 90%, el 50% y el 10% en volumen de las partículas totales. EJEMPLO DE UNA REALIZACIÓN DE LA INVENCIÓN Figure 3. -Graph showing the distribution of particle sizes for the synthesized toner particles as described in example 1 of the present specification. This particle size distribution has been obtained by wet laser diffraction. From this distribution of particle sizes the parameters have been determined
Figure imgf000022_0001
μιτι, d 5 o = 8.63 μιη and μιη, corresponding to the diameters below which 90%, 50% and 10% by volume of the total particles are respectively. EXAMPLE OF AN EMBODIMENT OF THE INVENTION
A continuación se exponen unos ejemplos que ilustran la realización de la presente invención pero que no constituyen una limitación de la misma: The following are examples that illustrate the embodiment of the present invention but not They constitute a limitation of it:
Ej emplo 1 :  Example 1 :
Para la funcionalización de los componentes inorgánicos se pesan 80 g de un pigmento rosa de esfena de estaño y cromo, y 20 g de una frita cerámica cuya composición química se incluye en la tabla 1. Estos componentes se dispersan en 300 mi de ácido clorhídrico al 0,01M, y se le adicionan 30 g de metacriloxi propil trimetoxisilano . La mezcla se mantiene en agitación durante 30 minutos, procediéndose posteriormente al filtrado, lavado y secado de los sólidos funcionalizados .  For the functionalization of the inorganic components, 80 g of a pink tin and chromium sphene pigment are weighed, and 20 g of a ceramic frit whose chemical composition is included in Table 1. These components are dispersed in 300 ml of hydrochloric acid at 0.01M, and 30 g of methacryloxy propyl trimethoxysilane are added. The mixture is kept under stirring for 30 minutes, subsequently filtering, washing and drying the functionalized solids.
Para llevar a cabo la polimerización por suspensión se preparan por separado, la fase continua (fase acuosa) y la fase discontinua (fase orgánica) :  To carry out the suspension polymerization, the continuous phase (aqueous phase) and the discontinuous phase (organic phase) are prepared separately:
Preparación de la fase continua:  Preparation of the continuous phase:
Se disuelven en caliente 50 g de alcohol polivinílico y 0,1 g de dodecilsulfonato sódico, en 1500 g de agua destilada .  50 g of polyvinyl alcohol and 0.1 g of sodium dodecylsulfonate are dissolved hot in 1500 g of distilled water.
Preparación de la fase discontinua:  Preparation of the discontinuous phase:
Se disuelven 5 g de parafina y 1,5 g de 3,5-di-tert- butilsalicilato de zinc, en una mezcla de 120 g de estireno y 40 g de n-butil acrilato. A continuación se añaden 4,8 g de peróxido de benzoilo y 80 g de la mezcla de pigmento y frita funcionalizadas .  5 g of paraffin and 1.5 g of 3,5-di-tert-butylsalicylate are dissolved in a mixture of 120 g of styrene and 40 g of n-butyl acrylate. Then 4.8 g of benzoyl peroxide and 80 g of the functionalized pigment and frit mixture are added.
La fase discontinua se agita a 3000 rpm durante 5 minutos. Posteriormente, se le adiciona la fase continua. La mezcla se mantiene en agitación a 4000 rpm durante 30 minutos más. Transcurrido este tiempo, el conjunto se introduce en un reactor de 2 litros de capacidad bajo una corriente de nitrógeno y se calienta a 80° C durante 10 horas, manteniendo una agitación constante de 500 rpm. El producto obtenido de la polimerización se lava con agua, se filtra y se deja secar obteniéndose las partículas de tóner . The discontinuous phase is stirred at 3000 rpm for 5 minutes. Subsequently, the continuous phase is added. The mixture is kept under stirring at 4000 rpm for an additional 30 minutes. After this time, the assembly is introduced into a 2-liter reactor under a stream of nitrogen and heated at 80 ° C for 10 hours, maintaining a constant stirring of 500 rpm. The product obtained from the polymerization is washed with water, It is filtered and allowed to dry obtaining the particles of toner.
A 100 g del tóner cerámico obtenido por polimerización según se ha descrito previamente se le adicionan 0,5 g de sílice de un tamaño medio de partícula de 15 nm y se mantiene la mezcla en agitación en un molino de bastidores durante 2 horas.  To 100 g of the ceramic toner obtained by polymerization as previously described, 0.5 g of silica of an average particle size of 15 nm is added and the mixture is kept under stirring in a rack mill for 2 hours.
TABLA 1: COMPOSICIÓN QUÍMICA DE LA FRITA EMPLEADA EN EL EJEMPLO 1. TABLE 1: CHEMICAL COMPOSITION OF FRIED EMPLOYED IN EXAMPLE 1.
Si02 59.0 % Si0 2 59.0%
A1203 9.6 % A1 2 0 3 9.6%
B203 2.28% B 2 0 3 2.28%
Fe203 0.18 % Faith 2 0 3 0.18%
CaO 13.4 %  CaO 13.4%
MgO 0.44 %  MgO 0.44%
Na20 0.67 % Na 2 0 0.67%
K20 3.68 % K 2 0 3.68%
Ti02 0.04 % Ti0 2 0.04%
Zr02 0.04 % Zr0 2 0.04%
BaO 0.08 %  BaO 0.08%
Li20 0.01 % Li 2 0 0.01%
PbO <0.01  PbO <0.01
ZnO 8.62 %  ZnO 8.62%
Hf02 <0.01 Hf0 2 <0.01
P2O5 0.04 %  P2O5 0.04%
SrO 0.09 %  SrO 0.09%
Pérdida por calcinación a 900°C 2.00 % Ej emplo 2 :  Loss on calcination at 900 ° C 2.00% Ex emplo 2:
Para la funcionalización de los componentes inorgánicos se pesan 80 g de un pigmento amarillo de silicato de circonio y praseodimio, y 20 g de una frita cerámica cuya composición química se incluye en la tabla 1. Estos componentes se dispersan en 300 mi de ácido clorhídrico al 0,01M, y se le adicionan 30 g de metacriloxi propil trimetoxisilano . La mezcla se mantiene en agitación durante 30 minutos, procediéndose posteriormente al filtrado, lavado y secado de los sólidos funcionalizados . For the functionalization of the inorganic components 80 g of a yellow pigment are weighed Zirconium and praseodymium silicate, and 20 g of a ceramic frit whose chemical composition is included in Table 1. These components are dispersed in 300 ml of 0.01M hydrochloric acid, and 30 g of methacryloxy propyl trimethoxysilane are added. The mixture is kept under stirring for 30 minutes, subsequently filtering, washing and drying the functionalized solids.
Para llevar a cabo la polimerización por suspensión se preparan por separado, la fase continua (fase acuosa) y la fase discontinua (fase orgánica) :  To carry out the suspension polymerization, the continuous phase (aqueous phase) and the discontinuous phase (organic phase) are prepared separately:
Preparación de la fase continua:  Preparation of the continuous phase:
Se disuelven en caliente 50 g de alcohol polivinílico y 0,1 g de dodecilsulfonato sódico, en 1500 g de agua destilada.  50 g of polyvinyl alcohol and 0.1 g of sodium dodecylsulfonate are dissolved hot in 1500 g of distilled water.
Preparación de la fase discontinua:  Preparation of the discontinuous phase:
Se disuelven 5 g de parafina y 1,5 g de 3,5-di-tert- butilsalicilato de zinc, en una mezcla de 120 g de estireno y 40 g de n-butil acrilato. A continuación se añaden 4,8 g de peróxido de benzoilo y 80 g de la mezcla de pigmento y frita funcionalizadas .  5 g of paraffin and 1.5 g of 3,5-di-tert-butylsalicylate are dissolved in a mixture of 120 g of styrene and 40 g of n-butyl acrylate. Then 4.8 g of benzoyl peroxide and 80 g of the functionalized pigment and frit mixture are added.
La fase discontinua se agita a 3000 rpm durante 5 minutos. Posteriormente, se le adiciona la fase continua. La mezcla se mantiene en agitación a 4000 rpm durante 30 minutos más. Transcurrido este tiempo, el conjunto se introduce en un reactor de 2 litros de capacidad bajo una corriente de nitrógeno y se calienta a 80° C durante 10 horas, manteniendo una agitación constante de 500 rpm. El producto obtenido de la polimerización se lava con agua, se filtra y se deja secar obteniéndose las partículas de tóner .  The discontinuous phase is stirred at 3000 rpm for 5 minutes. Subsequently, the continuous phase is added. The mixture is kept under stirring at 4000 rpm for an additional 30 minutes. After this time, the assembly is introduced into a 2-liter reactor under a stream of nitrogen and heated at 80 ° C for 10 hours, maintaining a constant stirring of 500 rpm. The product obtained from the polymerization is washed with water, filtered and allowed to dry to obtain the toner particles.
A 100 g del tóner cerámico obtenido por polimerización según se ha descrito previamente se le adicionan 0,5 g de sílice de un tamaño medio de partícula de 15 nm y se mantiene la mezcla en agitación en un molino de bastidores durante 2 horas. 100 g of the ceramic toner obtained by polymerization as previously described 0.5 g of silica of an average particle size of 15 nm is added and the mixture is kept under stirring in a rack mill for 2 hours.
Ejemplo 3: Example 3:
Para la funcionalización de los componentes inorgánicos se pesan 80 g de un pigmento azul de silicato de circonio y vanadio, y 20 g de una frita cerámica cuya composición química se incluye en la tabla 1. Estos componentes se dispersan en 300 mi de ácido clorhídrico al 0,01M, y se le adicionan 30 g de metacriloxi propil trimetoxisilano . La mezcla se mantiene en agitación durante 30 minutos, procediéndose posteriormente al filtrado, lavado y secado de los sólidos funcionalizados .  For the functionalization of the inorganic components, 80 g of a blue pigment of zirconium and vanadium silicate are weighed, and 20 g of a ceramic frit whose chemical composition is included in table 1. These components are dispersed in 300 ml of hydrochloric acid at 0.01M, and 30 g of methacryloxy propyl trimethoxysilane are added. The mixture is kept under stirring for 30 minutes, subsequently filtering, washing and drying the functionalized solids.
Para llevar a cabo la polimerización por suspensión se preparan por separado, la fase continua (fase acuosa) y la fase discontinua (fase orgánica) :  To carry out the suspension polymerization, the continuous phase (aqueous phase) and the discontinuous phase (organic phase) are prepared separately:
Preparación de la fase continua:  Preparation of the continuous phase:
Se disuelven en caliente 50 g de alcohol polivinílico y 0,1 g de dodecilsulfonato sódico, en 1500 g de agua destilada .  50 g of polyvinyl alcohol and 0.1 g of sodium dodecylsulfonate are dissolved hot in 1500 g of distilled water.
Preparación de la fase discontinua:  Preparation of the discontinuous phase:
Se disuelven 5 g de parafina y 1,5 g de 3,5-di-tert- butilsalicilato de zinc, en una mezcla de 120 g de estireno y 40 g de n-butil acrilato. A continuación se añaden 4,8 g de peróxido de benzoilo y 80 g de la mezcla de pigmento y frita funcionalizadas .  5 g of paraffin and 1.5 g of 3,5-di-tert-butylsalicylate are dissolved in a mixture of 120 g of styrene and 40 g of n-butyl acrylate. Then 4.8 g of benzoyl peroxide and 80 g of the functionalized pigment and frit mixture are added.
La fase discontinua se agita a 3000 rpm durante 5 minutos. Posteriormente, se le adiciona la fase continua. La mezcla se mantiene en agitación a 4000 rpm durante 30 minutos más. Transcurrido este tiempo, el conjunto se introduce en un reactor de 2 litros de capacidad bajo una corriente de nitrógeno y se calienta a 80° C durante 10 horas, manteniendo una agitación constante de 500 rpm. El producto obtenido de la polimerización se lava con agua, se filtra y se deja secar obteniéndose las partículas de tóner . The discontinuous phase is stirred at 3000 rpm for 5 minutes. Subsequently, the continuous phase is added. The mixture is kept under stirring at 4000 rpm for an additional 30 minutes. After this time, the set is it enters a reactor of 2 liters of capacity under a stream of nitrogen and is heated at 80 ° C for 10 hours, maintaining a constant stirring of 500 rpm. The product obtained from the polymerization is washed with water, filtered and allowed to dry to obtain the toner particles.
A 100 g del tóner cerámico obtenido por polimerización según se ha descrito previamente se le adicionan 0,5 g de sílice de un tamaño medio de partícula de 15 nm y se mantiene la mezcla en agitación en un molino de bastidores durante 2 horas.  To 100 g of the ceramic toner obtained by polymerization as previously described, 0.5 g of silica of an average particle size of 15 nm is added and the mixture is kept under stirring in a rack mill for 2 hours.
Ej emplo 4 : Ex emplo 4:
Para la funcionalización de los componentes inorgánicos se pesan 80 g de un pigmento negro de esfena de hierro, cromo, cobalto, níquel y manganeso y 20 g de una frita cerámica cuya composición química se incluye en la tabla 1. Estos componentes se dispersan en 300 mi de ácido clorhídrico al 0,01M, y se le adicionan 30 g de metacriloxi propil trimetoxisilano . La mezcla se mantiene en agitación durante 30 minutos, procediéndose posteriormente al filtrado, lavado y secado de los sólidos funcionalizados .  For the functionalization of the inorganic components 80 g of a black pigment of iron, chromium, cobalt, nickel and manganese sphene and 20 g of a ceramic frit whose chemical composition is included in table 1 are weighed. These components are dispersed in 300 ml of 0.01M hydrochloric acid, and 30 g of methacryloxy propyl trimethoxysilane are added. The mixture is kept under stirring for 30 minutes, subsequently filtering, washing and drying the functionalized solids.
Para llevar a cabo la polimerización por suspensión se preparan por separado, la fase continua (fase acuosa) y la fase discontinua (fase orgánica) :  To carry out the suspension polymerization, the continuous phase (aqueous phase) and the discontinuous phase (organic phase) are prepared separately:
Preparación de la fase continua:  Preparation of the continuous phase:
Se disuelven en caliente 50 g de alcohol polivinílico y 0,1 g de dodecilsulfonato sódico, en 1500 g de agua destilada.  50 g of polyvinyl alcohol and 0.1 g of sodium dodecylsulfonate are dissolved hot in 1500 g of distilled water.
Preparación de la fase discontinua:  Preparation of the discontinuous phase:
Se disuelven 5 g de parafina y 1,5 g de 3,5-di-tert- butilsalicilato de zinc, en una mezcla de 120 g de estireno y 40 g de n-butil acrilato. A continuación se añaden 4,8 g de peróxido de benzoilo y 80 g de la mezcla de pigmento y frita funcionalizadas . 5 g of paraffin and 1.5 g of 3,5-di-tert- are dissolved zinc butylsalicylate, in a mixture of 120 g of styrene and 40 g of n-butyl acrylate. Then 4.8 g of benzoyl peroxide and 80 g of the functionalized pigment and frit mixture are added.
La fase discontinua se agita a 3000 rpm durante 5 minutos. Posteriormente, se le adiciona la fase continua. La mezcla se mantiene en agitación a 4000 rpm durante 30 minutos más. Transcurrido este tiempo, el conjunto se introduce en un reactor de 2 litros de capacidad bajo una corriente de nitrógeno y se calienta a 80° C durante 10 horas, manteniendo una agitación constante de 500 rpm. El producto obtenido de la polimerización se lava con agua, se filtra y se deja secar obteniéndose las partículas de tóner .  The discontinuous phase is stirred at 3000 rpm for 5 minutes. Subsequently, the continuous phase is added. The mixture is kept under stirring at 4000 rpm for an additional 30 minutes. After this time, the assembly is introduced into a 2-liter reactor under a stream of nitrogen and heated at 80 ° C for 10 hours, maintaining a constant stirring of 500 rpm. The product obtained from the polymerization is washed with water, filtered and allowed to dry to obtain the toner particles.
A 100 g del tóner cerámico obtenido por polimerización según se ha descrito previamente se le adicionan 0,5 g de sílice de un tamaño medio de partícula de 15 nm y se mantiene la mezcla en agitación en un molino de bastidores durante 2 horas.  To 100 g of the ceramic toner obtained by polymerization as previously described, 0.5 g of silica of an average particle size of 15 nm is added and the mixture is kept under stirring in a rack mill for 2 hours.

Claims

REIVINDICACIONES
1. Un procedimiento para obtener un tóner cerámico, caracterizado porque comprende las siguientes etapas:  1. A procedure for obtaining a ceramic toner, characterized in that it comprises the following steps:
dispersar las partículas de una componente inorgánica del tóner, las cuales tienen una superficie hidrófoba, en una mezcla que comprende al menos: uno o más monómeros orgánicos y uno o más iniciadores, obteniendo una mezcla oleofílica,  dispersing the particles of an inorganic component of the toner, which have a hydrophobic surface, in a mixture comprising at least: one or more organic monomers and one or more initiators, obtaining an oleophilic mixture,
- dispersión de la mezcla oleofílica obtenida en la etapa anterior en un medio acuoso que comprende uno o más agentes estabilizantes disueltos, y opcionalmente uno o más surfactantes , obteniendo gotas suspendidas, - dispersion of the oleophilic mixture obtained in the previous stage in an aqueous medium comprising one or more dissolved stabilizing agents, and optionally one or more surfactants, obtaining suspended drops,
- polimerización de las gotas suspendidas obtenidas en la etapa anterior por aumento de la temperatura en un recipiente en agitación, obteniendo partículas, preferentemente esféricas, de tóner cerámico, - polymerization of the suspended drops obtained in the previous stage by increasing the temperature in a stirring vessel, obtaining particles, preferably spherical, of ceramic toner,
- lavado y posterior secado de las partículas de tóner cerámico sintetizadas,  - washing and subsequent drying of the synthesized ceramic toner particles,
incorporación y mezclado mecánico, de aditivos externos que favorecen la fluidez del tóner sintetizado .  incorporation and mechanical mixing of external additives that favor the fluidity of the synthesized toner.
2. Un procedimiento para obtener tóner cerámico según la reivindicación 2, que comprende la polimerización de uno o varios monómeros en presencia de las partículas de la componente inorgánica. 2. A process for obtaining ceramic toner according to claim 2, which comprises the polymerization of one or more monomers in the presence of the particles of the inorganic component.
3. Un procedimiento para obtener tóner cerámico según la reivindicación 1, en el que para la polimerización se emplea, al menos un monómero de entre las siguientes familias, monómeros vinílicos aromáticos, monómeros etilénicos insaturados, monómeros acrilados, monómeros metacrilados , y monómeros dienilos. 3. A process for obtaining ceramic toner according to claim 1, wherein at least one monomer from the following families is used for polymerization, aromatic vinyl monomers, unsaturated ethylenic monomers, acrylated monomers, monomers methacrylates, and dieneyl monomers.
4. Un procedimiento para obtener tóner cerámico según la reivindicación 1, en el que en la polimerización se usan uno o varios monómeros entrecruzadores , seleccionados de entre monómeros dienilos. 4. A process for obtaining ceramic toner according to claim 1, wherein in the polymerization one or more crosslinking monomers, selected from dienyl monomers, are used.
5. Un procedimiento para obtener tóner cerámico según la reivindicación 1, en el los iniciadores están seleccionados entre iniciadores de tipo peróxido, iniciadores de tipo azo y mezclas de los mismos. 5. A process for obtaining ceramic toner according to claim 1, wherein the initiators are selected from peroxide type initiators, azo type initiators and mixtures thereof.
6. Un procedimiento para obtener tóner cerámico según la reivindicación 5, en el que los iniciadores están presentes en un porcentaje de entre el 0,01 y el 10 % en peso con respecto al peso total de los monómeros. 6. A process for obtaining ceramic toner according to claim 5, wherein the initiators are present in a percentage of between 0.01 and 10% by weight with respect to the total weight of the monomers.
7. Un procedimiento para obtener tóner cerámico según la reivindicación 1, en el que se usan uno o varios agentes de control de carga seleccionados entre: nigrosinas, complejos de trifenilmetano, colorantes catiónicos, dioxacinas, bencimidazolonas , ftalocianinas de cobre, perilenos, quinacridonas , pigmentos azo, sales metálicas de pigmentos azo, complejos azo de cobre, complejos metálicos de ácido salicilico, derivados de tetrafenil borato, derivados de un ácido hidroxicarboxilico aromático, derivados de un ácido hidroxicarboxilico alifático, derivados del calixareno, sales de amonio cuaternario, sales de alquilamonio cuaternario, sales de piridinium cuaternarias, bisulfatos, parafina clorada, poliéster clorado, poliésteres con grupos ácidos, polímeros conteniendo grupos de ácido sulfonico, negro de humo, óxido negro de hierro, grafito, amarillo hansa, amarillo de bencidina y mezclas de ellos. 7. A process for obtaining ceramic toner according to claim 1, wherein one or more charge control agents selected from: nigrosines, triphenylmethane complexes, cationic dyes, dioxacins, benzimidazolones, copper phthalocyanines, perylenes, quinacridones are used, Azo pigments, metallic salts of azo pigments, copper azo complexes, salicylic acid metal complexes, tetraphenyl borate derivatives, derivatives of an aromatic hydroxycarboxylic acid, derivatives of an aliphatic hydroxycarboxylic acid, calixarene derivatives, quaternary ammonium salts, salts of quaternary alkylammonium, quaternary pyridinium salts, bisulfates, chlorinated paraffin, chlorinated polyester, polyesters with acid groups, polymers containing sulfonic acid groups, black smoke, black iron oxide, graphite, hansa yellow, benzidine yellow and mixtures thereof.
8. Un procedimiento para obtener tóner cerámico según la reivindicación 1, en el que se usan uno o más agentes de control de carga en porcentajes de entre el 0,01 y el 20 % en peso con respecto al peso total de los monómeros. 8. A process for obtaining ceramic toner according to claim 1, wherein one or more charge control agents are used in percentages between 0.01 and 20% by weight with respect to the total weight of the monomers.
9. Un procedimiento para obtener tóner cerámico según la reivindicación 1, en el que se usan una o varias ceras, seleccionadas entre: ceras poliolefinicas como polietileno de bajo peso molecular, polipropileno de bajo peso molecular, polibutileno de bajo peso molecular, ceras naturales como candelilla, carnauba, jojoba, cera de arroz, ceras de petróleo, como parafinas, microcristalinas , vaselina, ceras minerales como montan, ceresina, ozoquerita, y ceras sintéticas como ceras de Fischer-Tropsch, amidas grasas, aceites de silicona. 9. A process for obtaining ceramic toner according to claim 1, wherein one or more waxes are used, selected from: polyolefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight polybutylene, natural waxes such as Candelilla, carnauba, jojoba, rice wax, petroleum waxes, such as paraffins, microcrystallines, petrolatum, mineral waxes such as montan, ceresin, ozoquerite, and synthetic waxes such as Fischer-Tropsch waxes, fatty amides, silicone oils.
10. Un procedimiento para obtener tóner cerámico según la reivindicación 9, en el que las ceras están presentes en porcentajes de entre el 0,1 y el 20 % en peso con respecto al peso total de los monómeros. 10. A process for obtaining ceramic toner according to claim 9, wherein the waxes are present in percentages between 0.1 and 20% by weight with respect to the total weight of the monomers.
11. Un procedimiento para obtener tóner cerámico según la reivindicación 1, en el que se usan agentes fluidificantes externos, formados por partículas de materiales inorgánicos. 11. A process for obtaining ceramic toner according to claim 1, wherein external fluidizing agents, formed by particles of inorganic materials, are used.
12. Un procedimiento definido en una de las reivindicaciones 1 a 11 para obtener tóner cerámico para la decoración de materiales cerámicos, vidrio y metal. 12. A process defined in one of claims 1 to 11 for obtaining ceramic toner for the decoration of ceramic materials, glass and metal.
13. Un tóner para la decoración de materiales cerámicos, vidrio y metal, caracterizado porque ha obtenido a través del procedimiento definido en una de las reivindicaciones 1 a 12. 13. A toner for the decoration of ceramic materials, glass and metal, characterized in that it has been obtained through the procedure defined in one of claims 1 to 12.
14. Un tóner para la decoración de materiales cerámicos, vidrio y metal, según la reivindicación 13, caracterizado porque comprende: 14. A toner for the decoration of ceramic materials, glass and metal, according to claim 13, characterized in that it comprises:
- una componente inorgánica que está presente entre un - an inorganic component that is present between a
5 y un 90 % en peso, y que comprende: 5 and 90% by weight, and comprising:
o una fracción inorgánica activa en decoración Y  or an inorganic fraction active in decoration Y
o una fracción inorgánica que confiere fundencia,  or an inorganic fraction that confers fundence,
- un componente orgánico que está presente entre un 95 y un 10 % en peso y que comprende uno o más polímeros orgánicos .  - an organic component that is present between 95 and 10% by weight and that comprises one or more organic polymers.
15. Un tóner según la reivindicación 13, caracterizado porque la componente inorgánica está presente entre comprendida entre un 40 y un 80 % en peso respecto del peso del tóner. 15. A toner according to claim 13, characterized in that the inorganic component is present between 40 and 80% by weight with respect to the weight of the toner.
16. Un tóner cerámico, según la reivindicación 13, en el que la razón fracción inorgánica activa en decoración / fracción inorgánica para fundencia está comprendida entre de 10 y 0,1. 16. A ceramic toner according to claim 13, wherein the ratio inorganic fraction active in decoration / inorganic fraction for fundence is between 10 and 0.1.
17. Un tóner cerámico, según la reivindicación 13, caracterizado porque la fracción inorgánica activa en decoración está seleccionada entre al menos uno de los siguientes compuestos: óxidos metálicos, mezclas de óxidos, óxidos mixtos, soluciones sólidas de óxidos de metales, soluciones sólidas de compuestos coloreados, soluciones sólidas de compuestos no coloreados, metales en estado coloidal, sulfuros, pigmentos protegidos de inclusión o mordientes, óxidos metálicos con fosfatos metálicos, materias primas fundentes que comprenden cerio o wolframio metálico, materias primas fundentes que comprenden titanio. 17. A ceramic toner according to claim 13, characterized in that the inorganic fraction active in decoration is selected from at least one of the following compounds: metal oxides, mixtures of oxides, mixed oxides, solid solutions of metal oxides, solid solutions of colored compounds, solid solutions of non-colored compounds, colloidal metals, sulfides, protected inclusion pigments or mordants, metal oxides with metallic phosphates, melting raw materials comprising cerium or metallic tungsten, melting raw materials comprising titanium.
18. Un tóner cerámico, según la reivindicación 13, en el que las partículas de tóner tienen diámetros medios de partícula comprendidos entre 1 μτα y 30 μτα. 18. A ceramic toner according to claim 13, wherein the toner particles have average particle diameters between 1 μτα and 30 μτα.
19. Un tóner cerámico según la reivindicación 13, caracterizado porque es preparado por un proceso de polimerización en suspensión que se consolida tras un proceso de cocción a alta temperatura. 19. A ceramic toner according to claim 13, characterized in that it is prepared by a suspension polymerization process that is consolidated after a high temperature cooking process.
20. Uso del tóner cerámico definido en una de las reivindicaciones 13 a 19, caracterizado porque comprende depositar dicho tóner sobre un soporte seleccionado entre soporte cerámico, un vidrio y un metal mediante sistema de decoración electrostática, y 20. Use of the ceramic toner defined in one of claims 13 to 19, characterized in that it comprises depositing said toner on a support selected from ceramic support, a glass and a metal by electrostatic decoration system, and
- someter el soporte a un proceso de cocción a temperatura superior a 400°C quedando la imagen fijada de forma permanente. - subject the support to a cooking process at a temperature above 400 ° C, leaving the image permanently fixed.
21. Piezas obtenidas con el tóner definido en una de las reivindicaciones 13 a 19, y depositado según la reivindicación 20. 21. Parts obtained with the toner defined in one of claims 13 to 19, and deposited according to claim 20.
PCT/ES2012/070078 2011-02-11 2012-02-08 A method for obtaining a ceramic toner and ceramic toner obtained WO2012107622A1 (en)

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US20050106486A1 (en) * 2002-01-08 2005-05-19 Bernd Schultheis Ceramic toner for electro-photographic printing
US20070140748A1 (en) * 2005-12-08 2007-06-21 Hideki Sugiura Image forming apparatus, and carrier, toner and developer used therein

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US20050106486A1 (en) * 2002-01-08 2005-05-19 Bernd Schultheis Ceramic toner for electro-photographic printing
US20040191661A1 (en) * 2003-03-10 2004-09-30 Manabu Ohno Dry toner, method for producing dry toner, and method for forming an image
US20070140748A1 (en) * 2005-12-08 2007-06-21 Hideki Sugiura Image forming apparatus, and carrier, toner and developer used therein

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CN103869643A (en) * 2012-12-13 2014-06-18 周拯 Color ceramic carbon power and preparation method thereof
CN103869643B (en) * 2012-12-13 2016-09-28 周拯 The preparation method of chromatic ceramics carbon dust

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