EP0948459A1 - Utilisation comme pigment colorant d'un sulfure de terre rare de forme beta et son procede de preparation - Google Patents

Utilisation comme pigment colorant d'un sulfure de terre rare de forme beta et son procede de preparation

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Publication number
EP0948459A1
EP0948459A1 EP97945900A EP97945900A EP0948459A1 EP 0948459 A1 EP0948459 A1 EP 0948459A1 EP 97945900 A EP97945900 A EP 97945900A EP 97945900 A EP97945900 A EP 97945900A EP 0948459 A1 EP0948459 A1 EP 0948459A1
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EP
European Patent Office
Prior art keywords
sulfide
rare earth
sulphide
reaction
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP97945900A
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German (de)
English (en)
French (fr)
Inventor
Sylvain Busnot
Pierre Macaudiere
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Chimie SAS
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Rhodia Chimie SAS
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Filing date
Publication date
Application filed by Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP0948459A1 publication Critical patent/EP0948459A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/10—Preparation or treatment, e.g. separation or purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/288—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/68—Particle size between 100-1000 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/60—Compounds characterised by their crystallite size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/62—L* (lightness axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/63—Optical properties, e.g. expressed in CIELAB-values a* (red-green axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/65—Chroma (C*)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3009—Sulfides

Definitions

  • the present invention relates to the use as coloring pigment of a rare earth sulfide of beta form and to its preparation process.
  • Mineral coloring pigments are already widely used in many industries, particularly in paints, plastics and ceramics. In such applications, the properties of, among others, thermal and / or chemical stability, dispersibility (ability of the product to disperse correctly in a given medium), compatibility with the medium to be colored, intrinsic color, coloring power and opacifying power are all particularly important criteria to take into consideration when choosing a suitable pigment.
  • the object of the present invention is to provide such pigments, in the range of red in particular and, more particularly, in the range of burgundy red.
  • the process of the invention for the preparation of a rare earth sulfide of beta form is characterized in that a carbonate or a hydroxycarbonate of the rare earth is reacted with hydrogen sulfide.
  • the method is characterized in that a rare earth compound is reacted with a gaseous sulfurizing mixture based on hydrogen sulfide and carbon sulfide.
  • the invention applies to the preparation of a lanthanum, cerium, praseodymium, samarium or neodymium sulfide, but also to mixed sulphides, that is to say the sulphides of two or more rare earths of the group given above. Consequently, all that is described below for a simple sulfide also applies to mixed sulfides.
  • the method is characterized in that a carbonate or a hydroxycarbonate of the rare earth is reacted with hydrogen sulfide.
  • a mixture of these two gases is used.
  • This oxygen content can be modified by varying the content of carbon sulphide in the gas mixture.
  • a high content of carbon sulphide promotes the production of sulphides with low oxygen contents, that is to say products of lighter colors such as light burgundy for example while that a higher hydrogen sulfide content makes it possible to obtain products with higher oxygen concentrations and therefore of darker colors.
  • the gas or the mixture of sulfurous gases can be used with an inert gas such as argon or nitrogen.
  • the rare earth compound used for the reaction, in this second mode is preferably a carbonate or a hydroxycarbonate. Mention may also be made of nitrates. We could also use a rare earth oxide.
  • the sulfurization reaction is generally carried out at a temperature between 600 ° C and 1000 ° C, preferably between 600 and 800 ° C, in particular at 800 ° C or near this temperature.
  • reaction time corresponds to the time necessary to obtain the desired sulfide.
  • this duration may be between one and four hours approximately.
  • the sulfide formed is recovered. If it is desired to obtain a product with a finer grain size, this can be deagglomerated. Disagglomeration under mild conditions, for example wet grinding or of the air jet type under mild conditions, makes it possible to obtain a sulphide having, in particular, an average size of aggregates of at most 1.5 ⁇ m.
  • the rare earth sulfide obtained by the methods of the invention is a sulfide which has the beta crystallographic form.
  • beta form is meant here and for the whole of the description, a compound of formula Ce ⁇ oSi4 ⁇ xS-
  • a characteristic of the sulphide obtained by the processes of the invention lies in the fact that it consists of whole crystallites. These crystallites form aggregates and these aggregates constitute the powder in the form of which the sulphide is present.
  • whole crystallite is meant a crystallite which has not been broken or broken. In fact, crystallites can be broken or broken during grinding. The photos in scanning electron microscopy of the product of the invention make it possible to show that the crystallites which constitute it have not been broken.
  • the aggregates constituting the sulphide have an average size of at most 1.5 ⁇ m. This average size can be at most 1 ⁇ m and more particularly at most 0.8 ⁇ m.
  • the size and particle size characteristics are measured by the laser diffraction technique using a particle size analyzer of the CILAS HR 850 type (volume distribution).
  • the sulfide obtained by the methods of the invention is disaggregable. It may therefore not appear directly in the form of medium-sized aggregates in the values given above.
  • the aggregates can be agglomerated and / or slightly sintered and have a size greater than these values.
  • a simple disagglomeration under mild conditions makes it possible to obtain aggregates of average size of at most 1.5 ⁇ m or in the ranges given previously.
  • the sulfide is in the form of a pure phase, it is the only beta phase as defined above.
  • the sulphide obtained by the methods of the invention can also have a variable oxygen content. This content, expressed by weight of oxygen relative to the weight of all of the sulfide, can be at most 0.8%.
  • the cerium sulphide presents a burgundy red color.
  • the cerium sulphide has a chromatic coordinate L * of less than 40 and a ratio b * / a * of less than 0.6.
  • the chromaticity coordinates L *, a * and b * are given here and for the rest of the description in the CIE 1976 system (L *, a * and b *) as defined by the International Lighting Commission and listed in the Collection of French Standards (AFNOR), colorimetric n ° X08-12, n ° X08-14 (1983). They are determined with regard to the measurements made on products and plastics using a colorimeter sold by the company Pacific Scientific.
  • the nature of the illuminant is D65.
  • the observation surface is a circular patch with a surface area of 12.5 cm2.
  • the observation conditions correspond to a vision under an opening angle of 10 °.
  • the specular component is excluded.
  • the sulphide as described above, further comprises a layer based on at least one transparent oxide, deposited on its surface or its periphery.
  • a product of this type comprising such a layer, at French patent application FR-A-2703999 in the name of the Applicant, the teaching of which is incorporated here.
  • This peripheral layer coating the sulphide may not be perfectly continuous or homogeneous.
  • the sulfides according to this embodiment comprise a uniform coating layer and of controlled thickness of transparent oxide, and this so as not to alter the original color of the sulfide before coating.
  • transparent oxide is meant here an oxide which, once deposited on the sulfide in the form of a more or less fine film, absorbs little or no light rays in the visible range, and this of so as not to mask or little mask the intrinsic color of origin of said sulfide.
  • oxide which is used for convenience throughout the present description, should be understood as also covering hydrated type oxides. These oxides, or hydrated oxides, can be amorphous and / or crystallized.
  • silicon oxide silicon oxide
  • alumina aluminum oxide
  • zirconium oxide zirconia
  • titanium oxide silicate zirconium ZrSi ⁇ 4 (zircon) and rare earth oxides.
  • the coating layer is based on silica. Even more advantageously, this layer is essentially, and preferably only, made of silica.
  • the sulphide can also comprise fluorine atoms.
  • the fluorine atoms are distributed according to a decreasing concentration gradient from the surface to the heart of said sulfide.
  • the fluorine atoms are mainly distributed at the outer periphery of the sulfide.
  • external periphery is meant here a thickness of material measured from the surface of the particle, of the order of a few hundred Angstroms.
  • the majority means that more than 50% of the fluorine atoms present in the sulphide are found in said external periphery.
  • the percentage by weight of the fluorine atoms present in the sulphide does not exceed 10%, and preferably 5%.
  • the fluorine atoms are present in the form of fluorinated or sulfofluorinated compounds, in particular in the form of rare earth fluorides or rare earth sulfofluorides (thiofluorides).
  • the invention also relates to the combination of the embodiments which have been described above.
  • a sulfide comprising an oxide layer and further comprising fluorine atoms.
  • the preparation process can consist in bringing together the sulphide as it was obtained after the sulphurization reaction and a precursor of the transparent oxide forming a layer, and in precipitating this oxide.
  • the methods of precipitation of the oxides and the precursors to be used are described in particular in FR-A-2703999.
  • silica mention may be made of the preparation of silica by hydrolysis of an alkyl silicate, by forming a reaction medium by mixing water, alcohol, sulfide which is then suspended, and optionally d 'a base, and then introducing the alkyl silicate, or alternatively a preparation by reaction of the sulfide, a silicate, of the alkaline silicate type, and an acid.
  • the sulfide, an aluminate and an acid can be reacted, whereby alumina is precipitated.
  • This precipitation can also be obtained by bringing together and reacting the sulphide, an aluminum salt and a base.
  • alumina can be formed by hydrolysis of an aluminum alcoholate.
  • titanium oxide it can be precipitated by introducing into an aqueous suspension of sulfide according to the invention and a titanium salt on the one hand such as TiCl TiOCl2 or TiOSO and a base on the other hand.
  • a titanium salt on the one hand such as TiCl TiOCl2 or TiOSO and a base on the other hand.
  • One can also operate for example by hydrolysis of an alkyl titanate or precipitation of a titanium sol.
  • a zirconium oxide-based layer it is possible to proceed by cohydrolysis or coprecipitation of a suspension of the sulfide in the presence of an organometallic compound of zirconium, for example a zirconium alkoxide such as 'zirconium isopropoxide.
  • an organometallic compound of zirconium for example a zirconium alkoxide such as 'zirconium isopropoxide.
  • the process for preparing the sulfide according to the second variant, sulfide comprising fluorine atoms uses fluorination.
  • the fluorination can be carried out according to any technique known per se by bringing together the sulphide as it was obtained after the sulphurization reaction and a fluorinating agent.
  • the fluorinating agent can be liquid, solid or gaseous.
  • fluorinating agents suitable for carrying out the treatment according to the invention mention may more particularly be made of fluorine F2, fluorides of alkalis, ammonium fluoride, rare gas fluorides, nitrogen fluoride NF3, boron fluoride BF3, tetrafluoromethane, hydrofluoric acid HF.
  • the fluorinating agent can be used pure or in dilution in a neutral gas, for example nitrogen.
  • the reaction conditions are preferably chosen so that said treatment induces fluorination only on the surface of the sulphide (mild conditions).
  • the conduct of a fluorination to the core of the sulfide does not bring substantially improved results compared to an essentially surface fluorination.
  • one can follow and experimentally control the degree of progress of the fluorination reaction for example by measuring the evolution of the mass gain of materials (mass gain induced by the progressive introduction of fluorine) .
  • the fluorinating agent can more particularly be ammonium fluoride.
  • ammonium fluoride As indicated above, it is possible to envisage preparing a sulfide combining the characteristics constituting the different embodiments: the oxide layer and the presence of fluorine atoms. To obtain the combinations of these embodiments, the preparation methods which have just been described are combined.
  • the fluorination treatment can be carried out in a first step, then, in a second step, the sulfide thus treated is brought into contact with a precursor of the transparent oxide, and the transparent oxide is precipitated on the said sulfide.
  • a first step the sulfide is brought into contact with a precursor of the transparent oxide, then the transparent oxide is precipitated on the said sulfide and finally, in a last step, the fluorination treatment is carried out.
  • the sulfide of the invention as obtained after reaction with the gas or the sulfurizing mixture, can be treated so as to deposit a zinc compound thereon.
  • This deposition can be done by reaction of a zinc precursor with ammonia or an ammonium salt.
  • FR-A-2741629 the teaching of which is incorporated here.
  • the zinc precursor can be a zinc oxide or hydroxide which is used in suspension.
  • This precursor can also be a zinc salt, preferably a soluble salt. It can be an inorganic acid salt such as a chloride, or an organic acid salt such as an acetate.
  • the contact between the sulphide, the zinc precursor, the ammonia and / or the ammonium salt takes place in the presence of an alcohol.
  • the alcohol used is generally chosen from aliphatic alcohols such as by for example butanol or ethanol.
  • the alcohol can, in particular, be provided with the zinc precursor in the form of an alcoholic solution of zinc.
  • the sulphide, the zinc precursor, the ammonia and / or the ammonium salt can be brought into contact in the presence of a dispersant.
  • a dispersant is to avoid agglomeration of the sulphide particles forming a support during their suspension for the treatments described above. It also allows you to work in more concentrated environments. It promotes the formation of a homogeneous deposit layer on all of the particles.
  • This dispersant can be chosen from the group of dispersants by steric effect and in particular non-ionic water-soluble or organosoluble polymers. Mention may be made, as dispersing agent, of cellulose and its derivatives, of polyacrylamides, of polyethylene oxides, of polyethylene glycols, of polyoxyethylenated polyoxypropylene glycols, of polyacrylates, of polyoxyethylenated alkyl phenols, of long-chain polyoxyethylene alcohols, of polyvinyl alcohols, of alkanolamides, dispersants of the polyvinyipyrrolidone type, xanthan gum-based compounds.
  • dispersing agent of cellulose and its derivatives, of polyacrylamides, of polyethylene oxides, of polyethylene glycols, of polyoxyethylenated polyoxypropylene glycols, of polyacrylates, of polyoxyethylenated alkyl phenols, of long-chain polyoxyethylene alcohols, of polyvinyl alcohols
  • the sulfide described has a coloring power and a covering power and, therefore, is suitable for coloring many materials, such as plastics, paints and others.
  • thermoplastic resins capable of being colored according to the invention, mention may be made, purely by way of illustration, of polyvinyl chloride, polyvinyl alcohol, polystyrene, styrene-butadiene, styrene-acrylonitrile, acrylonitrile-butadiene-styrene copolymers.
  • ABS acrylic polymers, in particular polymethyl methacrylate, polyolefins such as polyethylene, polypropylene, polybutene, polymethylpentene, cellulose derivatives such as, for example, cellulose acetate, cellulose aceto-butyrate, ethylcellulose, polyamides including polyamide 6-6.
  • thermosetting resins for which the sulphide is also suitable mention may, for example, be made of phenoplasts, aminoplasts, in particular urea-formaldehyde, melamine-formaldehyde copolymers, epoxy resins and thermosetting polyesters.
  • the sulfide in special polymers such as fluoropolymers, in particular polytetrafluoroethylene (PTFE), polycarbonates, silicone elastomers, polyimides.
  • PTFE polytetrafluoroethylene
  • the sulphide can be used directly in the form of powders. It is also preferably possible to use it in a pre-dispersed form, for example in premix with part of the resin, in the form of a paste paste or a liquid which allows it to be introduced at any stage of the resin's manufacture.
  • the products according to the invention can be incorporated into plastics such as those mentioned above in a weight proportion generally ranging either from 0.01 to 5% (reduced to the final product) or from 20 to 70% in the case of a concentrate.
  • the products of the invention can also be used in the field of paints and stains and more particularly in the following resins: alkyd resins, the most common of which is called glycerophthalic; long or short oil modified resins; acrylic resins derived from esters of acrylic (methyl or ethyl) and methacrylic acid optionally copolymerized with ethyl acrylate, 2-ethylhexyl or butyl; vinyl resins such as, for example, polyvinyl acetate, polyvinyl chloride, butyral polyvinyl, formalpolyvinyl, and copolymers of vinyl chloride and vinyl acetate or vinylidene chloride; the aminoplast or phenolic resins most often modified; polyester resins; polyurethane resins; epoxy resins; silicone resins.
  • alkyd resins the most common of which is called glycerophthalic
  • long or short oil modified resins acrylic resins derived from esters of acrylic (methyl or ethyl)
  • the products are used in an amount of 5 to 30% by weight of the paint, and from 0.1 to 5% by weight of the stain.
  • the products according to the invention are also capable of being suitable for applications in the rubber industry, in particular in floor coverings, in the paper and printing ink industry, in the cosmetic field. , as well as many other uses such as for example, and not limited to, dyes, in leathers for the finishing thereof and laminate coatings for kitchens and other worktops, ceramics and glazes.
  • the products of the invention can also be used in the coloring of materials based on or obtained from at least one mineral binder.
  • This mineral binder can be chosen from hydraulic binders, aerial binders, plaster and binders of the anhydrous or partially hydrated calcium sulphate type.
  • hydraulic binders substances having the property of setting and hardening after addition of water by forming hydrates insoluble in water.
  • the products of the invention apply very particularly to the coloring of cements and, of course, of concretes produced from these cements by adding thereto water, sand and / or gravel.
  • the cement may, for example, be of the aluminous type.
  • any cement containing a high proportion of either alumina as such either aluminate or both may be made.
  • cements based on calcium aluminate in particular those of the SECAR type.
  • the cement can also be of the silicate type and more particularly based on calcium silicate.
  • PORTLAND cements can be given and, in this type of cements, Portiand, fast or very fast setting, white cements, those resistant to sulphates as well as those comprising slag from blast furnaces and / or fly ash and / or meta-kaolin.
  • cements based on hemihydrate, calcium sulphate as well as magnesium cements known as Sorel cements are also used for coloring aerial binders, that is to say binders hardening in the open air by the action of CO2, of the calcium or magnesium oxide or hydroxide type.
  • the products of the invention are finally used for coloring plaster and binders of the anhydrous or partially hydrated calcium sulphate type (CaS ⁇ 4 and CaSO I / 2H2O).
  • the invention relates to compositions of colored material, in particular of the plastics, paints, stains, rubbers, ceramics, glazes, papers, inks, cosmetic products, dyes, leathers, laminated coatings or of the type based on or obtained from at least one inorganic binder, which comprise as coloring pigment, a sulphide as defined above or obtained by methods of the type described above. Examples will now be given. In these examples, the particle size was determined according to the aforementioned technique.
  • 10 g of the pigment thus synthesized are mixed in a rotating cube at 2 kg of a reference polypropylene ELTEX® PHV 001.
  • the mixture is then injected at 220 ° C. using a KAPSA model Protoject 10/10 injection press with a cycle of 41 s.
  • the mold is maintained at the temperature of 35 ° C.
  • R400 / R700 2.4 / 60.2.
  • the following examples relate to products which have undergone additional treatments after their preparation to obtain a layer of a transparent oxide, to deposit zinc and fluorine.
  • the treatment for depositing the oxide layer and introducing zinc is as follows.
  • Polyvinyipyrrolidone (PVP) is dissolved in ethanol.
  • This example relates to the product of Example 2.
  • the reagents are used in the following proportions:
  • cerium sulfide used was previously fluorinated in the following manner. 10g of product are introduced into 100ml of an ammonium fluoride solution (5% by mass relative to b-Ce ⁇ oSi4 ⁇ o.8S ⁇ .2) -
  • the product thus obtained is treated by implementing the operating conditions given above using ammonia.
  • This example relates to the product of Example 1.
  • the reagents are used in the following proportions:
  • cerium sulfide used was previously fluorinated in the following manner. 10 g of product are introduced into 100 ml of an ammonium fluoride solution (5% by mass relative to b-Cei fjS14O0.i7S0.83) -
  • the product thus obtained is treated by implementing the operating conditions given above using ammonia.
  • the product obtained has the following chromatic coordinates after injection into polypropylene

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EP97945900A 1996-11-19 1997-11-10 Utilisation comme pigment colorant d'un sulfure de terre rare de forme beta et son procede de preparation Withdrawn EP0948459A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9614058A FR2755971B1 (fr) 1996-11-19 1996-11-19 Utilisation comme pigment colorant d'un sulfure de terre rare de forme beta et son procede de preparation
FR9614058 1996-11-19
PCT/FR1997/002018 WO1998022391A1 (fr) 1996-11-19 1997-11-10 Utilisation comme pigment colorant d'un sulfure de terre rare de forme beta et son procede de preparation

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EP0948459A1 true EP0948459A1 (fr) 1999-10-13

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EP97945900A Withdrawn EP0948459A1 (fr) 1996-11-19 1997-11-10 Utilisation comme pigment colorant d'un sulfure de terre rare de forme beta et son procede de preparation

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EP (1) EP0948459A1 (ja)
JP (1) JP2000505039A (ja)
KR (1) KR20000057133A (ja)
CN (1) CN1087273C (ja)
AU (1) AU729959B2 (ja)
CA (1) CA2272459A1 (ja)
FR (1) FR2755971B1 (ja)
WO (1) WO1998022391A1 (ja)

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DE19810317A1 (de) * 1998-03-11 1999-09-16 Merck Patent Gmbh Seltene Erdmetallsulfidpigmente und Yttriumsulfidpigmente
CN1120804C (zh) * 2000-01-31 2003-09-10 李波 稀土硫化物的制备方法
FR2807023B1 (fr) * 2000-03-30 2002-12-20 Rhodia Terres Rares Composition a base d'un sulfure de terre rare a stabilite chimique amelioree, son procede de preparation et son utilisation comme pigment
JP2002194208A (ja) * 2000-12-27 2002-07-10 Daicel Degussa Ltd 赤系色に着色されたポリアミド系樹脂組成物
CN102127317B (zh) * 2011-01-20 2013-04-17 中国科学院长春应用化学研究所 稀土着色剂及其制备方法
CN103011241B (zh) * 2012-12-31 2015-03-18 江西理工大学 一种稀土镨片状晶体及其制备方法
CN103819934A (zh) * 2014-02-25 2014-05-28 内蒙古大学 一种包覆型稀土硫化物颜料的制备方法
CN103965522B (zh) * 2014-04-15 2016-08-17 包头市宏博科技有限责任公司 一种稀土硫化物橡胶助剂及其制备方法
JPWO2018025866A1 (ja) * 2016-08-04 2019-06-06 国立大学法人名古屋大学 一硫化サマリウムの製造方法、体積変化材料、体積制御部材、負熱膨張材料、および化合物材料
CN106517295B (zh) * 2016-10-18 2018-02-23 西北工业大学 一种合成高稳定性γ‑Pr2S3粉体的方法
CN107151461B (zh) 2017-06-29 2019-04-26 包头中科世纪科技有限责任公司 着色剂及其制备方法
CN108084736B (zh) * 2017-12-19 2020-07-24 包头中科世纪科技有限责任公司 一种简单无污染处理稀土硫化物颜料的工艺
CN109929269A (zh) * 2017-12-19 2019-06-25 包头中科世纪科技有限责任公司 一种可连续化规模化生产稀土硫化物着色剂的方法
CN109651846B (zh) * 2017-12-28 2021-01-05 包头市宏博特科技有限责任公司 一种稀土硫化物的后处理方法
CN108715549B (zh) * 2018-06-05 2021-04-02 西北工业大学 一种制备稀土硫化物γ-Ln2S3透明陶瓷的方法

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FR2100551B1 (ja) * 1970-05-27 1973-11-23 Raffinage Cie Francaise
JPS5120437B2 (ja) * 1973-11-14 1976-06-24
FR2657599B1 (fr) * 1990-01-30 1992-04-03 Loire Atlantique Procedes Chim Procede d'elaboration de composes binaires du soufre.
FR2703999B1 (fr) * 1993-04-16 1995-05-24 Rhone Poulenc Chimie Nouveaux pigments minéraux colorés à base de sulfures de terres rares, procédé de synthèse et utilisations.
FR2706476B1 (fr) * 1993-06-09 1995-09-15 Rhone Poulenc Chimie Procédé de traitement de pigments à base de sulfures de terres, rares, nouveaux pigments ainsi obtenus et leurs utilisations.
FR2719576B1 (fr) * 1994-05-06 1996-07-12 Rhone Poulenc Chimie Composition à base d'un sulfure de terre rare comprenant au moins un élément alcalin, son procédé de préparation et son utilisation comme pigment coloré.
FR2732005B1 (fr) * 1995-03-22 1997-06-13 Rhone Poulenc Chimie Procede de preparation de sulfures de terres rares a partir d'halogenures

Non-Patent Citations (1)

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Also Published As

Publication number Publication date
JP2000505039A (ja) 2000-04-25
FR2755971A1 (fr) 1998-05-22
FR2755971B1 (fr) 1999-03-05
CN1087273C (zh) 2002-07-10
CN1241987A (zh) 2000-01-19
AU5123698A (en) 1998-06-10
KR20000057133A (ko) 2000-09-15
CA2272459A1 (fr) 1998-05-28
AU729959B2 (en) 2001-02-15
WO1998022391A1 (fr) 1998-05-28

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