CN1241987A - Use of a beta rare earth sulphide as colouring pigment and method for preparing same - Google Patents

Use of a beta rare earth sulphide as colouring pigment and method for preparing same Download PDF

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CN1241987A
CN1241987A CN97181084A CN97181084A CN1241987A CN 1241987 A CN1241987 A CN 1241987A CN 97181084 A CN97181084 A CN 97181084A CN 97181084 A CN97181084 A CN 97181084A CN 1241987 A CN1241987 A CN 1241987A
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sulfide
rare earth
sulphide
compound
beta
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CN1087273C (en
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S·布司诺特
P·马卡迪勒
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Rhodia Chimie SAS
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Rhone Poulenc Chimie SA
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    • 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
    • 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
    • C01F17/20—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
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    • 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
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    • 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
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2006/62—L* (lightness axis)
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    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)
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    • 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

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  • Nanotechnology (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Analytical Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Paper (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
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Abstract

The invention concerns the use of a beta rare earth sulphide as coloring pigment and its method of preparation. A beta rare-earth sulphide is used, the rare earth being lanthanum, cerium, praseodymium, samarium or neodymium. The sulphide consists of whole crystallites forming medium-sized aggregates of not more than 1.5 mum. The method of preparation of this rare earth sulphide is characterized in that a rare earth compound is reacted with at least one sulphidizing gas selected among hydrogen sulphide or carbon sulphide. The pigment can be part of compositions of the following types: plastic, paint, surface coating, rubber, ceramic, glazing, paper, ink, cosmetic products, dyes, leather, laminated coating or other types of compositions with a base of at least one mineral binder or obtained therefrom.

Description

Beta rare earth sulphide is as purposes of tinting pigment and preparation method thereof
The present invention relates to a kind of beta rare earth sulphide as the application of tinting pigment and the preparation method of this beta rare earth sulphide.
Inorganic coloring pigment has been widely used in many industrial circles, particularly in paint, plastics and the ceramic field.In these are used, when selecting suitable pigment, consider various performances, particularly heat and/or chemical stability, dispersiveness (product directly is dispersed in ability in the given medium), with dielectric compatibility to be colored, true qualities, tinting strength and hiding power, above all properties constitutes the standard of pigment particularly important.
Yet, be applicable to that above purposes and the present most of mineral dyes that really reach the industrial applications degree all have problems.This be because they usually use more and more be subjected to strict restriction in addition in many countries through the disabled metal (particularly cadmium, lead, chromium and cobalt) of legislation, and these metals are considered to have than high toxicity.
Find out thus: the inorganic replacement pigment of development of new is very urgent.
Purpose of the present invention just provides such pigment, particularly red pigment, and purplish red pigment more especially.
According to first kind of technical scheme of the present invention, the invention provides a kind of preparation method of beta rare earth sulphide, this rare earth metal is lanthanum, cerium, praseodymium, samarium or neodymium, wherein makes carbonate or the subcarbonate and the hydrogen sulfide reaction of rare earth metal.
According to second kind of technical scheme of the present invention, this method feature is: make rare earth compound and be the sulfiding gas mixture reaction of base with hydrogen sulfide and dithiocarbonic anhydride.
The present invention can be used for the sulfide for preparing lanthanum sulfide, cerium sulphide, praseodymium sulfide, samaric sulfide Sm2S3 or neodymium sulfide and mixed sulfides thereof, that is to say above two or more rare earth metals.Therefore, be equally applicable to mixed sulfides about the narration of simple sulfide below.
Under the situation of first technical scheme, this method feature is: make the reaction of rare earth metal carbonate or subcarbonate and hydrogen sulfide.
According to second technical scheme of the present invention, use the mixture of two kinds of gases.Need point out: by changing the color that oxygen level in this sulfide can change this sulfide.And can change this oxygen level by the dithiocarbonic anhydride content that changes in the gaseous mixture.Therefore, under all identical condition of other all processing parameters, higher dithiocarbonic anhydride content has promoted the generation of the sulfide that oxygen level is lower.That is to say that product has than bright color, as bright purplish red.Opposite higher hydrogen sulfide content can obtain the higher product of oxygen concn, thereby makes it have darker color.
Sulfiding gas or sulfiding gas mixture can use with rare gas element such as argon gas or nitrogen.
In second technical scheme, react employed rare earth compound and be preferably carbonate or subcarbonate.By the way nitrate also can.Also can use rare-earth oxide.
Vulcanization reaction usually 600-1000 ℃, preferred 600-800 ℃, particularly carry out or near this temperature, carry out under 800 ℃ the temperature.
Typically be 1-4 hour corresponding to obtaining the reaction times of required sulfide between in case of necessity.
When heating finishes, recyclable formed sulfide.If wish to obtain the less product of particle diameter, can grind to sulfide.Under the condition of appropriateness, grind, for example under the condition of appropriateness, adopt wet-milling mill or air spray grinding, can obtain particularly to show the sulfide that median size is not more than 1.5 μ m like this.
The rare earth sulphide that obtains with the inventive method is a kind of sulfide that shows beta-crystal.To be interpreted as that a kind of general formula is Ce at this used beta-crystal 10S 14O XS 1-XCompound, wherein X is 0-1, does not comprise 0; By the tetragonal spheroidal crystallization; Be I 4 1/ acd spacer.
The feature of the sulfide that obtains with the inventive method is: it is made up of whole crystal.These crystal formation aggregates, and these aggregates constitute the powder of producing with the inventive method." whole crystal " is interpreted as do not have fragmentation or disruptive crystal.In fact during grinding, can make crystal fracture or break.The electron scanning micrograph of product of the present invention can show: the crystal that constitutes this product does not break usually.
The aggregate that constitutes sulfide shows its median size usually and is not more than 1.5 μ m.This median size usually is not more than 1 μ m, and is not more than 0.8 μ m more in particular.In whole specification sheets, measure characteristics such as particle diameter and size distribution with laser diffraction technology and Cilas HR850 particle diameter instrument (volume distributed median).
Also need point out: can grind the sulfide that obtains with the inventive method.The sulfide of the aggregate form that the numerical value that therefore can directly not provide median size to provide in the above is interior.In this case, can make aggregate form agglomerate and/or carry out light-burned.And make it to have median size greater than above-mentioned numerical value.Under the condition of appropriateness, simply grind can obtain that median size is not more than 1.5 μ m or the scope that provides in the above in aggregate.
According to specific technical scheme, can provide pure phase attitude, the sulfide of single β phase form as defined above.
In addition, the sulfide that obtains with the inventive method can show various oxygen level.This content is used with respect to the oxygen weight of whole sulfide weight and is represented to be not more than 0.8%.
At rare earth metal is that sulfide is usually expressed as purplish red under the situation of cerium.According to a specific technical scheme, cerium sulphide shows and is less than 40 trichromatic coefficient L* and less than 0.6 b*/a* ratio.Trichromatic coefficient L*, a* and the b* of (in whole specification sheets) herein in CIE1976 system (L*, a* and b*), have been provided.They are by Commission Internationald ' Eclairage[International Commission on Illumination] define, and be set forth in Recueil desmormes Francaises[normes Francaises summary] (AFNOR), among colorimetric color No.X08-12, the No.X08-14 (1983).Use the colorimeter of selling by Company Pacific Scientific to determine these parameters.Light source characteristic is D 65Observing the surface is that surface-area is 12.5 square centimeters a ring segment.Observation condition corresponding in aperture angle be 10 the degree situations under observe.In given measurement, do not use mirror element.
The various selectable forms of the present invention are described now.
According to first kind of selectable form, above-mentioned sulfide also comprises the thin layer of at least a transparent oxide base in addition, and this veneer is on sulfide surface, or around it.For such product, also can be referring to french patent application FR-A-2703999.
This thin layer that is coated in around the sulfide can not be totally continuous or uniform fully.Yet preferably, the sulfide in this technical scheme comprises evenly, controllable thickness and the sulfide primitive color before applying do not had dysgenic transparent oxide coating.
With " transparent oxide " in case be interpreted as a kind of thin layer form with more or less and be deposited on the sulfide, its only degree very littlely absorb visible light or do not absorb visible light, and can not produce the oxide compound that hides or very slight covering is only arranged to the original true qualities of said sulfide.In addition, need point out: term used herein " oxide compound " should be interpreted as it also comprises hydrous oxide.
These oxide compounds or hydrous oxide be unformed and/or crystal type.
As the example of such oxide compound, what can list more especially has silicon oxide (silicon-dioxide), aluminum oxide (aluminium sesquioxide), zirconium white (zirconium dioxide), titanium oxide, a zirconium silicate ZrSiO 4(zircon) and rare-earth oxide.According to a kind of preferred optional form, coating is a silicon dioxide base.And more advantageously: this coating is mainly formed, preferably only is made up of silicon-dioxide by silicon-dioxide.
According to another selectable form, this sulfide also can comprise fluorine atom in addition.
In this case, at the arrangement of fluorine atom, also can be referring to french patent application FR-A-2706476.
Fluoridize sulfide and can show at least a following properties:
The distribution of-fluorine atom is the concentration gradient that reduces gradually by surface to the core place of said sulfide.
-fluorine atom mainly is distributed in the neighboring of sulfide, in the case, the neighboring is interpreted as from particle surface begin to measure the zone that material thickness is hundreds of dusts.In addition, " mainly " is interpreted as: find greater than 50% be present in fluorine atom in the sulfide in said outer circumference.
-the weight percentage that is present in the fluorine atom in the sulfide is no more than 10%, is no more than 5% and be preferably.
-fluorine atom exists with the form of fluorine cpd or fluorine sulphur compound, particularly exists with the fluorine cpd of rare earth metal or the form of rare earth metal fluorine sulphur compound (sulfo-fluorochemical).
Certainly, the present invention can combine above-mentioned various technical schemes.Like this.Can estimate that sulfide comprises thin oxide layer, also comprise fluorine atom in addition.
The preparation method of the sulfide of these optional forms is described now.
For above-mentioned first kind of optional form, that is to say that sulfide shows transparent thin oxide layer, the precursor that the preparation method can comprise the sulfide that will obtain behind the vulcanization reaction and form the transparent oxide of thin layer is put together, and is settled out this oxide compound.The method and the employed precursor that precipitate this oxide compound have particularly been described in FR-A-2703999.
Under the situation of silicon-dioxide, can list by the hydrolysis alkyl silicate and prepare silicon-dioxide, by with water, alcohol, sulfide (being suspended subsequently) thereby and optional a kind of alkali mix and form reaction mixture, then add alkyl silicate; Also can prepare silicon-dioxide by silicate and a kind of acid-respons that makes sulfide, silicate, alkalimetal silicate type.
Under the situation of alumina base thin layer, can make sulfide, aluminate and a kind of acid-respons, thereby be settled out aluminum oxide.By sulfide, aluminium salt and a kind of alkali being put together and making their reactions also can obtain this throw out.
At last, also can form aluminum oxide by hydrolysis of aluminum alkoxide.
For titanium oxide, by in the aqeous suspension of sulfide of the present invention, adding titanium salt such as TiCl on the one hand 4, TiOCl 2Or TiOSO 4, a kind of alkali is precipitable to go out titanium oxide and add on the other hand.For example, also can carry out the preparation of titanium oxide by hydrolysis alkyl titanate or precipitated titanium colloidal sol.
At last, under the situation of zirconia base thin layer, the suspension by cohydrolysis or co-precipitation sulfide in the presence of organo-metallic zirconium compounds such as zirconium alkoxide, for example zirconium iso-propoxide can carry out zirconic preparation.
But according to second kind of selection mode (sulfide comprises fluorine atom), the preparation method of sulfide uses flaorination process.
Can fluoridize according to any known technology, the sulfide and a kind of fluorizating agent that are about to obtain behind the vulcanization reaction are put together.
Particularly, but fluorizating agent liquid, solid or gas.Preferably, fluoridizing is that fluorizating agent is to carry out under the treatment condition of liquid or gas therein.
Example as being suitable for carrying out the fluorizating agent that the present invention handles can list: fluorine F more especially 2, alkaline metal fluoride cpd, Neutral ammonium fluoride, noble gas fluoride thing, Nitrogen trifluoride NF 3, boron fluoride BF 3, tetrafluoromethane or hydrofluoric acid HF.
With fluoridizing under the situation that atmosphere handles, available pure or with the fluorizating agent of neutral gas such as nitrogen dilution.
Selective reaction condition preferably like this, promptly said processing only make to fluoridize (appropriate condition) take place on sulfide surface.In this respect, when fluoridizing when proceeding to sulfide core place,, can not produce obvious improved effect with respect to main fluoridizing of taking place from the teeth outwards.In fact, can monitor the degree that fluoridation is carried out by experience, the variation that for example, increases (causing weight to increase owing to progressively introduce fluorine) by measuring material weight is monitored it.
Fluorizating agent is Neutral ammonium fluoride more in particular.
As mentioned above, can estimate to prepare with various technical scheme constitutive characteristics: the sulfide that exists thin oxide layer and fluorine atom to combine.In order to obtain such combination, the various preparation methods that described are combined.
Therefore, in the first step, can carry out fluoridation.Subsequently, in second step, the sulfide of so handling put together with the transparent oxide precursor to be contacted, and precipitates transparent oxide on said sulfide.
Estimate also can use other method.In this case, in the first step, sulfide put together with the transparent oxide precursor to be contacted, and precipitates transparent oxide subsequently on said sulfide, then, in last step, carries out fluoridation.
Sulfide of the present invention can further handle as the sulfide of the present invention that obtains with sulfiding gas or gaseous mixture reaction back so that deposition zinc precursor in the above.Can carry out this precipitation by making the reaction of zinc precursor and ammoniacal liquor or ammonium salt.For such processing, can be referring to french patent application FR-A-2741629, its content is hereby incorporated by.Recall this below and handle some necessary factors.
Zinc oxide or zinc hydroxide that the zinc precursor uses with form of suspension.This precursor is zinc salt, preferably soluble salt also.It is inorganic acid salt such as muriate, also organic acid salt such as acetate.
For the deposition zinc compound, the contact of under the situation that alcohol exists, sulfide, zinc precursor, ammoniacal liquor and/or ammonium salt being put together.Used alcohol is selected from Fatty Alcohol(C12-C14 and C12-C18) such as butanols or ethanol usually.Can with the form of pure zinc solution alcohol be introduced with the zinc precursor especially.
According to the favourable and different mode of another kind, the contact of under the situation that dispersion agent exists sulfide, zinc precursor, ammoniacal liquor and/or ammonium salt being put together, the purpose of dispersion agent are that to prevent to form the particle aggregation of carrier in the process of they being put into the suspension that is used for above-mentioned processing agglomerating.It also makes and can operate in denseer medium.Promoted on whole particle, to form uniform transparent thin oxide layer like this.
Dispersion agent can be selected from the dispersive dispersion agent by steric effect, and the particularly non-ionic polymkeric substance that is dissolved in organism or water.The dispersion agent that can list is Mierocrystalline cellulose and derivative thereof; Polyacrylamide; Polyethylene oxide; Polyoxyethylene glycol; Polyoxyethylene polyoxypropylene alcohol; Polyacrylic ester; Polyoxyethylene alkylphenol; The polyoxyethylene long-chain alcohol; Polyvinyl alcohol; Alkanolamide; Polyvinylpyrrolidone dispersion agent and synthesising biological polymeric gel compound.
Described sulfide has good tinting strength and hiding power, and for this reason, it is suitable for the painted of a lot of materials such as plastics, paint etc.
More in particular, it can be used for the painted of thermoplasticity or thermosetting resin polymkeric substance.
As carrying out painted thermoplastic resin according to the present invention, can list (only being used for explanation) poly-(vinylchlorid), poly-(vinyl alcohol), polystyrene, styrene butadiene, styrene-acrylonitrile, acrylonitrile-butadiene-styrene (ABS) (A.B.S) multipolymer, acrylate copolymer, particularly poly-(methyl methacrylate), polyolefine such as polyethylene, polypropylene, polybutene or polymethylpentene, derivatived cellulose such as cellulose acetate ester, acetobutyric acid cellulose ester or ethyl cellulose, or comprise the polymeric amide of polymeric amide-6,6.
For the thermosetting resin that also is suitable for sulfide, for example, can list phenoplast, aminoplastics, particularly melocol or melamine-copolyoxymethylenes, Resins, epoxy, or thermosetting polyester.
Also sulfide can be used in the specific polymers, as fluorinated polymer, tetrafluoroethylene (P.T.F.E) particularly, polycarbonate, silicone elastomer or polyimide.
In making the application-specific of coloring plastic, sulfide can directly use with form of powder.Preferably.Its also can be pre-dispersed form use, for example,, or use feasible like this can it adding in any stage of production of resins with the form of underflow or dope with itself and resin premixed the closing of a part.
Therefore, product of the present invention can be generally the part by weight of 0.01-5% (with respect to final product) or under the situation of enriched material the part by weight with 20-70% join plastics, in above-mentioned plastics.
Product of the present invention also can be used in paint or the varnish, and is used in more especially in the following resin: Synolac, it is prevailing is the glyceryl phthalate resin; With long oil or short oil modified resins; From vinylformic acid (methyl or ethyl) ester and methacrylic ester the deutero-acrylic resin, it can be at random and ethyl propenoate, vinylformic acid 2-b hexyl or butyl acrylate copolymerization; Vinylite, as polyvinyl acetate, polyvinyl chloride, poly-(vinyl butyral), polyvinylformal, and vinylchlorid and vinyl-acetic ester or dichloroethylene; Phenoplast or aminoplast(ic) resin (being modified usually); Vibrin; Urethane resin; Resins, epoxy; Or silicone resin.
The common consumption of this product is 5-30%, the 0.1-5% of varnish weight of paint weight.
In addition, product of the present invention also is applicable to dyestuff, kitchen and other workplace surface laminated coating, pottery and the glaze that is used for cover in rubber, particularly earth material, paper and printing-ink, makeup and many other fields such as the leather.
It is the painted of material base or that obtained by at least a inorganic jointing compound that product of the present invention also can be used on at least a inorganic jointing compound.
This inorganic jointing compound can typically be selected from hydraulic binding agent, air-setting jointing compound, gypsum and anhydrous or partially hydrated calcium sulfate type jointing compound.
" hydraulic binding agent " is interpreted as after adding entry formation water-insoluble hydrate to have the material that solidifies with hardening characteristics.Product of the present invention is used for cement and very especially by add concrete painted that entry, sand and/or gravel form to cement.
Within the scope of the present invention, for example, but the cement high-alumina cement promptly contains the aluminum oxide of higher proportion or any cement of aluminate or aluminum oxide and aluminate.As an example, can list aluminous cement, particularly its Secar cement.
Cement is silicate cement also, and Calucium Silicate powder cement more in particular.The example that can provide is a portland cement, in this kind cement, has fast hard and ultrafast hard portland cement, white cement, sulphate-resistant cement and comprise blast-furnace slag and/or the portland cement of flyash and/or metakaolin.
Also can list calcium sulphate hemihydrate cement and be the magnesia cement that is known as Sorel cement.
Product of the present invention also can be used for the painted of air-setting jointing compound, that is to say, passes through CO 2Effect can hardened in air jointing compound, as calcium oxide or magnesium oxide or calcium hydroxide or magnesium hydroxide type jointing compound.
At last.Product of the present invention can be used for gypsum and anhydrous calciumsulphate or partially hydrated calcium sulfate (CaSO 4And CaSO 41/2HO 2) jointing compound painted.
Therefore, the invention provides a kind of material, particularly plastics, paint, varnish, rubber, pottery, glaze, paper, printing ink, makeup, dyestuff, leather or lamination coating or be the coloured composition of material base or that obtain from least a inorganic jointing compound with at least a inorganic jointing compound, said composition comprises as tinting pigment and as defined above or pass through the sulfide that aforesaid method obtains.
Following examples further specify the present invention, in these embodiments, determine particle diameter according to above-mentioned technique means.This product is dispersed in the aqueous solution that contains 0.05 weight % Sodium hexametaphosphate 99 measures, the aqueous solution is used ultrasonic probe (the probe tip diameter is 13 millimeters, 20kHz, 120W) to carry out handling to reach 3 minutes in advance.Embodiment 1
Synthetic β-Ce 10S 14O 0.17S 0.03(bright red sulfide) process
Make H 2S (flow velocity=10 liter/hour) and CS 2Contain 70.7%CeO according to following temperature range calcining 16 grams under (flow velocity=1.4 liter/hour) mobile situation 2Basic carbonate cerium (Ce (OH) CO 3): with 8 ℃/minute speed temperature is risen to 800 ℃, under this temperature, kept 1 hour subsequently.The result:
Obtain the product (existing according to the form of X-ray diffraction method of masurement with single phase) that 13 grams have the general formula that provides above, its oxygen level is 0.15 weight % (determining according to unit cell parameters).
The particle diameter that obtains is 0.74 μ m (σ/m=0.49).
The color of determining with the CIE pilot system is:
L*/a*/b*＝38.9/36.3/16.7。
Absorption in 400 and 700 nanometers is as follows:
R400/R700＝5.06/65.63。
In the container of rotation with 10 gram synthetic pigment like this and 2 kilograms with reference to polypropylene Eltex PHV001 mixes.Inject this mixture with Kapsa injection molding machine (model Protoject10/10, the cycle is 41 seconds) down at 220 ℃ subsequently.
So obtain a kind of test sample of two-thickness (2 and 4 millimeters) of parallelepiped.
Observing this pigment can disperse well.Measure this coupons than thickness portion, trichromatic coefficient and absorption are as follows:
L*/a*/b*＝33.5/39.6/20.6。
R400/R700＝2.4/60.2。Embodiment 2
Synthetic β-Ce 10S 14O 0.8S 0.2(dark-red sulfide) process
Make H 2Contain 70.7%CeO according to following temperature range calcining 14 grams under S (flow velocity=10 liter/hour) the mobile situation 2Basic carbonate cerium (Ce (OH) CO 3): with 8 ℃/minute speed temperature is risen to 800 ℃, under this temperature, kept 3 hours subsequently.The result:
Obtain the product (existing according to the form of X-ray diffraction method of masurement with single phase) that 11.2 grams have the general formula that provides above, its oxygen level is 0.69 weight % (determining according to unit cell parameters).
The particle diameter that obtains is 0.76 μ m (σ/m=0.44).
Color and the absorption determined with the CIE pilot system are:
L*/a*/b*＝36.1/27.4/12。
R400/R700＝5.06/64.35。
Behind injection polypropylene under the condition of embodiment 1, color and absorption become:
L*/a*/b*＝29.7/31.4/16.4。
R400/R700＝2.05/59.5。
Following embodiment relates to some and carry out complementary processing so that obtain the product of transparent oxide layer and deposition zinc or fluorine after its preparation.
The processing of deposited oxide layer and adding zinc is as follows:
Polyvinylpyrrolidone is dissolved in the ethanol.
In this solution, add the fluorizated cerium sulphide, add ammonia soln subsequently, add the zinc precursor at last.In two hours, add tetraethyl silicate continuously.After adding tetraethyl silicate, this mixture of slaking reaches two hours.Clean the particle that so obtains by filtering with ethanol, and subsequently 50 ℃ dry 12 hours down.Embodiment 3
Present embodiment relates to the product of embodiment 2.
Use each reactant in following ratio:
Gram (product)/kilogram (suspension) β-Ce 10S 14O 0.8S 0.220095% ethanol, 643 ammoniacal liquor (32%) 100 zinc oxide, 20 tetraethyl silicate 32PVP K10 (Aldrich company) 5Mw=10000
Employed cerium sulphide is fluoridized in advance according to the following procedure: 10 gram products are joined 100 milliliters of ammonium fluoride solutions (with respect to β-Ce 10S 14O 0.8S 0.2Be 5 weight %) in.
By adding ammonia soln the PH of this mixture is transferred to 8, and agitated medium reaches 1 hour.Then filter this product, and in moisture eliminator, under vacuum condition, carry out drying subsequently.
Handle the product that so obtains in the above under the operational condition that provides.
The product that is obtained has following trichromatic coefficient after in being expelled to polypropylene:
L*/a*/b*＝36/20/10。Embodiment 4
Present embodiment relates to the product of embodiment 1.
Use each reactant in following ratio:
Gram (product)/kilogram (suspension) β-Ce 10S 14O 0.17S 0.8320095% ethanol, 643 ammoniacal liquor (32%) 100 zinc oxide, 20 tetraethyl silicate 32PVP K40 (Aldrich company) 5Mw=10000
Employed cerium sulphide is fluoridized in advance according to the following procedure: 10 gram products are joined 100 milliliters of ammonium fluoride solutions (with respect to β-Ce 10S 14O 0.17S 0.83Be 5 weight %) in.
By adding ammonia soln the PH of this mixture is transferred to 8, and agitated medium reaches 1 hour.Then filter this product, and in moisture eliminator, under vacuum condition, carry out drying subsequently.
Handle the product that so obtains in the above under the operational condition that provides.
The product that is obtained has following trichromatic coefficient after in being expelled to polypropylene:
L*/a*/b*＝38/33/15。

Claims (10)

1. the preparation method of a beta rare earth sulphide, this rare earth metal is lanthanum, cerium, praseodymium, samarium or neodymium, it is characterized in that: make carbonate or the subcarbonate and the hydrogen sulfide reaction of rare earth metal.
2. the preparation method of a beta rare earth sulphide, this rare earth metal is lanthanum, cerium, praseodymium, samarium or neodymium, it is characterized in that: make the compound of rare earth metal and the sulfiding gas mixture reaction of hydrogen sulfide and dithiocarbonic anhydride.
3. the method for claim 2, it is characterized in that: rare earth compound is carbonate or subcarbonate.
4. claim 2 or 3 method is characterized in that: by changing the oxygen level that dithiocarbonic anhydride content in the gaseous mixture changes prepared sulfide.
5. any one method during aforesaid right requires is characterized in that: react under 600 ℃-800 ℃ temperature.
6. any one method during aforesaid right requires is characterized in that: will put together with the transparent oxide precursor with the sulfide that sulfiding gas or gaseous mixture reaction back obtain contacts so that deposit this oxide compound on sulfide.
7. any one method of claim 1-6 is characterized in that contacting putting together with fluorizating agent with the sulfide that sulfiding gas or gaseous mixture reaction back obtain.
8. any one method of claim 1-7 is characterized in that: by making the reaction of zinc precursor and ammoniacal liquor or ammonium salt zn cpds is deposited on the sulfide that obtains with sulfiding gas or gaseous mixture reaction back.
9. a sulfide that obtains with the method for above-mentioned any one claim is as the purposes of tinting pigment.
10. make material such as plastics, paint, varnish, rubber, pottery, glaze, paper, printing ink, makeup, dyestuff, leather or lamination coating or be the painted composition of material base or that obtain from least a inorganic jointing compound with at least a inorganic jointing compound, it is characterized in that: they prepare with the sulfide that the method for above-mentioned claim 1-8 obtains.
CN97181084A 1996-11-19 1997-11-10 Use of a beta rare earth sulphide as colouring pigment and method for preparing same Expired - Fee Related CN1087273C (en)

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FR96/14058 1996-11-19

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CN102127317A (en) * 2011-01-20 2011-07-20 中国科学院长春应用化学研究所 Rare earth colorant and preparation method thereof
CN102127317B (en) * 2011-01-20 2013-04-17 中国科学院长春应用化学研究所 Rare earth colorant and preparation method thereof
CN103011241A (en) * 2012-12-31 2013-04-03 江西理工大学 Rare-earth praseodymium lamellar crystal and preparation method for same
CN103011241B (en) * 2012-12-31 2015-03-18 江西理工大学 Rare-earth praseodymium lamellar crystal and preparation method for same
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CN103965522A (en) * 2014-04-15 2014-08-06 包头市宏博科技有限责任公司 Tombarthite sulfide rubber ingredient and preparation method for rubber composite material
CN103965522B (en) * 2014-04-15 2016-08-17 包头市宏博科技有限责任公司 A kind of rare-earth sulfide rubber chemicals and preparation method thereof
CN106517295A (en) * 2016-10-18 2017-03-22 西北工业大学 Method for synthesizing high-stability gamma-Pr2S3 powder
CN108084736A (en) * 2017-12-19 2018-05-29 中国科学院包头稀土研发中心 A kind of technique of simple pollution-free processing rare earth sulfide pigment
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CN109651846A (en) * 2017-12-28 2019-04-19 包头市宏博特科技有限责任公司 A kind of post-processing approach of rare-earth sulfide
CN109651846B (en) * 2017-12-28 2021-01-05 包头市宏博特科技有限责任公司 Post-treatment method of rare earth sulfide
CN108715549A (en) * 2018-06-05 2018-10-30 西北工业大学 It is a kind of to prepare rare-earth sulfide γ-Ln2S3The method of crystalline ceramics
CN116143160A (en) * 2023-02-08 2023-05-23 包头市宏博特科技有限责任公司 Rare earth sulfide with wave absorbing characteristic and preparation method thereof

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