ES2351468B1 - PROCEDURE FOR THE PREPARATION OF AN ORGANIC NANOCRISTALINE-COLORING CALCIUM HYBRID CERAMIC MATERIAL. - Google Patents
PROCEDURE FOR THE PREPARATION OF AN ORGANIC NANOCRISTALINE-COLORING CALCIUM HYBRID CERAMIC MATERIAL. Download PDFInfo
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- ES2351468B1 ES2351468B1 ES200901633A ES200901633A ES2351468B1 ES 2351468 B1 ES2351468 B1 ES 2351468B1 ES 200901633 A ES200901633 A ES 200901633A ES 200901633 A ES200901633 A ES 200901633A ES 2351468 B1 ES2351468 B1 ES 2351468B1
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- Prior art keywords
- calcium phosphate
- pigment
- organic dye
- preparation
- hybrid
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- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011575 calcium Substances 0.000 title claims abstract description 11
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910010293 ceramic material Inorganic materials 0.000 title description 2
- 238000004040 coloring Methods 0.000 title 1
- 239000000975 dye Substances 0.000 claims abstract description 50
- 239000000049 pigment Substances 0.000 claims abstract description 32
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 27
- 235000011010 calcium phosphates Nutrition 0.000 claims abstract description 27
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 27
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 26
- 239000000919 ceramic Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004568 cement Substances 0.000 claims abstract description 7
- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-nitrobenzaldehyde Chemical class [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004753 textile Substances 0.000 claims abstract description 4
- 238000009833 condensation Methods 0.000 claims abstract description 3
- 230000005494 condensation Effects 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 150000002739 metals Chemical class 0.000 claims abstract description 3
- 239000004068 calcium phosphate ceramic Substances 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000003980 solgel method Methods 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 239000003093 cationic surfactant Substances 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- -1 clays Substances 0.000 claims description 3
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 claims description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012860 organic pigment Substances 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 3
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 claims description 2
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- KDQPSPMLNJTZAL-UHFFFAOYSA-L disodium hydrogenphosphate dihydrate Chemical compound O.O.[Na+].[Na+].OP([O-])([O-])=O KDQPSPMLNJTZAL-UHFFFAOYSA-L 0.000 claims description 2
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 241000656145 Thyrsites atun Species 0.000 claims 2
- 239000000725 suspension Substances 0.000 claims 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims 1
- 229910000019 calcium carbonate Inorganic materials 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims 1
- 229910052622 kaolinite Inorganic materials 0.000 claims 1
- 239000004922 lacquer Substances 0.000 claims 1
- 235000011007 phosphoric acid Nutrition 0.000 claims 1
- 229910001848 post-transition metal Inorganic materials 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 229910052723 transition metal Inorganic materials 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 5
- 239000004005 microsphere Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 description 6
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052586 apatite Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229960005069 calcium Drugs 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 239000004053 dental implant Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical group [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910007676 ZnO—SiO2 Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 229940052299 calcium chloride dihydrate Drugs 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B59/00—Artificial dyes of unknown constitution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B51/00—Nitro or nitroso dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0092—Dyes in solid form
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/54—Pigments; Dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Cosmetics (AREA)
Abstract
Procedimiento para la preparación de un material híbrido cerámico de fosfato de calcio nanocristalino-colorante orgánico.#El pigmento híbrido preparado está formado por un colorante orgánico que funcionaliza y dirige la estructura de un cerámica de fosfato de calcio nanocristalina. El colorante orgánico se obtiene por condensación de un nitrobenzaldehido sustituido y se enlaza covalentemente y/o electrostáticamente a la matriz fosfato de calcio nanocristalino formando también microesferas que se sitúan en la matriz de fosfato cálcico.#Tanto el pigmento híbrido como el colorante orgánico no contienen metales y son resistentes al agua y pueden utilizarse en numerosas aplicaciones como colorantes de cementos, colorantes textiles y colorantes de otros productos de consumo.Procedure for the preparation of a ceramic hybrid nanocrystalline calcium phosphate-organic dye material. # The prepared hybrid pigment is formed by an organic dye that functionalizes and directs the structure of a nanocrystalline calcium phosphate ceramic. The organic dye is obtained by condensation of a substituted nitrobenzaldehyde and is covalently and / or electrostatically bound to the nanocrystalline calcium phosphate matrix also forming microspheres that are located in the calcium phosphate matrix. # Both the hybrid pigment and the organic dye do not contain metals and are water resistant and can be used in numerous applications such as cement dyes, textile dyes and dyes of other consumer products.
Description
Procedimiento parala preparaciónde un material híbrido cerámicode fosfatodecalcio nanocristalino-colorante orgánico. Procedure for the preparation of a hybrid ceramic nanocrystalline phosphate-organic dye material.
Sector de la técnica Technical sector
La presente invención se encuadra dentro del campo técnico defabricación pigmentosy colorantes. De manera más concreta, la invención se refiere a la preparación de pigmentos híbridos constituidos por un colorante orgánico que funcionalizaunfosfatodecalcio nanocristalinoypuedeaplicarsecomo colorantede cementos,textiles,productos generales de consumo, implantes dentales o células solares sensibles a los tintes. The present invention falls within the technical field of manufacturing pigments and dyes. More specifically, the invention relates to the preparation of hybrid pigments consisting of an organic dye that functionalizes a nanocrystalline calcium phosphate and can be applied as a dye from cements, textiles, general consumer products, dental implants or solar cells sensitive to dyes.
Estado del arte State of the art
Los pigmentos basados en materiales cerámicos son ampliamente utilizados para inducir color y/o opacidad a muchos artículos sintéticosy son generalmente incorporados como pequeñas partículasa pinturas, plásticosy otros materiales. Pigments based on ceramic materials are widely used to induce color and / or opacity to many synthetic items and are generally incorporated as small particles into paints, plastics and other materials.
Existen diferentes documentos donde se describen pigmentos cerámicos para una gran variedad de aplicaciones obtenidos por distintos procedimientos. There are different documents describing ceramic pigments for a wide variety of applications obtained by different procedures.
El documento EP02014451 describe un compuesto de fórmula general M5(AO)4X3 donde M es Ba, Sr, Ca o mezclade ambos,A esP,V o mezcladelos mismosyXrepresenta una mezcladeCu,O,OH−,F, Cl, Br, y/o I. El compuesto tiene estructura apatita conXsituadoenlos canaleshexagonalese incluyendo átomosdeCr.Para preparar el compuesto, se mezclanprecursores de los elementosM,AyXy después se sometela mezclaa un tratamiento térmico entre 200y1700ºC.El tono del color deseado se regula utilizando elementosMyAdiferentes.La presencia de cobre es una característica esencial del pigmento pues aporta brillo al color. El compuesto puede utilizarse como pigmento en pinturas, plásticosyotros materiales. EP02014451 describes a compound of general formula M5 (AO) 4X3 where M is Ba, Sr, Ca or mixture of both, A is P, V or mixture thereof and X represents a mixture of Cu, O, OH -, F, Cl, Br, and / or I. The compound has apatite structure with Xsituated in the hexagonal channels and including C atoms. To prepare the compound, precursors of the elements M, AyXy are then mixed, a thermal treatment is mixed between 200 and 1700 ° C. The tone of the desired color is regulated using elements My and Different. The presence of copper is a Essential characteristic of the pigment because it brings brightness to the color. The compound can be used as a pigment in paints, plastics and other materials.
US 6630019 se refierea colorantesde fosfatode calcio no tóxico para uso en alimentación,farmaciaycosmética, que incluyen fosfato de calcio, hidróxido de aluminioytintes. El fosfato de calcio está en forma de partículas recubiertas con hidróxido de aluminio que fija el tinte. US 6630019 refers to non-toxic calcium phosphate dyes for use in food, pharmaceuticals and cosmetics, including calcium phosphate, aluminum hydroxide and nitrates. Calcium phosphate is in the form of particles coated with aluminum hydroxide that fixes the dye.
En la literatura también se describen otros pigmentos cerámicos obtenidos por el método sol-gel basados en sistemas CoO-ZnO-SiO2 (Djambazov et al. Ceramics International 24, 1998).Partiendode disolucionesde precursores deZnyCoyde disolucióndeSiO2,se formaelgelpor gelificación.Paraqueel pigmento resultantetenga estructura cristalina es necesario realizar un tratamiento térmico por encima de 500ºC. Other ceramic pigments obtained by the sol-gel method based on CoO-ZnO-SiO2 systems (Djambazov et al. Ceramics International 24, 1998) are also described in the literature. Starting from solutions of precursors of ZnyCoyde dissolution of SiO2, the gel is formed by gelation. Crystalline heat treatment is necessary above 500ºC.
Yuanet al.(J. Phys. Chem. B, 2006, 110, 388-394) han descrito un método para recubrir partículas de pigmentos orgánicos con titanio,a travésde un procedimiento sol-gel, para mejorar su resistenciaala intemperiey su capacidad de dispersión en sistemas alagua. Yuanet al. (J. Phys. Chem. B, 2006, 110, 388-394) have described a method for coating organic pigment particles with titanium, through a sol-gel process, to improve their weather resistance and dispersibility in alagua systems.
Aunque en el mercado hay muchos compuestos que son eficazmente aplicados como pigmentos, sería deseable encontrar nuevos compuestos y mezclas que presenten colores brillantes y sean relativamente baratos, estables al calentamientoy a la luz, resistentes al agua, compatibles químicamente con los materiales deseados, no-tóxicos e inofensivos para el medio ambiente. Although there are many compounds on the market that are effectively applied as pigments, it would be desirable to find new compounds and mixtures that have bright colors and are relatively cheap, stable to heating and light, water resistant, chemically compatible with the desired materials, not Toxic and harmless to the environment.
Paraello,la presenteinvenciónse refiereapigmentos híbridosorgánicos-inorgánicos basadosenfosfatosde calcio. El colorante por símismo o el pigmento híbrido podrían ser una alternativa a los colorantes existentes basados en el grupo azo (-N=N-). Los compuestos azo pueden producir efectos indeseados (como reacciones alérgicas o presentar carácter cancerígeno) por lo que muchos de ellos han sido prohibidos. For this, the present invention is inorganic-inorganic hybrid rerefigments based on calcium phosphates. The dye by itself or the hybrid pigment could be an alternative to the existing dyes based on the azo group (-N = N-). Azo compounds can produce unwanted effects (such as allergic reactions or have a carcinogenic nature) and therefore many of them have been banned.
El colorante objetodela presenteinvención no contiene ningún grupo azoyel pigmento híbrido colorante-apatita tampoco contiene iones metálicos con posibles efectos nocivos para lo seres vivos como aluminio o cromo, habitualmente presentes en otros colorantes, lo que supone una ventaja desde el punto de vista ambiental. The dye object of the present invention does not contain any azo group and the hybrid pigment dye-apatite does not contain metal ions with possible harmful effects for living things such as aluminum or chromium, usually present in other dyes, which is an advantage from the environmental point of view.
Descripción Description
El material híbrido al que se refiere la presente invención es un nanocomposite fosfato de calcio (con estructura apatita)-colorante orgánico que se obtiene mediante un sencillo método sol-gel. El proceso se realiza a temperaturas entre30y120ºCyel materialhíbrido final presenta una matriz uniformea escala nanométrica. The hybrid material referred to in the present invention is a calcium phosphate nanocomposite (with apatite structure) -organic color obtained by a simple sol-gel method. The process is carried out at temperatures between 30 and 120 ° C and the final hybrid material has a uniform matrix at a nanometric scale.
En una primera etapa, una disolución acuosa de una sal precursora de fosfato se calienta a una temperatura 30120ºCyagita en presenciade un surfactante catiónico. Este surfactante catiónico puede ser un surfactantede amonio cuaternario como bromuro de deciltrimetil amonio [CH3(CH2)9N(CH3)3Br], bromuro de dodeciltrimetil amonio [CH3 (CH2)11N(CH3)3Br], cloruro de dodeciltrimetil amonio [CH3(CH2)11N(CH3)3Cl], bromuro de tetradeciltrimetil amonio [CH3(CH2)13N(Br)(CH3)3], cloruro de tetradeciltrimetil amonio [CH3(CH2)13N(Cl)(CH3)3], bromuro de hexadeciltrimetil amonio[CH3(CH2)15N(Br)(CH3)3]o clorurodehexadeciltrimetilamonio[CH3(CH2)15N(Cl)(CH3)3]. In a first stage, an aqueous solution of a phosphate precursor salt is heated to a temperature of 30120 ° C and in the presence of a cationic surfactant. This cationic surfactant can be a quaternary ammonium surfactant such as decyltrimethyl ammonium bromide [CH3 (CH2) 9N (CH3) 3Br], dodecyltrimethyl ammonium bromide [CH3 (CH2) 11N (CH3) 3Br], dodecyltrimethyl ammonium chloride [CH3 (CH2 (CH2 (CH2) ) 11N (CH3) 3Cl], tetradecyltrimethyl ammonium bromide [CH3 (CH2) 13N (Br) (CH3) 3], tetradecyltrimethyl ammonium chloride [CH3 (CH2) 13N (Cl) (CH3) 3], hexadecyltrimethyl ammonium bromide [CH3 (CH2) 15N (Br) (CH3) 3] or chloridedehexadecyltrimethylammonium [CH3 (CH2) 15N (Cl) (CH3) 3].
A continuación, se añade un nitrobenzaldehído sustituido disuelto en un alcohol de bajo peso molecular (como metanolo etanol)y se agitala mezcla. Unavez completada esta etapa, se disminuyela temperatura hasta alcanzar 40-80ºCy se llevaala mezcla hasta unpH básico próximoa 10.En este medio básico, comienzaun procesode condensación dondeseformaun colorante poliméricoorgánico presente principalmenteen formade esferasytambién como entidades poliméricas disueltas. Next, a substituted nitrobenzaldehyde dissolved in a low molecular weight alcohol (such as methanol or ethanol) is added and the mixture is stirred. Once this stage is completed, the temperature is lowered to 40-80 ° C and the mixture is brought to a basic level near 10. In this basic medium, a condensation process begins where a polymeric organic dye is formed mainly in the form of spheres and also as dissolved polymeric entities.
Sobre la mezcla resultante se añade una sal precursora de calcio. A calcium precursor salt is added to the resulting mixture.
Se obtiene así un gel del que se recupera el pigmento híbrido fosfato de calcio nanocristalino -colorante orgánico. A gel is thus obtained from which the nanocrystalline calcium phosphate hybrid pigment -organic organic pigment is recovered.
El colorantese enlazacovalentementey/o electrostáticamenteala matrizdefosfatode calcio nanocristalinoytambiénforma microesferas.Las microesferasdepigmentoestán distribuidashomogéneamenteenunamatrizypermitirán obteneruna macroporosidaduniformeenel material (diámetrodeporo entre2,5y4,7 µm) tras su extracción. The dye is covalently and / or electrostatically bonded to the nanocrystalline calcium phosphate matrix and also forms microspheres.The pigment microspheres are homogeneously distributed in a matrix and will allow to obtain a uniform macroporosity in the material (pore diameter between 2.5 and 4.7 µm) after their extraction.
Elpigmento híbrido resultanteno contieneningúnión metálicoque induzcacolor.El colorantepurotieneunpunto de fusión de alrededor de 230ºC pero soporta temperaturas de 250ºC sin descomponerse. The resulting hybrid pigment does not contain any metallic bond that induces color. The dye has a melting point of about 230 ° C but withstands temperatures of 250 ° C without decomposing.
Laapatitapuedesermolidaomezcladacon arcillaoyeso(sulfatodecalcio)segúnsu aplicación.El híbridoapatitacoloranteorgánicopodría también utilizarseen otros materiales compuestos, resinas, porcelanasymetales.El cemento ordinario es de color gris pero también existe cemento blanco. El colorante o el sistema híbrido apatita-colorante orgánico podrían utilizarse como un colorante duradero (resistente al agua) para sistemas de cemento (cementosde uso generalyclinkers). Lapatita can be demolished with clay or clay (calcium sulfate) according to its application. The hybrid organic-colored clay could also be used in other composite materials, resins, porcelain and metals. Ordinary cement is gray but there is also white cement. The dye or the organic apatite-dye hybrid system could be used as a durable dye (water resistant) for cement systems (general-purpose cement and clinkers).
Además, dado que el colorante orgánico parece ser térmicamente estable hasta 230ºC, podría aplicare en otros campos, tales como la industria textil, que requiere colorantes estables hasta 220ºC-245ºC. In addition, since the organic dye appears to be thermally stable up to 230 ° C, it could be applied in other fields, such as the textile industry, which requires stable dyes up to 220 ° C-245 ° C.
Por otra parte, tanto el colorante orgánico como el pigmento híbrido pueden utilizarse en productos generales de consumo, tales como pigmentos alimentos, fármacos o cosméticos. On the other hand, both the organic dye and the hybrid pigment can be used in general consumer products, such as food, drug or cosmetic pigments.
El pigmento híbrido también puede aplicarse como implante dental coloreado para recubrir la parte gingival del diente. The hybrid pigment can also be applied as a colored dental implant to coat the gingival part of the tooth.
El colorante orgánico o el pigmento híbrido pueden aplicarse en el campo de las “dye-sensitizied solar cells” (DSSCs). The organic dye or hybrid pigment can be applied in the field of "dye-sensitizied solar cells" (DSSCs).
Breve descripción de las figuras Brief description of the fi gures
LaFigura1muestraunamicrografíaobtenidapormicroscopía electrónicadebarridodelpigmentohíbridofosfato de calcio nanocristalino. Figure 1 shows a micrograph obtained by electron microscopy of the nanocrystalline calcium phosphate hybrid phosphate.
Modo de realización de la invención Embodiment of the invention
La invención se ilustra mediante el siguiente ejemplo, el cual no pretende ser limitativo de su alcance. The invention is illustrated by the following example, which is not intended to limit its scope.
Ejemplo1 Example 1
Se mezclan una solución acuosa de una salde fosfato de concentración 0,26M(precursor:hidrógeno-fosfato de sodiodihidratado,Na2HPO4*2H2O)ybromurodehexadeciltrimetil amonio(CTAB)o clorurodehexadecil trimetil amonio(CTAC)a una temperaturade80ºC duranteun tiempo comprendido entre10y12 horas.Se añaden 0,955gde 4-nitro benzaldehído en80mLde metanol(o etanol)y se agita durante un tiempo comprendido entre1y10 horas.A continuaciónse disminuyelatemperaturaa60ºCyse adicionan entre10y20mLde hidróxidode amonio(NH4OHó NaOHal25% hasta alcanzarunpH superiora10.Acontinuaciónse añaden60mLdela solución acuosade unasal de calciode concentración 0,26M(precursor: clorurode calcio dihidratado CaCl2*2H2O)yse agita entre1y4horas. An aqueous solution of a 0.26M concentration phosphate salt (precursor: sodium hydrogen phosphate dihydrate, Na2HPO4 * 2H2O) and bromide dehexadecyltrimethyl ammonium (CTAB) or trimethyl ammonium chloride (CTAC) are mixed at a temperature of 80 ° C for a time between 10 and 12 hours. 0.955g of 4-nitro benzaldehyde in 80mL of methanol (or ethanol) and stir for a time between 1 and 10 hours.Then the temperature is lowered to 60 ° C and ammonium hydroxide is added between 10 and 20mL until reaching a higher pH of 10 ° C. Continuation of the concentration of water is added at a concentration of 60m. : calcium chloride dihydrate CaCl2 * 2H2O) and stir between 1 and 4 hours.
El gel formado se filtra obteniéndose un pigmento híbrido fosfato de calcio nanocristalino-colorante orgánico de color rojo intenso. Si se deja envejecer antes de filtrar manteniéndolo en una disolución durante 5 días a 40ºC, el material híbrido obtenido se oscurece pasando a un color púrpura profundo. The gel formed is fi ltered to obtain a hybrid nanocrystalline calcium phosphate hybrid dye - an intense red color. If it is allowed to age before filtering, keeping it in a solution for 5 days at 40 ° C, the hybrid material obtained darkens into a deep purple color.
El gelhíbrido fosfato de calcio-colorarite orgánico filtrado selava con agua destiladaydesionizada. El material obtenido se seca a temperatura ambiente a presión o a temperatura más baja en condiciones de vacío. The filtered calcium phosphate-colorarite gel hydride is washed with distilled and deionized water. The material obtained is dried at room temperature under pressure or at a lower temperature under vacuum conditions.
Siel pigmento híbrido fosfatode calcio-colorante filtrado se secaa una temperatura entre30y90ºC,el color pasa de rojo profundo a naranja. Pero si el material se vuelve a sumergir en agua a temperatura ambiente vuelve a mostrar el color rojo original. If the hybrid phosphate of calcium-filtrate dye is dried at a temperature between 30 and 90 ° C, the color changes from deep red to orange. But if the material is submerged in water at room temperature it returns to show the original red color.
Traslaextracciónysecado,el coloranteorgánico recogidopuedecalentarsea temperaturasde hasta 250ºCsinque pierda su color. After extraction and drying, the collected organic dye can be heated to temperatures up to 250 ° C without losing its color.
Claims (16)
- 2. 2.
- Procedimiento para la preparación de un pigmento cerámico de fosfato de calcio-colorante orgánico, según reivindicación1, donde las sales precursorasde fosfatode calcio son hidrogenofosfatode sodio dihidratadoycloruro de calcio dihidratado que forman una fosfato de calcio cristalino. Process for the preparation of a ceramic calcium phosphate pigment-organic dye according to claim 1, wherein the calcium phosphate precursor salts are sodium hydrogen phosphate dihydrate and calcium dihydrate chloride forming a crystalline calcium phosphate.
- 3. 3.
- Procedimiento para la preparación de un pigmento cerámico de fosfato de calcio-colorante orgánico, según reivindicaciones anteriores, donde el alcohol de bajo peso molecular es metanol o etanol. Process for the preparation of a calcium phosphate ceramic dye-organic dye according to previous claims, wherein the low molecular weight alcohol is methanol or ethanol.
- 4. Four.
- Procedimiento para la preparación de un pigmento cerámico de fosfato de calcio-colorante orgánico, según reivindicaciones anteriores, dondeelnitrobenzaldehído sustituido es meta-, orto-para-nitrobenzaldehído sustituidoy el surfactante es un surfactante catiónico. Process for the preparation of a ceramic calcium phosphate pigment-organic dye according to previous claims, wherein the substituted nitrobenzaldehyde is meta-, ortho-para-nitrobenzaldehyde substituted and the surfactant is a cationic surfactant.
- 5. 5.
- Procedimiento para la preparación de un pigmento cerámico de fosfato de calcio-colorante orgánico, según reivindicaciones anteriores, donde el surfactante catiónico es un surfactante de amonio cuaternario como bromuro de deciltrimetil amonio [CH3(CH2)9N(CH3)3Br], bromuro de dodeciltrimetil amonio [CH3(CH2)11N(CH3)3Br], cloruro de dodeciltrimetil amonio[CH3(CH2)11N(CH3)3Cl], bromurode tetradeciltrimetil amonio[CH3(CH2)13N(Br)(CH3)3], cloruro de tetradeciltrimetilamonio [CH3(CH2)13N(Cl)(CH3)3], bromuro de hexadeciltrimetil amonio [CH3(CH2)15N (Br)(CH3)3]o clorurodehexadeciltrimetilamonio[CH3(CH2)15N(Cl)(CH3)3]. Process for the preparation of a ceramic calcium phosphate pigment-organic dye according to previous claims, wherein the cationic surfactant is a quaternary ammonium surfactant such as decyltrimethyl ammonium bromide [CH3 (CH2) 9N (CH3) 3Br], dodecyltrimethyl bromide ammonium [CH3 (CH2) 11N (CH3) 3Br], dodecyltrimethyl ammonium chloride [CH3 (CH2) 11N (CH3) 3Cl], tetradecyltrimethyl ammonium bromide [CH3 (CH2) 13N (Br) (CH3) 3], tetradecyltrimethylammonium chloride [CH3 (CH2) 13N (Cl) (CH3) 3], hexadecyltrimethyl ammonium bromide [CH3 (CH2) 15N (Br) (CH3) 3] or chloridedehexadecyltrimethylammonium [CH3 (CH2) 15N (Cl) (CH3) 3].
- 6. 6.
- Procedimiento para la preparación de un pigmento cerámico de fosfato de calcio-colorante orgánico, según reivindicaciones anteriores, donde el pH se eleva hasta un valor próximo a 10 añadiendo hidróxido de amonio o hidróxido de sodio. Process for the preparation of a ceramic calcium phosphate pigment-organic dye according to previous claims, wherein the pH is raised to a value close to 10 by adding ammonium hydroxide or sodium hydroxide.
- 7. 7.
- Procedimiento para la preparación de un pigmento cerámico de fosfato de calcio-colorante orgánico, según reivindicaciones anteriores, donde el pigmento híbrido se recupera por filtración Process for the preparation of a ceramic calcium phosphate pigment-organic dye according to previous claims, wherein the hybrid pigment is recovered by filtration
- 9. 9.
- Uso del pigmento híbrido reivindicado para aportar color en materiales compuestos, arcillas, resinas, porcelanas, metalesycementos. Use of the hybrid pigment claimed to provide color in composite materials, clays, resins, porcelains, metals and cement.
- 10. 10.
- Uso del pigmento híbrido reivindicado para colorear materiales textiles. Use of the hybrid pigment claimed to color textile materials.
- 11. eleven.
- Uso del pigmento híbrido reivindicado como colorante en productos generales de consumo. Use of the hybrid pigment claimed as a dye in general consumer products.
- 12. 12.
- Uso del pigmento híbrido reivindicado en la obtención de la células solares del tipo DSSC. Use of the hybrid pigment claimed in obtaining the solar cells of the DSSC type.
- 13. 13.
- Procedimiento paralapreparaciónde un colorante orgánico que comprendela condensaciónde 4-nitrobenzaldehído en metanolóetanoly en presenciao ausenciade un surfactante cuaternario cono sin adiciónde aguaa una temperatura entre30y120ºCyposterior enfriamientopor debajode 80ºCyadiciónde hidróxidode sodioo hidróxido de amonio hasta alcanzar un pH superior a 10. Procedure for the preparation of an organic dye comprising the condensation of 4-nitrobenzaldehyde in methanol or methanol and in the absence or absence of a cone quaternary surfactant without addition of water at a temperature between 30 and 120 ° C and subsequent cooling below 80 ° C and addition of sodium hydroxide or ammonium hydroxide to reach a pH greater than 10.
- 14. 14.
- Procedimiento para la preparación de un colorante orgánico, según reivindicación 13, donde el surfactante cuaternario es un surfactante de amonio cuaternario como bromuro de deciltrimetil amonio [CH3(CH2)9N (CH3)3Br], bromuro de dodeciltrimetil amonio [CH3(CH2)11N(CH3)3Br], cloruro de dodeciltrimetil amonio [CH3 (CH2)11N(CH3)3Cl], bromuro de tetradeciltrimetil amonio [CH3(CH2)13N(Br)(CH3)3], cloruro de tetradeciltrimetil amonio [CH3(CH2)13N(Cl)(CH3)3], bromuro de hexadeciltrimetil amonio [CH3(CH2)15N(Br)(CH3)3]o cloruro de hexadeciltrimetil amonio[CH3(CH2)15N(Cl)(CH3)3]. Process for the preparation of an organic dye according to claim 13, wherein the quaternary surfactant is a quaternary ammonium surfactant such as decyltrimethyl ammonium bromide [CH3 (CH2) 9N (CH3) 3Br], dodecyltrimethyl ammonium bromide [CH3 (CH2) 11N (CH3) 3Br], dodecyltrimethyl ammonium chloride [CH3 (CH2) 11N (CH3) 3Cl], tetradecyltrimethyl ammonium bromide [CH3 (CH2) 13N (Br) (CH3) 3], tetradecyltrimethyl ammonium chloride [CH3 (CH2) 13N (Cl) (CH3) 3], hexadecyltrimethyl ammonium bromide [CH3 (CH2) 15N (Br) (CH3) 3] or hexadecyltrimethyl ammonium chloride [CH3 (CH2) 15N (Cl) (CH3) 3].
- Categoría Category
- Documentos citados Reivindicaciones afectadas Documents cited Claims Affected
- A TO
- US 2003129149 A1 ( PIKE KATHLEEN S ET AL.) 10/07/2003 todo el documento. 1-15 US 2003129149 A1 (PIKE KATHLEEN S ET AL.) 07/10/2003 the whole document. 1-15
- A TO
- JP 9328623 A (MARUO CALCIUM ) 22/12/1997 resumen; 1-15 JP 9328623 A (MARUO CALCIUM) 12/22/1997 summary; 1-15
- A TO
- WO 0032700 A1 (ENGELHARD CORP ) 08/06/2000 todo el documento. 1-15 WO 0032700 A1 (ENGELHARD CORP) 06/08/2000 the whole document. 1-15
- A TO
- HOFACKER, S., et al., Hybrid pigments via sol-gel processing, Journal of Sol-Gel Science and Technology, 1998, Vol.13, págs.479-484. Todo el documento. 1-15 HOFACKER, S., et al., Hybrid pigments via sol-gel processing, Journal of Sol-Gel Science and Technology, 1998, Vol. 13, pp. 479-484. Whole document. 1-15
- Categoría de los documentos citados X: de particular relevancia Y: de particular relevancia combinado con otro/s de la misma categoría A: refleja el estado de la técnica O: referido a divulgación no escrita P: publicado entre la fecha de prioridad y la de presentación de la solicitud E: documento anterior, pero publicado después de la fecha de presentación de la solicitud Category of the documents cited X: of particular relevance Y: of particular relevance combined with other / s of the same category A: reflects the state of the art O: refers to unwritten disclosure P: published between the priority date and the date of priority submission of the application E: previous document, but published after the date of submission of the application
- El presente informe ha sido realizado • para todas las reivindicaciones □ para las reivindicaciones nº: This report has been prepared • for all claims □ for claims no:
- Fecha de realización del informe 07.12.2010 Date of realization of the report 07.12.2010
- Examinador M. García Poza Página 1/4 Examiner M. García Poza Page 1/4
- Novedad (Art. 6.1 LP 11/1986) Novelty (Art. 6.1 LP 11/1986)
- Reivindicaciones Reivindicaciones 1-15 SI NO Claims Claims 1-15 IF NOT
- Actividad inventiva (Art. 8.1 LP11/1986) Inventive activity (Art. 8.1 LP11 / 1986)
- Reivindicaciones Reivindicaciones 1-15 SI NO Claims Claims 1-15 IF NOT
- Documento Document
- Número Publicación o Identificación Fecha Publicación Publication or Identification Number publication date
- D01 D01
- US 2003129149 A1 ( PIKE KATHLEEN S ET AL.) 10.07.2003 US 2003 129149 A1 (PIKE KATHLEEN S ET AL.) 10.07.2003
- D02 D02
- JP 9328623 A (MARUO CALCIUM ) 22.12.1997 JP 9328623 A (MARUO CALCIUM) 22.12.1997
- D03 D03
- WO 0032700 A1 (ENGELHARD CORP ) 08.06.2000 WO 0032700 A1 (ENGELHARD CORP) 08.06.2000
- D04 D04
- HOFACKER, S., et al., Hybrid pigments via sol-gel processing, Journal of Sol-Gel Science and Technology, 1998, Vol.13, págs.479-484. Todo el documento. HOFACKER, S., et al., Hybrid pigments via sol-gel processing, Journal of Sol-Gel Science and Technology, 1998, Vol. 13, pp. 479-484. Whole document.
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