WO2015131979A1 - Pigments - Google Patents

Pigments Download PDF

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Publication number
WO2015131979A1
WO2015131979A1 PCT/EP2015/000378 EP2015000378W WO2015131979A1 WO 2015131979 A1 WO2015131979 A1 WO 2015131979A1 EP 2015000378 W EP2015000378 W EP 2015000378W WO 2015131979 A1 WO2015131979 A1 WO 2015131979A1
Authority
WO
WIPO (PCT)
Prior art keywords
compounds
compounds according
doped
pigments
compound
Prior art date
Application number
PCT/EP2015/000378
Other languages
German (de)
English (en)
Inventor
Ralf Petry
Holger Winkler
Thomas Juestel
Matthias Mueller
David BOEHNISCH
Original Assignee
Merck Patent Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Merck Patent Gmbh filed Critical Merck Patent Gmbh
Publication of WO2015131979A1 publication Critical patent/WO2015131979A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/22—Magnesium silicates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/32—Alkali metal silicates
    • 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
    • C09D7/41—Organic pigments; Organic dyes
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • 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
    • 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
    • C08K3/34—Silicon-containing compounds

Definitions

  • the present invention relates to blue pigments, a process for their preparation and their use in paints, lacquers, powder coatings, printing inks, plastics, ceramic materials, glasses, in
  • cosmetic formulations for laser marking and for the preparation of pigment preparations and dry preparations.
  • Blue pigments have been used in painting since ancient times, with the first pigments found to be widespread as ultramarine (Lapis lazuli Na2Al6Si6024S3), Egyptian blue (CaCuSi40io), and Han blue (BaCuSi4Oio).
  • the main problem of these pigments is their relatively low
  • blue pigments that have been developed in recent years include azurite ([Cu3 (CO3) 2 (OH) 2]) and Mn 3+ -doped indates, in which the trivalent manganese is trigonal-bipyramidal coordinated, which explains the unusual Absorption spectrum of Mn 3+ with an [Ar] 3d 4
  • Mn 5+ -doped ortho-silicates of the alkali and alkaline earth metals have a blue body color.
  • the present invention therefore relates to compounds of the following formula (I) A 2 EASiO 4 : Mn (I) with
  • A Li, Na, K, Rb and / or Cs
  • EA Mg, Ca, Sr and / or Ba
  • A is preferably Na or Li, in particular Na.
  • Na or Li may preferably be doped with 20% K, Rb, and / or Cs.
  • EA Ca, Mg, or Sr, in particular Ca.
  • Ca, Mg or Sr may preferably be doped with 20% Ba.
  • the blue color may be explained by the fact that the manganese ions are incorporated on the tetrahedral Si + sites.
  • ionic radius of Mn 5+ in tetrahedral coordination is 47 pm, while the ionic radius of tetrahedral Si 4+ is 40 pm.
  • the compounds claimed here absorb strongly in the green, yellow and red spectral range of visible light, resulting in a color point in the blue spectral range.
  • the new compounds can be characterized by their reflection spectra and their L * a * b * coordinates in the CIE color space
  • Temperature stability from, i. multi-day annealing at 300 ° C does not lead to a relevant shift of the color point.
  • Another object of the invention is a process for the preparation of the compounds of formula (I) comprising the following steps:
  • thermal treatment of the mixture Preference is given to using the corresponding carbonates, oxides and / or oxalates, in particular carbonates and / or oxalates.
  • silica is used in nanoparticulate form.
  • 20% of potassium, rubidium and / or cesium compounds, preferably carbonates, may be added.
  • 20% of barium compounds, preferably carbonates, may be added.
  • Manganese oxalate in particular as hydrate, is preferably used.
  • the combination of the preferred compounds is advantageous for the preparation of the novel compounds.
  • the ratio of the starting compounds in the mixture in step a) can be determined by one skilled in the art on the basis of the intended composition of the reaction product.
  • Particularly preferred are 5 to 20% of a manganese compound. 2% and 10% of a manganese compound are particularly preferably used.
  • the mixture in step a) may preferably be prepared in a mortar, preferably in a solvent.
  • the solvent used is preferably acetone or an alcohol, in particular ethanol, propanol or isopropanol.
  • Step b) usually comprises a thermal treatment at a temperature> 800 ° C.
  • the compounds of formula (I) can be prepared under oxidizing conditions, preferably by calcining under air. Preferably, calcination at a temperature> 1000 ° C under air.
  • the mixture Before calcination, the mixture is preferably dried. This is preferably carried out in air first at room temperature and then in a drying oven at elevated temperature, preferably at 60-120 ° C, in particular at about 80 ° C.
  • the starting components S1O2, CaCO3, Na2C03 and MnC204-2H2O are mixed together in the solvent corresponding to the desired end product in a solvent to dryness.
  • the compounds of the invention can also by the Pechini method, the citrate method, the Combustion method and the
  • Hydrothermal method can be produced.
  • the invention furthermore also relates to the use of the novel pigments in formulations such as paints, printing inks,
  • the pigments according to the invention can advantageously be used in admixture with fillers, organic dyes and / or other pigments, such as transparent and opaque white, colored and black pigments and platelet-shaped
  • the pigments according to the invention can be mixed in any ratio with commercially available pigments and fillers.
  • fillers are e.g. Mention may be made of natural and synthetic mica, nylon powder, pure or filled melanin resins, talcum, glasses, kaolin, oxides or hydroxides of aluminum, magnesium, calcium, zinc, BiOCl, barium sulfate, calcium sulfate, calcium carbonate, magnesium carbonate, carbon, as well as physical or chemical combinations of these substances.
  • particle shape of the filler It can meet the requirements according to e.g. be platy, spherical or needle-shaped.
  • the pigments according to the invention can preferably be used in paints (automotive and industrial coatings, solvent-based and water-based, powder coatings), plastics, printing inks, ceramic glazes or cosmetic formulations. They can also be prepared in the form of preparations (pearlets, pastes,
  • Inclinations e.g. for use in printing inks or plastics.
  • the pigments according to the invention are furthermore suitable for the preparation of flowable pigment preparations and dry preparations comprising one or more pigments according to the invention, binders and optionally one or more additives.
  • dry preparations are also preparations too from 0 to 8% by weight, preferably from 2 to 8% by weight, in particular from 3 to 6% by weight, of water and / or of a solvent or
  • the dry preparations are preferably in the form of pellets, granules, chips, sausages or briquettes and have particle sizes of 0.2-80 mm. Find the dry preparations
  • the pigments of the invention are compatible with a variety of color systems, preferably from the field of paints, inks and
  • Printing inks For the production of the printing inks a variety of binders, in particular water-soluble types, are suitable, as e.g. from BASF, Marabu, Pröll, Sericol, Hartmann, Gebr. Schmidt, Sicpa, Aarberg, Siegberg, GSB-Wahl, Follmann, Ruco or Coates Screen INKS GmbH.
  • the printing inks may be water-based or solvent-based.
  • the pigments are also suitable for the laser marking of paper and plastics, as well as for agricultural applications, e.g. for greenhouse films, and z. B. for the color of tarpaulins suitable.
  • the phase formation of the samples is checked in each case by means of X-ray diffractometry.
  • An X-ray diffractometer Miniflex II from Rigaku with Bragg-Brentano geometry is used for this purpose.
  • the tube is operated with a current of 15 mA and a voltage of 30 kV. It is measured in an angle range of 10 to 80 ° with 5 ° min ⁇ 1 .
  • Reflection spectra are determined with a fluorescence spectrometer from Edinburgh Instruments Ltd.
  • the samples are placed in a BaS0 4 coated Ulbricht sphere and measured.
  • Reflection spectra are in a range of 250 to 800 nm
  • the white standard used is BaSO4 (Alfa Aesar 99.998%).
  • a 450 W Xe lamp serves as an excitation source.
  • Compound is characterized by its X-ray powder diffraction pattern (Figure 2) and its reflection spectrum (Figure 3).
  • Fig. 1 Reflection spectrum of C0AI2O4 as a comparison (against BaSO4 as white standard).
  • Fig. 3 Reflectance spectrum of the pigment according to Example 1 against BaSO4 and its CIELAB coordinates.
  • Fig. 5 Reflectance spectrum of the pigment according to Example 2 against BaS04 and its CIELAB coordinates.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Cosmetics (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

La présente invention concerne des pigments bleus, un procédé de fabrication de ces pigments ainsi que leur utilisation dans des colorants, peintures, peintures en poudre, encres d'imprimerie, matières plastiques, matériaux céramiques, verres, dans des formulations cosmétiques, pour le marquage au laser et pour la fabrication de préparations de pigments et de préparations sèches.
PCT/EP2015/000378 2014-03-05 2015-02-19 Pigments WO2015131979A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP14000792 2014-03-05
EP14000792.3 2014-03-05

Publications (1)

Publication Number Publication Date
WO2015131979A1 true WO2015131979A1 (fr) 2015-09-11

Family

ID=50235877

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2015/000378 WO2015131979A1 (fr) 2014-03-05 2015-02-19 Pigments

Country Status (1)

Country Link
WO (1) WO2015131979A1 (fr)

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
ANDREW E. SMITH ET AL: "Mn 3+ in Trigonal Bipyramidal Coordination: A New Blue Chromophore", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 131, no. 47, 2 December 2009 (2009-12-02), pages 17084 - 17086, XP055183650, ISSN: 0002-7863, DOI: 10.1021/ja9080666 *
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; YANG, ZHIPING ET AL: "Luminescence characteristics and crystallographic sites of Ce3+ in Na2Ca1-xSiO4:xCe3+", XP002738654, retrieved from STN Database accession no. 2012:1416990 *
PENG JIANG ET AL: "Intense Turquoise and Green Colors in Brownmillerite-Type Oxides Based on Mn 5+ in Ba 2 In 2- x Mn x O 5+ x", INORGANIC CHEMISTRY, vol. 52, no. 3, 4 February 2013 (2013-02-04), pages 1349 - 1357, XP055183644, ISSN: 0020-1669, DOI: 10.1021/ic3020332 *
YANG, ZHIPING ET AL: "Luminescence characteristics and crystallographic sites of Ce3+ in Na2Ca1-xSiO4:xCe3+", GUISUANYAN XUEBAO , 40(9), 1346-1350 CODEN: KSYHA5; ISSN: 0454-5648, 2012 *
Z. WANG ET.AL.: "Luminescent properties of Na2CaSiO4:Eu2+ and its potential application in white light emitting diodes", MATERIALS RESEARCH BULLETIN, vol. 48, 2013, pages 2393 - 2395, XP002738653 *

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