WO2005052067A1 - Inorganic pigments - Google Patents

Inorganic pigments Download PDF

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Publication number
WO2005052067A1
WO2005052067A1 PCT/GB2004/004785 GB2004004785W WO2005052067A1 WO 2005052067 A1 WO2005052067 A1 WO 2005052067A1 GB 2004004785 W GB2004004785 W GB 2004004785W WO 2005052067 A1 WO2005052067 A1 WO 2005052067A1
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pigment
pigments
tin
glass
general formula
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PCT/GB2004/004785
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French (fr)
Inventor
Jonathan Charles Shepley Booth
Sandra Elizabeth Dann
Duncan Lee John O'brien
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Johnson Matthey Public Limited Company
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Publication of WO2005052067A1 publication Critical patent/WO2005052067A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C09C1/0009—Pigments for ceramics
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/62—L* (lightness axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/63—Optical properties, e.g. expressed in CIELAB-values a* (red-green axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/65—Chroma (C*)
    • C—CHEMISTRY; METALLURGY
    • 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
    • C01P2006/66—Hue (H*)

Definitions

  • This invention relates to inorganic pigments and their use for the colouration of substrates, particularly plastic and glass substrates.
  • Some of the most commonly used inorganic pigments for colour shades from yellow through orange to red are those based on cadmium sulphide and cadmium selenide. These have excellent colour strength and are used widely for the colouration of plastics and other substrates.
  • Cadmium is toxic, and thus there is concern over the build up of cadmium pigments in the environment. The perceived risk is greater than the actual risk due to the extremely low solubility of cadmium sulphide and selenide, nevertheless pigment manufacturers have long identified the need to find replacement pigments for the cadmium systems.
  • Cadmium sulphide and selenide are also not always suitable for the colouration of glasses.
  • yellow and red inorganic pigments include those based on iron oxide, Ti-Ni-Sb rutile pigments, bismuth vanadate, praseodymium zircon yellow and lead chromates.
  • Solid State Chem., 13, (1975) 118-130 also report crystallographic studies on tin-niobium oxides as well as tin-tantalum oxides. Neither of the above mentioned references discusses any practical usage of the compounds whatsoever; they are merely academic studies aimed at elucidating certain structural parameters.
  • tin-niobium oxides can be used advantageously as inorganic pigments in the yellow to red colour range. They have good colour properties and show stability in a range of substrates. Furthermore, they do not have any of the toxicity issues associated with cadmium based pigments.
  • the present invention provides the use of a tin-niobium oxide corresponding to the general formula Sn 1+x Nb 2 ⁇ 6+ ⁇ , wherein 0 ⁇ x ⁇ 1, as an inorganic pigment.
  • the present invention provides a pigmented composition
  • a pigmented composition comprising a substrate matrix and a pigment; wherein the pigment comprises a tin-niobium oxide corresponding to the general formula Sn 1+ ⁇ Nb 2 O 6+x ; and wherein 0 ⁇ x ⁇ 1.
  • the present invention provides a method for the pigmentation of a substrate matrix comprising combining the matrix with a tin-niobium oxide pigment corresponding to the general formula Sn 1+ ⁇ Nb 2 ⁇ 6 +x ; wherein 0 ⁇ x ⁇ 1.
  • tin-niobium oxides are particularly effective for the pigmentation of plastic substrates.
  • Pure Foordite, SnNb 2 O 6 for example, when added to plastics such as PVC gives a very strong and vibrant yellow colouration.
  • Other plastics and other pigments are also, of course, included in the invention.
  • the pigments are also thermally stable at high temperatures making them suitable for addition to glasses.
  • Any type of glass may be used, for example, leaded and non-leaded glasses and bismuth containing glasses.
  • the thus-pigmented glass may be used as a glass frit, in the preparation of glazes and many other uses.
  • the pigments may be used in any amount.
  • the pigment is present in an amount of between 1 and 50 wt% preferably, between 1 and 10 wt% for example, 5wt%.
  • the pigments may be used alone or in combination with other pigments.
  • the pigments may be combined with substrate matrices by methods known in the art.
  • the pigment may be added whilst the plastic is molten using manual or automatic mixing, or by adding to an extruder/mixer.
  • Pigmented plastics may be used as masterbatches.
  • the pigments are preferably used in the form of fine powders. Methods for the production of fine pigment powders are known in the art and include methods such are ball milling and grinding.
  • the particle size of the pigments will depend on their intended use; suitably the pigments will have a particle size in the range from 0.1 to 50 ⁇ m preferably between 0.1 and 20 ⁇ m, more preferably between 0.1 and lO ⁇ m, for example approximately 2 ⁇ m.
  • a stoichiometric mix of stannous oxide and niobium (V) oxide were mixed in a coffee grinder. ( 38.5g SnO + 75.9g Nb 2 O 5 ) The material was packed into an aluminosilicate crucible. A ceramic tile was then cemented on the top of the crucible to act as a lid. The sample was fired at 900°C. On removal a bright yellow powder was produced, the colour properties of which are given in Table 1.
  • Example 1 The materials produced in Examples 1 and 2 above were mixed with a ground low melting glass enamel frit (B5320f), at a pigment loading of 8wt%.
  • the mixed powders were dispersed into a pine oil based resin using a triple roll mill.
  • the ink produced was screen printed onto float glass pieces with a wet thickness of about 50 ⁇ m.
  • the decorated glass tiles were fired at 600°C to give a glossy enamel finish.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The use of a tin-niobium oxide corresponding to the formula Sn1+xNb206+x, wherein 0 ≤ x ≤ 1, or a doped version thereof, as an inorganic pigment. The pigment is suitable for the colouration of substrates such as plastics and glass.

Description

INORGANIC PIGMENTS
This invention relates to inorganic pigments and their use for the colouration of substrates, particularly plastic and glass substrates.
Some of the most commonly used inorganic pigments for colour shades from yellow through orange to red are those based on cadmium sulphide and cadmium selenide. These have excellent colour strength and are used widely for the colouration of plastics and other substrates. There are however problems associated with the use of cadmium based pigments. Cadmium is toxic, and thus there is concern over the build up of cadmium pigments in the environment. The perceived risk is greater than the actual risk due to the extremely low solubility of cadmium sulphide and selenide, nevertheless pigment manufacturers have long identified the need to find replacement pigments for the cadmium systems. Cadmium sulphide and selenide are also not always suitable for the colouration of glasses.
Other yellow and red inorganic pigments include those based on iron oxide, Ti-Ni-Sb rutile pigments, bismuth vanadate, praseodymium zircon yellow and lead chromates.
Cruz et al., in Jn. Solid State Chem., 156, (2001) 349-354 have studied the synthesis and crystallographic properties of tin-niobium oxides. The naturally occurring mineral Foordite has the formula SnNb2O6. A further tin-niobium oxide has the pyrochlore structure and the formula Sn2Nb2O . Cruz et al., used sealed tube methods to prepare a range of oxide materials corresponding to the general formula Sn1+xNb2O6+x, choosing x equal to 0, 0.5 and 1. Birchall and Sleight inJ . Solid State Chem., 13, (1975) 118-130 also report crystallographic studies on tin-niobium oxides as well as tin-tantalum oxides. Neither of the above mentioned references discusses any practical usage of the compounds whatsoever; they are merely academic studies aimed at elucidating certain structural parameters.
The present applicants have found that tin-niobium oxides can be used advantageously as inorganic pigments in the yellow to red colour range. They have good colour properties and show stability in a range of substrates. Furthermore, they do not have any of the toxicity issues associated with cadmium based pigments.
Thus in accordance with a first aspect, the present invention provides the use of a tin-niobium oxide corresponding to the general formula Sn1+xNb2θ6+χ , wherein 0 < x < 1, as an inorganic pigment.
In a second aspect, the present invention provides a pigmented composition comprising a substrate matrix and a pigment; wherein the pigment comprises a tin-niobium oxide corresponding to the general formula Sn1+χNb2O6+x; and wherein 0 < x < 1.
In a third aspect, the present invention provides a method for the pigmentation of a substrate matrix comprising combining the matrix with a tin-niobium oxide pigment corresponding to the general formula Sn1+χNb2θ6+x; wherein 0 < x < 1.
We have found that tin-niobium oxides are particularly effective for the pigmentation of plastic substrates. Pure Foordite, SnNb2O6, for example, when added to plastics such as PVC gives a very strong and vibrant yellow colouration. Other plastics and other pigments are also, of course, included in the invention.
Furthermore, the pigments are also thermally stable at high temperatures making them suitable for addition to glasses. Any type of glass may be used, for example, leaded and non-leaded glasses and bismuth containing glasses. The thus-pigmented glass may be used as a glass frit, in the preparation of glazes and many other uses.
Other applications include any for which inorganic pigments are presently used. For example, the colouration of paints and inks, use as pigments in the manufacture of glazes and stains for ceramic applications, and the manufacture of electrostatic toners, both conventional toners for printing and copying onto paper, and also ceramic toners. The pigments may be used in any amount. Suitably, the pigment is present in an amount of between 1 and 50 wt% preferably, between 1 and 10 wt% for example, 5wt%. The pigments may be used alone or in combination with other pigments. The pigments may be combined with substrate matrices by methods known in the art. For example, in the case where the substrate matrix is a plastic, the pigment may be added whilst the plastic is molten using manual or automatic mixing, or by adding to an extruder/mixer. Pigmented plastics may be used as masterbatches. The pigments are preferably used in the form of fine powders. Methods for the production of fine pigment powders are known in the art and include methods such are ball milling and grinding. The particle size of the pigments will depend on their intended use; suitably the pigments will have a particle size in the range from 0.1 to 50 μm preferably between 0.1 and 20μm, more preferably between 0.1 and lOμm, for example approximately 2μm.
It has been found to be possible to alter the colour of the pigments of the invention by the addition of dopant elements. For example, the replacement of 5% niobium for tungsten in a yellow pigment of formula SnNb2O6 gave an orange colour. It is presently thought that dopant elements substitute for niobium in the crystal structure, although this has not yet been confirmed by experiment. A postulated general formula for such doped pigments may be given as:
Figure imgf000004_0001
O6+x , where 0 < x < 1, where 0 < y < 2, and where M is a dopant element, for example tungsten, molybdenum or tantalum. More than one dopant element may be used and the list is not exhaustive.
The invention will now be described by way of example only.
EXAMPLE 1 Synthesis of Yellow Pigment SnNbgOfi
A stoichiometric mix of stannous oxide and niobium (V) oxide were mixed in a coffee grinder. ( 38.5g SnO + 75.9g Nb2O5) The material was packed into an aluminosilicate crucible. A ceramic tile was then cemented on the top of the crucible to act as a lid. The sample was fired at 900°C. On removal a bright yellow powder was produced, the colour properties of which are given in Table 1.
Table 1.
Figure imgf000005_0001
EXAMPLE 2 Synthesis of Yellow Pigment SnNbgOfi The experiment of Example 1 was repeated using a controlled nitrogen atmosphere tube furnace. Similar quality pigment was obtained
EXAMPLE 3 Addition to Plastic
The materials produced in Examples 1 and 2 above were ball milled to give a D90 particle size of <2 μm. 0.4 g of each pigment was dispersed in 8g of PNC through manual mixing with a palette knife. 16 drops of dioctylphthalate was added as a plasticiser. The dispersions were drawn down onto float glass with a k-bar to give a thickness of approximately 200 μm. The glass/PVC were heated in an oven at 150°C for 3 minutes. The cured PNC was peeled off the glass support and placed over white card. Strong, yellow pigmented PNC was obtained.
EXAMPLE 4 Addition to Glass
The materials produced in Examples 1 and 2 above were mixed with a ground low melting glass enamel frit (B5320f), at a pigment loading of 8wt%. The mixed powders were dispersed into a pine oil based resin using a triple roll mill. The ink produced was screen printed onto float glass pieces with a wet thickness of about 50 μm. The decorated glass tiles were fired at 600°C to give a glossy enamel finish. EXAMPLE S Doping
Substitutions were made to the pigment lattice with different elements. The most dramatic effect was found with tungsten. 5% of the niobium was replaced by tungsten. This altered the yellow pigment into an orange colour.

Claims

1. The use of a tin-niobium oxide corresponding to the general formula Sn1-rχNb2θ6+χ or SN1+xNb2.yMyO6+χ, wherein 0 < x < 1, O<y<2 and M is a dopant element as an inorganic pigment.
2. Use according to claim 1 as a pigment for the pigmentation of a plastic or glass substrate matrix.
3. A pigmented composition, the composition comprising a substrate matrix and a pigment; wherein the pigment comprises a tin-niobium oxide corresponding to the general formula Sn1+xNb2Og+x or Sni+xNb2-yMyO6+x and wherein 0 < x ≤ l, O < y < 2 and M is a dopant element.
4. A composition according to claim 3, wherein the substrate matrix comprises a plastic or a glass.
5. A composition according to claim 3 or claim 4, wherein the pigment comprises between 1 and 50 wt% of the composition.
6. A composition according to any of claims 3 to 5, wherein the pigment is in the form of a fine powder with a particle size range of between 0.1 and 50 μm.
7. A method for the pigmentation of a substrate matrix, the method comprising combining the matrix with a tin-niobium oxide pigment corresponding to the general formula Sn1+xNb2O6+x or Snι+χNb2-yMyO6+x wherein 0 < x ≤ l, O < y < 2 and M is a dopant element.
PCT/GB2004/004785 2003-11-20 2004-11-15 Inorganic pigments WO2005052067A1 (en)

Applications Claiming Priority (2)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170175271A1 (en) * 2014-09-04 2017-06-22 Byd Company Limited Polymer composition, ink composition and method for selectively metallizing insulating substrate
CN107601564A (en) * 2017-09-04 2018-01-19 北京工业大学 A kind of method of alcoholic solvent hot preparation niobic acid tin nanosphere
EP3587350A4 (en) * 2017-02-23 2020-12-23 National Institute of Advanced Industrial Science and Technology Oxide semiconductor and semiconductor device
US11239322B2 (en) 2017-02-23 2022-02-01 National Institute Of Advanced Industrial Science And Technology P-type oxide semiconductor and semiconductor device having pyrochlore structure

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4548741A (en) * 1982-06-01 1985-10-22 E. I. Du Pont De Nemours And Company Method for doping tin oxide

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4548741A (en) * 1982-06-01 1985-10-22 E. I. Du Pont De Nemours And Company Method for doping tin oxide

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; CRUZ, L. P. ET AL: "Synthesis and Characterization of Tin Niobates", XP002314919, retrieved from STN Database accession no. 134:320061 *
JOURNAL OF SOLID STATE CHEMISTRY , 156(2), 349-354 CODEN: JSSCBI; ISSN: 0022-4596, 2001 *
SORLI S ET AL: "Structure and color of NixA1-3xB2xO2 (A=Ti, Sn; B=Sb, Nb) solid solutions", JOURNAL OF THE EUROPEAN CERAMIC SOCIETY, ELSEVIER SCIENCE PUBLISHERS, BARKING, ESSEX, GB, vol. 24, no. 8, July 2004 (2004-07-01), pages 2425 - 2432, XP004490445, ISSN: 0955-2219 *
T. BIRCHALL, A.W. SLEIGHT: "Nonstoichiometric phases in the sn-nb-o and sn-ta-o systems having pyrochlore-related structures", JOURNAL OF SOLID STATE CHEMISTRY, vol. 13, 1975, pages 118 - 130, XP002316219 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170175271A1 (en) * 2014-09-04 2017-06-22 Byd Company Limited Polymer composition, ink composition and method for selectively metallizing insulating substrate
EP3587350A4 (en) * 2017-02-23 2020-12-23 National Institute of Advanced Industrial Science and Technology Oxide semiconductor and semiconductor device
US11239322B2 (en) 2017-02-23 2022-02-01 National Institute Of Advanced Industrial Science And Technology P-type oxide semiconductor and semiconductor device having pyrochlore structure
CN107601564A (en) * 2017-09-04 2018-01-19 北京工业大学 A kind of method of alcoholic solvent hot preparation niobic acid tin nanosphere
CN107601564B (en) * 2017-09-04 2019-06-07 北京工业大学 A kind of method of alcoholic solvent hot preparation niobic acid tin nanosphere

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