WO2009092104A1 - Compositions de pigments hybrides renfermant de l'argile et des colorants naturels - Google Patents

Compositions de pigments hybrides renfermant de l'argile et des colorants naturels Download PDF

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Publication number
WO2009092104A1
WO2009092104A1 PCT/US2009/031572 US2009031572W WO2009092104A1 WO 2009092104 A1 WO2009092104 A1 WO 2009092104A1 US 2009031572 W US2009031572 W US 2009031572W WO 2009092104 A1 WO2009092104 A1 WO 2009092104A1
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WO
WIPO (PCT)
Prior art keywords
natural dye
hybrid pigment
natural
clay
pigment composition
Prior art date
Application number
PCT/US2009/031572
Other languages
English (en)
Inventor
Lori A. Niewold
Gary Williams
Robyn Torres
Original Assignee
Mayan, Pigments, Inc.
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 Mayan, Pigments, Inc. filed Critical Mayan, Pigments, Inc.
Publication of WO2009092104A1 publication Critical patent/WO2009092104A1/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
    • C09C1/40—Compounds of aluminium
    • C09C1/42—Clays
    • 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
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • 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

Definitions

  • Hybrid Pigment Compositions Comprising Clay and Natural Dyes
  • This invention relates to hybrid pigment compositions comprising clay and natural dyes and methods of preparing the hybrid pigments.
  • Natural earth minerals lend themselves to a wide range of decorations, from body paint to painting on natural or constructed walls. The colors are extremely stable, as can be seen in ancient paintings that have lasted to this day. The use of colored earth pigments is found even in the oldest civilizations.
  • Maya blue refers to a "turquoise” brilliant shade of blue that is found on murals and archaeological artifacts, for example, throughout Mesoamerica. It is described in the literature as being composed of palygorskite clay and indigo, that when mixed and heated, produce the stable brilliant blue color similar to that found in Mesoamerica. Proposed methods of preparation were performed with the intent of trying to replicate the blue color found at the historical sites and to reproduce the techniques employed by the original Maya.
  • PCT Publication No. WO 01/04216 also describes ionic interactions in color compositions, wherein organic dyes undergo ion exchange with charged inorganic clays.
  • U.S. Patent 3,950,180 covers a method of manufacturing color compositions that include zeolite and montmorillonite.
  • U.S. Patent 5,061,290 covers a method of using indigo derivatives as a dyeing agent.
  • U.S. Patent 4,246,036 covers the method of manufacturing color compositions that are comprised of asbestos-cement.
  • U.S. Patent 4,640,862 covers color compositions that are used for coating an expanded polystyrene "drop-out" ceiling tile.
  • U.S. Patent 4,868,018 covers color compositions that are used with a mixture of epoxy resin, epoxy resin hardener, and portland cement to form a coating which can be applied to a surface to form simulated marble products.
  • Patent 4,874,433 covers a method for encapsulating color compositions in and/or to a zeolite.
  • U.S. Patent 5,574,081 covers a method of manufacturing waterborne clay-containing emulsion paints with improved application performance using color compositions.
  • U.S. Patent 5,972,049 covers the method of manufacturing and using color compositions to form dye carriers used in the dyeing process for hydrophobic textiles.
  • U.S. Patent 5,993,920 covers the method of manufacturing and using color compositions with stone powder and/or cement powder, fine sawdust and/or the heart of a kaoliang stalk and other materials to form an incombustible artificial marble.
  • U.S. Patent 6,339,084 covers the method of manufacturing thiazine-indigo pigments.
  • U.S. Patent 6,402,826 covers the method and manufacturing of color compositions for paper coating.
  • U.S. Patents 7,052,541 and 7,429,294 describe color compositions comprising neutral indigo derivative pigments and dyes complexed to the surface of inorganic clays. These materials are useful as paints and coatings for artistic and industrial purposes, including use in cements, plastics, papers and polymers. Upon grinding and heating the organic and inorganic component as solid mixtures or in aqueous solutions, the resulting color compositions have unprecedented stability relative to the original starting materials.
  • U.S. Patent No. 7,425,235 describes the use of similar starting materials in methods that rely on UV-light for preparing color compositions.
  • natural dyes are reacted with a naturally occurring, FDA approved clay to produce a line of natural pigments containing unique colors and improved properties at a lower cost.
  • the natural dyes are reacted onto the surface of the clay to provide a novel pigment with enhanced stability.
  • the ability to produce stable colors with natural pigments in plastic resins makes them useful for food and food packaging applications.
  • plastics / resins are now commercially available that are biodegradable.
  • a hybrid pigment composition comprising a fibrous clay and a natural dye selected from the group consisting of carmine, beta carotene, carmine hydrosoluble, turmeric, beet, and annato.
  • the fibrous clay is a palygorskite, sepiolite, or a combination thereof.
  • the composition comprises the natural dye in a range of 0.01 wt.% to about 75 wt.% based on the total weight of the hybrid dye composition.
  • the hybrid pigment composition can further comprise water or a biodegradable polymer.
  • a hybrid pigment composition comprising a charged bentonite and a natural dye.
  • the natural dye is selected from the group consisting of natural indigo, carmine, beta carotene, carmine hydrosoluble, turmeric, beet, and annato.
  • the composition comprises the natural dye in a range of 0.01 wt.% to about 75 wt.% based on the total weight of the hybrid pigment composition.
  • the hybrid pigment composition can further comprise water or a biodegradable polymer.
  • a method of forming a hybrid pigment comprising the steps of providing a natural dye selected from the group consisting of carmine, beta carotene, carmine hydrosoluble, turmeric, beet, and annato and a fibrous clay, and mixing the natural dye and fibrous clay.
  • the method further comprises heating the mixture of the natural dye and fibrous clay to react the natural dye with the fibrous clay.
  • the method further comprises grinding the fibrous clay or natural dye prior to mixing the clay and natural dye, or grinding the natural dye and clay together after mixing the fibrous clay and natural dye.
  • the method further comprises heating the fibrous clay and organic-inorganic hybrid pigment to a temperature of about 90 0 C to about 200 0 C for about 10 minutes to about 24 hours to react the natural dye with the fibrous clay.
  • a method of forming a hybrid pigment comprising the steps of providing a natural dye and a charged bentonite, and mixing the natural dye and charged bentonite.
  • the natural dye is selected from the group consisting of natural indigo, carmine, beta carotene, carmine hydrosoluble, turmeric, beet, and annato.
  • the method further comprises heating the mixture of the natural dye and charged bentonite to react the natural dye with the charged bentonite.
  • the method further comprises grinding the charged bentonite or natural dye prior to mixing the charged bentonite and natural dye, or grinding the natural dye and charged bentonite together after mixing the natural dye and charged bentonite.
  • the method further comprises heating the charged bentonite and natural dye to a temperature of about 90 °C to about 200 °C for about 10 minutes to about 24 hours to react the natural dye with the charged bentonite.
  • Fig. 1 are differential scanning calorimetry curves of embodiments according to the present disclosure comprising natural indigo.
  • Fig. 2 are differential scanning calorimetry curves of embodiments according to the present disclosure comprising carmine.
  • a hybrid pigment composition comprising a fibrous clay or charged bentonite and a natural dye selected from the group consisting of natural indigo, carmine, beta carotene, carmine hydrosoluble, turmeric, beet, and annato.
  • the fibrous clay is a palygorskite, sepiolite, or a combination thereof.
  • the palygorskite can be Attagel 50, an FDA approved palygorskite.
  • the charged bentonite is also known as bleaching earth, activated clay, Fuller's earth, and spent earth.
  • the composition comprises the natural dye in a range of about 0.01 wt.% to about 75 wt.% based on the total weight of the hybrid pigment composition. In certain embodiments, the composition comprises the natural dye in a range of about 1 wt.% to about 50 wt.% based on the total weight of the hybrid pigment composition. In certain embodiments, the composition comprises the natural dye in a range of about 10 wt.% to about 35 wt.% based on the total weight of the hybrid pigment composition. In certain embodiments of the present disclosure, the hybrid pigment is used to color biodegradable polymers. Biodegradable polymers that can be colored by the hybrid pigment comprising a natural dye include: polylactic acid made from corn starch, poly(3-hydroxybutyric acid) made from sugar cane, and poly hydroxyl alkanoates made from starch.
  • the hybrid pigment composition according to the present disclosure can be prepared by mixing a natural dye, such as natural indigo, carmine, beta carotene, carmine hydrosoluble, turmeric, beet, and annato; and a fibrous clay or charged bentonite.
  • a natural dye such as natural indigo, carmine, beta carotene, carmine hydrosoluble, turmeric, beet, and annato
  • a fibrous clay or charged bentonite such as natural indigo, carmine, beta carotene, carmine hydrosoluble, turmeric, beet, and annato.
  • the natural dye can be reacted with the clay.
  • the method of the present disclosure further comprises heating the mixture of the natural dye and fibrous clay to react the natural dye with the fibrous clay or charged bentonite.
  • the natural dye can be reacted onto the surface of the fibrous clay or charged bentonite to provide a pigment with enhanced stability.
  • the mixture can be heated to a temperature of about 90 °C to about 200 °C.
  • the natural dye and clay are heated to a temperature of about 120 °C to about 180 0 C.
  • the natural dye and clay are heated to a temperature of about 150 °C to about 170 0 C.
  • the mixture can be heated for about 10 minutes to about 24 hours.
  • the natural dye and clay mixture is heated for about 1 to about 9 hours.
  • the natural dye and clay mixture is heated for about 2 to about 4 hours.
  • the natural dye and/or clay can be ground prior to mixing in certain embodiments. In other embodiments, the natural dye and clay are mixed together and then ground. Grinding can be performed by any suitable means, including mortar and pestle, coffee grinder, or kitchen blender.
  • the natural dyes are soluble in water and will only react in the presence of water. In such cases, water can be added to the mix of natural dye and clay to create a paste.
  • the natural dye and clay were ground. Water was added to mixtures with water soluble dyes, beta carotene, carmine hydrosoluble, beet, and annatto, to form a paste. The mixtures, both with and without water, were reacted by heating a mixture of clay and natural dye. Samples of the mixtures of dye and clay, both with and without water, were heated in a static oven at 90 °C, 150 °C, and 170 0 C for about 3 hours. A change of color was observed at all temperatures indicating the natural dyes reacted with the clay, as shown in Table 1.
  • Fig. 1 illustrates DSC curves of natural indigo; 20 wt.% natural indigo, 80 wt.% Attagel 50 (palygorskite) unheated; and 20 wt.% natural indigo, 80 wt.% Attagel 50 (palygorskite) heated.
  • Fig. 1 illustrates DSC curves of natural indigo; 20 wt.% natural indigo, 80 wt.% Attagel 50 (palygorskite) unheated; and 20 wt.% natural indigo, 80 wt.% Attagel 50 (palygorskite) heated.
  • Fig. 1 illustrates DSC curves of natural indigo; 20 wt.% natural indigo, 80 wt.% Attagel 50 (palygorskite) unheated; and 20 wt.% natural indigo, 80 wt.% Attagel 50 (palygorskite) heated.
  • FIG. 2 illustrates DSC curves of natural carmine; 20 wt.% natural carmine, 80 wt.% Attagel 50 (palygorskite) heated; and 50 wt.% natural carmine, 50 wt.% Attagel 50 (palygorskite) heated.
  • the embodiments illustrated in the instant disclosure are for illustrative purposes only. They should not be construed to limit the claims. As is clear to one of ordinary skill in the art, the instant disclosure encompasses a wide variety of embodiments not specifically illustrated herein.
  • compositions and methods of this disclosure have been described in terms of exemplary embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention.

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une composition de pigment hybride qui renferme une argile fibreuse ou une bentonite chargée et un colorant naturel pouvant être carmin, bêta-carotène, carmin hydrosoluble, curcuma, bétanine et rocou. L'argile fibreuse est palygorskite, sépiolite, ou leurs combinaisons. Le colorant naturel est présent dans la composition selon une teneur comprise, en poids, entre 0,01 % et environ 75 % par rapport au poids total de la composition décrite. Cette composition renferme éventuellement de l'eau et un polymère biodégradable.
PCT/US2009/031572 2008-01-17 2009-01-21 Compositions de pigments hybrides renfermant de l'argile et des colorants naturels WO2009092104A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US2178308P 2008-01-17 2008-01-17
US61/021,783 2008-01-17

Publications (1)

Publication Number Publication Date
WO2009092104A1 true WO2009092104A1 (fr) 2009-07-23

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013110841A1 (fr) * 2012-01-27 2013-08-01 Universidad De Alicante Procédé permettant la synthèse de pigments hybrides nanostructurés présentant des propriétés accordables
US9629796B2 (en) * 2013-10-28 2017-04-25 Cqv Co., Ltd. Colored glossy pigment using vegetable type natural dye and method for preparing same
US10662340B2 (en) 2015-12-11 2020-05-26 Coloris Global Coloring Concept Liquid concentrate of solid particles of hybrid pigments containing grafted copolymers and use of same for preparing paints in an aqueous and/or organic medium
CN114195163A (zh) * 2020-09-02 2022-03-18 韩国地质资源研究院 用于染色膨润土的组合物及膨润土染色方法
CN115335030A (zh) * 2020-03-24 2022-11-11 奇华顿股份有限公司 包含萝卜提取物和蒙脱石的颜料
CN115418741A (zh) * 2022-09-21 2022-12-02 常州大学 一种抗菌涤纶植物染料色母粒及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5962553A (en) * 1996-09-03 1999-10-05 Raychem Corporation Organoclay-polymer composites
US20040011254A1 (en) * 2002-06-19 2004-01-22 Board Of Regents, The University Of Texas System Color compositions
US20070189996A1 (en) * 2006-02-13 2007-08-16 L'oreal Nail compositions in gelled form

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5962553A (en) * 1996-09-03 1999-10-05 Raychem Corporation Organoclay-polymer composites
US20040011254A1 (en) * 2002-06-19 2004-01-22 Board Of Regents, The University Of Texas System Color compositions
US20070189996A1 (en) * 2006-02-13 2007-08-16 L'oreal Nail compositions in gelled form

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013110841A1 (fr) * 2012-01-27 2013-08-01 Universidad De Alicante Procédé permettant la synthèse de pigments hybrides nanostructurés présentant des propriétés accordables
ES2421303A1 (es) * 2012-01-27 2013-08-30 Universidad De Alicante Método para la síntesis de pigmentos híbridos nanoestructurados con propiedades sintonizables
US9629796B2 (en) * 2013-10-28 2017-04-25 Cqv Co., Ltd. Colored glossy pigment using vegetable type natural dye and method for preparing same
US10662340B2 (en) 2015-12-11 2020-05-26 Coloris Global Coloring Concept Liquid concentrate of solid particles of hybrid pigments containing grafted copolymers and use of same for preparing paints in an aqueous and/or organic medium
CN115335030A (zh) * 2020-03-24 2022-11-11 奇华顿股份有限公司 包含萝卜提取物和蒙脱石的颜料
CN114195163A (zh) * 2020-09-02 2022-03-18 韩国地质资源研究院 用于染色膨润土的组合物及膨润土染色方法
CN115418741A (zh) * 2022-09-21 2022-12-02 常州大学 一种抗菌涤纶植物染料色母粒及其制备方法和应用
CN115418741B (zh) * 2022-09-21 2024-04-19 常州大学 一种抗菌涤纶植物染料色母粒及其制备方法和应用

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