EP1902101A2 - Composites organiques/inorganiques a base d'acides de lewis - Google Patents

Composites organiques/inorganiques a base d'acides de lewis

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Publication number
EP1902101A2
EP1902101A2 EP06785002A EP06785002A EP1902101A2 EP 1902101 A2 EP1902101 A2 EP 1902101A2 EP 06785002 A EP06785002 A EP 06785002A EP 06785002 A EP06785002 A EP 06785002A EP 1902101 A2 EP1902101 A2 EP 1902101A2
Authority
EP
European Patent Office
Prior art keywords
composition
lewis acid
support
amorphous
indigo
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP06785002A
Other languages
German (de)
English (en)
Inventor
Russell Chianelli
Lori A. Polette
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Texas System
Original Assignee
University of Texas System
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 University of Texas System filed Critical University of Texas System
Publication of EP1902101A2 publication Critical patent/EP1902101A2/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • 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
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0002—Grinding; Milling with solid grinding or milling assistants
    • 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
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0004—Coated particulate pigments or dyes
    • C09B67/0005—Coated particulate pigments or dyes the pigments being nanoparticles
    • 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
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0004—Coated particulate pigments or dyes
    • C09B67/0007—Coated particulate pigments or dyes with inorganic coatings
    • 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
    • C09B7/00—Indigoid 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
    • C09B7/00—Indigoid dyes
    • C09B7/02—Bis-indole indigos
    • C09B7/04—Halogenation thereof
    • 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
    • C09B7/00—Indigoid dyes
    • C09B7/10—Bis-thionapthene indigos
    • 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
    • C09C1/30—Silicic acid
    • 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
    • C09C1/30—Silicic acid
    • C09C1/3063—Treatment with low-molecular organic compounds
    • 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
    • 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
    • C09C1/405—Compounds of aluminium containing combined silica, e.g. mica
    • 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
    • C09C1/407—Aluminium oxides or hydroxides
    • 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
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings

Definitions

  • the present invention relates to the field of pigment and dye compositions. More specifically, it provides for novel compositions comprising an organic dye or pigment complexed with a support comprising a metal oxide, wherein the complex comprises a coordinate covalent bond between the dye and the support.
  • 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.
  • Littman has synthesized indigo-attapulgite complexes and verified that his synthetic version was indistinguishable from the original pigments found in the pre-Hispanic murals and artifacts (Littman, 1980; Littman, 1982).
  • the prepared samples had the same physical and chemical characteristics as the authentic Maya blue examined. Littman concluded that the remarkable stability of the attapulgite was due to the heat treatment the attapulgite received during the synthesis.
  • Others have also synthesized compounds similar to that of Maya blue by a number of routes (Torres, 1988). They employed the Gettens test to determine whether the laboratory synthesis of Maya blue was indeed authentic with the same chemical resistant properties (Gettens, 1962). The test was necessary because initial attempts of simply mixing the palygorskite clay produced the color of Maya blue but the mixture did not possess the same chemical properties as the original organic/inorganic complex samples.
  • U.S. Patent No. 7,052,541 describes color compositions comprising indigo derivatives 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 material.
  • U.S. Serial No. 11/351,577, filed February 10, 2006 further provides improved methods for making color compositions comprising organic pigments and dyes complexed to inorganic clays. Upon grinding and treating with UV light, the organic and inorganic elements combine to form a color composition having unprecedented stability relative to the original starting material alone.
  • control of the final color can be attained within any given set of clay/pigment materials. Additionally, by selecting a particular particle size of the clay starting material, a wide range of colors and hues can also be created.
  • a composition comprising an organic dye coordinately covalently bonded to a support comprising a Lewis acid metal.
  • the color/hue of said composition can determined by the concentration of said dye and pH of said composition.
  • the support may comprise silica, alumina, zeolite, amorphous Al(OH) 3 , amorphous AlO(OH), amorphous Al/SiO 2 , crystalline Al(OH) 3 , crystalline AlO(OH), gibbsite or bayerite.
  • the organic dye may be indigo, thioindigo, dibromoindigo, Vat Orange 5 (diethoxythioindigo), oralith pink, novoperm red, Solvent Yellow 33, Maya blue, Maya purple, Maya red, Maya ultra blue, or have the formula:
  • R 1 -R 8 are individually H, CH 3 , CH 2 CH 3 , F, Cl, Br, I, CN, OH, SH, OCH 3 or OCH 2 CH 3 ;
  • Y is N, O, S, or Se; and
  • X is O or S.
  • the Lewis acid metal may be Zr +4 , Fe +3 , Ti +4 , Al +3 , V +5 , Sn +4 , Nb +5 and Cr +3 , or may be a Lewis acid substitute, such as one having the SiO 2 - ⁇ Al x , wherein O ⁇ X ⁇ 0.5, or SiO 2- ⁇ M x , wherein O ⁇ X ⁇ 0.5, and M is Zr +4 , Fe +3 , Ti +4 , Al +3 , V +5 , Sn +4 , Nb +5 and Cr +3 .
  • the composition may be a powder or a liquid.
  • the composition may be resistant to decomposition by light, acids, alkalis, and solvents.
  • the composition may further comprise a cement, polymer, plastic and/or an organic binding agent.
  • the composition may also further comprise a gum arabic, a linseed oil, a copal, a polycarbonate, an egg tempura, or a turpentine.
  • the composition may have a pH of between 3 and 11 , or a pH of between 3 and 7.5.
  • the composition may comprise a support selected from a group consisting of a three- dimensional support, a two-dimensional support, a one-dimensional support and an amorphous support.
  • a method of producing a composition comprising a) combining an organic dye with a support comprising a Lewis acid metal to form a coordinate covalent bond between the dye and the Lewis acid metal; and b) heating said composition or subjecting said composition to UV radiation.
  • the method may further comprise adjusting the pH of the organic dye.
  • the method may further comprise applying said composition to a surface.
  • the method may further comprise blending said composition with a polymer or organic binder.
  • the method may further comprise homogenizing said dye by blending, grinding, milling or stirring.
  • the method may further comprise adding a binding agent to said coating composition.
  • the method may comprise a support is selected from a group consisting of a three-dimensional support, a two-dimensional support, a one- dimensional support and an amorphous support.
  • the heating may comprise heating at a temperature of between 100°C and 300 0 C, or between 115°C and 200°C. The heating may last up to four days.
  • the composition may contain water.
  • the composition may have a pH of between 3 and 7.5.
  • the composition may contain the organic dye in the range of about 0.01% to about 25% by weight.
  • the support may comprise silica, alumina, zeolite, amorphous Al(OH) 3 , amorphous AlO(OH), amorphous Al/SiO 2 ⁇ crystalline Al(OH) 3 , crystalline AlO(OH), gibbsite or bayerite.
  • the organic dye may be indigo, thioindigo, dibromoindigo, Vat Orange 5 (diethoxythioindigo), oralith pink, novoperm red, Solvent Yellow 33, Maya blue, Maya purple, Maya red, Maya ultra blue, or novoperm red.
  • the composition may contain indigo or a molecular derivative of indigo in the range of about 0.1% to 25% by weight.
  • the composition may contain indigo or a molecular derivative of indigo at about 10% by weight at neutral or acidic pH.
  • the Lewis acid metal may be selected from a group consisting of Zr +4 , Fe +3 , Ti +4 , Al +3 , V +5 , Sn +4 , Nb +5 and Cr +3 .
  • the Lewis acid metal may be a Lewis acid substitute, such as one having the formula SiO 2- ⁇ Al x , wherein 0 ⁇ X ⁇ 0.5, or the formula SiO 2-x M x , wherein 0 ⁇ X ⁇ 0.5, and M is Zr +4 , Fe +3 , Ti +4 , Al +3 , V +5 , Sn +4 , Nb +5 and Cr +3 .
  • the UV radiation may comprise ultraviolet light is in the range of about 200 to about 500 nm.
  • the composition may be subjected to ultraviolet light for about 1 minute to about 8 hours.
  • the composition may have a pH of between 3 to 11.
  • another may mean at least a second or more.
  • FIG. 1 Color of SiAl-Novoperm Red before and after heating in oven at 125°C for 24 hrs.
  • FIG. 2 TGA (Thermogravimetric Analysis) and DTA (Differential Thermal Analysis) of Novoperm Red.
  • FIG. 3 TGA and DTA of SiAl-Novoperm Red Complex.
  • FIG. 4 Comparison of TGA/DTA of Novoperm Red and SiAl-Novoperm Red Complex.
  • FIG. 5 Thioindigo/Al doped SiO 2 before and after heating.
  • the present invention provides a new class of materials combining organic dyes/pigments (e.g., indigo) and a support comprising a Lewis acid metal, such as Si, Al, Ti and/or Zr.
  • a Lewis acid metal such as Si, Al, Ti and/or Zr.
  • the metal substitution in the support framework provides Lewis acid sites that interact with the organic dye/pigment, producing the required charge transfer complex that characteristic of the Maya Blue class of materials.
  • the charge transfer complex comprises a coordinate covalent bond, as described below.
  • the Lewis acid in the support matrix can be any metal that is classified as a Lewis acid - Ti +4 , Al +3 , V +5 , etc. Further, the Lewis acid may be comprised in any type of oxide, including an oxide, a hydroxide, and/or an oxyhydroxide.
  • the invention has great potential in the dye and pigment industry.
  • the color for the color composition comes from an organic dye or pigment.
  • the dyes and/or pigments are typically commercially available (e.g., Clariant Co.).
  • This chromophore may be indigo or a molecular derivative of indigo such as thioindigo, dibromoindigo, Vat Orange 5 (diethoxythioindigo), oralith pink, novoperm red, or Solvent Yellow 33.
  • Other derivatives of indigo are shown in Schemes 1 and 2.
  • the chromophore may also be a different derivative, such as one containing an additional conjugated ring or ligand.
  • Ri-R 8 are individually H, CH 3 , CH 2 CH 3 , F, Cl, Br, I, CN, OH, SH, OCH 3 or OCH 2 CH 3; Y is N, O, S, or Se; X is O or S;
  • R 1 -R 8 are individually H, CH 3 , CH 2 CH 3 , F, Cl, Br, I, CN, OH, SH, OCH 3 or OCH 2 CH 3 ;
  • R 9 -R 11 are individually SiO 3 , SiOH or H 2 O;
  • Y is NH, O, S, or Se;
  • X is O or S;
  • M (n+ ⁇ is Al, Sn, Nb, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Pt, Pd or Zn; and n is 1, 2, 3, or 4.
  • compositions of the present invention will comprise a support comprising a metal oxide, such as those containing, Si, Al, Ti and Zr.
  • Metal oxides comprise metal oxides (e.g., Al 2 O 3 ), metal hydroxides (e.g., Al(OH) 3 ), or metal oxyhydroxides (e.g., AlO(OH) 3 ).
  • metal oxides e.g., Al 2 O 3
  • metal hydroxides e.g., Al(OH) 3
  • metal oxyhydroxides e.g., AlO(OH) 3
  • high surface area silica and alumina oxide powders are contemplated for their use.
  • One or more metal oxides may comprise compositions of the present invention.
  • the supports may be of any structure including, in non-limiting examples, amorphous, polymorphic, one- dimensional, two-dimensional, three-dimensional, non-crystalline, crystalline, micro- crystalline, quasi-crystalline, or any combination of these types.
  • Non-limiting examples of three-dimensional supports include zeolites and alumina (Al 2 O 3 ).
  • Non-limiting examples of two-dimensional supports include crystalline Al(OH) 3 and crystalline AlO(OH).
  • Non-limiting examples of amorphous supports include amorphous AVSiO 2 , amorphous Al(OH) 3 and amorphous AlO(OH). Further, hydrates of any of the supports are also contemplated by the present invention.
  • Silica-based supports The chemical compound silicon dioxide, also known as silica, is the oxide of silicon, with the chemical formula Of SiO 2 .
  • Hi-SiI silicas (PPG Industries) offer consistent and high loadings of active ingredients in agricultural products such as pesticides, insecticides, and herbicides, and are effective in vitamin premixes for animal feed.
  • Hi-SiI silicas used as free flow agents are excellent grinding and suspension aids in animal feed supplements.
  • Hi-SiI silicas are also used as carriers in the rubber industry for dry liquid powder blends of rubber compounding additives, such as plasticizers, bonding agents and antioxidants.
  • Hi-SiI ABS silica is a synthetic amorphous silicon dioxide designed as a carrier to convert liquid plasticizers, process oils and other rubber compounding ingredients to free-flowing powders for introduction into rubber compounds.
  • Hi-SiI ABS silica is a white precipitated silica powder with a uniform spherical shape and a median agglomerate diameter of 20 micrometers. It is amorphous in structure and highly porous with a surface area of 150 m 2 /g. Hi-SiI ABS silica is pure white in color, has a neutral pH and is chemically inert.
  • SUNSIL-130 (Sunjin Chemicals) is spherical porous silica powders and its mean particle size is about 6-9 ⁇ m.
  • SUNSIL-130SC series are silicone oil coated silica. This silicone oil coating gives silica excellent water-repellant property, better smoothness, softer feeling, improved affinity and spread when applied to the skin.
  • SUNSIL-130SC series are produced through slurry process (wet process) so its silicone coating is more durable and tight compared to the products produced through dry process.
  • SUNSIL-130 has better smoothness, adhesiveness and smoothness to the skin due to its much sharper particle size distribution. There is almost no >15 ⁇ m particle which causes several disadvantages to cosmetic formulation including coarse feeling, loose touch, and diminished adhesiveness to the skin due to its much bigger size and heavier weight.
  • AB 762M International Resources white precipitated silica powder has a median agglomerate size of seven micrometers and a neutral pH.
  • Efficiency AB 762M silica is a premium grade antiblock which provides efficient antiblock at an equivalent silica loading, resulting in a very cost effective formulating alternative.
  • SinoSi's Nano-Meter Silicon Materials is a powder which main includes SiPowder, SiC Powder, Si 2 N 4 Powder, Si/N/C Powder and C Powder and so on.
  • the primary principle of laser synthesis Nano powder is that the gas phase synthesis reaction induced by the laser takes place as gas reactants coming into the laser beam to form the reaction zone, making use of the property of some gas reactants strongly absorbing the power of the energy of the laser due to their absorbing line nearly according with the wave line of the laser, and Nan powders are finally formed by a rapid condensing course.
  • the powders present very small size, high purity and high uniformity.
  • the reacting system is pumped into vacuum and filled with high pure protected gas before the production, the oxygen content is controlled with the oxygen analytic apparatus during the production. Finally, keeping from oxygen, the products are gathered and parked at nitride gas condition.
  • U.S. Patents 6,855,751, 6,849,242, 6,749,823, 6,696,034, 6,569,922, 6,387,302, 6,386,373, 6,333,013, 6,235,270, 6,225,245, 6,071,838, 6,071,487, 6,047,568, 6,007,786, RE36,396, 5,897,888, 5,888,587, 5,720,909, 5,604,163, 5,486,420, 5,480,755, 5,480,696, 5,395,604, 5,376,449, 5,307,122, 5,306,588, 5,211,733, 5,156,498, 5,145,510, 5,083,713, 5,049,596, 4,837,011, 4,804,532, 4,767,433, 4,755,368, 4,678,652, 4,593,007, 4,375,373 and 4,345,015 describe silica powders and methods for their production.
  • Zeolites Zeolite is an inorganic porous material having a highly regular structure of pores and chambers that allows some molecules to pass through, and causes others to be either excluded, or broken down. What a zeolite does, and how it does it, depends upon the exact shape, size, and charge distribution of the lattice structure of the zeolite. There are hundreds of different zeolites found in nature and made by man. In nature, zeolites are often formed where volcanic rock of specific chemical composition is immersed in water so as to leach away some of the components. Composition and pore size, of course, depend upon what kind of rock minerals are involved. Industry has mimicked some of the natural zeolites, and formed many new ones targeted towards very specific purposes.
  • Zeolyst International provides a variety of zeolite products. Five general groups are provided: Zeolite Y products, Beta type Zeolite products, Mordenite type Zeolite products, ZSM-5 Zeolite type products and Ferrierite type Zeolite products. The characteristics of the groups are set out below:
  • U.S. Patents 6,357,678, 5,387,564, 4,594,332, 4,551,322, 4,405,484, 4,339,419, 4,305,916, 4,303,629, 4,303,628, 4,303,627 and 4,303,626 provide zeolite compositions and methods of making them.
  • Aluminum-containing supports A wide variety of supports containing aluminum exist are well-known to those of skill in the art. Non-limiting examples of aluminum- containing supports include alumina, amorphous Al(OH) 3 , amorphous AlO(OH), amorphous Al/SiO 2 (Al substituted SiO 2 ), crystalline Al(OH) 3 , crystalline AlO(OH), gibbsite and bayerite. Minerals such as boehmite and diaspore comprise the chemical formula AlO(OH). Minerals such as gibbsite, bayerite, doyleite and nordstrandite comprise the chemical formula Al(OH) 3 .
  • Alumina also known as aluminum oxide, is a chemical compound of aluminum and oxygen with the chemical formula Al 2 O 3 . It is also commonly referred to as alumina in, for example, the mining, ceramic, and materials science communities.
  • Gibbsite is also known as hydrargyllite and comprises the chemical formula Al(OH) 3 .
  • Gibbsite is an important ore of aluminium and is one of three minerals that make up the rock bauxite.
  • Bauxite is often thought of as a mineral but is really a rock composed of aluminium oxide and hydroxide minerals such as gibbsite, boehmite, and diaspore (HAlO 2 ), as well as clays, silt, and iron oxides and hydroxides.
  • Bauxite is a laterite, a rock formed from intense weathering environments such as found in richly forested, humid, tropical climates.
  • Gibbsite has three named structural polymorphs or polytypes: bayerite, doyleite, and nordstrandite. Gibbsite and bayerite are monoclinic, whereas doyleite and nordstrandite are triclinic forms.
  • the structure of gibbsite is interesting and analogous to the basic structure of the micas.
  • the basic structure forms stacked sheets of linked octahedrons of aluminium hydroxide.
  • the octahedrons are composed of aluminium ions with a +3 charge bonded to six octahedrally coordinated hydroxides with a -1 charge.
  • Each of the hydroxides is bonded to only two aluminiums because one third of the octahedrons are vacant a central aluminium.
  • the lack of a charge on the gibbsite sheets means that there is no charge to retain ions between the sheets and act as a "glue" to keep the sheets together.
  • the sheets are only held together by weak residual bonds and this results in a very soft easily cleaved mineral.
  • Gibbsite's structure is closely related to the structure of brucite, Mg(OH) 2 .
  • the lower charge in brucite's magnesium (+2) as opposed to gibbsite's aluminium (+3) does not require that one third of the octahedrons be vacant of a central ion in order to maintain a neutral sheet.
  • the different symmetry of gibbsite and brucite is due to the different way that the layers are stacked.
  • gibbsite layer that in a way forms the "floor plan" for the mineral corundum, Al 2 O 3 .
  • the basic structure of corundum is identical to gibbsite except the hydroxides are replaced by oxygen. Since oxygen has a charge of -2 the layers are not neutral and require that they must be bonded to other aluminiums above and below the initial layer producing the framework structure that is the structure of corundum. Gibbsite is often found as a part of the structure of other minerals.
  • the neutral aluminium hydroxide sheets are found sandwiched between silicate sheets in important clay groups: the illite, kaolinite, and montmorillonite/smectite groups.
  • the individual aluminium hydroxide layers are identical to the individual layers of gibbsite and are referred to as "gibbsite layers.”
  • U.S. Patents 5,514,316, 5,880,196, 6,555,496, 6,593,265, 6,689,333, 6,710,004 and 7,022,304 provide aluminum-containing compositions and methods of making them.
  • Lewis Acid Metals A Lewis acid is an electron pair acceptor. A Lewis base is an electron pair donor.
  • any Arrhenius acid or base, or any Br ⁇ nsted-Lowry acid or base can also be viewed as a Lewis acid or base.
  • the reaction of H 1+ with OH 1" involves donation and acceptance of a proton, so it is certainly legitimate to call it a Br ⁇ nsted- Lowry acid-base reaction. But if one looks at the Lewis structures for the reactants and products, one sees that it is also legitimate to call this a Lewis acid-base reaction.
  • the hydroxide ion donates a pair of electrons for bond formation, thus OH 1" is a Lewis base in this reaction.
  • the hydrogen ion accepts the pair of electrons so it is acting as a Lewis acid. Shown below is an example of a Lewis acid-base reaction that cannot be viewed as a Br ⁇ nsted-Lowry acid-base reaction.
  • the BF 3 is the Lewis acid and the N(CH 3 )3 is the Lewis base.
  • Both of the electrons in the bond formed by a Lewis acid-base reaction come from the same atom (in the above example, the nitrogen donates both electrons).
  • Such bonds are called coordinate covalent bonds.
  • compounds of the present invention feature such coordinate covalent bonds.
  • a coordinate covalent bond is represented by an arrow pointing from the donor of the electron pair to the acceptor of the electron pair:
  • a coordinate covalent bond (also known as dative covalent bond) is a special type of covalent bond in which the shared electrons come from one of the atoms only. Coordinate covalent bonds are formed when a Lewis base (an electron donor) donates a pair of electrons to a Lewis acid (an electron accepter). The resultant compound may then be called an adduct (a compound formed by the addition reaction between two molecules). The process of forming a dative bond is typically called coordination. Once the bond has been formed, its strength is no different from that of a covalent bond.
  • a compound that contains a lone pair of electrons is capable of forming a coordinate bond.
  • Coordinate covalent bonds can be found in many different substances, such as in simple molecules like carbon monoxide (CO), which contains one coordinate covalent bond and two normal covalent bonds between the carbon atom and the oxygen atom, or the ammonium ion (NH 4 + ), where a coordinate covalent bond is formed between a proton (a H + ion) and the nitrogen atom.
  • CO carbon monoxide
  • NH 4 + ammonium ion
  • Coordinate covalent bonds are also formed in electron deficient compounds, such as in solid beryllium chloride (BeCl 4 2" ), in which every beryllium atom is bonded to four chlorine atoms, two with normal covalent bonding, and the other two with coordinate covalent bonds, which will give it a stable octet of electrons.
  • Coordinate covalent bonding can also be found in coordination complexes involving metal ions, as in certain embodiments of the present invention, especially if they are transition metal ions. In such complexes, substances in a solution act as Lewis bases and donate their free pairs of electrons to the metal ion, which acts as a Lewis acid and accepts the electrons.
  • the resulting compound may be called a coordination complex, while the electron donors are often called ligands.
  • electron donors are often called ligands.
  • a common ligand is water (H 2 O), which will form coordination complexes with metal ions, like Cu 2+ , which will form [Cu(H 2 O) 6 J 2+ in aqueous solution.
  • Other common simple ligands are ammonia (NH 3 ), fluoride ions (F “ ), chloride ions (CF) and cyanide ions (CN “ ).
  • Lewis acids There are six classes of Lewis acids: (heavy) metal Lewis acids, pi-LUMO Lewis acids, Lobe- LUMO Lewis acids, onium ion Lewis acids, s-LUMO Lewis acids and the proton Lewis acid. Of particular interest in the present invention are (heavy) metal Lewis acids. Heavy metal Lewis acids may be categorized as hard, borderline or soft (correlating with high-to-low oxidation states).
  • heavy metal Lewis acids include Sc 3+ , Ti 2+ , Ti 3+ , Ti 4+ , V 2+ , V 3+ , V 4+ , V 5+ , Cr 2+ , Cr 3+ , Cr 6+ , Mn 2+ , Mn 3+ , Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Ni2 + , Ni3 + , Cu + , Cu 2+ , Zn 2+ , Y 3+ , Zr 3+ , Zr 4+ , Nb 3+ , Nb 5+ , Mo 2+ , Mo 3+ , Mo 4+ , Mo 5+ , Ru 2+ , Ru 3+ , Ru 4+ , Ru 8+ , RIi 2+ , Rh 3+ , Pd 2+ , Pd 4+ , Ag + , Cd 2+ , In + , In 3+ , Sn 2+ , Sn 4+ , La 3+ , Ce 3+ , Ce 3
  • binding agent or modifiers may be added to the paint composition to increase stability, uniformity, spreadability, adhesion, coating thickness, etc. Binding agents and modifiers are well known in the art of paint formulation and may be included in the current coating composition. Binding agents such as solvent-containing binding agents (acryl, cyclized rubber, butyl rubber, hydrocarbon resin, ⁇ -methylstyrene-acrylonitrile copolymers, polyester imide, acryl acid butyl esters, polyacrylic acid esters, polyurethanes, aliphatic polyurethanes and chloro sulphonated polyethylene), and thermoplastic materials (polyolefins, ⁇ -ethylstyrene-acrylonitrile copolymers, polyester imide and polyamide) may be added to the paint composition.
  • solvent-containing binding agents acryl, cyclized rubber, butyl rubber, hydrocarbon resin, ⁇ -methylstyrene-acrylonitrile copolymers, polyester imide, acryl acid butyl est
  • polymers such as acrylate, styrene acrylate, acrylonitrile copolymer, polyethylene, polyethylene oxidate, chlorosulfonated polyethylene, ethylene- acrylic acid copolymer, methacrylate, vinylpyrrolidone-vinyl acetate copolymer, vinylidene chloride copolymer, polyvinylpyrrolidone, polyisopropyl acrylate, polyurethane, cyclized rubber, butyl rubber, hydrocarbon resin, ⁇ -methylstyrene-acrylonitrile copolymer, polyester imide, acryl acid butyl esters, or polyacrylic acid esters may be added.
  • polymers such as acrylate, styrene acrylate, acrylonitrile copolymer, polyethylene, polyethylene oxidate, chlorosulfonated polyethylene, ethylene- acrylic acid copolymer, methacrylate, vinylpyrrolidone-vinyl acetate copolymer
  • the paint composition can be blended with a variety of other medium including gum arabic, linseed oil, copal, polycarbonate, egg tempura, and turpentine to create blended systems.
  • the blended paint color can be altered depending on the medium in which it is blended. Grinding the initial powder to various particle sizes prior to or during blending with a medium can result in color control.
  • composition when exposed to strong sunlight or other light sources as is common for painted surfaces, the composition will not noticeably change in color and the intensity, as measured by IR spectroscopy or x-ray diffraction, and will not decrease more than 10% over a 1 year period.
  • the composition is also resistant to decomposition by acids, alkalis, and solvents. When exposed to acidic or basic solutions, the composition will not noticeably change in color and the intensity, as measured by IR spectroscopy or x-ray diffraction, will not decrease more than 10% over a 1 year period.
  • the general method for producing a color composition comprises providing a molecular derivative of indigo, indigo derivative or any cationic organic dye or cationic pigment.
  • the derivative of indigo can be selected from any indigo derivative shown in Scheme 1.
  • the amount of dye or pigment used can be in the range of 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 2.0%, 3.0%, 4.0%, 5.0%, 6.0%, 7.0%, 8.0%, 9.0%, 10.0%, 11.0%, 12.0%, 13.0%, 14.0%, 15.0%, 16.0%, 17.0%, 18.0%, 19.0%, 20.0%, 21%, 22%, 23%, 24% or 25% by weight or more preferably 0.1 % to 25% by weight or ideally at about 6% by weight.
  • the next step comprises combining the dye/pigment with a support.
  • This step may further comprise the grinding of the dye or pigment with the support, for example, in a blender, industrial blender, industrial mixer, shear blender, or a precise solid state blender.
  • the support and the dye/pigment may be ground separately and then ground together or they may be combined and ground to both mix the two components in order to obtain the preferred ratio.
  • Techniques for grinding and blending the dye/pigment and support compositions are found in Mixing of Solids (Weinekotter and Gericke, 2000), Powder and Bulk Solids Handling Processes (Iinoya et ah, 1988), or Bulk Solids Mixing (Gyenis and Gyenis, 1999). De-ionized water may be added during blending to attain a homogenized mixture.
  • the next step comprises heating the color composition.
  • the heating may comprise heating at a temperature of 100°C, 110 0 C, 115 0 C, 120°C, 125°C, 130 0 C, 135°C, 14O 0 C, 145 0 C, 150 0 C, 155°C, 160 0 C, 165°C, 17O 0 C, 175°C, 18O 0 C, 185°C, 190 0 C, 195°C, 200 0 C, 205 0 C, 21O 0 C, 215°C, 220 0 C, 225°C, 230 0 C, 235°C, 24O 0 C, 245 0 C, 250 0 C, 255°C, 260 0 C, 265 0 C, 270 0 C, 275°C, 280°C, 285°C, 29O 0 C, 295°C or 300 0 C, or more particularly between 115 0 C and 200°C.
  • the heating may
  • An alternative to heating comprises treating the color composition with radiation, including ultraviolet.
  • Light radiation in the range from 10 run to 500 nm will be used in accordance with the present invention, particularly 200-400 nm (i.e., near UV). Treatment times will vary from very brief— as short as one minute — to several hours (1, 2, 3, 4, 5, 7, 8, 9, 10, 11, 12, 18, 24, 36, 48 or more hours).
  • Suitable devices for providing UV exposure exist including chambers and reactor vessels.
  • the pH of the color composition may be adjusted to an acidic or neutral pH, depending on the final color desired.
  • Exemplary examples of the acid used to adjust the pH comprise: any protonic acid, H 2 SO 4 , HClO 4 , HClO 3 , H 3 PO 4 , HNO 3 , HCN, HF, HBr, HI, H 3 O + , or CH 3 COOH, or more preferably HCl.
  • Exemplary examples of the base used to adjust the pH comprise: LiOH, NaOH, KOH, RbOH, CsOH, Ca(OH) 2 , Sr(OH) 2 , Ba(OH) 2 or more preferably NaOH.
  • the pH of the color composition can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.
  • the pH of the system can be monitored with a pH meter that is calibrated with buffers of pH 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.
  • Additional steps in making the color composition may comprise: treating the color composition with acid such as but not limited to any protonic acid, H 2 SO 4 , HClO 4 , HClO 3 , H 3 PO 4 , HNO 3 , HCN, HF, HBr, HI, H 3 O + , or CH 3 COOH, or more preferably HCl, to remove impurities from the clay; applying the color composition to a surface; blending the color composition with a polymer, plastic or organic binder as discussed in Encyclopedia of Polymer Science and Engineering, 2 nd ed. (Herman, 1990) and Paint and Surface Coatings: Theory and Practice, 2 nd ed. (Lambourne and Strivens, 1999).
  • acid such as but not limited to any protonic acid, H 2 SO 4 , HClO 4 , HClO 3 , H 3 PO 4 , HNO 3 , HCN, HF, HBr, HI, H 3 O + , or CH 3 COOH, or more preferably
  • U.S. Patent 3,950,180 covers the method of manufacturing color compositions that include zeolite and montmorillonite.
  • U.S. Patent 5,061,290 covers the 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.
  • U.S. 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.
  • 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.
  • organic/inorganic complex refers to a complex featuring a coordinate covalent bond among one or more organic molecules and one or more inorganic molecules.
  • color composition refers to a pigment or dye complexed to a support material comprising a Lewis acid metal as described herein.
  • coating composition is synonymous with “color composition” and "paint powder.”
  • cement refers to Portland cement types I, II, III, IV, IA, HA, IIIA or as covered in The Chemistry of Portland Cement, 2 nd ed.
  • the Maya/Blue concept is based on the electronic interaction between the organic molecule (indigo) and the clay (palygorskite). Though we and others have studied authentic
  • Maya Blue pigments and many theories as to the origin of the Maya Blue color were described, it was not until we began to produce synthetic samples with molecules unknown to the Maya that the real chemical nature of the complexes were revealed.
  • the basic concept was that the organic compound interacted with "sites" at the surface of the clay through gentle heating of the two starting phases. Electron density was exchanged, stabilizing the complex and leading to a change in the color.
  • the organic/inorganic complexes (OICs) described above use common clays as the inorganic portion. These clays, though inexpensive and abundant, contain variable amounts of metals such as Al and Fe. This variation is not a problem for quality control if the clay is obtained from a common source. However, because the clays are difficult to synthesize in the laboratory, it is difficult to distinguish between the role played by Fe and Al in developing the final properties of the OIC. Further, the ability to form OICs using other inorganic materials that are inexpensive and readily available would be very advantageous.
  • SiAl-Novaperm Red complex preparation SiAl (3111) (Silica Alumina, a white zeolite powder) purchased from Davidson Catalysts was mixed with Novoperm Thi red 4G-70 purchased from Clariant corporation 95:5% by weight and mixed in a blender for 5 min. The mixture was then ball milled in a ball mill for 18 hrs and subsequently heated in an oven at
  • Paint Preparation The above material was used as a pigment in paint at a pigment content of 11.78% and percentage non volatile matter of 38.60%.
  • the formulation is listed in
  • the paint was applied on a pre-printed Al panel with a 10 mil wet film applicator and allowed to mature for 7 days.
  • TGA and DTA Analysis TGA and DTA analysis was done for the dye Novoperm Red and the heated SiAl-Novoperm Red mixture. The results are as shown in the FIGS. 2-4. From FIGS. 2 and 4 it can be observed that the DTA graph of Novoperm red shows a negative change in temperature at 473.55°C that corresponds to endothermic decomposition of Novoperm red. In FIG. 1 the TGA plot shows a drastic reduction in mass of Novoperm Red from 385°C to 485°C; this corresponds to the decomposition temperature of Novoperm red. The DTA of the SiAl-Novoperm red complex in FIGS. 3 and 4 does not show such a change and the loss in mass is gradual over temperature range of 150°C to 600°C. This clearly indicates the formulation of the SiAl-Novoperm red complex.
  • Si/ Al and zeolites materials commonly used as chemical and petroleum refining catalysts, have the advantage of being synthesized with known controllable compositions.
  • Cracking catalysts for example, are made with varying amounts of Al replacing Si in the amorphous SiO 2 lattice (i.e., Al substituted SiO 2 ). The amount of Al is adjusted to create Lewis acid sites for various applications.
  • An example of a thioindigo complex with a 10% Al doped amorphous SiO 2 is shown in FIG. 5. Again the required color change is apparent but different from the complex formed with palygorskite:

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Abstract

La présente invention concerne de nouvelles compositions comprenant un pigment ou un colorant organique complexé à un support par l'intermédiaire d'une liaison bipolaire. Le support se caractérise par le fait qu'il comprend un acide de Lewis ou un substitut d'acide de Lewis.
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KR20080047343A (ko) 2008-05-28
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CA2615514A1 (fr) 2006-12-28
WO2006138566A2 (fr) 2006-12-28
CN101243142A (zh) 2008-08-13

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