WO2000032700A1 - Pigments hybrides de kaolin a opacite elevee - Google Patents

Pigments hybrides de kaolin a opacite elevee Download PDF

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Publication number
WO2000032700A1
WO2000032700A1 PCT/US1999/028235 US9928235W WO0032700A1 WO 2000032700 A1 WO2000032700 A1 WO 2000032700A1 US 9928235 W US9928235 W US 9928235W WO 0032700 A1 WO0032700 A1 WO 0032700A1
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Prior art keywords
metal oxide
pigment
clay
percent
weight
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PCT/US1999/028235
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English (en)
Inventor
Amy S. Jensen
Sharad Mathur
Kevin C. Riggs
Tracey A. Burbank
Michael G. Londo
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Engelhard Corporation
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Priority to AU19266/00A priority Critical patent/AU1926600A/en
Publication of WO2000032700A1 publication Critical patent/WO2000032700A1/fr

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
    • 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
    • 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
    • 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
    • C09D7/66—Additives characterised by particle size
    • C09D7/68—Particle size between 100-1000 nm
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • 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
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • 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
    • C01P2006/80—Compositional purity
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays

Definitions

  • This invention relates to novel mineral-based pigments for providing opacity and brightness to paper. More particularly, the present invention relates to the thermal aggregation of hydrous clay particles with metal oxides and/or metal oxide precursors.
  • the present invention offers an advance from known techniques and compositions of clay-based opacifying pigments as hereinafter described.
  • the present invention relates to a composition and method of making compositions of hybrid opacifying pigments useful as paper filling or paper coating pigments.
  • the composition comprises a pigment derived from heating a hydrous clay with metal oxides and/or metal oxide precursors, the metal being selected from the group consisting of a transition metals, post-transition metals, and their combinations, the heating being applied to an extent sufficient to change the crystalline structure of the clay while aggregating or structuring the clay with the metal oxides, their precursors, and/or combinations thereof.
  • hybrid pigments of the present invention include pigments of significantly higher opacity when compared to a simple physically combined blend (i.e., not heated) of commercially available calcined kaolin pigments and the corresponding metal oxide and/or metal oxide precursor.
  • a further surprising and quite unexpected advantage of this invention includes that when the hybrid pigments are used in sheet paper applications, they impart equal or comparable sheet brightness and significantly greater opacity at equivalent net mineral content than commercially available calcined kaolin pigments.
  • the hybrid pigments of the invention may have lower GE Brightness (GEB) values than some of the best commercially available calcined clay opacifying pigments, the hybrid pigments of this invention provide comparable coated sheet brightness but surprisingly superior sheet opacity at equivalent net mineral contents compared to these commercially available pigments.
  • GEB GE Brightness
  • hydroxous clay is intended to describe a clay which has not been subjected to calcination, i.e., a temperature at which the basic crystalline structure of the clay would be altered. In the case of kaolin, maintaining the clay at temperatures under 450°C will not alter the kaolin's crystalline structure.
  • Hydrous clays are widely known in the art and are typically produced from crude clays which have been subjected to beneficiation, as for example to, froth flotation, magnetic separation, mechanical delamination, grinding, or similar commutation.
  • hydrous clays examples include kaolinite, halloysite, montmorillonoids (e.g.. talc, pyrophyllite, hectorite, bentonite and montmorillonite), smectites, attapulgite, illite, and sepiolite. Characteristic of these hydrous clay is that they contain chemically bound water (i.e., water of hydration) which is driven off by heating.
  • Kaolinite is an aluminum hydroxide silicate having the approximate composition of Al 2 (OH) 4Si 2 O 5 .
  • a clay having the following particle size distribution characteristics has been found to provide excellent rheology: a median particle size of 0.55 micrometers and a particle size distribution such that about 88 +/- 2% of the particles have an equivalent spherical diameter less than about 2 micrometers and not more than about 25% by weight, preferably not more than about 20% by weight, have an equivalent spherical diameter less than 0.3 micrometers. If the quantity of ultrafine particles, i.e., particles 0.3 micrometers and finer, is too great, the rheology of the pigment may be such that it has limited, if any, use.
  • the hydrous clay In order to achieve the desired particle size distribution of the hydrous clay, it is generally necessary to perform one or more particle size separations on the crude clay.
  • processing includes degritting, followed by differential gravitational or centrifugal sedimentation to recover a size fraction of desired particle size, such as for example, a fraction that is 90%) by weight finer than 1 micrometers and does not contain an excessive amount of ultrafine particles.
  • the content of ultrafines and median (weight) particle size of such fraction will vary, depending on the particle size distribution of the crude clay.
  • the clay particles are therefore treated with a deflocculant (dispersing agent) which will give all the particles a negative electric charge, and cause them to repel each other when the particles are suspended in water.
  • the clay dispersant used at this stage is generally referred to as a "primary" dispersant.
  • Dispersants used to deflocculate suspensions of previously processed clay are termed “secondary" dispersants or deflocculants.
  • Suitable dispersing agents used for primary dispersion in practice of the present invention are conventional and include water soluble salts of a condensed phosphate, e.g., sodium hexametaphosphate or tetrasodium pyrophosphate, a water soluble salt of a polysilicic acid, for example, sodium silicate, or a water soluble organic polymeric dispersing agent, for example a polyacrylate or a polymethylmethacrylate salt having a molecular weight in the range of about 500 to about 10,000.
  • the amount of dispersing agent used will generally be in the range of from about 0.025 to 0.2% by weight based on the weight of the dry clay.
  • particle size separations are performed using defloculated aqueous suspensions having a solids content of about 20-60% by weight. Other solids levels may be used to carry out such separations.
  • the median particle size of the clay particles should range from 0.4 to 0.7 micrometers, equivalent spherical diameter (e.s.d.), preferably 0.5 to 0.6 micrometers, as determined by conventional sedimentation techniques using the SEDIGRAPH ® particle size analyzer, supplied by Micromeretics, Inc. From about 75% to 95% by weight of the particles should be finer than 2 micrometers, e.s.d. The content of fines below 0.3 micrometer e.s.d.
  • weight percent should be below 35 weight percent, preferably below 25 weight percent, and most preferably 20 weight percent or below. It should be understood that the measurements of the size of clay particles that are 0.3 micrometer or finer are of limited reproducibility. Thus, when a SEDIGRAPH ® analyzer is employed, the value for weight percent may be +/- 5% when tested by another operator or a different
  • SEDIGRAPH ® analyzer is employed. Most preferably, median particle size is 0.6 +/- 0.05 micrometers, e.s.d., with 85 to 95% by weight of the particles finer than 2 micrometers, e.s.d., and less than about 20% by weight or less finer than 0.30 micrometers, e.s.d. Blending of clay fractions may be advantageous or necessary with some crudes to provide a clay feed having a desirable particle size distribution. Also useful are hydrous clays derived from fine grained East Georgia crudes; e.g., a hydrous clay product with approximately 90 percent of the particles finer than 0.5 micrometer.
  • Illustrative of particle size distributions for beneficiated hydrous clays useful in this invention excellent results have been obtained using hydrous clays ranging from about 75 to 100 percent by weight finer than 1 micrometer with approximately 70-90 percent of the particles finer than 0.5 micrometer.
  • a particularly useful hydrous clay characteristic of the hydrous clays used in the examples of this application has a particle size distribution of about 85 to 95 percent by weight finer than 1 micrometer with approximately 70 to 80 percent by weight of the particles finer than 0.5 micrometer.
  • the metal oxides and metal oxide precursors useful in this invention are derived from transition metals, post-transition metals, and their combinations.
  • the term "precursor" as used herein when referring to metal oxide precursors is intended to describe a metal composition that when sufficiently heated will form the metal composition's corresponding metal oxide.
  • the corresponding titania precursor may be a metal composition in the form of titanyl sulfate. titanyl chloride, or other appropriate forms.
  • Typical heating temperature wherein an oxide will be formed from its precursor can readily be determined by one skilled in the art by thermogravimetric analysis. In the case of titanyl sulfate, titania will be formed at approximately 800 C.
  • Transition metals are metals having atomic numbers of 21 to 29 (scandium through copper). 39 to 47 (yttrium through silver), 57 to 79 (lanthanum through gold), and 89 and higher (actinium and higher).
  • a preferred transition metal is titanium which forms its corresponding metal oxide in the form of titania.
  • Post-transition metals are metals having atomic numbers of 30 to 32 (zinc through germanium), 48 to 51 (cadmium through antimony), and 80 to 84 (mercury through polonium).
  • Preferred post-transition metals are zinc and tin which form the corresponding metal oxides of zinc oxide for zinc and stannous oxide (SnO) and/or stannic oxide (SnO 2 ) for tin.
  • the metal oxides and their precursors will typically be in the form of powders having particle sizes in the range of less than 5 ⁇ m, and in the case of titania particle sizes of 1 ⁇ m. typically between 0.3 to 0.6 ⁇ m.
  • An essential feature of the invention is that the transition or post- transition metals oxides and/or their precursors be added to the hydrous clay prior to heat treatment.
  • heating is applied to the extent necessary to alter the crystalline structure of the clay and cause the metal oxide to aggregate with the altered clay.
  • heating needs to also be sufficient to form the corresponding metal oxide along with aggregation with the altered clay.
  • heating of the metal oxide or its precursor with a hydrous clay is carried out at temperatures not higher than about 1200°C when the clay is kaolinite. Above this temperature, the resulting pigment may be too abrasive for application as a filling or coating pigment. Thus, the upper temperature limit of the heating may vary somewhat according to the acceptable abrasiveness of the pigment's application and based on the type of hydrous clay being used.
  • heating with the metal oxide is preferably in the range of 400 to 1 100°C.
  • the precise degree of heating will depend on a number of considerations that should be apparent to one of ordinary skill in the art. For example, if the application for a kaolin pigment requires low abrasion as in newsprint, lower heating temperatures in the range of 400 to 800°C (i.e., covering temperature range not exceeding metakaolin temperature of 760°C by too much) will result in a lower abrasive pigment than if the foregoing temperature range is exceeded. If coarser pigments are required, for example, to help improve pigment retention within the fiber web of paper, heating above the foregoing temperature range near or around the fully calcined temperature of 1200°C. The amount of metal oxide and/or its precursor used in accordance with this invention may widely vary.
  • metal oxide and/or its precursor with respect to the hydrous clay, i.e., less than 50 weight percent based on the total dry weight of the clay and metal oxide and/or precursor, e.g., from 0.5 to 50 weight percent.
  • excellent results have been achieved in amounts ranging from 5 to 20, more preferably from 8 to 12 weight percent of metal oxide and/or precursor.
  • improved results will likely be achieved at majority amounts of metal oxide and/or precursors. However, these will be a less economically viable embodiments as the invention will contain a higher fraction of the more costly metal oxide/precursor.
  • Pigments of this invention may be prepared by wet blending or dry blending of the hydrous clay (spray-dried hydrous clay if dry blending) and metal oxide and/or its precursor prior to heating.
  • Dry blending may be accomplished in any type of conventional mixing devices such as a V-blender, paddle mixer, helical screw or roller mill.
  • wet blending of the invention's constituents may be done in any of a number of wet blending devices such as impeller mixers, sigma mixers, double planetary mixers, or drill presses with an up-lift blade. After sufficient rnixing, the mixture of constituents, may be screened through a mesh screen and spray dried.
  • the resulting mixtures may be pulverized before the heating step to break up agglomerates to form discrete particles. Typical milling is done until the particle size of the mixture is approximately 90 percent less than 1 ⁇ m.
  • the pigments of this invention are minerals which find uses as paper fillers and in paper coatings which are essential components of many paper grades and represent the largest non-fibrous component of paper. These minerals are utilized by papermakers to enhance certain printing and writing characteristics, such as paper brightness, opacity, gloss, smoothness and ink absorption. Filler addition levels usually range from 3 percent to 30 percent of the total weight of paper.
  • Typical mineral fillers used in papermaking include TiO : (rutile and anatase forms), kaolin clay, talc, calcium carbonate, aluminum trihydrate, synthetic silicas and plastic pigments. Crystalline filler minerals are used in concert with several wet end papermaking additives: retention/drainage aids (polyacrylamides.
  • polyamines polydadmacs and polyethyleneimines
  • wet strength additives urea- formaldehydes, melamine formaldehydes or polyamine epichlorohydrins
  • dry strength additives starches, gums
  • sizing agents ASA, AKD and alum-rosin
  • a sheet low in opacity allows the printed material on the reverse side to show through, thereby making the page difficult to read.
  • a highly filled sheet contains discrete mineral particles that serve as scattering centers, which scatter light back to the viewers eye, rather than allowing it to be transmitted through the sheet to illuminate the print on the reverse side.
  • the ability to effectively scatter light is related to the refractive index of the mineral filler.
  • a higher refractive index serves to decrease the velocity of light as it passes through the material and increases the angle at which the light ray is bent upon entering the media.
  • the rutile form of TiO 2 has the highest refractive index, and is the most expensive, of the common paper filler minerals.
  • Calcined kaolin clay is a cheaper alternative, but is also a distant second in terms of refractive index. Accordingly, calcined kaolin is used to "extend" TiO 2 , in order to reduce the cost of the papermaking process, while not tremendously sacrificing opacity.
  • the hybrid pigment of the invention is fully compatible with all of the common wet end papermaking additives.
  • a paper coating consists of a pigment plus an adhesive used to bind the particles to one another as well as to the paper or paperboard basestock.
  • Pigment coatings on paper promote improved smoothness, as well as controlled porosity, brightness and gloss, while pigment coatings on paperboard are used primarily for coverage of the unbleached baseboard.
  • improved opacity is the primary function of the coating and a hybrid pigment of the invention would have application.
  • the hybrid pigments of the invention are combined with an adhesive (casein, starches, polyvinyl alcohol, styrene-butadiene latex, etc.), a rheology modifier (either a secondary dispersant, such as a polyacrylate, or a thickener, such as carboxymethylcellulose), a microbial inhibitor (isothiazoline) and a pH modifier (ammonium hydroxide or caustic).
  • an adhesive casein, starches, polyvinyl alcohol, styrene-butadiene latex, etc.
  • a rheology modifier either a secondary dispersant, such as a polyacrylate, or a thickener, such as carboxymethylcellulose
  • a microbial inhibitor isothiazoline
  • a pH modifier ammonium hydroxide or caustic
  • Hybrid pigments of the invention have additional application as opacifiers in paint formulations as well.
  • the reflectance values are converted by the use of Kubelka- Munk equations to light scattering values (m 2 /g).
  • the light scattering values are a measure of the opacity potential of the clay because the higher values indicate that light rather than passing through is reflected and scattered back. The higher the light scattering value, the higher the opacity potential of the clay.
  • This example illustrates the improved properties and that the hybrid pigment of this invention possess including a comparative example against a simple mixture (i.e.. non-heated) of the hybrid pigment's starting components.
  • a hydrous clay was heated to a temperature of approximately 930 C (1700°F) (metakaolin range) to form clay pigment, C-1, having the characteristics as reported in Table 1A.
  • a hybrid pigment, H-l, characteristic of the present invention was made by co-heating to a temperature of 930 C a mixture of 90 percent by weight of the hydrous clay used to make C-1 and 10 percent by weight of TiO 2 commercially available from DuPont Corporation under the tradename of RPS VANTANGE. The properties of H-l are reported in Table 1 A. In each case prior to heat treatment, C-1 and H-l were pulverized by conducting 3 passes of each material through a Micro Mill brand pulverizer.
  • H-2 suffered from a lower GEB value versus comparative pigments C-2 and C-3
  • H-2 provided significantly higher scatter coefficients compared to C-2 and C-3.
  • H-2 performed quite unexpectedly in coating formulations as reported in Example 4, wherein it is demonstrated that the lower GEB value for pigments of this invention did not have a negative effect on coated sheet brightness.
  • Example 2 This example exhibits the benefits of this invention are also obtainable by using a metal oxide precursor in the form of titanyl sulfate purchased from Kemira Pigments, Inc.. of Savannah. GA, and available under the trade name UNITI 909.
  • C-1 of Example 1 is also used for comparative purposes.
  • Pigment C-4 was a physical dry blend of 90 percent by weight C-1 and 10 percent by weight UNITI 909 having been pulverized by 3 passes through the Micro Mill pulverizer.
  • Inventive pigment, H-3 was comprised of 90 percent by weight of the hydrous clay used to made C-1 and 10 percent by weight UNITI 909 having been wet mixed prior to spray drying H-3 was then pulverized (3 passes through the Micro Mill pulverizer) and heated to a temperature of 930 C.
  • the properties of C-1, C-4, and H-3 are reported in TABLE 2.
  • This example exhibits the effect of TiO 2 purity on the properties of the hybrid pigments of this invention.
  • the compositions of the TiO 2 pigments tested are as follows:
  • inventive pigment H-4 was made by heating to 930 C a mixture of 90 percent by weight of the same hydrous clay as used to make pigments C-1 and H-l with 10 percent by weight of the purer KRONOS TiO 2 .
  • inventive pigment H-5 was made by heating to 1090 C a mixture of 90 percent by weight of the same hydrous clay as used to make pigments C-2 and H-2 with 10 percent by weight of the purer KRONOS TiO 2 .
  • H-4 and H-5 were pulverized in the Micro Mill pulverizer (3 passes) prior to heat treatment. Results for pigment property comparisons at 930 C and 1090 C are provided in TABLE 3 A and TABLE 3B, respectively.
  • the example demonstrates the coated sheet properties of this invention and compares them to conventional clay-based pigments.
  • Four (4) comparative coated sheets were prepared from three (3) pigments and a base coating hydrous clay have the following properties:
  • GEB GEB value

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Nanotechnology (AREA)
  • Paper (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une composition et un procédé relatifs à de nouveaux pigments d'argile comprenant un oxyde métallique et/ou un précurseur d'oxyde métallique (oxydes métalliques et précurseurs d'oxydes métalliques de métaux de transition, de métaux de post-transition, ou leurs mélanges) qui sont agrégés thermiquement à de l'argile hydratée. Le procédé consiste à chauffer un mélange argile/oxyde métallique, précurseur d'oxyde métallique et/ou combinaisons de ces derniers à une température nécessaire pour agréger l'oxyde métallique et/ou le précurseur d'oxyde métallique à l'argile. Les pigments selon l'invention permettent de produire un nouveau pigment dont l'opacité convient pour des applications de couchage et de charge du papier.
PCT/US1999/028235 1998-12-02 1999-11-30 Pigments hybrides de kaolin a opacite elevee WO2000032700A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU19266/00A AU1926600A (en) 1998-12-02 1999-11-30 High opacity kaolin hybrid pigments

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US20461098A 1998-12-02 1998-12-02
US09/204,610 1998-12-02

Publications (1)

Publication Number Publication Date
WO2000032700A1 true WO2000032700A1 (fr) 2000-06-08

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/028235 WO2000032700A1 (fr) 1998-12-02 1999-11-30 Pigments hybrides de kaolin a opacite elevee

Country Status (2)

Country Link
AU (1) AU1926600A (fr)
WO (1) WO2000032700A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6743286B2 (en) 2001-07-30 2004-06-01 Millennium Inorganic Chemicals, Inc. Inorganic particles and methods of making
WO2006119063A2 (fr) * 2005-05-02 2006-11-09 Imerys Pigments, Inc. Methodes de traitement thermique de matiere particulaire
WO2006076725A3 (fr) * 2005-01-14 2007-06-28 Engelhard Corp Pigments
US7285162B2 (en) 2001-07-30 2007-10-23 Millennium Inorganic Chemicals, Inc. Titanium dioxide pigment having improved light stability
WO2011009980A2 (fr) * 2009-07-23 2011-01-27 Universidad Complutense De Madrid Procédé de préparation d'un matériau céramique hybride à base de phosphate de calcium nanocristallin-colorant organique
US8016936B2 (en) 2004-05-03 2011-09-13 Imerys Pigments, Inc. Methods of calcining particulate material
CN104047207A (zh) * 2013-03-14 2014-09-17 罗门哈斯公司 纸涂料制剂
WO2018073320A1 (fr) 2016-10-20 2018-04-26 Oberthur Fiduciaire Sas Substrat de sécurité

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US3586523A (en) * 1968-01-15 1971-06-22 Engelhard Min & Chem Calcined kaolin clay pigment
EP0012290A1 (fr) * 1978-12-06 1980-06-25 Bayer Ag Procédé d'obtention de pigments d'argiles calcinées et leur utilisation
US4578118A (en) * 1985-02-13 1986-03-25 Engelhard Corporation Kaolin clay-based pigment
EP0274430A2 (fr) * 1987-01-09 1988-07-13 E.C.C. America Inc. Procédé de préparation de kaolins pigmentaires structurés
GB2234990A (en) * 1989-08-18 1991-02-20 Tioxide Group Plc Fibrous sheet material
US5011534A (en) * 1990-02-14 1991-04-30 Engelhard Corporation Calcined kaolin clay filler pigment for enhancing opacity and printing properties of newsprint and mechanical papers
US5030445A (en) * 1987-08-25 1991-07-09 Sunstar Kabushiki Kaisha Cosmetic composition

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US3586523A (en) * 1968-01-15 1971-06-22 Engelhard Min & Chem Calcined kaolin clay pigment
GB1198599A (en) * 1969-03-24 1970-07-15 Du Pont Inorganic Blue to Green Pigments.
EP0012290A1 (fr) * 1978-12-06 1980-06-25 Bayer Ag Procédé d'obtention de pigments d'argiles calcinées et leur utilisation
US4578118A (en) * 1985-02-13 1986-03-25 Engelhard Corporation Kaolin clay-based pigment
EP0274430A2 (fr) * 1987-01-09 1988-07-13 E.C.C. America Inc. Procédé de préparation de kaolins pigmentaires structurés
US5030445A (en) * 1987-08-25 1991-07-09 Sunstar Kabushiki Kaisha Cosmetic composition
GB2234990A (en) * 1989-08-18 1991-02-20 Tioxide Group Plc Fibrous sheet material
US5011534A (en) * 1990-02-14 1991-04-30 Engelhard Corporation Calcined kaolin clay filler pigment for enhancing opacity and printing properties of newsprint and mechanical papers

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7686882B2 (en) 2001-07-30 2010-03-30 Millennium Inorganic Chemicals, Inc. Titanium dioxide pigment having improved light stability
US6743286B2 (en) 2001-07-30 2004-06-01 Millennium Inorganic Chemicals, Inc. Inorganic particles and methods of making
US7285162B2 (en) 2001-07-30 2007-10-23 Millennium Inorganic Chemicals, Inc. Titanium dioxide pigment having improved light stability
US8016936B2 (en) 2004-05-03 2011-09-13 Imerys Pigments, Inc. Methods of calcining particulate material
US7811375B2 (en) 2005-01-14 2010-10-12 Basf Corporation Pigment
WO2006076725A3 (fr) * 2005-01-14 2007-06-28 Engelhard Corp Pigments
WO2006119063A3 (fr) * 2005-05-02 2007-12-13 Imerys Pigments Inc Methodes de traitement thermique de matiere particulaire
WO2006119063A2 (fr) * 2005-05-02 2006-11-09 Imerys Pigments, Inc. Methodes de traitement thermique de matiere particulaire
WO2011009980A2 (fr) * 2009-07-23 2011-01-27 Universidad Complutense De Madrid Procédé de préparation d'un matériau céramique hybride à base de phosphate de calcium nanocristallin-colorant organique
ES2351468A1 (es) * 2009-07-23 2011-02-07 Universidad Complutense De Madrid Procedimiento para la preparacion de un material hibrido ceramico de fosfato de calcio nanocristalino-colorante organico.
WO2011009980A3 (fr) * 2009-07-23 2011-07-14 Universidad Complutense De Madrid Procédé de préparation d'un matériau céramique hybride à base de phosphate de calcium nanocristallin-colorant organique
CN104047207A (zh) * 2013-03-14 2014-09-17 罗门哈斯公司 纸涂料制剂
US20140272389A1 (en) * 2013-03-14 2014-09-18 Rohm And Haas Company Paper coating formulation
WO2018073320A1 (fr) 2016-10-20 2018-04-26 Oberthur Fiduciaire Sas Substrat de sécurité
FR3057881A1 (fr) * 2016-10-20 2018-04-27 Oberthur Fiduciaire Sas Substrat de securite

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