US20150152242A1 - Methods and compositions for increasing ink clay loading in heatset ink formulations while maintaining ink gloss, and ink formulations produced therefrom - Google Patents

Methods and compositions for increasing ink clay loading in heatset ink formulations while maintaining ink gloss, and ink formulations produced therefrom Download PDF

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US20150152242A1
US20150152242A1 US14/402,533 US201314402533A US2015152242A1 US 20150152242 A1 US20150152242 A1 US 20150152242A1 US 201314402533 A US201314402533 A US 201314402533A US 2015152242 A1 US2015152242 A1 US 2015152242A1
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clay particles
microns
organic
clay
ink formulation
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Ching Yih Chen
Richard Douglas Carter
Brent Ashley Nobles
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KAMIN LLC
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Publication of US20150152242A1 publication Critical patent/US20150152242A1/en
Assigned to KAMIN LLC reassignment KAMIN LLC RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT
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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
    • 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
    • C09D11/00—Inks
    • 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
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • C08K5/17—Amines; Quaternary ammonium compounds
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/5403—Silicon-containing compounds containing no other elements than carbon or hydrogen
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing

Definitions

  • This disclosure relates to ink formulations (such as heatset ink formulations), as well as methods of making inks that incorporate increased clay loadings while maintaining desired physical and chemical properties.
  • Printing ink is a complex mixture of ingredients that are combined in a specific formulation to meet desired characteristics of the printing application of the ink. It is well-known that printing inks utilized today are typically modified with various types of additives to provide required rheological properties to ensure quality printing on high-speed printing presses. Generally, polymer (or resin), solvent, and pigment types determine the intrinsic rheology of the ink formulation. It has been known that clays can be used to control rheology and reduce ink misting on high-speed presses.
  • Offset color ink is generally formulated with various amounts of an extender pigment to achieve the rheological requirements of the process.
  • Clays are often used for this purpose since they are low in cost and have the ability of decreasing the misting and slinging of the inks when printed at high speeds.
  • the amount of clay used in such applications varies from about 2-10 wt % for letter press color inks and from 10-25 wt % for web offset color inks
  • Heatset ink formulations presently can include up to about 5 wt % clays, but at higher loadings there is a negative impact on ink gloss.
  • clay presents difficulty in dispersing itself in the ink if the ink is manufactured using high-speed mixing without roller milling.
  • clays have a hydrophilic surface and consequently are very difficult to be wetted and dispersed by hydrocarbons such as mineral oils and varnishes.
  • dispersions of conventional clays and hydrocarbons are not very stable on aging, and some agglomeration of clay particles occurs.
  • the second problem occurs during printing of lithographic inks (offset inks) whereby the clay in the ink is leached by the fountain solution and slowly migrates in it.
  • the hydrophilicity of the clays is such that the clay is extracted from the ink and begins to dissolve into the water together with traces of color pigments. This causes a bleeding problem.
  • the presence of clay in the fountain solution causes a variety of printability problems resulting in inadequate reproduction of colors.
  • ink clay loadings in heatset ink formulations may be increased from 3-5% to 10-15% without losing ink gloss, by incorporating certain treatments to the clay particles, as disclosed herein.
  • fine clay particles may be treated with quaternary ammonium compounds.
  • the quaternary ammonium compounds react with the clay, such as by electrostatic bonding.
  • the clay particles transition from hydrophilic to hydrophobic. The result is to engender or enhance a glossing effect, extend the resin in the composition (allowing to reduce the amount of resin), and lower overall cost.
  • compositions and formulations will first be summarized, followed by compositions and formulations.
  • This disclosure includes modified clays for ink formulations produced by any of the disclosed methods, as well as ink formulations produced by any of the disclosed processes.
  • a method of producing a surface-modified clay for an ink formulation comprises:
  • the organic compound may be selected, for example, from quaternary ammonium compounds, organic acids (including, but not limited to, saturated or unsaturated fatty acids having at least four carbon atoms, such as stearic acid), organic silanes, organic polysilanes, or any mixtures thereof.
  • organic acids including, but not limited to, saturated or unsaturated fatty acids having at least four carbon atoms, such as stearic acid
  • organic silanes organic polysilanes, or any mixtures thereof.
  • a method of producing a surface-modified clay for an ink formulation comprises:
  • At least 50% or at least 60% of the clay particles are smaller than 0.2 microns. In some embodiments, at least 80% or at least 95% of the clay particles are smaller than 0.5 microns. In some embodiments, substantially all of the clay particles are less than 2 microns, 3 microns, or 4 microns.
  • the clay particles may comprise one or more clays selected from the Kaolin group of minerals comprising kaolinite, dickite, halloysite, nacrite, montmorrilite, or any other polymorph of Al 2 Si 2 O 5 (OH) 4 .
  • the clay particles are kaolin clay particles.
  • the quaternary ammonium compound may vary widely.
  • at least one or two of R 1 , R 2 , R 3 , and R 4 is selected from C 10 -C 24 chains.
  • at least one or two of R 1 , R 2 , R 3 , and R 4 is selected from C 1 -C 9 chains.
  • at least one or two of R 1 , R 2 , R 3 , and R 4 may be a methyl group.
  • two of R 1 , R 2 , R 3 , and R 4 are methyl groups and the other two are selected from C 16 -C 18 chains.
  • the X group or element may be is an organic anion or an inorganic anion, such as chloride (Cl ⁇ ) or another halide anion.
  • the quaternary ammonium compound may be present in a concentration of at least about 1 wt % of the mass of the clay particles in the reactor. In some embodiments, the quaternary ammonium compound is present in a concentration of at least about 2 wt %, 2.5 wt %, 3 wt %, 3.5 wt %, 4 wt %, 5 wt % or more of the mass of the clay particles in the reactor.
  • the dryer may be a spray dryer coupled with a heated air chamber.
  • the dryer may be a flash dryer that simultaneously mixes and dries the treated clay slurry in a heated air chamber.
  • the method may be conducted continuously, semi-continuously, or in a batch process.
  • the treatment reactor may be continuous.
  • each of steps (a)-(d) is continuous.
  • the method may include grinding the product to reduce the density of the surface-modified clay, such as in a grinding mill or other suitable apparatus.
  • a method of producing a surface-modified clay for an ink formulation comprises:
  • quaternary ammonium compound is given by the formula [R 1 R 2 R 3 R 4 N + ][X ⁇ ], wherein each of R 1 , R 2 , R 3 , and R 4 are independently selected hydrocarbon groups or chains, and wherein X is a monovalent anion.
  • a method of producing a surface-modified clay for an ink formulation comprises:
  • a method of producing a surface-modified clay for an ink formulation comprises:
  • This disclosure also provides systems and apparatus for producing surface-modified clay for an ink formulation.
  • Some embodiments provide a system for modifying clay particles for an ink formulation, comprising:
  • a reactor in operable communication with the slurry vessel, for receiving the slurry and a quaternary ammonium compound, wherein the reactor is configured with heating means and mixing means to modify a surface of the fine clay particles, to form a treated clay slurry;
  • a dryer in operable communication with the reactor, for receiving the treated clay slurry, wherein the dryer is configured to remove water from the treated clay slurry to form a surface-modified clay;
  • system is continuous. In other embodiments, the system is configured for a batch process.
  • the dryer is a spray dryer coupled with a heated air chamber. In some embodiments, the dryer is a flash dryer that simultaneously mixes and dries the treated clay slurry in a heated air chamber.
  • a system for modifying clay particles for an ink formulation comprises a treatment unit for modifying fine clay particles in the presence of an organic compound; and optionally further comprises a grinding mill, in operable communication with the treatment unit, for reducing particle size of the surface-modified clay.
  • Certain variations provide a process to produce a heatset ink formulation, the process comprising:
  • compositions for inks are also provided.
  • a surface-modified hydrophobic clay composition for an ink formulation comprises, in some embodiments:
  • a surface-modified hydrophobic clay composition for an ink formulation comprises:
  • the composition includes from about 2 wt % to about 4 wt % of the one or more quaternary ammonium compounds. Some water may also be present, such as up to about 2 wt % H 2 O.
  • At least 50% or at least 60% of the clay particles are smaller than 0.2 microns. In these or other embodiments, at least 80% or at least 95% of the clay particles are smaller than 0.5 microns. In these or still other embodiments, substantially all of the clay particles are less than 2 microns, 3 microns, or 4 microns.
  • the clay particles preferably include one or more clays selected from the Kaolin group of minerals comprising kaolinite, dickite, halloysite, nacrite, montmorrilite, or any other polymorph of Al 2 Si 2 O 5 (OH) 4 .
  • the clay particles are kaolin clay particles, in certain embodiments.
  • At least one (such as one, two, or three) of R 1 , R 2 , R 3 , and R 4 is selected from C 10 -C 24 chains, in some embodiments. At least one (such as one, two, or three) of R 1 , R 2 , R 3 , and R 4 is selected from C 1 -C 9 chains, such as methyl (—CH 3 ), in some embodiments. In certain embodiments, two of R 1 , R 2 , R 3 , and R 4 are methyl groups and the other two of R 1 , R 2 , R 3 , and R 4 are selected from C 16 -C 18 chains.
  • the monovalent anion X may be organic or inorganic, but is preferably inorganic such as Cl ⁇ or Br ⁇ .
  • clay particles with a particle-size distribution characterized in that at least 40% of the clay particles are smaller than 0.2 microns, at least 70% of the clay particles are smaller than 0.5 microns, and substantially all of the clay particles are less than 5 microns;
  • the resin may be present at about 25-35 wt % or less in the heatset ink formulation.
  • the clay particles may be present at about 5-15 wt % or more in the heatset ink formulation.
  • clay particles with a particle-size distribution characterized in that at least 40% of the clay particles are smaller than 0.2 microns, at least 70% of the clay particles are smaller than 0.5 microns, and substantially all of the clay particles are less than 5 microns;
  • the resin is present at about 35 wt % or less in the heatset ink formulation, such as about 30 wt %, 25 wt %, or less in the heatset ink formulation.
  • the clay particles are present at about 5 wt % or more in the heatset ink formulation, such as about 10 wt %, about 15 wt %, or more in the heatset ink formulation.
  • a UV-curable ink formulation comprising:
  • clay particles with a particle-size distribution characterized in that at least 40% of the clay particles are smaller than 0.2 microns, at least 70% of the clay particles are smaller than 0.5 microns, and substantially all of the clay particles are less than 5 microns;
  • a UV-curable ink formulation as disclosed may comprise:
  • clay particles with a particle-size distribution characterized in that at least 40% of the clay particles are smaller than 0.2 microns, at least 70% of the clay particles are smaller than 0.5 microns, and substantially all of the clay particles are less than 5 microns;
  • FIG. 1 is a graph depicting the experimental influence of particle size on ink gloss development.
  • FIG. 2 is a graph depicting the experimental influences of both particle size and treatment level of a quaternary ammonium compound on ink gloss development.
  • FIG. 3A is an SEM micrograph (100 ⁇ ) of a fine-particle kaolin clay that has not been treated with a quaternary ammonium compound.
  • FIG. 3B is an SEM micrograph (100 ⁇ ) of a fine-particle kaolin clay that has been treated with a quaternary ammonium compound, in some embodiments.
  • FIG. 4A is an SEM micrograph (1000 ⁇ ) of a fine-particle kaolin clay that has not been treated with a quaternary ammonium compound.
  • FIG. 4B is an SEM micrograph (1000 ⁇ ) of a fine-particle kaolin clay that has been treated with a quaternary ammonium compound, in some embodiments.
  • FIG. 5 summarizes experimental ink-gloss data associated with Example 4 of this disclosure.
  • FIG. 6 summarizes additional experimental data associated with Example 4 of this disclosure.
  • phase “consisting of” excludes any element, step, or ingredient not specified in the claim.
  • phrase “consists of” (or variations thereof) appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.
  • phase “consisting essentially of” limits the scope of a claim to the specified elements or method steps, plus those that do not materially affect the basis and novel characteristic(s) of the claimed subject matter.
  • ink clay loadings in heatset ink formulations may be increased from 3-5% to 10-15% without losing ink gloss, by incorporating certain treatments to the clay particles.
  • fine clay particles may be treated with organic compounds, such as (but not limited to) quaternary ammonium compounds.
  • the organic compounds react with the clay, such as by electrostatic bonding.
  • the clay particles transition from hydrophilic to hydrophobic. The result is to engender or enhance a glossing effect, extend the resin in the composition (allowing to reduce the amount of resin), and lower overall cost.
  • the invention provides a method of producing a surface-modified clay for an ink formulation, the method comprising:
  • the fine clay particles are treated with one or more organic compounds to modify the surface and make them hydrophobic.
  • the organic compound may be selected from the group consisting of a quaternary ammonium compound, an organic acid, a fatty acid, an organic silane, an organic polysilane, and combinations thereof
  • Quaternary ammonium compounds may be given by the formula [R 1 R 2 R 3 R 4 N + ][X ⁇ ], wherein each of R 1 , R 2 , R 3 , and R 4 are independently selected hydrocarbon groups or chains, and wherein X is a monovalent anion.
  • quaternary ammonium compounds are particularly effective owing to the anchoring effect of the N + center onto the clay surface.
  • At least one or at least two of R 1 , R 2 , R 3 , and R 4 is selected from C 10 -C 24 chains. In some embodiments, at least one or at least two of R 1 , R 2 , R 3 , and R 4 is selected from C 1 -C 9 chains. In some embodiments, at least one or at least two of R 1 , R 2 , R 3 , and R 4 is a methyl group. In certain embodiments, two of R 1 , R 2 , R 3 , and R 4 are methyl groups and the other two of R 1 , R 2 , R 3 , and R 4 are selected from C 16 -C 18 chains.
  • R groups (R 1 , R 2 , R 3 , and R 4 ) can be linear, branched, olefinic, cyclic, aromatic, or functionalized in any way.
  • X may be an organic or inorganic anion.
  • X is a halide anion such as chlorine or bromine.
  • Organic acids may include fatty acids, which generally are regarded as having at least four carbon atoms. Any known unsaturated fatty acid, such as oleic acid, or saturated fatty acid, such as stearic acid may be employed. In some embodiments, organic acid may be selected from short-chain acids such as lactic acid, acetic acid, formic acid, citric acid, and oligomers or polymers thereof
  • Organic silanes or polysilanes may include any suitable linear or branched silanes with at least one organic group having one to 20 carbon atoms.
  • Silanes are chemical compounds of silicon and another atom such as carbon or hydrogen, which are analogues of alkane hydrocarbons.
  • Silanes consist of a chain of silicon atoms covalently bonded to each other, to carbon, or to hydrogen atoms.
  • any suitable clay basic material may be used including kaolin, bentonite, montmorillonite, synthetic layered silicates such as laponites, hectorites, as well as analogous aluminosilicate compositions which would be functionally equivalent.
  • Preferred clay particles comprise clays selected from the Kaolin group of minerals comprising kaolinite, dickite, halloysite, nacrite, montmorrilite, or any other polymorph of Al 2 Si 2 O 5 (OH) 4 .
  • the clay particles are kaolinite.
  • a preferred range of particle sizes of the base clay is as follows: 40-60% less than 0.2 microns; 70-98% less than 0.5 microns; and substantially all less than 5 microns.
  • coarser clay particles are utilized, although still less than 5 microns.
  • the range of particle sizes of the base clay may be 5-20% less than 0.2 microns; 10-40% less than 0.5 microns; and substantially all less than 5 microns. “Substantially all” means about 100%, but there can be a few particles present (in a given sample) that are larger than 5 microns, such as due to impurities or random clay particles.
  • the treatment includes a quaternary ammonium compound in a concentration of at least about 1 wt %, 2 wt %, 2.5 wt %, 3 wt %. 3.5 wt %, 4 wt %, 5 wt %, or more, of the mass of the clay particles.
  • a spray dryer When a spray dryer is employed, it will typically contain a set of nozzles to spray treated slurry in micron-sized beads, which are then dried in a heated air chamber. When a flash dryer is employed, it will typically utilize mechanical drying and mixing simultaneously in a heated chamber. Hot air will push dried ground material upward to a cyclone.
  • slurry solids content or treatment time or temperature.
  • a quantity of one or more organic compounds will be contacted with suitable fine clay particles, and allowed to react (chemically and/or physically) under effective conditions of time, temperature, pressure, and mixing so that the clay surface is modified to become more hydrophobic.
  • Some embodiments thus provide a surface-modified hydrophobic clay composition for an ink formulation, comprising:
  • the composition may include about 0.5 wt %, 1.0 wt %, 1.5 wt %, 2.0 wt %, or more water.
  • the surface-modified hydrophobic clay composition may be characterized in a number of ways.
  • the Fineness of Grind (NPIRI Grinding, ASTM) shows a Scratches value of 0 and a Speckles value less than or equal to 9.
  • the brightness by % Reflectance (TAPPI) may be 84 or higher.
  • the surface-modified hydrophobic clay composition may be incorporated into any known ink formulation, in various embodiments.
  • the surface-modified hydrophobic clay composition is combined with an organic solvent and a resin, along with a pigment and/or dye, to form a heatset ink formulation. It is theorized, without limitation, that the surface-treated clay causes the clay to become more hydrophobic and therefore more easily dispersible in the various ink formulations.
  • a surface-modified hydrophobic clay composition for an ink formulation comprises, in some embodiments:
  • a surface-modified hydrophobic clay composition for an ink formulation comprises:
  • the composition includes from about 2 wt % to about 4 wt % of the one or more quaternary ammonium compounds. Some water may also be present, such as up to about 2 wt % H 2 O.
  • At least 50% or at least 60% of the clay particles are smaller than 0.2 microns. In these or other embodiments, at least 80% or at least 95% of the clay particles are smaller than 0.5 microns. In these or still other embodiments, substantially all of the clay particles are less than 2 microns, 3 microns, or 4 microns.
  • the clay particles preferably include one or more clays selected from the Kaolin group of minerals comprising kaolinite, dickite, halloysite, nacrite, montmorrilite, or any other polymorph of Al 2 Si 2 O 5 (OH) 4 .
  • the clay particles are kaolin clay particles, in certain embodiments.
  • At least one (such as one, two, or three) of R 1 , R 2 , R 3 , and R 4 is selected from C 10 -C 24 chains, in some embodiments. At least one (such as one, two, or three) of R 1 , R 2 , R 3 , and R 4 is selected from C 1 -C 9 chains, such as methyl (—CH 3 ), in some embodiments. In certain embodiments, two of R 1 , R 2 , R 3 , and R 4 are methyl groups and the other two of R 1 , R 2 , R 3 , and R 4 are selected from C 16 -C 18 chains.
  • the monovalent anion X may be organic or inorganic, but is preferably inorganic such as Cl ⁇ or Br ⁇ .
  • clay particles with a particle-size distribution characterized in that at least 40% of the clay particles are smaller than 0.2 microns, at least 70% of the clay particles are smaller than 0.5 microns, and substantially all of the clay particles are less than 5 microns;
  • the resin may be present at about 25-35 wt % or less in the heatset ink formulation.
  • the clay particles may be present at about 5-15 wt % or more in the heatset ink formulation.
  • clay particles with a particle-size distribution characterized in that at least 40% of the clay particles are smaller than 0.2 microns, at least 70% of the clay particles are smaller than 0.5 microns, and substantially all of the clay particles are less than 5 microns;
  • the resin is present at about 35 wt % or less in the heatset ink formulation, such as about 30 wt %, 25 wt %, or less in the heatset ink formulation.
  • the clay particles are present at about 5 wt % or more in the heatset ink formulation, such as about 10 wt %, about 15 wt %, or more in the heatset ink formulation.
  • a UV-curable ink formulation comprising:
  • clay particles with a particle-size distribution characterized in that at least 40% of the clay particles are smaller than 0.2 microns, at least 70% of the clay particles are smaller than 0.5 microns, and substantially all of the clay particles are less than 5 microns;
  • a UV-curable ink formulation as disclosed may comprise:
  • clay particles with a particle-size distribution characterized in that at least 40% of the clay particles are smaller than 0.2 microns, at least 70% of the clay particles are smaller than 0.5 microns, and substantially all of the clay particles are less than 5 microns;
  • ink clay bases are tested for their ability to impart ink gloss in a heatset ink formulation, using the methods disclosed herein. As shown in FIG. 1 , finer clay particles lead to better ink gloss.
  • the sample labeled “Lithosperse” corresponds to the smallest particle size tested, while the sample labeled “Hydrafine” corresponds to the largest particle size tested.
  • HG90 HG90 and HuberFine
  • HF90 kaolin clay particle types
  • the particle size of HG90 is 40-60% less than 0.2 microns; 70-98% less than 0.5 microns; and substantially all less than 5 microns.
  • the particle size of HF90 is 5-20% less than 0.2 microns; 10-40% less than 0.5 microns; and substantially all less than 5 microns.
  • ink gloss development of ink clay is primarily associated with its particle size, and secondarily with the concentration of the quaternary ammonium compound used in the treatment.
  • Jet-milled (dispersed) clay samples are compared against beads (undispersed), using a large spray dryer. It is found that there are no significant differences.
  • the dispersed filter cake contains anionic dispersant which was added after dewatering.
  • the undispersed filter cake contains no added anionic dispersant after dewatering.
  • FIGS. 3A and 3B A fine-particle kaolin clay is subjected to the disclosed treatment with a quaternary ammonium compound.
  • SEM micrographs of two different spray-dried beads are shown at 100 ⁇ in FIGS. 3A and 3B .
  • FIG. 3A is an SEM image showing regular spray-dried beads, without treatment.
  • FIG. 3B is an SEM image showing soft-dried beads, with treatment.
  • FIGS. 4A and 4B show the same materials, except at 1000 ⁇ .
  • the soft spray-dried beads reveal better dispersion. Soft beads are formed due to the coating of fatty acid to the clay surface in the treatment process.
  • a test procedure for conducting ink clay performance test is the following:
  • FIG. 5 shows that Lithosperse NextGen (“Lsperse Nextgen” in the legend) shows the highest gloss for a given % ink clay in extender. At 20% ink clay loading, Lithosperse NextGen is 25 points higher than ASP101. At 15% ink clay loading, Lithosperse NextGen is 19 points higher than ASP101.
  • FIG. 6 shows other property data.
  • This disclosure reveals utility and benefits in several areas, such as improved product performance, lower organic solvent emissions, and overall cost reduction.

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US14/402,533 2012-05-30 2013-05-21 Methods and compositions for increasing ink clay loading in heatset ink formulations while maintaining ink gloss, and ink formulations produced therefrom Abandoned US20150152242A1 (en)

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US20170081531A1 (en) * 2014-05-06 2017-03-23 Imerys Minerals Limited Ink compositions
US10384959B2 (en) * 2014-07-03 2019-08-20 Shlomo Nir Method of making and using granulated micelle-clay complexes for removal of pollutants from water

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JP7104656B2 (ja) * 2018-04-25 2022-07-21 Ｊｆｅミネラル株式会社 ハロイサイト粉末およびハロイサイト粉末の製造方法

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EP2864405A1 (en) 2015-04-29
KR20150024358A (ko) 2015-03-06
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US20180194923A1 (en) 2018-07-12
KR102112101B1 (ko) 2020-05-18
EP2864405B1 (en) 2018-12-19

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