WO2019194806A1 - Particules composites et procédé pour leur fabrication - Google Patents
Particules composites et procédé pour leur fabrication Download PDFInfo
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- WO2019194806A1 WO2019194806A1 PCT/US2018/026214 US2018026214W WO2019194806A1 WO 2019194806 A1 WO2019194806 A1 WO 2019194806A1 US 2018026214 W US2018026214 W US 2018026214W WO 2019194806 A1 WO2019194806 A1 WO 2019194806A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/18—In situ polymerisation with all reactants being present in the same phase
-
- 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
- C09C3/12—Treatment with organosilicon compounds
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/165—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on translational movement of particles in a fluid under the influence of an applied field
- G02F1/166—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on translational movement of particles in a fluid under the influence of an applied field characterised by the electro-optical or magneto-optical effect
- G02F1/167—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on translational movement of particles in a fluid under the influence of an applied field characterised by the electro-optical or magneto-optical effect by electrophoresis
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
-
- 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
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/10—Interference pigments characterized by the core material
- C09C2200/1062—Interference pigments characterized by the core material the core consisting of an organic compound, e.g. Liquid Crystal Polymers [LCP], Polymers or natural pearl essence
-
- 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
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/50—Interference pigments comprising a layer or a core consisting of or comprising discrete particles, e.g. nanometric or submicrometer-sized particles
- C09C2200/507—Organic particles, e.g. polymers or dyes
-
- 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
- C09C2210/00—Special effects or uses of interference pigments
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/165—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on translational movement of particles in a fluid under the influence of an applied field
- G02F1/1675—Constructional details
- G02F2001/1678—Constructional details characterised by the composition or particle type
Definitions
- This invention relates to composite particles used in electrophoretic display media, as well as to the improved methods of manufacturing the composite particles.
- optical property is typically color perceptible to the human eye, it may be another optical property, such as optical transmission, reflectance, luminescence, or, in the case of displays intended for machine reading, pseudo-color in the sense of a change in reflectance of electromagnetic wavelengths outside the visible range.
- solid electro-optic displays include rotating bichromal member displays, encapsulated electrophoretic displays, microcell electrophoretic displays and encapsulated liquid crystal displays.
- bistable and “bistability” are used herein in their conventional meaning in the art to refer to displays comprising display elements having first and second display states differing in at least one optical property, such as black and white, and such that after any given element has been driven, by means of an addressing pulse of finite duration, to assume either its first or second display state, after the addressing pulse has terminated, that state will persist for at least several times, for example at least four times, the minimum duration of the addressing pulse required to change the state of the display element.
- Some particle-based electrophoretic displays are stable not only in their extreme black and white states but also in three or more states, such as multi- color displays having three or more colors.
- the term “bistable” may be used herein to cover display elements having two or more display states.
- Electrophoretic displays can have attributes of good brightness and contrast, wide viewing angles, state bistability, and low power consumption when compared with liquid crystal displays. Nevertheless, problems with the long-term image quality of these displays have prevented their widespread usage. For example, particles that make up electrophoretic displays tend to settle, resulting in inadequate service-life for these displays.
- Encapsulated electrophoretic media comprise numerous small capsules, each of which itself comprises an internal phase containing electrophoretically-mobile particles in a fluid medium, and a capsule wall surrounding the internal phase. Typically, the capsules are themselves held within a polymeric binder to form a coherent layer positioned between two electrodes.
- the charged particles and the fluid are not encapsulated within microcapsules but instead are retained within a plurality of cavities formed within a carrier medium, typically a polymeric film.
- the technologies described in these patents and applications include:
- Electrophoretic particles, fluids and fluid additives see for example U.S. Patents Nos. 5,961,804; 6,017,584; 6,120,588; 6,120,839; 6,262,706; 6,262,833;
- An electrophoretic display normally comprises a layer of electrophoretic material and at least two other layers disposed on opposed sides of the electrophoretic material, one of these two layers being an electrode layer.
- both the layers are electrode layers, and one or both of the electrode layers are patterned to define the pixels of the display.
- one electrode layer may be patterned into elongate row electrodes and the other into elongate column electrodes running at right angles to the row electrodes, the pixels being defined by the intersections of the row and column electrodes.
- one electrode layer has the form of a single continuous electrode and the other electrode layer is patterned into a matrix of pixel electrodes, each of which defines one pixel of the display.
- electrophoretic display which is intended for use with a stylus, print head or similar movable electrode separate from the display
- only one of the layers adjacent the electrophoretic layer comprises an electrode, the layer on the opposed side of the electrophoretic layer typically being a protective layer intended to prevent the movable electrode damaging the electrophoretic layer.
- An encapsulated electrophoretic display typically does not suffer from the clustering and settling failure mode of traditional electrophoretic devices and provides further advantages, such as the ability to print or coat the display on a wide variety of flexible and rigid substrates.
- printing is intended to include all forms of printing and coating, including, but without limitation: pre-metered coatings such as patch die coating, slot or extrusion coating, slide or cascade coating, curtain coating; roll coating such as knife over roll coating, forward and reverse roll coating; gravure coating; dip coating; spray coating; meniscus coating; spin coating; brush coating; air knife coating; silk screen printing processes; electrostatic printing processes; thermal printing processes; ink jet printing processes; electrophoretic deposition (See U.S. Patent No. 7,339,715); and other similar techniques.)
- pre-metered coatings such as patch die coating, slot or extrusion coating, slide or cascade coating, curtain coating
- roll coating such as knife over roll coating, forward and reverse roll coating
- gravure coating dip coating
- spray coating meniscus coating
- spin coating brush coating
- a composite particle that comprises, a base particle and a plurality of hydrophilic oligomeric groups on an exterior portion of the base particle, the base particle including a cross-linked polyrurea and at least one of a pigment and a dye.
- the cross-linked polyurea may form a network throughout the base particle.
- a method of making a composite particle comprises providing either a solution containing a dye or a dispersion containing a pigment in a water-dispersible polyfunctional isocyanate dissolved in a water-miscible solvent, forming an emulsion of the solution/dispersion in water, agitating the emulsion while the polyfunctional isocyanate is converted into a cross-linked polyurea, and separating the composite particle containing the cross-linked polyurea and the dye/pigment from the emulsion.
- an electrophoretic medium comprising a plurality of electrically charged particles disposed in a fluid and capable of moving through the fluid under the influence of an electric field, wherein at least one of the particles is produced by a process according to an embodiment of the present invention.
- the electrically charged particles and the fluid may be confined within a plurality of capsules or microcells.
- the electrically charged particles and the fluid may be present as a plurality of discrete droplets surrounded by a continuous phase comprising a polymeric material.
- the fluid may be liquid or gaseous.
- the electrophoretic material containing the electrophoretic medium may be incorporated into an electrophoretic display comprising a layer of the electrophoretic material and at least one electrode arranged to apply an electric field to the layer of electrophoretic material.
- the displays incorporating the electrophoretic medium made according to the various embodiments of the present invention may be used in any application in which prior art electro-optic displays have been used.
- the present displays may be used in electronic book readers, portable computers, tablet computers, cellular telephones, smart cards, signs, watches, shelf labels, variable transmission windows and flash drives.
- Figure 1 is a schematic representation of a Prior Art method of forming a microcapsule
- Figure 2 is a schematic representation of a method of forming a composite particle according to an embodiment of the present invention.
- the composite particles according to the various embodiments of the present invention comprise a cross-linked polyurea that forms a network throughout a base particle.
- forming“a network throughout a base particle” means that the cross-linked polyurea is present at multiple locations/radii within the entire thickness of the base particle. Therefore, excluded from the definition of“a network throughout a base particle” would be a polyurea shell of a microcapsule because the shell is generally present only around the outer periphery of the microcapsule, for example.
- the cross-linked polyurea may be obtained from a water-dispersible polyfunctional isocyanate.
- the isocyanate group of a polyfunctional isocyanate hydrolyzes, releasing carbon dioxide and forming an amine.
- Amino groups react more readily than water with isocyanates; therefore, the newly-formed amine is likely to react with a neighboring, unhydrolyzed isocyanate.
- This reaction produces a urea group, and thus the final result of the reaction is a crosslinked polyurea that also contains some free amino groups.
- Water-dispersible polyfunctional isocyanates typically contain a hydrophilic oligomeric group (often an aliphatic oligomer, such as poly(ethylene oxide)) and multiple isocyanate groups. The portion of the molecule that bears the isocyanate groups is essentially insoluble in water.
- the polyfunctional isocyanates When the polyfunctional isocyanates are combined with an immiscible solvent and emulsified in a continuous aqueous phase, the mixture of polyfunctional isocyanates and solvent form micelles, as illustrated in Figure 1, wherein the poly(ethylene oxide) units (11) of the polyfunctional isocyanates are solvated by water and stabilize the water interface while the more hydrophobic interior of the micelle contains most of the isocyanate functionality (10).
- the isocyanate groups (10) may react as described above to form a polyurea shell (13) around the immiscible solvent (12) to form a microcapsule.
- a composite particle may be formed having a polyurea network throughout a base particle of the composite.
- FIG. 2 is a schematic representation of an embodiment of the invention
- a mixture of a water-dispersible polyfunctional isocyanate and water-miscible solvent is introduced to water (with agitation), such that solvent droplets (14) stabilized at the aqueous interface by the hydrophilic oligomeric groups (11) will be formed.
- Diffusion of water into the solvent droplet (14) will cause the polyfunctional isocyanates to polymerize by the hydrolysis reaction and amine condensation described above, while diffusion of the solvent (14) from the droplets into the aqueous phase will cause the droplets to shrink.
- a base particle comprising mostly cross- linked polyurea (15) throughout the thickness of the base particle and whatever other materials were originally dissolved or dispersed in the solvent.
- a composite particle results having a base particle in which the dye or pigment is captured within a polyurea network formed after polymerization in the aqueous phase.
- the various methods for manufacturing a composite particle according to the present invention include first either dissolving a dye and a water- dispersible polyfunctional isocyanate in a water-miscible solvent or dispersing a pigment in a solution of the water-dispersible polyfunctional isocyanate and water- miscible solvent.
- the weight ratio of water-dispersible polyfunctional isocyanate to water-miscible solvent is preferably 1:3 to 3:1, most preferably 1:2 to 2:1.
- the amount of dye or pigment may be dependent on the desired opacity or transparency of the final composite particle.
- a second step the mixture of dye/pigment, polyfunctional isocyanate, and water miscible solvent is added to an aqueous phase.
- surfactants may be added to the aqueous phase and/or agitation rate may be varied, for example, to control the final particle size.
- the resulting composite particles containing the crosslinked polyurea network and dye/pigment may be separated from the aqueous phase (which contains the dissolved solvent). This may be achieved using any separation methods known by those of skill in the art including, but not limited to, filtration, centrifugation, drying, and combinations thereof. It is preferred that most if not all of the water be removed from the composite for further processing, as will be described in greater detail below. Preferably the particles are separated from the aqueous phase by centrifugation, after which they may be dried to remove residual water and solvent.
- Water-dispersible polyfunctional isocyanates that may be used to form the composite particles according to the various embodiments of the present invention are known to those of skill in the art, such as those sold under the tradename Bayhydur manufactured by Bayer Corporation.
- the water dispersible polyfunctional isocyanates preferably have an NCO content of about 5 to 35%, more preferably about 15-25%.
- Water-miscible solvents that may be used in the methods for forming the composite particles according to the various embodiments of the present invention are preferably organic solvents in which the water-dispersible polyfunctional isocyanates are soluble. Such solvents are known to those of skill in the art and include, but are not limited to, tetrahydrofuran (THF), ketones and esters. The solvent should not contain nucleophilic groups that might react with the isocyanates.
- One especially preferred water-miscible solvent is methyl acetate.
- the preferred water solubility of the water miscible solvent is at least 5%, more preferably at least 25% by weight.
- the dyes and pigments that may be used in the composite particles according to the various embodiments of the present invention are also known to those of skill in the art.
- the dyes are preferably soluble in one or both of the water-dispersible polyfunctional isocyanates and the water-miscible solvent.
- the dyes and pigments are also preferably insoluble in water and insoluble in the non-polar solvent of the electrophoretic medium in which the composite particles will be added.
- Soluble dyes that may be incorporated in the composite particles according to the present invention include, but are not limited to Solvent Blue 70, Solvent Blue 67, Solvent Blue 136, Solvent Red 127, Solvent Red 130, Solvent Red 233, Solvent Red 125, Solvent Red 122, Solvent Yellow 88, Solvent Yellow 146, Solvent Yellow 25, Solvent Yellow 89, Solvent Orange 11, Solvent Orange 99, Solvent Brown 42, Solvent Brown 43, Solvent Brown 44, Solvent Black 28, and Solvent Black 29.
- Pigments that are insoluble in the water- miscible solvents and water- dispersible polyfunctional isocyanates may alternatively be used in the methods to prepare the composite particles of the present invention.
- the pigments may be combined with the polyfunctional isocyanate/solvent solutions to form a pigment dispersion and that are subsequently introduced into the aqueous phase.
- Pigments that may be incorporated in the composite particles according to the present invention include, but are not limited to inorganic pigments, neat pigments, laked pigments, and organic pigments.
- inorganic pigments include, but are not limited to, TiCk, ZrCh, ZnO, AI2O3, Cl pigment black 26 or 28 or the like (e.g., manganese ferrite black spinel or copper chromite black spinel). Particles, such as titania particles may be coated with a metal oxide, such as aluminum oxide or silicon oxide, for example.
- Useful neat pigments include, but are not limited to, PbCrCU, Cyan blue GT 55-3295 (American Cyanamid Company, Wayne, N.J.), Cibacron Black BG (Ciba Company, Inc., Newport, Del.) , Cibacron Turquoise Blue G (Ciba), Cibalon Black BGL (Ciba), Orasol Black BRG (Ciba), Orasol Black RBL (Ciba), Acetamine Black, CBS (E. I.
- CF (GAF) (15710), Diamond Black PBBA Ex (GAF) (16505); Direct Deep Black EA Ex CF (GAF) (30235), Hansa Yellow G (GAF) (11680); Indanthrene Black BBK Powd. (GAF) (59850), Indocarbon CLGS Cone. CF (GAF) (53295), Katigen Deep Black NND Hi Cone. CF (GAF) (15711), Rapidogen Black 3 G (GAF) (Azoic Black 4); Sulphone Cyanine Black BA-CF (GAF) (26370), Zambezi Black VD Ex Cone.
- Laked pigments are particles that have a dye precipitated on them or which are stained. Lakes are metal salts of readily soluble anionic dyes. These are dyes of azo, triphenylmethane or anthraquinone structure containing one or more sulphonic or carboxylic acid groupings. They are usually precipitated by a calcium, barium or aluminum salt onto a substrate. Typical examples are peacock blue lake (Cl Pigment Blue 24) and Persian orange (lake of Cl Acid Orange 7), Black M Toner (GAF) (a mixture of carbon black and black dye precipitated on a lake).
- peacock blue lake Cl Pigment Blue 24
- Persian orange lake of Cl Acid Orange 7
- GAF Black M Toner
- Organic pigment particles may include, but are not limited to, Cl pigment PR 254, PR122, PR149, PG36, PG58, PG7, PB28, PB15T, PBl5:2, PBl5:3, PBl:4, PY83, PY138, PY150, PY155 or PY20, as well as other commonly used organic pigments described in color index handbooks,“New Pigment Application Technology” (CMC Publishing Co, Ltd, 1986) and“Printing Ink Technology” (CMC Publishing Co, Ltd, 1984).
- Clariant Hostaperm Red D3G 70-EDS Hostaperm Pink E-EDS, PV fast red D3G, Hostaperm red D3G 70, Hostaperm Blue B2G-EDS, Hostaperm Yellow H4G-EDS, Novoperm Yellow HR-70-EDS, Hostaperm Green GNX, BASF Irgazine red L 3630, Cinquasia Red L 4100 HD, and Irgazin Red L 3660 HD; Sun Chemical phthalocyanine blue, phthalocyanine green, diarylide yellow or diarylide AAOT yellow.
- the color provided by the dyes/pigments of the composite particles according to the present invention may be white, black, red, green, blue, cyan, magenta, or yellow, for example.
- the particles may have other distinct optical characteristics, such as optical transmission, reflectance, luminescence, or, in the case of display media intended for machine reading, pseudo-color in the sense of a change in reflectance of electromagnetic wavelengths outside the visible range.
- the composite particles may have different particle sizes. Useful sizes may range from 1 nm up to about 100 pm. For example, smaller particles may have a size which ranges from about 50 nm to about 800nm. Larger particles may have a size which is about 2 to about 50 times, and more preferably about 2 to about 10 times, the sizes of the smaller particles.
- the composite particles made according to the various embodiments of the present invention may be further treated for surface modification.
- Such surface modification processes are known to those of skill in the art, like the processes disclosed in U.S. Patent Application No. 2015/0218384, the contents of which are incorporated herein by reference.
- the stability of electrophoretic media may be improved by either chemically bonding or cross-linking a steric stabilizing polymer around the outside of the composite particle.
- the polymeric stabilizer determines the particle size and colloidal stability of the system and preferably has a long polymeric chain which may stabilize the composite particles in a hydrocarbon solvent.
- the steric stabilizing polymer is preferably from about 1 to about 15 percent by weight of the composite particle.
- These polymer-coated composite particles may be prepared by a process comprising (a) reacting the particle with a reagent having a functional group capable of reacting with, and bonding to, the particle, and also having a polymerizable or polymerization-initiating group, thereby causing the functional group to react with the particle surface and attach the polymerizable group thereto; and (b) reacting the product of step (a) with at least one monomer or oligomer under conditions effective to cause reaction between the polymerizable or polymerization-initiating group on the particle and the at least one monomer or oligomer, thereby causing the formation of polymer bonded to the particle.
- the available amine groups may be with a reagent in a step (a) as described above having at least one functional group capable of reacting with the amine and at least one polymerizable group.
- the reagent for use in step (a) may include an isocyanate group and an acrylate group, such as isocyanate ethyl acrylate.
- step (a) and (b) may be replaced with a single step by using a reagent that is already in polymeric form, if the steric stabilizing polymer includes a functional group, such as an isocyanate group, that may react with the amine groups on the surface of the composite particle.
- a reagent that is already in polymeric form
- the steric stabilizing polymer includes a functional group, such as an isocyanate group, that may react with the amine groups on the surface of the composite particle.
- the polymeric stabilizer may be derived from one or more monomers or macromonomers using various polymerization techniques known by those of skill in the art.
- the polymeric stabilizer may be obtained by random graft polymerization (RGP), ionic random graft polymerization (IRGP), and atom transfer radical polymerization (ATRP), as described in U.S. Patent No. 6,822,782, the contents of which are incorporated herein by reference in its entirety.
- RGP random graft polymerization
- IRGP ionic random graft polymerization
- ATRP atom transfer radical polymerization
- “macromonomer” means a macromolecule with one end-group that enables it to act as a monomer.
- Suitable monomers for forming the polymeric stabilizer may include, but are not limited to, styrene, alpha methyl styrene, methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, vinyl pyridine, N-vinylpyrrolidone, 2-hydoxyethyl acrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, lauryl acrylate, lauryl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, hexyl acrylate, hexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, n-octadecyl acrylate, n-oc
- polymeric stabilizer may be“bifunctional.”
- polymerization initiators such as 4,4'- azobis(4-cyanovaleric acid) having more than one ionic site, and such initiators may be used in the present process.
- a bifunctional compound may have the form of a macromonomer containing repeating units having the capacity to bond to the particle surface and other repeated units having the desired polymerizable or initiating functionality, and such macromonomeric bifunctional compounds may form polymeric stabilizers that will normally contain multiple repeating units of both these types.
- the composite particles may be treated by phy si- sorption of a reagent comprising polymerizable groups on to the surface of the composite particles by treating the particle with a solution of a reagent having a polymerizable or polymerization-initiating group, thereby causing the reagent to become physi-sorbed on to the particle surface such that the reagent will not desorb from the particle surface when the particle is placed in a hydrocarbon medium.
- 2015/0218384 may further comprise reacting the composite particle with the reagent physi-sorbed thereon with at least one monomer or oligomer under conditions effective to polymerize the polymerizable or polymerization-initiating group on the particle with the at least one monomer or oligomer.
- the physi-sorption reagent may be dissolved in an ionic solvent or solvent mixture, such as a water/ethanol mixture.
- the process may include adjusting the pH of the solution of the reagent to control the charge on the composite particle, and choosing the reagent to physi-sorb depending upon the desired charge on the particle.
- the charge on many pigment particles in ionic liquids depends upon the pH of the liquid, there typically being one pH (the isoelectric point) at which the particle is uncharged.
- the pigment is negatively charged and the reagent may contain a quaternary ammonium salt grouping (much in the way organo- clays are prepared), while below the isoelectric point, the positively charged pigment surface can be modified by adsorption of reagents containing anionic functional groups.
- Reagents with quaternary ammonium salt groupings include: [3- (methacryloyloxy)ethyl]trimethylammonium chloride (MAETAC), [3- (methacryloyloxy)ethyl]trimethylammonium methyl sulfate, and [3- (methacryloylamino)propyl]trimethylammonium chloride.
- Reagents with anionic functional groups include 3-sulfopropyl methacrylate potassium salt (SPMK) and sodium 4-vinylbenzenesulfonate.
- SPMK 3-sulfopropyl methacrylate potassium salt
- the process is not restricted to pigments having inorganic oxide surfaces, and in principle may be extended to any pigments which can be charged sufficiently to promote adsorption of the functionalizing reagent.
- the reagent which is physi-sorbed on to the surface of the pigment particle should desirably be chosen so that it becomes essentially irreversibly bound to the composite particle in the low dielectric constant solvents (typically aliphatic hydrocarbons) used in the polymerization step and in the internal phase of the final electrophoretic display.
- the composite particles may be treated with a reagent having a polymerizable or polymerization-initiating group, and also comprising at least one electrophilic group.
- the electrophilic groups on the reagent react with the nucleophilic groups on the particle surfaces, thus attaching the polymerizable or polymerization-initiating groups to the particle surface.
- This process may further comprise reacting the polymerizable or polymerization-initiating groups with at least one of the monomers or macromonomers previously described.
- Electrophilic reagents useful in this process include acid halides, such as 4- vinylbenzyl chloride and methacryloyl chloride, and 2-isocyanatoethyl methacrylate. Both benzylic halides and acid chlorides are very reactive with respect to nucleophilic substitution reactions. For example, the coupling reaction with 4-vinylbenzyl chloride results in a styrene group tethered to the surface.
- the reagent may exclude a polymerizable or polymerization-initiating group so that a residue of the reagent is chemically bonded to the pigment particle.
- the reagent may be chosen so that the treatment of the composite particle therewith affects the zeta potential of the pigment particle.
- the preferred reagents for use in this process are alkyl halides, especially benzyl chloride or bromide. Treatment with either benzyl chloride or bromide shifts the zeta potential of the pigment particle to more positive values.
- a silica coating may be applied to the composite particle in a first step followed by a polymeric coating obtained by a dispersion polymerization technique, such as the methods described in U.S. Patent Application No. 20160085132, the contents of which are incorporated herein by reference in its entirety.
- the polymeric coating will serve as a steric stabilizer of the composite particle in an electrophoretic medium, such as a non-polar solvent.
- Various coating methods may be employed to provide the composite particle with a silica coating, for example, the coating method described in U.S. Patent 3,639,133, the contents of which are incorporated herein by reference in its entirety.
- the particles Prior to coating the composite particles, the particles may be prepared by first de- agglomerating and homogenizing an aqueous slurry of the composite particles using methods such as sonication, ball milling, or jet milling.
- a silica precursor may then be added to the aqueous slurry, such as sodium silicate or tetraethyl orthosilicate.
- the composite particles are dispersed in a solution of ethanol and tetraethyl orthosilicate and react at room temperature for 20hrs under basic conditions to form a generally uniform coating of silica over the particles, wherein the silica content of the coated particles is about 2% to 35% by weight.
- the pH of the reaction mixture may be reduced below about 4, and preferably to about 3, before the silica- coated particles are separated from the reaction mixture.
- the reduction in pH is conveniently effected using sulfuric acid, although other acids, for example, nitric, hydrochloric and perchloric acids, may be used.
- the silica coated particles are conveniently separated from the reaction mixture by centrifugation. Following this separation, it is not necessary to dry the particles. Instead, the silica-coated particles can be readily re-dispersed in the medium, typically an aqueous alcoholic medium, to be used for the next step of the process for the formation of polymer on the particles.
- silica-coated particles to be maintained in a non-agglomerated and non- fused form as they are subjected to the dispersion polymerization processes for attachment of polymerizable or polymerization-initiating groups, thus allowing for thorough coverage of the silica coated particle with such groups, and preventing the formation of large aggregates of particles.
- monomer or a macromonomer containing a radically polymerizable group is polymerized around the silica coated particles in the presence of a bifunctional reagent.
- the solvent selected as the reaction medium must be a good solvent for both the monomer or macromonomer and the bifunctional reagent, but a non-solvent for the polymer shell being formed.
- a good solvent for both the monomer or macromonomer and the bifunctional reagent but a non-solvent for the polymer shell being formed.
- monomer methylmethacrylate is soluble; but after polymerization, the resulting polymethylmethacrylate is not soluble.
- the polymeric coating may be derived from various monomers and polymerization techniques known by those of skill in the art, such as those described above (e.g. random graft polymerization (RGP), ionic random graft polymerization (IRGP), and atom transfer radical polymerization (ATRP)).
- the bifunctional reagent may be a reactive and polymerizable macromonomer which adsorbs, becomes incorporated or is chemically bonded onto the surface of the silica shell and the polymeric coating. It will be appreciated that because the silica coating completely covers the composite particles, any bifunctional reagent used to attach an initiator or polymerizable group to the surface of the particle must react with the silica coating.
- the bifunctional reagent may also be an acrylate- terminated or vinyl-terminated macromolecule, which are suitable because the acrylate or vinyl group can co-polymerize with the monomer in the reaction medium that will form the polymer shell.
- the macromonomer preferably has a long hydrocarbon chain, which may stabilize the composite particles in a hydrocarbon solvent.
- the preferred class of functional groups for bonding the bifunctional reagents to silica-coated particles are silane coupling groups, especially trialkoxy silane coupling groups.
- One especially preferred reagent for attaching a polymerizable group to the silica coating is 3-(trimethoxysilyl)propyl methacrylate, which is available commercially from Dow Chemical Company, Wilmington, Del. under the trade name Z6030. The corresponding acrylate may also be used.
- One type of macromonomer for use as a steric stabilizer may be acrylate terminated polysiloxane, such as Gelest, MCR-M11, MCR-M17, or MCR-M22, for example.
- acrylate terminated polysiloxane such as Gelest, MCR-M11, MCR-M17, or MCR-M22, for example.
- the rate of reaction of a polymerizable or initiating group bonded to a particle may vary greatly depending upon whether the group is held rigidly close to the particle surface, or whether the group is spaced (on an atomic scale) from that surface and can thus extend into a reaction medium surrounding the particle, this being a much more favorable environment for chemical reaction of the group.
- the polymeric shell on the silica coated organic pigment particles may be prepared by living radical dispersion polymerization.
- the living radical dispersion polymerization technique is similar to the dispersion polymerization described above by starting the process with silica coated composite particles and monomer and/or macromonomer dispersed in a reaction medium.
- multiple living ends are formed on the surface of the shell.
- the living ends may be created by adding an agent such as TEMPO (2,2,6,6-tetramethyl-l-piperidinyloxy), a RAFT (reversible addition- fragmentation chain transfer) reagent or the like, in the reaction medium, for the living radical polymerization.
- a second monomer and/or macromonomer added to the reaction medium will react with the living ends of the bifunctional reagent to form the polymeric coating.
- the monomers may include any of the monomers or comonomers previously listed.
- the quantities of the reagents, composite particles, monomer and/or macromonomers used may be adjusted and controlled to achieve the desired organic content in the resulting composite pigment particles.
- the processes of the present invention may include more than one stage and/or more than one type of polymerization.
- the composite pigments of the present invention may be incorporated into electrophoretic media used for electro-optic displays.
- One or more of the composite particles may be dispersed in an encapsulated dispersion fluid, such as a dielectric solvent or solvent mixture.
- the dispersion fluid may be encapsulated according to any method known to those of skill in the art, e.g. microcapsules, microcells, or a polymer matrix, and to any size or shape, such as spherical, for example, and may have diameters in the millimeter range or the micron range, but are preferably from about ten to about a few hundred microns.
- the percentages of the composite particles in the fluid may vary. For example, the particles may take up 0.1% to 50%, preferably 0.5% to 15%, by volume of the electrophoretic fluid.
- the polymeric stabilizer be highly compatible with the encapsulated dispersion fluid.
- the suspending fluid in an electrophoretic medium is normally hydrocarbon-based and non-polar (e.g. C6-C18 branched alkanes), although the fluid can include a proportion of halocarbon, which is used to increase the density of the fluid and thus to decrease the difference between the density of the fluid and that of the particles.
- the polymeric stabilizer formed in the present processes be highly compatible with the encapsulated fluid, and thus that the polymeric stabilizer itself comprise a major proportion of hydrocarbon chains; except for groups provided for charging purposes, as discussed below, large numbers of strongly ionic groups are undesirable since they render the polymeric stabilizer less soluble in the hydrocarbon suspending fluid and thus adversely affect the stability of the particle dispersion.
- the medium in which the particles are to be used comprises an aliphatic hydrocarbon suspending fluid (as is commonly the case)
- Each of these side chains should have at least about four, and preferably at least about six, carbon atoms. Substantially longer side chains may be advantageous; for example, some of the preferred polymeric stabilizers may have lauryl (Ci 2 ) side chains.
- the side chains may themselves be branched; for example, each side chain could be a branched alkyl group, such as a 2-ethylhexyl group.
- a mixture of monomers for example, a mixture of lauryl methacrylate and methyl methacrylate
- a first polymerization reaction is carried out using a mixture of monomers, at least one of these monomers bearing an initiating group, thus producing a first polymer containing such initiating groups.
- the product of this first polymerization reaction is then subjected to a second polymerization, typically under different conditions from the first polymerization, so as to cause the initiating groups within the polymer to cause polymerization of additional monomer on to the original polymer, thereby forming the desired side chains.
- a second polymerization typically under different conditions from the first polymerization, so as to cause the initiating groups within the polymer to cause polymerization of additional monomer on to the original polymer, thereby forming the desired side chains.
- Free radical polymerization of ethylenic or similar radical polymerizable groups attached to particles may be effected at elevated reaction temperatures, preferably 60 to 70 C, using conventional free radical initiators, such as azobis(isobutyryinitrile) (AIBN), while ATRP polymerization can be effected using the conventional metal complexes, as described in Wang, J. S., et al., Macromolecules 1995, 23, 7901, and J. Am. Chem. Soc. 1995, 117, 5614, and in Beers, K. et al., Macromolecules 1999, 32, 5772-5776. See also U.S. Pat. Nos.
- conventional free radical initiators such as azobis(isobutyryinitrile) (AIBN)
- ATRP polymerization can be effected using the conventional metal complexes, as described in Wang, J. S., et al., Macromolecules 1995, 23, 7901, and J. Am. Chem. Soc.
- the presently preferred catalyst for carrying out ATRP is cuprous chloride in the presence of bipyridyl (Bpy).
- the particles should be coated with at least about 2, and desirably at least about 4, percent by weight of the particle.
- the optimum proportion of polymer will range from about 4 to about 15 percent by weight of the particle, and typically is about 6 to about 15 percent by weight, and most desirably about 8 to about 12 percent by weight.
- a co-monomer may be added to the polymerization reaction medium.
- the co monomer may either directly charge the composite pigment particles or have interaction with a charge control agent in the display fluid to bring a desired charge polarity and charge density to the composite pigment particles.
- Suitable co-monomers may include acrylic acid, methacrylic acid, vinyl phosphoric acid, 2-acrylamino-2-methylpropane sulfonic acid, 2-(dimethylamino)ethyl methacrylate, N-[3-
- Suitable co-monomers may also include fluorinated acrylate or methacrylate such as 2-perfluorobutylethyl acrylate, 2,2,2 trifluoroethyl methacrylate, 2, 2, 3, 3 tetrafluoropropyl methacrylate, 1, 1,1, 3,3,3- hexafluoroisopropyl acrylate, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 2, 2, 3,3,3- pentafluoropropyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2, 2, 3, 4,4,4- hexafluorobutyl methacrylate or 2,2,3,3,4,4,4-heptafluorobutyl methacrylate.
- charged or chargeable groups may be incorporated into the polymer via the bifunctional stabilizer used to provide polymerizable or initiating functionality to the pigment
- Functional groups such as acidic or basic groups, may be provided in a "blocked" form during polymerization, and may then be de-blocked after formation of the polymer.
- esters such as t-butyl acrylate or isobornyl methacrylate may be used, and the residues of these monomers within the final polymer hydrolyzed to provide acrylic or methacrylic acid residues.
- the two reagents have the same, or essentially the same, functional group which reacts with the particle surface so that, if minor variations in reaction conditions occur, the relative rates at which the reagents react with the particles will change in a similar manner, and the ratio between the number of charged or chargeable groups and the number of polymerizable or polymerization-initiating groups will remain substantially constant. It will be appreciated that this ratio can be varied and controlled by varying the relative molar amounts of the two (or more) reagents used in the mixture.
- the density of the electrophoretic particle may be substantially matched to that of the suspending (i.e., electrophoretic) fluid.
- a suspending fluid has a density that is "substantially matched" to the density of the particle if the difference in their respective densities is between about zero and about two grams/milliliter (“g/ml"). This difference is preferably between about zero and about 0.5 g/ml.
- the solvent in which the composite particles are dispersed may be clear and colorless. It preferably has a low viscosity and a dielectric constant in the range of about 2 to about 30, preferably about 2 to about 15 for high particle mobility.
- suitable dielectric solvent include hydrocarbons such as isopar, decahydronaphthalene (DECALIN), 5-ethylidene-2-norbomene, fatty oils, paraffin oil, silicon fluids, aromatic hydrocarbons such as toluene, xylene, phenylxylylethane, dodecylbenzene or alkylnaphthalene, halogenated solvents such as perfluorodecalin, perfluorotoluene, perfluoroxylene, dichlorobenzotrifluoride, 3,4,5- trichlorobenzotrifluoride, chloropentafluorobenzene, dichlorononane or pentachlorobenzene, and perfluorinated solvent
- Charge control agents may be used, with or without charged groups in polymer coatings, to provide good electrophoretic mobility to the electrophoretic particles.
- Stabilizers may be used to prevent agglomeration of the electrophoretic particles, as well as prevent the electrophoretic particles from irreversibly depositing onto the capsule wall.
- Either component can be constructed from materials across a wide range of molecular weights (low molecular weight, oligomeric, or polymeric), and may be a single pure compound or a mixture.
- the charge control agent used to modify and/or stabilize the particle surface charge is applied as generally known in the arts of liquid toners, electrophoretic displays, non-aqueous paint dispersions, and engine-oil additives.
- charging species may be added to non-aqueous media in order to increase electrophoretic mobility or increase electrostatic stabilization.
- the materials can improve steric stabilization as well. Different theories of charging are postulated, including selective ion adsorption, proton transfer, and contact electrification.
- An optional charge control agent or charge director may be incorporated in the electrophoretic fluid. These constituents typically consist of low molecular weight surfactants, polymeric agents, or blends of one or more components and serve to stabilize or otherwise modify the sign and/or magnitude of the charge on the electrophoretic particles. Additional pigment properties which may be relevant are the particle size distribution, the chemical composition, and the lightfastness.
- Charge adjuvants may also be added. These materials increase the effectiveness of the charge control agents or charge directors.
- the charge adjuvant may be a polyhydroxy compound or an aminoalcohol compound, and is preferably soluble in the suspending fluid in an amount of at least 2% by weight.
- polyhydroxy compounds which contain at least two hydroxyl groups include, but are not limited to, ethylene glycol, 2,4,7,9-tetramethyldecyne-4,7-diol, poly(propylene glycol), pentaethylene glycol, tripropylene glycol, triethylene glycol, glycerol, pentaerythritol, glycerol tris(l2-hydroxystearate), propylene glycerol monohydroxystearate, and ethylene glycol monohydroxystearate.
- the charge adjuvant is preferably present in the suspending fluid in an amount of about 1 to about 100 milligrams per gram ("mg/g") of the particle mass, and more preferably about 50 to about 200 mg/g.
- charge control agents which are useful include organic sulfates or sulfonates, metal soaps, block or comb copolymers, organic amides, organic zwitterions, and organic phosphates and phosphonates.
- Useful organic sulfates and sulfonates include, but are not limited to, sodium bis(2-ethylhexyl) sulfosuccinate, calcium dodecylbenzenesulfonate, calcium petroleum sulfonate, neutral or basic barium dinonylnaphthalene sulfonate, neutral or basic calcium dinonylnaphthalene sulfonate, dodecylbenzenesulfonic acid sodium salt, and ammonium lauryl sulfate.
- Useful metal soaps include, but are not limited to, basic or neutral barium petronate, calcium petronate, Co-, Ca— , Cu— , Mn-, Ni— , Zn-, and Fe- - salts of naphthenic acid, Ba-, A1-, Zn— , Cu-, Pb— , and Fe— salts of stearic acid, divalent and trivalent metal carboxylates, such as aluminum tristearate, aluminum octanoate, lithium heptanoate, iron stearate, iron distearate, barium stearate, chromium stearate, magnesium octanoate, calcium stearate, iron naphthenate, zinc naphthenate, Mn- and Zn— heptanoate, and Ba-, A1-, Co-, Mn— , and Zn— octanoate.
- Useful block or comb copolymers include, but are not limited to, AB diblock copolymers of (A) polymers of 2-(N,N-dimethylamino)ethyl methacrylate quatemized with methyl p- toluenesulfonate and (B) poly(2-ethylhexyl methacrylate), and comb graft copolymers with oil soluble tails of poly(l 2-hydroxy stearic acid) and having a molecular weight of about 1800, pendant on an oil-soluble anchor group of poly(methyl methacrylate- methacrylic acid).
- Useful organic amides include, but are not limited to, polyisobutylene succinimides such as OLOA 371 or 1200 (available from Chevron Oronite Company LLC, Houston, Tex.), or Solsperse 19000 and Solsperse 17000 (available from Avecia Ltd., Blackley, Manchester, United Kingdom; "Solsperse” is a Registered Trade Mark), and N-vinylpyrrolidone polymers.
- Useful organic zwitterions include, but are not limited to, lecithin.
- Useful organic phosphates and phosphonates include, but are not limited to, the sodium salts of phosphated mono- and di-glycerides with saturated and unsaturated acid substituents.
- Particle dispersion stabilizers may be added to prevent particle flocculation or attachment to the capsule walls.
- non-aqueous surfactants include, but are not limited to, glycol ethers, acetylenic glycols, alkanolamides, sorbitol derivatives, alkyl amines, quaternary amines, imidazolines, dialkyl oxides, and sulfosuccinates.
- a bistable electrophoretic medium it may be desirable to include in the suspending fluid a polymer having a number average molecular weight in excess of about 20,000, this polymer being essentially non-absorbing on the electrophoretic particles; poly(isobutylene) is a preferred polymer for this purpose. See U.S. Patent No. 7,170,670, the entire disclosure of which is herein incorporated by reference.
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Abstract
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CN201880091689.XA CN111902491A (zh) | 2018-04-05 | 2018-04-05 | 复合颗粒及其制备方法 |
KR1020207024223A KR102435839B1 (ko) | 2018-04-05 | 2018-04-05 | 복합재 입자 및 그의 제조 방법 |
EP18913730.0A EP3775054A4 (fr) | 2018-04-05 | 2018-04-05 | Particules composites et procédé pour leur fabrication |
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JP4436189B2 (ja) * | 2004-05-24 | 2010-03-24 | セイコーエプソン株式会社 | 電気泳動表示装置用マイクロカプセルの製造方法 |
CN1298420C (zh) * | 2005-08-02 | 2007-02-07 | 天津大学 | 聚脲-脲醛树脂双层微胶囊的制备方法 |
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JP7155273B2 (ja) | 2022-10-18 |
KR20200103126A (ko) | 2020-09-01 |
JP2022010003A (ja) | 2022-01-14 |
JP2021515272A (ja) | 2021-06-17 |
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KR102435839B1 (ko) | 2022-08-23 |
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