JP4863762B2 - Particles for display media and information display panels - Google Patents

Description

  INDUSTRIAL APPLICABILITY The present invention is used for an information display panel that displays information such as an image by moving a display medium by enclosing the display medium between two substrates, at least one of which is transparent, and applying an electric field to the display medium. The present invention relates to a display medium particle constituting a display medium and an information display panel using the same.

  2. Description of the Related Art Conventionally, information display devices using techniques such as electrophoresis, electrochromic, thermal, and two-color particle rotation have been proposed as information display devices that replace liquid crystal (LCD).

  Compared to LCDs, these conventional technologies have advantages such as a wide viewing angle close to that of ordinary printed materials, low power consumption, and a memory function. It is considered as a technology that can be used for mobile phones, and is expected to expand to information display for mobile terminals, electronic paper, and the like. Particularly recently, an electrophoretic method in which a dispersion liquid composed of dispersed particles and a colored solution is encapsulated and disposed between opposing substrates has been proposed and is expected.

  However, the electrophoresis method has a problem that the response speed becomes slow due to the viscous resistance of the liquid because the particles migrate in the liquid. In addition, since particles with high specific gravity such as titanium oxide are dispersed in a solution with low specific gravity, it is easy to settle, and it is difficult to maintain the stability of the dispersed state, and there is a problem that the stability of repeated information display is lacking. ing. Even when microencapsulation is performed, the cell size is set to the microcapsule level, and the above-described drawbacks are hardly made to appear, and the essential problems are not solved at all.

As a method for solving the above-described problems, a display medium is sealed between two substrates, at least one of which is transparent, and an electric field is applied to the display medium, whereby the display medium is moved to display information such as an image. An information display panel to be displayed is known.
趙 Kuniori and three others, “New Toner Display Device (I)”, July 21, 1999, Annual Meeting of the Imaging Society of Japan (83 times in total) “Japan Hardcopy'99” Proceedings, p.249-252

  As particles constituting the display medium used in the information display panel described above (particles for display medium), fine particles are adhered or fixed to the surface of charged colored particles such as toner particles for electrophotography. Attempts have been made to use composite particles or composite particles in which fine particles are attached or fixed to the surface of colored particles so as to be charged. However, at that time, if microscopic particles having a high water absorption rate are used, a specific charge (q / m) at a level required for particles for a display medium, that is, a level that can be driven in a panel cannot be obtained, or the ratio The phenomenon that the charge (q / m) is attenuated to a required level or less in a short time occurs, and the display stability is deteriorated in an information display panel using the display medium particles as a display medium. was there.

  An object of the present invention is to solve the above-mentioned problems, and in a display medium particle in which fine particles are attached or fixed to the surface of a mother particle, a favorable specific charge can be obtained, and in a panel using the same An object of the present invention is to provide particles for a display medium and an information display panel capable of obtaining good display stability.

The particles for display medium of the present invention are information for displaying information such as images by moving the display medium by enclosing the display medium between two transparent substrates at least one and applying an electric field to the display medium. In the display medium particles constituting the display medium used in the display panel, at least one type of micron particle is attached or fixed to the surface layer of the mother particle, and the equilibrium water absorption A (weight) of the at least one type of micron particle. %) Satisfying A ≦ 0.7 and the mixing ratio of n kinds of micron particles (1 to n) with respect to the mother particles is φn, the sum of the effective equilibrium water absorption Anφn is ΣAnφn <0.05. (Weight%) (where φn = (mixing weight of micron particles n) / (mixing weight of mother particles)) .

In addition, as a suitable example of the particles for a display medium of the present invention, when there are a plurality of types of micron particles, the equilibrium water absorption A1 (% by weight) of the micron particle having the smallest primary particle size is expressed as A1 ≦ be a 0.7, there is.

  In addition, the information display panel of the present invention displays information such as images by moving the display medium by enclosing the display medium between two substrates, at least one of which is transparent, and applying an electric field to the display medium. In the information display panel, the display medium particles having the above-described configuration are used as the display medium.

  According to the present invention, an information display panel for displaying information such as an image by moving a display medium by enclosing the display medium between two substrates, at least one of which is transparent, and applying an electric field to the display medium. In the display medium particles constituting the display medium used in the above, at least one kind of micron particles is attached or fixed to the surface layer of the mother particle, and the equilibrium water absorption A (wt%) of the at least one kind of micron particles is set. , By satisfying A ≦ 0.7, it is possible to obtain a favorable specific charge in the display medium particles in which the microparticles are adhered or fixed to the surface of the mother particles, and in a panel using the same Thus, it is possible to obtain a display medium particle and an information display panel capable of obtaining good display stability.

  First, the basic configuration of the information display panel of the present invention will be described. In the information display panel which is an object of the present invention, an electric field is applied to a display medium sealed between two opposing substrates. Along with the applied electric field direction, the charged display medium is attracted by the electric field force or Coulomb force, etc., and the display medium changes the moving direction by the electric field direction change due to the potential switching, thereby displaying information such as images. Made. Therefore, it is necessary to design the information display panel so that the display medium can move uniformly and maintain stability when rewriting the display repeatedly or when displaying the display information continuously. Here, as the force applied to the particles constituting the display medium, in addition to the force attracting each other by the Coulomb force between the particles, an electric mirror image force between the electrode and the substrate, an intermolecular force, a liquid crosslinking force, gravity, and the like can be considered.

  An example of an information display panel that is an object of the present invention will be described with reference to FIGS. 1 (a) and 1 (b) to FIGS.

  In the example shown in FIGS. 1A and 1B, at least two kinds of display media 3 (here, white display medium particles 3Wa) having at least one kind of particles and having different optical reflectance and charging characteristics. A white display medium 3W composed of a group of particles and a black display medium 3B composed of a group of particles 3Ba for black display medium) are perpendicular to the substrates 1 and 2 according to the electric field applied from the outside of the substrates 1 and 2. The black display medium 3B is visually recognized by the observer and black display is performed, or the white display medium 3W is visually recognized by the observer and white display is performed. In the example shown in FIG. 1B, in addition to the example shown in FIG. 1A, a partition 4 is provided between the substrates 1 and 2, for example, in the form of a lattice to form a cell. In addition, in FIG. 1B, the partition in front is omitted.

  In the example shown in FIGS. 2A and 2B, at least two or more types of display media 3 (here, white display medium particles 3Wa) having different optical reflectance and charging characteristics composed of at least one type of particles. Between the electrode 5 provided on the substrate 1 and the electrode 6 provided on the substrate 2 is a voltage between the electrode 5 provided on the substrate 1 and the electrode 6 provided on the substrate 2. In accordance with the electric field generated by applying, the substrate is moved perpendicularly to the substrates 1 and 2 so that the black display medium 3B is visually recognized by the observer and black display is performed, or the white display medium 3W is provided to the observer. A white display is made by visual recognition. In the example shown in FIG. 2B, a cell is formed by providing partition walls 4 between the substrates 1 and 2, for example, in a lattice shape. Further, in FIG. 2 (b), the front partition is omitted.

  In the example shown in FIGS. 3A and 3B, the display medium 3 (in this case, from the particle group of white display medium particles 3Wa) having at least an optical reflectance and a charging property composed of at least one kind of particles. The white display medium 3W is moved in a direction parallel to the substrates 1 and 2 in accordance with an electric field generated by applying a voltage between the electrode 5 and the electrode 6 provided on the substrate 1 to display a white color. The medium 3W is visually recognized by the observer and white display is performed, or the color of the electrode 6 or the substrate 1 is visually recognized by the observer and the color of the electrode 6 or the substrate 1 is displayed. In the example shown in FIG. 3B, for example, a lattice-shaped partition wall 4 is provided between the substrates 1 and 2 to form a cell. Moreover, in FIG.3 (b), the partition in front is abbreviate | omitted.

  The above description applies in the same manner to the case where the white display medium 3W including the particle group is replaced with the white medium including the powder fluid and the black display medium 3B including the particle group is replaced with the black display medium including the powder fluid. I can do it. The powder fluid will be described later.

  Among the display medium particles used in the information display panel having the above-described configuration, various studies are made on the water absorption rate of the microparticle particles for the display medium particles formed by attaching or fixing the microparticle particles to the surface layer of the mother particles. As a result, it was found that by setting the equilibrium water absorption A (% by weight) of at least one kind of micronized particles to 0.7 (% by weight) or less, particles for a display medium that can constitute a panel with good driving performance can be obtained. did. This led to the discovery of the present invention.

  As a preferred example of the present invention, by setting the equilibrium water absorption A1 (% by weight) of the micronized particle G1 having the smallest primary particle size to 0.7 (% by weight) or less, the blending of the micronized particles is further performed. Particles for display media that can constitute a panel with even better driving performance by making the amount ΣAφ less than 0.05 (wt%) using the mixing ratio φ between the equilibrium water supply rate A (wt%) and the mother particles Was found to be obtained.

In the present invention, when a plurality of types of micronized particles are used, among the display medium composed of adhering / adhering type composite particles, the central particle having the maximum particle size is the mother particle, and other particles adhering or adhering to the surface of the mother particle When there are n types, the microparticles 1, 2, 2,... One type of micron particle may be used. Moreover, the measuring method of the water absorption A in this invention is as follows. That is, the water content Ww (g) that volatilizes when heated at 200 ° C./45 minutes from a micron particle sample having a weight Wp (g) that has been left in an environment of 25 ° C./50% RH for one week or longer is Karl Fischer current titration. It measures with apparatus CA-100 (made by Mitsubishi Chemical Corporation), and calculates | requires equilibrium water absorption A (weight%) as A = Ww / (Wp-Ww). Furthermore, an example of a processing method for obtaining composite particles by attaching or fixing micron particles to the surface layer of the mother particles is as follows. Using a carbon mixer (manufactured by SMT Co., Ltd.), mixed powder (bulk volume = apparent volume: mixed volume) in which mother particles and micronized particles are mixed at a predetermined ratio under conditions of 30 ° C. or less and 4000 rpm × 15 minutes. 130 cm ³ or more) was put into the apparatus at a time and composite treatment was performed under the above conditions.

  Hereinafter, each member which comprises the information display panel of this invention is demonstrated.

  As for the substrate, at least one substrate is the transparent substrate 2 from which the color of the display medium can be confirmed from the outside of the information display panel, and a material having high visible light transmittance and good heat resistance is preferable. The substrate 1 may be transparent or opaque. Examples of substrate materials include polymer sheets such as polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyethylene, polycarbonate, polyimide, and acrylic, flexible materials such as metal sheets, and glass and quartz. An inorganic sheet having no flexibility is mentioned. The thickness of the substrate is preferably from 2 to 5000 μm, more preferably from 5 to 2000 μm. If it is too thin, it will be difficult to maintain the strength and the spacing uniformity between the substrates, and if it is thicker than 5000 μm, it will be a thin information display panel. Is inconvenient.

  As an electrode forming material when an electrode is provided on an information display panel as required, metals such as aluminum, silver, nickel, copper, and gold, ITO, indium oxide, conductive tin oxide, conductive zinc oxide, etc. Conductive polymers such as conductive metal oxides, polyaniline, polypyrrole, and polythiophene are exemplified and appropriately selected and used. As a method for forming an electrode, a method of forming the above-described materials into a thin film by sputtering, vacuum deposition, CVD (chemical vapor deposition), coating, or the like, or mixing a conductive agent with a solvent or a synthetic resin binder. The method of apply | coating is used. The electrode provided on the display surface side substrate 2 which is on the viewing side and needs to be transparent needs to be transparent, but the electrode provided on the back side substrate 1 does not need to be transparent. In any case, the above-mentioned material that can be patterned and is electrically conductive can be suitably used. Note that the electrode thickness is not particularly limited as long as the conductivity can be secured and the light transmittance is not hindered, and is preferably 3 to 1000 nm, preferably 5 to 400 nm. The material and thickness of the electrode provided on the back side substrate 1 are the same as those of the electrode provided on the display surface side substrate described above, but need not be transparent. In this case, the external voltage input may be superimposed with direct current or alternating current.

The shape of the partition 4 provided on the substrate as necessary is appropriately set according to the type of display medium involved in display, the shape and arrangement of electrodes to be arranged, and is not limited in general. The height of the partition is adjusted to 100 to 100 μm, preferably 3 to 50 μm, and the height of the partition wall to 10 to 100 μm, preferably 10 to 50 μm.
In forming the partition wall, a both-rib method in which ribs are formed on each of the opposing substrates 1 and 2 and then bonded, and a single-rib method in which ribs are formed only on one substrate are conceivable. In the present invention, any method is preferably used.
As shown in FIG. 4, the cells formed by the partition walls made up of these ribs are illustrated in a square shape, a triangular shape, a line shape, a circular shape, and a hexagonal shape as viewed from the substrate plane direction. And a mesh shape. It is better to make the portion corresponding to the cross section of the partition wall visible from the display surface side (the area of the cell frame) as small as possible, and the display becomes clearer.
Examples of the method for forming the partition include a mold transfer method, a screen printing method, a sand blast method, a photolithography method, and an additive method. Any of these methods can be suitably used for the information display panel of the present invention, and among these, a photolithography method using a resist film and a mold transfer method are suitably used.

  Next, the powder fluid used as a display medium composed of the display medium particles of the present invention will be described. As for the name of the powder fluid used in the information display panel of the present invention, the present applicant has obtained the right of “Electronic Powder Fluid (registered trademark): Registration No. 4636931”.

  The “powder fluid” in the present invention is a substance in an intermediate state of both fluid and particle characteristics that exhibits fluidity by itself without borrowing the force of gas or liquid. For example, liquid crystal is defined as an intermediate phase between a liquid and a solid, and has fluidity that is a characteristic of liquid and anisotropy (optical properties) that is a characteristic of solid (Heibonsha: Encyclopedia) . On the other hand, the definition of particle is an object with a finite mass even if it is negligible, and is said to be affected by gravity (Maruzen: Physics Encyclopedia). Here, even in the case of particles, there are special states of gas-solid fluidized bed and liquid-solid fluids. When gas is flowed from the bottom plate to the particles, upward force is applied to the particles according to the velocity of the gas. Is a gas-solid fluidized bed that is in a state where it can easily flow when it balances with gravity, and it is also called a liquid-solid fluidized state that is fluidized by a fluid (ordinary) Company: Encyclopedia). As described above, the gas-solid fluidized bed body and the liquid-solid fluid are in a state of using a gas or liquid flow. In the present invention, it has been found that a substance in a state of fluidity can be produced specifically without borrowing the force of such gas and liquid, and this is defined as powder fluid.

  That is, the pulverulent fluid in the present invention is in an intermediate state having both the characteristics of particles and liquid, as in the definition of liquid crystal (liquid and solid intermediate phase), and is the characteristic of the above-mentioned particles. It is a substance that is extremely unaffected and exhibits a unique state with high fluidity. Such a substance can be obtained in an aerosol state, that is, in a dispersion system in which a solid or liquid substance is stably suspended as a dispersoid in a gas, and the solid substance is regarded as a dispersoid in the information display panel of the present invention. To do.

The information display panel of the present invention encloses a powder fluid exhibiting high fluidity in an aerosol state in which solid particles are stably suspended as a dispersoid, for example, in a gas between opposing substrates, at least one of which is transparent. In addition, such a powder fluid can be easily and stably moved by a Coulomb force or the like with a force of a small electric field.
As described above, for example, the powder fluid used as the display medium in the present invention is a substance in the intermediate state between the fluid and particles that exhibits fluidity by itself without borrowing the force of gas or liquid. It is. This powder fluid can be in an aerosol state in particular, and in the information display panel of the present invention, it is used as a display medium in a state where a solid substance floats relatively stably as a dispersoid in the gas.

Next, display medium particles (hereinafter also referred to as particles) constituting the display medium in the information display panel of the present invention will be described. The display medium particles are composed of the display medium particles as they are to form a display medium, or are combined with other particles to form a display medium, or adjusted and configured to become a powder fluid to form a display medium. Or used.
The particles can contain a charge control agent, a colorant, an inorganic additive, and the like, if necessary, in the resin as the main component, as in the conventional case. Examples of resins, charge control agents, colorants, and other additives will be given below.

  Examples of the resin include urethane resin, urea resin, acrylic resin, polyester resin, acrylic urethane resin, acrylic urethane silicone resin, acrylic urethane fluororesin, acrylic fluororesin, silicone resin, acrylic silicone resin, epoxy resin, polystyrene resin, styrene Acrylic resin, polyolefin resin, butyral resin, vinylidene chloride resin, melamine resin, phenol resin, fluororesin, polycarbonate resin, polysulfone resin, polyether resin, polyamide resin and the like can be mentioned, and two or more kinds can be mixed. In particular, acrylic urethane resin, acrylic silicone resin, acrylic fluororesin, acrylic urethane silicone resin, acrylic urethane fluororesin, fluororesin, and silicone resin are suitable from the viewpoint of controlling the adhesive force with the substrate.

  The charge control agent is not particularly limited. Examples of the negative charge control agent include salicylic acid metal complexes, metal-containing azo dyes, metal-containing oil-soluble dyes (including metal ions and metal atoms), and quaternary ammonium salt systems. Examples thereof include compounds, calixarene compounds, boron-containing compounds (benzyl acid boron complexes), and nitroimidazole derivatives. Examples of the positive charge control agent include nigrosine dyes, triphenylmethane compounds, quaternary ammonium salt compounds, polyamine resins, imidazole derivatives, and the like. In addition, metal oxides such as ultrafine silica, ultrafine titanium oxide, ultrafine alumina, nitrogen-containing cyclic compounds such as pyridine and derivatives and salts thereof, various organic pigments, resins containing fluorine, chlorine, nitrogen, etc. are also charged. It can also be used as a control agent.

  As the colorant, various organic or inorganic pigments and dyes as exemplified below can be used.

Examples of the black colorant include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon and the like.
Examples of blue colorants include C.I. I. Pigment blue 15: 3, C.I. I. Pigment Blue 15, Bituminous Blue, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Metal-free Phthalocyanine Blue, Phthalocyanine Blue Partial Chlorides, Fast Sky Blue, Indanthrene Blue BC and the like.
Examples of red colorants include bengara, cadmium red, red lead, mercury sulfide, cadmium, permanent red 4R, resol red, pyrazolone red, watching red, calcium salt, lake red D, brilliant carmine 6B, eosin lake, rhodamine lake B, Alizarin Lake, Brilliant Carmine 3B, C.I. I. Pigment Red 2 etc.

As yellow colorants, yellow lead, zinc yellow, cadmium yellow, yellow iron oxide, mineral first yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hansa Yellow G, Hansa Yellow 10G, Benzidine Yellow G, Benzidine Yellow GR, Quinoline Yellow Lake, Permanent Yellow NCG, Tartrazine Lake, C.I. I. Pigment Yellow 12 etc.
Examples of green colorants include chrome green, chromium oxide, pigment green B, C.I. I. Pigment Green 7, Malachite Green Lake, Final Yellow Green G, etc.
Examples of the orange colorant include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, Indanthrene Brilliant Orange RK, Benzidine Orange G, Indanthren Brilliant Orange GK, C.I. I. Pigment Orange 31 etc.
Examples of purple colorants include manganese purple, first violet B, and methyl violet lake.
Examples of white colorants include zinc white, titanium oxide, antimony white, and zinc sulfide.

  Examples of extender pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white. Examples of various dyes such as basic, acidic, disperse, and direct dyes include nigrosine, methylene blue, rose bengal, quinoline yellow, and ultramarine blue.

Examples of inorganic additives include titanium oxide, zinc white, zinc sulfide, antimony oxide, calcium carbonate, lead white, talc, silica, calcium silicate, alumina white, cadmium yellow, cadmium red, cadmium orange, titanium yellow, Examples include bitumen, ultramarine blue, cobalt blue, cobalt green, cobalt violet, iron oxide, carbon black, manganese ferrite black, cobalt ferrite black, copper powder, and aluminum powder.
These pigments and inorganic additives can be used alone or in combination. Of these, carbon black is particularly preferable as the black pigment, and titanium oxide is preferable as the white pigment.

  The particles for display media of the present invention (hereinafter also referred to as particles) preferably have an average particle diameter d (0.5) in the range of 0.1 to 20 μm and are uniform and uniform. If the average particle diameter d (0.5) is larger than this range, the display is not clear. If the average particle diameter d (0.5) is smaller than this range, the cohesive force between the particles becomes too large, which hinders movement as a display medium.

Furthermore, in the present invention, regarding the particle size distribution of each particle, the particle size distribution Span represented by the following formula is less than 5, preferably less than 3.
Span = (d (0.9) −d (0.1)) / d (0.5)
(However, d (0.5) is a numerical value expressing the particle diameter in μm that 50% of the particles are larger than this and 50% is smaller than this, and d (0.1) is a particle in which the ratio of the smaller particles is 10%. (Numerical value expressed in μm, and d (0.9) is a numerical value expressed in μm for a particle diameter of 90% or less.)
By keeping Span within a range of 5 or less, the size of each particle is uniform, and movement as a uniform display medium becomes possible.

  Furthermore, regarding the correlation between the particles, the ratio of d (0.5) of the particles having the minimum diameter to d (0.5) of the particles having the maximum diameter among the used particles is set to 50 or less, preferably 10 or less. It is essential. Even if the particle size distribution Span is reduced, particles with different charging characteristics move in opposite directions, so that the particle size is close to each other and each particle can be easily moved in the opposite direction by the equivalent amount. This is within this range.

The particle size distribution and the particle size can be obtained from a laser diffraction / scattering method or the like. When laser light is irradiated onto particles to be measured, a light intensity distribution pattern of diffracted / scattered light is spatially generated, and this light intensity pattern has a corresponding relationship with the particle diameter, so that the particle diameter and particle diameter distribution can be measured. .
Here, the particle size and particle size distribution in the present invention are obtained from a volume-based distribution. Specifically, using a Mastersizer2000 (Malvern Instruments Ltd.) measuring instrument, particles are introduced into a nitrogen stream, and the attached analysis software (software based on volume-based distribution using Mie theory) The diameter and particle size distribution can be measured.

  The charge amount of the display medium particles naturally depends on the measurement conditions, but the charge amount of the display medium particles in the information display panel is almost the same as the initial charge amount, the contact with the partition walls, the contact with the substrate, and the elapsed time. It was found that depending on the charge decay, the saturation value of the charging behavior of the particles for the display medium is a dominant factor.

  As a result of intensive studies, the present inventors have been able to evaluate the range of proper charging characteristics of display medium particles by measuring the charge amount of the particles used in the display medium using the same carrier particles in the blow-off method. I found.

Furthermore, when a display medium such as a particle group or a powder fluid composed of display medium particles is applied to the information display panel of the present invention, it is important to manage the gas in the void surrounding the display medium between the substrates. Contributes to improved display stability. Specifically, it is important that the relative humidity at 25 ° C. is 60% RH or less, and preferably 50% RH or less for the humidity of the gas in the gap.
1A, 1B, 3B, 3B, and 3B, the gaps are defined as electrodes 5 and 6 (electrodes on the inner side of the substrate). 2), a gas portion in contact with a so-called display medium excluding an occupied portion of the display medium 3, an occupied portion of the partition wall 4 (when a partition wall is provided), and a seal portion of the information display panel.
The gas in the gap is not limited as long as it is in the humidity region described above, but dry air, dry nitrogen, dry argon, dry helium, dry carbon dioxide, dry methane, and the like are preferable. This gas needs to be sealed in an information display panel so that the humidity is maintained, for example, filling a display medium, assembling an information display panel, etc. in a predetermined humidity environment, It is important to apply a sealing material and a sealing method that prevent moisture from entering from the outside.

The distance between the substrates in the information display panel that is the subject of the present invention is not limited as long as the display medium can be moved and the contrast can be maintained, but is usually adjusted to 10 to 500 μm, preferably 10 to 200 μm.
The volume occupation ratio of the display medium in the space between the opposing substrates is preferably 5 to 70%, more preferably 5 to 60%. If it exceeds 70%, the movement of the display medium is hindered, and if it is less than 5%, the contrast tends to be unclear.

  A display medium driveability evaluation test panel using a display medium composed of the display medium particles of the present invention was prepared as follows, and the display medium drive voltage and the display medium endurance drive voltage were measured. The display medium was evaluated.

(1) Preparation of positively charged mother particles and composite treatment of fine particles As positively charged particles, 60 parts by weight of methyl methacrylate monomer (Kanto Chemical Reagent), and ethylene glycol as a polyfunctional monomer having a plurality of polymerization reactive groups in one molecule A black inorganic pigment is obtained by dispersing 3 parts by weight of a nigrosine compound (Bontron N07: manufactured by Orient Chemical Co., Ltd.) as a positively charged monomer hardly soluble charge control agent in 40 parts by weight (about 25 mol%) of dimethacrylate (Wako Pure Chemicals Reagents) with a sand mill. As a colorant, 12.5 parts by weight of a master batch in which 40 parts by weight of carbon black (MA100: manufactured by Mitsubishi Chemical) was previously dispersed in 60 parts by weight of a methacrylic resin (Delpet 560F: manufactured by Asahi Kasei); System) Resin-hydrocarbon resin copolymer (acrylic and methacrylic) Resin-fluororesin block copolymer (Modiper F600: manufactured by NOF Corporation) was used as a surfactant containing a polyoxyalkylene chain and a sulfonate in its molecule as a surfactant containing polyoxyethylene alkyl ether sodium sulfate (Latemul E) -118B (manufactured by Kao) was suspended in purified water at 40 ° C. to which 0.5 wt% was added to obtain a suspension having an average oil droplet diameter of about 80 μm. In this suspension, a dispersion obtained by previously dispersing an acyl peroxide lauryl peroxide (Perroyl L: manufactured by NOF Corporation / 10-hour half-life temperature 61.6 ° C.) in water is added in an amount of 2 parts by weight of the peroxide. Then, the suspension is heated and polymerized again so that the average oil droplet size becomes about 10 μm, filtered and dried, and then the particle size is measured using a classifier (MDS-2: Nippon Pneumatic Industry). In the range of 0.5 to 50 μm, mother particles 1 having an average particle diameter R0 = 9.8 μm were obtained.

  Base particles 1 and micron particles (A) HDK H3050VP (WACKER) were premixed at a micron particle mixing ratio φ = 0.02, and 27 ° C. and 4000 rpm × 15 using a carbon mixer (manufactured by SMT). Then, the surface adhesion composite treatment was performed to obtain a black display medium 1A.

(2) Preparation of negatively charged mother particles and composite treatment of fine particles As negatively charged particles, 100 parts by weight of PBT resin (Torcon 1401X31: manufactured by Toray Industries, Inc.) and titanium dioxide (Taipaque CR-50: manufactured by Ishihara Sangyo Co., Ltd.) 100 parts by weight are biaxially kneaded, finely pulverized and classified with a jet mill (Lab Jet Mill IDS-LJ type: manufactured by Nippon Pneumatic Co., Ltd.), and the average particle diameter is in the range of 0.5 to 50 μm. Base particles 2 having a diameter of 9.1 μm were obtained.

  The mother particles 2 and the micronized particles (B), (C), (D), and (E) are premixed at various mixing ratios φ, and 27 ° C., 4000 rpm × using a carbon mixer (manufactured by SMT Co., Ltd.) It was treated for 15 minutes and combined with the surface to obtain white display media 2B, 2C and 2E. In addition, the base particle 2, the micron particle (B), and the micron particle (F) were subjected to a surface adhesion composite treatment to obtain a white display medium 2BF. Similarly, a white display medium 2BD was obtained from the mother particle 2 micron particle (B) and the micron particle (D).

  The list of micron particles used is shown in Table 1 below.

(3) Initial drive voltage measurement method Equal amounts of the positively charged display medium X and the negatively charged display medium Y are mixed and stirred to perform tribocharging, and are arranged via a 100 μm spacer. A connected glass substrate and a cell having a copper substrate on the other side were filled at a volume occupation ratio of 30% to obtain a panel for driving performance evaluation test. When each of the ITO glass substrate and the copper substrate is connected to a power source and a direct current voltage is applied so that the ITO glass substrate is at a low potential and the copper substrate is at a high potential, the positively charged display medium X is negatively charged to the low potential electrode side. The display medium Y moves to the high potential electrode side. Here, when the positively charged display medium X is black and the negatively charged display medium Y is white, a black display state is observed through the glass substrate. Next, when the potential of the applied voltage is reversed, the display medium moves in the opposite direction. Thus, a white display state is observed. The applied voltage was gradually changed, the reflectance was measured in each display state, and the voltage at which the ratio of the reflectance during white display to the reflectance during black display was defined as a drive voltage was measured. . The results are shown in Table 2 below.

(4) Durability driving voltage measurement method A panel for driving performance evaluation test was prepared in the same manner as in (3), and after applying the durability stress by switching the glass substrate side applied voltage from +250 V to −250 V continuously 100000 times, The drive voltage was measured as in 3). The results are shown in Table 2 below.

  From the results of Table 2, it was determined that the equilibrium water absorption A (% by weight) of at least one type of micron particle satisfies A ≦ 0.7, and when there are a plurality of types of micron particles, at least primary. When the equilibrium water absorption A1 (% by weight) of the micron particle having the smallest particle diameter is set to A1 ≦ 0.7, and the mixing ratio of n kinds of micron particles n to the mother particle is φn, the effective equilibrium It can be seen that the sum of the water absorption rates Anφn satisfies ΣAnφn <0.05 (wt%) (where φn = (mixing weight of micron particles n) / (mixing weight of mother particles)).

  The information display panel of the present invention uses the particles for display medium of the present invention that can obtain a good specific charge in the particles for display medium in which fine particles are adhered or fixed to the surface of the mother particles. Display units for mobile devices such as notebook PCs, PDAs, mobile phones, handy terminals, electronic papers such as electronic books and electronic newspapers, bulletin boards such as signboards, posters, and blackboards, display units for calculators, home appliances, automobile supplies, etc. Suitable for card displays such as cards and IC cards, electronic advertisements, information boards, electronic POPs (Point Of Presence, Point Of Purchase advertising), electronic price tags, electronic shelf labels, electronic musical scores, and display parts of RF-ID devices Used.

(A), (b) is a figure which shows an example of the information display panel of this invention, respectively. (A), (b) is a figure which shows the other example of the information display panel of this invention, respectively. (A), (b) is a figure which shows the further another example of the information display panel of this invention, respectively. It is a figure which shows an example of the shape of the partition in the information display panel of this invention.

Explanation of symbols

1, 2 Substrate 3 Display medium (particle group, powder fluid)
3W White display medium 3Wa White display medium particles 3B Black display medium 3Ba Black display medium particles 4 Bulkhead 5, 6 Electrode

Claims (3)

A display medium used for an information display panel that displays information such as an image by moving the display medium by enclosing the display medium between two substrates transparent at least one and applying an electric field to the display medium In the display medium particles, at least one type of micron particle is attached or fixed to the surface layer of the mother particle, and the equilibrium water absorption A (wt%) of the at least one type of micron particle is A ≦ 0.7. And the sum of effective equilibrium water absorption Anφn is ΣAnφn <0.05 (% by weight) (where φn = (Particle weight of microparticles n) / (Blend weight of mother particles)) .   The equilibrium water absorption A1 (% by weight) of the micron particle having the smallest primary particle diameter when a plurality of types of micron particles are present is set to A1 ≦ 0.7. Particles for display media. An information display panel that displays information such as an image by moving the display medium by enclosing the display medium between two substrates transparent at least one and applying an electric field to the display medium as a display medium Item 3. An information display panel using the display medium particle according to Item 1 or 2 .

Images