JP2006309212A - Particle for display medium and panel for information display using same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide particles for a display medium, which can have their particle surfaces made uneven and also have gaps in the particles controlled, and a panel for information display capable of eliminating display defects and a decrease in contrast ratio by using the same. <P>SOLUTION: Disclosed are the particles for the display medium which displays information by applying an electric field to the display medium charged between two substrates to move the display medium. The particles for the display medium are characterized in that: (1) the particles are nearly spherical particles obtained by polymerizing a particle raw material containing monomers, the particle raw material contains a copolymer of (acrylic and methacrylic) resin and hydrocarbon based resin or a copolymer of (acrylic and methacrylic resin) and (acrylic and methacrylic resin having hydrocarbon or hydro fluorocarbon at a side chain), some or all of the monomers are multifunctional monomers having a plurality of polymerization reaction groups in one molecule, the particles having fine unevenness uniformly on particle surfaces; and (2) the relation between the density Dc of a core portion and the density Ds of a shell portion is Dc>Ds. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention provides a display medium used for an information display panel for displaying information by moving a display medium by enclosing the display medium between two substrates transparent at least one and applying an electric field to the display medium. The present invention relates to a display medium particle to be configured 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.

  On the other hand, a method in which conductive particles and a charge transport layer are incorporated into a part of a substrate without using a solution is proposed instead of an electrophoresis method using behavior in a solution (see, for example, Non-Patent Document 1). ). However, the structure is complicated because the charge transport layer and further the charge generation layer are arranged, and it is difficult to uniformly inject the charge into the conductive particles.

As a method for solving the various problems described above, 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, thereby moving the display medium to display information. An information display panel 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

  In the information display panel of the type that moves the display medium described above, the particle diameter of the display medium particles (hereinafter also referred to as particles) constituting the display medium can be moved by an electric potential is 0.5. About 50 μm is preferable. If it is too small, the physical adhesion between the particles and between the particles and the substrate will increase, and a large electric field will be required for movement. If it is too large, the distance between the substrates will have to be large. Is required. However, even when the particle diameter is within the above range, when smooth surface particles are used for the information display panel described above, the voltage applied to generate the electric field necessary for flying (driving) the particles is high. The problem that became. If this is a smooth surface, the physical adhesion between the particles and between the particles and the substrate will increase, and the energy required to separate them and fly through the space inside the substrate will increase. It is because it ends.

  As a method for solving this problem, the most easily performed method is a method in which metal oxide fine particles or the like (external additive) are attached to the particle surface to make the particle surface uneven, thereby reducing the adhesion force. When this method is used for the display medium particles used in the information display panel described above, transfer of external additives between particles and between particles and substrates, and adhesion of external additives to particle surfaces and substrate surfaces There is a problem that display defects occur due to the influence of the above. In addition, there is a method in which a reaction-inactive solvent or the like is added to the particle raw material to be polymerized to polymerize, and then the solvent is removed by heating or extraction to produce porous particles, thereby making the surface uneven. In addition, a process and equipment for removing the solvent and the like are required, which is not efficient.

  In addition, even if the particle has a rough surface, if there is a void not only in the particle surface but also inside the particle, the void does not contribute to the reflection and absorption of incident light. In the case of an information display panel using these particles as particles for a display medium, the contrast ratio between the white display state and the black display state is lowered. there were.

  The object of the present invention is to solve the above-mentioned problems, to obtain irregularities firmly fixed on the particle surface, and to control the voids inside the particles, and to display using the particles for display media An object of the present invention is to provide an information display panel that can eliminate defects and a decrease in contrast ratio.

  The display medium particle of the present invention is an information display panel that displays information 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 display medium particles constituting the display medium used in (1), (1) the particles are substantially spherical particles obtained by polymerizing a particle raw material containing a monomer, and (acrylic and methacrylic) resin-hydrocarbon in the particle raw material -Based resin copolymer or copolymer of (acrylic and methacrylic) resin-(acrylic and methacrylic having hydrocarbon or fluorinated hydrocarbon in the side chain) resin, and a part or all of the monomer is one molecule It is a polyfunctional monomer having a plurality of polymerization reactive groups inside, and has a uniform surface with fine irregularities on the particle surface. The area inside 3/4 of radius R is defined as the core part of the particle, and the outer part from the core part is defined as the shell part of the particle. The relationship between the sparse density of the core part Dc and the sparse density of the shell part Ds is Dc> Ds (Here, assuming that the void volume of the core portion is Vcv and the true particle volume of the core portion obtained by subtracting Vcv from the total volume Vc of the core portion is Vcb, Dc = Vcb / (Vcv + Vcb), and the void of the shell portion When the volume is Vsv and the true particle volume of the shell portion obtained by subtracting Vsv from the total volume Vs of the shell portion is Vsb, Ds = Vsb / (Vsv + Vsb)).

As a preferred example of the display medium particle of the present invention, the core portion has a sparse density Dc of 0.66 <Dc <1.0, and the shell portion has a sparse density Ds of 0.1 <Ds. <0.9, minute irregularities are convex or concave portions having an equivalent diameter of 0.01 to 0.5 μm, and fluorinated hydrocarbon components of acrylic and methacrylic resins having fluorinated hydrocarbons Is C ₈ F ₁₇ , the hydrocarbon resin component of the (acrylic and methacrylic) resin-hydrocarbon resin copolymer is polystyrene, and the particle diameter is in the range of 0.5 to 50 μm. In some cases, the particle color is white, and the particle color is black.

  The information display panel of the present invention is an information display for displaying information 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 display panel is characterized by using the particles for a display medium having the above-described configuration.

  According to the particles for display media of the present invention, (1) (acrylic and methacrylic) resin-hydrocarbon resin copolymer or (acrylic and methacrylic) resin- (hydrocarbon or fluorocarbon in the side chain) is contained in the particle raw material. Acrylic and methacrylic (having hydrocarbons) resins are included, and some or all of these monomers are polyfunctional monomers with multiple polymerization reactive groups in one molecule, so they are firmly attached to the particle surface. Fixed irregularities can be obtained. Further, (2) since the relationship between the sparse density Dc of the core part and the sparse density Ds of the shell part is Dc> Ds, it is possible to obtain particles having few voids inside the particles. Therefore, according to the information display panel using the display medium particles of the present invention as the display medium, the display contrast and the response speed are not lowered even when the display is rewritten repeatedly, and the information display panel having good durability. Can be obtained.

  First, a basic configuration of an information display panel using the display medium particles of the present invention (hereinafter also referred to as particles) as a display medium 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. In accordance with the applied electric field direction, the charged display medium is attracted by the force of the electric field or Coulomb force, and the moving direction of the display medium is switched by the change in the electric field direction, whereby information such as an image is displayed. Therefore, it is necessary to design the information display panel so that the display medium can move uniformly and maintain the stability when the display information is rewritten or when the displayed information is continuously displayed. 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, the electric mirror image force between the electrode and the substrate, the intermolecular force, the liquid cross-linking 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 (b) to FIGS. 3 (a) and 3 (b).

  In the example shown in FIGS. 1A and 1B, at least two or more types of display media 3 (here, white display) each having at least one or more types of particles, each having different optical reflectance and charging characteristics. White display medium 3W composed of particles composed of particles for medium and black display medium 3B composed of particles composed of particles for black display medium) to the electric field applied from the outside of the substrates 1 and 2 Accordingly, the black display medium 3B is moved vertically to the substrates 1 and 2 and the black display medium 3B is visually recognized by the observer, or black display is performed, or the white display medium 3W is visually recognized by the observer and white display is performed. Yes. 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) each having at least one or more types of particles, each having different optical reflectance and charging characteristics. A white display medium 3W composed of a particle group composed of particles for the medium and a black display medium 3B composed of a particle group composed of particles for a black display medium) are provided on the electrode 5 and the substrate 2 provided on the substrate 1 Depending on the electric field generated by applying a voltage between the electrodes 6 provided, the substrate 6 is moved perpendicularly to the substrates 1 and 2 so that the black display medium 3B is visually recognized by the observer, or black display is performed. The white display medium 3 </ b> W is visually recognized by the observer to display white. In the example shown in FIG. 2B, in addition to the example shown in FIG. 2A, for example, a partition 4 is provided between the substrates 1 and 2 to form a cell. Further, in FIG. 2 (b), the front partition is omitted.

  In the example shown in FIGS. 3A and 3B, at least one type of display medium 3 (here, white display medium particles) having at least an optical reflectance and a chargeability composed of at least one type of particles. In the direction parallel to the substrates 1 and 2 according to the electric field generated by applying a voltage between the electrode 5 and the electrode 6 provided on the substrate 1). The white display 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. Yes. In the example shown in FIG. 3B, in addition to the example shown in FIG. 3A, for example, a grid-like 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 features of the present invention are (1) roughly spherical particles obtained by polymerizing a particle raw material containing a monomer as a display medium particle, and (acrylic and methacrylic) resin-hydrocarbon type in the particle raw material. Resin copolymer or (acrylic and methacrylic) resin- (copolymer of (acrylic and methacrylic) having a hydrocarbon or fluorinated hydrocarbon in the side chain) resin and a part or all of the monomer in one molecule A polyfunctional monomer having a plurality of polymerization reactive groups, and using particles having uniformly fine irregularities on the particle surface, and (2) among the inside of the particles of radius R, 3 / 4 defines the area inside the particle as the core of the particle and the outside of the core as the shell of the particle, and the relationship between the sparse density Dc of the core and the sparse density Ds of the shell is Dc> Ds (where core Part of the sky When the volume is Vcv, the true particle volume of the core part obtained by subtracting Vcv from the total volume Vc of the core part is Vcb, Dc = Vcb / (Vcv + Vcb), the void volume of the shell part is Vsv, The point is to use particles that satisfy Ds = Vsb / (Vsv + Vsb), where Vsb is the true particle volume of the shell portion obtained by subtracting Vsv from the total volume Vs.

  By configuring as in the above (1), fixed irregularities without dropping off are formed at the time of polymerization without steps such as volatilization or extraction of solvents, etc., so that the voltage necessary for driving the display medium is increased. Particles that are low and hardly cause display defects can be stably produced. Regarding the size of the surface irregularities, the convex portion or the concave portion is preferably in the range of 0.01 to 0.5 μm in diameter equivalent diameter. If the surface unevenness is too small, a sufficient adhesion reducing effect cannot be obtained, and if the surface unevenness is too large, the surface of the uneven portion itself adheres and the effect of unevenness is lost.

  Here, when the amount of the polyfunctional monomer having a plurality of polymerization reactive groups in one molecule is less than 15 mol%, the particle surface unevenness does not appear, or the unevenness becomes small and the effect is small. . Further, when the total amount is a polyfunctional monomer, the structure of the resin constituting the particles becomes strong, and particles having excellent heat resistance and display durability can be obtained. In addition, it is more preferable that the polyfunctional monomer having a plurality of polymerization reactive groups in one molecule is an acrylic or methacrylic monomer because irregularities on the particle surface are easily produced.

  When a suspension polymerization method is used as the polymerization method, a nonionic surfactant having a polyoxyethylene chain is preferable as a material used as a suspension stabilizer. It has a relatively good suspension stability and has little residue on the particle surface, and has little influence on the charging performance of the produced particles. Further, it is more desirable to use a surfactant having a surfactant effect of both polyoxyethylene chain and sulfonate nonion and anion as suspension stability. Suspension stability is higher than in the case of only polyoxyethylene chains. Moreover, the method of using water-soluble resin, such as PVA and a cellulose resin, can also be taken as a suspension stabilizer. In this case, the suspension stability is very high, but there is also a problem that it remains on the particle surface and affects the chargeability of the particle.

  There is also a method of using a powder composed of inorganic fine particles of 10 to 1000 nm as a suspension stabilizer. This method is a method in which an inorganic oxide dissolved under acidity is returned to neutrality and precipitated as fine particles and used as a stabilizer. After the polymerization is completed, the inorganic oxide is dissolved again and removed from the particle surface. This method also exhibits very good suspension stability. However, there is a drawback that a system such as treatment of acidic waste liquid is required. As the polymerization initiator, it is optimal to use a substance having a 10-hour half-life temperature of 40 to 75 ° C. If the temperature is too low, polymerization proceeds even at room temperature, making it difficult to produce a good suspension. Further, when the viscosity of the particle raw material is excessively increased by polymerization, the droplets due to the surface tension are not spheroidized, and almost spherical particles cannot be obtained. On the other hand, if the temperature is too high, the polymerization takes too much time and is not efficient. As a polymerization initiator, when it dissolves in a suspension such as water, emulsion polymerization proceeds, and a large amount of uncolored fine particles are produced and mixed in the display medium. In order to prevent this, it is desirable to use an oil-soluble substance. Among the initiators, acyl peroxides may be mentioned, or azo initiators having 10 or more carbon atoms in the molecule are applicable.

Also, (acrylic and methacrylic) resin-hydrocarbon resin copolymer or (acrylic and methacrylic) resin-copolymer with (acrylic and methacrylic resin having hydrocarbon or fluorohydrocarbon in the side chain) resin Is more preferably a block copolymer. This is because each resin is in the form of a block, which makes it easier to express the characteristics than the random structure, and the particle surface can be efficiently roughened. Further, it is more preferable that the fluorinated hydrocarbon component of the acrylic and methacrylic resin having a fluorinated hydrocarbon is C ₈ F ₁₇ . Furthermore, since the hydrocarbon resin of the (acrylic and methacrylic) resin-hydrocarbon resin copolymer is a polystyrene resin or a fluororesin, a difference in compatibility with the (acrylic and methacrylic) resin is exhibited. It is easy to make the particle surface uneven and efficient. About a coloring agent, in order to prevent that the efficiency of coloring by transfer to the suspension medium at the time of suspension deteriorates, it is necessary to hydrophobize by surface treatment. Moreover, the resin coating of the colorant by masterbatch production is also effective. Regarding the type of colorant to be surface-treated or masterbatched, any of inorganic pigments, organic pigments, and organic dyes can be used, and they can be used in combination.

  When the display medium particles contain a charge control agent in order to obtain chargeability, a clear charge performance can be obtained and the desired performance can be easily obtained. The target charging performance includes charge amount, charging uniformity, reverse charging prevention, and the like. As a charge control agent, there is a method in which a hardly soluble substance is dispersed and contained in a monomer as a particle raw material. This method actively generates a non-uniform charge distribution, and is a trigger particle that is low in charge and easily moves by voltage. It is effective as a method for simultaneously manufacturing. There is also a method using a monomer-soluble charge control agent. This method is advantageous in terms of uniform dispersion of the charge control agent, enables particles to move at the same potential with uniform chargeability, and facilitates obtaining information display quality such as a good image.

  There is also a method in which a copolymerizable monomer having a chargeable functional group in the molecule is blended in the particle raw material and used as a charge control agent that is copolymerized during polymerization and chemically immobilized in the resin. This method can localize the chargeable site by orienting the chargeable functional group on the particle surface, and has the advantage that the effect can be obtained with a small amount, and the charge control agent bleed-out and dropping off. It is effective in ensuring the durability of charging property in that it hardly occurs.

  The display medium particles must have a heat resistance of 60 ° C. or higher in view of the use environment in the information display panel, but considering the heat resistance necessary to have a physical and sufficient charge amount, the resin The Tg is preferably 60 ° C. or higher. In addition, when particles are obtained by polymerizing a particle raw material having a larger proportion of monomers having a plurality of polymerizable functional groups in the molecule, good heat resistance can be obtained, but in this case, Tg is not observed.

  FIG. 4 shows an example in which particles for a display medium used in the information display panel of the present invention are imaged with a scanning electron microscope (SEM). The example of FIG. 4 shows a state where the particle surface is enlarged at an enlargement rate of 3000 times on the left side and an enlargement rate of 15000 times on the right side, and fine irregularities on the order of several tens of nanometers are formed on the particle surface. I can see the situation.

  Further, in the present invention, by configuring as in the above (2), preferably, in addition to the configuration in (2), the sparse density Dc of the core portion is set to 0.66 <Dc <1.0. In addition, by setting the sparse density Ds of the shell portion to 0.1 <Ds <0.9, void portions that do not contribute to reflection and absorption of incident light can be suitably controlled, and voids do not exist inside the particles. Particles can be obtained.

  FIG. 5 is a diagram showing the relationship between the core portion and the shell portion in the particles constituting the display medium 3 of the present invention. In the example shown in FIG. 5, the inside of the particle of radius R from the center to the area inside 3/4 (= 3R / 4) of radius R is the core part of the particle, and the inside of the particle is the particle outside the core part. Is defined as the shell part. Using the true particle volume Vcb of the core part obtained by subtracting the void volume Vcv of the core part, which is a part not containing the resin and other compounding agents, from the total volume Vc of the core part of the particle, It is defined as Dc = Vcb / (Vcv + Vcb). Similarly, the sparse density Ds of the shell portion can be defined as Ds = Vsb / (Vsv + Vsb).

  To actually obtain Dc, it is easy to do the following. That is, if the void area of the portion corresponding to the core portion of the meridional section of the particle (example in FIG. 5) is Scv and the area of the true particle portion is Scb, Dc = Scb / (Scv + Scb). Scv and Scb are obtained by image processing a portion corresponding to the core portion of the TEM image of the meridional section of the particle, and Dc is calculated. Similarly, the sparse density Ds of the shell portion can be calculated by performing image processing on a portion corresponding to the shell portion of the TEM image of the meridional section.

  Hereinafter, a basic configuration of display medium particles (also simply referred to as particles) used in the information display panel of the present invention will be described.

  The particles are preferably spherical. 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.

The main component of the particle raw material of the present invention is (acrylic and methacrylic) resin-hydrocarbon resin copolymer or (acrylic and methacrylic) resin- (acrylic having side chain hydrocarbon or fluorohydrocarbon and Copolymers with (methacrylic) resin, but in addition, 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 also be a mixture of two or more. In particular, from the viewpoint of controlling the adhesion to the substrate, even if resin components such as acrylic urethane resin, acrylic silicone resin, acrylic fluororesin, acrylic urethane silicone resin, acrylic urethane fluororesin, fluororesin, and silicone resin are included Good.
Is preferred.

  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, risor 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.

Yellow colorants include chrome yellow, 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 chrome yellow, molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, indanthrene brilliant orange RK, benzidine orange G, indanthrene 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 used in the present invention have a particle diameter in the range of 0.5 to 50 μm and are preferably uniform and uniform. If the particle diameter is larger than this range, the display is not clear, and if the particle diameter is smaller than this range, the cohesive force between the particles becomes too large, which hinders the movement of the particles.

Furthermore, in the present invention, regarding the particle size distribution of each particle, the particle size distribution Span represented by the following formula is set to 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 indicating 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 size of 90% or less.)
By keeping Span within a range of 5 or less, the size of each particle is uniform and uniform particle movement is possible.

  Furthermore, regarding the correlation between the particles, the ratio of the d (0.5) of the particles having the minimum diameter to the 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 particles of 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 composed of particles for a display medium is applied to a dry information display panel, it is important to manage the gas in the void surrounding the display medium between the substrates, which contributes to improved display stability. . Specifically, it is important that the relative humidity at 25 ° C. is 60% RH or less, preferably 50% RH or less, with respect to the gas humidity in the void portion.
1A, 1B, 3A, and 3B, the gaps are defined as electrodes 5 and 6 (electrodes on the inner side of the substrate). ), An occupied portion of the display medium 3, an occupied portion of the partition wall 4 (when a partition wall is provided), and a gas portion in contact with a so-called display medium, excluding 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.

  Hereinafter, each member which comprises the information display panel used as the object 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 3 can be confirmed from the outside of the 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.

  Electrode forming materials for providing electrodes on information display panels include metals such as aluminum, silver, nickel, copper, and gold, indium tin oxide (ITO), indium oxide, antimony tin oxide (ATO), and conductivity. Examples include conductive metal oxides such as tin oxide and conductive zinc oxide, and conductive polymers such as polyaniline, polypyrrole, and polythiophene, which are 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 viewing side (display surface side) substrate needs to be transparent, but the electrode provided on the back side substrate does not need to be transparent. In any case, the above-mentioned material that is conductive and capable of pattern formation 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 are the same as those of the electrode provided on the display 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 partition 4 provided on the substrate as needed is optimally set according to the type of display medium involved in the display and is not limited in general, but the width of the partition is 2 to 100 μm, preferably 3 to 50 μm. The height of the partition wall is adjusted to 10 to 500 μm, preferably 10 to 200 μm. As shown in FIG. 6, the cells formed by the partition walls made up of these ribs are exemplified by a square shape, a triangular shape, a line shape, a circular shape, and a hexagonal shape as viewed from the plane of the substrate. 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 state becomes clearer.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples of the present invention and comparative examples, but the present invention is not limited to the following. In addition, the information display panel of an Example and a comparative example evaluated what produced by the following method according to the following reference | standard.

<Example 1>
60 parts by weight of methyl methacrylate monomer (Kanto Chemical Reagent) as positively charged particles, and 40 parts by weight (about 25 mol%) of ethylene glycol dimethacrylate (Wako Pure Chemical Reagent) as a multifunctional monomer having a plurality of polymerization reactive groups in one molecule ) 3 parts by weight of a nigrosine compound (Bontron N07: manufactured by Orient Chemical Co., Ltd.) as a positively charged monomer poorly soluble charge control agent is dispersed by a sand mill, and carbon black (MA100: manufactured by Mitsubishi Chemical) 40 is used as a black inorganic pigment-based colorant. 12.5 parts by weight of a master batch in which parts by weight are dispersed in advance in 60 parts by weight of a methacrylic resin (Delpet 560F: manufactured by Asahi Kasei), and Modiper F600 (acrylic resin having a fluorocarbon in the side chain with an acrylic resin) Nippon Oil & Fats: Main component C ₈ F ₁₇ ) Suspended in purified water at 40 ° C. containing 0.5 wt% of sodium polyoxyethylene alkyl ether sulfate (Latemul E-118B: manufactured by Kao) as a surfactant containing a polyoxyalkylene chain and a sulfonate in the mean, A suspension having an oil droplet diameter of about 80 μm was obtained. 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, particles 1 having an average particle diameter of 9.8 μm were obtained. The sparse density of the shell part and the core part obtained by image analysis of the TEM image of the meridional section of the particle 1 was Ds = 0.65 and Dc = 0.85, respectively. When the surface of the particle 1 was observed with an SEM, irregularities having an equivalent diameter of about 0.1 μm were confirmed.

  As negatively charged particles, 100 parts by weight of PBT resin (Toraycon 1401X31: manufactured by Toray Industries, Inc.) and 100 parts by weight of titanium dioxide (Taipaque CR-50: manufactured by Ishihara Sangyo Co., Ltd.) are biaxially kneaded, and a jet mill (lab jet) Mill IDS-LJ type: manufactured by Nippon Pneumatic Co., Ltd.) and finely pulverized to obtain particles 2 having an average particle size of 9.1 μm in the range of 0.5 to 50 μm. The sparse density of the shell part and the core part was Ds = 1.0 and Dc = 1.0, respectively. Particle 2 did not have irregularities on the surface.

  Equivalent amounts of particles 1 and 2 are mixed and stirred to perform tribocharging, and placed in a cell that is placed through a 100 μm spacer, one with an inner ITO treatment, and the other with a copper substrate. An information display panel was obtained by filling with an occupation ratio of 30%. When each of the ITO glass substrate and copper substrate is connected to a power source and a direct current voltage of 250 V 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 particles are negatively charged on the low potential electrode side. Each particle moves to the high potential electrode side, and a black display state is observed through the glass substrate.Next, when the potential of the applied voltage is reversed, each particle moves in the opposite direction, and a white display state is observed. It was. In any case, there was no mixture of particles desired to be displayed on the ITO glass substrate and different color particles, and good display quality was obtained. In addition, when the voltage is gradually applied, the reflectance in each display state is measured, and the voltage at which the ratio of the reflectance during white display to the reflectance during black display is 10 times as a driving voltage, The voltage was 120V.

<Example 2>
Particles 3 were prepared under the same conditions as Particles 1 described in Example 1 except that (acrylic and methacrylic) resin-fluororesin block copolymer (Modiper F600: manufactured by NOF Corporation, main component C ₈ F ₁₇ ) was 7 weights. did. The particles 3 had an average particle size of 9.6 μm within a particle size range of 0.5 to 50 μm. The sparse density of the shell portion and the core portion of the particle 3 was Ds = 0.53 and Dc = 0.71, respectively, and the surface had a concave portion with an equivalent diameter of 0.15 μm.

  An equal amount of particles 3 and particles 2 described in Example 1 are mixed and stirred to perform tribocharging, and are arranged through a 100 μm spacer, one is a glass substrate treated with an inner ITO, and the other is a copper substrate. An information display panel was obtained by filling a certain cell with a volume occupation ratio of 30%. When each of the ITO glass substrate and copper substrate is connected to a power source and a direct current voltage of 250 V 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 particles are negatively charged on the low potential electrode side. Each particle moves to the high potential electrode side, and a black display state is observed through the glass substrate.Next, when the potential of the applied voltage is reversed, each particle moves in the opposite direction, and a white display state is observed. It was. In any case, there was no mixture of particles desired to be displayed on the ITO glass substrate and different color particles, and good display quality was obtained. In addition, when the voltage is gradually applied, the reflectance in each display state is measured, and the voltage at which the ratio of the reflectance during white display to the reflectance during black display is 10 times as a driving voltage, The voltage was 115V.

<Example 3>
(Acrylic and methacrylic) Resin-Fluorine resin block copolymer (Modiper F600: manufactured by NOF Corporation, main component C ₈ F ₁₇ ) was used in the same conditions as Particle 1 described in Example 1 except that the weight was 10 weight. did. The particles 4 had an average particle size of 9.2 μm in a particle size range of 0.5 to 50 μm. The sparse density of the shell part and the core part of the particles 4 were Ds = 0.39 and Dc = 0.68, respectively, and the surface had a recess with an equivalent diameter of 0.36 μm.

  An equal amount of particles 4 and particles 2 described in Example 1 are mixed and stirred to perform tribocharging, and are arranged through a 100 μm spacer, one is a glass substrate treated with an inner ITO, and the other is a copper substrate. An information display panel was obtained by filling a certain cell with a volume occupation ratio of 30%. When a power supply is connected to each of the ITO glass substrate and the copper substrate, and a direct current voltage of 250 V 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 particles are negatively charged on the low potential electrode side. Each particle moves to the high potential electrode side, and a black display state is observed through the glass substrate.Next, when the potential of the applied voltage is reversed, each particle moves in the opposite direction, and a white display state is observed. It was. In any case, there was no mixture of particles desired to be displayed on the ITO glass substrate and different color particles, and good display quality was obtained. In addition, when the voltage is gradually applied, the reflectance in each display state is measured, and the voltage at which the ratio of the reflectance during white display to the reflectance during black display is 10 times as a driving voltage, The voltage was 125V.

<Example 4>
60 parts by weight of methyl methacrylate monomer (Kanto Chemical Reagent) as positively charged particles, and 40 parts by weight (about 25 mol) of ethylene glycol dimethacrylate (Wako Pure Chemical Reagent) as a multifunctional monomer having a plurality of polymerization reactive groups in one molecule %)) As a black inorganic pigment-based colorant, 40 parts by weight of carbon black (MA100: manufactured by Mitsubishi Chemical) was previously dispersed in 60 parts by weight of an acrylic resin (Delpet 80NH: manufactured by Asahi Kasei Chemicals). A solution in which 5 parts by weight and 5 weight parts of acrylic base FCA-201-PS which is a copolymer of acrylic resin and hydrocarbon resin (Fujikura Kasei, the hydrocarbon resin component is polystyrene made of styrene monomer) is dissolved, Polyoxyethylene as a surfactant containing polyoxyalkylene chain and sulfonate in the molecule Ruki ether sodium sulfate (LATEMUL E-118B: manufactured by Kao Corporation) was suspended in 40 ° C. purified water were added 0.5 wt%, to obtain a suspension with an average oil droplet diameter of approximately 80 [mu] m. 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, particles 5 having an average particle diameter R0 = 9.1 μm were obtained. The sparse density of the shell part and the core part of the obtained particle 5 were Ds = 0.62 and Dc = 0.80, respectively, and the surface had a recess with an equivalent diameter of 0.16 μm.

  Equivalent amounts of particles 5 and 2 are mixed and agitated to perform tribocharging, and are placed in a cell that is disposed through a 100 μm spacer, one of which is an inner ITO-treated glass substrate and the other is a copper substrate. An information display panel was obtained by filling with an occupation ratio of 30%. When each of the ITO glass substrate and copper substrate is connected to a power source and a direct current voltage of 250 V 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 particles are negatively charged on the low potential electrode side. Each particle moves to the high potential electrode side, and a black display state is observed through the glass substrate.Next, when the potential of the applied voltage is reversed, each particle moves in the opposite direction, and a white display state is observed. It was. In any case, there was no mixture of particles desired to be displayed on the ITO glass substrate and different color particles, and good display quality was obtained. In addition, when the voltage is gradually applied, the reflectance in each display state is measured, and the voltage at which the ratio of the reflectance during white display to the reflectance during black display is 10 times as a driving voltage, The voltage was 120V.

<Comparative Example 1>
(Acrylic and methacrylic) Resin-Fluororesin block copolymer (Modiper F600: manufactured by NOF Corporation, main component C ₈ F ₁₇ ) Particles 6 were produced under the same conditions. The particles 6 had an average particle size of 10.1 μm in a particle size range of 0.5 to 50 μm. The sparse density of the shell part and the core part obtained by image analysis of the TEM image of the meridional section of the particle 6 was Ds = 0.94 and Dc = 0.99, respectively. When the surface of the particle 6 was observed with an SEM, irregularities having an equivalent diameter of about 0.06 μm were confirmed.

  An equal amount of particles 6 and particles 2 described in Example 1 are mixed and stirred to perform tribocharging, and are arranged through a 100 μm spacer, one is a glass substrate treated with an inner ITO, and the other is a copper substrate. An information display panel was obtained by filling a certain cell with a volume occupation ratio of 30%. When each of the ITO glass substrate and copper substrate is connected to a power source and a direct current voltage of 250 V 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 particles are negatively charged on the low potential electrode side. Each particle moves to the high potential electrode side, and a black display state is observed through the glass substrate.Next, when the potential of the applied voltage is reversed, each particle moves in the opposite direction, and a white display state is observed. It was. In any case, there was no mixture of particles desired to be displayed on the ITO glass substrate and different color particles, and good display quality was obtained. In addition, when the voltage is gradually applied, the reflectance in each display state is measured, and the voltage at which the ratio of the reflectance during white display to the reflectance during black display is 10 times as a driving voltage, The voltage was 160 V, and a higher driving voltage was required than in Examples 1-4.

<Comparative Example 2>
Particle 7 was produced under the same conditions as Particle 1 described in Example 1, except that 80 parts by weight of 3-methylbutyl acetate (special grade reagent: manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 5 parts by weight of Modiper F600. Particles 7 had an average particle diameter of 9.7 μm in a particle diameter range of 0.5 to 50 μm. The sparse density of the shell portion and the core portion obtained by image analysis of the TEM image of the meridional section of the particle 7 was Ds = 0.41 and Dc = 0.57, respectively. When the surface of the particle 7 was observed with an SEM, irregularities having an equivalent diameter of about 0.01 μm were confirmed.

  An equal amount of particles 7 and the particles 2 described in Example 1 are mixed and stirred to perform tribocharging, and are arranged through a 100 μm spacer, one is a glass substrate treated with an inner ITO, and the other is a copper substrate. An information display panel was obtained by filling a certain cell with a volume occupation ratio of 30%. When each of the ITO glass substrate and copper substrate is connected to a power source and a direct current voltage of 250 V 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 particles are negatively charged on the low potential electrode side. Each particle moves to the high potential electrode side, and a black display state is observed through the glass substrate.Next, when the potential of the applied voltage is reversed, each particle moves in the opposite direction, and a white display state is observed. It was. In any case, there was no mixture of particles desired to be displayed on the ITO glass substrate and different color particles, and good display quality was obtained. In addition, when the voltage is gradually applied, the reflectance in each display state is measured, and the voltage at which the ratio of the reflectance during white display to the reflectance during black display is 10 times as a driving voltage, The voltage was 175 V, and a higher drive voltage was required than in Examples 1-4.

  The information display panel according to the present invention includes display units for mobile devices such as notebook computers, PDAs, mobile phones, and handy terminals, electronic papers such as electronic books and electronic newspapers, bulletin boards such as signboards, posters, and blackboards, calculators, and home appliances. , Display parts for car supplies, card display parts such as point cards, IC cards, electronic advertisements, information boards, electronic POPs (Point Of Presence, Point Of Purchase advertising), electronic price tags, electronic shelf labels, electronic musical scores, RF- It is suitably used for a display unit of an ID device.

(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 which imaged the particle | grains for display media used for the information display panel of this invention with the scanning electron microscope (SEM). It is a figure which shows the relationship between the core part and shell part in the particle | grains which comprise the display medium of this invention. 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 3W White display medium 3B Black display medium 4 Bulkhead 5, 6 Electrode

Claims (9)

  A display medium constituting a display medium used for an information display panel that displays information 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 (1) The particle is a substantially spherical particle obtained by polymerizing a particle raw material containing a monomer, and (acrylic and methacrylic) resin-hydrocarbon resin copolymer or (acrylic and methacrylic) is contained in the particle raw material. Type) resin-(acrylic and methacrylic type having hydrocarbon or fluorohydrocarbon in the side chain) and a copolymer of resin, and some or all of the monomers have multiple polymerization reactive groups in one molecule. It is a functional monomer, and has fine irregularities uniformly on the particle surface. (2) Among the inside of the particle having the radius R, the inside of the particle having a radius R of 3/4 of the radius R The rear is defined as the core part of the particle, and the outside of the core part is defined as the shell part of the particle, and the relationship between the sparse density Dc of the core part and the sparse density Ds of the shell part is Dc> Ds (where the void volume of the core part is Vcv, where the true particle volume of the core part obtained by subtracting Vcv from the total volume Vc of the core part is Vcb, Dc = Vcb / (Vcv + Vcb), the void volume of the shell part is Vsv, and the total volume of the shell part A particle for a display medium, wherein Ds = Vsb / (Vsv + Vsb), where Vsb is a true particle volume of a shell part obtained by subtracting Vsv from Vs.   The sparse density Dc of the core portion is 0.66 <Dc <1.0, and the sparse density Ds of the shell portion is 0.1 <Ds <0.9. Particles for display media as described in 1.   3. The display medium particle according to claim 1, wherein the minute irregularities are convex portions or concave portions having an equivalent diameter of 0.01 to 0.5 μm. 4. The display medium particle according to claim 1, wherein the fluorinated hydrocarbon component of the acrylic and methacrylic resin having the fluorinated hydrocarbon is C ₈ F _{17. 5} .   4. The display medium particle according to claim 1, wherein the hydrocarbon resin component of the (acrylic and methacrylic) resin-hydrocarbon resin copolymer is polystyrene. 5.   The particle for a display medium according to any one of claims 1 to 5, wherein the particle diameter of the particle is 0.5 to 50 µm.   The particle for display medium according to any one of claims 1 to 6, wherein the color of the particle is white.   The particle for display medium according to any one of claims 1 to 6, wherein the color of the particle is black.   An information display panel for displaying information 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. An information display panel comprising the display medium particle according to any one of the above.