JP2003186060A - Particles for image display and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image display device which is a dry display device in which particles are sealed between two substrates and is excellent in stability and repetitive durability. <P>SOLUTION: The particles for image display of ≥100 J/m in Izod impact strength (notched) are used in the image display device for displaying images by sealing ≥2 kinds of the particles varying in their colors and electrification characteristics or one kind of the particles between the substrates, at least one of which is transparent, and moving the particles by impressing an electric field between the substrates. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image display particle and an image display device capable of repeatedly displaying and erasing an image by moving particles utilizing Coulomb force or the like.

[0002]

2. Description of the Related Art As an image display device replacing liquid crystal (LCD), an image display device (display) using a technique such as an electrophoretic system, an electrochromic system, a thermal system, and a two-color particle rotation system has been proposed. These image display devices are considered as next-generation inexpensive display devices because they have a wider viewing angle than ordinary printed matter, lower power consumption, and a memory function than LCDs. Therefore, it is expected to be applied to displays for mobile terminals and electronic papers.

Recently, an electrophoretic method has been proposed in which a dispersion liquid composed of dispersed particles and a coloring solution is formed into microcapsules and the microcapsules are arranged between opposed substrates. However, in the electrophoretic method, particles of high specific gravity such as titanium oxide are dispersed in a solution of low specific gravity, so it is easy to settle down, it is difficult to maintain the stability of the dispersed state, and the solution for coloring is added. Due to the addition of a dye or the like to the above, there is a problem in long-term storability, and there is a problem that the image repeating stability is lacking. Even in the case of microencapsulation, the cell size is set to the microcapsule level, and such defects are apparently difficult to appear, and no essential problem is solved.

In contrast to the electrophoretic method that utilizes the behavior in a solution as described above, a method that does not use a solution but incorporates conductive particles and a charge transport layer in a part of the substrate has also been proposed.
However, in such a dry display device, the structure is complicated because the charge transport layer and further the charge generation layer are arranged on a part of the substrate, and it is difficult to dissipate the charges from the conductive particles at a constant level. Lacks sex. (For example, see Non-Patent Document 1)

[0005]

[Non-Patent Document 1] Japan Imaging Society "Japan Hardcopy '99"
Proceedings July 21, 1999, p. 249-252

[0006]

SUMMARY OF THE INVENTION Under the circumstances described above, an object of the present invention is to provide an image display device which is excellent in stability, particularly in repeated durability, in an image display device which displays an image by moving particles by Coulomb force or the like. The object is to provide particles for use and an image display device.

[0007]

Means for Solving the Problems As a result of intensive studies for achieving the above object, the present inventors have found that stability, particularly repeated durability, can be improved by controlling the mechanical properties of the resin constituting the particles. The present invention has been accomplished by finding that particles for image display and an image display device having excellent properties can be obtained.

That is, the present invention provides the following image display particles and image display device. 1. An image display in which two or more kinds of particles having different color and charging characteristics or one kind of particles are encapsulated between opposing substrates, at least one of which is transparent, and an electric field is applied between the substrates to move the particles to display an image. Image display particles used in a device, having an Izod impact strength (notched) of 1
Particles for image display characterized by being at least 00 J / m. 2. The image display particle according to the above 1, wherein the solvent insolubility represented by the following formula is 50% or more. Solvent insolubility rate (%) = (B / A) × 100 (where A is the weight of the particles before soaking in the solvent, and B is the weight after soaking the particles in a good solvent at 25 ° C. for 24 hours). The image display particle according to the above 1 or 2, which has a water absorption rate of 3% by mass or less. 4. The image display particle as described in any one of 1 to 3 above, which is an insulating particle having a volume resistivity of 1 × 10 ¹⁰ Ω · cm or more. 5. An image display device comprising the image display particle according to any one of 1 to 4 above. 6. 6. The image display device according to the above 5, wherein the volume occupancy of particles in the space between the opposing substrates is 10 to 80%.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the image display device of the present invention, electric charges are applied to the surface of the substrate by some means in the display device in which particles are enclosed between opposed substrates. Negatively charged particles are attracted by the Coulomb force toward the positively charged substrate site, and positively charged particles are attracted by the Coulomb force toward the negatively charged substrate site. An image is displayed by reciprocating between the substrates facing each other. Therefore, it is necessary to design the display device so that the particles can move uniformly and can maintain stability during repeated or storage. Here, the force applied to the particles may be a force that attracts each other due to the Coulomb force between the particles, an electric image force with the electrode plate, an intermolecular force, a liquid bridge force, and gravity.

However, in the conventional display devices,
Since the motive force of the movement of particles is emphasized, the electrical characteristics of particles, that is, so-called charge imparting, is emphasized, or the characteristics that cannot be covered by the electrical characteristics of the particles are attempted to be supplemented by a driving method such as a driving voltage. Was the current situation. For example, if particles with high chargeability are used to reduce the drive voltage, the particles will move rapidly and the drive voltage can be lowered, but due to its high chargeability, it can be used repeatedly. Occasionally, particles start to aggregate with each other. Further, in order to improve the repeated durability, if the low-charged particles are used, the aggregation of the particles is unlikely to occur, and the stability is improved, but the chargeability of the particles is insufficient, and uniform particle migration becomes difficult to occur. However, even if the particles move to the surface of the substrate, there is a problem that it is difficult to obtain a clear image because the adhesion between the particles and the surface of the substrate, that is, the so-called memory property is not sufficient.

The present invention has found that the hints for improving the stability are not only the electrical characteristics of the particles and the driving method, but also the mechanical characteristics of the particles. As described above, since the particles reciprocate, the reciprocating motion should not be hindered. By controlling the mechanical properties of the particles, it is possible to improve the display stability, especially the repeating stability. The mechanical properties of the particles were not so much a problem when the particles moved in the liquid as in the electrophoretic method, but especially in the case of the particle movement in the dry display device without the liquid, the durability was improved. Is an important factor.

FIG. 1 is an explanatory view showing an example of the structure of the image display device of the present invention. The substrates 1 and 2 facing each other are placed at a predetermined interval, and one or more kinds of particles are enclosed therein. In addition,
FIG. 1 shows a case where two kinds of particles 3 having different colors and different charging characteristics are encapsulated. At least one of the substrate 1 and the substrate 2 is a transparent substrate from which the color of particles can be confirmed from the outside of the device,
A material having a high visible light transmittance and good heat resistance is suitable. Whether or not the image display device is flexible is appropriately selected depending on the application. For example, for an application such as electronic paper, a flexible material, a mobile phone, a PDA, and a display of a portable device such as a notebook computer are used. An inflexible material is used.

Examples of the substrate material include polyethylene terephthalate, polyether sulfone, polyethylene,
Examples include polymer sheets such as polycarbonate and inorganic sheets such as glass and quartz. Substrate thickness is 2-5
000 μm, preferably 5 to 1000 μm is suitable, and when it is too thin, it becomes difficult to maintain strength and uniformity of spacing between substrates, and when it is too thick, sharpness as a display function and deterioration of contrast occur. It lacks flexibility in paper applications.

In the image display device of the present invention, the electrodes may be provided on the substrate or may be provided at other portions, for example, both ends, partition walls, or the outside of the substrate, apart from the substrate. When the electrodes are not provided on the substrate but are provided separately from the substrate, an electrostatic latent image is given to the outer surface of the substrate, and an electric field generated according to the electrostatic latent image causes the electrostatic charge of a color charged to a predetermined characteristic. By attracting or repelling the picked-up particles to the substrate, the particles arranged corresponding to the electrostatic latent image are visually recognized from the outside of the display device through the transparent substrate. The electrostatic latent image is formed by a method of transferring and forming the electrostatic latent image on the substrate of the image display device, which is performed in a normal electrophotographic system using an electrophotographic photosensitive member,
There is a method of directly forming an electrostatic latent image on a substrate by ion flow.

When an electrode is provided on the substrate, an external voltage is applied to the electrode portion to cause an electric field generated at each electrode position on the substrate to attract or repel particles of a color charged to a predetermined characteristic. The particles arranged corresponding to the electrostatic latent image are visually recognized from the outside of the display device through the transparent substrate. The electrode at this time is formed of a transparent and patternable conductive material, and, for example, indium oxide,
Metals such as aluminum, conductive polymers such as polyaniline, polypyrrole, polythiophene, etc.,
A forming method such as vacuum deposition or coating can be exemplified. The thickness of the electrode may be 3 to 1000 nm, preferably 5 to 400 nm, as long as the conductivity can be secured and the light transmittance is not hindered. In this case, the external voltage input may be DC or AC superimposed.

In the image display device of the present invention, in order to prevent excessive movement of particles in the direction parallel to the substrate, regular unevenness may be formed on the substrate by etching or the like.
As shown in FIG. 5, examples thereof include a triangular shape, a square shape, and a semicircular shape when viewed from the substrate cross-sectional direction, and a rectangular shape, a triangular shape, a round shape, and a line shape when viewed from the substrate plane direction. The area size or height may be any, but it is better to make the part corresponding to the convex part (frame area) visible from the display side as small as possible, and the image display clarity can be reduced by reducing the frame area. Will increase. Therefore, by forming the convex portion,
Durability and repeatability and memory retention are improved. Also,
In the image display device of the present invention, the partition wall 4 as shown in FIG.
Alternatively, a spacer 5 as shown in FIG. 4 is used to subdivide the space between the substrates to prevent excessive movement of particles in the direction parallel to the substrate, improve durability and repeatability, and retain memory. It is also possible to increase the strength of the display device itself by making the intervals uniform and reinforced.

The particles may be any particles as long as they can move by Coulomb force or the like. The particles can be prepared by kneading and pulverizing the necessary resin, charge control agent, colorant, and other additives, or polymerizing from a monomer, or existing particles are made into resin, charge control agent, colorant. Alternatively, it may be coated with other additives. In the present invention, the Izod impact strength (notched) of the particles is 100 J / m or more, preferably 130 J / m or more. If the Izod impact strength (notched) is less than 100 J / m, the particles collide with each other when the particles reciprocate, and some of the particles are abraded and the charge control agent falls off, which hinders the movement of the particles themselves. In addition, the abrasion debris generated also hinders the movement of particles, and the durability is significantly reduced. The Izod impact strength is AST
It is a value measured at 23 ° C. according to MD526. The volume occupancy of particles in the space between opposed substrates is preferably 10 to 80%, more preferably 10 to 60%.
Is. If it exceeds 80%, the movement of particles may be hindered, and if it is less than 10%, the contrast tends to be unclear.

Examples of resins, charge control agents, colorants, and other additives are shown below. Examples of the resin include urethane resin, acrylic resin, polyester resin, urethane-modified acrylic resin, silicone resin, nylon resin, epoxy resin, styrene resin, butyral resin, vinylidene chloride resin, melamine resin, phenol resin, and fluororesin. It is also possible to mix two or more kinds, and in particular, from the viewpoint of controlling the adhesive force to the substrate, polyester resin, acrylic urethane resin, acrylic urethane silicone resin,
Acrylic urethane fluororesin, urethane resin, and fluororesin are suitable.

Examples of the charge control agent include quaternary ammonium salt compounds, nigrosine dyes, triphenylmethane compounds and imidazole derivatives in the case of imparting a positive charge, and in the case of imparting a negative charge. Examples thereof include metal-containing azo dyes, salicylic acid metal complexes, and nitroimidazole derivatives. Examples of colorants include basic and acidic dyes such as nigrosine, methylene blue, quinoline yellow, and rose bengal. Examples of inorganic additives include titanium oxide, zinc oxide, zinc sulfide, antimony oxide, calcium carbonate, lead white, talc,
Silica, calcium silicate, alumina white, cadmium yellow, cadmium red, cadmium orange, titanium yellow, navy blue, ultramarine blue, cobalt blue, cobalt green, cobalt violet, iron oxide, carbon black, manganese ferrite black, cobalt ferrite black, copper powder , Aluminum powder and the like.

In the present invention, it is necessary to control the mechanical properties (Izod impact strength) of the above-mentioned particles in order to improve the repeated durability, but in order to further improve the display stability. For this purpose, it is effective to control the stability of the particles, in other words, the stability of the constituent resin, especially the water content and the solvent insolubility. The water absorption is preferably 3% by mass or less, more preferably 2% by mass or less. The water absorption is measured at 23 ° C. and 24 ° C. according to ASTM D570.
Perform under time measurement conditions. Regarding the solvent insolubility rate, the solvent insolubility rate represented by the following relational expression is preferably 50% or more, and particularly preferably 70% or more. Solvent insolubility (%) = (B / A) × 100 (where A is the weight of the particles before soaking in the solvent, and B is the weight after soaking the particles in a good solvent at 25 ° C. for 24 hours). If the ratio is less than 50%, bleeding may occur on the surface of the particles during long-term storage, which may affect the adhesive force with the particles and hinder the movement of the particles, which may impair the durability of image display. In addition, as a solvent (good solvent) for measuring the solvent insolubility ratio, methyl ethyl ketone or the like for a fluororesin, methanol or the like for a polyamide resin, methyl ethyl ketone, toluene or the like for an acrylic urethane resin, acetone, isopropanol or the like for a melamine resin, and a silicone. For the resin, toluene or the like is preferable.

Each particle is preferably spherical. The distance between the substrate 1 and the substrate 2 is adjusted so that particles can move and the contrast can be maintained, but it is usually adjusted to 10 to 5000 μm, preferably 10 to 500 μm. Since the particles need to retain their charged electric charge, the volume resistivity is 1
× preferably ¹⁰ 10 Ω · cm or more insulating particles, especially 1 ×
Insulating particles of 10 ¹² Ω · cm or more are preferable. In addition, controlling the humidity of the gas in the space surrounding the particles between the substrates also contributes to improving the display stability. Specifically, it is preferable that the humidity of the gas in the space portion has a relative humidity at 25 ° C. of 60% RH or less, preferably 50% RH or less, and more preferably 35% RH or less. The space portion is a gas portion in contact with particles, which is a portion sandwiched between the substrates 1 and 2 facing each other, excluding a portion occupied by the particles 3, a device sealing portion, and a partition wall or a spacer portion which will be described later, which is provided as necessary. Shall be pointed out. The gas may be of any type as long as it is in the above-mentioned humidity range, but dry air, nitrogen, argon, helium and the like are preferable. The gas needs to be sealed in the device so that its humidity is maintained. For example, particles, which will be described later, and the substrate are assembled in a predetermined humidity environment, and a sealing material that prevents humidity from entering from the outside, A display device in which a gas and particles are enclosed by a sealing method is manufactured. The image display device of the present invention is a laptop computer,
Displays of mobile devices such as PDAs and mobile phones, electronic books such as electronic books and electronic newspapers, signs, posters,
It is used for bulletin boards such as blackboards, copiers, rewritable paper as a substitute for printer paper, calculators, display parts for home appliances, and display parts for point cards.

[0022]

EXAMPLES Next, the present invention will be described more specifically by showing Examples and Comparative Examples. However, the present invention is not limited to the following examples. Regarding the particles and display devices obtained in Examples and Comparative Examples, according to the following criteria,
An evaluation was made.

(1) Izod impact strength of particles Measured at 23 ° C. according to ASTM D256. (2) Water absorption rate of particles According to ASTM D570, it was measured under measurement conditions of 23 ° C. and 24 hours. (3) Solvent-insoluble rate of particles The particles were immersed in a methyl ethyl ketone solvent at 25 ° C for 24 hours and dried at 100 ° C for 5 hours, and then the weight was measured. From the weight change before and after immersion, the solvent insolubility was measured according to the following formula. Solvent insolubility rate (%) = (B / A) × 100 (where A is the weight of the particles before soaking in the solvent, and B is the weight after immersing the particles in a methyl ethyl ketone solvent at 25 ° C. for 24 hours) (4) Evaluation of Display Function By applying 250 V to the manufactured display device and inverting the polarity, black to white display was repeated. The display function was evaluated in terms of the contrast ratio at an initial value of 100.
After repeated display of 00 times, measurement was performed using a reflection image densitometer. Here, the contrast ratio is defined as: contrast ratio = reflection density during black display / reflection density during white display. Also,
The contrast ratio retention ratio of the initial contrast was also obtained.

Example 1 Particle A is a thermoplastic polyetherester elastomer: Hytrel 6347 (manufactured by Toray DuPont) 100
4 parts by weight of carbon black (CB) (ph)
r) and 2 parts by mass (phr) of the charge control agent Bontron N07 (manufactured by Orient Chemical Co., Ltd.) were added, kneaded, and then pulverized and classified by a jet mill to prepare particles. Particle B is a thermoplastic polyetherester elastomer: Hytrel 6
347 (manufactured by Toray DuPont) 100 parts by mass of titanium oxide 10 parts by mass (phr), charge control agent Bontron E89
(Orient Chemical Co., Ltd.) 2 parts by mass (phr) was added,
After kneading, particles were prepared by pulverizing and classifying with a jet mill. Particles A and B are put between a pair of glass substrates provided with indium oxide electrodes having a thickness of about 500 Å and the spacers are adjusted to have a spacing of 400 μm.
A display device was manufactured by adhering the periphery of the glass substrate with an epoxy adhesive and encapsulating the particles. The mixing ratios of the particles A and the particles B were set to the same weight, and the volume occupancy ratio of the particles between the glass substrates was adjusted to be 60% by volume.
The evaluation results are shown in Table 1.

Example 2 In Example 1, the resin constituting the particles was made of thermoplastic polyether ester elastomer: Hytrel 6347M.
A display device was prepared in the same manner except that the display device was changed to (Toray DuPont). The evaluation results are shown in Table 1.

Reference Example 1 A display device was produced in the same manner as in Example 1 except that the volume occupancy of the particles on the glass substrate was changed to 90% by volume. The evaluation results are shown in Table 1.

Comparative Example 1 In Example 1, the resin forming the particles was made of thermoplastic polyether ester elastomer: Hytrel 7247M.
A display device was prepared in the same manner except that the display device was changed to (Toray DuPont). The evaluation results are shown in Table 1.

COMPARATIVE EXAMPLE 2 In Example 1, the resin constituting the particles was replaced with the resin thermoplastic polyether ester elastomer: Hytrel 72.
A display device was manufactured in the same manner except that the display device was changed to 47F (manufactured by DuPont Toray). The evaluation results are shown in Table 1.

[0029]

[Table 1]

[0030]

INDUSTRIAL APPLICABILITY The image display device of the present invention can display an image excellent in stability, especially in repeated durability by controlling mechanical properties of particles, particularly by controlling Izod impact strength. Display device can be obtained.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing an example of a structure of an image display device of the present invention.

FIG. 2 is a diagram showing an example of the shape of a substrate in the image display device of the present invention.

FIG. 3 is a diagram showing an example of the shape of a substrate in the image display device of the present invention.

FIG. 4 is a diagram showing an example of the shape of a substrate in the image display device of the present invention.

[Explanation of symbols]

1, 2: substrate 3: Particle 4: Partition wall 5: Spacer

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Norio Nihei             3-5-5 Ogawahigashi-cho, Kodaira-shi, Tokyo (72) Inventor Yakushiji Manabu             3-2- 6-408 Ogawahigashi-cho, Kodaira-shi, Tokyo (72) Inventor Hajime Kitano             3-5-5 Ogawahigashi-cho, Kodaira-shi, Tokyo (72) Inventor Takahiro Kawagoe             1302-57 Aobadai, Tokorozawa, Saitama Prefecture

Claims (6)

[Claims] 1. An image in which two or more kinds of particles having different colors and different charging characteristics or one kind of particles are enclosed between opposing substrates, at least one of which is transparent, and an electric field is applied between the substrates to move the particles. A particle for image display used in an image display device for displaying, wherein the Izod impact strength (with notch) is 100 J / m or more. 2. The particles for image display according to claim 1, wherein the solvent insolubility represented by the following formula is 50% or more. Solvent insolubility rate (%) = (B / A) × 100 (where A is the weight of the particles before soaking in the solvent, and B is the weight after soaking the particles in a good solvent at 25 ° C. for 24 hours) 3. The image display particle according to claim 1, which has a water absorption of 3% by mass or less. 4. The image display particle according to claim 1, which is an insulating particle having a volume resistivity of 1 × 10 ¹⁰ Ω · cm or more. 5. An image display device using the particles for image display according to claim 1. 6. The image display device according to claim 5, wherein the volume occupancy of particles in the space between the opposed substrates is 10 to 80%.