JP4774693B2 - Image display medium and image display device - Google Patents
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- JP4774693B2 JP4774693B2 JP2004194983A JP2004194983A JP4774693B2 JP 4774693 B2 JP4774693 B2 JP 4774693B2 JP 2004194983 A JP2004194983 A JP 2004194983A JP 2004194983 A JP2004194983 A JP 2004194983A JP 4774693 B2 JP4774693 B2 JP 4774693B2
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Description
本発明は、電界により着色粒子を移動させて画像表示を行う画像表示媒体および画像表示装置に関し、特に、画質維持性の改善（ドット欠陥の防止等）、及び駆動電源の低電圧化ができる画像表示媒体および画像表示装置に関する。 The present invention relates to an image display medium and an image display apparatus that perform image display by moving colored particles by an electric field, and in particular, an image that can improve image quality maintainability (such as prevention of dot defects) and lower the voltage of a drive power supply. The present invention relates to a display medium and an image display device.
電界により着色粒子を移動させて画像表示を行う画像表示媒体および画像表示装置として、例えば、特許文献１に記載された画像表示媒体および画像表示装置が知られている。 As an image display medium and an image display device that perform image display by moving colored particles by an electric field, for example, an image display medium and an image display device described in Patent Document 1 are known.
特許文献１に記載された画像表示媒体は、対向配置された一対の基板と、該一対の基板間の空隙に封入された少なくとも２種類以上の粒子からなる粒子群と、からなり、該２種類以上の粒子が、そのうちの少なくとも１種類が正に、他の少なくとも１種類が負に帯電し得る性質を有し、かつ、前記正負に帯電し得る粒子が相互に異なる色である画像表示媒体であって、前記正負に帯電し得る双方の粒子の形状係数が、形状係数＝（Ｌ2／Ｓ）／４π×１００（ここでＬは、Ｓは粒子面積、Ｌは周囲長を表す）としたとき、１００＜形状係数≦１４０であることを特徴とするものである。 The image display medium described in Patent Document 1 includes a pair of substrates arranged opposite to each other, and a particle group including at least two types of particles sealed in a gap between the pair of substrates. An image display medium in which at least one of the above particles has a property of being positively charged and at least one of the other particles can be negatively charged, and the positively and negatively charged particles have different colors. The shape factor of both particles that can be positively and negatively charged is shape factor = (L 2 / S) / 4π × 100 (where L is the particle area and L is the perimeter). In this case, 100 <shape factor ≦ 140.
この構成によれば、駆動電圧を低く設定でき、長期にわたって繰返し書換えても画像濃度の変化が小さく、また濃度均一性の変化が小さく、濃度コントラストを安定させることができる。
しかしながら、さらなる性能向上が要求され、画像濃度の安定性や均一性、濃度コントラストの安定性、ドット欠陥の防止、などの画質維持性の改善、さらには、駆動回路の設計の自由度をさらに拡大させるため、駆動電圧の改善が求められているのが現状である。 However, further performance improvements are required, improving image quality stability such as image density stability and uniformity, density contrast stability, and dot defect prevention, and further expanding the degree of freedom in designing the drive circuit. Therefore, the current situation is that the drive voltage is required to be improved.
従って、本発明の目的は、画質維持性の改善、及び駆動電源の低電圧化ができる画像表示媒体および画像表示装置を提供することにある。 Accordingly, it is an object of the present invention to provide an image display medium and an image display device that can improve image quality maintainability and can reduce the voltage of a drive power supply.
本発明は、上記目的を達成するため、透明性を有する表面基板と、前記表面基板に対向配置された背面基板と、前記表面基板と前記背面基板との空間を複数のセルに仕切る仕切り部材と、前記複数のセル内に封入され、付与された電界に応じて前記セル内を移動する正又は負に帯電した粒子群とを備えた画像表示媒体であって、前記正又は負に帯電した粒子群は、前記粒子群が移動を開始する前記電界を形成させる移動開始電圧が相違する同一色の２種類以上の粒子群として、主粒子群及び前記主粒子群よりも前記移動開始電圧が低い低電圧粒子群を混合して構成されてなり、前記主粒子群と前記低電圧粒子群との混合比率は、５１：４９〜９９：１（質量％）であり、前記移動開始電圧が相違する同一色の２種類以上の粒子群は、前記表面基板表面又は前記背面基板表面と前記粒子群との間に働く付着力が相違する２種類以上の粒子群であることを特徴とする画像表示媒体、およびこれを備えた画像表示装置を提供する。
上記画像表示媒体において、前記付着力が相違する同一色の２種類以上の粒子群は、所定の平均粒子径を有する前記主粒子群と、前記主粒子群の平均粒子径の１．１〜３．０倍の平均粒子径を有する前記低電圧粒子群とを混合して構成されてなる、形状係数＝［（Ｌ 2 ／Ｓ）／４］×π×１００（Ｌは粒子の周囲長、Ｓは粒子面積を表す）としたとき、１００≦形状係数≦１１０の前記主粒子群と、１２０≦形状係数≦１４０の前記低電圧粒子群とを混合して構成されてなる、又は水との接触角がおよそ５５度から７５度である前記主粒子群と、前記主粒子群よりも前記移動開始電圧が低い、水との接触角がおよそ８０度から１５０度の前記低電圧粒子群とを混合して構成されてなることを特徴とする。
また、本発明は、上記目的を達成するため、透明性を有する表面基板と、前記表面基板に対向配置された背面基板と、前記表面基板と前記背面基板との空間を複数のセルに仕切る仕切り部材と、前記複数のセル内に封入され、付与された電界に応じて前記セル内を移動する正又は負に帯電した粒子群とを備えた画像表示媒体であって、前記正又は負に帯電した粒子群は、前記粒子群が移動を開始する前記電界を形成させる移動開始電圧が相違する同一色の２種類以上の粒子群として、主粒子群及び前記主粒子群よりも前記移動開始電圧が低い低電圧粒子群を混合して構成されてなり、前記主粒子群と前記低電圧粒子群との混合比率は、５１：４９〜９９：１（質量％）であり、前記移動開始電圧が相違する同一色の２種類以上の粒子群は、前記粒子群の平均電荷量が相違する２種類以上の粒子群であり、所定の平均電荷量を有する前記主粒子群と、前記主粒子群よりも前記移動開始電圧が低い、前記主粒子群の平均電荷量の１．３〜３．０倍の平均電荷量を有する前記低電圧粒子群とを混合して構成されてなることを特徴とする画像表示媒体、およびこれを備えた画像表示装置を提供する。
In order to achieve the above object, the present invention provides a transparent front substrate, a rear substrate opposed to the front substrate, and a partition member that partitions a space between the front substrate and the rear substrate into a plurality of cells. An image display medium comprising a group of positively or negatively charged particles enclosed in the plurality of cells and moving in the cells according to an applied electric field, wherein the positively or negatively charged particles The group includes two or more types of particle groups of the same color that have different movement start voltages for forming the electric field at which the particle groups start moving, and the movement start voltage is lower than that of the main particle group and the main particle group. it is constituted by mixing a voltage particles, the mixing ratio of the low voltage the particle group and the main group of particles, 51: 49-99: 1 (wt%) der is, the movement starting voltage is different Two or more types of particles of the same color To provide an image display device having an image display medium, wherein two or more types of particle groups der Rukoto adhesive force are different acting between the plate surface or the rear substrate surface and the particles, and this .
In the image display medium, the two or more types of particle groups of the same color having different adhesion forces are the main particle group having a predetermined average particle size and 1.1 to 3 of the average particle size of the main particle group. The shape factor = [(L 2 / S) / 4] × π × 100 (L is the perimeter of the particle, S is formed by mixing the low voltage particle group having an average particle size of 0.0 times Represents a particle area), the main particle group of 100 ≦ shape factor ≦ 110 and the low voltage particle group of 120 ≦ shape factor ≦ 140, or contact with water The main particle group having an angle of about 55 to 75 degrees is mixed with the low voltage particle group having a lower movement start voltage than the main particle group and a contact angle with water of about 80 to 150 degrees. It is characterized by comprising.
In order to achieve the above object, the present invention provides a transparent front substrate, a rear substrate disposed opposite to the front substrate, and a partition for partitioning a space between the front substrate and the rear substrate into a plurality of cells. An image display medium comprising a member and a group of positively or negatively charged particles enclosed in the plurality of cells and moving in the cells in response to an applied electric field, the positively or negatively charged The particle group has two or more types of particle groups of the same color having different movement start voltages that form the electric field at which the particle group starts moving, and the movement start voltage is higher than that of the main particle group and the main particle group. A low low voltage particle group is mixed and the mixing ratio of the main particle group and the low voltage particle group is 51:49 to 99: 1 (mass%), and the movement start voltage is different. Two or more particle groups of the same color Two or more types of particle groups having different average charge amounts of the particle groups, the main particle group having a predetermined average charge amount, and the average of the main particle groups having a lower movement start voltage than the main particle group Provided is an image display medium comprising the low voltage particle group having an average charge amount 1.3 to 3.0 times the charge amount, and an image display device including the image display medium To do.
ここで、「移動開始電圧」とは、粒子群が移動を開始したときの電界を生じさせる電圧をいい、移動開始電圧が相違する２種類以上の粒子群のうち、より移動開始電圧が低い粒子群の存在により、本発明の効果が発生する。 Here, the “movement start voltage” refers to a voltage that generates an electric field when the particle group starts moving, and particles having a lower movement start voltage among two or more types of particle groups having different movement start voltages. The effect of the present invention is generated by the presence of the group.
また、本発明は、上記目的を達成するため、上記本発明の画像表示媒体と、前記画像表示媒体と一体又は別体に構成される、電圧が印加されることにより前記電界を付与する一対の電極と、前記電圧を印加する電圧印加手段と、前記一対の電極への前記電圧の印加を制御する制御手段とを備えたことを特徴とする画像表示装置を提供する。
In order to achieve the above object, the present invention provides a pair of the image display medium of the present invention and the image display medium that is configured integrally with or separate from the image display medium to apply the electric field by applying a voltage. Provided is an image display device comprising: an electrode; a voltage applying unit that applies the voltage; and a control unit that controls application of the voltage to the pair of electrodes.
本発明の画像表示媒体および画像表示装置によれば、画質維持性の改善（ドット欠陥の防止等）及び駆動電源の低電圧化を実現することができる。 According to the image display medium and the image display apparatus of the present invention, it is possible to realize improvement in image quality maintainability (such as prevention of dot defects) and reduction in the voltage of the drive power supply.
以下、本発明の実施の形態を図を参照して説明するが、本発明はこれらに限定されるものではない。
（画像表示装置の構成）
図１は、本発明の第１の実施の形態に係る画像表示装置を示す。この画像表示装置１０は、透明電極３Ａと誘電体層４Ａを有する表面基板２Ａ、電極３Ｂと誘電体層４Ｂを有する背面基板２Ｂ、仕切り部材５、および粒子６Ａ，６Ｂ、６Ｃからなる粒子群を主体に構成される画像表示媒体１と、画像表示媒体１に電圧を印加して電界を付与する電界付与手段としての電圧印加手段１１とを有して概略構成されている。画像表示装置１０は、そのほか、表示する画像データを記憶する画像記憶部、画像記憶部に記憶された画像データに基づいて電圧印加手段１１を制御する制御回路、バッテリー電源等を備えて構成される。
Hereinafter, embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited thereto.
(Configuration of image display device)
FIG. 1 shows an image display apparatus according to a first embodiment of the present invention. The image display device 10 includes a surface substrate 2A having a transparent electrode 3A and a dielectric layer 4A, a back substrate 2B having an electrode 3B and a dielectric layer 4B, a partition member 5, and particles including particles 6A, 6B, and 6C. The image display medium 1 is mainly configured and includes a voltage applying unit 11 as an electric field applying unit that applies an electric field to the image display medium 1 to apply an electric field. In addition, the image display device 10 includes an image storage unit that stores image data to be displayed, a control circuit that controls the voltage application unit 11 based on the image data stored in the image storage unit, a battery power source, and the like. .
電圧印加手段１１は、初期化用の交番電圧を発生する交番電圧発生部と、白色粒子６Ａ（移動開始電圧の低い粒子６Ｂを混合），黒色粒子６Ｃによる２色表示を行うための直流電圧を発生する直流電圧発生部とを備えている。 The voltage application means 11 includes an alternating voltage generating unit that generates an alternating voltage for initialization, a DC voltage for performing two-color display using white particles 6A (mixed with particles 6B having a low movement start voltage) and black particles 6C. And a DC voltage generator for generating.
交番電圧発生部は、初期状態、例えば、白色粒子６Ａ（移動開始電圧の低い粒子６Ｂを混合）を一方の基板側に付着させ、黒色粒子６Ｂを他方の基板側に付着させるために用いられ、所定の周波数（例えば、２００Ｈｚ〜１０ｋＨｚ）の交番電圧（例えば、±１００Ｖ〜３００Ｖ）を全部の画素に印加する。 The alternating voltage generator is used to attach an initial state, for example, white particles 6A (mixed with particles 6B having a low movement start voltage) to one substrate side and black particles 6B to the other substrate side, An alternating voltage (for example, ± 100 V to 300 V) having a predetermined frequency (for example, 200 Hz to 10 kHz) is applied to all the pixels.
直流電圧発生部は、直流電圧（例えば、＋１４０Ｖ〜＋２１０Ｖ又は−１４０Ｖ〜−２１０Ｖ）を出力して白色粒子６Ａ（移動開始電圧の低い粒子６Ｂを混合）と黒色粒子６Ｂを用いて２色表示を行う際に用いられる。 The DC voltage generator outputs a DC voltage (for example, + 140V to + 210V or −140V to −210V) to display two colors using white particles 6A (mixed with particles 6B having a low movement start voltage) and black particles 6B. Used when doing.
図示していない制御回路は、例えば、ＣＰＵ、ＲＯＭ、ＲＡＭ、入出力インターフェース（Ｉ／Ｆ）回路等を備えて構成されている。ＣＰＵは、ＲＯＭに格納された制御プログラムに従って交番電圧発生部および直流電圧発生部の１つを選択して動作させるとともに、画像記憶部からの画像データに基づいて各電極３Ａ，３Ｂに電圧を印加させる。 A control circuit (not shown) includes, for example, a CPU, a ROM, a RAM, an input / output interface (I / F) circuit, and the like. The CPU selects and operates one of the alternating voltage generator and the DC voltage generator in accordance with a control program stored in the ROM, and applies a voltage to the electrodes 3A and 3B based on the image data from the image storage unit. Let
（画像表示媒体の全体の構成）
画像表示媒体１は、表面基板２Ａの方向から表示内容が見られる構成である。画像表示媒体１は、透明電極３Ａと誘電体層４Ａを有する表面基板２Ａと、この表面基板２Ａに対向するように配置された電極３Ｂと誘電体層４Ｂを有する背面基板２Ｂと、基板２Ａ，２Ｂ間を微小な間隔に対向配置させて保持するとともに、基板２Ａ，２Ｂに平行な方向に仕切って複数のセルを形成する仕切り部材５と、基板２Ａ，２Ｂ間の微小な間隔に封入されるとともに、色および帯電特性が異なる白色粒子６Ａ（移動開始電圧の低い粒子６Ｂを混合）および黒色粒子６Ｂからなる２色の帯電性粒子群とを有して構成されている。なお、図１において、１つのセルのみを図示したが、実際には、更に多数のセルが２次元アレイ状に配列されており、単純マトリックス駆動による表示が可能となっている。
(Overall configuration of image display medium)
The image display medium 1 is configured such that display contents can be seen from the direction of the front substrate 2A. The image display medium 1 includes a surface substrate 2A having a transparent electrode 3A and a dielectric layer 4A, a back substrate 2B having an electrode 3B and a dielectric layer 4B arranged so as to face the surface substrate 2A, a substrate 2A, Between 2B and 2B, the partition member 5 that partitions and holds in a direction parallel to the substrates 2A and 2B and forms a plurality of cells is enclosed in a minute interval between the substrates 2A and 2B. At the same time, it is configured to have two-color chargeable particle groups including white particles 6A (mixed with particles 6B having a low movement start voltage) and black particles 6B having different colors and charging characteristics. Although only one cell is shown in FIG. 1, actually, a larger number of cells are arranged in a two-dimensional array, and display by simple matrix driving is possible.
（画像表示媒体の各部の構成）
表面基板２Ａは、透明性を有しており、例えば、１．１ｍｍ厚さの透明ガラス基板等からなり、インジウム錫酸化物（ＩＴＯ）等からなる透明な帯状の透明電極３Ａと、透明電極３Ａを保護するとともに粒子６Ａ，６Ｂ，６Ｃの帯電特性を安定化させるポリカーボネート等からなる誘電体層４Ａとを積層して構成されている。なお、本発明でいう透明性とは、できる限り透明度が高いことが望ましいが、半透明又は有色透明であってもよい。
(Configuration of each part of the image display medium)
The surface substrate 2A has transparency, for example, a transparent glass substrate having a thickness of 1.1 mm, a transparent strip-shaped transparent electrode 3A made of indium tin oxide (ITO), and the like, and the transparent electrode 3A And a dielectric layer 4A made of polycarbonate or the like that protects the particles 6A, 6B, and 6C and stabilizes the charging characteristics of the particles 6A, 6B, and 6C. In addition, although the transparency as used in the present invention is desirably as high as possible, it may be translucent or colored and transparent.
透明電極３Ａは、ＩＴＯ、インジウム酸化亜鉛酸化物（ＩＺＯ）、酸化亜鉛、酸化錫、酸化鉛、酸化インジウム、ヨウ化銅等の透明導電性材料を用い、蒸着、イオンプレーティング、スパッタリング等の方法により形成したもの、あるいはＡｌ，Ｎｉ，Ａｕ等の金属を蒸着やスパッタリングにより半透明になる程度に薄く形成したものが用いられる。 The transparent electrode 3A uses a transparent conductive material such as ITO, indium zinc oxide oxide (IZO), zinc oxide, tin oxide, lead oxide, indium oxide, copper iodide, etc., and methods such as vapor deposition, ion plating, sputtering, etc. Or a metal thin film formed to be semitransparent by vapor deposition or sputtering is used.
誘電体層４Ａは、透明性を有しており、封入する粒子６Ａ，６Ｂ，６Ｃの帯電特性に応じて、ポリカーボネート、ポリエステル、ポリイミド、エポキシ等の絶縁性樹脂を用いることができる。また、誘電体層４Ａは、その絶縁性材料中に電荷輸送物質を含有させることができる。電荷輸送物質を含有させることにより、粒子帯電性の向上や、粒子の帯電量を安定させるなどの効果を得ることができる。 The dielectric layer 4A has transparency, and an insulating resin such as polycarbonate, polyester, polyimide, or epoxy can be used according to the charging characteristics of the encapsulated particles 6A, 6B, and 6C. The dielectric layer 4A can contain a charge transport material in the insulating material. By including a charge transport material, it is possible to obtain effects such as improvement in particle chargeability and stabilization of the charge amount of particles.
背面基板２Ｂは、例えば、０．２ｍｍ厚さのガラスエポキシ樹脂等からなり、その片面には、紙面と垂直方向に所定間隔で平行に配設された銅箔等からなる帯状の電極３Ｂと、電極３Ｂを保護するとともに、粒子６Ａ，６Ｂの帯電性特性を安定化させる誘電体層４Ｂとを有して構成されている。 The back substrate 2B is made of, for example, a glass epoxy resin having a thickness of 0.2 mm, and on one side thereof, a strip-like electrode 3B made of copper foil or the like disposed in parallel at a predetermined interval in a direction perpendicular to the paper surface; It has a dielectric layer 4B that protects the electrode 3B and stabilizes the charging characteristics of the particles 6A and 6B.
電極３Ｂは、１つのセルに１本設けられるが、解像度を上げるために複数本設けてもよい。同様に、透明電極３Ａも１つのセルに１本ではなく、複数設けてもよい。透明電極３Ａと電極３Ｂは交差するように配置され、単純マトリックス駆動により電極３Ａ，３Ｂ間の画素に電圧が印加されるように構成されている。 One electrode 3B is provided in one cell, but a plurality of electrodes 3B may be provided in order to increase the resolution. Similarly, a plurality of transparent electrodes 3A may be provided instead of one for each cell. The transparent electrode 3A and the electrode 3B are arranged so as to intersect with each other, and a voltage is applied to the pixel between the electrodes 3A and 3B by simple matrix driving.
誘電体層４Ｂの母材には、誘電体層４Ａと同様に絶縁性、あるいは半導電性の素材を用い、電極３Ｂへの電圧印加が終了した後でも、背面基板２Ｂ側に付着した粒子の帯電が保持されるようにする。 As the base material of the dielectric layer 4B, an insulating or semiconductive material is used as in the case of the dielectric layer 4A, and even after the voltage application to the electrode 3B is finished, the particles adhered to the back substrate 2B side. The charge is maintained.
誘電体層４Ｂは、着色層、例えば、着色材を背面基板２Ｂに塗布、あるいはフィルム状にしたものを貼付して形成した層としても良く、この場合、白黒粒子の２色とあわせて３色表示とすることができる。背面基板色を画面表示させるには、その対象画素に対応する電極間に所定の周波数の交番電圧を印加することにより、対象画素に存在する粒子を周辺に退避させ、着色層上に白色粒子および黒色粒子が存在しないようにし、表面基板を通して背面基板色が見えるようにする。 The dielectric layer 4B may be a colored layer, for example, a layer formed by applying a coloring material to the back substrate 2B or affixing a film-like material. In this case, three colors are combined with two colors of black and white particles. It can be a display. In order to display the back substrate color on the screen, by applying an alternating voltage of a predetermined frequency between the electrodes corresponding to the target pixel, the particles present in the target pixel are retreated to the periphery, and white particles and The black particles should be absent and the back substrate color can be seen through the front substrate.
仕切り部材５は、例えば、熱硬化性樹脂からなるインクをスクリーン印刷し、オーブン中で加熱焼成する処理を仕切り部材５が所望の高さになるまで複数回繰り返すことにより、背面基板２Ｂの誘電体層４Ｂ上に形成される。あるいは、ドライレジストフィルムなどの感光性樹脂を誘電体層４Ｂ上に積層して貼り付け、フォトリソグラフィ法により所定のパターンに露光・現像して形成しても良い。誘電体層４Ｂ上に形成された仕切り部材５の端面と表面基板２Ａ側の誘電体層４Ａとは、接着剤により接合される。仕切り部材５としては、熱硬化性樹脂の他に、熱可塑性樹脂、電子線硬化樹脂、光硬化性樹脂、ゴム等の絶縁材料を用いることができる。仕切り部材５と誘電体層４Ａとを接合する接着剤としては、熱可塑性接着剤、熱活性型接着剤、熱圧接着剤、紫外線硬化型接着剤等を用いることができる。 The partition member 5 is, for example, screen-printed with an ink made of a thermosetting resin, and repeatedly performing a process of heating and baking in an oven until the partition member 5 reaches a desired height, whereby the dielectric of the rear substrate 2B is obtained. Formed on layer 4B. Alternatively, a photosensitive resin such as a dry resist film may be laminated and pasted on the dielectric layer 4B, and exposed and developed into a predetermined pattern by a photolithography method. The end face of the partition member 5 formed on the dielectric layer 4B and the dielectric layer 4A on the surface substrate 2A side are joined by an adhesive. As the partition member 5, in addition to the thermosetting resin, an insulating material such as a thermoplastic resin, an electron beam curable resin, a photocurable resin, or rubber can be used. As an adhesive for joining the partition member 5 and the dielectric layer 4A, a thermoplastic adhesive, a thermally activated adhesive, a hot pressure adhesive, an ultraviolet curable adhesive, or the like can be used.
白色粒子６Ａ，６Ｂと黒色粒子６Ｃは、相互の摩擦による摩擦帯電により、互いに異なる極性に帯電する。ここでは、白色粒子６Ａ，６Ｂは負に帯電しており、黒色粒子６Ｃは正に帯電している。 The white particles 6A and 6B and the black particles 6C are charged with different polarities due to frictional charging caused by mutual friction. Here, the white particles 6A and 6B are negatively charged, and the black particles 6C are positively charged.
白色粒子６Ａ，６Ｂは、例えば、体積平均粒径２０μｍの酸化チタン含有架橋ポリメチルメタクリレートの球状微粒子（積水化成品工業（株）製テクポリマーＭＢＸ−２０−ホワイトを分級）１００質量部にイソプロピルトリメトキシシラン処理したチタニアの微粉末０．４質量部を外添して、適宜条件を変えて得ることができる。 The white particles 6A and 6B are, for example, spherical particles of titanium oxide-containing crosslinked polymethyl methacrylate having a volume average particle diameter of 20 μm (classified by Sekisui Plastics Co., Ltd. Techpolymer MBX-20-White) in 100 parts by mass. It can be obtained by adding 0.4 parts by mass of titania fine powder treated with methoxysilane and changing the conditions as appropriate.
本実施の形態における白色粒子は、白色粒子６Ａ（以下、「主粒子群６Ａ」ということがある）と移動開始電圧の低い白色粒子６Ｂ（以下、「低電圧粒子群６Ｂ」ということがある）とを所定の割合で混合して得られる混合粒子である。低電圧粒子群６Ｂを混合しているため、画質維持性の改善（ドット欠陥の防止等）、及び駆動電源の低電圧化、を実現することができる。 The white particles in the present embodiment are white particles 6A (hereinafter sometimes referred to as “main particle group 6A”) and white particles 6B having a low movement start voltage (hereinafter also referred to as “low voltage particle group 6B”). Are mixed particles obtained by mixing at a predetermined ratio. Since the low voltage particle group 6B is mixed, it is possible to improve the image quality maintainability (such as prevention of dot defects) and lower the voltage of the drive power supply.
低電圧粒子群６Ｂとは、主粒子群６Ａに対して移動開始電圧の低い粒子群のことである。「移動開始電圧が低い」とは、いくつか原因が考えられるが、その１つとして、基板間に形成される電界にしたがって、粒子が基板間を移動する際、粒子が移動を開始する電圧は粒子に作用する電界強度によるクーロン力が、粒子と基板表面との間に働く付着力（静電気力、ファンデルワールス力）に打ち勝ったときであることから、この付着力が弱いことを意味する。基板間に封入された粒子群が移動開始しやすくなるメカニズムとして、動きやすい粒子、すなわち移動開始電圧の低い粒子が先ず移動を開始し、これらがより移動開始電圧の高い他の粒子に衝突してほぼ同電圧にて移動を開始させ、全体として移動開始電圧の低下を実現していると考えられる。また、これに伴い、多くの粒子が移動して画像表示濃度がほぼ飽和する電圧も低くすることが可能となり、駆動電圧の低減化が図られる。 The low voltage particle group 6B is a particle group having a lower movement start voltage than the main particle group 6A. There are several possible causes for “low movement start voltage”. One of them is that when particles move between substrates according to the electric field formed between the substrates, the voltage at which the particles start moving is Since the Coulomb force due to the electric field strength acting on the particles overcomes the adhesion force (electrostatic force, van der Waals force) acting between the particle and the substrate surface, this means that the adhesion force is weak. As a mechanism that makes it easy for particles encapsulated between the substrates to start moving, particles that move easily, that is, particles with a low movement start voltage, start to move first, and they collide with other particles with a higher movement start voltage. It is considered that the movement is started at substantially the same voltage, and the movement start voltage is lowered as a whole. As a result, the voltage at which many particles move and the image display density is almost saturated can be lowered, and the drive voltage can be reduced.
また、画像表示を繰り返していると、移動開始電圧が上昇し、粒子が凝集して移動しにくくなり、画像のドット欠陥等が生じることが知られているが、低電圧粒子群６Ｂを添加混合することにより、ドット欠陥を防止し、画質を維持した画像表示の繰り返し回数の増加が可能となる。 In addition, it is known that when the image display is repeated, the movement start voltage increases, the particles aggregate and become difficult to move, and dot defects of the image occur. However, the low voltage particle group 6B is added and mixed. By doing so, it is possible to prevent dot defects and increase the number of repetitions of image display while maintaining image quality.
低電圧粒子群６Ｂは、付着力が小さいことをその特性とし、斯かる低電圧粒子群６Ｂとして、例えば、（１）粒子の表面形状において凹凸部が多い形状の粒子、（２）粒子の表面特性において表面エネルギーが低い特性を持った粒子、（３）粒子径が主粒子群より大きな粒子、を適用できる。 The low-voltage particle group 6B has a characteristic of having a low adhesive force. Examples of the low-voltage particle group 6B include (1) particles having many irregularities in the surface shape of the particles, and (2) the surface of the particles. Particles having characteristics with low surface energy can be applied, and (3) particles having a particle diameter larger than that of the main particle group.
（１）粒子の表面形状において凹凸部が多い形状の粒子
粒子表面が滑らかな主粒子群６Ａに、粒子表面に微細な凹凸部のある低電圧粒子群６Ｂを添加する。低電圧粒子群６Ｂの粒子は、主粒子群６Ａの粒子よりも表面積が大きければよいので、形状は特に限定されるものではない。例えば、ジャガイモのようなポテト型であってもよい。斯かる低電圧粒子群６Ｂは、例えば、特開２００３−５７６８８号公報に記載の方法により作製することができる。
(1) Particles having many irregularities in the surface shape of the particles The low voltage particle group 6B having fine irregularities on the particle surface is added to the main particle group 6A having a smooth particle surface. The shape of the particles of the low voltage particle group 6B is not particularly limited, as long as the surface area is larger than the particles of the main particle group 6A. For example, a potato type such as potato may be used. Such a low voltage particle group 6B can be produced by, for example, a method described in JP-A-2003-57688.
粒子表面の形状特性を示すものとして、例えば、下記式で表される形状係数がある。
形状係数＝［（Ｌ2／Ｓ）／４］×π×１００（Ｌは粒子の周囲長、Ｓは粒子面積を表す）
この形状係数は、走査型電子顕微鏡（ＳＥＭ）により観察し、画像解析装置ルーゼックス（ニレコ社製）を用いて、粒子の顕微鏡写真から粒子の面積（Ｓ）と周囲長（Ｌ）を求め、上記式から粒子形状を定量化し求めることができる。
Examples of the shape characteristic of the particle surface include a shape factor represented by the following formula.
Shape factor = [(L 2 / S) / 4] × π × 100 (L represents the perimeter of the particle, and S represents the particle area)
This shape factor is observed with a scanning electron microscope (SEM), and using an image analyzer Luzex (manufactured by Nireco), the area (S) and the perimeter (L) of the particle are determined from the micrograph of the particle. The particle shape can be quantified and determined from the equation.
この形状係数が、１００であると、粒子表面の凹凸がないため、１００に近づくほど粒子相互の付着力や粒子と基板表面間の付着力が増大する。また、１４０を超えると、粒子の表面凹凸が大きすぎて、繰り返し表示における、粉体（粒子）移動で生じる粒子間の衝突により、粒子表面の凹凸がとれやすくなり（破壊されやすくなり）、粒度分布がブロード化し、これに伴い帯電のブロード化も発生し、表示画像が不良化することがある。したがって、主粒子群６Ａについては、１００≦形状係数≦１１５の粒子を用いることが好ましく、低電圧粒子群６Ｂについては、１１５＜形状係数≦１４０の粒子を用いることが好ましい。より好ましくは、主粒子群６Ａについては、１０２≦形状係数≦１１５の粒子であり、低電圧粒子群６Ｂについては、１１５＜形状係数≦１３５の粒子である。さらに好ましくは、主粒子群６Ａについては、１０５≦形状係数≦１１５の粒子であり、低電圧粒子群６Ｂについては、１１５＜形状係数≦１３０の粒子である。 When this shape factor is 100, there is no unevenness on the particle surface, so that the adhesion force between particles and the adhesion force between particles and the substrate surface increase as the shape factor approaches 100. On the other hand, if the particle size exceeds 140, the surface irregularities of the particles are too large, and in the repeated display, the irregularities on the particle surface are easily removed (prone to breakage) due to collisions between particles caused by the movement of the powder (particles). The distribution is broadened, and accordingly, the charge is broadened and the display image may be deteriorated. Therefore, for the main particle group 6A, particles of 100 ≦ shape factor ≦ 115 are preferably used, and for the low-voltage particle group 6B, particles of 115 <shape factor ≦ 140 are preferably used. More preferably, the main particle group 6A is a particle of 102 ≦ shape factor ≦ 115, and the low-voltage particle group 6B is a particle of 115 <shape factor ≦ 135. More preferably, for the main particle group 6A, 105 ≦ shape factor ≦ 115, and for the low-voltage particle group 6B, 115 <shape factor ≦ 130.
（２）粒子の表面特性において表面エネルギーが低い特性を持った粒子
粒子表面がシランカップリング剤処理、あるいはフッ素処理された微粒子を粒子表面に固定した低電圧粒子群６Ｂを主粒子群６Ａに添加する。斯かる低電圧粒子群６Ｂは、例えば、特開２００２−７２２５６号公報に記載の方法により作製することができる。
(2) Particles with low surface energy in the surface characteristics of the particles Add low voltage particle group 6B in which fine particles whose surface is treated with silane coupling agent or fluorine are fixed to the particle surface are added to main particle group 6A To do. Such a low voltage particle group 6B can be produced by, for example, the method described in JP-A-2002-72256.
粒子の表面特性において表面エネルギーが低い特性を持った粒子とは、接触角が大きな粒子と同義であり、表面エネルギーは以下の方法によって制御することが可能であるが、これらに限定されるものではない。 Particles with low surface energy in the surface characteristics of the particles are synonymous with particles having a large contact angle, and the surface energy can be controlled by the following methods, but is not limited to these. Absent.
表面エネルギー（σ）は、σ＝σ１（１＋ｃｏｓθ）２／４により定義される。ここでσは表面エネルギー、σ１は液体の表面張力を、θは粒子単独または粒子を構成するバルク材料に対する液体の接触角をそれぞれ意味する。ここで、液体を水として、水との接触角を尺度とした場合、水との接触角が８０°以上の材料は表面エネルギーが２Ｊ／ｍ２以下である。主粒子群６Ａ（接触角は、およそ５５度から７５度）に添加する低電圧粒子群６Ｂの接触角は７０度から１５０度が好ましく、より好ましくは８０度から１２０度である。 Surface energy (sigma) is defined by σ = σ1 (1 + cosθ) 2/4. Here, σ is the surface energy, σ 1 is the surface tension of the liquid, and θ is the contact angle of the liquid with the particle alone or the bulk material constituting the particle. Here, when the liquid is water and the contact angle with water is taken as a scale, a material having a contact angle with water of 80 ° or more has a surface energy of 2 J / m 2 or less. The contact angle of the low-voltage particle group 6B added to the main particle group 6A (contact angle is approximately 55 to 75 degrees) is preferably 70 to 150 degrees, more preferably 80 to 120 degrees.
低表面エネルギーな材料としては、ポリテトラフルオロエチレン（テトラフルオロエチレン：ＴＦＥ），ポリ弗化ビニリデン，ポリクロロトリフルオロエチレン，ＰＦＡ，エチレン−ＴＦＥ共重合体，ＴＦＥ−ヘキサフルオロプロピレン共重合体（ＦＥＰ），エチレン−クロロトリフルオロエチレン共重合体，ＴＦＥ−ＰＦＡ共重合体，ＰＦＡ−ＦＥＰ共重合体等の弗素系樹脂、ポリジメチルシロキサン，ポリメチルフェニルシロキサン，ジメチルシロキサン−メチルフェニルシロキサン共重合体，ジメチルシロキサン−メチルビニルシロキサン共重合体，ジメチルシロキサン−メチルトリフルオロプロピルシロキサン共重合等のシリコーンゴムまたは樹脂などが挙げられる。また、弗素基を持った各種樹脂や、上記の材料からなる微粉末を含有した樹脂、例えば、弗素系微粒子（ルブロン）、コロイダルシリカ、あるいはシロキサン、シラン、フッ素等の化合物で表面処理されたカーボンブラック、黒鉛、シリカ、アルミナ、などの無機顔料を含有した樹脂が挙げられる。 Low surface energy materials include polytetrafluoroethylene (tetrafluoroethylene: TFE), polyvinylidene fluoride, polychlorotrifluoroethylene, PFA, ethylene-TFE copolymer, TFE-hexafluoropropylene copolymer (FEP). ), Fluorine-based resins such as ethylene-chlorotrifluoroethylene copolymer, TFE-PFA copolymer, PFA-FEP copolymer, polydimethylsiloxane, polymethylphenylsiloxane, dimethylsiloxane-methylphenylsiloxane copolymer, Examples thereof include silicone rubber or resin such as dimethylsiloxane-methylvinylsiloxane copolymer and dimethylsiloxane-methyltrifluoropropylsiloxane copolymer. In addition, various types of resins having fluorine groups and resins containing fine powders of the above materials, such as fluorine-based fine particles (lubron), colloidal silica, or carbon treated with a compound such as siloxane, silane, or fluorine. Examples thereof include resins containing inorganic pigments such as black, graphite, silica, and alumina.
（３）粒子径が主粒子群より大きな粒子
主粒子群６Ａの平均粒子径よりも大きな平均粒子径を持つ低電圧粒子群６Ｂを添加する。低電圧粒子群６Ｂの平均粒子径は、主粒子群６Ａの平均粒子径の１．１〜３．０倍であることが好ましく、より好ましくは、１．２〜２．０倍であり、さらに好ましくは、１．３〜１．６倍である。主粒子群６Ａの平均粒子径は、およそ３〜２５μｍのものを好適に使用することができる。斯かる主粒子群６Ａ、低電圧粒子群６Ｂは、公知の方法により作製することができる。
(3) Particles having a larger particle diameter than the main particle group The low voltage particle group 6B having an average particle diameter larger than the average particle diameter of the main particle group 6A is added. The average particle size of the low voltage particle group 6B is preferably 1.1 to 3.0 times the average particle size of the main particle group 6A, more preferably 1.2 to 2.0 times, Preferably, it is 1.3 to 1.6 times. The main particle group 6A having an average particle diameter of approximately 3 to 25 μm can be preferably used. Such main particle group 6A and low voltage particle group 6B can be produced by a known method.
低電圧粒子群６Ｂは付着力が小さいので、電源を切っても表示画像が保持されるという特性を良好に維持させるために、主粒子群６Ａとの混合比率が適宜調整される。低電圧粒子群６Ｂを主粒子群６Ａへ添加混合する割合は、主粒子群６Ａに対して４９質量％から１質量％が好ましく、より好ましくは３０質量％から２質量％、さらに好ましくは２０質量％から３質量％である。 Since the low-voltage particle group 6B has a small adhesive force, the mixing ratio with the main particle group 6A is appropriately adjusted in order to maintain a good characteristic that a display image is maintained even when the power is turned off. The mixing ratio of the low voltage particle group 6B to the main particle group 6A is preferably 49% by mass to 1% by mass, more preferably 30% by mass to 2% by mass, and still more preferably 20% by mass with respect to the main particle group 6A. % To 3% by mass.
主粒子群６Ａと低電圧粒子群６Ｂとの上記特性の差あるいは移動開始電圧の差が小さい場合ほど、低電圧粒子群６Ｂを多めに添加混合する必要がある。主粒子群６Ａと差が小さい低電圧粒子群６Ｂを大量に加えるよりも、主粒子群６Ａと差が大きい低電圧粒子群６Ｂを少量加えた方がより大きな効果が望める点で好ましい。 The smaller the difference in the above characteristics or the difference in movement start voltage between the main particle group 6A and the low voltage particle group 6B, the more the low voltage particle group 6B needs to be added and mixed. Rather than adding a large amount of the low voltage particle group 6B having a small difference from the main particle group 6A, it is preferable to add a small amount of the low voltage particle group 6B having a large difference from the main particle group 6A because a greater effect can be expected.
また、低電圧粒子群６Ｂは、粒子に働くクーロン力が大きいことをその特性とし、斯かる低電圧粒子群６Ｂとして、例えば、（４）電荷量が高い粒子、を適用できる。 Further, the low voltage particle group 6B has a characteristic that the Coulomb force acting on the particles is large, and for example, (4) particles having a high charge amount can be applied as the low voltage particle group 6B.
（４）電荷量が高い粒子
主粒子群６Ａよりも平均電荷量（帯電量）が高い低電圧粒子群６Ｂを主粒子群６Ａに添加する。低電圧粒子群６Ｂの平均電荷量（帯電量）は、主粒子群６Ａの平均電荷量（帯電量）の１．３〜３．０倍であることが好ましく、より好ましくは、１．５〜２．５倍であり、さらに好ましくは、１．６〜２．３倍である。後述する混合比率を調整して、主粒子群６Ａと低電圧粒子群６Ｂの混合粒子群の平均電荷量（帯電量）を主粒子群６Ａのみの平均電荷量（帯電量）に比べて、１．０３〜１．８倍とすることが好ましく、より好ましくは、１．０５〜１．６倍であり、さらに好ましくは、１．０７〜１．４倍である。主粒子群６Ａの平均電荷量（帯電量）は、主粒子群の体積平均粒子径がおよそ２０μｍのとき、およそ１５〜２５ｆｃ/個のものを好適に使用することができる。斯かる低電圧粒子群６Ｂは、公知の方法により作製することができる。
(4) Particles with a High Charge A low voltage particle group 6B having an average charge amount (charge amount) higher than that of the main particle group 6A is added to the main particle group 6A. The average charge amount (charge amount) of the low-voltage particle group 6B is preferably 1.3 to 3.0 times the average charge amount (charge amount) of the main particle group 6A, more preferably 1.5 to It is 2.5 times, and more preferably 1.6 to 2.3 times. By adjusting the mixing ratio described later, the average charge amount (charge amount) of the mixed particle group of the main particle group 6A and the low voltage particle group 6B is 1 as compared with the average charge amount (charge amount) of only the main particle group 6A. The ratio is preferably 0.03 to 1.8 times, more preferably 1.05 to 1.6 times, and still more preferably 1.07 to 1.4 times. As the average charge amount (charge amount) of the main particle group 6A, about 15 to 25 fc / piece can be suitably used when the volume average particle diameter of the main particle group is about 20 μm. Such a low voltage particle group 6B can be produced by a known method.
低電圧粒子群６Ｂは、粒子に働くクーロン力が大きく、単独で用いると粒子間の凝集を起こし易いので、適度な流動性を確保するために、主粒子群６Ａとの混合比率が適宜調整される。低電圧粒子群６Ｂを主粒子群６Ａへ添加混合する割合は、主粒子群６Ａに対して４９質量％から１質量％が好ましく、より好ましくは３０質量％から２質量％、さらに好ましくは２０質量％から３質量％である。 The low-voltage particle group 6B has a large Coulomb force acting on the particles and, when used alone, easily causes aggregation between the particles, so that the mixing ratio with the main particle group 6A is appropriately adjusted in order to ensure appropriate fluidity. The The mixing ratio of the low voltage particle group 6B to the main particle group 6A is preferably 49% by mass to 1% by mass, more preferably 30% by mass to 2% by mass, and still more preferably 20% by mass with respect to the main particle group 6A. % To 3% by mass.
主粒子群６Ａと低電圧粒子群６Ｂとの上記特性の差あるいは移動開始電圧の差が小さい場合ほど、低電圧粒子群６Ｂを多めに添加混合する必要がある。主粒子群６Ａと差が小さい低電圧粒子群６Ｂを大量に加えるよりも、主粒子群６Ａと差が大きい低電圧粒子群６Ｂを少量加えた方がより大きな効果が望める点で好ましい。 The smaller the difference in the above characteristics or the difference in movement start voltage between the main particle group 6A and the low voltage particle group 6B, the more the low voltage particle group 6B needs to be added and mixed. Rather than adding a large amount of the low voltage particle group 6B having a small difference from the main particle group 6A, it is preferable to add a small amount of the low voltage particle group 6B having a large difference from the main particle group 6A because a greater effect can be expected.
黒色粒子６Ｃは、例えば、体積平均粒径２０μｍのカーボン含有架橋ポリメチルメタクリレートの球状微粒子（積水化成品工業（株）製テクポリマーＭＢＸ−２０−ブラックを分級）を用いることができる。 As the black particles 6C, for example, spherical fine particles of carbon-containing crosslinked polymethyl methacrylate having a volume average particle diameter of 20 μm (classified by Sekisui Plastics Co., Ltd. Techpolymer MBX-20-Black) can be used.
なお、本実施の形態においては、黒色粒子６Ｃは混合粒子としていないが、白色粒子でなく、黒色粒子を混合粒子とすることも可能である。また、白色粒子および黒色粒子をともに、主粒子群と低電圧粒子群とからなる混合粒子として用いることがより好ましい。 In the present embodiment, the black particles 6C are not mixed particles, but black particles may be mixed particles instead of white particles. It is more preferable to use both white particles and black particles as mixed particles composed of a main particle group and a low voltage particle group.
また、本実施の形態においては、白色粒子について、２種類の粒子群を混合したものを示したが、２種類に限られず、３種類以上であってもよい。例えば、主粒子群に対し、２種類以上の低電圧粒子群を混合してもよい。さらに、白色、黒色に限られず、赤色、青色等であってもよい。 Moreover, in this Embodiment, what mixed two types of particle groups was shown about the white particle, However, It is not restricted to two types, Three or more types may be sufficient. For example, two or more types of low voltage particle groups may be mixed with the main particle group. Furthermore, it is not limited to white and black, but may be red or blue.
（画像表示装置の動作）
次に、この第１の実施の形態に係る画像表示装置１０の動作を説明する。
(Operation of image display device)
Next, the operation of the image display device 10 according to the first embodiment will be described.
白色粒子６Ａ，６Ｂと黒色粒子６Ｃにより２色表示を行う場合、制御部１５は、バッテリー電源から電圧印加手段１１へ電力供給をして、画像記憶部に記憶された画像データに基づいて電圧印加手段１１の直流電圧発生部を動作させる。直流電圧発生部は、透明電極３Ａに順次選択電圧（例えば、０Ｖ）を印加し、電極３Ｂには、画像データに応じて正又は負の画像電圧（例えば、＋１４０Ｖ又は−１４０Ｖ）を所定の時間（例えば、３０ｍｓ）印加する。 When performing two-color display using the white particles 6A and 6B and the black particles 6C, the control unit 15 supplies power from the battery power source to the voltage application unit 11 and applies a voltage based on the image data stored in the image storage unit. The DC voltage generator of the means 11 is operated. The DC voltage generator sequentially applies a selection voltage (for example, 0V) to the transparent electrode 3A, and applies a positive or negative image voltage (for example, + 140V or -140V) to the electrode 3B according to the image data for a predetermined time. (For example, 30 ms) is applied.
透明電極３Ａ，電極３Ｂへの電圧の印加を停止しても、粒子６Ａ，６Ｂ，６Ｃと誘電体層４Ａ，４Ｂとの間の静電付着力が維持されるため、粒子６Ａ，６Ｂ，６Ｃは誘電体層４Ａ，４Ｂの内面に付着したまま保持され、長時間に渡り白黒画像が表示される。 Even if the application of voltage to the transparent electrodes 3A and 3B is stopped, the electrostatic adhesion force between the particles 6A, 6B, and 6C and the dielectric layers 4A and 4B is maintained, so that the particles 6A, 6B, and 6C are maintained. Is held while adhering to the inner surfaces of the dielectric layers 4A and 4B, and a black and white image is displayed for a long time.
初期状態にする場合には、制御部は、電圧印加手段１１の交番電圧発生部を動作させ、透明電極３Ａに所定の周波数（例えば、４００Ｈｚ）の交番電圧（例えば、±２１０Ｖ）を印加するとともに、これと逆位相の交番電圧（例えば、±２１０Ｖ）を電極３Ｂに印加し、最終パルスとして例えば透明電極３Ａに正の直流電圧を印加することにより、白色粒子６Ａが表面基板２Ａの誘電体層４Ａの内面全体に付着し、黒色粒子６Ｂが背面基板２Ｂの誘電体層４Ａの内面全体に付着し、初期状態に戻される。このとき、画像表示媒体１を表示基板２Ａ側から見ると、白色粒子６Ａによる白色画面のみが見えている。 In the initial state, the control unit operates the alternating voltage generating unit of the voltage applying unit 11 and applies an alternating voltage (for example, ± 210 V) having a predetermined frequency (for example, 400 Hz) to the transparent electrode 3A. By applying an alternating voltage (for example, ± 210 V) having an opposite phase to this to the electrode 3B, and applying a positive DC voltage to the transparent electrode 3A as the final pulse, for example, the white particles 6A become the dielectric layer of the surface substrate 2A. The black particles 6B adhere to the entire inner surface of the dielectric layer 4A of the back substrate 2B and return to the initial state. At this time, when the image display medium 1 is viewed from the display substrate 2A side, only a white screen by the white particles 6A is visible.
なお、上記の実施の形態においては、一対の電極（列電極、行電極）を一対の基板（表面基板、背面基板）に設けたが、一対の電極は画像表示媒体の外に設けてもよい。これにより、表示画面の透明度が高くなる点で本発明の望ましい一態様である。また、一対の電極は、全面電極と画素電極、画素電極同士の組み合わせでもよい。 In the above embodiment, the pair of electrodes (column electrode, row electrode) is provided on the pair of substrates (front substrate, rear substrate), but the pair of electrodes may be provided outside the image display medium. . This is a desirable mode of the present invention in that the transparency of the display screen is increased. The pair of electrodes may be a combination of a full-surface electrode, a pixel electrode, and pixel electrodes.
以下、本発明を実施例によりさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
（白色粒子の作製）
（１）主粒子群の作製
分散液Ａの調製：下記組成ａを混合し、１０ｍｍΦのジルコニアボールにてボールミル粉砕を２０時間実施して分散液Ａを調製した。
＜組成ａ＞
・メタクリル酸シクロヘキシル ５３質量部
・酸化チタン ４５質量部（タイペークＣＲ６３：石原産業社製）
・帯電制御剤 ２質量部（ＣＯＰＹ ＣＨＡＲＧＥＰＳＹ ＶＰ２０３８：クラリアントジャパン社製）
・シクロヘキサン ５質量部
(Production of white particles)
(1) Production of Main Particle Group Preparation of Dispersion A: The following composition a was mixed, and ball milling was carried out with 10 mmφ zirconia balls for 20 hours to prepare Dispersion A.
<Composition a>
-53 parts by mass of cyclohexyl methacrylate-45 parts by mass of titanium oxide (Taipaque CR63: manufactured by Ishihara Sangyo Co., Ltd.)
・ 2 parts by mass of charge control agent (COPY CHARGEPSY VP2038: manufactured by Clariant Japan)
・ Cyclohexane 5 parts by mass
分散液Ｂの調製：下記組成ｂを混合し、分散液Ａと同様にボールミルにて微粉砕して分散液Ｂを調製した。
＜組成ｂ＞
・炭酸カルシウム ４０質量部
・水 ６０質量部
Preparation of Dispersion B: The following composition b was mixed and finely pulverized with a ball mill in the same manner as Dispersion A to prepare Dispersion B.
<Composition b>
・ 40 parts by weight of calcium carbonate ・ 60 parts by weight of water
混合液Ｃの調製：下記組成ｃを混合し、超音波機で脱気を１０分間行い、ついで乳化機で攪拌して混合液Ｃを調製した。
＜組成ｃ＞
・２％セロゲン水溶液 ４．３ｇ
・分散液Ｂ ８．５ｇ
・２０％食塩水 ５０ｇ
Preparation of liquid mixture C: The following composition c was mixed, degassed with an ultrasonic machine for 10 minutes, and then stirred with an emulsifier to prepare liquid mixture C.
<Composition c>
・ 4.3g of 2% serogen aqueous solution
・ Dispersion B 8.5g
・ 20% saline 50g
分散液Ａ３５ｇと、ジビニルベンゼン１ｇと、重合開始剤であるアゾビスイソブチロニトリル（ＡＩＢＮ）０．３５ｇとを秤量して充分混合し、超音波機で脱気を１０分行った。この混合液を上記混合液Ｃの中に入れ、乳化機で乳化を実施した。この乳化液を瓶に入れ、シリコーン栓をし、注射針を使用し、減圧脱気を充分行い、窒素ガスで封入した。次に、６０℃で１０時間反応させ、粒子を得た。冷却後、粒子を含む分散液を、凍結乾燥機により、−３５℃，０．１Ｐａの下で２日間、シクロヘキサンを除いた。得られた微粒子粉をイオン交換水中に分散させ、塩酸水で炭酸カルシウムを分解させ、ろ過を行った。その後、充分な蒸留水で洗浄し、目開き：２０μｍ、２５μｍのナイロン篩にかけ、粒度を揃えた。これを乾燥させ、平均粒子径２３μｍの白色粒子（主粒子群）を得た。得られた粒子をＳＥＭ写真で観察したところ球形であり、形状係数を求めたところ、形状係数は、１０７であった。 35 g of dispersion A, 1 g of divinylbenzene, and 0.35 g of azobisisobutyronitrile (AIBN) as a polymerization initiator were weighed and mixed thoroughly, and deaerated with an ultrasonic machine for 10 minutes. The mixed solution was put into the mixed solution C and emulsified with an emulsifier. This emulsion was put into a bottle, sealed with a silicone stopper, sufficiently degassed under reduced pressure using an injection needle, and sealed with nitrogen gas. Next, it was made to react at 60 degreeC for 10 hours, and particle | grains were obtained. After cooling, the dispersion containing the particles was freed from cyclohexane with a freeze dryer at −35 ° C. and 0.1 Pa for 2 days. The obtained fine particle powder was dispersed in ion exchange water, calcium carbonate was decomposed with hydrochloric acid water, and filtration was performed. Then, it was washed with sufficient distilled water, and passed through a nylon sieve having openings of 20 μm and 25 μm to make the particle sizes uniform. This was dried to obtain white particles (main particle group) having an average particle size of 23 μm. When the obtained particles were observed with an SEM photograph, they were spherical. When the shape factor was determined, the shape factor was 107.
（２）低電圧粒子群の作製
分散液Ａの調製に際し、組成ａのシクロヘキサンの量を８質量部とした以外は、白色粒子（主粒子群）と同様にして、平均粒子径２１．５μｍの白色粒子（低電圧粒子群）を得た。得られた粒子をＳＥＭ写真で観察したところ球形であり、形状係数を求めたところ、形状係数は、１２０であった。
(2) Preparation of low-voltage particle group When preparing dispersion A, the average particle diameter was 21.5 μm in the same manner as white particles (main particle group) except that the amount of cyclohexane of composition a was 8 parts by mass. White particles (low voltage particle group) were obtained. When the obtained particles were observed with an SEM photograph, they were spherical. When the shape factor was determined, the shape factor was 120.
（黒色粒子の作製）
（１）主粒子群の作製
分散液Ａの代わりに、下記分散液Ｋを用いた以外は、白色粒子（主粒子群）と同様にして、平均粒子径２３．２μｍの黒色粒子（主粒子群）を得た。得られた粒子をＳＥＭ写真で観察したところ球形であり、形状係数を求めたところ、形状係数は、１１０であった。
(Production of black particles)
(1) Preparation of main particle group Black particles (main particle group) having an average particle diameter of 23.2 μm are obtained in the same manner as white particles (main particle group) except that the following dispersion K is used instead of dispersion A. ) When the obtained particles were observed with an SEM photograph, they were spherical and the shape factor was determined to be 110.
分散液Ｋの調製：下記組成ｋを混合し、１０ｍｍΦのジルコニアボールにてボールミル粉砕を２０時間実施して分散液Ｋを調製した。
＜組成ｋ＞
・スチレンモノマー ８７質量部
・黒顔料（カーボンブラック（ＣＦ９：三菱化学製）） １０質量部
・シクロヘキサン ２質量部
Preparation of Dispersion K: The following composition k was mixed, and ball milling was performed for 20 hours with 10 mmφ zirconia balls to prepare Dispersion K.
<Composition k>
-Styrene monomer 87 parts by mass-Black pigment (carbon black (CF9: manufactured by Mitsubishi Chemical)) 10 parts by mass-Cyclohexane 2 parts by mass
（２）低電圧粒子群の作製
分散液Ａの代わりに、下記分散液Ｋ２を用い、さらにシクロヘキサン除去工程において、分散液を３０℃，１．３×１０4Ｐａで５時間、乾燥させた以外は、白色粒子（主粒子群）と同様にして、平均粒子径２１．２μｍの黒色粒子（低電圧粒子群）を得た。得られた粒子をＳＥＭ写真で観察したところ球形であり、形状係数を求めたところ、形状係数は、１２０であった。
(2) Preparation of low-voltage particle group In place of dispersion A, the following dispersion K2 was used, and in the cyclohexane removal step, the dispersion was dried at 30 ° C. and 1.3 × 10 4 Pa for 5 hours. Obtained black particles (low voltage particle group) having an average particle diameter of 21.2 μm in the same manner as white particles (main particle group). When the obtained particles were observed with an SEM photograph, they were spherical. When the shape factor was determined, the shape factor was 120.
分散液Ｋ２の調製：下記組成ｋ２を混合し、１０ｍｍΦのジルコニアボールにてボールミル粉砕を２０時間実施して分散液Ｋ２を調製した。
＜組成ｋ２＞
・スチレンモノマー ８９質量部
・黒顔料（カーボンブラック（ＣＦ９：三菱化学製）） ８質量部
・シクロヘキサン ８質量部
Preparation of Dispersion K2: The following composition k2 was mixed, and ball milling was performed for 20 hours with 10 mmφ zirconia balls to prepare Dispersion K2.
<Composition k2>
-Styrene monomer 89 parts by mass-Black pigment (carbon black (CF9: manufactured by Mitsubishi Chemical)) 8 parts by mass-Cyclohexane 8 parts by mass
作製した白色粒子（主粒子群）９０質量％に対して、白色粒子（低電圧粒子群）を１０質量％添加した。また、作製した黒色粒子（主粒子群）９０質量％に対して、黒色粒子（低電圧粒子群）を１０質量％添加した。このようにして混合白色粒子および混合黒色粒子を準備した。 10 mass% of white particles (low voltage particle group) were added with respect to 90 mass% of produced white particles (main particle group). Moreover, 10 mass% of black particles (low voltage particle group) were added with respect to 90 mass% of produced black particles (main particle group). In this way, mixed white particles and mixed black particles were prepared.
次に、準備した混合白色粒子および混合黒色粒子を質量比７：５で混合して、白黒混合粒子を準備した。準備した白黒混合粒子を、上述の第１の実施の形態に係る画像表示媒体における対向配置された基板（表示基板２Ａ、背面基板２Ｂ）間の空隙に所定量封入し、実施例１の画像表示媒体とした。 Next, the prepared mixed white particles and mixed black particles were mixed at a mass ratio of 7: 5 to prepare black and white mixed particles. The prepared black and white mixed particles are sealed in a predetermined amount in the gap between the substrates (display substrate 2A, rear substrate 2B) arranged opposite to each other in the image display medium according to the first embodiment, and the image display of Example 1 is performed. The medium.
この表示媒体を駆動したところ、移動開始電圧は、主粒子群のみを封入した画像表示媒体の場合の１２０Ｖから、９０Ｖへ３０Ｖ低減された。また、表示駆動を繰返したところ、反射率が維持され、画像欠陥もなく安定した表示特性を示した。繰返し表示特性の評価結果を図２に示す。 When this display medium was driven, the movement start voltage was reduced by 30 V from 90 V to 90 V in the case of the image display medium in which only the main particle group was enclosed. Further, when display driving was repeated, the reflectance was maintained, and stable display characteristics were exhibited without image defects. The evaluation results of the repeated display characteristics are shown in FIG.
（黒色粒子の作製）
表面エネルギーの低いシランカップリング剤処理されたシリカ（無機顔料）微粒子を表面に固定させた黒色粒子を以下のようにして準備した。
(Production of black particles)
Black particles having silica (inorganic pigment) fine particles treated with a silane coupling agent treated with a low surface energy fixed on the surface were prepared as follows.
（１）微粒子の作成
シリカ微粒子（日本アエロジル社製Ａ−１３０）１００部をミキサーに入れ、撹拌しながらアミノプロピルトリメトキシシラン５０部をメタノール５０部で希釈したものを噴霧した。このようにして得られた微粒子を乾燥させ、サンプルミルを用いて２分間解砕して、平均一次粒子径１３０ｎｍ、抵抗（２５℃）２×１０９Ω・ｃｍの微粒子を得た。
(1) Preparation of fine particles 100 parts of silica fine particles (A-130 manufactured by Nippon Aerosil Co., Ltd.) were put in a mixer and sprayed with 50 parts of aminopropyltrimethoxysilane diluted with 50 parts of methanol while stirring. The fine particles thus obtained were dried and pulverized for 2 minutes using a sample mill to obtain fine particles having an average primary particle size of 130 nm and a resistance (25 ° C.) of 2 × 10 9 Ω · cm.
（２）母粒子の作成
カーボンブラック１０部、メタクリル酸メチル５０部、スルホコハク酸ラウリル２ナトリウム１０部をボールミル中で１０時間分散処理してカーボンブラック分散液を調製した。次に、得られたカーボンブラック分散液８０部、メタクリル酸メチル１０部、エチレングリコールジメタクリレート１０部、２，２−アゾビス−２，４−ジメチルバレロニトリル０．２部からなるＡ液を十分攪拌混合し、一方、ポリビニルアルコール１０部と水５００部からなるＢ液を混合攪拌し、液滴が２０μｍになるよう調製し、Ｂ液にＡ液を添加した。その後、窒素下で、混合溶液の脱気を十分実施し、６５℃で、７時間、混合液を加熱して重合させた。その後、液温を室温まで冷却し、吸引ろ過により生成物を分離し、温水で洗浄した後、メタノールで洗浄し、乾燥させた。その後、風力分級機で粗大粉と微粉を除去して、平均粒径２０μｍ、標準偏差５μｍ、の黒色の球状粒子を得た。本黒色粒子を平面上に塗布したのち、水との接触角を測定したところ、接触角は６５度であった。
(2) Preparation of mother particles 10 parts of carbon black, 50 parts of methyl methacrylate and 10 parts of disodium lauryl sulfosuccinate were dispersed in a ball mill for 10 hours to prepare a carbon black dispersion. Next, the liquid A consisting of 80 parts of the obtained carbon black dispersion, 10 parts of methyl methacrylate, 10 parts of ethylene glycol dimethacrylate, and 0.2 part of 2,2-azobis-2,4-dimethylvaleronitrile is sufficiently stirred. On the other hand, liquid B consisting of 10 parts of polyvinyl alcohol and 500 parts of water was mixed and stirred to prepare droplets of 20 μm, and liquid A was added to liquid B. Thereafter, the mixed solution was sufficiently deaerated under nitrogen, and the mixed solution was heated and polymerized at 65 ° C. for 7 hours. Then, the liquid temperature was cooled to room temperature, the product was separated by suction filtration, washed with warm water, washed with methanol, and dried. Thereafter, coarse powder and fine powder were removed with an air classifier to obtain black spherical particles having an average particle diameter of 20 μm and a standard deviation of 5 μm. After applying the black particles on a flat surface and measuring the contact angle with water, the contact angle was 65 degrees.
（３）母粒子と微粒子の混合による低電圧粒子群の作製
上記により得られた微粒子０．３部と、体積平均粒径２０μｍのカーボン含有ポリメチルメタクリレートの黒色球状の母粒子１００部を混合し、高速気流衝撃処理装置（奈良器械製作所製）へ投入した。ロータの回転速度１００００回転／分、処理時間２分の条件下で処理した後、排出放冷して、微粒子が母粒子表面に付着固定された黒色球状粒子（平均粒径２０μｍ）を得た。本黒色粒子を平面上に塗布したのち、水との接触角を測定したところ、接触角は８０度であった。
(3) Preparation of low voltage particle group by mixing mother particles and fine particles 0.3 parts of the fine particles obtained above and 100 parts of black spherical mother particles of carbon-containing polymethyl methacrylate having a volume average particle diameter of 20 μm were mixed. The high-speed airflow impact treatment device (manufactured by Nara Instruments Co., Ltd.) was used. After processing under conditions of a rotor rotational speed of 10,000 rotations / minute and a processing time of 2 minutes, the product was discharged and allowed to cool to obtain black spherical particles (average particle size 20 μm) in which fine particles were adhered and fixed on the surface of the mother particles. After applying the black particles on a flat surface and measuring the contact angle with water, the contact angle was 80 degrees.
作製した母粒子のみからなる黒色粒子を主粒子群として、黒色粒子（主粒子群）９０質量％に、作製した黒色粒子（低電圧粒子群）１０質量％を添加して、混合黒色粒子を準備した。 Prepared mixed black particles by adding 10% by mass of the produced black particles (low voltage particle group) to 90% by mass of the black particles (main particle group) using the produced black particles only as the main particle group. did.
（白色粒子の作製）
カーボンブラックを酸化チタン（平均粒径０．３μｍ）４０部に代えて酸化チタン分散液を調製した他は、黒色粒子の母粒子と同様の方法で、体積平均粒径２０μｍの白色粒子を作製した。
(Production of white particles)
White particles with a volume average particle diameter of 20 μm were prepared in the same manner as the base particles of the black particles, except that carbon black was replaced with 40 parts of titanium oxide (average particle diameter 0.3 μm) and a titanium oxide dispersion was prepared. .
準備した混合黒色粒子と白色粒子とを１：２（質量比）で混合して、白黒混合粒子を準備した。準備した白黒混合粒子を基板間ギャップ２００μｍの２０ｍｍ角のテストデバイスに３ｍｇ/ｃｍ２封入して表示媒体を作成した。この表示媒体を駆動したところ、移動開始電圧は、混合黒色粒子に代えて黒色粒子（主粒子群）のみからなる黒色粒子を使用したものが１２０Ｖであったのに対し、１００Ｖへと、２０Ｖ低減された。 The prepared mixed black particles and white particles were mixed at a ratio of 1: 2 (mass ratio) to prepare black and white mixed particles. The prepared black and white mixed particles were sealed in 3 mg / cm 2 in a 20 mm square test device with a substrate gap of 200 μm to prepare a display medium. When this display medium was driven, the movement start voltage was reduced to 20V, down to 100V, compared to 120V using black particles consisting only of black particles (main particle group) instead of mixed black particles. It was done.
公知の方法により、体積平均粒子径１４μｍ，２０μｍの白色粒子、および体積平均粒子径１５μｍの黒色粒子を作製した。次に、体積平均粒子径１４μｍの白色粒子（主粒子群）９０質量％に、体積平均粒子径２０μｍの白色粒子（低電圧粒子群）１０質量％を添加して、混合白色粒子を準備した。 White particles having a volume average particle diameter of 14 μm and 20 μm and black particles having a volume average particle diameter of 15 μm were prepared by a known method. Next, 10% by mass of white particles (low voltage particle group) having a volume average particle size of 20 μm was added to 90% by mass of white particles (main particle group) having a volume average particle size of 14 μm to prepare mixed white particles.
混合白色粒子と体積平均粒子径１５μｍの黒色粒子とを６：５（質量比）で混合して、白黒混合粒子を準備した。準備した白黒混合粒子を基板間ギャップ２００μｍの２０ｍｍ角のテストデバイスに２ｍｇ/ｃｍ２封入して表示媒体を作製した。この表示媒体を駆動したところ、移動開始電圧は、混合白色粒子に代えて白色粒子（主粒子群）のみからなる白色粒子を使用したものが１００Ｖであったのに対し、７０Ｖへと、３０Ｖ低減された。また、多くの粒子が移動して表示濃度がほぼ飽和する電圧もおよそ３００Ｖから２５０Ｖへと５０Ｖ低減された。印加電圧と画像表示媒体の反射濃度との関係を図３に示す。また、表示駆動を繰返したところ、反射率が維持され、画像欠陥もなく安定した表示特性を示した。繰返し表示特性の評価結果を図４に示す。 Mixed white particles and black particles having a volume average particle diameter of 15 μm were mixed at 6: 5 (mass ratio) to prepare black and white mixed particles. The prepared white mixed particles in the test device of 20mm square gap between the substrates 200 [mu] m 2 mg / cm 2 sealed was manufactured a display medium. When this display medium was driven, the movement start voltage was reduced by 30V to 70V, compared to 100V using white particles consisting only of white particles (main particle group) instead of mixed white particles. It was done. In addition, the voltage at which the display density is almost saturated due to the movement of many particles is reduced by 50 V from about 300 V to 250 V. FIG. 3 shows the relationship between the applied voltage and the reflection density of the image display medium. Further, when display driving was repeated, the reflectance was maintained, and stable display characteristics were exhibited without image defects. The evaluation results of the repeated display characteristics are shown in FIG.
なお、本実施例においては、白色粒子（主粒子群）と白色粒子（低電圧粒子群）とを別々に作製して混合させたが、主粒子群とこれに添加する低電圧粒子群の組成が同一で粒子径が異なる場合は、同一組成の粒子群を作製する際に、その粒子群の粒径分布を主粒子群と低電圧粒子群を混合した粒子群に近似した分布となるように制御することによって作製することもできる。 In this example, white particles (main particle group) and white particles (low voltage particle group) were separately prepared and mixed. However, the composition of the main particle group and the low voltage particle group added thereto was mixed. Are the same and the particle size is different, when preparing particle groups of the same composition, the particle size distribution of the particle groups should be a distribution that approximates the particle group that is a mixture of the main particle group and the low-voltage particle group. It can also be produced by controlling.
（主粒子群の作製）
以下のように白色粒子および黒色粒子１を作製し、白色粒子と黒色粒子１を質量比６：５にて混合し、混合白黒粒子（主粒子群）を準備した。
(Preparation of main particle group)
White particles and black particles 1 were prepared as follows, and white particles and black particles 1 were mixed at a mass ratio of 6: 5 to prepare mixed black and white particles (main particle group).
（１）白色粒子の作製
分散液Ａの調製：下記組成を混合し、１０ｍｍΦのジルコニアボールにてボールミル粉砕を２０時間実施して分散液Ａを調製した。
＜組成＞
・メタクリル酸シクロヘキシル：６４質量部
・酸化チタン（白色顔料）（一次粒子径０．３μｍ、タイペークＣＲ６３：石原産業製）：３０質量部
・ポリマー微粒子（中空粒子）（一次粒子径０．３μｍ、ＳＸ８６６（Ａ）：ＪＳＲ製）：５質量部
・帯電制御剤（ＳＢＴ−５−００１６：オリエント化学工業製）：１質量部
(1) Preparation of White Particles Preparation of Dispersion A: The following composition was mixed and subjected to ball milling with 10 mmφ zirconia balls for 20 hours to prepare Dispersion A.
<Composition>
-Cyclohexyl methacrylate: 64 parts by mass-Titanium oxide (white pigment) (primary particle diameter 0.3 µm, Type CR63: manufactured by Ishihara Sangyo): 30 parts by mass-Polymer fine particles (hollow particles) (primary particle diameter 0.3 µm, SX866) (A): manufactured by JSR): 5 parts by mass / charge control agent (SBT-5-0016: manufactured by Orient Chemical Industries): 1 part by mass
分散液Ｂの調製：下記組成を混合し、分散液Ａと同様にボールミルにて微粉砕して分散液Ｂを調製した。
＜組成＞
・炭酸カルシウム：４０質量部
・水：６０質量部
Preparation of Dispersion B: The following composition was mixed and finely pulverized with a ball mill in the same manner as Dispersion A to prepare Dispersion B.
<Composition>
-Calcium carbonate: 40 parts by mass-Water: 60 parts by mass
混合液Ｃの調製：下記組成を混合し、超音波機で脱気を１０分間行い、ついで乳化機で攪拌して混合液Ｃを調製した。
＜組成＞
・分散液Ｂ：７．０ｇ
・２０％食塩水：５０ｇ
Preparation of liquid mixture C: The following composition was mixed, degassed with an ultrasonic machine for 10 minutes, and then stirred with an emulsifier to prepare liquid mixture C.
<Composition>
-Dispersion B: 7.0 g
・ 20% saline: 50 g
次に、分散液Ａ３５ｇと、ジビニルベンゼン１ｇと、重合開始剤Ｖ６０１（ジメチル２，２’−アゾビス２−メチルプロピオナート、和光純薬製）０．３５ｇとを秤量して充分混合し、超音波機で脱気を１０分行った。この混合液を上記混合液Ｃの中に入れ、乳化機で乳化を実施した。続いて、この乳化液を瓶に入れ、シリコーン栓をした後、注射針を使用して減圧脱気を充分行い、窒素ガスで封入する。次に、７０℃で１０時間反応させ粒子を得た。得られた微粒子粉をイオン交換水中に分散させ、塩酸水で炭酸カルシウムを分解させ、ろ過を行った。その後、充分な蒸留水で洗浄し、目開き：１０μｍ、１５μｍのナイロン篩にかけ、粒度を揃えた。これを乾燥させ、平均粒子径１２．５６μｍの白色粒子を得た。 Next, 35 g of dispersion A, 1 g of divinylbenzene, and 0.35 g of polymerization initiator V601 (dimethyl 2,2′-azobis-2-methylpropionate, manufactured by Wako Pure Chemical Industries, Ltd.) were weighed and mixed well, Deaeration was performed for 10 minutes with a sonicator. The mixed solution was put into the mixed solution C and emulsified with an emulsifier. Subsequently, the emulsified liquid is put in a bottle, sealed with a silicone stopper, sufficiently degassed under reduced pressure using an injection needle, and sealed with nitrogen gas. Next, it was made to react at 70 degreeC for 10 hours, and particle | grains were obtained. The obtained fine particle powder was dispersed in ion exchange water, calcium carbonate was decomposed with hydrochloric acid water, and filtration was performed. Then, it was washed with sufficient distilled water, and passed through a nylon sieve having openings of 10 μm and 15 μm to make the particle sizes uniform. This was dried to obtain white particles having an average particle size of 12.56 μm.
（２）黒色粒子１の作製
分散液Ａの代わりに、下記分散液Ａ１を用いた以外は、上記の白色粒子の作製と同様にして、黒色粒子１を作製した。得られた黒色粒子の平均粒子径は１２．５μｍであった。
(2) Production of black particles 1 Black particles 1 were produced in the same manner as the production of the white particles except that the following dispersion A1 was used instead of the dispersion A. The average particle diameter of the obtained black particles was 12.5 μm.
分散液Ａ１の調製：下記組成を混合し、１０ｍｍΦのジルコニアボールにてボールミル粉砕を２０時間実施して分散液Ａ１を調製した。
＜組成＞
・メチルメタクリレート：８７．２質量部
・ジエチルアミノエチルメタクリレート：０．４５質量部
・カーボンブラック（♯２６５０、三菱化学社製）：１０質量部
・帯電制御剤（ＣＯＰＹ ＣＨＡＲＧＥ ＰＳＹ ＶＰ２０３８：クラリアントジャパン製）：１質量部
Preparation of Dispersion A1: The following composition was mixed, and ball milling was performed with 10 mmφ zirconia balls for 20 hours to prepare Dispersion A1.
<Composition>
-Methyl methacrylate: 87.2 parts by mass-Diethylaminoethyl methacrylate: 0.45 parts by mass-Carbon black (# 2650, manufactured by Mitsubishi Chemical Corporation): 10 parts by mass-Charge control agent (COPY CHARGE PSY VP2038: manufactured by Clariant Japan): 1 part by mass
（低電圧粒子群の作製）
白色粒子と黒色粒子２とを質量比６：５で混合した混合粒子の帯電量が、上記の主粒子群の混合粒子よりも高い組合せを以下のようにして準備した。
(Production of low voltage particles)
A combination in which white particles and black particles 2 were mixed at a mass ratio of 6: 5 and the charge amount of the mixed particles was higher than that of the mixed particles of the main particle group was prepared as follows.
黒色粒子１の分散液Ａ１の組成のひとつであるジエチルアミノエチルメタクリレートの配合量を４倍にして、黒色粒子２を作製した。白色粒子と黒色粒子２を質量比６：５にて混合し、混合白黒粒子（低電圧粒子群）を準備した。 Black particles 2 were prepared by increasing the blending amount of diethylaminoethyl methacrylate, which is one of the compositions of dispersion A1 of black particles 1, by a factor of four. White particles and black particles 2 were mixed at a mass ratio of 6: 5 to prepare mixed black and white particles (low voltage particle group).
混合白黒粒子（低電圧粒子群）の黒色粒子の平均帯電量は、＋２０ｆｃ/個であり、混合白黒粒子（主粒子群）の黒色粒子の平均帯電量＋１０ｆｃ/個に対して約２倍高い帯電性を示した。次に、混合白黒粒子（低電圧粒子群）５部を混合白黒粒子（主粒子群）９５部へ添加し、新たな混合粒子とした。この新たな混合粒子の黒色粒子の平均帯電量は＋１１ｆｃ/個であった。 The average charge amount of the black particles of the mixed black and white particles (low voltage particle group) is +20 fc / particle, which is about twice as high as the average charge amount of the black particles of the mixed black and white particles (main particle group) +10 fc / particle. Showed sex. Next, 5 parts of mixed black and white particles (low voltage particle group) were added to 95 parts of mixed black and white particles (main particle group) to obtain new mixed particles. The average charge amount of the black particles of the new mixed particles was +11 fc / piece.
上記の白黒混合粒子を基板間に所定量封入して、表示駆動実験を行ったところ、移動開始電圧は、混合白黒粒子（主粒子群）のみの７０Ｖから、５０Ｖへ２０Ｖ低減された。また、表示駆動を繰返したところ、安定した表示特性を示した。 When a predetermined amount of the black and white mixed particles was sealed between the substrates and a display driving experiment was performed, the movement start voltage was reduced by 20 V from 70 V of the mixed black and white particles (main particle group) alone to 50 V. When display driving was repeated, stable display characteristics were shown.
１ 画像表示媒体
２Ａ 表面基板
２Ｂ 背面基板
３Ａ 透明電極
３Ｂ 電極
４Ａ，４Ｂ 誘電体層
５ 仕切り部材
６Ａ 白色粒子
６Ｂ 移動開始電圧の低い粒子（白色粒子）
６Ｃ 黒色粒子
１０ 画像表示装置
１１ 電圧印加手段
DESCRIPTION OF SYMBOLS 1 Image display medium 2A Front substrate 2B Rear substrate 3A Transparent electrode 3B Electrode 4A, 4B Dielectric layer 5 Partition member 6A White particle 6B Particle with low movement start voltage (white particle)
6C Black particles 10 Image display device 11 Voltage application means
Claims (7)
前記表面基板に対向配置された背面基板と、
前記表面基板と前記背面基板との空間を複数のセルに仕切る仕切り部材と、
前記複数のセル内に封入され、付与された電界に応じて前記セル内を移動する正又は負に帯電した粒子群とを備えた画像表示媒体であって、
前記正又は負に帯電した粒子群は、前記粒子群が移動を開始する前記電界を形成させる移動開始電圧が相違する同一色の２種類以上の粒子群として、主粒子群及び前記主粒子群よりも前記移動開始電圧が低い低電圧粒子群を混合して構成されてなり、
前記主粒子群と前記低電圧粒子群との混合比率は、５１：４９〜９９：１（質量％）であり、
前記移動開始電圧が相違する同一色の２種類以上の粒子群は、前記表面基板表面又は前記背面基板表面と前記粒子群との間に働く付着力が相違する２種類以上の粒子群であり、
前記付着力が相違する同一色の２種類以上の粒子群は、所定の平均粒子径を有する前記主粒子群と、前記主粒子群の平均粒子径の１．１〜３．０倍の平均粒子径を有する前記低電圧粒子群とを混合して構成されてなることを特徴とする画像表示媒体。 A surface substrate having transparency;
A rear substrate disposed opposite to the front substrate;
A partition member that partitions the space between the front substrate and the rear substrate into a plurality of cells;
An image display medium comprising a group of positively or negatively charged particles enclosed in the plurality of cells and moving in the cells according to an applied electric field,
The positively or negatively charged particle group is composed of two or more types of particle groups of the same color having different movement start voltages that form the electric field at which the particle group starts to move, from the main particle group and the main particle group. Is composed of a mixture of low voltage particles having a low movement start voltage,
The mixing ratio of the main particle group and the low voltage particle group is 51:49 to 99: 1 (mass%),
The two or more types of particle groups of the same color having different movement start voltages are two or more types of particle groups having different adhesion forces acting between the surface substrate surface or the back substrate surface and the particle group,
The two or more types of particle groups of the same color having different adhesion forces are the main particle group having a predetermined average particle size and an average particle 1.1 to 3.0 times the average particle size of the main particle group images display medium wherein you characterized by comprising constructed by mixing the low voltage the particle group having a diameter.
前記表面基板に対向配置された背面基板と、
前記表面基板と前記背面基板との空間を複数のセルに仕切る仕切り部材と、
前記複数のセル内に封入され、付与された電界に応じて前記セル内を移動する正又は負に帯電した粒子群とを備えた画像表示媒体であって、
前記正又は負に帯電した粒子群は、前記粒子群が移動を開始する前記電界を形成させる移動開始電圧が相違する同一色の２種類以上の粒子群として、主粒子群及び前記主粒子群よりも前記移動開始電圧が低い低電圧粒子群を混合して構成されてなり、
前記主粒子群と前記低電圧粒子群との混合比率は、５１：４９〜９９：１（質量％）であり、
前記移動開始電圧が相違する同一色の２種類以上の粒子群は、前記表面基板表面又は前記背面基板表面と前記粒子群との間に働く付着力が相違する２種類以上の粒子群であり、
前記付着力が相違する同一色の２種類以上の粒子群は、形状係数＝［（Ｌ2／Ｓ）／４］×π×１００（Ｌは粒子の周囲長、Ｓは粒子面積を表す）としたとき、１００≦形状係数≦１１０の前記主粒子群と、１２０≦形状係数≦１４０の前記低電圧粒子群とを混合して構成されてなることを特徴とする画像表示媒体。 A surface substrate having transparency;
A rear substrate disposed opposite to the front substrate;
A partition member that partitions the space between the front substrate and the rear substrate into a plurality of cells;
An image display medium comprising a group of positively or negatively charged particles enclosed in the plurality of cells and moving in the cells according to an applied electric field,
The positively or negatively charged particle group is composed of two or more types of particle groups of the same color having different movement start voltages that form the electric field at which the particle group starts to move, from the main particle group and the main particle group. Is composed of a mixture of low voltage particles having a low movement start voltage,
The mixing ratio of the main particle group and the low voltage particle group is 51:49 to 99: 1 (mass%),
The two or more types of particle groups of the same color having different movement start voltages are two or more types of particle groups having different adhesion forces acting between the surface substrate surface or the back substrate surface and the particle group,
Two or more particle groups of the same color having different adhesion forces have a shape factor = [(L 2 / S) / 4] × π × 100 (L represents the perimeter of the particle, and S represents the particle area). when, 100 ≦ shape coefficient ≦ 110 the main particle group, 120 ≦ shape factor ≦ 140 of the low-voltage images displayed medium characterized in that the particles are mixed formed by composed.
前記表面基板に対向配置された背面基板と、
前記表面基板と前記背面基板との空間を複数のセルに仕切る仕切り部材と、
前記複数のセル内に封入され、付与された電界に応じて前記セル内を移動する正又は負に帯電した粒子群とを備えた画像表示媒体であって、
前記正又は負に帯電した粒子群は、前記粒子群が移動を開始する前記電界を形成させる移動開始電圧が相違する同一色の２種類以上の粒子群として、主粒子群及び前記主粒子群よりも前記移動開始電圧が低い低電圧粒子群を混合して構成されてなり、
前記主粒子群と前記低電圧粒子群との混合比率は、５１：４９〜９９：１（質量％）であり、
前記移動開始電圧が相違する同一色の２種類以上の粒子群は、前記表面基板表面又は前記背面基板表面と前記粒子群との間に働く付着力が相違する２種類以上の粒子群であり、
前記付着力が相違する同一色の２種類以上の粒子群は、水との接触角がおよそ５５度から７５度である前記主粒子群と、前記主粒子群よりも前記移動開始電圧が低い、水との接触角がおよそ８０度から１５０度の前記低電圧粒子群とを混合して構成されてなることを特徴とする画像表示媒体。 A surface substrate having transparency;
A rear substrate disposed opposite to the front substrate;
A partition member that partitions the space between the front substrate and the rear substrate into a plurality of cells;
An image display medium comprising a group of positively or negatively charged particles enclosed in the plurality of cells and moving in the cells according to an applied electric field,
The positively or negatively charged particle group is composed of two or more types of particle groups of the same color having different movement start voltages that form the electric field at which the particle group starts to move, from the main particle group and the main particle group. Is composed of a mixture of low voltage particles having a low movement start voltage,
The mixing ratio of the main particle group and the low voltage particle group is 51:49 to 99: 1 (mass%),
The two or more types of particle groups of the same color having different movement start voltages are two or more types of particle groups having different adhesion forces acting between the surface substrate surface or the back substrate surface and the particle group,
Wherein two or more types of particle groups of the same color which adhesion is different from, and the main particles contact angle with water is 75 degrees approximately 55 degrees, the movement starting voltage is lower than the main particle group, contact angle images displayed medium you characterized by comprising constructed by mixing the approximately 80 degrees from 150 degrees the low voltage the particle group with water.
前記表面基板に対向配置された背面基板と、
前記表面基板と前記背面基板との空間を複数のセルに仕切る仕切り部材と、
前記複数のセル内に封入され、付与された電界に応じて前記セル内を移動する正又は負に帯電した粒子群とを備えた画像表示媒体であって、
前記正又は負に帯電した粒子群は、前記粒子群が移動を開始する前記電界を形成させる移動開始電圧が相違する同一色の２種類以上の粒子群として、主粒子群及び前記主粒子群よりも前記移動開始電圧が低い低電圧粒子群を混合して構成されてなり、
前記主粒子群と前記低電圧粒子群との混合比率は、５１：４９〜９９：１（質量％）であり、
前記移動開始電圧が相違する同一色の２種類以上の粒子群は、前記粒子群の平均電荷量が相違する２種類以上の粒子群であり、所定の平均電荷量を有する前記主粒子群と、前記主粒子群よりも前記移動開始電圧が低い、前記主粒子群の平均電荷量の１．３〜３．０倍の平均電荷量を有する前記低電圧粒子群とを混合して構成されてなることを特徴とする画像表示媒体。 A surface substrate having transparency;
A rear substrate disposed opposite to the front substrate;
A partition member that partitions the space between the front substrate and the rear substrate into a plurality of cells;
An image display medium comprising a group of positively or negatively charged particles enclosed in the plurality of cells and moving in the cells according to an applied electric field,
The positively or negatively charged particle group is composed of two or more types of particle groups of the same color having different movement start voltages that form the electric field at which the particle group starts to move, from the main particle group and the main particle group. Is composed of a mixture of low voltage particles having a low movement start voltage,
The mixing ratio of the main particle group and the low voltage particle group is 51:49 to 99: 1 (mass%),
Two or more types of particle groups of the same color having different movement start voltages are two or more types of particle groups having different average charge amounts of the particle groups, and the main particle group having a predetermined average charge amount, It is configured by mixing the low-voltage particle group having an average charge amount that is 1.3 to 3.0 times the average charge amount of the main particle group that has a lower movement start voltage than the main particle group. images display medium you wherein a.
前記画像表示媒体と一体又は別体に構成される、電圧が印加されることにより前記電界を付与する一対の電極と、
前記電圧を印加する電圧印加手段と、
前記一対の電極への前記電圧の印加を制御する制御手段とを備えたことを特徴とする画像表示装置。
The image display medium according to any one of claims 1 to 5 ,
A pair of electrodes configured to be integrated with or separate from the image display medium and applying the voltage to apply the electric field;
Voltage applying means for applying the voltage;
An image display device comprising: control means for controlling application of the voltage to the pair of electrodes.
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| JP5119674B2 (en) | 2006-02-14 | 2013-01-16 | 富士ゼロックス株式会社 | Image display medium, image display device, writing device, and image display program |
| JP5315962B2 (en) * | 2008-12-10 | 2013-10-16 | コニカミノルタ株式会社 | Display particles for image display device and image display device |
| JP5298920B2 (en) * | 2009-02-16 | 2013-09-25 | コニカミノルタ株式会社 | Display particles for image display device and image display device |
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| JP4613424B2 (en) * | 2000-02-04 | 2011-01-19 | 富士ゼロックス株式会社 | Image display device, image display medium, and image display control device |
| JP2003241229A (en) * | 2002-02-21 | 2003-08-27 | Minolta Co Ltd | Reversible image display medium and method of forming image |
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