CN102246094A - Bicolored particles having improved display performance - Google Patents

Bicolored particles having improved display performance Download PDF

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Publication number
CN102246094A
CN102246094A CN2009801516289A CN200980151628A CN102246094A CN 102246094 A CN102246094 A CN 102246094A CN 2009801516289 A CN2009801516289 A CN 2009801516289A CN 200980151628 A CN200980151628 A CN 200980151628A CN 102246094 A CN102246094 A CN 102246094A
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China
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double
colored particle
particle
colored
background color
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CN102246094B (en
Inventor
高桥孝德
泷泽容一
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Soken Kagaku KK
Soken Chemical and Engineering Co Ltd
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Soken Chemical and Engineering Co Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/17—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on variable-absorption elements not provided for in groups G02F1/015 - G02F1/169
    • G02F1/172—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on variable-absorption elements not provided for in groups G02F1/015 - G02F1/169 based on a suspension of orientable dipolar particles, e.g. suspended particles displays
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/165—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on translational movement of particles in a fluid under the influence of an applied field
    • G02F1/166—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on translational movement of particles in a fluid under the influence of an applied field characterised by the electro-optical or magneto-optical effect
    • G02F1/167—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on translational movement of particles in a fluid under the influence of an applied field characterised by the electro-optical or magneto-optical effect by electrophoresis
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/17—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on variable-absorption elements not provided for in groups G02F1/015 - G02F1/169
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/19—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on variable-reflection or variable-refraction elements not provided for in groups G02F1/015 - G02F1/169
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B2207/00—Coding scheme for general features or characteristics of optical elements and systems of subclass G02B, but not including elements and systems which would be classified in G02B6/00 and subgroups
    • G02B2207/113—Fluorescence
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B26/00—Optical devices or arrangements for the control of light using movable or deformable optical elements
    • G02B26/02—Optical devices or arrangements for the control of light using movable or deformable optical elements for controlling the intensity of light
    • G02B26/026—Optical devices or arrangements for the control of light using movable or deformable optical elements for controlling the intensity of light based on the rotation of particles under the influence of an external field, e.g. gyricons, twisting ball displays
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/165—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on translational movement of particles in a fluid under the influence of an applied field
    • G02F1/1675—Constructional details
    • G02F2001/1678—Constructional details characterised by the composition or particle type
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2203/00—Function characteristic
    • G02F2203/34—Colour display without the use of colour mosaic filters

Abstract

Disclosed are bicolored particles which exhibit excellent rotation performance when a voltage is applied thereto, in particular, particles having a color combination other than the combination of black and white, wherein high rotation performance can be achieved when a voltage is applied thereto. The bicolored particles are resin spherical particles, each having an appearance colored roughly half and half in two different colors. The bicolored particles are characterized in that one roughly hemisphere of each bicolored particle contains a conductive white pigment forming a ground color, and the other roughly hemisphere is colored in an arbitrary color other than the ground color.

Description

Improved the double-colored particle of display performance
Technical field
The present invention relates to double-colored particle and image display device.More specifically, the present invention relates to be suitable as the rotary-type image display device of particle display element double-colored particle and comprise this particle as the rotary-type image display device of the particle of display element.
Background technology
The display packing of image is varied.CRT (Braun tube), PDP (plasma display), LCD (LCD), FED (field-emitter display) are for example arranged.
CRT is by making the electron ray that is formed by the electronics convergence scan the display device that makes fluorescent material luminous to fluorescent material.PDP is a rare gas of enclosing high pressure in being clipped in two interelectrode zones with luminescent coating, and this rare gas is applied voltage and makes it produce the next luminous display device of ultraviolet ray.LCD is the light transmission liquid crystal that makes from backlight, polarized state of light is changed according to the orientation of liquid crystal carry out device shown.FED is released into electronics in the vacuum, makes the collision of electronics and fluorophor and makes its luminous display device.
Except that above-mentioned display device, the particle that will be divided into two kinds of colors in addition is configured in the insulating resin and makes this display packing of the rotary-type demonstration of particle of this double-colored particle rotation.In this display packing, make particle be scattered in light transmission supporting masses such as silicon rubber with free rotation mode with two or more color regions, clamp this light transmission supporting mass and apply voltage with electrode, the specific color region that makes all particles by this is towards same direction.The reason that realizes said method is the charged characteristic difference of each color region of particle.In addition, if make the proportion unanimity of each color region of particle, then the verticity of particle improves.In addition, by making the proportion unanimity, once applying particle behind the voltage towards be fixed as this towards, even cut off the power supply of the device that is used to apply voltage, this state also can continue (being referred to as memory characteristic).Therefore, the rotary-type demonstration of particle is an electrically good display packing of province.On the other hand, in this method, because the rotation of particle needs the time, so rotary-type demonstration is not suitable for for example showing the fast-changing display device of image that the display device of dynamic menu etc. shows.But because above-mentioned memory characteristic, the rotary-type demonstration of particle is suitable for still frames such as display text, picture, can expect its application in so-called electronic paper etc.
As the particle that uses in the rotary-type demonstration of this particle, various particles have been developed.For example, disclosed in the patent documentation 1 (the Jap.P. spy opens clear 64-42683 communique) and to have used the particle that by this material and pigment, dyestuff form of waxy substance as main material.
Disclosed in the patent documentation 2 (Japanese patent laid-open 11-352421 communique) with glass, titanium dioxide, zinc paste, zirconia, aluminium oxide etc. and formed the hemisphere of small ball of white, made the painted particle that gets of this hemisphere by sputtering method etc. with TiC etc. as material.
Disclosed the twin color ball that applies black material on the glass bead of titania and get being filled with in the patent documentation 3 (the Jap.P. spy opens the 2000-122103 communique).
Patent documentation 1: the Jap.P. spy opens clear 64-42683 communique
Patent documentation 2: Japanese patent laid-open 11-352421 communique
Patent documentation 3: the Jap.P. spy opens the 2000-122103 communique
The announcement of invention
But the particle that discloses in these patent documentations mainly is white/black double-colored particle, for the particle of in addition color combination, and the verticity of particle (rotational speed) deficiency when applying voltage, but it is agnogenio.
The object of the present invention is to provide the good double-colored particle of the verticity of particle when applying voltage, particularly in vain/high verticity when realizing applying voltage in the particle of color combination beyond the black color combination.
The inventor finds, hemispherical portion by a kind of color of the formation that makes double-colored particle (background color) contains the electric conductivity Chinese white, even in vain/high verticity in the time of also realizing applying voltage in the particle of color combination beyond the black color combination, thereby finished the present invention.
Promptly, double-colored particle of the present invention is the resinous double-colored particle that each spherical particle roughly is divided into two kinds of different colours in appearance, it is characterized in that, the approximate hemisphere of described double-colored particle contains the electric conductivity Chinese white, thereby the formation background color, the approximate hemisphere of all the other of described double-colored particle is coloured to the random color except that described background color.
The electric conductivity Chinese white for example can be made by with the conductive material that is selected from antimony oxide/tin ash, indium oxide/tin ash Chinese white being handled the method for giving electric conductivity.
The powder resistance rate that constitutes the electric conductivity Chinese white that mixes in the approximate hemisphere of background color of described double-colored particle is usually in the scope of 1～100 Ω cm.
Like this double-colored particle that specific inductive capacity is high and interhemispheric specific inductive capacity there are differences of the approximate hemisphere of background color apply voltage the time the verticity height.
The approximate hemisphere that is coloured to the random color except that described background color is for example by chromatic colour dyestuff or chromatic colour pigment coloring, and at this moment, the approximate hemispherical portion that is coloured to the random color except that described background color contains chromatic colour dyestuff or chromatic colour pigment.
Consider the rotation efficiency of particle, the mean grain size of described double-colored particle is represented usually in the scope of 30～200 μ m with volume reference.
In addition, double-colored particle of the present invention is suitable as the display element of the rotary-type image display device of particle.The rotary-type display device of particle of the present invention is by contain the rotary-type image display device of particle that the insulating resin of double-colored particle forms in the mode of freely rotating between pair of electrodes, it is characterized in that, described double-colored particle is the resinous double-colored particle that each spherical particle roughly is divided into two kinds of different colours in appearance, the approximate hemisphere of described double-colored particle contains the electric conductivity Chinese white, thereby formation background color, the approximate hemisphere of all the other of described double-colored particle is coloured to the random color except that described background color, by being applied to described interelectrode voltage, described double-colored particle rotates in described insulating resin.
In the rotary-type image display device of described particle, better be that described double-colored particle swims in the mode of freely rotating and soaks in the insulativity liquid that is contained in the described insulating resin.
In the rotary-type image display device of described particle, the voltage that is applied between described pair of electrodes better is in the scope of 50～300V.
By the present invention, the double-colored particle of the color combination beyond the good white/black color combination of the verticity of the particle when applying voltage good double-colored particle, particularly verticity can be provided, and comprise this double-colored particle as the rotary-type image display device of the particle of display element.
The simple declaration of accompanying drawing
Fig. 1 is that expression Jap.P. spy opens and is used to transfer first microchannel of painted external phase in the manufacture method of the double-colored particle of putting down in writing in the 2004-197083 communique and is used to make the synoptic diagram of second microchannel of double-colored particle and the figure that represents the formation of double-colored particle.
Fig. 2 is the synoptic diagram that expression Jap.P. spy opens the example of a kind of mode that forms painted external phase in the manufacture method of the double-colored particle of putting down in writing in the 2004-197083 communique.
Fig. 3 is the figure of a kind of mode of the expression Jap.P. spy manufacture method of opening the double-colored particle of putting down in writing in the 2004-197083 communique.
The best mode that carries out an invention
Below to double-colored particle of the present invention with comprise this double-colored particle and be elaborated as the rotary-type image display device of the particle of display element.
[double-colored particle of the present invention]
Double-colored particle of the present invention is the resinous double-colored particle that each spherical particle roughly is divided into two kinds of different colours in appearance.The approximate hemisphere of this double-colored particle contains the electric conductivity Chinese white, and the Chinese white that is the main body composition with this electric conductivity Chinese white constitutes background color.And the approximate hemisphere of all the other of this double-colored particle is coloured to the random color except that described background color.
That is, double-colored particle of the present invention is made of irritability zone and painted areas, and described irritability zone is half zone of a pact in the particle, contain the electric conductivity Chinese white, described painted areas is half zone of remaining pact, does not contain the electric conductivity composition, but contains coloured material.
Half the irritability zone of pact that forms a particle of double-colored particle of the present invention is formed by resin, this resin contain the powder resistance rate usually at 1～100 Ω cm, better be electric conductivity Chinese white in the scope of 1～30 Ω cm.Better be to be formed with cross-linked structure in this irritability zone.
In this irritability zone, the content of electric conductivity Chinese white with respect to general assembly (TW) 100 weight portions of electric conductivity Chinese white and resin usually at 1～10 weight portion, better be in the scope of 2～5 weight portions.By containing the electric conductivity Chinese white with this amount, half the zone of pact that accounts for double-colored particle demonstrates electric conductivity, and demonstrates high-k.
Irritability in this double-colored particle zone and the potential difference (PD) that contains between the painted areas of coloured material become the driving force that of the present invention double-colored particle that places between pair of electrodes and the voltage that puts on electrode are rotated accordingly.
The irritability zone of containing the electric conductivity Chinese white reflects the color of electric conductivity Chinese white usually and is white in color, but also can make it painted in the scope of the characteristic of not damaging this irritability zone.For example, if with irritability area coloring yellowly, then the background color of double-colored particle of the present invention is yellow.That is, in the double-colored particle of the present invention, decision accounts for approximately that the composition of the characteristic in the irritability zone of half is the electric conductivity Chinese white and since this electric conductivity Chinese white this as white, therefore the original background color of double-colored particle of the present invention be white.Therefore, also the background color of this double-colored particle can be adjusted into white or light color random color to dark color or black.Above-mentioned characteristic is can be by use the characteristic of the double-colored particle of the present invention that the electric conductivity Chinese white realizes in the irritability zone, and under the situations as conductive material such as conductive carbon black of using black, can't carry out the adjustment of background color by the stack of above-mentioned color.
In the double-colored particle of the invention described above, can freely carry out paintedly to the irritability zone, half the painted areas of remaining pact that therefore constitutes double-colored particle can suitably be selected according to the color in irritability zone.In general, painted by coming with the opposite color of the color in irritability zone or approximate with it color, form image and become distinct more.
Ratio about resin in the painted areas and coloured material, as long as the consumption of coloured material can make the color in irritability zone see through painted areas and appear, total amount 100 weight portions with respect to resin and coloured material, the consumption of coloured material in the scope of 1～70 weight portion, better is in the scope of 2～50 weight portions usually.
This painted areas is formed by resin and the coloured material that is dispersed or dissolved in this resin.Better be that this painted areas also similarly is formed with cross-linked structure with the irritability zone.
Of the present invention double-colored particle with said structure can be by the whole bag of tricks manufacturing, and the manufacture method of double-colored particle of the present invention can roughly be divided into three types usually.Particularly, can roughly be divided into microchannel method (for example opening the 2004-197083 communique), the method for dripping (for example opening the 2004-199022 communique) and comminuting method (for example opening the 2004-294628 communique) with reference to the Jap.P. spy with reference to the Jap.P. spy with reference to the Jap.P. spy.Below these methods are described.
(microchannel method)
This microchannel method is transferred the painted external phase 6 of dividing the two kinds of colors of coordinating as shown in Figure 1 in first microchannel 1, it is spued continuously or off and on successively to second microchannel 2 that mobile media flow is arranged.The insoluble relation that has O/W or W/O between described painted external phase and the described mobile medium becomes spherical particle 12 ' because of surface tension when therefore the painted external phase that spues flows in second microchannel.And, this painted external phase contains resin or monomer whose, resin or monomer whose are by being spued in painted external phase and being carried out UV irradiation and/or heating during spheroidizing and polymerizing curable, by this, can be made into the resinous double-colored particle that each spherical particle roughly is divided into two kinds of different colours in appearance.
＜painted external phase 〉
The described painted external phase branch two kinds of colors of coordinating, this two-phase all contains resin or painted material and other any compositions such as monomer whose, dyestuff or pigment.In the double-colored particle of the present invention, the phase (background color phase) that is approximate hemisphere that constitutes background color contains coloured material and electric conductivity Chinese white, and this electric conductivity Chinese white is used to give the approximate hemisphere of formation background color with electric conductivity.The phase that is approximate hemisphere (beyond the background color any form and aspect) that is coloured to random color except that background color contains any coloured material except that background color.Described background color any the form and aspect mutually and beyond the background color can obtain by the composition mixing that contains with them.
(resin or monomer whose)
As described resin, but exemplified by acrylic resinoid, styrene resin, vinyl resins, vinyl chloride resin, vinyl acetate esters resin etc. as described monomer, can exemplify the monomer that can form described resin.
The concrete example of described monomer is as described below.
As principal monomer used among the present invention, can exemplify (methyl) acrylic monomer, styrene monomer and vinyl monomer.
Example as described (methyl) acrylic monomer, can exemplify alkyl acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) acrylic acid cycloalkyl esters such as (methyl) cyclohexyl acrylate, the ester of (methyl) acrylic acid such as isobornyl acrylate and bicyclic alcohols, (methyl) acrylic acid aryl ester classes such as (methyl) phenyl acrylate, (methyl) benzyl acrylate.
As the example of described styrene monomer, can exemplify styrene, methyl styrene, dimethyl styrene, trimethylbenzene ethene, ethyl styrene, diethylbenzene ethene, triethylbenzene ethene, propylstyrene, butylstyrene, hexyl benzene ethene, heptyl benzene ethene, octyl group styrene, fluorobenzene ethene, chlorostyrene, bromstyrol, Dowspray 9,1-chloro-4-methyl-benzene, nitrostyrolene, acetylbenzene ethene, methoxy styrene, α-Jia Jibenyixi, vinyltoluene, sodium p styrene sulfonate.
As the example of described vinyl monomer, can exemplify vinyl acetate, propionate, vinyl propionate, isobutyric acid vinyl acetate, trimethylace tonitric vinyl acetate, vinyl caproate, tertiary ethylene carbonate, vinyl laurate, stearic acid vinyl ester, vinyl benzoate, p-tert-butyl benzoic acid vinyl acetate, vinyl salicylate.
As the example of other used among the present invention monomer, can exemplify vinylidene chloride, chlorohexane vinyl carboxylates, Beta-methyl acryloxy ethyl hydrogen phthalic ester, perfluoroethylene, perfluoropropene, vinylidene, vinyltrimethoxy silane, vinyltriethoxysilane.
In addition, in order to improve the dispersiveness of coloured material in monomer, perhaps in order to adjust the specific inductive capacity of each hemisphere that constitutes double-colored particle, can and with the monomer that has at least a functional group in the molecule, described functional group for example is carboxyl, amide group, amino, hydroxyl, epoxy radicals, itrile group.
Example as the monomer that has carboxyl in the molecule, can exemplify acrylic acid, methacrylic acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, maleic acid, fumaric acid, iso-crotonic acid, norbornene dicarboxylic acids, dicyclo [2 as unsaturated carboxylic acid, 2,1] hept-2-ene"-5,6-dicarboxylic acid etc.In addition, as their derivant, can exemplify maleic anhydride, itaconic anhydride, citraconic anhydride, tetrabydrophthalic anhydride, dicyclo [2,2,1] hept-2-ene"-5,6-dicarboxylic anhydride, carboxylic acid halides, these compounds also can exemplify the example for the monomer that has carboxyl in the molecule.
Example as the monomer that has amide group in the molecule, can exemplify acrylamide as the vinyl monomer of amide-containing, Methacrylamide, the N-methylol methacrylamide, N-methoxy ethyl Methacrylamide, N-butoxymethyl Methacrylamide, N, the N-DMAA, N, N-dimethylaminopropyl acrylamide, acrylamide analog derivative and (methyl) acrylic amides such as N-methylol (methyl) acrylamide and diacetone acrylamide such as N methacrylamide, the amino hexyl succinimide of 6-, 2-amino-ethyl succinimide.
As the example that has amino monomer in the molecule; can exemplify as (methyl) acrylic-amino ethyl ester that contains amino vinyl monomer; (methyl) acrylic acid propyl group amino ethyl ester; dimethylaminoethyl methacrylate; (methyl) acrylic-amino propyl ester; methacrylic acid phenyl amino ethyl ester; the alkyl esters derivant of acrylic or methacrylic acid such as methacrylic acid cyclohexyl amino ethyl ester; N-vinyl diethylamine; vinylamine analog derivatives such as N-acetyl group vinylamine; allylamine; the methyl-prop enamine; propylamine derivants such as N-methyl-prop enamine, aminobenzene vinyl such as p-aminophenyl ethene.
As the example of the monomer that has hydroxyl in the molecule, can exemplify the addition product of monoesters, lactone and (methyl) 2-Hydroxy ethyl acrylate of (methyl) 2-Hydroxy ethyl acrylate, (methyl) acrylic acid-2-hydroxy propyl ester, (methyl) acrylic acid and polypropylene glycol or polyglycol.
As the example of the monomer that has epoxy radicals in the molecule, can exemplify (methyl) glycidyl acrylate, the single ethylene oxidic ester and the 2-glycidyl ester of maleic acid, the single ethylene oxidic ester and the 2-glycidyl ester of fumaric acid, the single ethylene oxidic ester and the 2-glycidyl ester of crotonic acid, the single ethylene oxidic ester and the 2-glycidyl ester of tetrahydrophthalic acid, the single ethylene oxidic ester and the 2-glycidyl ester of itaconic acid, tricarboxylic single ethylene oxidic ester of butylene and 2-glycidyl ester, the single ethylene oxidic ester and the 2-glycidyl ester of citraconic acid, the single ethylene oxidic ester and the alkyl glycidyl ester of dicarboxylic acid such as single ethylene oxidic ester of allyl succinic acid and 2-glycidyl ester, alkyl glycidyl ester to the styrene carboxylic acid.
As the example of the monomer that has itrile group in the molecule, can exemplify vinyl cyanide, methacrylonitrile.
Among the present invention, can use a kind of above-mentioned monomer separately, perhaps also the multiple above-mentioned combination of monomers more than 2 kinds can be used.
Above-mentioned resin can obtain by making corresponding monomer polymerization.For example by being spued in described painted external phase and carry out UV irradiation and/or heating during spheroidizing, monomer or resin solidify spherical the time because of surface tension becomes, and become the resin cured matter with spherical-like morphology.
(electric conductivity Chinese white)
Described electric conductivity Chinese white for example obtains by with any conductive material that is selected from antimony oxide/tin ash, indium oxide/tin ash Chinese white being handled the method for giving electric conductivity, is used to give the approximate hemisphere of formation background color with electric conductivity.As described Chinese white, can exemplify for example titanium dioxide, zinc paste.
Here, handle and specifically to be meant the operation that is covered or floods as nuclear, with described conductive material with spherical Chinese white (for example titanium dioxide).Chinese white is under the situation of titanium dioxide, and titanium dioxide both can be that rutile-type also can be a Detitanium-ore-type.In addition, described lining or dipping are by carrying out Chinese white and conductive material with wet method or dry mixed.The electric conductivity Chinese white that obtains is as mentioned above also sold on market.For example also can use commercially available electric conductivity Chinese whites such as (the former industry of stone (the former industry of stone) Co., Ltd.'s systems) with trade name ET-500W.
Among the present invention, constituting the Chinese white of electric conductivity Chinese white and the amount of lining material or impregnated material can suitably set, the weight ratio of Chinese white and lining material or impregnated material (Chinese white: lining material or impregnated material) is set in 95: 5～70: 30 the scope usually, better is to be set in 90: 10～80: 20 the scope.By in above-mentioned scope, using lining material or impregnated material, can give Chinese white with good electrical conductivity.
The particle diameter of electric conductivity Chinese white is generally 0.10～5 μ m, is preferably 0.10～0.5 μ m.
The powder resistance rate of electric conductivity Chinese white is generally 1～100 Ω cm, is preferably 1～30 Ω cm.
Among the present invention, also above-mentioned electric conductivity Chinese white can be mixed use with the Chinese white of handling without electric conductivity.
(coloured material)
As described coloured material, can exemplify netrual colour dyestuff, netrual colour pigment, chromatic colour dyestuff, chromatic colour pigment.
Particularly can exemplify: black ... Olesolol Fast Black, BONJET BLACK CW-1, Solvent Black 27 contain 5% Cr (3 valency), pigment black (Pigment Black) 7;
Water colour, redness ... VALIFAST RED 3306, Olesolol Fast RED BL, Solvent RED 8 contain 5.8% Cr (3 valency), Permanent Carmain FBB02-JP;
Blue ... Kayaset Blue, Solvent Blue 35, cyanines indigo plant (Cyanine Blue);
Yellow ... VALIFAST YELLOW 4120, Oil Yellow 129, Solvent Yellow 16, Solvent Yellow 33, Disperse Yellow 54, PV Fast Yellow H2G;
Lemon yellow ... Piast Yellow 8005;
Green ... Oil Green 502, Opias Green 502, Solvent Green 3,
Magenta ... VALIFAST PINK 2310N, Plast RED D-54, Plast RED 8355, Plast RED 8360, Plast Vioiet 8850, Disperse Violet 28, Solvent RED 149, Solvent RED 49, Solvent RED 52, Solvent RED 218 contain 4% Cr (3 valency);
Cyan ... VALIFAST BLUE 2610, VALIFAST BLUE 2606, Oil BLUE 650, Plast BLUE 8580, Plast BLUE 8540, Oil BLUE 5511, Solvent Blue 70 contain 4%Cu;
Orange ... Oil Orange 201, VALIFAST ORANGE 3210, Solvent Orange 70, Kayaset Orange G;
Brown ... VALIFAST BROWN 2402, Solvent Yellow 116, Kayaset Flavine FG etc.
In addition, as the example of coloured material, for example can exemplify also that solvent blue, solvent red, solvent orange, solvent are green, Lumogen F Orange etc.
In addition, as described coloured material, also can exemplify for example curare bases; the perylene class, dicyano is vinyl-based, the azo class, the quinophthalone class, amino pyrazoles, the methine class, the dicyano imidazole class, the indoaniline class, the dyestuff of using always in the note taking liquid such as phthalocyanines, as the leuco dye of electrothermal sensitive recording paper or temperature sensitive coloured material, and rhodamine B stearate (red No. 215), tetrachloro-tetrabromfluorescein's (red No. 218), eosin (red No. 223), soudan III (red No. 225), dibromofluorescein (orange No. 201), diiodofluorescein (orange No. 206), fluorescein (yellow No. 201), quinoline yellow SS (yellow No. 204), the green SS of quinizarin (green No. 202), the purple SS (No. 201, purple) of zaurine, medicinal scarlet red (red No. 501), oil red XO (red No. 505), orange SS (orange No. 403), yellow AB (yellow No. 404), yellow OB (yellow No. 405), the tar class dyestuff that the blue B of the Sudan (blue No. 403) etc. uses in cosmetics.
These dyestuffs can use separately or mix more than 2 kinds and use; As the example of coloured material, also can exemplify various direct dyess, acid dyes, basic-dyeable fibre, azo dyes, chemically-reactive dyes, fluorescent dye and fluorescer as required, they can also be dispersed in described (methyl) acrylic monomer.
For example also can use permanent yellow DHG, Lionol Yellow 1212B, Si Mule fast yellow (Symuler Fast Yellow) 4400, pigment Yellow 12 as yellow uitramarine;
Paratonere 57:1, Lionol Red 6B-4290G, Irgalite Rubine 4BL, Fastogen SuperMagenta RH as magenta pigment;
Lionol Blue 7027, Fastogen Blue BB, Cromophtal Blue 4GNP as green pigment;
Carbon black, Black Pearls 430, iron oxide red, ultramarine as black pigment;
As various inorganic pigments such as the titanium white that does not have electric conductivity of Chinese white, zinc sulphide, zinc paste, alumina white, lime carbonate and organic pigment etc.
Among the present invention, constitute the phase (background color phase) that is approximate hemisphere of background color and be coloured to total amount that being of random color except that background color be similar to coloured material contained in (background color any form and aspect in addition) mutually of hemisphere and be generally 0.1～50 weight portion, be preferably 2～40 weight portions with respect to each the described resin in mutually and total amount 100 weight portions of monomer whose.When representing, be preferably 1～20% with volume fraction.
(polymerization initiator)
Among the present invention, better be make background color mutually and background color any form and aspect in addition contain polymerization initiator.
Particularly, described polymerization initiator is used to make to be polymerized and is the easier polyreaction that begins of the described monomer of resin, better is to make painted external phase contain polymerization initiator among the present invention.
As polymerization initiator, can exemplify for example persulfate such as potassium persulfate, ammonium persulfate, superoxide such as benzoyl peroxide, lauroyl peroxide, azo-compounds such as azoisobutyronitrile etc.The polymerization initiator that preferably uses during as painted or polymerization, can exemplify for example as 2 of azo class polymerization initiator, 2 '-azo two (2-methyl propionitrile), 2,2 '-azo two (2-methylbutyronitrile), 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (2-cyclopropyl propionitrile), 1,1 '-azo two (cyclohexane-1-formonitrile HCN), 2, two (2 Methylpropionic acid) dimethyl esters of 2 '-azo.
It is 0.01～5 weight portion that the consumption of these polymerization initiators is generally with respect to the described monomer of per 100 weight portions, better is 0.5～2 weight portion.
As other polymerization initiator, for example can exemplify existing known acetophenone class as Photoepolymerizationinitiater initiater, acetophenone, 2 for example, 2-diethoxy acetophenone, to dimethylamino acetyl benzene, *-methoxy acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2-hydroxyl-2-cyclohexyl acetophenone;
Ketone, for example benzophenone, 2-chloro benzophenone, p, p '-two chloro benzophenone, p, p '-two (diethylamino) benzophenone, N, N '-tetramethyl-4,4 '-diamido benzophenone (Michler's keton), 4-(2-hydroxyl-oxethyl) phenyl (2-hydroxyl-2-propyl group) ketone;
Benzoin ethers, for example benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether, benzil dimethyl ketal, benzoylbenzoic acid ester, α-acyl group oxime ester, thioxanthene ketone.
As thermal decomposition type polymerization initiator, can exemplify for example peroxyesters, organic peroxide class, organic hydroperoxide class, organic peroxy ketal class and azo-compound class.
As described peroxyesters, can exemplify for example own ester of peroxide neopentanoic acid uncle, the peroxide neodecanoic acid tert-butyl ester, t-butyl peroxybenzoate, the peroxidating-own ester of 2 ethyl hexanoic acid uncle, the own ester of peroxide neodecanoic acid, peroxide neodecanoic acid cumyl ester, peroxidating-2 ethyl hexanoic acid-1,1,3,3-tetramethyl butyl ester.
As described organic peroxide class, can exemplify for example dicumyl peroxide, di-t-butyl peroxide, tert-butyl peroxide cumyl, dilauroyl peroxide, dibenzoyl peroxide, diacetyl peroxide, didecanoyl peroxide, peroxidating two different nonanoyls, peroxidating-2-methyl valeryl.
As described organic hydroperoxide class, can exemplify for example t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethyl-2,5-two hydroperoxy hexanes, p-methane hydroperoxide, di-isopropylbenzene hydroperoxide.
As described organic peroxy ketal class, for example can exemplify 1, two (the uncle's hexyl peroxies)-3,3 of 1-, 5-trimethyl-cyclohexane, 1, two (the uncle's hexyl peroxy) cyclohexanes, 1 of 1-, 1-bis(t-butylperoxy)-3,3,5-trimethyl-cyclohexane.
As described azo-compound class, for example can exemplify 2,2 '-azoisobutyronitrile, 2,2 '-azo two-(2, the 4-methyl pentane nitrile), 2,2 '-azo two (cyclohexanenitriles), 1,1 '-azo two (cyclohexane-1-formonitrile HCN), 2-phenylazos-4-methoxyl-2,4-methyl pentane nitrile, 2,2 '-azo-bis-iso-dimethyl.
These polymerization initiators can use a kind separately, also can be used in combination more than 2 kinds.
(multi-functional monomer)
Among the present invention, can be mutually and mix multi-functional monomer more than two senses in background color any form and aspect in addition at background color, make used principal monomer or other monomer reaction in itself and the invention described above.
Example as the multi-functional monomer more than described two senses, can exemplify diacrylate class, triacrylate class, the tetraacrylate class of (gathering) aklylene glycol, perhaps (gather) dimethylacrylate class, trimethyl acrylic ester class, the tetramethyl esters of acrylic acid of aklylene glycol.
As their example, can exemplify ethylene glycol bisthioglycolate (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, diethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, 1,1,1-trihydroxy methyl ethane diacrylate, 1,1,1-trihydroxy methyl ethane triacrylate, 1,1,1-trihydroxy methyl propane triacrylate, N hydroxymethyl acrylamide, 1,9-nonanediol diacrylate, 2-butyl-2-ethyl-1, the ammediol diacrylate.
The above multi-functional monomer of described two senses is used for introducing cross-linked structure at described resin.Cross-linked structure is not essential, but has cross-linked structure by double-colored particle, in the rotary-type image display device of following particle of the present invention, even the insulativity liquid of silicone oil and so on contacts with double-colored particle of the present invention, double-colored particle of the present invention can not make in the double-colored insulativity liquid that swims in the insulative resin because of insulativity liquid swelling particle-stabilisedly yet.
The consumption of this multi-functional monomer is generally 10～90 weight portions in monomer 100 weight portions that will become described resin.In addition,, also can only use multi-functional monomer, make its polymerization and form cross-linked structure about multi-functional monomer, with multi-functional polymer of monomers as the resin in the double-colored particle of the present invention.
(other any composition)
As other contained any composition in the described painted external phase (being any form and aspect of background color mutually and beyond the background color), can exemplify UV sensitizer, charged controlling agent, pigment dispersing agent, thermal stabilizer, conductive agent, antiseptic, surface tension adjustment agent, defoamer, rust preventive, antioxidant, near infrared absorbent, ultraviolet light absorber, fluorescer, fluorescer etc.
Described UV sensitizer is the composition that uses for the effect of having given play to described Photoepolymerizationinitiater initiater better, as its example, can exemplify n-butylamine, triethylamine, tri-n-butyl phosphine etc.
The purposes of described charged controlling agent is as follows: contain this charged controlling agent by making described background color any the form and aspect mutually and/or beyond the background color, the charged characteristic of each approximate hemisphere of the double-colored particle of scalable gained, the verticity of the double-colored particle when raising applies voltage.Here, as the example of charged controlling agent, can exemplify slaine, copper phthalocyanine sulfonamide, hydrocarbon black, metal naphthenate, 4-hydroxyl naphthalene-quaternary ammonium salts such as 1-sulfonic acid benzyl tributyl ammonium of the simple substance of styrene acrylic base polymer, Calixarene Derivatives, hindered amine, azines, salicylic acid metal complex, phenolic condensate, lecithin, paramagenta, nigrosine class dyestuff, alkoxylated amines, alkylamide, phosphorus and tungsten and compound, molybdic acid chelate pigment, fluorine class activator, hydrophobic silica, monoazo dyes etc.But charged controlling agent is the double as coloured material also, but the also charged controlling agent of double as of coloured material.
The consumption of charged controlling agent is generally 0.05～5 weight portion with respect to monomer 100 weight portions that will become described resin, is preferably 0.5～2 weight portion.
＜mobile medium 〉
In the method for microchannel used mobile medium as mentioned above, be and described painted external phase between have the medium of the relation of O/W or W/O.In other words, mobile medium is a medium as described below: itself does not dissolve painted external phase, and painted external phase is spherical, and therefore painted external phase can distortion freely in this flowability medium.
As mobile medium, can exemplify the polyvinyl alcohol water solution, carboxymethyl cellulose aqueous solution, the Carboxymethyl Cellulose aqueous solution that for example make polyvinyl alcohol (PVA) be dissolved in ion exchange water and get.Because painted external phase mostly is the phase (O phase) of oiliness greatly, so as mobile medium, the phase (W phase) of preferred water-based.
The manufacture method of＜double-colored particle 〉
In the microchannel method as an example of the method that forms double-colored particle of the present invention, as shown in Figure 1, in first microchannel 1, transfer the painted external phase 6 of dividing the two kinds of colors of coordinating, it is spued continuously or off and on successively to second microchannel 2 that mobile media flow is arranged.There is insoluble relation between described painted external phase and the described mobile medium, promptly forms O/W or W/O state and exist.When flowing, the painted external phase that therefore, spues becomes spherical particle 12 ' because of surface tension in second microchannel.And, this painted external phase contains resin or monomer whose, resin or monomer whose are by being spued in painted external phase and being carried out UV irradiation and/or heating during spheroidizing and polymerizing curable, by this, usually can form the solidfied material of resin, thereby generate the double-colored particle that each spherical particle roughly is divided into two kinds of different colours in appearance.
In this method, the microchannel is superfine, its flow path width is that the viscosity of the fluid of Liu Donging (painted external phase) is occupied an leading position therein, so the tendency that becomes laminar condition at Reynolds number under the condition below 1000 is arranged under the situation about hundreds of micron.Two kinds of colors divide the painted external phase of the two kinds of colors of coordinating that the tendency of transferring with the STATIC CORRECTION USING APPROXIMATE LAYER stream mode is arranged too even painted external phase branch coordinates, and therefore, can be used as external phase handover easily in first microchannel that two kinds of colors can not mix.
Speed when painted external phase is transferred in first microchannel depends on viscosity, surface tension, density, fluidity (polar group) of painted external phase etc., usually can be with the flow velocity of flow F1=0.01～10ml/hr, better be that the flow velocity of 0.01～5ml/hr is suitably transferred or spued to second microchannel.
In addition, the flow F2 ml/hr of the mobile medium that flows in second microchannel is as long as when the painted external phase that is spuing flows in the scope of spheroidizing, be not particularly limited, be generally the flow velocity of flow F2=1～100ml/hr, better be the flow velocity of 1～50ml/hr.
The throughput ratio of representing with F2/F1 can be considered fluidity such as the fluid viscosity, density, surface tension of growing amount, mean grain size and particle monodispersity, painted external phase and the mobile medium of the double-colored particle that desire is made and suitably set.
The painted external phase to second microchannel of spuing is spuing under branch coordinates the state of two kinds of colors, is disperseing, spherical particleization takes place in the handover process, and resin in this painted external phase that spues or monomer whose are by UV irradiation and/or heating and polymerizing curable.Because the spherical shape of the painted external phase that spues after the spheroidizing is stable, so in this polymerizing curable, even painted external phase is complete polymerizing curable in the process of flowing in this second microchannel not, also can in other container of the double-colored particle accumulator tank of conduct be arranged at the second microchannel system outside, suitably carry out polymerizing curable under the UV irradiation and/or under heating.
Exposure during irradiation UV is generally 300～1500mJ/cm 2, the heating-up temperature during heating is generally 60～100 ℃ temperature, and be 20～120 minutes heat time heating time.
In order in first microchannel 1, to transfer the painted external phase 6 of double-colored phase [6a/6b], for example double-colored phase [6a/6b] is supplied to the flow of liquid inbound port of first microchannel in the mode shown in Fig. 2 (a).Shown in Fig. 2 (a), the flow of liquid inbound port place in first microchannel 1 makes the 3rd microchannel 3 and the 4th microchannel 4 engage in the mode that forms the V font.By the 3rd microchannel and the 4th microchannel in first microchannel 1, supply with background color mutually with background color beyond any form and aspect 6a and 6b, the painted external phase 6 of the double-colored phase of formation [6a/6b] first microchannel 1 in.In the mode shown in this Fig. 2 (a), form the 3rd microchannel 3 of V font and the 4th microchannel 4 and better be arranged to first microchannel 1 in the same plane.In addition, angle theta 5=90 ± 80 of the formation V font at place, this junction ° better are angle theta 5=90 ± 60 °.
In addition, also can the coordinate painted external phase of two kinds of colors of branch be supplied to first microchannel in the mode shown in Fig. 2 (b).In the mode shown in Fig. 2 (b), for example engage the 3rd microchannel 8, make angle (or angular aperture) θ 6 with the transfer direction of form and aspect 6b in the scope of acute angle at the position midway of first microchannel 1 of transferring form and aspect 6b.And, by supplying with form and aspect 6a, can in first microchannel 1, form the painted external phase 6 of double-colored phase [6a/6b] by the 3rd microchannel 8.
Double-colored particle of the present invention can also be made in mode shown in Figure 3.The flow of liquid inbound port of second microchannel 2 of the flow of liquid outbound port of first microchannel 1 and tubular engages along coaxial rectilinear direction each other, and in described second microchannel 2, mobile medium 7 is mobile with the flow F of the regulation represented with unit/ml/hr.
Both sides near the same plane this connecting portion, two sides microchannel 5a, 5b engage with second microchannel 2 along the transfer direction of the painted external phase 6 in first microchannel, and its angle theta 3 and θ 4 are respectively in 45 ± 5～40 ° scope.
As shown in Figure 3, the painted external phase 6 of the double-colored phase of transferring in first microchannel 1 [6a/6b] is located to be nipped off taking-up by the mobile medium of being supplied with by two sides microchannel 5a, 5b 7 and spue to second microchannel 2 at this front port as first microchannel 1 of junction (or connecting portion) (flow of liquid outbound port), thereby forms the spheroidizing thing 12 ' of painted external phase 6.
Angle theta 3 that microchannel, two sides is become with first microchannel and θ 4 better are θ 3=θ 4, and in addition, in above-mentioned Fig. 3, this angle theta 3 and θ 4 are interior acute angles of scope of 45 ± 5～40 °.Though not shown, also this angle theta 3 and θ 4 can be made as right angle or obtuse angle more than 90 °.
As the shape of the vertical incision of above-mentioned first microchannel～the 3rd microchannel and microchannel, side, can exemplify for example circular, ellipse and quadrilateral (square, rectangle, trapezoidal).The angle of the microfabrication when forming the microchannel of above-mentioned shape with starting material such as glass plate, plastic plate for example is as the shape of the vertical incision of microchannel, preferred quadrilateral (square, rectangle).The otch of these microchannels is under the situation of rectangle (or rectangle), and the long limit that better is this otch is in the scope of 0.5～500 μ m, and the minor face of this otch is in the scope of 0.5～500 μ m.The lower limit that is more preferably the length on each limit is 1 μ m.
(sessile drop method)
In the sessile drop method, second drop of any form and aspect beyond making first drop that is background color and having background color contacts in air or in the liquid and forms a drop, it is contacted and moment solidifies with reactant liquor, thereby makes double-colored particle of the present invention.
As making described first drop and the painted coloured material of second drop, can use with described microchannel method in the used identical coloured material of coloured material.In the sessile drop method, in the method for microchannel the used composition, also can use 1, amines such as 6-hexane diamine, sodium alginate, sodium carboxymethyl cellulose, polyvinyl alcohol (PVA) be as the composition that contains of described first drop and second drop, their can and the reaction of described reactant liquor.In addition, first drop contains the electric conductivity Chinese white.As described first drop and second drop contain composition arbitrarily, also can mix charge control agent or charged controlling agent.
＜the method for formation drop in air or in the liquid 〉
At first, the method that forms drop in air is described.Described first drop and second drop can be by being formed with for example spray nozzle, inkjet nozzle ejection by the liquid (first liquid and second liquid) that composition forms that contains separately.
Then, the method that forms drop in liquid is described.Described first drop and second drop can form to the liquid that does not dissolve first liquid and second liquid by first liquid and second liquid are spued.For example, first liquid and second liquid are under the situation of hydrophilic liquid, they can be spued to the non-hydrophilic solvent of for example wet goods.
＜reactant liquor 〉
As described reactant liquor, can exemplify for example acid such as multivalent cations such as isocyanates such as acyl chlorides, TDI, lime chloride, borax, hydrochloric acid such as sebacoyl chloride.They can suitably be selected according to the composition of formed first drop and second drop.
The manufacture method of＜double-colored particle 〉
As mentioned above, for example contact in air with second drop and form a drop by first drop made from inkjet nozzle ejection.As long as prepare described reactant liquor in the position of this droplets fall, drop just can contact and instantaneous solidification with reactant liquor.Make double-colored particle of the present invention thus.
(comminuting method)
In the comminuting method, the layer that will form by thermoplastic resin background color composition (A) and form duplexer (C) by the thermoplastic resin coloured composition (B) that is coloured to the random color beyond the background color, by with the direction of lamination surface approximate vertical on the impact of point-like this duplexer (C) pulverized obtained crushing piece, to this crushing piece heating, thereby make double-colored particle of the present invention.In the comminuting method, because described crushing piece need be deformed into sphere by heating, so must be thermoplastic resin as the resin of the resin that constitutes double-colored particle.
Thermoplastic resin as using in described thermoplastic resin background color composition (A) and the described thermoplastic resin coloured composition (B) can use known thermoplastic natural resin or synthetic resin.
Particularly, can use for example pentaerythritol ester, the dammar natural resins such as (dammar) of rosin, rosin, the acrylic monomer polymerization that can in the method for described microchannel, use or copolymerization and synthetic resin such as acrylic resin, styrene-(methyl) acrylate copolymer, styrene-(methyl) acrylic copolymer, polystyrene, maleic acid resin, Polyvinylchloride, polyester, thermoplastic polyurethane.
Above-mentioned resene can use separately or mix more than 2 kinds and use.But, in the comminuting method, make to pulverize behind the duplexer that forms by described thermoplastic resin and make its panelization, make its particlized by heating then, so preferably have the flexibility that is adapted to crush force and glass temperature at the resin more than 60 ℃.
The manufacture method of＜duplexer (C) 〉
Method as making duplexer (C) can exemplify for example following method.
(1) after coating on the matrix contained the coating (A1) of thermoplastic resin background color composition (A) and makes its drying, stacked coating contained the coating (B1) of thermoplastic resin coloured composition (B), the stacked rubbing method that peel off from matrix dry back.
(2) after being sprayed at coating (A1) on the matrix and making its drying, spray coatings (B1), the method that peel off from matrix dry back.
(3) method that will extend with warm-up mill etc. by thermoplastic resin background color composition (A) and the overlapping plate object that forms of thermoplastic resin coloured composition (B) or ingot.
Need solvent in these methods,, can exemplify alcohols, ester class, ketone, dibasic alcohol ethers, binary alcohol esters class and diatomic alcohol ether acid ester class etc. as solvent.
The manufacture method of＜double-colored particle 〉
In the comminuting method, by with the direction of lamination surface approximate vertical on the impact of point-like described duplexer (C) pulverized obtained crushing piece, to this crushing piece heating.
The impact of described point-like applies with impact, this impact has the shape that for example needle-like or taper etc. can apply bump to the narrow and small area of point-like, and the material that can be applied the bump of the above size of the breakdown strength of duplexer (C) by for example steel or stainless steel etc. is made.
Described approximate vertical direction particularly is vertical direction ± 15 °.
Utilize the described son that impacts duplexer (C) to be applied the impact of the point-like on the direction with the lamination surface approximate vertical and it is pulverized, to the crushing piece heating of gained.More specifically, it is above and make its fusion to utilize hot blast etc. that crushing piece is heated to the fusing initial temperature of the higher thermoplastic resin of fusing initial temperature in the thermoplastic resin contained in thermoplastic resin background color composition (A) or the thermoplastic resin coloured composition (B).Crushing piece is just spherical because of the surface tension sphere of thermoplastic resin changes into, and the crushing piece after the spheroidizing is cooled off, thereby obtained double-colored particle.
(double-colored particle of the present invention)
The of the present invention double-colored particle of making by for example said method is formed by resin, each spherical particle roughly is divided into two kinds of different colours in appearance, the approximate hemisphere of this double-colored particle contains the electric conductivity Chinese white, thereby the formation background color, the approximate hemisphere of all the other of this double-colored particle is coloured to the random color except that described background color.
As mentioned above, in the double-colored particle of the present invention, the specific inductive capacity of the approximate hemisphere of its background color has very big-difference with the specific inductive capacity that is coloured to the approximate hemisphere of the random color except that background color, and therefore the charged characteristic of above-mentioned each approximate hemisphere has very big-difference.Therefore, double-colored particle of the present invention apply voltage the time the verticity of particle good, particularly also can realize high verticity for the double-colored particle of the color combination beyond the white/black color combination of existing verticity deficiency.
The mean grain size of double-colored particle of the present invention is represented common in the scope of 30～200 μ m with volume reference, better be in the scope of 70～150 μ m.The double-colored particle of mean grain size in this scope rotates when applying voltage easily.The deviation of particle diameter usually below 20%, better is below 5% with uniformity coefficient Cv value representation, is more preferably below 3%.
Described mean grain size can as described belowly be adjusted.
Adopt under the situation of microchannel method, by the restriction of the quantitative limitation that spues, nozzle, the restriction of resin viscosity etc., the mean grain size of the double-colored particle of gained reduces.
Adopt under the situation of sessile drop method, for example make under the situation of first drop and second drop with ejection such as spray nozzle, by reducing the aperture of nozzle, the particle diameter of two kinds of drops reduces, so consequently, the particle diameter of double-colored particle also reduces.In the sessile drop method, with the sodium alginate of reactant liquor reaction etc. to be dissolved in solvent the form of solution use, therefore described first drop and second drop also comprise solvent.If make double-colored particle and dry, then described solvent evaporation, littler before the particle diameter ratio solvent evaporation.Therefore, by the concentration of the composition beyond the solvent of regulating first drop and second drop, can adjust the mean grain size of double-colored particle.
Adopt under the situation of comminuting method, impact of the impact by will applying point-like is made by pin and is tied up pencil thing that forms and the density of adjusting pin, the size of the double-colored particle of may command gained.That is, change the density of pin and after obtaining double-colored particle, measure its particle diameter, can determine to obtain efficiently the density of the pin of required particle diameter by this.The relation of the density of particle diameter and pin is subjected to utilizing the influence of the size of impacting the sub crushing piece that cracks.
[the rotary-type image display device of particle]
As mentioned above, double-colored particle of the present invention apply voltage the time verticity good, therefore be suitable as the display element of the rotary-type image display device of particle.
Comprising double-colored particle of the present invention is by contain the rotary-type image display device of particle that the insulating resin of double-colored particle forms in the mode of freely rotating between pair of electrodes as the rotary-type display device of the particle of display element, it constitutes: described double-colored particle is the resinous double-colored particle that each spherical particle roughly is divided into two kinds of different colours in appearance, the approximate hemisphere of described double-colored particle contains the electric conductivity Chinese white, thereby formation background color, the approximate hemisphere of all the other of described double-colored particle is coloured to the random color except that described background color, by being applied to described interelectrode voltage, described double-colored particle rotates in described insulating resin.
The rotary-type image display device of particle of the present invention is generally chip shape, can be via following operation manufacturing.
(1) preparation is dispersed with the operation of the compositions of thermosetting resin of double-colored particle of the present invention;
(2) make its heat curing after this compositions of thermosetting resin is coated base material, thereby make the operation of the insulativity transparent resin sheet material that is dispersed with described double-colored particle;
(3) make this sheet material swelling in the insulativity liquid by this insulation transparent resin sheet be impregnated in, the mode that encases with the double-colored particle that will be dispersed in inside forms the vacuole of insulativity liquid, thereby makes the operation of the display member that is formed with described vacuole;
(4) in the operation of the two sides of this display member multilayer electrode member.
As the thermoset resin that uses in the compositions of thermosetting resin in the operation (1), so long as insulativity and all good resin of the transparency get final product, be not particularly limited, can preferably use and make the two-solution curing type organic siliconresin that has flexibility when showing sheet material.Below, describe as the rotary-type image display device of the particle of thermoset resin using the two-solution curing type organic siliconresin.
Compositions of thermosetting resin acquisition as described below: according to the containing ratio of double-colored particle of the present invention is that the condition of 40～60 volume % is mixed the two-solution curing type organic siliconresin with it, mixes with stirring machine then.If the containing ratio of this double-colored particle is less than 40 volume %, the covering property deficiency of the demonstration sheet material of gained then, the display characteristic of image display device worsens sometimes.On the other hand, if more than 60 volume %, amount of resin deficiency then, thereby when making sheet material, be difficult to sometimes compositions of thermosetting resin is coated base material equably.
Described compositions of thermosetting resin can be coated base material by known customary way.The viscosity of this compositions of thermosetting resin is usually up to 5000～10000mPas, as the coating process that is suitable for said composition, for example can exemplify lithographic plate coating machines such as the coating of ring rod (ワ イ ヤ バ Yi Tu worker), spreader coating, rotary coating, in addition also can exemplify knife type coater, comma doctor knife coater, mould and be coated with continous way coating machines such as machine, lip coating machine etc.
About used base material this moment, as long as normal use the under can the temperature as the curing of the thermoset resin of subsequent handling the time is not particularly limited the polyethylene terephthalate of preferred intensity and excellent size stability (PET).
The coating thickness of compositions of thermosetting resin better is 2～4 times of the mean grain size of representing with volume reference of double-colored particle of the present invention.If less than 2 times, then not only can be when coating substrate former thereby be easy to generate crawling because of oversize grain etc., and also the covering property of the demonstration sheet material of gained may be not enough.Otherwise if greater than 4 times, then double-colored particle is arranged in multilayer along thickness direction, thereby shows that the reflectivity of sheet material descends, and display quality may worsen.
The filming heating of described compositions of thermosetting resin made its curing.Solidify better is to carry out under high as far as possible temperature in the scope of glass temperature of thermoplastic resin used in being no more than double-colored particle.
The thermosetting paint film of described compositions of thermosetting resin is peeled off from base material, obtained being dispersed with the insulativity transparent resin sheet material of double-colored particle of the present invention.Be dispersed in this insulativity transparent resin sheet material double-colored particle with solidify after the matrix resin driving fit, can not rotate even therefore apply electric field yet.So, this insulativity transparent resin sheet material be impregnated in the insulativity liquid, make the solidfied material swelling of described compositions of thermosetting resin, can form around the double-colored particle vacuole of this insulativity liquid abrim by this.
Employed insulativity liquid must be able to make the thermoset resin swelling after the curing, and can not make any dissolving or swelling in the resin that uses in the induction region of double-colored particle of the present invention and the painted areas.As such insulativity liquid, can exemplify silicone oil, high-grade aliphatic ester, polyene hydrocarbyl ether, isoalkane, fluorinated polyether as an example.
Thermoset resin is under the situation of described organic siliconresin, and what can be preferably used as insulativity liquid is silicone oil.Because the compatibility of silicone oil and organic siliconresin is good, so, can not make any resin dissolves or the swelling used in described irritability zone and the painted areas though can make organic siliconresin solidfied material swelling.
As silicone oil, can use for example methyl phenyl silicone, dimethyl polysiloxane etc.The viscosity of silicone oil under 25 ℃ better is below 100mPas.If viscosity is higher than 100mPas, the rotation difficulty of the double-colored particle in the vacuole then, the response speed of demonstration may descend.If improve electric field intensity, the tendency of problems such as power consumption increase required when producing image switching etc. is arranged then in order to remedy this deficiency.The proportion that the proportion of silicone oil is preferably close with the proportion of double-colored particle.
Condition when impregnated in the insulativity transparent resin sheet material that is dispersed with double-colored particle in the insulativity liquid depends on the kind of employed thermoset resin and insulativity liquid, the state of cure of thermoset resin.Above-mentioned thermoset resin is the two-solution curing type organic siliconresin, and insulativity liquid is under the situation of silicone oil, and at room temperature the dipping by 10～24 hours forms vacuole usually.This time can shorten by improving the temperature that insulativity transparent resin sheet material be impregnated in the insulativity liquid as much as possible, but in the scope of the glass temperature of the resin that must in not being higher than double-colored particle, use.
Then, at the two sides of the sheet display member that obtains by said method multilayer electrode layer, thereby obtain the rotary-type image display device of particle of the present invention.For this reason, as long as the stacked one side at base material as substrate is provided with the pellet electrode member of electrode layer on the two sides of this sheet display member, for example simultaneously be provided with the plastic sheeting of electrode layer.At this moment, may not make the face driving fit of the electrode surface and the sheet display member of this substrate, also can make face and this sheet display member driving fit of opposition side of the electrode surface of this substrate.In order to prevent between this sheet display member and this substrate etc. that spilling of insulativity liquid appears in the place, and the blocking-up ambient atmos, the single or multiple lift plastic sheeting with barrier properties for gases is clipped in wherein.
As the base material that is used for stacked described electrode layer, can use film or the sheet material and the glass plate etc. of plastics such as vinylidene chloride, vinyl chloride, tygon, polypropylene, polyethylene terephthalate.Electrode layer can use the paper tinsel of aluminium, copper, metal that nickel constant resistance value is low or the film that forms by evaporation or sputter, perhaps also can use the transparent electrode thin film of tin indium oxide (ITO), antimony tin (ATO), tin oxide etc. etc.
In the rotary-type image display device of particle of the present invention that gets by the two sides that this electrode layer is laminated in described sheet display member, at least the electrode layer of Zhuan Zhi observation side, be used for the base material of multilayer electrode layer and the plastic sheeting that uses as required etc. all must be transparent.This is because if opaque, then can't see the image that device shows.
When the multilayer board of the two sides of sheet display member, can use bonding agent or double-sided adhesive sheet etc.At this moment, also must select material according to the condition of the transparency that can not influence the observation side that shows sheet material.
In the rotary-type image display device of particle of the present invention that obtains by said method, by applying the voltage in the scope that is generally 50～500V, is preferably 50～300V between electrode, can make the double-colored particle rotation in the insulativity liquid in the solidfied material that swims in compositions of thermosetting resin to this substrate.
And, in the rotary-type image display device of particle of the present invention, described thermoset resin (insulativity and the transparency are good) contains double-colored particle of the present invention in the mode of freely rotating, and the verticity of the double-colored particle when therefore applying voltage is good, thereby can realize showing rapidly.
In addition, if the proportion of the approximate hemisphere of the background color of double-colored particle is roughly the same with the proportion of the approximate hemisphere that is coloured to the random color except that background color (calling painted approximate hemisphere arbitrarily in the following text), then the center of double-colored particle is the center or the close center of ball, and double-colored particle rotates easily.And after applying voltage and making the rotation of double-colored particle, double-colored particle can not cause the demonstration of display device to change because of gravity rotates yet, and can give play to memory characteristic.Though proportion has difference to a certain degree, because the viscosity of insulativity liquid such as silicone oil produces constraining force to double-colored particle, therefore the unordered rotation of double-colored particle is suppressed, and the rotary-type image display device of particle of the present invention has memory characteristic usually.
Carry out as mentioned above under the situation of proportion coupling, the proportion coupling of the approximate hemisphere of background color and any painted approximate hemisphere for example can as described belowly be carried out.
The approximate hemisphere of background color of the present invention contains the electric conductivity Chinese white.Therefore, the proportion of the approximate hemispherical portion of background color is arranged than any heavier tendency of painted approximate hemisphere.
Therefore, by content that reduces electric conductivity Chinese white contained in the approximate hemisphere of background color or the content that increases the lighter composition of other contained in the approximate hemisphere of background color proportion, can alleviate the proportion of the approximate hemisphere of background color.
On the other hand, for any painted approximate hemisphere, content by increasing the heavier coloured material of proportion or contain under can not be the situation that the color of painted approximate hemisphere impact arbitrarily proportion heavier than readjust agent, can increase the weight of the proportion of painted approximate hemisphere arbitrarily.Than readjust agent, is under the situation of black at any painted approximate hemisphere as described for example, can exemplify magnetic iron ore etc.
By mating the approximate hemisphere of background color and the proportion of painted approximate hemisphere arbitrarily as mentioned above, the verticity in the time of can obtaining applying voltage is good and can be as the double-colored particle of the display element of the rotary-type image display device of particle with memory characteristic.
In the rotary-type image display device of the particle of the invention described above, even as the double-colored particle of its display element white/the double-colored particle of color combination beyond the black color combination, verticity is also good, and by certain adjustment, therefore also have memory characteristic, can expect the application in electronic paper etc.
Embodiment
The present invention will be described in more detail by the following examples, but the present invention is not limited thereto.
[preparation of reactive solution A-1]
Make titanium white as 30 weight portions of coloured material (Ishihara Sangyo Kaisha, Ltd.'s system: CR-50-2) and the electric conductivity titanium of 5 weight portions (Ishihara Sangyo Kaisha, Ltd.'s system: ET-500W) be dispersed in the trimethylolpropane triacrylate (TMPTA) as the methyl methacrylate (MMA) of 20 weight portions of the monomer that forms resin and 80 weight portions with bowl mill.Dissolving is as the quaternary ammonium salt (4-hydroxyl naphthalene-1-sulfonic acid benzyl tributyl ammonium) of 0.5 weight portion of charged controlling agent in the gained mixed liquor, dissolve the own ester of peroxide neodecanoic acid again, obtain painted external phase reactive solution A-1 as 5 weight portions of thermal polymerization.
Described electric conductivity titanium ET-500W is that the spherical titanium dioxide with rutile-type is a nuclear and by the material of tin ash and antimony pentaoxide lining, in the electric conductivity Chinese white, the weight of titania is 83%, the weight of tin ash is 10%, the weight of antimony pentaoxide is 4%, the particle diameter of electric conductivity Chinese white is 0.2～0.3 μ m, and the powder resistance rate under the pressure of 9.8MPa is 2～5 Ω cm.The powder resistance rate is as described below to be calculated: carry out press molding and make coupons with the condition of the 9.8MPa powder to the electric conductivity Chinese white, under pressurized state, measure coupons up and down between resistance value, the thickness of determination test sheet is calculated the volume resistance value according to the thickness and the sectional area of resistance value that records and test film simultaneously.
[preparation of reactive solution A-2]
With bowl mill the 6 weight portion cyanines indigo plants (elite industry in big day (industry of refining big day) Co., Ltd.'s system) as coloured material are dispersed among the 20 weight portion MMA and 80 weight portion TMPTA as the monomer that forms resin.Dissolving is as salicylic acid metal complex (east chemical industry (オ リ エ Application ト chemical industry) Co., Ltd.'s system: BONTRON E-84) of 1 weight portion of charged controlling agent in the gained mixed liquor, dissolve the own ester of peroxide neodecanoic acid again, obtain painted external phase reactive solution A-2 as 5 weight portions of thermal polymerization.
[embodiment 1]
Then, 88% saponified polyvinyl alcohol of dissolving 1 weight portion in 100 weight portion ion exchange waters is with its mobile medium B as water-based.
With the micro-channel device shown in Fig. 2 (a) (θ 5=90 °) described solution A-1 and A-2 are converged, it is transferred to (θ 3=45 ° of micro-channel device shown in Figure 3, θ 4=45 °) first microchannel, then, from microchannel, side 5a, these three streams of the 5b and first microchannel intersect first microchannel of center of the microchannel that forms and with the amount that amounts to 1ml/hr described solution A-1 and A-2 are spued to the mobile medium B that flows with the amount of 20ml/hr in the microchannel, side of its both sides, make then in its PTFE tube that flow to bore 1mm and also pass through in 70 ℃ of tepidariums simultaneously, thereby carry out polymerizing curable.
By above operation, obtain the double-colored particle of the particle diameter unanimity of white/blue.The mean grain size of representing with volume reference of this double-colored particle is 100 μ m, and the CV value is 2%.
The affirmation of the display performance of the double-colored particle of gained is as described below to be carried out.
The above-mentioned double-colored particle of 6g is well dispersed in the two-solution curing type organic siliconresin, it is coated on the PET base material, make it after solidifying end, become long 200mm * wide 200mm * high 0.3mm, finish curing, obtain containing the resin sheet of particle in 80 ℃ of times with 10 hours.
Then, the gained resin sheet is peeled off from the PET base material, silicone oil (viscosity: dipping is 15 hours 2mPas), thus the vacuole that obtains that double-colored particle is encased by silicone oil and can in organic siliconresin, freely rotate.
The glass plate that has the ITO electrode with the coated processing in surface is clamped the organic siliconresin that this comprises vacuole across laminated plastics, thereby makes electronic paper.
The evaluation of＜particle verticity 〉
According to the condition that produces the potential difference (PD) of 100V between electrode described electronic paper is applied voltage, make the orientation of double-colored particle unified.By making the positive and negative counter-rotating of interelectrode voltage application method, thereby make double-colored particle counter-rotating.Confirm the counter-rotating situation of the double-colored particle of this moment, the population (in 200) of counter-rotating has taken place in counting.There is the note that counter-rotating has taken place more than 150 to do zero, the number of counter-rotating is less than 150 note to be done *, be shown in following table 1.The size of affirming score is in the square scope of about 1mm.Mean value with N=5 is estimated.
The evaluation of＜particle response performance 〉
According to the condition that produces the potential difference (PD) of 100V between electrode described electronic paper is applied voltage, make the orientation of double-colored particle unified.By making the positive and negative counter-rotating of interelectrode voltage application method, thereby make double-colored particle counter-rotating.At this moment, the time of instrumentation till can't confirming the particle that rotation has taken place.The size of affirming score is in the square scope of about 1mm, estimates with the mean value of N=5.
The evaluation of＜aberration 〉
According to the condition that produces the potential difference (PD) of 100V between electrode described electronic paper is applied voltage, make the positive and negative counter-rotating of interelectrode voltage application method, thereby make double-colored particle counter-rotating.Measure double-colored particle and be arranged in aberration when single direction by this.Measure and use (() East capital Electricity look is arranged) system TC-8600A of Tokyo electricity look Co., Ltd..The results are shown in following table 1.
[embodiment 2～6, comparative example 1～2]
Except the composition of the painted external phase of change as shown in table 1 with reactive solution A-1 and A-2, make double-colored particle and electronic paper similarly to Example 1, carry out the evaluation of particle verticity and particle response performance and the evaluation of aberration similarly to Example 1.The results are shown in table 1.The evaluation of particle response performance is only carried out embodiment 1 and comparative example 1.Consequently, the required time of the counter-rotating of the double-colored particle of embodiment 1 is 1/3rd of the required time of the double-colored particle counter-rotating of comparative example 1.That is, the speed reversal of the double-colored particle of embodiment 1 is 3 times of speed reversal of the double-colored particle of comparative example 1.
In the following table 1, " part " expression weight portion.
Shown in abbreviation in the last table 1 etc. thes contents are as follows.
IBXA ... isobornyl acrylate
EGDMA ... ethylene glycol dimethacrylate
CR-50-2 ... the titanium white of Ishihara Sangyo Kaisha, Ltd.'s system
PV Fast Yellow H2G ... the yellow coloring material of Japan's Clariant (Network ラ リ ア Application ト ジ ヤ パ Application) Co., Ltd.'s system
R-980 ... the titanium white of Ishihara Sangyo Kaisha, Ltd.'s system
ET-500W ... the electric conductivity Chinese white of Ishihara Sangyo Kaisha, Ltd.'s system
Electroconductive zinc oxide ... plain boiled water chemical industry (Ha Network ス イ テ Star Network) Co., Ltd.'s system
Cyanines indigo plant ... the industry of refining in big day (industry of refining big day) Co., Ltd.'s system: 4920
Permanent Carmain FBB02-JP ... the red colored material of Japan Clariant Co., Ltd. system
1,9-ND-A ... 1,9-nonanediol diacrylate
BMA ... butyl methacrylate
NPA ... neopentylglycol diacrylate
BEPGA ... 2-butyl-2-ethyl-1, the ammediol diacrylate
CR-58 ... the titanium white of Ishihara Sangyo Kaisha, Ltd.'s system
KA-20 ... the titanium white of titanium industry (industry of チ タ Application) Co., Ltd.'s system
The explanation of symbol
1 first microchannel
2 second microchannels
3 the 3rd microchannels
4 the 4th microchannels
5a, microchannel, 5b side
6 painted external phases
7 mobile media
8 the 3rd microchannels
The spew of 10 painted external phases
11 ' the spew of spheroidizing gradually
12 ' double-colored particle

Claims (8)

1. double-colored particle, this double-colored particle is the resinous double-colored particle that each spherical particle roughly is divided into two kinds of different colours in appearance, it is characterized in that,
The approximate hemisphere of described double-colored particle contains the electric conductivity Chinese white, thereby constitutes background color,
The approximate hemisphere of all the other of described double-colored particle is coloured to the random color except that described background color.
2. double-colored particle as claimed in claim 1, it is characterized in that, constitute that contained electric conductivity Chinese white is to give the pigment that electric conductivity is made by with the conductive material that is selected from antimony oxide/tin ash, indium oxide/tin ash Chinese white being handled in the approximate hemisphere of background color of described double-colored particle.
3. double-colored particle as claimed in claim 1 is characterized in that, the powder resistance rate that constitutes the electric conductivity Chinese white that mixes in the approximate hemisphere of background color of described double-colored particle is in the scope of 1～100 Ω cm.
4. double-colored particle as claimed in claim 1 is characterized in that, the approximate hemisphere that is coloured to the random color except that described background color contains chromatic colour dyestuff or chromatic colour pigment.
5. double-colored particle as claimed in claim 1 is characterized in that the mean grain size of described double-colored particle is illustrated in the scope of 30～200 μ m with volume reference.
6. rotary-type image display device of particle, this device is formed by the insulating resin that contains double-colored particle in the mode of freely rotating between pair of electrodes, it is characterized in that,
Described double-colored particle is the resinous double-colored particle that each spherical particle roughly is divided into two kinds of different colours in appearance,
The approximate hemisphere of described double-colored particle contains the electric conductivity Chinese white, thereby constitutes background color,
The approximate hemisphere of all the other of described double-colored particle is coloured to the random color except that described background color,
By being applied to described interelectrode voltage, described double-colored particle rotates in described insulating resin.
7. the rotary-type image display device of particle as claimed in claim 6 is characterized in that, described double-colored particle swims in the mode of freely rotating and soaks in the insulativity liquid that is contained in the described insulating resin.
8. the rotary-type image display device of particle as claimed in claim 6 is characterized in that, is applied to voltage between described pair of electrodes in the scope of 50～300V.
CN2009801516289A 2008-12-17 2009-11-18 Bicolored particles having improved display performance Expired - Fee Related CN102246094B (en)

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KR20180066061A (en) * 2015-10-08 2018-06-18 다이니폰 인사츠 가부시키가이샤 Particle, optical sheet, screen, display device, particle inspection apparatus and particle production apparatus, particle inspection method, particle production method, screen inspection method, and screen manufacturing method
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