CN100357819C - Particle used for image display medium, image display panel using same, and image display - Google Patents

Particle used for image display medium, image display panel using same, and image display Download PDF

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Publication number
CN100357819C
CN100357819C CNB2004800131801A CN200480013180A CN100357819C CN 100357819 C CN100357819 C CN 100357819C CN B2004800131801 A CNB2004800131801 A CN B2004800131801A CN 200480013180 A CN200480013180 A CN 200480013180A CN 100357819 C CN100357819 C CN 100357819C
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particle
image display
kinds
image
particles
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CN1788233A (en
Inventor
加贺纪彦
药师寺学
田泽晴列
增谷真纪
小林太一
荒井利晃
村田和也
櫻井良
小林米次
田村一
安西弘行
山崎博贵
西室阳一
町田邦郎
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Bridgestone Corp
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Bridgestone Corp
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Abstract

In the image display device, in which the image display media are sealed between opposed substrates, at least one of two substrates being transparent, and in which the image display media, to which an electrostatic field is applied, are made to move so as to display an image, a construction of the particles utilizing as the image display media is improved (the first, second, fourth, fifth, sixth, eighth and ninth aspects of the invention), and, a material of the particles utilizing as the image display media is improved (the third, seventh and tenth aspects of the invention). Therefore, the whiteness of the particles and the liquid powder using the particles can be improved, and it is possible to prevent the particle agglutination and to control the charge property. Moreover, in the image display panel in which the particles and the liquid powder are used as the image display media, it is possible to obtain a durability such that a contrast of the image display during a repetition display is not decreased. As a result, in the image display device in which the image display panel mentioned above is installed, an excellent image display can be achieved.

Description

The particle that uses in the image display medium, use the image of this particle to show with flat board and image display device
Technical field
The present invention relates to utilize electrostatic force such as Coulomb force that particle or powder fluid are moved and carry out particle, the powder fluid that uses in the reversibility image display device that image shows repeatedly and the image that uses this particle shows with flat board and image display device.
Background technology
The image display device of liquid crystal (LCD) has proposed to adopt electrophoresis mode, electricity to cause the image display device (display) of technology such as colored display mode, hot mode, double-colored particle rotation mode as an alternative.Above-mentioned image display device is compared with LCD, have big field-of-view angle, the consumed power that can obtain near common printed product little, have an advantage such as memory function, therefore consider to expect in the expansion of portable terminal device with aspects such as demonstration, electronic papers used as next generation's low price display device.
Recently, proposed and to have made microcapsules by the dispersion liquid that dispersed particle and coloring solution constitute, it has been configured in electrophoresis mode between counter substrate.But, when adopting the electrophoresis mode, because therefore particle swimming in liquid exists the viscous resistance of liquid to cause answer speed problem slowly.In addition, because the particle of high specific gravity such as titanium dioxide is dispersed in low-gravity solution, therefore have easy sedimentation, be difficult to keep disperse state stability, lack the image problem of stability repeatedly.Even make microcapsules, make unit size reach the microcapsules level, also just make above-mentioned shortcoming be difficult to show from the teeth outwards, and unresolved any substantive issue.
For the electrophoresis mode of utilizing the behavior in above-mentioned solution, also proposed not use solution, electroconductive particle and electric charge transmitting layer be assembled in mode in the part of substrate (for example, State of Zhao comes, other 3 people, " novel ink display device (I) ", on July 21st, 1999, Japanese iconology can annual general meetings (the 83rd) " Japan Hardcopy ' 99 ", p.249-252).Also there is following problem in this mode: the structure that is used to dispose electric charge transmitting layer even charge generating layer becomes complicated, be difficult to simultaneously electric charge is stably overflowed from electroconductive particle, and deficient in stability.
In order to address the above problem, fast, simple in structure as dry type, answer speed, at a low price and the image display device of excellent in stability, known have a dry type image display device that video display board has been installed, above-mentioned video display board is enclosed 2 kinds of different particle groups of color and charged characteristic or powder fluid between transparency carrier and counter substrate, 2 kind electrode pair particle group or the powder fluids different by current potential apply electric field, make particle or powder fluid move display image, above-mentioned video display board has 1 or 1 the above image-displaying member that is isolated from each other by dividing plate.Above-mentioned image display device disposes dividing plate between transparency carrier and counter substrate, form image-displaying member.
But, have following problem.
＜the 1 invention problem 〉
Above-mentioned dry type image display device is compared the advantage that the moving resistance with particle is little, answer speed is fast with the electrophoresis mode.The image displaying principle of above-mentioned dry type image display device forms pattern for utilizing each particle, by the tone acquisition contrast of each particle, thus identification icon.Therefore, the briliancy rate as the white particles of catoptrical matrix is important.Generally speaking, white particles is made by the particulate that mixes high-index material in low-index material, and still, hiding rare is not enough after a little while for above-mentioned white particles quantity, and the briliancy rate that can realize is limited.
＜the 2 invention problem 〉
Use repeatedly if above-mentioned dry type image shows with dull and stereotyped, the particle that then occurs enclosing adheres to and irremovable phenomenon each other gradually, has the problem that influences picture contrast, and the useful life longevity aspect exists not enough repeatedly.
＜the 3 invention problem 〉
Show with in the flat board at above-mentioned dry type image, as the particle behavior in the actual substrate that possesses electrode, common following phenomenon: all the same polarity particle according to circumstances, might be observed the phenomenon that forms the aggegation piece between identical particle in substrate also anisotropically attached on the lateral electrode.Under the above-mentioned situation, exist the particle that adheres in the show electrode face to tail off and cause the significantly reduced problem of display characteristic.
If the interparticle aggegation piece of heteropolarity, then it is former because under the effect of Coulomb force etc. aggegation takes place between 2 kinds of particles, therefore can pulverize above-mentioned aggegation piece with comparalive ease by increasing electric field intensity.But, adopt said method to be difficult to pulverize the aggegation piece that the same polarity particle forms, and can not solve, so its solution is not determined yet by electric stress from the outside.
＜the 4 invention problem 〉
Above-mentioned dry type image display device is compared with the electrophoresis mode has the advantage that the particle moving resistance is little, answer speed is fast.The image displaying principle of above-mentioned dry type image display device forms pattern for utilizing each particle, utilizes the tone of each particle to obtain contrast, thus identification icon.Therefore, the color of white particles as colour developing matrix is important.
At present, as colored particles such as white particles, known have with pigment, dyestuff be blended in the polymkeric substance, pulverize, classification and the sized particles that obtains, utilize the polymer particles that bag pigment, dyestuff obtain in various polymerizations, for example suspension polymerization, emulsion polymerization, the seeding polymerization etc., make composite particle that pigment, dyestuff etc. form attached to the master batch surface etc.But there is following problem in sized particles: the shape of particle inequality, the loading of pigment or dyestuff is limited, can't demonstrate the color of regulation, causes the cracking equivalent damage during pulverizing.There is the problem that the loading of pigment or dyestuff is littler, can't demonstrate specified color in polymer particles.And there is following problems in composite particle: because master batch inside do not exist pigment, dyestuff, therefore colour developing is not enough, or pigment, dyestuff is easily from sur-face peeling, or manufacturing step increases.
＜the 5 invention problem 〉
But, if showing with dull and stereotyped, uses repeatedly above-mentioned dry type image, and the particle that then occurs enclosing is attached to each other and irremovable phenomenon gradually, has the problem that influences picture contrast, and useful life longevity is not enough repeatedly.
＜the 6 invention problem 〉
Above-mentioned dry type image display device is compared the advantage that the moving resistance with particle is little, answer speed is fast with the electrophoresis mode.The image displaying principle of above-mentioned dry type image display device forms pattern for utilizing each particle, utilizes the tone of each particle to obtain contrast, identification icon thus.Therefore, the color of white particles as colour developing matrix is important.
At present, above-mentioned white particles is by filling titanium dioxide (TiO in the resin as matrix 2), Chinese white such as zinc paste, zirconia and making.As its method for making, polymerization and mixing comminuting method are arranged, mixing comminuting method can add pigment such as titanium dioxide in a large number, and whiteness is good.As shape, obtain spheroidite when adopting polymerization, and obtain when adopting mixing comminuting method unsetting.As the loading of Chinese white, with respect to resin 100 weight portions as matrix, the maximum loading when adopting polymerization is 50 weight portions, adopts mixing comminuting method can be filled to about 300 weight portions.As mentioned above, polymerization and mixing comminuting method respectively have relative merits, consider from most important whiteness aspect, in most cases use mixing comminuting method.
But, when adopting mixing comminuting method, if titanium dioxide loading height, the problem that then exists insufficient, the white reflectivity that disperses to become to reduce.For example, with respect to resin 100 weight portions as matrix, when titanium dioxide is the 200 weight portion left and right sides, the whiteness maximum.Therefore, if titanium dioxide is 300 weight portions or more than 300 weight portions, then mixingly also become difficult, white reflectivity also reduces.When particularly using titanium dioxide etc., exist to be difficult to make loading to reach 300 weight portions or the problem more than 300 weight portions with respect to resin 100 weight portions as matrix.
＜the 7 invention problem 〉
Show with one of the particle that uses in dull and stereotyped image display device example as possessing above-mentioned dry type image, at present, sometimes use with polycarbonate thermoplastic resins such as (PC) to be base resin, fusions such as pigment, charged controlling agent, mixing back are pulverized and the particle that obtains.As mentioned above, be base resin with the thermoplastic resin, utilize the thermotolerance of the particle that mixing-comminuting method obtains low, image show with dull and stereotyped when in hot environment, using, and the operation carried out under showing with dull and stereotyped high temperature such as bonding process of image in, have pellet melting, adhere to aggegation in the problem of image demonstration on the flat board.
＜the 8 invention problem 〉
The picture contrast of above-mentioned dry type image display device is still insufficient, in addition, if use repeatedly, then causes the particle of enclosing and is attached to each other and irremovable phenomenon gradually, has the problem that influences picture contrast, and the permanance when using repeatedly is also insufficient.
＜the 9 invention problem 〉
The picture contrast of above-mentioned dry type image display device is still insufficient, in addition, if use repeatedly, then causes the particle of enclosing and is attached to each other and irremovable phenomenon gradually, has the problem that influences picture contrast, and the permanance when using repeatedly is also insufficient.
＜the 10 invention problem 〉
At present, uncontrollable formation is equipped with the dry type image and shows that above-mentioned charging property is the material eigenvalue of the resin of composing images display medium with the charging property (Positively chargeable and negative charging) of the particulate material of the image display medium that uses in the dull and stereotyped image display device.
Summary of the invention
The content of＜the 1 invention 〉
The purpose of the 1st invention of the present invention is for providing a kind of image display device that has solved the white particles of the problems referred to above and used above-mentioned white particles, above-mentioned white particles is the white particles of using in the image display medium, even above-mentioned image display medium also can weaken the light that sees through for thin image display medium layer, backscattering is big, and the briliancy rate of white is improved.
The 1st white particles that invention relates to of the present invention is the white particles of using in the image display device, this image display device is enclosed image display medium between the transparent counter substrate of at least one side, image display medium is applied electric field, image display medium is moved, display image, it is characterized by, this white particles is made of the outer layer segment of core and this core of lining, core core and outside the interface of layer segment have total reflectivity more than 70% or 70%, being characterized as of outer layer segment, be made of one or more layers at least resin bed, this resin bed mixes high-index material in low-index material particulate forms.White particles of the present invention has the core that shows high total reflectivity, therefore can improve the briliancy rate of white.
Preference as the 1st white particles that invention relates to of the present invention has following example: core is the metallics of middle reality or hollow; Core is the particle of metal film of being covered on resin bed; The reflectance coating of the interface of core and outer layer segment for constituting by multilayer film; The diameter of core is 50～95% of a particle diameter; Mean grain size d (0.5) is 0.1～50 μ m; Handle through coupling agent on surface as the resin bed of outer layer segment; Has the electrical transparent resin of strong band as the resin bed of outer layer segment surface-coated.Under any situation, specialize by constituting respectively, can further improve the briliancy rate of white particles.
In addition, the 1st image display device that invention relates to of the present invention is to enclose image display medium between the transparent counter substrate of at least one side, image display medium is applied electric field, makes image display medium move the image display device of display image, it is characterized by, as at least a kind of image display medium, use the white particles of above-mentioned formation.
The content of＜the 2 invention 〉
Even the purpose of the 2nd invention of the present invention is for providing a kind of the problems referred to above also good demonstration of low price image flat board and image display device of useful life longevity repeatedly that solved.
The 2nd image that invention relates to of the present invention shows that with flat board be inclosure more than at least 2 kinds or 2 kinds between the transparent counter substrate of at least one side, the image display medium that color is different with charged characteristic, above-mentioned image display medium is applied electric field, make above-mentioned image display medium move the image of display image to show with dull and stereotyped, it is characterized by, more than at least 2 kinds or 2 kinds, the image display medium that color is different with charged characteristic is made of 3 kinds of particles at least, and above-mentioned particle comprises 2 kinds of nearly spherical particles that color is different with charged characteristic, with the 3rd kind particle of particle diameter less than above-mentioned 2 kinds of nearly spherical particles.
The 2nd image that invention relates to of the present invention shown with the dull and stereotyped image demonstration flat board of having enclosed the particle group between 2 substrates that is formed in, above-mentioned particle group is made of 3 kinds of particles that add the 3rd kind of particle in 2 kinds of different nearly spherical particles of charged characteristic, make thus to be difficult to aggegation between particle and to adhere to, image shows that permanance is improved.Herein, when the 3rd kind of particle made particle (fine particle) less than other 2 kinds of particles, this particle is present in the surface perimeter (because of electric attraction adheres to more weakly) of arbitrary particle usually, the result constitutes the 3rd kind of particle and hinders because of charged characteristic different the 1st kind of particle of aggegations and the 2nd kind of form that particle directly contacts each other easily, can prevent particles aggregate.
In addition, it is spherical that 2 kinds of nearly spherical particles are, and preferred surface is level and smooth from macroscopic view.If the surface is not to be level and smooth or to be not spherical from macroscopic view, then be difficult to show the tumble action of the 3rd kind of particle, be difficult to bring into play lubricant effect, so aggegation takes place in particle easily.And the 3rd kind of particle also is preferably spherical.By making the 3rd kind of particle is spherical, has strengthened other 2 kinds of interparticle tumble actions, and the 1st kind of particle and the 2nd kind of particle become and move (2 kinds of interparticle lubricant effects improve) easily, prevent that the effect of both aggegations from improving.
As other preferred embodiments, following example is arranged: the mean grain size of 2 kinds of nearly spherical particles that color is different with charged characteristic is in the scope of 0.5～50 μ m, and the mean grain size of the two about equally; The mean grain size of the 3rd kind of particle is 20～200nm; Be filled in the volume occupation rate of image display medium more than at least 2 kinds or 2 kinds between substrate in the scope of 5～70vol%.All can implement the present invention more well under arbitrary situation.
In addition, being characterized as of the 2nd image display device that invention relates to of the present invention is equipped with above-mentioned image demonstration with dull and stereotyped.
The content of＜the 3 invention 〉
The purpose of the 3rd invention of the present invention is to provide a kind of and has solved the problems referred to above, can reduce the image display medium of the aggegation piece that the same polarity particle forms and uses the image display device of this image display medium.
The 3rd image display medium that invention relates to of the present invention is the image display medium that uses in the image display device, this image display device is between transparent 2 substrates of opposite each other and at least one side, inclosure is by the image display medium that colored particles constitutes more than at least 2 kinds or 2 kinds with charging property, or enclose by a kind of image display medium that colored particles constitutes with charging property, the 2 kind electrode pair particles different by current potential apply electric field, particle is moved, display image; It is characterized by, this medium is made of the particle that the low-dielectric megohmite insulant constitutes.In addition, being characterized as of image display device of the present invention utilized above-mentioned image display medium.
Preference as the 3rd image display medium that invention relates to of the present invention has following example: the DIELECTRIC CONSTANT of particle rBe ε r≤ 5.0, ε r≤3.0 more preferably; High dielectric property filler, electroconductive stuffing are not contained in particle inside; Particle surface does not adhere to high dielectric property material, high conductivity material; The mean grain size of particle is 0.1～50 μ m; The surface charge density of particle is used absolute value representation, at 5～150 μ C/m 2Scope in.Under any situation, all can implement the present invention more well.
Herein, the DIELECTRIC CONSTANT of particle rBe preferably ε r≤ 5.0.DIELECTRIC CONSTANT rIf surpass 5.0, then as can be known, can't fully prevent the formation of aggegation piece by aftermentioned embodiment.
Image display medium of the present invention and use the image display device of this image display medium preferably to use the image display medium that is made of particle, this particle is by DIELECTRIC CONSTANT rSatisfy ε r≤ 5.0 low-dielectric megohmite insulant constitutes, and thus, even be the same polarity particle, also can avoid forming the aggegation piece between particle, can carry out preferable image display.
The content of＜the 4 invention 〉
The purpose of the 4th invention of the present invention is for providing a kind of white particles that has solved the problems referred to above, can increase substantially covering power (reflectivity), use the image display medium of this white particles and using the image display device of this image display medium.
The 4th white particles that invention relates to of the present invention is the white particles of using in the image display device, this image display device is enclosed image display medium between the transparent counter substrate of at least one side, image display medium is applied electric field, make image display medium move display image; It is characterized by, above-mentioned white particles is by 1 particles aggregate of the Chinese white of the bonding agent that will be covered or be a granulated into 2 particles that the regulation particle diameter obtains and constitute, and micro-bubble is contained in its inside.
In the 4th white particles that invention relates to of the present invention, made the Chinese white of bonding agent surface-coated, preferred titanium oxide pigments aggegation or granulation, import most micro-bubbles in inside, can increase substantially covering power (reflectivity) thus.Particularly the covering power of titanium dioxide does not increase pro rata with loading, according to the theory of Mie, increases with loading, and the light scattering efficiency of pigment reduces, and therefore is about at 30% o'clock at volume ratio, the covering power peak value display.If further increase loading, then near the most closely knit occupied state, import micro air bubble, improve covering power at one stroke.The present invention has utilized above-mentioned phenomenon.
Preference as the 4th white particles that invention relates to of the present invention has following example: Chinese white is a titanium dioxide; Bonding agent is made of low-index material; In air flow or carry out mechanicalness and mix to stir, import most micro air bubbles and carry out the aggegation or the granulation of 2 particles; Mean grain size d (0.5) is 0.1～50 μ m.Select the material of white particles as described above and the mean grain size of particle is in the specialized range, can further improve the covering power (reflectivity) of white particles thus.
In addition, image display device of the present invention is to enclose image display medium between the transparent counter substrate of at least one side, image display medium is applied electric field, makes image display medium move the image display device of display image, it is characterized by, as at least a kind in the image display medium, use above-mentioned white particles.
The content of＜the 5 invention 〉
Even the purpose of the 5th invention of the present invention is for providing a kind of the problems referred to above also good demonstration of low price image flat board and image display device of useful life longevity repeatedly that solved.
Image that the 1st embodiment of the 5th invention of the present invention relates to shows that with flat board be inclosure image display medium more than at least 2 kinds or 2 kinds between the transparent counter substrate of at least one side, the 2 kind electrode pair above-mentioned image display mediums different by current potential apply electric field, make image display medium move the image of display image to show with dull and stereotyped, it is characterized by, there is concavo-convex particle in one of 2 kinds of particles that charged characteristic that comprises in the image display medium more than at least 2 kinds or 2 kinds and optical reflectivity are different on the surperficial macroscopic view, and another particle is not have concavo-convex particle on the surperficial macroscopic view.
The image that the 1st embodiment of the 5th invention of the present invention relates to shows with in the flat board, there is concavo-convex particle (for example sized particles) in one of particle that uses in the different 2 kinds of image display mediums of charged characteristic on the surperficial macroscopic view, another particle is not have concavo-convex nearly spherical particle (for example polymer particles) on the surperficial macroscopic view, make the surface state difference of the particle that uses in 2 kinds of image display mediums, the different particle of charged characteristic becomes each other and is difficult to aggegation and adheres to thus, and the permanance that image shows improves.The particle interphase interaction repulsive force that charged characteristic is identical, even therefore have the also rare aggegation of identical macro surface shape, even act on each other between the different particle of the charged characteristic of attractive force, also, surface configurations different on the macroscopic view is difficult to aggegation each other because of making particle.
Image that the 2nd embodiment of the 5th invention of the present invention relates to shows that with flat board be inclosure image display medium more than at least 2 kinds or 2 kinds between the transparent counter substrate of at least one side, the 2 kind electrode pair above-mentioned image display mediums different by current potential apply electric field, make image display medium move the image of display image to show with dull and stereotyped, it is characterized by, there is concavo-convex particle in one of particle that uses in the different 2 kinds of image display mediums of charged characteristic that comprises in the image display medium more than at least 2 kinds or 2 kinds and optical reflectivity on the surperficial macroscopic view, another particle be do not exist on the surperficial macroscopic view concavo-convex, and the fine-grained particle of electrostatic adhesion on the surface.
The image that the 2nd embodiment of the 5th invention of the present invention relates to shows with in the flat board, one of particle that constitutes 2 kinds of different image display mediums of charged characteristic is to have concavo-convex particle (for example sized particles) on the surperficial macroscopic view, another particle is not have concavo-convex nearly spherical particle (for example polymer particles) on the surperficial macroscopic view, and do not exist on the above-mentioned macroscopic view concavo-convex nearly spherical particle surface electrostatic be attached with charged polarity be different from do not have concavo-convex particle on the above-mentioned macroscopic view particulate as the 3rd kind of particle, thus, not only between the different 2 kinds of particles of charged characteristic, and be difficult to that also aggegation takes place between the identical particle of charged characteristic and adhere to, improved the permanance that image shows.That is, between the identical particle of charged characteristic, though there is not the tendency that exists easy aggegation to adhere under the concavo-convex state in the interaction repulsive force on the surperficial macroscopic view; Even do not exist on the above-mentioned surperficial macroscopic view between the identical particle of concavo-convex charged characteristic, also can pass through, and positively prevent aggegation at its surface electrostatic adhesion of particles.Even between the different 2 kinds of particles of charged characteristic, also can go up different surface configurations (exist on the surperficial macroscopic view on concavo-convex particle and the surperficial macroscopic view and do not have concavo-convex particle), and make it be difficult to aggegation by making it have macroscopic view.
The 1st embodiment and the common preference of the 2nd embodiment that relate to as the 5th invention of the present invention, following example is arranged: constitute in the particle of 2 kinds of different image display mediums of charged characteristic and optical reflectivity, having concavo-convex particle on the surperficial macroscopic view is crushing resin piece and the particle that obtains; Constitute in the particle of 2 kinds of different image display mediums of charged characteristic and optical reflectivity, having concavo-convex particle on the surperficial macroscopic view is the particle that obtains at the powerful adhesion of particles in master batch surface; When master batch and particulate brute force are adhered to, use mechanical impact force; Constitute in the particle of 2 kinds of different image display mediums of charged characteristic and optical reflectivity, so the nearly spherical particle that does not exist concavo-convex grain resin monomer to be polymerized on the surperficial macroscopic view; Constitute in the particle of 2 kinds of different image display mediums of charged characteristic and optical reflectivity, not having concavo-convex particle on the surperficial macroscopic view is that the particle after pulverizing is exposed to the nearly spherical particle that makes its surface smoothing under the fusing point of this particle or the temperature more than the fusing point and obtain; Be filled in the volume occupation rate of image display medium more than at least 2 kinds or 2 kinds between substrate in the scope of 5～70vol%; The mean grain size that constitutes the particle of 2 kinds of different image display mediums of charged characteristic and optical reflectivity is 0.5～50 μ m.All can implement the 1st embodiment and the 2nd embodiment that the 5th invention of the present invention relates under any situation more well.
In addition, preference as the 2nd embodiment of the 5th invention of the present invention, following example is arranged: constitute in the particle of 2 kinds of different image display mediums of charged characteristic and optical reflectivity, electrostatic adhesion the particulate that does not have concavo-convex particle surface on the surperficial macroscopic view have with above-mentioned surperficial macroscopic view on do not have the charged opposite polarity polarity of concavo-convex particle, and, after adhering to from the teeth outwards, can not change the charged polarity that does not have concavo-convex particle on the above-mentioned surperficial macroscopic view; There is not the mean grain size of the particulate of concavo-convex particle surface in electrostatic adhesion on surperficial macroscopic view be 20～200nm.All can implement the 5th the 2nd embodiment that invention relates to of the present invention under any situation more well.
And the image that has carried above-mentioned formation that is characterized as of the 5th image display device that invention relates to of the present invention shows with dull and stereotyped.
＜the 6 summary of the invention 〉
Even the purpose of the 6th invention of the present invention is for providing a kind of loading that has solved the problems referred to above and do not increase Chinese white such as titanium dioxide also can improve the white particles of whiteness (white reflectivity), utilizing the white powder fluid of this white particles and with the image display device of above-mentioned white powder fluid as image display medium.
The 6th white particles that invention relates to of the present invention is the white particles of using in image display device, and this image display device is enclosed image display medium, image display medium is applied electric field, makes image display medium move display image between the transparent counter substrate of at least one side; It is characterized by, in as the resin of matrix, fill Chinese white and hollow-particle.
In the 6th white particles that invention relates to of the present invention, in as the resin of matrix, fill Chinese white and hollow-particle, utilize the covering effect of hollow-particle, can improve the whiteness (white reflectivity) of white particles.
Preference as the 6th white particles that invention relates to of the present invention, following example is arranged: the loading in resin for Chinese white and hollow-particle, with respect to resin 100 weight portions, Chinese white is 100～300 weight portions, and hollow-particle is 10～60 weight portions.Herein, with respect to resin 100 weight portions as matrix, the loading of hollow-particle is preferably 10～60 weight portions; During less than 10 weight portions, almost do not observe the improvement of white reflectivity; If surpass 60 weight portions, then be difficult to resin mixing.
In addition, other preferences as the 6th white particles that invention relates to of the present invention have following example: Chinese white is any in titanium dioxide, zinc paste, the zirconia; Hollow-particle consist of cross-linked styrene-acrylic acid; Mean grain size d (0.5) is 1.0～50 μ m.All can improve the whiteness of white particles under any situation more well.
In addition, image display device of the present invention is to enclose image display medium between the transparent counter substrate of at least one side, image display medium is applied electric field, makes image display medium move the image display device of display image, it is characterized by, as at least a kind in the image display medium, use above-mentioned white particles.
The content of＜the 7 invention 〉
The purpose of the 7th invention of the present invention solved the problems referred to above for providing a kind of, improve thermotolerance, do not adhere to the image display medium of aggegation on image shows with flat board and use the image display device of this image display medium.
The 7th image display medium that invention relates to of the present invention is the image display medium that uses in the image display device, and this image display device is enclosed image display medium, image display medium is applied electric field, makes image display medium move display image between the transparent counter substrate of at least one side; It is characterized by, as the base resin of the particle of composing images display medium, use thermoset resin, the heat cross-linking reaction takes place in the mixing back of resin material that will contain thermoset resin, pulverizes then and obtains this medium.
In the 7th image display medium that invention relates to of the present invention, base resin as the particle of composing images display medium, the thermoset resin of heat cross-linking reaction has taken place in use, can improve thermotolerance thus, and the result does not adhere to aggegation on image shows with flat board.
Preference as the particle that uses in the 7th image display medium that invention relates to of the present invention has following example: as the thermoset resin of base resin is in vibrin+blocked isocyanate class, alkyd resin+melamine cured dose class, epoxy resin+amine hardener class, the urea resin+formaldehydes wantonly a kind; Except thermoset resin, contain organotin catalysts, pigment, charged controlling agent as base resin.All can implement the present invention more well under any situation.
In addition, the 7th image display device that invention relates to of the present invention is characterized as has installed the image demonstration with dull and stereotyped, and this image shows the image display medium that utilizes above-mentioned particle with dull and stereotyped use.
The content of＜the 8 invention 〉
The purpose of the 8th invention of the present invention shows with flat board and image display device for a kind of low price image that has solved the problems referred to above is provided, even this image shows that picture contrast with flat board is good and uses repeatedly that picture contrast does not reduce, permanance is good yet.
It is to enclose image display medium more than at least 2 kinds or 2 kinds between transparent 2 counter substrate of at least one side, image display medium is applied electric field, makes image display medium move the image of display image to show to use flat board that the 8th image that invention relates to of the present invention shows with flat board, it is characterized by, the shape of particle of at least one the particle group in the different 2 kinds of particle groups of charged characteristic that comprises in the image display medium more than at least 2 kinds or 2 kinds and optical reflectivity is a flattened round.
The 8th image that invention relates to of the present invention shows with in the flat board, at least a in the particle that uses in the different 2 kinds of image display mediums of charged characteristic and optical reflectivity is the flattened round particle, thus when moving and being arranged in the display base plate surface, particle is seamlessly arranged easily each other, because interparticle gap tails off, so the contrast of image improves.In addition, when the particle both sides that use in the different 2 kinds of image display mediums of charged characteristic and optical reflectivity are the flattened round particle, be difficult to take place aggegation between particle, the conflict when particle moves simultaneously relaxes, and the permanance that image shows improves.In addition, flat degree is not particularly limited, so long as, can obtain effect of sufficient than just spherical slightly flat degree.
Show that as the 8th image that invention relates to of the present invention following example is arranged: the flattened round particle is a white particles with dull and stereotyped preference; The look material of flattened round white particles is a titanium dioxide; The flinders that the flattened round particle is made the crushing resin sheet material is exposed under the fusing point of above-mentioned resin or the temperature more than the fusing point and makes; The mean grain size of the particle that uses in the different 2 kinds of image display mediums of charged characteristic that comprises in the image display medium more than at least 2 kinds or 2 kinds and optical reflectivity is 0.1～50 μ m in arbitrary particle; Be filled in the volume occupation rate of image display medium more than at least 2 kinds or 2 kinds between substrate in the scope of 5～70vol%.All can implement the present invention more well under any situation.
In addition, the image that has carried the image display medium that uses above-mentioned formation that is characterized as of the 8th image display device that invention relates to of the present invention shows with dull and stereotyped.
The content of＜the 9 invention 〉
The purpose of the 9th invention of the present invention shows that for a kind of low price image that has solved the problems referred to above is provided this image shows with dull and stereotyped picture contrast good with flat board and image display device, even use picture contrast also not reduce repeatedly, permanance is good.
The 9th image that invention relates to of the present invention shows that with flat board be the image display medium that inclosure contains 2 kinds of particle groups that color and charged characteristic are different at least between transparent 2 counter substrate of at least one side, image display medium is applied electric field, make image display medium move the image of display image to show with dull and stereotyped, it is characterized by, the mean grain size of shallow light tone particle group is being represented with Dbright, when the mean grain size of deep dark particle group was represented with Ddark, the particle diameter of 2 kinds of particle groups (deep dark particle group and shallow light tone particle group) that color that comprises in the above-mentioned image display medium and charged characteristic are different relation was represented with Ddark＜Dbright.
The 9th image that invention relates to of the present invention shows with in the flat board, when representing with the mean grain size Dbright of the mean grain size Ddark of deep dark particle group and shallow light tone particle group, it is Ddark＜Dbright that the particle diameter of 2 kinds of particle groups that color is different with charged characteristic closes, thus, move round about each other along the direction of an electric field between substrate, and be arranged in display base plate when surface, and the situation opposite with above-mentioned particle diameter relation compared, and contrast improves.Above-mentioned reason is not also illustrated, but can think and fitly be arranged in when showing side group plate surface in shallow light tone particle group, and contrast improves, and during Ddark＜Dbright, shallow light tone particle group fitly is arranged in and shows side group plate surface, and contrast improves.
The 9th image that invention relates to of the present invention shows with in the flat board, the reflection density of the white solid display image when particularly using white particles as shallow light tone particle group, it is respond well, preferably making the particle that constitutes deep dark particle group is black, makes the particle that constitutes shallow light tone particle group be white.In addition, there is no particular specification,, under widely different situation, obtain relatively poor result on the contrary as long as slightly variant for the degree of relationship of Ddark＜Dbright.Therefore, the scope of preferred 1＜Dbright/Ddark＜2.And, preferably make all particles of constituent particle group all satisfy above-mentioned relation, therefore, preferably, shallow light tone particle group is carried out downward classification (undercut) to the classification (overcut) that makes progress of deep dark particle group in order to make particle diameter consistent and when carrying out classification.
And, show with dull and stereotyped preference that as the 9th image that invention relates to of the present invention following example is arranged: at least the particle diameter of the different 2 kinds of particle groups of color and charged characteristic for arbitrary particle group all in the scope of 1～50 μ m; The image display medium that contains 2 kinds of particle groups that color and charged characteristic are different at least is in the scope of volume occupation rate at 5～70vol% of filling between substrate.All can implement the present invention more well under any situation.
In addition, the 9th image display device that invention relates to of the present invention is characterized as the image demonstration flat board that has carried the image display medium that uses above-mentioned formation.
The content of＜the 10 invention 〉
The purpose of the 10th invention of the present invention solved the problems referred to above for providing a kind of, can show the particle that uses in the image display medium of charged control ability, utilize the powder fluid of this particle and use the image display device of this powder fluid.
The 1st embodiment that the 10th invention of the particle that uses in the image display medium of the present invention relates to is the image display medium that uses in the image display device, and this image display device is enclosed image display medium, image display medium is applied electric field, makes image display medium move display image between the transparent counter substrate of at least one side; It is characterized by complexed metal oxide (MOx) in the base resin of the particle that uses in the image display medium;
Herein, M: metallic element, O: oxygen, the ratio of x:O/M.
In addition, the 2nd embodiment that the 10th invention of the particle that uses in the image display medium of the present invention relates to is the image display medium that uses in the image display device, and this image display device is enclosed image display medium, image display medium is applied electric field, makes image display medium move display image between the transparent counter substrate of at least one side; It is characterized by, be combined with fatty acid metal salt compound (CmHnCOO) yMz in the base resin of the particle that uses in the image display medium;
Herein, M: metallic element, m, n, y, z are integer, 4＜m＜22.
Preference as the particle that uses in the 10th image display medium that invention relates to of the present invention has following example: the polarization electronegativity χ of the ion of metallic element (M) is 0.79＜χ＜1.91, has Positively chargeable; And in these cases, metallic element is wantonly a kind among Mg, Zn, Ca, Li, Zr, Al, Ni, Cu, Ba, the Ti.In addition, other preferences as the particle that uses in the image display medium of the present invention have following example: the polarization electronegativity χ of the ion of metallic element (M) is 1.50＜χ＜2.58, has negative charging; And in these cases, metallic element is wantonly a kind among Fe, Ti, Cu, Si, Sb, W, Sn, Ge, the Co.All can implement the present invention more well under any situation.
Description of drawings
Fig. 1 (a) and (b) are represented respectively as one of the display mode of the image display device of object of the present invention example.
Fig. 2 (a) and (b) are represented other examples as the display mode of the image display device of object of the present invention respectively.
Fig. 3 (a) and (b) are represented other examples as the display mode of the image display device of object of the present invention respectively.
Fig. 4 represents to show with one of dull and stereotyped display mode example as the image of the object of the 2nd invention of the present invention.
Fig. 5 represents to show with one of dull and stereotyped slab construction example as the image of the object of the 2nd invention of the present invention.
Fig. 6 is used to illustrate that image as the object of the 2nd invention of the present invention shows the figure with dull and stereotyped particle group state.
Fig. 7 (a)～(c) represents one of the manufacture method example of the 4th white particles that invention relates to of the present invention respectively by process sequence.
Fig. 8 (a) and (b) are respectively and are used for the figure that the key diagram picture shows the particle group state of using flat board, and above-mentioned image shows the image display medium that uses the object of the 1st embodiment that relates to as the 5th invention of the present invention with dull and stereotyped.
Fig. 9 (a) and (b) are respectively and are used for illustrating that the image that uses the conventional images display medium shows the figure with the particle group state of flat board.
Figure 10 is used for the figure that the key diagram picture shows the particle group state of using flat board, and above-mentioned image shows the image display medium that uses the object of the 2nd embodiment that relates to as the 5th invention of the present invention with dull and stereotyped.
Figure 11 is used for the figure that the key diagram picture shows the particle group state of using flat board, and above-mentioned image shows the image display medium that uses the object of the 2nd embodiment that relates to as the 5th invention of the present invention with dull and stereotyped.
Figure 12 represents the structure of one of hollow-particle of using in the 6th white particles that invention relates to of the present invention example.
One of the form that the flattened round particle that Figure 13 represents to use in the 8th image display medium that invention relates to of the present invention is seamlessly arranged at substrate surface example.
One of the form that the spheroidal particle that uses in Figure 14 presentation video display medium is arranged with a gap at substrate surface example.
Figure 15 represents to use the image of image display medium of the present invention to show with one of the partition shape in dull and stereotyped example.
Embodiment
The formation of the image display device that uses image display medium of the present invention at first, is described.In image display device of the present invention, show with on the flat board, by any way to applying electric field in the aforesaid substrate at the image of having enclosed image display medium between counter substrate.Charged image display medium for electronegative potential is attracted to the direction of an electric field of noble potential by Coulomb force etc., and charged image display medium for noble potential is attracted to the direction of an electric field of electronegative potential by Coulomb force etc., above-mentioned image display medium is along direction of an electric field to-and-fro movement, display image thus.Therefore, must designed image show, image display medium is moved equably with dull and stereotyped, and can keep repeatedly the time or the stability in when preservation., be applied to the power that the particle that uses in the image display medium or the power on the powder fluid attracts each other because of the Coulomb force except between particle or powder fluid herein, also have and interelectrode Electronic Speculum image force, intermolecular force, the crosslinked power of liquid, gravity etc.
Illustrate that based on Fig. 1 (a) and (b)～Fig. 3 (a) and (b) the image that uses in the image display device of the present invention shows with dull and stereotyped example.
In the example shown in Fig. 1 (a) and (b), make color is different more than 2 kinds or 2 kinds particle 3 (herein, being expressed as white particles 3W and black particles 3B) electric field and the substrate 1,2 that apply corresponding to the outside from substrate 1,2 vertically move, make the observer discern black particles 3B, carry out black display, perhaps, make the observer discern white particles 3W, carry out white and show.In addition, in the example that Fig. 1 (b) illustrates, the example except Fig. 1 (a) illustrates for example is provided with dividing plate 41,2 of substrates trellis, forms display unit (cell).
In the example shown in Fig. 2 (a) and (b), apply voltage being arranged on the electrode 5 on the substrate 1 and being arranged between the electrode 6 on the substrate 2, the particle 3 that color is different more than 2 kinds or 2 kinds (being expressed as white particles 3W and black particles 3B herein) is vertically moved corresponding to electric field that produces and substrate 1,2, make the observer discern black particles 3B, carry out black display, or, make the observer discern white particles 3W, carry out white and show.In addition, in the example that Fig. 2 (b) illustrates, the example except Fig. 2 (a) illustrates for example is provided with dividing plate 4 trellis between substrate 1,2, forms display unit.
In the example shown in Fig. 3 (a) and (b), apply voltage being arranged between electrode 5 on the substrate 1 and the electrode 6, the particle 3 (being expressed as white particles 3W herein) of a kind of color is moved abreast corresponding to electric field that produces and substrate 1,2, make the observer discern white particles 3W, carrying out white shows, or, make the observer discern the color of electrode 6 or substrate 1, carry out the demonstration of the color of electrode 6 or substrate 1.In addition, in the example that Fig. 3 (b) illustrates, the example except Fig. 3 (a) illustrates for example is provided with dividing plate 4 trellis between substrate 1,2, forms display unit.
Above-mentioned explanation goes for white particles 3W is changed into white powder fluid, black particles 3B changed into the situation of black powder fluid equally.
Below ,～the 10 invention of the 1st invention of the present invention is described successively.
The explanation of＜the 1 invention 〉
The feature of the 1st invention of the present invention relates to the white particles 3W in the particle that uses and utilizes the white powder fluid of white particles 3W in image display medium.Below, make colored particle clear.
At first, white particles 3W is described.The outer layer segment that is characterized as by core and lining core of white particles 3W of the present invention constitutes, core core and outside the interface of layer segment have total reflectivity more than 70% or 70%, outer layer segment is made of resin bed, and above-mentioned resin bed is sneaked into high-refraction material in one or more layers at least low refractive material particulate forms., the total reflectivity at interface is defined as that reason more than 70% or 70% is if the total reflectivity less than 70% at interface herein, then the hiding rare of minority particle reduces, and is as good as at aspect of performance and existing particle.
As at the interface total reflectivity is the material of the core more than 70% or 70%, can enumerate the particle that is coated with metal film on metallics, the resin bed, with the interface of outer layer segment be the particle etc. of the reflectance coating that constitutes by multilayer film.Metallics can be middle real particle, also can be hollow-particle, and hollow-particle can be made the more core of light weight, is preferred therefore.As the material of metallics, can enumerate the material that is selected from aluminium, silver, nickel, chromium, iron, titanium, gold and above-mentioned alloy.In addition, as the material that is overlayed on the metal film on the resin bed, can enumerate the material that is selected from aluminium, silver, nickel, chromium, iron, titanium, gold and above-mentioned alloy.The manufacture method that is overlayed on the metal film on the resin bed is not particularly limited, and can utilize technology such as plating, evaporation, (cathode) sputtering.For multilayer film, can utilize design, material, the manufacture method of normal optical reflectance coating.
And the relation of core diameter and particle integral diameter is not particularly limited, and the diameter of core is preferably 50～95% of particle diameter.If 50% of the not enough particle diameter of the diameter of core, then the light quantity at incident interface diminishes with respect to the ratio of whole light quantities of a particle of incident, performance and existing particle indifference.In addition, if the diameter of core surpasses 95% of particle diameter, then owing to insufficient as the scattering of outer field resin bed, so the normal reflection composition increases.This result makes it have the metal-like outward appearance, can't be as the display image display medium of similar paper.
Next, the resin bed of the outer layer segment that constitutes white particles 3W is described.The preparation of the resin bed of outer layer segment can be mixing with the resin of necessity, charged controlling agent, colorant, other adjuvants, pulverizes; Or by monomer polymerization; Or with existing part as matrix with resin, charged controlling agent, colorant, other adjuvants linings.The example of resin, charged controlling agent, colorant, other adjuvants is identical with the particle content of following explanation.In addition, by utilizing above-mentioned white particles, can make following powder fluid (white powder fluid).
The explanation of＜the 2 invention 〉
The 2nd image that invention relates to of the present invention shows with in the flat board, 2 kind nearly spherical particles and the 3rd kind particles different with charged characteristic by color constitute image display medium more than at least 2 kinds or 2 kinds, can prevent to take place between the particle aggegation thus and adhere to, improve the permanance when using repeatedly.
Fig. 4 and Fig. 5 illustrate the 2nd image that invention relates to of the present invention respectively and show with the routine formation of one of flat board.Image of the present invention shown in Fig. 5 shows with in the flat board, to enclose 11,12 of substrates as image display medium by the particle group 13 of color 2 kind nearly spherical particles different (being white particles 13-1 and black particles 13-2) and the 3rd kind of particle 13-3 formation herein with charged characteristic, particle group 13 by 15,16 pairs of inclosures of electrode applies electric field, it is moved to the direction vertical with substrate 11,12, carry out image and show.When adopting aforesaid way, also can as shown in Figure 5 the space of 11,12 of substrates be separated with dividing plate 14, make the structure with a plurality of unit, enclose particle group 13 therein, composing images shows with dull and stereotyped.In addition, in the example shown in Fig. 4 and Fig. 5, because the 3rd kind of particle 13-3 is less than 2 kinds of particle 13-1,13-2, there is the state of the 3rd kind of particle 13-3 in the surface of therefore suitably not expressing a kind of therein particle 13-1, but, in fact, as shown in Figure 6, be in the 3rd kind of particle 13-3 attached to the state on the whole surface of a kind of particle 13-1 wherein.
2 kinds of nearly spherical particles that use in the 2nd invention of the present invention are the color particle different with charged characteristic.The preparation of 2 kinds of nearly spherical particles can be mixing with the resin of necessity, charged controlling agent, colorant, other adjuvants, pulverizes; Perhaps also can form by monomer polymerization; Perhaps also can use resin, charged controlling agent, colorant, the existing particle of other adjuvants linings, because 2 kinds are used in combination, therefore the color of two kinds of particles is different with charged characteristic extremely important.
In addition, closely spherical in order to make, preferably adopt polymerization to be prepared, still, also can utilize mechanical impact force etc. that the corner angle of the particle of making through pulverizing are come off, or in fusing point or the temperature atmosphere more than the fusing point, make surface flowization, make spherical.The example of resin, charged controlling agent, colorant, other adjuvants is identical with the particle content of following explanation.
The 3rd kind of particle that uses in the 2nd invention of the present invention is present between above-mentioned 2 kinds of nearly spherical particles for the particle less than above-mentioned 2 kinds of nearly spherical particles, the effect of performance lubricant.
The mean grain size of the 3rd kind of particle is preferably 20nm～200nm, and 20nm～150nm more preferably is most preferably in the scope of 20nm～100nm.If surpass 200nm, then separate from above-mentioned 2 kinds of nearly spherical particles easily, can't be present in the effect of the aggegation adhesion of 2 kinds of particles of performance reduction between 2 kinds of particles.In addition, if not enough 20nm, then the 3rd kind of particle is absorbed in above-mentioned 2 kinds of nearly spherical particle surfaces, can't bring into play the effect of the aggegation adhesion of the 2 kinds of particles of reduction that produced by tumble action.
As the material that can be used as the 3rd kind of particle, can enumerate metal oxides such as titanium dioxide, tin oxide, zirconia, tungsten oxide, iron oxide, nitride such as titanium nitride, monox, titanium compound etc., and the particulate that constitutes by nitride, titanium compounds such as metal oxide, titanium nitride such as the monox of hydrophobization, titanium dioxide, tin oxide, zirconia, tungsten oxide, iron oxide, the preferably particulate that constitutes by the monox of hydrophobization.
Hydrophobization can utilize the hydrophobization treating agent to handle, and as the hydrophobization treating agent, can use in chlorosilane, alkoxy silane, silazane, the silylanizing isocyanates any.Particularly, can enumerate methyl trichlorosilane, dimethyldichlorosilane, trimethyl chlorosilane, methyltrimethoxy silane, dimethyldimethoxysil,ne, methyl triethoxysilane, dimethyldiethoxysilane, isobutyl trimethoxy silane, decyl trimethoxy silane, hexamethyldisilazane, tert-butyl chloro-silicane, vinyl trichlorosilane, vinyltrimethoxy silane, vinyltriethoxysilane etc.
The explanation of＜the 3 invention 〉
The inventor etc. further investigate, and found that aggegation piece in the same polarity particle results from the permittivity that particle has, thereby finish the 3rd invention of the present invention.That is, enclose the dielectric particle between substrate,, then under electric field effects, induce out reciprocal positive and negative charge at particle surface if between electrode, form electric field with electrode.Above-mentioned phenomenon is called as polarization, thus, produces eelctric dipole and interact between particle, produces gravitation between particle.In addition, as another character of dielectric, existence can be attracted and concentrate on the phenomenon at highfield place.Can judge that above 2 kinds of phenomenons all promote the aggegation of particle of the same race between electrode.The permittivity of particle is big more, and it is remarkable more that above-mentioned phenomenon becomes.In addition, when having electric conductivity, it is big that the polarization of particle still becomes for particle itself (or only its surface).That is, mean that the apparent capacity rate improves.Can judge in these cases, produce the power that makes identical particles aggregate too.
As solution to the problems described above, adopt following scheme to avoid between the same polarity particle aggegation taking place in the 3rd invention of the present invention, realize good display characteristic, described scheme is: the particulate material of the image display medium that uses in showing as image, select DIELECTRIC CONSTANT rBe ε r≤ 5.0, ε more preferably r≤ 3.0 low-dielectric megohmite insulant; When using high dielectric property material, conductive material as the particle constituent material, lure isoelectric substance by in main material, using to hang down, the apparent capacity rate of guaranteeing particle integral body is a low value; Particle surface is adhered under the situation of any material, select attachment material, control adhesion amount, make not have high dielectric property material, conductive material on the particle surface.
The image that uses in the image display device of the present invention shows with flat board also can select in the following flat board any: as the different image display medium of color more than 2 kinds or 2 kinds, the flat board that charging property particle 3 (referring to Fig. 1 (a) and (b) and Fig. 2 (a) and (b), being expressed as white particles 3W and black particles 3B herein) is used in the display mode that the direction vertical with substrate 1,2 moves; The flat board that the charging property particle 3W (referring to Fig. 3 (a) and (b)) that makes a kind of color uses in the display mode that the direction parallel with substrate 1,2 moves.In addition, among Fig. 1～Fig. 3,4 is the dividing plate that is provided with as required, the 5, the 6th, and the electrode that is provided with as required for particle 3 is applied electric field.
Image display medium of the present invention be characterized as the specific inductive capacity that defines particle 3.At first, common particle is described.The preparation of particle can be mixing with essential resin, charged controlling agent, colorant, other adjuvants, pulverizes; Perhaps also can form by monomer polymerization; Perhaps also can be covered with resin, charged controlling agent, colorant, other adjuvants having particle now.The example of resin, charged controlling agent, colorant, other adjuvants is identical with the particle content of following explanation.
Shown under the concrete disposal for example of reduction particle permittivity.
When (1) titanium dioxide high dielectric property materials such as (II) being used as Chinese white, making the resin as particle master material is low-dielectric materials such as polystyrene resin, the high dielectric property material is dispersed in the main body with the weight ratio (volume ratio) below 50% or 50%, reduces the permittivity of particle integral body.
When (2) preparing black particles, use the low black dyes of electrical insulating property that lures to replace the pigment of use at present: carbon black.In addition, do not use other conductive materials as the particle constituent material.Just in case in the time of need containing conductive material, adopt the prescription identical to reduce the permittivity of particle integral body with above-mentioned (1).In addition, reduce the conductive material amount that separate out on the surface, make particle surface not have electric conductivity.
When (3) liquid etc. that molecule is had polarity is enclosed in the particle, also cause permittivity to increase substantially, therefore not used as the particle constituent material.For example can enumerate water etc.
The explanation of＜the 4 invention 〉
The white particles 3W that being characterized as of the 4th invention of the present invention relates in the particle that uses in image display medium and utilize the white powder fluid of above-mentioned white particles 3W.The following describes white particles.
At first, the 4th white particles that invention relates to of the present invention is described.
Fig. 7 (a)～(c) illustrates one of the 4th the white particles preparation method that invention relates to of the present invention example by process sequence respectively.Order by Fig. 7 (a)～(c) illustrates white particles of the present invention, at first, shown in Fig. 7 (a), as one of herein Chinese white example, prepares 1 particle of titanium dioxide 21.As titanium dioxide 21, preferably use the pigment titanium dioxide.In addition, the mean grain size of above-mentioned 1 particle needs only the mean grain size less than the final white particles that requires, as one of them example, preferably in the scope of 0.01～1.0 μ m.The more preferably scope of 0.2～0.3 μ m that reflectivity is the highest.
Then, at 1 particle surface of the titanium dioxide of preparing 21 bonding agent 22 that is covered thinly.As above-mentioned bonding agent 22, so long as low-index material, can be covered gets final product, can use any material, for example, preferably use acrylic acid, PS (polystyrene), PE (tygon), PET (polyethylene terephthalate), PC (polycarbonate), POM (polyacetal), fluorine, epoxy resin, various silane coupling agent, various siloxane etc.In addition,, preferably adopt following method: bonding agent 22 is dissolved in the solvent, is spin-coated on the method on 1 particle of titanium dioxide 21 as the lining method; Or in the solution of bonding agent 22, disperse 1 particle of titanium dioxide 21, be rotated the method for spraying, drying.
Then, with 1 particle of the surface-coated titanium dioxide 21 that bonding agent 22 arranged in air flow or mechanicalness mix and stir, when importing a large amount of micro air bubble, make its aggegation, granulation to the regulation particle diameter.The result is shown in Fig. 7 (c), and micro-bubble 23 is contained in its inside, makes 1 particles aggregate or the granulation of the titanium dioxide 21 of the bonding agent 22 that has been covered, and 2 particles that obtain the regulation particle diameter are as white particles 24.In addition, aggegation, granulation are operated in the time of can being covered bonding agent 22 on 1 particle of titanium dioxide 22 and are carried out.Also can use zinc paste to replace above-mentioned pigment titanium dioxide.In addition, by using above-mentioned white particles, can make following powder fluid (white powder fluid).
The explanation of＜the 5 invention 〉
Image that the 1st embodiment of the 5th invention of the present invention relates to shows that to make one of 2 kinds of different particles of the charged characteristic that uses in the image display medium more than at least 2 kinds or 2 kinds and optical reflectivity be to have concavo-convex particle on the surperficial macroscopic view with dull and stereotyped, another particle is not have concavo-convex particle on the surperficial macroscopic view, prevent thus particle each other aggegation adhere to, improve the permanance when using repeatedly.
In addition, image that the 2nd embodiment of the 5th invention of the present invention relates to shows that to make one of 2 kinds of different particles of the charged characteristic that uses in the image display medium more than at least 2 kinds or 2 kinds and optical reflectivity be to have concavo-convex particle on the surperficial macroscopic view with dull and stereotyped, another particle be do not exist concavo-convex on the surperficial macroscopic view and, particulate electrostatic adhesion particle from the teeth outwards, prevent thus particle each other aggegation adhere to, improve the permanance when using repeatedly.
Fig. 1 (a) and (b)～Fig. 3 (a) and (b) represent that respectively image of the present invention shows the formation with one of flat board example.Image of the present invention shown in Fig. 1 (a) and (b) and Fig. 2 (a) and (b) shows with in the flat board, as charged characteristic and 2 kinds of different image display mediums of optical reflectivity, particle group (herein being white particles group 3W and black particles group 3B) is enclosed 1,2 of substrates, apply electric field (examples of Fig. 1 (a) and (b)) or apply electric field (examples of Fig. 2 (a) and (b)) from the outside to the particle group 3 of enclosing by electrode 5,6, it is moved to the direction vertical with substrate 1,2, carry out image thus and show.In addition, image of the present invention shown in Fig. 3 (a) and (b) shows with in the flat board, as a kind of image display medium, particle group (herein being white particles group 3W) is enclosed 1,2 of substrates, particle group 3 by 5,6 pairs of inclosures of electrode applies electric field, it is moved to the direction parallel with substrate 1,2, carry out image thus and show.In aforesaid way, also can shown in Fig. 1 (b), Fig. 2 (b), Fig. 3 (b), the space of 1,2 of substrates be separated with dividing plate 4, make structure with a plurality of unit, enclose particle group 3 therein, composing images shows with dull and stereotyped.
The particle that uses among the 1st embodiment of the 5th invention of the present invention at first is described.
Shown in Fig. 8 (a) and (b), charged characteristic and the optical reflectivity different 2 kind particles of the particle that uses among the 1st embodiment of the 5th invention of the present invention for comprising in the image display medium more than at least 2 kinds or 2 kinds, one is the particle 3W that has concavo-convex shape on the surperficial macroscopic view, and another particle is the particle 3B that does not have concavo-convex shape on the surperficial macroscopic view.The preparation of particle can be mixing with essential resin, charged controlling agent, colorant, other adjuvants, pulverizes; Perhaps also can form by monomer polymerization; Perhaps also can be covered with resin, charged controlling agent, colorant, other adjuvants having particle now; Owing to can make up 2 kinds of methods, therefore make exist on wherein a kind of particle surface macroscopic view concavo-convex, make that not exist concavo-convex on the another kind of particle surface macroscopic view be very important.
Generally speaking, shown in Fig. 9 (a), between the different 2 kinds of particles of charged characteristic, be at 2 kinds of particles and do not exist on surface smoothing, the macroscopic view when concavo-convex, can't guarantee the space between different 2 kinds of particles that attract each other, so aggegation takes place and adheres in particle each other easily because of charged characteristic, shown in Fig. 9 (b), be at 2 kinds of particles and exist on the surperficial macroscopic view when concavo-convex, attract each other between 2 kinds of particles, aggegation still takes place between the particle easily adhere to.In the particle that uses among the 1st embodiment of the 5th invention of the present invention, shown in Fig. 8 (a) and (b), by making the macro surface shape difference of 2 kinds of different particles of the charged characteristic that is used in combination, can guarantee the space between different 2 kinds of particles that attract each other because of charged characteristic, can prevent particle each other aggegation adhere to.
In addition, general particle among the 1st embodiment that relates to for the 5th invention of the present invention and the 2nd embodiment, shown in Fig. 8 (b), make particulate 31 brute forces attached to not existing on the concavo-convex master batch 3W on the surface smoothing for preparing, the macroscopic view, prepare when having concavo-convex particle on the surperficial macroscopic view, it is important that particulate 31 does not break away from from master batch 3W, even preferred the employing makes its brute force adhere to the method that becomes to use mechanical impact force particulate 31 also not break away from from master batch 3W.
Below, the particle that uses among the 2nd embodiment of the 5th invention of the present invention is described.
As shown in figure 10, charged characteristic and the optical reflectivity different 2 kind particles of the particle that uses among the 2nd embodiment of the 5th invention of the present invention for comprising in the image display medium more than at least 2 kinds or 2 kinds, one is the particle 3B that has concavo-convex shape on the surperficial macroscopic view, another kind of particle be do not exist concavo-convex on the surperficial macroscopic view and, the particle 3W of particulate 32 electrostatic adhesion shape from the teeth outwards.The preparation of particle can be mixing with essential resin, charged controlling agent, colorant, other adjuvants, pulverizes; Perhaps also can form by monomer polymerization; Perhaps also can be covered with resin, charged controlling agent, colorant, other adjuvants having particle now; Owing to be used in combination 2 kinds of methods, therefore make exist on a kind of particle surface macroscopic view concavo-convex, make that not exist concavo-convex on the another kind of particle surface macroscopic view be important.The preparation method of above-mentioned particle is identical with the 1st embodiment.
Generally speaking, between 2 kinds of different particles of common charged characteristic, shown in Fig. 9 (a), 2 kinds of particles are and do not exist on surface smoothing, the macroscopic view when concavo-convex, can't guarantee the space between 2 kinds of particles, so particle aggegation takes place each other easily adheres to, shown in Fig. 9 (b), 2 kinds of particles are and exist on the surperficial macroscopic view when concavo-convex, and 2 kinds of particles attract each other, aggegation still takes place between particle easily adhere to.In the particle that uses among the 2nd embodiment of the 5th invention of the present invention, as shown in figure 10, by making the macro surface shape difference of 2 kinds of different particles of the charged characteristic that is used in combination, can guarantee the space between different 2 kinds of particles that attract each other because of charged characteristic, can prevent particle each other aggegation adhere to.Above-mentioned effect is identical with the 1st embodiment.
In addition, in the particle that uses among the 2nd embodiment of the 5th invention of the present invention, except with the identical effect of above-mentioned the 1st embodiment, as shown in figure 11, even because of there not being the concavo-convex identical particle of the charged characteristic aggegation each other that makes on the surperficial macroscopic view, also since the particulate electrostatic adhesion on its surface, guarantee interparticle space, and adhering to of above-mentioned particulate is electrostatic means, be not that brute force is adhered to, therefore particulate rolls at particle surface, brings into play the effect of lubricant between particle thus, thus can prevent particle each other aggegation adhere to.
The following describes in the particle that uses among the 1st embodiment that the 5th invention of the present invention relate to and the 2nd embodiment, be used for powerful attached to do not have concavo-convex particle (master batch) on the surperficial macroscopic view, the concavo-convex particulate (seed) of formation on its surperficial macroscopic view.
The mean grain size of this particulate is 20nm～200nm, 20nm～150nm, further preferred in the scope of 20nm～100nm more preferably.If surpass 200nm, then the solid attached property that does not have concavo-convex particle surface on the above-mentioned surperficial macroscopic view is weakened, on surperficial macroscopic view, do not exist concavo-convex particle surface to break away from easily, can't bring into play the effect of the aggegation adhesion that reduces by 2 kinds of particles.In addition, if not enough 20nm then can't form and has concavo-convex particle on the surperficial macroscopic view, even particulate is solid attached, also become with surperficial macroscopic view on do not exist concavo-convex particle identical, can't bring into play the effect of the aggegation adhesion that reduces by 2 kinds of particles.
The charged polarity of this particulate also can with surperficial macroscopic view on do not exist concavo-convex particle (master batch) polarity identical, but attached admittedly with the master batch brute force is important, preferably have opposite polarity for this reason, do not have concavo-convex particle (master batch) surface on the surperficial macroscopic view thereby particulate (seed) positively is attached to.
As the material that can be used as particulate (seed), can enumerate metal oxides such as titanium dioxide, tin oxide, zirconia, tungsten oxide, iron oxide, nitride such as titanium nitride, monox, titanium compound etc., can also enumerate the particulate that constitutes by by nitride, titanium compounds such as metal oxides such as the monox of hydrophobization, titanium dioxide, tin oxide, zirconia, tungsten oxide, iron oxide, titanium nitrides, preferably by the particulate that is constituted by the monox of hydrophobization.
Hydrophobization can be handled with the hydrophobization treating agent, as the hydrophobization treating agent, can use in chlorosilane, alkoxy silane, silazane, the silylanizing isocyanates any.Particularly, can enumerate methyl trichlorosilane, dimethyldichlorosilane, trimethyl chlorosilane, methyltrimethoxy silane, dimethyldimethoxysil,ne, methyl triethoxysilane, dimethyldiethoxysilane, isobutyl trimethoxy silane, decyl trimethoxy silane, hexamethyldisilazane, tert-butyl chloro-silicane, vinyl trichlorosilane, vinyltrimethoxy silane, vinyltriethoxysilane etc.
Making above-mentioned particulate, positively powerful to be attached to the method that does not have concavo-convex particle surface on the surperficial macroscopic view be important, for example, can use Hybridizer (nara machinery make institute (strain) system) or Mechanofusion (HOSOKAWAMICRON (strain) system) etc. that particle surface is applied the device of mechanical impact force, make particulate (seed) positively brute force be attached to and do not have concavo-convex particle (master batch) surface on the surperficial macroscopic view.
The following describes the particulate that uses among the 2nd embodiment of the 5th invention of the present invention.
The particulate that uses among the 2nd embodiment of the 5th invention of the present invention is the little particle of particle that color is different with charged characteristic than 2 kinds, and there is not concavo-convex particle surface in electrostatic adhesion on the surperficial macroscopic view in 2 kinds of colors particle different with charged characteristic, as not existing the lubricant that (has between the particle of identical charged characteristic) between concavo-convex particle to play a role on the surperficial macroscopic view in 2 kinds of colors particle different with charged characteristic.
The mean grain size of this particulate is 20nm～200nm, 20nm～150nm, further preferred in the scope of 20nm～100nm more preferably.If surpass 200nm, then be difficult to electrostatic adhesion and on surperficial macroscopic view, do not have concavo-convex particle surface, the effect that can't be present between 2 kinds of particles, performance reduces the aggegation adhesion of 2 kinds of particles.In addition, if not enough 20nm, then electrostatic adhesive force became strong, did not show the lubricant effect that is produced by the tumble action at particle surface, therefore can't bring into play the effect that reduces by 2 kinds of identical interparticle aggegation adhesion of charged characteristic.
Do not exist concavo-convex particle polarity opposite on the surperficial macroscopic view in the charged polarity of this particulate particle different with charged characteristic with 2 kinds of colors, there is not concavo-convex particle surface in the particulate electrostatic adhesion on surperficial macroscopic view.When not existing concavo-convex particle polarity identical on the surperficial macroscopic view, there is concavo-convex particle surface in electrostatic adhesion on surperficial macroscopic view, can't bring into play the effect of the aggegation adhesion that reduces by 2 kinds of particles.When not existing concavo-convex particle opposite on polarity and the surperficial macroscopic view, if changing to make, charging property do not exist the charged polarity of concavo-convex particle to change on the surperficial macroscopic view, exist on the then surperficial macroscopic view not exist the charged characteristic balance of concavo-convex particle destroyed on concavo-convex particle and the surperficial macroscopic view, therefore not preferred.
As the material that can be used as particulate, can enumerate metal oxides such as titanium dioxide, tin oxide, zirconia, tungsten oxide, iron oxide, nitride such as titanium nitride, monox, titanium compound etc., and can enumerate the particulate that constitutes by by nitride, titanium compounds such as metal oxides such as the monox of hydrophobization, titanium dioxide, tin oxide, zirconia, tungsten oxide, iron oxide, titanium nitrides, preferably by the particulate that is constituted by the monox of hydrophobization.
Hydrophobization can use the hydrophobization treating agent to handle, and as the hydrophobization treating agent, can use in chlorosilane, alkoxy silane, silazane, the silylanizing isocyanates any.Particularly, can enumerate methyl trichlorosilane, dimethyldichlorosilane, trimethyl chlorosilane, methyltrimethoxy silane, dimethyldimethoxysil,ne, methyl triethoxysilane, dimethyldiethoxysilane, isobutyl trimethoxy silane, decyl trimethoxy silane, hexamethyldisilazane, tert-butyl chloro-silicane, vinyl trichlorosilane, vinyltrimethoxy silane, vinyltriethoxysilane etc.
The explanation of＜the 6 invention 〉
The feature of the 6th invention of the present invention relates to the white particles 3W in the particle that uses in the image display medium and utilizes the white powder fluid of this white particles 3W.The following describes white particles.
White particles of the present invention at first is described.
Being characterized as of white particles of the present invention when adopting mixing comminuting method to be prepared, will partly be replaced into hollow-particle for the white Chinese white that mixes in order to make the resin as matrix.Herein, adopt mixing comminuting method to be because when adopting polymerization, when the preparation polymer particles, must in liquid, make monomer and pigment aggegation, even utilize hollow-particle to replace pigment as autofrettage, also hollow-particle swims in the liquid because of in liquid the time, and can't utilize hollow-particle.
When adopting mixing comminuting method to prepare white particles, to wait to grind as the resin of matrix, Chinese white (all or part of be hollow-particle), CCA (charged controlling agent), various filling agent (mobility donor, anti-adhesion dose etc.) and carry out mixingly, piece or the sheet that obtains will be ground into the regulation particle diameter with biaxial extruder or plasticity.Pulverizing can utilize freezing comminuting method or various comminuting method.As the resin of matrix, preferably use resins such as PMMA (polymethylmethacrylate), PC (polycarbonate), acroleic acid polyurethane, acrylic acid herein.In addition, as Chinese white, preferably use titanium dioxide, zinc paste, zirconia etc.
Figure 12 illustrates the structure of one of hollow-particle of using in the white particles of the present invention example.In the example shown in Figure 12, hollow-particle 41 is by the space part 42 of inside and surround the spherical high crosslinked polymer layer 43 that the whole periphery ground of space part 42 forms and constitute.As high crosslinked polymer layer 43, can preferably use cross-linked styrene-acrylic acid.This hollow-particle 41 have be called light scattering characteristic, thermal insulation result from hollow feature and be called the feature that results from cross-linked polymer of thermotolerance, anti-solution.The air of particularly high crosslinked polymer layer 43 and space part 42 causes light scattering, and the performance covering effect can pass through the replacing section Chinese white thus, obtains white particles.
The 6th white particles that invention relates to of the present invention fills Chinese white in as the resin of matrix and hollow-particle constitutes.At present, with respect to resin 100 weight portions as matrix, when titanium dioxide is the 200 weight portion left and right sides, the whiteness of the white particles when only using the titanium dioxide as Chinese white shows maximal value, if the addition of titanium dioxide reaches 300 weight portions, then mixing change is difficult, poor dispersion, so whiteness reduces.With respect to resin 100 weight portions, add 10～50 parts by weight of titanium oxide hollow-particle in addition, the whiteness when making whiteness be higher than filling 200 parts by weight of titanium oxide thus as matrix.Simultaneously also can improve mixing property, compare when filling separately and can carry out the height filling with titanium dioxide.In addition, by utilizing above-mentioned white particles, can make following powder fluid (white powder fluid).
The explanation of＜the 7 invention 〉
The image of the 7th particle that invention relates to of the present invention as image display medium shown with in the flat board, adopt any method to give substrate with electric charge, this substrate is at the substrate of the demonstration of having enclosed image display medium more than at least 2 kinds or 2 kinds between counter substrate with flat board, produces electric field between substrate.Charged image display medium for electronegative potential is attracted to the charged substrate position of noble potential that is by Coulomb force etc., in addition, charged image display medium for noble potential is attracted to the charged substrate position of electronegative potential that is by Coulomb force etc., the to-and-fro movement between 2 substrates of above-mentioned image display medium is carried out image thus and is shown.Therefore, must become image display medium to move equably with slab design with showing, and can keep repeatedly the time or the stability in when preservation.
Fig. 1 (a) and (b)～Fig. 3 (a) and (b) illustrate respectively the image of the 7th particle that invention relates to of the present invention as image display medium are shown with the routine formation of one of flat board.Image of the present invention shown in Fig. 1 (a) and (b) and Fig. 2 (a) and (b) shows with in the flat board, as charged characteristic and 2 kinds of different image display mediums of optical reflectivity, particle group (herein being white particles group 3W and black particles group 3B) is enclosed 1,2 of substrates, apply electric field (examples of Fig. 1 (a) and (b)) or apply electric field (examples of Fig. 2 (a) and (b)) from the outside to the particle group 3 of enclosing by electrode 5,6, it is moved to the direction vertical with substrate 1,2, carry out image thus and show.In addition, image of the present invention shown in Fig. 3 (a) and (b) shows with in the flat board, as a kind of image display medium, particle group (herein being white particles group 3W) is enclosed 1,2 of substrates, particle group 3 by 5,6 pairs of inclosures of electrode applies electric field, it is moved to the direction parallel with substrate 1,2, carry out image thus and show.In the aforesaid way, also can shown in Fig. 1 (b), Fig. 2 (b), Fig. 3 (b) space of 1,2 of substrates be separated with dividing plate 4, make the structure with a plurality of unit, enclose particle group 3 therein, composing images shows with dull and stereotyped.
The formation that is characterized as the particle that in the image of above-mentioned formation shows with flat board, uses in the image display medium of the 7th invention of the present invention.That is, use thermoset resin, will contain the resin material of thermoset resin and make it that heat cross-linking reaction take place after mixing, then, pulverize, obtain particle as the base resin of particle.Discovery is compared as the example of base resin with using existing thermoplastic resin by using the thermoset resin that obtains through above-mentioned heat cross-linking reaction, thermotolerance can be improved about 30 ℃.
As the cooperation of thermoset resin, generally speaking, most preferably be called the vibrin+blocked isocyanate class (more specifically the above blocked isocyanate of vibrin+3 functional groups or 3 functional groups) of polyurethane for having the OH end.In addition, as the cooperation that the heat cross-linking reaction the mixing back of resin material can be taken place, alkyd resin+melamine cured dose class, epoxy resin+amine hardener class, urea resin+formaldehyde etc. are arranged under the high temperature that is higher than the temperature when mixing.As the other materials of the thermoset resin that is used as above-mentioned host material, can similarly suitably select to use pigment (titanium dioxide, carbon black etc.), charged controlling agent (CCA), organotin catalysts etc. with existing particle.
In order to prepare particle of the present invention, can be with by the mixing potpourri for preparing of resin material that constitutes as the thermoset resin of host material and other materials, for example pigment, charged controlling agent, organotin catalysts etc.After stipulated time * temperature (high temperature that is higher than the temperature when mixing) made said mixture generation cross-linking reaction, it was broken to carry out micro mist with jet pulverizer, obtains particle.
The explanation of＜the 8 invention 〉
The 8th image that invention relates to of the present invention shows with flat board and is characterised in that the shape of particle of at least a particle in 2 kinds of different particles of the charged characteristic that will comprise in the image display medium more than at least 2 kinds or 2 kinds and optical reflectivity makes the shape of flattened round.According to the 8th invention of the present invention, the form that form of seamlessly arranging at substrate surface by the flattened round particle shown in Figure 13 relatively and the spheroidal particle shown in Figure 14 are arranged with a gap at substrate surface, can determine because particle is seamlessly arranged each other easily, interparticle gap tails off, so contrast improves.
Charged characteristic and the optical reflectivity different 2 kind particles of the particle that uses in the 8th invention of the present invention for comprising in the image display medium more than at least 2 kinds or 2 kinds, one of them plants particle is the flattened round particle.The preparation of particle can followingly be carried out: with essential resin, charged controlling agent, colorant, other adjuvants mixing after, at first the potpourri of fine sheet shape is pulverized, its flinders is exposed under the fusing point of resin or the temperature more than the fusing point, makes the bight fusion of flinders, make spherical.In addition, also can be prepared, but be difficult to obtain the particle diameter (mean grain size: flattened round particle 0.1～50 μ m) that the present invention preferably uses by monomer polymerization.The example of resin, charged controlling agent, colorant, other adjuvants is identical with the content of the particle of following explanation.
The explanation of＜the 9 invention 〉
The 9th image that invention relates to of the present invention show with dull and stereotyped be characterized as with the mean grain size of shallow light tone particle group with Dbright represent, when the mean grain size of deep dark particle group is represented with Ddark, the particle diameter of 2 kinds of particle groups (deep dark particle group and shallow light tone particle group) that color that comprises in the image display medium and charged characteristic are different pass is Ddark＜Dbright.That is, the mean grain size Dbright by making shallow light tone particle group shows with dull and stereotyped even can obtain the good also good low price image of picture contrast that uses repeatedly of picture contrast greater than deep dark particle group Ddark.
In addition, to the degree not specially provided for of the relation of Ddark＜Dbright,, obtain relatively poor result when differing big on the contrary as long as exist fine difference just enough.Therefore, preferably in the scope of 1＜Dbright/Ddark＜2.Herein, preferred Dbright/Ddark＜2nd is because if particle diameter differs more than 2 times or 2 times, then in the gap of the big shallow light tone particle proper alignment of particle diameter, there is the little deep dark particle of particle diameter, the problem that exists the deep dark particle to cause whiteness to reduce because of the gap at the shallow light tone particle of arranging takes place this moment.
Below, color and the different particle group of charged characteristic used among the present invention are described.
In the different particle group of color of using among the present invention and charged characteristic, the particle group of a kind of particle group for constituting, the particle group of another kind of particle group for constituting by shallow light tone particle by the deep dark particle.Particle can adopt following method to be prepared: essential resin, charged controlling agent, colorant, other adjuvants are pulverized after mixing, the method for classification; Perhaps, carry out the method for classification by monomer polymerization.The example of resin, charged controlling agent, colorant, other adjuvants is identical with the particle content of following explanation.
The explanation of＜the 10 invention 〉
The formation that is characterized as the particle that uses in the image display medium of image demonstration that is used for above-mentioned formation of the 10th invention of the present invention with flat board.That is, complexed metal oxide or fatty acid metal salt compound are controlled charging property in the base resin of particle.Complexed metal oxide or fatty acid metal salt compound in base resin are compared with the example of present uncontrollable charging property as described above, the charging property control that can wish.
As the metal oxide in the base resin that is engaged in particle (MOx, herein, M: metallic element, O: oxygen, the ratio of x:O/M), also can utilize up to now as the known arbitrary example of metal oxide, for example can enumerate MgO, ZnO, Al 2O 3, SiO 2, SnO 2, Fe 3O 4, Fe 2O 3Deng.
As ((CmHnCOO) yMz of the fatty acid metal salt compound in the base resin that is engaged in particle, herein, M: metallic element, m, n, y, z are integer, 4＜m＜22), also can utilize at present as the known arbitrary example of fatty acid metal salt compound, for example can enumerate the caprylate (m=10), laurate (m=12), myristate (m=14), palmitate (m=16), stearate (m=18), oleate (m=18), linoleate (m=18) of Mg, Ca, Al, Fe, Li, Ba etc.
In addition, as the preference that metal oxide or fatty acid metal salt compound is engaged in the particle in the base resin, following example is arranged: the polarization electronegativity χ of the ion of metallic element (M) is 0.79＜χ＜1.91, has Positively chargeable; In these cases, metallic element is among Mg, Zn, Ca, Li, Zr, Al, Ni, Cu, Ba, the Ti wantonly a kind.Herein, the polarization electronegativity χ of the ion of metallic element (M) is preferably 0.79＜χ＜1.91st, if because electronegativity χ is below 0.79 or 0.79, and then carried charge becomes too high, when composing images showed with flat board, image display medium became and can't change; If electronegativity χ is more than 1.91 or 1.91, then carried charge became low, and when composing images showed with flat board, image display medium became and can't change.
And as other preferences that metal oxide or fatty acid metal salt compound are engaged in the particle in the base resin, following example is arranged: the polarization electronegativity χ of the ion of metallic element (M) is 1.50＜χ＜2.58, has negative charging; And in these cases, metallic element is wantonly a kind among Fe, Ti, Cu, Si, Sb, W, Sn, Ge, the Co.Herein, the polarization electronegativity χ of the ion of metallic element (M) is preferably 1.50＜χ＜2.58th, if because electronegativity χ is below 1.50 or 1.50, and then carried charge became low, when composing images showed with flat board, image display medium became and can't change; If electronegativity χ is more than 2.58 or 2.58, then carried charge becomes too high, and when composing images showed with flat board, image display medium became and can't change.
The explanation of＜common ground 〉
The formation of image display device common in～the 10 invention of the 1st invention of the present invention is described by the order of substrate, electrode, dividing plate below, and explanation particle group and powder fluid.
For substrate, at least one side group plate is can be from the transparency carrier 2 of the color of device outside recognition image display medium, preferred visible light transmittance height and the good material of thermotolerance.Substrate 1 can be transparent, also can be opaque.If enumerate baseplate material, then can enumerate polymer sheets such as polyethylene terephthalate, polyethersulfone, tygon, polycarbonate, polyimide, acryl resin or metal sheet and so on and have flexual material, reach glass, quartz etc. and do not have flexual inorganic sheet, the thickness of substrate is preferably 2～5000 μ m, 5～2000 μ m more preferably, if cross thin, then be difficult to guarantee intensity, substrate distance homogeneity, if thickness surpasses 5000 μ m, there is unfavorable condition when then making flat type image display device.
For the electrode that is provided with as required, forming by conductive material transparent and that can form pattern as identification side, the electrode 6 that is necessary for the 2 side settings of transparent substrate, if give an example, then electroconductive polymer classes such as metal species such as indium oxide, aluminium, gold, silver, copper, polyaniline, polypyrrole, polythiophene can be enumerated, formation methods such as vacuum evaporation, coating can be enumerated.In addition, if thickness of electrode can guarantee electric conductivity, not influence light transmission, can be for 3～1000nm, be preferably 5～400nm.It is identical with above-mentioned electrode 6 to be arranged on the material of electrode 5 of substrate 1 side or thickness etc., needn't be for transparent.In addition, the external voltage power input under the above-mentioned situation can overlapping direct current or interchange.
For the dividing plate 4 that is provided with as required, its shape suitably is set at optimum range according to the image display medium kind that demonstration relates to, cannot treat different things as the same, the width of dividing plate is 2～100 μ m, be preferably 3～50 μ m, and the height of dividing plate is 10～500 μ m, be preferably 10～200 μ m.In addition, when forming dividing plate, can adopt following method: the two flange methods that after forming flange respectively on the opposed two substrates, engage, only single flange method of formation flange on a side group plate.Among the present invention, preferably adopt any method.
The display unit that the dividing plate that is made of above-mentioned flange forms as shown in figure 15, is observed from the base plan direction, is quadrilateral, triangle, wire, circle, hexagon for example, as configuration, can enumerate trellis, cellular or latticed.Can dwindle as far as possible and be equivalent to increase the bright acutance that image shows from showing the part (the frame portion area of display unit) of the observed dividing plate of side cross section part.If enumerate the formation method of dividing plate, then can enumerate silk screen print method, sand-blast, photoetching process, additive process herein.Wherein, the preferred photoetching process of using resist film that adopts.
Below, the particle that uses in the image display device of the present invention is described.Particle can similarly comprise charged controlling agent, colorant, inorganic additive etc. with existing situation as required in as the resin of its major component.Below, enumerate resin, charged controlling agent, colorant, other adjuvants.
As the resin example, can enumerate urethane resin, urea resin, acryl resin, vibrin, acrylated polyurethane resin, acroleic acid polyurethane silicones, acroleic acid polyurethane fluororesin, acrylic acid fluororesin, silicones, acrylic silicon resin, epoxy resin, polystyrene resin, styrene acrylic resin, polyolefin resin, butyral resin, permalon, melamine resin, phenolics, fluororesin, polycarbonate resin, polysulfone resin, polyether resin, polyamide etc., also can use mixing more than 2 kinds or 2 kinds.Consider preferred especially acrylated polyurethane resin, acrylic silicon resin, acrylic acid fluororesin, acroleic acid polyurethane silicones, acroleic acid polyurethane fluororesin, fluororesin, silicones from the control and the adhesion aspect of substrate.
As charged controlling agent, be not particularly limited, as the negative charging controlling agent, for example can enumerate oil-soluble dyes, quaternary ammonium compound, calixarene compound, boron-containing compound (benzoic acid boron coordination compound), nitro imidazole derivatives of salicylic acid metal coordination compound, containing metal azo dyes, containing metal (comprising metallic ion or metallic atom) etc.As just charged controlling agent, for example can enumerate aniline black byestuffs, triphenyl methane compounds, quaternary ammonium compound, polyamino resin, imdazole derivatives etc.In addition, also can use nitrogenous ring compound such as metal oxide, pyridine and derivant or salt, various organic pigments such as ultra micron silicon dioxide, ultra micron titanium dioxide, ultra micron aluminium oxide, contain the resin etc. of fluorine, chlorine, nitrogen etc. as charged controlling agent.
As colorant, versicolor pigment, the dyestuff of the organic or inorganic of enumerating below can using.
As black colorant, carbon black, cupric oxide, manganese dioxide, nigrosine, activated charcoal etc. are arranged.
As cyan colorant, the C.I. pigment blue 15 is arranged: 3, C.I. pigment blue 15, dark blue, cobalt blue, alkali blue lake, Victoria blue color lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue part chloride, fast sky blue, indanthrene blue BC etc.
As red stain, colcother (Bengala), cadmium red, red lead, mercuric sulphide, cadmium, water red 4R of a specified duration, lithol red (Lithol red), pyrazolone red, C lake red CAN'T, calcium salt, C lake red CAN'T D, bright famille rose (Brilliant carmine) 6B, eosine lake, rhodamine color lake B, alizarine lake, bright carmine 3B, C.I. paratonere 2 etc. are arranged.
As yellow colorants, chrome yellow, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, orange, naphthol yellow S, hansa yellow G, hansa yellow 10G, benzidine yellow G, benzidine yellow G R, quinoline yellow lake, permanent yellow NCG, tartrazine lake, C.I. pigment Yellow 12 etc. are arranged.
As green colourant, chrome green, chromium oxide, pigment green B, C.I. pigment Green 7, malachite green color lake, final yellow green G etc. are arranged.
As orange colorant, red chrome yellow, molybdate orange, permanent orange GTR, pyrazolone orange, Balkan orange, indanthrene brilliant orange RK, Benzidine orange G, indanthrene brilliant orange GK, C.I pigment orange 31 etc. are arranged.
As violet colorant, manganese violet, Fast violet B, methyl violet color lake etc. are arranged.
As white color agents, zinc white, titanium dioxide, stibium trioxide, zinc sulphide etc. are arranged.
As extender pigment, there are ground barium sulfate, barium carbonate, clay, silicon dioxide, white carbon, talcum, aluminium oxide white etc.In addition, as various dyestuffs such as alkalescence, acidity, dispersion, direct dyess, nigrosine, methylene blue, rose-red, quinoline yellow, mazarine etc. are arranged.
As the example of mineral-type adjuvant, can enumerate that titanium dioxide, zinc white, zinc sulphide, antimony oxide, lime carbonate, white lead, talcum, silicon dioxide, calcium silicate, aluminium oxide are white, cadmium yellow, cadmium red, cadmium orange, titan yellow, dark blue, ultramarine, cobalt blue, cobalt green, cobalt violet, iron oxide, carbon black, the manganese ferrite is black, the cobalt ferrite is black, copper powder, aluminium powder etc.
Above-mentioned pigment and mineral-type adjuvant can use separately, also can severally be used in combination.Wherein, especially preferably use carbon black, use titanium dioxide as Chinese white as black pigment.
In addition, the mean grain size d of particle of the present invention (0.5) preferably neatly is evenly distributed in the scope of 0.1～50 μ m.If mean grain size d (0.5) is higher than above-mentioned scope, then lack the bright acutance on showing, if be lower than above-mentioned scope, then interparticle cohesive force becomes excessive, therefore hinders particle to move.
And, in the present invention, for the size distribution of each particle, the size distribution Span less than of representing with following formula 5, preferred less than 3.
Span＝(d(0.9)-d(0.1))/d(0.5)
(wherein, the grain diameter value of d (0.5) for representing with μ m, 50% in the particle is greater than this particle diameter, and 50% less than this particle diameter; The grain diameter value of d (0.1) for representing with μ m, the particle ratio that particle diameter is lower than above-mentioned numerical value is 10%; The grain diameter value of d (0.9) for representing with μ m, the particle ratio that particle diameter is lower than above-mentioned numerical value is 90%.)
Make Span in the scope below 5 or 5, make the consistent size of each particle, particle can move equably.
And, for the relation of each particle, the d (0.5) that makes the particle of particle diameter minimum in the employed particle with respect to the ratio of the d (0.5) of the particle of particle diameter maximum be below 50 or 50, be preferably below 10 or 10 extremely important.Even dwindle size distribution Span, the particle that charged characteristic differs from one another also can move round about, therefore preferably makes each particle size approaching, whenever the amount particle can easily move round about, promptly obtains above-mentioned scope.
In addition, above-mentioned size distribution and particle diameter can adopt laser diffraction/scattering method etc. to obtain.If to particle-irradiation laser as determination object, then in the space, form the light intensity distributions pattern of diffraction/scattered light, because there are corresponding relation in above-mentioned light intensity pattern and particle diameter, therefore can measure particle diameter and size distribution.
Herein, particle diameter of the present invention and size distribution are distributed by volume reference and obtain.Particularly, can use Mastersizer2000 (Malvern Instruments Ltd.) mensuration machine, in nitrogen stream, drop into particle,, measure particle diameter and size distribution with subsidiary parsing software (based on the software of the volume reference distribution of adopting the Mie theory).
The carried charge of particle depends on its condition determination certainly, image shows that the carried charge with the particle that uses in the dull and stereotyped image display medium depends on the initial stage carried charge basically, is to arrange the factor with the contacting of dividing plate, with the saturation value of the charged behavior of the charge decay, particularly particle that contact, pass in time generation of substrate.
The inventor etc. further investigate, and found that when adopting the ejection method, by using the same vehicle particle, measure the carried charge of particle, can estimate the suitable charged characteristic value scope of the particle that uses in the image display medium.
Below, the powder fluid that uses in the image display medium of image display device of the present invention is described.Need to prove the title of the powder fluid that uses in the image display medium for image display device of the present invention, the applicant obtains the right of " electronics powder fluid (registered trademark) ".
" powder fluid " among the present invention is not rely on the power of the power of gas or liquid and demonstrate self flowability, have the material of both intermediatenesses of the characteristic of fluid and particle concurrently.For example, liquid crystal be defined as liquid and solid in the middle of mutually, have as the mobile of fluid characteristics with as anisotropy (optical property) (the ordinary society: big encyclopaedia dictionary) of solid features.In addition, even particle is defined as to ignoring the object that size also has limited quality, (ball is kind: the physics dictionary) to be subjected to the influence of gravity.Herein, even particle also is in the special state that is called gas-solid fluidized bed body, liquid-solid liquid, from base plate to particle jet flow gas, then the speed corresponding to gas applies power upwards to particle, when this power and gravitational equilibrium, the particle that is in the state that can easily flow as fluid is called gas-solid fluidized bed body, similarly utilizes fluid to make the state of its liquidation be called liquid-solid liquid (ordinary society: big encyclopaedia dictionary).As mentioned above, gas-solid fluidized bed body or liquid-solid liquid are the state that flows that utilizes gas or liquid.Among the present invention, can make the power that do not rely on above-mentioned gas specifically, also not rely on the power of liquid and show the material of the state of self flowability, it is defined as powder fluid.
That is, the powder fluid that uses in the image display medium of the present invention is similarly to be in the intermediateness, the utmost point that have particle and liquid two specific characters concurrently with the definition of liquid crystal (liquid and solid in the middle of mutually) to feel bad as the gravity effect of the feature of above-mentioned particle, show the material of the distinguished state of high fluidity.Above-mentioned substance can with aerosol state, promptly in gas as obtaining in the stably floating dispersed system that solid shape or liquid material arranged of dispersed substance, in the image display device of the present invention with solid shape material as dispersed substance.
Show with dull and stereotyped between the transparent counter substrate of at least one side, enclose powder fluid as the image of object of the present invention as image display medium, this powder fluid is in the gas as the stably floating aerosol state that solids are arranged of dispersed substance, show high fluidity, above-mentioned powder fluid stably moves under the effect of Coulomb force etc. when applying low-voltage easily.
The powder fluid that uses in the image display medium of the present invention as mentioned above, is not rely on the power of gas, also do not rely on the power of liquid and demonstrate self flowability, have the material of both intermediatenesses of the characteristic of fluid and particle concurrently.Above-mentioned powder fluid particularly can be in aerosol state, in the image display device of the present invention, can be in gas as using this powder fluid under the floating more stablely state that solid shape material arranged of dispersed substance.
The scope of aerosol state be preferably the maximum apparent volume when floating of powder fluid when not floating more than 2 times or 2 times, be preferably in the scope more than 3 times or 3 times more preferably more than 2.5 times or 2.5 times, especially.The upper limit is not particularly limited, and is preferably below 12 times or 12 times.
If the apparent volume of powder fluid when maximum is floating 2 times when not floating, the control that then shows becomes difficult; If greater than 12 times, then operational inconvenience such as excessively floating are taken place in time in the powder fluid sealed in unit.In addition, maximum as described below mensuration of apparent volume when floating.That is, powder fluid put into to see through the closed container that powder fluid is observed, make container vibration itself or fall, make maximum floating state, measure apparent volume at this moment from outside of containers.Particularly, in the polypropylene system lidded container (trade name I-BOY:AS ONE (strain) system) of diameter (internal diameter) 6cm, height 10cm, powder fluid when not floating is put into the powder fluid that is equivalent to 1/5 volume, container is placed in the vibrating machine, in the distance of 6cm with 3 times back and forth/velocity fluctuation of sec 3 hours.With the apparent volume of vibration after just having stopped as maximum the apparent volume when floating.
In addition, preferably make the time variation of powder fluid apparent volume satisfy following formula among the present invention.
V 10/V 5＞0.8
Herein, V 5For begin the apparent volume (cm after 5 minutes when floating from maximum 3), V 10For begin the apparent volume (cm after 10 minutes when floating from maximum 3).In addition, image display device of the present invention preferably makes the time of the apparent volume of powder fluid change V 10/ V 5Greater than 0.85, be preferably greater than 0.9 especially.V 10/ V 5Be 0.8 or 0.8 when following, same when using common so-called particle, can't guarantee high-speed responsive of the present invention, permanance effect.
In addition, the mean grain size (d (0.5)) that constitutes the particulate material of powder fluid be preferably 0.1～20 μ m, more preferably 0.5～15 μ m, be preferably 0.9～8 μ m especially.If less than 0.1 μ m, the control that then shows becomes difficult; If greater than 20 μ m, then lack the bright acutance on showing.In addition, it is identical with d (0.5) among the following size distribution Span to constitute the mean grain size (d (0.5)) of particulate material of powder fluid.
The particulate material that constitutes powder fluid preferably makes the size distribution Span less than 5 shown in the following formula, and more preferably less than 3.
Size distribution Span=(d (0.9)-d (0.1))/d (0.5)
Herein, d (0.5) is the grain diameter value of representing with μ m, constitute powder fluid particulate material 50% greater than this particle diameter, 50% less than this particle diameter; D (0.1) is the grain diameter value of representing with μ m, and the ratio of the particulate material of the formation powder fluid that this value is following is 10%; D (0.9) is the grain diameter value of representing with μ m, and the ratio of the particulate material of the formation powder fluid that this value is following is 90%.Size distribution Span by making the particulate material that constitutes powder fluid is below 5 or 5, and consistent size, the powder fluid that can produce homogeneous can move.
In addition, above size distribution and particle diameter are for being obtained by laser diffraction/scattering method etc.If to powder fluid irradiating laser as determination object, then in the space, form the light intensity distributions pattern of diffraction/scattered light, there are corresponding relation in above-mentioned light intensity pattern and particle diameter, therefore can measure particle diameter and size distribution.Above-mentioned particle diameter and size distribution can be distributed by volume reference and obtain.Particularly, use Mastersizer2000 (Malvern Instruments Ltd.) mensuration machine drops into powder fluid in nitrogen stream, can measure with subsidiary parsing software (based on the software of the volume reference distribution of adopting the Mie theory).
The preparation of powder fluid can be mixing with essential resin, charged controlling agent, colorant, other adjuvants, pulverizes; Also can form by monomer polymerization; Also can be covered with resin, charged controlling agent, colorant, other adjuvants having particle now.Enumerate resin, charged controlling agent, colorant, other adjuvants of constituting powder fluid below.
Example as resin, can enumerate urethane resin, acryl resin, vibrin, polyurethane denaturing acrylamide acid resin, silicones, nylon resin, epoxy resin, styrene resin, butyral resin, permalon, melamine resin, phenolics, fluororesin etc., also can use mixing more than 2 kinds or 2 kinds, consider preferred especially acrylated polyurethane resin, acroleic acid polyurethane silicones, acroleic acid polyurethane fluororesin, urethane resin, fluororesin from the control and the adhesion aspect of substrate.
As the example of charged controlling agent, giving under the situation of positive charge, can enumerate quaternary ammonium compound, aniline black byestuffs, triphenyl methane compounds, imdazole derivatives etc.; Give under the situation of negative charge, can enumerate containing metal azo dyes, salicylic acid metal coordination compound, nitro imidazole derivatives etc.
As colorant, versicolor pigment, the dyestuff of the organic or inorganic of enumerating below can using.
As black colorant, carbon black, cupric oxide, manganese dioxide, nigrosine, activated charcoal etc. are arranged.
As cyan colorant, the C.I. pigment blue 15 is arranged: 3, C.I. pigment blue 15, dark blue, cobalt blue, alkali blue lake, Victoria blue color lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue part chloride, fast sky blue, indanthrene blue BC etc.
As red stain, colcother, cadmium red, red lead, mercuric sulphide, cadmium, permanent red 4R, lithol red, pyrazolone red, C lake red CAN'T, calcium salt, C lake red CAN'T D, brilliant carmine 6B, eosine lake, rhodamine color lake B, alizarine lake, bright carmine 3B, C.I. paratonere 2 etc. are arranged.
As yellow colorants, chrome yellow, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, orange, naphthol yellow S, hansa yellow G, hansa yellow 10G, benzidine yellow G, benzidine yellow G R, quinoline yellow lake, permanent yellow NCG, tartrazine lake, C.I. pigment Yellow 12 etc. are arranged.
As green colourant, chrome green, chromium oxide, pigment green B, C.I. pigment Green 7, malachite green color lake, final yellow green G etc. are arranged.
As orange colorant, red chrome yellow, molybdate orange, permanent orange GTR, pyrazolone orange, Balkan orange, indanthrene brilliant orange RK, Benzidine orange G, indanthrene brilliant orange GK, C.I. pigment orange 31 etc. are arranged.
As violet colorant, manganese violet, Fast violet B, methyl violet color lake etc. are arranged.
As white color agents, zinc white, titanium dioxide, stibium trioxide, zinc sulphide etc. are arranged.
As extender pigment, there are ground barium sulfate, barium carbonate, clay, silicon dioxide, white carbon, talcum, aluminium oxide white etc.In addition, as various dyestuffs such as alkalescence, acidity, dispersion, direct dyess, nigrosine, methylene blue, rose-red, quinoline yellow, mazarine etc. are arranged.
As the example of mineral-type adjuvant, can enumerate that titanium dioxide, zinc white, zinc sulphide, antimony oxide, lime carbonate, white lead, talcum, silicon dioxide, calcium silicate, aluminium oxide are white, cadmium yellow, cadmium red, cadmium orange, titan yellow, dark blue, ultramarine, cobalt blue, cobalt green, cobalt violet, iron oxide, carbon black, the manganese ferrite is black, the cobalt ferrite is black, copper powder, aluminium powder etc.
Above-mentioned pigment and mineral-type adjuvant can use separately or be used in combination multiple.Wherein, especially preferably use carbon black, use titanium dioxide as Chinese white as black pigment.
But, even mixing easily above-mentioned material, or above-mentioned material implemented lining etc., also can't prepare the powder fluid that shows aerosol state.The specific method for making that shows the powder fluid of aerosol state is not stipulated, is exemplified below.
At first, the solid attached mean grain size in particulate material surface that constitutes powder fluid be 20nm or more than the 20nm, 100nm or below the 100nm, be preferably 20nm or more than the 20nm, 80nm or the inorganic particles below the 80nm be suitable.And it is suitable that above-mentioned inorganic particles is made of particulate more than 2 kinds or 2 kinds.And it is suitable that above-mentioned inorganic particles is handled through silicone oil.As inorganic particles, can enumerate silicon dioxide (silicon dioxide), zinc paste, aluminium oxide, magnesium oxide, cerium oxide, iron oxide, cupric oxide etc. herein.
Admittedly it is important enclosing the method for stating inorganic particles, for example can use Hybridizer (nara machinery is made institute's (strain) system) or Mechanofusion devices such as (HOSOKAWAMICRON (strain) systems), (for example processing time) preparation shows the powder fluid of aerosol state only under given conditions.
And among the present invention, the gas of the gap of the image display medium between the curling substrate of management is important, helps to improve exhibit stabilization.Particularly, for the humidity of the gas of gap, make relative humidity under 25 ℃ be 60%RH or 60%RH following, be preferably 50%RH or 50%RH is following, 35%RH or be important below the 35%RH more preferably.
In Fig. 1～Fig. 3, above-mentioned gap is meant the gas part that the so-called image display medium that occupies part (when having dividing plate 4), device hermetic unit that occupies part, dividing plate 4 that deducts electrode 5,6 (having electrode at 5,6 o'clock), image display medium (particle group or powder fluid 3) in the part from be clipped in counter substrate 1, substrate 2 connects.
The gas of gap is as long as in above-mentioned humidity zone, and is unrestricted to its kind, preferred dry air, drying nitrogen, dry argon gas, dry helium gas, dry carbon dioxide, dry methane etc.Above-mentioned gas must sealed in unit in to keep its humidity, for example, under the specified humidity environment, carry out the filling of image display medium, the assembling of substrate etc., and, prevent that encapsulant, the encapsulating method of the humidity of invading from the outside is extremely important.
Image that image display device of the present invention possesses shows that the interval with substrate in the flat board and substrate needs only image display medium and can move, can keep contrast, is adjusted into 10～500 μ m usually, is preferably 10～200 μ m.
The volume occupation rate of image display medium is preferably 5～70% in the space between counter substrate, and more preferably 5～60%.Under 70% the situation of surpassing, hinder moving, moving of image display medium, under the situation of less than 5%, it is indeterminate that contrast becomes easily.
Below ,～the 10 embodiment that invention relates to of the 1st invention of the present invention is described successively.
＜the 1 embodiment that invention relates to 〉
＜embodiment 1 (particle) 〉
The aluminium ball that with mean grain size is 7.0 μ m is as the core of examining.The total reflectivity on the aluminium ball surface of the formation core that uses (interface that is equivalent to core and outer layer segment) is 85%.On aluminium ball as above-mentioned core, use the existing white material of Agglomaster (HOSOKAWAMICRON Co., Ltd. system) lining, prepare outer layer segment, obtain white particles of the present invention.
White material is prepared as follows: add titanium dioxide 10phr, charged controlling agent BONTRON E89 (Orient chemistry (strain) system) 2phr in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), carry out mixing after, carry out crushing and classification with jet pulverizer and prepared.
The mean grain size of the white particles that obtains is that 9.0 μ m, surface charge density are-60 μ C/m 2In addition, when measuring the briliancy rate as the white particles on basis and white particles of the present invention, the briliancy rate of white particles of the present invention improves 5% with comparing as the briliancy rate of the existing white particles on basis.
＜embodiment 2 (particle) 〉
Be the aluminium of evaporation 500nm on the PMMA ball of 5.0 μ m in mean grain size, will obtain particle as the core of examining.The total reflectivity on the surface of the aluminium-vapour deposition film of the formation core that uses (interface that is equivalent to core and outer layer segment) is 82%.Use Agglomaster (HOSOKAWA MICRON Co., Ltd. system) that existing white material is overlayed on the above-mentioned core similarly to Example 1, prepare outer layer segment, obtain white particles of the present invention.
The mean grain size of the white particles that obtains is 8.0 μ m, and surface charge density is-50 μ C/m 2In addition, when measuring the briliancy rate as the white particles on basis and white particles of the present invention, the briliancy rate of white particles of the present invention improves 4% with comparing as the briliancy rate of the existing white particles on basis.
＜embodiment 3 (particle) 〉
On the PC ball of mean grain size 5.0 μ m, replace the titanium dioxide of the thick 80nm of vapor-deposited film and the monox of thickness 100nm, the particle that obtains is used as the core of examining.The total reflectivity on the surface of the vapor-deposited film of the formation core that uses (interface that is equivalent to core and outer layer segment) is 91%.Use Agglomaster (HOSOKAWA MICRON Co., Ltd. system) on above-mentioned core, to be covered similarly to Example 1 and have white material now, prepare outer layer segment, obtain white particles of the present invention.
The mean grain size of the white particles that obtains is 7.0 μ m, and surface charge density is-60 μ C/m 2In addition, when measuring the briliancy rate as the white particles on basis and white particles of the present invention, the briliancy rate of white particles of the present invention improves 7% with comparing as the briliancy rate of the existing white particles on basis.
＜comparative example 1 (particle) 〉
With the mixing potpourri crushing and classification that obtains of titanium dioxide 20 weight portions of acryl resin 100 weight portions and mean grain size 200nm, obtain the particle that mean grain size is 4～8 μ m.When similarly to Example 1 this particle being measured, the briliancy rate is 40%.
＜comparative example 2 (particle) 〉
The total reflectivity of the PMMA ball of mean grain size 50 μ m is 10%.With it is nuclear, uses the existing white material of Agglomaster (HOSOKAWA MICRON Co., Ltd.) lining.Mean grain size is 80 μ m, and surface charge density is-40 μ C/m 2When similarly to Example 1 this particle being measured, the briliancy rate is 28%.
＜embodiment 4 (powder fluid) 〉
In the white particles of embodiment 1, use Hybridizer device (nara machinery is made institute's (strain) system) in above-mentioned particle, to drop into external additive A (silicon dioxide H2000/4, Wacker society system) and external additive B (silicon dioxide SS20, Japanese SILICA system), rotating speed with 4800 was handled 5 minutes, external additive is fixed on the white particles surface, prepares white powder fluid.The briliancy rate of white powder fluid of the present invention improves 6% with comparing as the briliancy rate of the existing white powder fluid on basis.
＜embodiment 5 (powder fluid) 〉
In the white particles of embodiment 2, use Hybridizer device (nara machinery is made institute's (strain) system) in above-mentioned particle, to drop into external additive A (silicon dioxide H2000/4, Wacker society system) and external additive B (silicon dioxide SS20, Japanese SILICA system), rotating speed with 4800 was handled 5 minutes, external additive is fixed on the white particles surface, prepares white powder fluid.The briliancy rate of white powder fluid of the present invention improves 4% with comparing as the briliancy rate of the existing white powder fluid on basis.
＜embodiment 6 (powder fluid) 〉
In the white particles of embodiment 3, use Hybridizer device (nara machinery is made institute's (strain) system) in above-mentioned particle, to drop into external additive A (silicon dioxide H2000/4, Wacker society system) and external additive B (silicon dioxide SS20, Japanese SILICA system), rotating speed with 4800 was handled 5 minutes, external additive is fixed on the white particles surface, prepares white powder fluid.The briliancy rate of white powder fluid of the present invention improves 6% with comparing as the briliancy rate of the existing white powder fluid on basis.
＜comparative example 3 (powder fluid) 〉
In the white particles of comparative example 1, use Hybridizer device (nara machinery is made institute's (strain) system) in above-mentioned particle, to drop into external additive A (silicon dioxide H2000/4, Wacker society system) and external additive B (silicon dioxide SS20, Japanese SILICA system), rotating speed with 4800 was handled 5 minutes, external additive is fixed on the white particles surface, prepares white powder fluid.When itself and comparative example 1 were similarly measured, the briliancy rate was 42%.
＜comparative example 4 (powder fluid) 〉
In the white particles of comparative example 2, use Hybridizer device (nara machinery is made institute's (strain) system) in above-mentioned particle, to drop into external additive A (silicon dioxide H2000/4, Wacker society system) and external additive B (silicon dioxide SS20, Japanese SILICA system), rotating speed with 4800 was handled 5 minutes, external additive is fixed on the white particles surface, prepares white powder fluid.When itself and comparative example 1 were similarly measured, the briliancy rate was 28%.
＜the 2 embodiment that invention relates to 〉
The image for preparing embodiment and comparative example as follows shows with dull and stereotyped, and estimates by following benchmark.
" image shows with dull and stereotyped preparation "
Preparing image as described below shows with dull and stereotyped.
At first, prepare electroded substrate (7cm * 7cm), on substrate, make the flange of height 400 μ m, form banded dividing plate.
Form flange as described below.At first, preparation thickener:, prepare SiO as inorganic particle 2, Al 2O 3, B 2O 3, Bi 2O 3And the glass powder that obtains of potpourri fusion, cooling, the pulverizing of ZnO, as resin, prepare thermosetting epoxy resin, be 12000cps with solvent adjustment to viscosity, make thickener.Then, thickener is coated on the whole surface of ready substrate, is heated curing under 150 ℃, be coated with repeatedly～solidify, adjusting thickness (height that is equivalent to dividing plate) thus is 400 μ m.Then, paste to do and carve glue, expose～etching, preparation forms the mask of the dividing plate pattern of line length 50 μ m, space 400 μ m, spacing 250 μ m thus.Then, remove redundance, form the partition shape of regulation, form desirable banded dividing plate through sandblast.Then, between the dividing plate on the substrate, form unit (cell).
As image display medium, prepare the color 2 kind nearly spherical particles different respectively with charged characteristic, with quantitatively different the 3rd kind of particle group that particle obtains of hybrid regulatory in any nearly spherical particle with its charged characteristic as particle group A, with the particle group that constitutes by other nearly spherical particles as particle group B.
It is in the following drying receptacle of 40%RH or 40%RH that flanged substrate (counter substrate) is moved to humidity, at first, with particle group A is the 1st particle group, from the nozzle that is arranged on the container internal upper part it is dispersed in the container, be dispersed in the unit on the substrate that is arranged at the container bottom, thus particle filled composite group A.Then, with particle group B as the 2nd particle group, from another nozzle that is arranged on the container internal upper part it is dispersed in the container, is dispersed in the unit on the substrate that is arranged at the container bottom and (has filled particle group A), thus overlapping particle filled composite group B on particle group A.Making the filling configuration amount of particle group A and particle group B is identical weight, adjusts, and making the cumulative volume occupation rate of two particle group between the substrate of 2 substrates of can fitting is 25vol%.
Then, be filled another substrate of substrate superimposed layer that is configured in the unit in the particle group, substrate periphery is bonding with epoxy adhesive, enclose the particle group simultaneously, the preparation image shows with dull and stereotyped.
" evaluation of Presentation Function "
Show that to the image of making has been installed the image display device with dull and stereotyped applies the voltage of 250V, current potential is reversed, carry out the demonstration of black～white thus repeatedly.Being evaluated as of Presentation Function: for the contrast ratio, back, 10000 times are placed flat board after 5 days after repeatedly more repeatedly to use the reflected image densimeter to measure initial stage, 10000 times.Reflection density when herein, contrast reflection density/white when being defined as contrast ratio=black display shows.Need to prove with 10000 times repeatedly the back and placed in 5th after contrast than with respect to the ratio of initial stage contrast ratio as conservation rate.
＜embodiment 11 〉
Show that according to above-mentioned image preparing image with dull and stereotyped preparation method shows with dull and stereotyped, carries out the evaluation of above-mentioned Presentation Function.Need to prove the particle group A and the particle group B that utilize among the preparation embodiment 1 as described below.
The nearly spherical particle of constituent particle group A prepares as described below: add carbon black (MA100: Mitsubishi Chemical's (strain)) 4 weight portions, charged controlling agent BONTRON N07 (Orient chemistry (strain) system) 2 weight portions in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), carry out mixing after, pulverize with jet pulverizer, re-use Hybridizer device (nara machinery is made institute's (strain) system) and apply mechanical impact force, make near spherical after, carry out classification and prepared.The nearly spherical particle of constituent particle group A of preparation is that mean grain size be 9.1 μ m, closely spherical, surface from macroscopic view is level and smooth negative charging black particles.Drop into silicon dioxide SS20 (Japanese SILICA society system) as the 3rd kind of particle therein, mix preparation particle group A with Henschel mixer.
The nearly spherical particle of constituent particle group B is prepared as follows: in metering system tert-butyl acrylate monomer 80 weight portions and methacrylic acid 2-(diethylamino) ethyl ester monomer 20 weight portions, dissolve the AIBN (azoisobutyronitrile) of 0.5 weight portion, dispersion is processed into oil loving titanium dioxide 20 weight portions with coupling agent, make that the liquid that obtains suspends, polymerization in 0.5% surfactant (lauryl sodium sulfate) aqueous solution of 10 times of amounts, after filtration, the drying, use grader (MDS-2: Japanese Pneumatic industry) prepared.The nearly spherical particle of constituent particle group B of preparation is that mean grain size be 8.5 μ m, surface from macroscopic view is the level and smooth spherical white particles of Positively chargeable, is particle group B with it.Evaluation result is as shown in table 1 below.
＜embodiment 12 〉
Show that according to above-mentioned image preparing image with dull and stereotyped preparation method shows with dull and stereotyped, carries out the evaluation of above-mentioned Presentation Function.Need to prove the particle group A and the particle group B preparation as described below that utilize among the embodiment 12.
The nearly spherical particle of constituent particle group A is prepared as follows: the AIBN (azoisobutyronitrile) of dissolving 0.5 weight portion and as containing metal azo compound (BONTRON S34:Orient chemistry) 5 weight portions of the charged controlling agent of negative charging in styrene monomer, disperse carbon black (MA100: 3 weight portions Mitsubishi Chemical's (strain)) again as black pigment, the liquid that obtains is suspended in 0.5% surfactant (lauryl sodium sulfate) aqueous solution of 10 times of amounts, polymerization, filter, after the drying, use grader (MDS-2: Japanese Pneumatic industry (strain)) prepared.The nearly spherical particle of constituent particle group A of preparation is that mean grain size be 8.9 μ m, surface from macroscopic view is the level and smooth spherical black particles of negative charging.Drop into silicon dioxide H2000/4 (Waker society system) therein, mix with Henschel mixer and prepare particle group A as the 3rd kind of particle.
The nearly spherical particle of constituent particle group B is prepared as follows: add titanium dioxide 10 weight portions, charged controlling agent BONTRON E89 (Orient chemistry (strain) system) 2 weight portions in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), carry out mixing after, pulverize with jet pulverizer, re-use Hybridizer device (nara machinery is made institute's (strain) system) and apply mechanical impact force, make near spherical after, carry out classification and prepared.The nearly spherical particle of constituent particle group B of preparation is that mean grain size be 7.0 μ m, surface from macroscopic view is level and smooth Positively chargeable white spherical particle, is particle group B with it.Evaluation result is as shown in table 1 below.
＜comparative example 11 〉
Show that according to above-mentioned image preparing image with dull and stereotyped preparation method shows with dull and stereotyped, carries out the evaluation of above-mentioned Presentation Function.Need to prove the particle group A and the particle group B preparation as described below that utilize in the comparative example 11.
The particle of constituent particle group A is prepared as follows: add carbon black (MA100: Mitsubishi Chemical's (strain)) 4 weight portions, charged controlling agent BONTRONN07 (Orient chemistry (strain) system) 2 weight portions in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), carry out mixing after, carry out crushing and classification with jet pulverizer and prepared.The particle of constituent particle group A of preparation is that mean grain size is that the concavo-convex negative charging black particles of macroscopic view is made on 9.3 μ m, amorphous, surface.Drop into silicon dioxide SS20 (Japanese SILICA system) therein, be mixed with particle group A with Henschel mixer as the 3rd kind of particle.
The nearly spherical particle of constituent particle group B is prepared as follows: in metering system tert-butyl acrylate monomer 80 weight portions and methacrylic acid 2-(diethylamino) ethyl ester monomer 20 weight portions, dissolve the AIBN (azoisobutyronitrile) of 0.5 weight portion, dispersion is processed into oil loving titanium dioxide 20 weight portions with coupling agent, make that the liquid that obtains suspends, polymerization in 0.5% surfactant (lauryl sodium sulfate) aqueous solution of 10 times of amounts, after filtration, the drying, use grader (MDS-2: Japanese Pneumatic industry) prepared.The nearly spherical particle of constituent particle group B of preparation is that mean grain size be 8.5 μ m, surface from macroscopic view is the level and smooth spherical white particles of Positively chargeable, is particle group B with it.Evaluation result is as shown in table 1 below.
＜comparative example 12 〉
Show that according to above-mentioned image preparing image with dull and stereotyped preparation method shows with dull and stereotyped, carries out the evaluation of above-mentioned Presentation Function.Need to prove the particle group A and the particle group B preparation as described below that utilize in the comparative example 12.
The nearly spherical particle of constituent particle group A is prepared as follows: the AIBN (azoisobutyronitrile) of dissolving 0.5 weight portion and as containing metal azo compound (BONTRON S34:Orient chemistry) 5 weight portions of the charged controlling agent of negative charging in styrene monomer, disperse carbon black (MA100: 3 weight portions Mitsubishi Chemical) again as black pigment, make that the liquid that obtains suspends, polymerization in 0.5% surfactant (lauryl sodium sulfate) aqueous solution of 10 times of amounts, filter, after the drying, use grader (MDS-2: Japanese Pneumatic industry) prepared.The nearly spherical particle of constituent particle group A of preparation is that mean grain size be 8.9 μ m, surface from macroscopic view is the level and smooth spherical black particles of negative charging.Drop into silicon dioxide H2000/4 (Wacker society system) therein, be mixed with particle group A with Henschel mixer as the 3rd kind of particle.
The particle of constituent particle group B is prepared as follows: add titanium dioxide 10 weight portions, charged controlling agent BONTRON E89 (Orient chemistry (strain) system) 2 weight portions in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), carry out mixing after, carry out crushing and classification with jet pulverizer and prepared.The particle of the constituent particle group B of preparation is that mean grain size is 7.0 μ m, amorphous, the concavo-convex Positively chargeable white particles of surface macroscopic view, is particle group B with it.Evaluation result is as shown in table 1 below.
＜comparative example 13 〉
Show that according to above-mentioned image preparing image with dull and stereotyped preparation method shows with dull and stereotyped, carries out the evaluation of above-mentioned Presentation Function.Need to prove the particle group A and the particle group B preparation as described below that utilize in the comparative example 13.
The nearly spherical particle of constituent particle group A is prepared as follows: in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), add carbon black (MA100: Mitsubishi Chemical's (strain)) 4 weight portions, charged controlling agent BONTRON N07 (Orient chemistry (strain) system) 2 weight portions, carry out mixing after, pulverize with jet pulverizer, re-use Hybridizer device (nara machinery is made institute's (strain) system) and apply mechanical impact force, make near spherical after, carry out classification and prepared.The nearly spherical particle of constituent particle group A of preparation is that mean grain size be 9.1 μ m, closely spherical, surface from macroscopic view is level and smooth negative charging black particles, is particle group A with it.
The nearly spherical particle of constituent particle group B is prepared as follows: the AIBN (azoisobutyronitrile) of dissolving 0.5 weight portion in metering system tert-butyl acrylate monomer 80 weight portions and methacrylic acid 2-(diethylamino) ethyl ester monomer 20 weight portions, dispersion is processed into oil loving titanium dioxide 20 weight portions with coupling agent, make that the liquid that obtains suspends, polymerization in 0.5% surfactant (lauryl sodium sulfate) aqueous solution of 10 times of amounts, after filtration, the drying, use grader (MDS-2: Japanese Pneumatic industry) prepared.The nearly spherical particle of constituent particle group B of preparation is that mean grain size be 8.5 μ m, surface from macroscopic view is the level and smooth spherical white particles of Positively chargeable, is particle group B with it.Evaluation result is as shown in table 1 below.
Table 1
Embodiment 11 Embodiment 12 Comparative example 11 Comparative example 12 Comparative example 13
Shape of particle and the surface configuration of particle group A Near spherical level and smooth Near spherical level and smooth Amorphous concavo-convex Near spherical level and smooth Near spherical level and smooth
Shape of particle and the surface configuration of particle group B Near spherical level and smooth Near spherical level and smooth Near spherical level and smooth Amorphous concavo-convex Near spherical level and smooth
The 3rd kind of particle diameter (nm) SS20 20 H2000/4 25 SS20 20 H2000/4 25 Do not have
Initial stage contrast ratio 1. 8.2 8.0 7.8 7.9 8.2
10000 back repeatedly contrast ratios 2. 7.9 7.8 7.0 6.7 6.6
Conservation rate is (%) 2./1. 96 98 89 85 80
Placed back contrast ratio on the 5th 3. 7.8 7.6 6.8 6.6 6.2
Conservation rate is (%) 3./1. 95 95 87 83 75
As shown in Table 1, utilize the 3rd kind of particle, simultaneously particle group A and particle group B be closely spherical, to have from macroscopic view be that embodiment 11 and embodiment 12 and the comparative example 13 that does not utilize the 3rd kind of particle, particle group A and the particle group B on level and smooth surface arbitrary group is that comparative example 11,12 amorphous, that the surface macroscopic view is concavo-convex is compared, have higher contrast ratio and compare conservation rate.Hence one can see that, if adopt image of the present invention to show that even then use repeatedly, its permanance is also good with dull and stereotyped.
＜the 3 embodiment that invention relates to 〉
＜embodiment 21 〉
Evaluation will be hanged down the particles aggregate of the flat board that the white particle of permittivity and black track producing particle that permittivity has nothing in common with each other together enclose as image display medium.
At first, the particle of preparation composing images display medium as described below.Change the amounts of carbon black of adding in the styrene acrylic resin, shown in test No.1～3 of embodiment as shown in table 2 below and the comparative example test No.4,5, the different black particles of preparation permittivity.
Then, as described below particle is enclosed between electrode of substrate.The different black particles of permittivity of preparation is together enclosed in the flat board with the white particles of low permittivity respectively, prepare test No.1～3 of the different embodiment of the permittivity of black particles only and comparative example test No.4,5 flat board.
Estimate as described below.At first, in the stage of preparation particle, measure the permittivity of particle.Particle is processed into sheet, and measuring with it is the static capacity that lures the plane-parallel capacitor of isoelectric substance, measures the permittivity of particle integral body thus.Calculate permittivity by measured value, polar plate spacing from, pole plate area, as the permittivity of particle.Measure to use system impedance/gain phase analyzer: the HP4194A of Hewlett-Packard and use electrode: HP16451B to carry out, the measured value when putting down in writing frequency herein and being 100Hz as this dielectric mensuration of installing peripheral machine.
In addition, the evaluation of the test panel of preparation is following to be carried out: apply 1Hz200V from the spoon alternating voltage between 2 electrode of substrate of above-mentioned test panel, make internal particle repeatedly reciprocal between pole plate with the vibration number identical with applying voltage.Observe the reciprocal process of particle, measure particles aggregate, can not be because of applying the mobile time of voltage.This tested progress row 10000 seconds.The particle that aggegation does not take place till the off-test yet is non-defective unit (being designated as zero in the following table 2), and the particle that aggegation takes place midway is substandard products (being designated as in the following table 2 *).The aggegation of particle is judged in range estimation.The result is as shown in table 2 below.
Table 2
Test No. Embodiment Comparative example
1 2 3 4 5
Particle permittivity (specific inductive capacity) White particles 2.7 2.7 2.7 2.7 2.7
Black particles 2.5 3.0 5.5 10 33
Whether particle aggegation takes place White particles Do not have Do not have Do not have Do not have Do not have
Black particles Do not have Do not have Do not have Take place Take place
Total judgement ○ ○ ○ × ×
＜embodiment 22 〉
Estimate the particles aggregate in the flat board only enclose the black track producing particle that permittivity has nothing in common with each other.
Prepare similarly to Example 21 as test No.1～3 and the comparative example of embodiment and test the different black particles of permittivity shown in the No.4,5.Then, only that the permittivity made is different similarly to Example 21 black particles is enclosed between flat board, only makes test No.1～3 of the embodiment that permittivity has nothing in common with each other and comparative example test No.4,5 flat board with black particles.Then, the flat board of making is carried out the evaluation identical with embodiment 1.The result is as shown in table 3 below.
Table 3
Test No. Embodiment Comparative example
1 2 3 4 5
Particle permittivity (specific inductive capacity) Black particles 2.5 3.0 5.5 10 33
Whether particles aggregate takes place Black particles Do not have Do not have Do not have Take place Take place
Total judgement ○ ○ ○ × ×
By the result of table 2 and table 3 as can be known, the particle of composing images display medium must be made of the low low-dielectric megohmite insulant of specific inductive capacity, and the specific inductive capacity of the particle of composing images display medium is preferably below 5.0 or 5.0.
＜the 4 embodiment that invention relates to 〉
＜embodiment 31 (particle) 〉
Use titanium dioxide (CR-50, the former industry of stone (strain) system) and bonding agent (mixed solution of acrylic acid and toluene, methyl ethyl ketone, ethyl acetate, concentration are below 1% or 1%), handle with improving particle surface device (Agglomaster, HOSOKAWAMICRON (strain) system), the bonding agent that is covered on titanium dioxide carries out aggegation, granulation simultaneously.The result as mean grain size be 10 μ m, 2 particles of the aggegation of acrylic acid titanium dioxide that has been covered, obtain white particles of the present invention.
Then, measure the reflectivity (covering power) of the white particles that obtains.White particles is dispersed on the glass substrate, obtains above-mentioned reflectivity as the per 1 layer reflectivity that records by wheat Jan Quast densimeter.Measurement result is 57%.
＜comparative example 31 (particle) 〉
With the mixing titanium dioxide of twin shaft mixing roll (CR-50, the former industry of stone (strain) system) 50 weight portions and acryl resin 100 weight portions, carry out crushing and classification, the volume ratio that obtains titanium dioxide is 12%, mean grain size is the white particles of 9 μ m.When similarly measuring the reflectivity of the white particles that obtains with embodiment 31, reflectivity is 18%.
＜comparative example 32 (particle) 〉
With the mixing titanium dioxide of twin shaft mixing roll (CR-50, the former industry of stone (strain) system) 100 weight portions and acryl resin 100 weight portions, carry out crushing and classification, the volume ratio that obtains titanium dioxide is 23%, mean grain size is the white particles of 9 μ m.When similarly measuring the reflectivity of the white particles that obtains with embodiment 31, reflectivity is 38%.
＜embodiment 32 (powder fluid) 〉
Use Hybridizer device (nara machinery is made institute's (strain) system), in the white particles of embodiment 1, drop into external additive A (silicon dioxide H2000/4, Wacker society system), rotating speed with 4800 was handled 5 minutes, external additive is fixed on the white particles surface, make white powder fluid, obtain white powder fluid of the present invention.When similarly measuring the reflectivity of the white powder fluid of the present invention that obtains with embodiment 31, reflectivity is 59%.
＜comparative example 33 (powder fluid) 〉
Use Hybridizer device (nara machinery is made institute's (strain) system), in the white particles of comparative example 1, drop into external additive A (silicon dioxide H2000/4, Wacker society system), rotating speed with 4800 was handled 5 minutes, and external additive is fixed on the white particles surface, prepared white powder fluid.When similarly measuring the reflectivity of the white powder fluid that obtains with embodiment 31, reflectivity is 19%.
＜comparative example 34 (powder fluid) 〉
Use Hybridizer device (nara machinery is made institute's (strain) system), in the white particles of comparative example 2, drop into external additive A (silicon dioxide H2000/4, Wacker society system), rotating speed with 4800 was handled 5 minutes, and external additive is fixed on the white particles surface, prepared white powder fluid.When similarly measuring the reflectivity of the white powder fluid that obtains with embodiment 31, reflectivity is 40%.
＜the 5 embodiment that invention relates to 〉
The image of embodiment and comparative example shows with dull and stereotyped and adopts following method preparation, the flat board of making by following benchmark evaluation.
" image shows with dull and stereotyped preparation "
Image shows and prepares as described below with flat board.
At first, prepare electroded substrate (7cm * 7cm), making on substrate is the flange of 400 μ m highly, forms banded dividing plate.
Form flange as described below.At first, prepare thickener:, prepare with SiO as inorganic particle 2, Al 2O 3, B 2O 3, Bi 2O 3And the glass powder that obtains of potpourri fusion, cooling, the pulverizing of ZnO, prepare thermosetting epoxy resin as resin, transferring to viscosity with solvent is 12000cps, makes thickener.Then, thickener is coated on the whole surface of the substrate of preparation, under 150 ℃ it is heating and curing, carry out above-mentioned coating～curing repeatedly, transferring to thickness (height that is equivalent to dividing plate) thus is 400 μ m.Then, fit to do carve glue, expose～etching, preparation has formed the mask of the dividing plate pattern of line length 50 μ m, space 400 μ m, spacing 250 μ m thus.Then, remove redundance, form the partition shape of regulation, form desirable banded dividing plate through sandblast.Then, between the dividing plate on the substrate, form the unit.
Prepare 2 kinds of different image display mediums of charged characteristic and optical reflectivity (particle group A and particle group B) respectively, it is in the following drying receptacle of 40%RH or 40%RH that flanged substrate (counter substrate) is moved to humidity, at first, with particle group A as the 1st particle group, by the nozzle that is arranged on the container internal upper part it is dispersed in the container, be dispersed in the unit on the substrate that is arranged at the container bottom, thus particle filled composite group A.Then, with particle group B as the 2nd kind of particle group, by another nozzle that is arranged on the container internal upper part it is dispersed in the container, is dispersed in the unit on the substrate that is arranged at the container bottom and (has filled particle group A), thus overlapping particle filled composite group B on particle group A.Making the filling configuration amount of particle group A and particle group B is identical weight, adjusts, and making the cumulative volume occupation rate of two particle group between the substrate of 2 substrates of can fitting is 26vol% (the 1st invention) or 28vol% (the 2nd invention).
Then, in the unit, fill another substrate of substrate superimposed layer that disposes the particle group, substrate periphery is bonding with epoxy adhesive, enclose the particle group simultaneously, the preparation image shows with dull and stereotyped.
" evaluation of Presentation Function "
Show that to the image of making has been installed the image display device with dull and stereotyped applies the voltage of 250V, current potential is reversed, carry out the demonstration of black～white thus repeatedly.The evaluation of Presentation Function: for the contrast ratio, back, 10000 times are placed flat board after 5 days after repeatedly more repeatedly to use the reflected image densimeter to measure initial stage, 10000 times.Reflection density when herein, contrast reflection density/white when being defined as contrast ratio=black display shows.Need to prove with 10000 times repeatedly the back and placed in 5th after contrast be conservation rate than ratio with respect to initial stage contrast ratio.
＜embodiment 41 (the 1st embodiment) 〉
Show that according to above-mentioned image preparing image with dull and stereotyped preparation method shows with dull and stereotyped, carries out the evaluation of above-mentioned Presentation Function.Need to prove the particle group A and the particle group B preparation as described below that utilize among the embodiment 41.
Particle group A is prepared as follows: add carbon black (MA100: Mitsubishi Chemical's (strain) system) 4 weight portions, charged controlling agent BONTRON N07 (Orient chemistry (strain) system) 2 weight portions in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), carry out mixing after, carry out crushing and classification with jet pulverizer and prepared.The particle group A of preparation is that mean grain size is to have concavo-convex negative charging black particles group on 9.1 μ m, the surperficial macroscopic view.
Particle group B is prepared as follows: in metering system tert-butyl acrylate monomer 80 weight portions and methacrylic acid 2-(diethylamino) ethyl ester monomer 20 weight portions, dissolve the AIBN (azoisobutyronitrile) of 0.5 weight portion, dispersion is processed into oil loving titanium dioxide 20 weight portions with coupling agent, make that the liquid that obtains suspends, polymerization in 0.5% surfactant (lauryl sodium sulfate) aqueous solution of 10 times of amounts, after filtration, the drying, use grader (MDS-2: Japanese Pneumatic industry (strain) system) prepared.The particle group B of preparation is that mean grain size is not have the spherical white particles of concavo-convex Positively chargeable on 8.5 μ m, the surperficial macroscopic view.Evaluation result is as shown in table 4 below.
＜embodiment 42 (the 1st embodiment) 〉
Show that according to above-mentioned image preparing image with dull and stereotyped preparation method shows with dull and stereotyped, carries out the evaluation of above-mentioned Presentation Function.Need to prove the particle group A and the particle group B preparation as described below that utilize among the embodiment 42.
Particle group A is prepared as follows: the AIBN (azoisobutyronitrile) of dissolving 0.5 weight portion and as containing metal azo compound (BONTRONS34:Orient chemistry (strain) system) 5 weight portions of the charged controlling agent of negative charging in styrene monomer, disperse carbon black (MA100: Mitsubishi Chemical's (strain) system) 3 weight portions again as black pigment, make that the liquid that obtains suspends, polymerization in 0.5% surfactant (lauryl sodium sulfate) aqueous solution of 10 times of amounts, after filtration, the drying, use grader (MDS-2: Japanese Pneumatic industry (strain) system) prepared.The particle group A of preparation is that mean grain size is not have the spherical black particles group of concavo-convex negative charging on 8.9 μ m, the surperficial macroscopic view.
Particle group B is prepared as follows: add titanium dioxide 10 weight portions, charged controlling agent BONTRON E89 (Orient chemistry (strain) system) 2 weight portions in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), carry out mixing after, carry out crushing and classification with jet pulverizer and prepared.The particle group B of preparation is that mean grain size is to have concavo-convex Positively chargeable white particles group on 7.0 μ m, the surperficial macroscopic view.Evaluation result is as shown in table 4 below.
＜embodiment 43 (the 1st embodiment) 〉
Show that according to above-mentioned image preparing image with dull and stereotyped preparation method shows with dull and stereotyped, carries out the evaluation of above-mentioned Presentation Function.Need to prove the particle group A and the particle group B preparation as described below that utilize among the embodiment 43.
Particle group A is prepared as follows: at first, after using styrene monomer, azo compound (5 weight portion), charged controlling agent BONTRON N07 (Orient chemistry (strain) system, 5 weight portions), initiator A IBN (0.5 weight portion) to carry out suspension polymerization, unify particle diameter with grading plant.Then, use Hybridizer device (nara machinery is made institute's (strain) system) to drop into silica particle (H2050, Wacker society system) and silica particle (SS20, Japanese SILICA society system), rotating speed with 4800 was handled 5 minutes, utilize mechanical impact force to make above-mentioned particulate, preparation particle group A attached to the polymer particles surface.The particle group A of preparation is that mean grain size is to have concavo-convex negative charging black particles group on 8.2 μ m, the surperficial macroscopic view.
Particle group B is prepared as follows: the AIBN (azoisobutyronitrile) of dissolving 0.5 weight portion in methyl methacrylate monomer 80 weight portions and methacrylic acid 2-(diethylamino) ethyl ester monomer 20 weight portions, dispersion is processed into oil loving titanium dioxide 20 weight portions with coupling agent, make that the liquid that obtains suspends, polymerization in 0.5% surfactant (lauryl sodium sulfate) aqueous solution of 10 times of amounts, after filtration, the drying, use crushing and classification machine (FM-120: Japanese Pneumatic industry (strain) system) preparation particle group B.The particle group B of preparation is that mean grain size is that 7.8 μ m, surface do not exist the spherical white particles of concavo-convex Positively chargeable on macroscopic view.Evaluation result is as shown in table 4 below.
＜comparative example 41 (the 1st embodiment) 〉
Show that according to above-mentioned image preparing image with dull and stereotyped preparation method shows with dull and stereotyped, carries out the evaluation of above-mentioned Presentation Function.Need to prove the particle group A and the particle group B preparation as described below that utilize in the comparative example 41.
Particle group A is prepared as follows: add carbon black (MA100: Mitsubishi Chemical's (strain)) 4 weight portions, charged controlling agent BONTRON N07 (Orient chemistry (strain) system) 2 weight portions in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), carry out mixing after, carry out crushing and classification with jet pulverizer and prepared.The particle group A of preparation is that mean grain size is to have concavo-convex negative charging black particles group on 9.1 μ m, the surperficial macroscopic view.
Particle group B is prepared as follows: add titanium dioxide 10 weight portions, charged controlling agent BONTRON E89 (Orient chemistry (strain) system) 2 weight portions in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), carry out mixing after, carry out crushing and classification with jet pulverizer and prepared.The particle group B of preparation is that mean grain size is to have concavo-convex Positively chargeable white particles group on 7.0 μ m, the surperficial macroscopic view.Evaluation result is as shown in table 4 below.
＜comparative example 42 〉
Show that according to above-mentioned image preparing image with dull and stereotyped preparation method shows with dull and stereotyped, estimates above-mentioned Presentation Function.Need to prove the particle group A and the particle group B preparation as described below that utilize in the comparative example 42.
Particle group A is prepared as follows: the AIBN (azoisobutyronitrile) of dissolving 0.5 weight portion and as containing metal azo compound (BONTRONS34:Orient chemistry (strain) system) 5 weight portions of the charged controlling agent of negative charging in styrene monomer, disperse carbon black (MA100: Mitsubishi Chemical's (strain) system) 3 weight portions again as black pigment, make that the liquid that obtains suspends, polymerization in 0.5% surfactant (lauryl sodium sulfate) aqueous solution of 10 times of amounts, after filtration, the drying, use grader (MDS-2: Japanese Pneumatic industry (strain) system) prepared.The particle group A of preparation is that mean grain size is not have the spherical black particles of concavo-convex negative charging on 8.9 μ m, the surperficial macroscopic view.
Particle group B is prepared as follows: in metering system tert-butyl acrylate monomer 80 weight portions and methacrylic acid 2-(diethylamino) ethyl ester monomer 20 weight portions, dissolve the AIBN (azoisobutyronitrile) of 0.5 weight portion, dispersion is processed into oil loving titanium dioxide 20 weight portions with coupling agent, make that the liquid that obtains suspends, polymerization in 0.5% surfactant (lauryl sodium sulfate) aqueous solution of 10 times of amounts, after filtration, the drying, use grader (MDS-2: Japanese Pneumatic industry (strain) system) prepared.The particle group B of preparation is that mean grain size is not have the spherical white particles of concavo-convex Positively chargeable on 8.5 μ m, the surperficial macroscopic view.Evaluation result is as shown in table 4 below.
Table 4
Embodiment 41 Embodiment 42 Embodiment 43 Comparative example 41 Comparative example 42
Particle group A surface macroscopical concavo-convex Have Do not have Have Have Do not have
Particle group B surface macroscopical concavo-convex Do not have Have Do not have Have Do not have
The form of concave-convex surface Comminution surface Comminution surface Particulate adheres to Comminution surface Smoothly
The solid attached method of particulate - - Hybridizer - -
Initial stage contrast ratio 1. 8.2 8.2 8.2 8.2 8.2
10000 back repeatedly contrast ratios 2. 7.9 8.0 8.0 6.6 7.0
Conservation rate is (%) 2./1. 96 98 98 80 85
Contrast ratio after placing in 5th 3. 7.8 7.9 8.0 6.2 6.8
Conservation rate is (%) 3./1. 95 96 98 76 83
As shown in Table 4, a kind of particle is that to have concavo-convex particle, another kind of particle on the surperficial macroscopic view be the embodiment 41～43 that do not have concavo-convex particle on the surperficial macroscopic view and is the comparative example 41 that there is concavo-convex particle on the macroscopic view and any particle with any particle to be the comparative example 42 that does not have concavo-convex particle on the macroscopic view and to compare, and a time point in office all has higher contrast ratio and compares conservation rate.Hence one can see that, uses repeatedly even the image that the 1st embodiment of the 5th invention of the present invention relates to shows with dull and stereotyped, and its permanance is also good.
＜embodiment 51 (the 2nd embodiment) 〉
Show that according to above-mentioned image preparing image with dull and stereotyped preparation method shows with dull and stereotyped, carries out the evaluation of above-mentioned Presentation Function.Need to prove the particle group A and the particle group B preparation as described below that utilize among the embodiment 51.
Particle group A is prepared as follows: add carbon black (MA100: Mitsubishi Chemical's (strain) system) 4 weight portions, charged controlling agent BONTRON N07 (Orient chemistry (strain) system) 2 weight portions in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), carry out mixing after, carry out crushing and classification with jet pulverizer and prepared.The particle group A of preparation is that mean grain size is to have concavo-convex negative charging black particles group on 9.1 μ m, the surperficial macroscopic view.
Particle group B is prepared as follows: in metering system tert-butyl acrylate monomer 80 weight portions and methacrylic acid 2-(diethylamino) ethyl ester monomer 20 weight portions, dissolve the AIBN (azoisobutyronitrile) of 0.5 weight portion, dispersion is processed into oil loving titanium dioxide 20 weight portions with coupling agent, the liquid that obtains is suspended in 0.5% surfactant (lauryl sodium sulfate) aqueous solution of 10 times of amounts, polymerization, filter, after the drying, (MDS-2: Japanese Pneumatic industry (strain) system) the preparation mean grain size is 8.5 μ m earlier to use grader, there is not the spherical white particles group of concavo-convex Positively chargeable on the macroscopic view of surface, then, use Henschel mixer, in above-mentioned spherical white particles group, drop into negative charging silica particle (H2050, Wacker society system), mix, prepare the particle group B of above-mentioned particulate electrostatic adhesion on spherical white particles surface.The particle group B of preparation is not for to exist concavo-convex particle surface to adhere to fine-grained Positively chargeable white particles group on surperficial macroscopic view.Evaluation result is as shown in table 5 below.
＜embodiment 52 (the 2nd invention) 〉
Show that according to above-mentioned image preparing image with dull and stereotyped preparation method shows with dull and stereotyped, carries out the evaluation of above-mentioned Presentation Function.Need to prove the particle group A and the particle group B preparation as described below that utilize among the embodiment 52.
Particle group A is prepared as follows: the AIBN (azoisobutyronitrile) of dissolving 0.5 weight portion and as containing metal azo compound (BONTRONS34:Orient chemistry (strain) system) 5 weight portions of the charged controlling agent of negative charging in styrene monomer, disperse carbon black (MA100: Mitsubishi Chemical's (strain) system) 3 weight portions again as black pigment, the liquid that obtains is suspended in 0.5% surfactant (lauryl sodium sulfate) aqueous solution of 10 times of amounts, polymerization, filter, after the drying, use grader (MDS-2: Japanese Pneumatic industry (strain) system), at first preparing mean grain size is 8.9 μ m, there is not the spherical black particles group of concavo-convex negative charging on the macroscopic view of surface, then, use Henschel mixer, in above-mentioned spherical black particles group, drop into the Positively chargeable particulate titanium dioxide, mix, prepare the particle group A of above-mentioned particulate electrostatic adhesion on spherical black particles surface.The particle group A of preparation is not for to exist concavo-convex particle surface to adhere to fine-grained negative charging black particles group on surperficial macroscopic view.
Particle group B is prepared as follows: add titanium dioxide 10 weight portions, charged controlling agent BONTRON E89 (Orient chemistry (strain) system) 2 weight portions in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), carry out mixing after, carry out crushing and classification with jet pulverizer and prepared.The particle group B of preparation is that mean grain size is to have concavo-convex Positively chargeable white particles group on 7.0 μ m, the surperficial macroscopic view.Evaluation result is as shown in table 5 below.
＜comparative example 51 (the 2nd embodiment) 〉
Show that according to above-mentioned image preparing image with dull and stereotyped preparation method shows with dull and stereotyped, estimates above-mentioned Presentation Function.Need to prove the particle group A and the particle group B preparation as described below that utilize in the comparative example 51.
Particle group A is prepared as follows: add carbon black (MA100: Mitsubishi Chemical's (strain)) 4 weight portions, charged controlling agent BONTRON N07 (Orient chemistry (strain) system) 2 weight portions in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), carry out mixing after, carry out crushing and classification with jet pulverizer and prepared.The particle group A of preparation is that mean grain size is to have concavo-convex negative charging black particles group on 9.1 μ m, the surperficial macroscopic view.
Particle group B is prepared as follows: add titanium dioxide 10 weight portions, charged controlling agent BONTRON E89 (Orient chemistry (strain) system) 2 weight portions in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), carry out mixing after, carry out crushing and classification with jet pulverizer and prepared.The particle group B of preparation is that mean grain size is to have concavo-convex Positively chargeable white particles group on 7.0 μ m, the surperficial macroscopic view.Evaluation result is as shown in table 5 below.
＜comparative example 52 (the 2nd embodiment) 〉
Show that according to above-mentioned image preparing image with dull and stereotyped preparation method shows with dull and stereotyped, carries out the evaluation of above-mentioned Presentation Function.Need to prove the particle group A and the particle group B preparation as described below that utilize in the comparative example 52.
Particle group A is prepared as follows: the AIBN (azoisobutyronitrile) of dissolving 0.5 weight portion and as containing metal azo compound (BONTRONS34:Orient chemistry (strain) system) 5 weight portions of the charged controlling agent of negative charging in styrene monomer, disperse carbon black (MA100: Mitsubishi Chemical's (strain) system) 3 weight portions again as black pigment, make that the liquid that obtains suspends, polymerization in 0.5% surfactant (lauryl sodium sulfate) aqueous solution of 10 times of amounts, after filtration, the drying, use grader (MDS-2: Japanese Pneumatic industry (strain) system) prepared.The particle group A of preparation is that mean grain size is not have the spherical black particles of concavo-convex negative charging on 8.9 μ m, the surperficial macroscopic view.
Particle group B is prepared as follows: the AIBN (azoisobutyronitrile) of dissolving 0.5 weight portion in metering system tert-butyl acrylate monomer 80 weight portions and methacrylic acid 2-(diethylamino) ethyl ester monomer 20 weight portions, dispersion is processed into oil loving titanium dioxide 20 weight portions with coupling agent, make that the liquid that obtains suspends, polymerization in 0.5% surfactant (lauryl sodium sulfate) aqueous solution of 10 times of amounts, after filtration, the drying, use grader (MDS-2: Japanese Pneumatic industry (strain) system) prepared.The particle group B of preparation is that mean grain size is not have the spherical white particles of concavo-convex Positively chargeable on 8.5 μ m, the surperficial macroscopic view.Evaluation result is as shown in table 5 below.
Table 5
Embodiment 51 Embodiment 52 Comparative example 51 Comparative example 52
Particle group A surface macroscopical concavo-convex Have Do not have Have Do not have
Particle group B surface macroscopical concavo-convex Do not have Have Have Do not have
Particulate (the 3rd kind of particle) Have Have Do not have Do not have
The charged polarity of the particle of macroscopic view no concave-convex Just Negative - -
The charged polarity of particulate (the 3rd kind of particle) Negative Just - -
The charged polarity of the particle group of macroscopical no concave-convex that particulate adheres to Just Negative - -
Initial stage contrast ratio 1. 8.0 8.0 8.0 8.0
10000 back repeatedly contrast ratios 2. 7.7 7.8 6.4 6.2
Conservation rate is (%) 2./1. 96 98 80 78
Placed back contrast ratio on the 5th 3. 7.6 7.7 6.0 6.0
Conservation rate is (%) 3./1. 95 96 75 75
As shown in Table 5, a kind of particle is to have concavo-convex particle on the surperficial macroscopic view, another kind of particle is gone up the particulate that no concave-convex and surface electrostatic adhere to the embodiment 51,52 of fine-grained particle and do not use electrostatic adhesion for the surface is macroscopical, and any particle is macroscopic view and exists the comparative example 51 of concavo-convex particle and any particle to be macroscopic view not exist the comparative example 52 of concavo-convex particle to compare, a time point in office all has higher contrast ratio and compares conservation rate.Hence one can see that, uses repeatedly even the image that the 2nd embodiment of the 5th invention of the present invention relates to shows with dull and stereotyped, and its permanance is also good
＜the 6 embodiment that invention relates to 〉
＜embodiment 61 (white particles) 〉
At base resin: PMMA (the system Delpet 80NH of Asahi Chemical Industry's (strain), proportion 1.19) in 100 weight portions, as shown in table 6 below, interpolation is as the titanium dioxide of Chinese white: the former industry of stone (strain) system TIPAQUE CR95 (proportion 4.0) 100 weight portions, 200 weight portions or 300 weight portions, hollow-particle: JSR (strain) system SX866 (A) (external diameter 0.3 μ m (primary particle), internal diameter 0.2 μ m, cross-linked styrene-acrylic acid) 10～60 weight portions, other CCA, various filling agents (each example is a same amount), carry out mixing after, carry out crushing and classification with jet pulverizer, obtain the white particles of the present invention's example test No.1～5.
In addition, in above-mentioned base resin 100 weight portions, as shown in table 6 below, add above-mentioned titanium dioxide 100 weight portions～300 weight portions, other CCA, various filling agent (each example is same amount), carry out mixing after, carry out crushing and classification with jet pulverizer, obtain the white particles of comparative example test No.1～4.
The white reflectivity (whiteness) of the example of the present invention that mensuration obtains and the white particles of comparative example.The assay method of white reflectivity is as follows: the base plate glass face do not have omit ground coating particle after, be 1.1mm at thickness, the glass plate outside of the transparency electrode body that is made of ITO measures, obtain as the white reflectivity of per 1 layer of 10 μ m particle.In addition, the volume filling rate is obtained as { (volume of the volume+hollow-particle of titanium dioxide)/(volume of particle integral body (resin+titanium dioxide+hollow-particle)) } * 100.The result is as shown in table 6 below.
Table 6
Test No. Titanium dioxide (weight portion) Hollow-particle (weight portion) Volume filling rate (%) Whiteness (%)
Example of the present invention 1 2 3 4 5 100 200 200 200 300 60 10 30 50 20 55.3 42.9 51.6 57.9 54.7 45.5 47.2 48.0 47.0 45.2
Comparative example 1 2 3 4 100 150 200 300 - - - - 22.9 30.9 37.3 47.2 42.6 45.9 46.4 44.2
As shown in Table 6, the hollow-particle loading is that the present invention's example test No.1～5 of 10～50 weight portions are compared with comparative example test No.1～4 of not filling hollow-particle, and whiteness improves more than 45% or 45%.
＜embodiment 62 (powder fluid) 〉
Use Hybridizer device (nara machinery is made institute's (strain) system), in the white particles of the about 10 μ m of volume average particle size that the present invention example test No.3 (titanium dioxide 200 weight portions, hollow-particle 30 weight portions) of embodiment 1 relates to, drop into external additive A (silicon dioxide H2000/4, Wacker society system) and external additive B (silicon dioxide SS20, Japanese SILICA system), rotating speed with 4800 was handled 5 minutes, external additive is fixed on the white particles surface, prepares white powder fluid.Similarly measure the whiteness of the present invention white powder fluid that obtains with embodiment 61, the result, whiteness is more than 45% or 45%, shows good value.When carrying out volume filling rate, plates assessed, obtain the result identical with embodiment 61.
＜the 7 embodiment that invention relates to)
＜embodiment 71 〉
At first, proportioning shown in the according to the form below 7, following material is mixing with the twin shaft mixing roll, obtain potpourri, described material is: as the thermoset resin of base resin, use the Upicacoat GV-570 (Japanese Upica (strain) system) of vibrin (the PCM powder body coating is used)+blocked isocyanate class herein, crosslinking chemical: VESTAGON B1530 (Degussa society system), and curing catalysts: NEOSTANNU-100 (day east changes into (strain) system), titanium dioxide: TIPAQUE CR-95 (the former industry of stone (strain) system), CCA:BONTRON E-84 (Orient chemistry (strain) system).Melting temperature is 120 ℃.Then, the potpourri that obtains is applied hot pressing under 200 ℃ * 10 minutes condition, the thermoset resin generation heat cross-linking as base resin is solidified.Then, it is broken to carry out micro mist with jet pulverizer, obtains the particle of the present invention's example test No.1～4.
Proportioning shown in the according to the form below 7 similarly, will be as polystyrene resin (PS), TOYO STYROL MW1C (Japan STYLENE (strain) system), the titanium dioxide of the thermoplastic resin of base resin: TIPAQUE CR-95 (the former industry of stone (strain) system), CCA:BONTRON E-84 (Orient chemistry (strain) system) carry out mixing with the twin shaft mixing roll, obtain potpourri.Melting temperature is 180 ℃.Then, it is broken that the potpourri that obtains is directly carried out micro mist with jet pulverizer, obtains the particle of comparative example test No.1.
Sheet material model with 150mm * 150mm * 2.5mm is tested the particle of No.1～4 and the particle enforcement curing reaction of comparative example test No.1 to the present invention's example that obtains.Then, slowly improve temperature, temperature and particle that the mensuration particle begins to be out of shape begin the temperature of clinkering on glass substrate.
The result is as shown in table 7 below.
Table 7
Test No. Material (weight portion) The beginning temperature (℃)
Resin Crosslinking chemical TiO 2 Catalyzer CCA Distortion Clinkering
Example of the present invention 1 2 3 4 100 100 100 100 10 10 20 20 - 100 100 100 0.5 0.5 0.5 0.5 - - - 5 115 118 123 123 98 103 103 103
Comparative example 1 100 - 100 - 5 80 75
As shown in Table 7, the thermoset resin heat cross-linking is made the particle of the present invention's example test No.1～4 of using after its curing compare with the particle of the comparative example test No.1 that uses thermoplastic resin, also do not deform and clinkering even rise to high temperature, thermotolerance increases substantially.
Need to prove in the above-mentioned explanation, is object with the base resin of particle, still, utilizes the powder fluid of particle of the present invention also can access same result.
＜the 8 embodiment that invention relates to 〉
Show with dull and stereotyped by the image that obtains in following benchmark evaluation embodiment and the comparative example.
" image shows with dull and stereotyped preparation "
At first, prepare electroded substrate (7cm * 7cm), making on substrate is the flange of 400 μ m highly, forms banded dividing plate.
Form flange as described below.At first prepare thickener:, prepare with SiO as inorganic particle 2, Al 2O 3, B 2O 3, Bi 2O 3And the glass powder that obtains of potpourri fusion, cooling, the pulverizing of ZnO, as resin, prepare thermosetting epoxy resin, be 12000cps with solvent furnishing viscosity, make thickener.Then, thickener is coated on the ready substrate, under 150 ℃ it is heating and curing, repeat above-mentioned coating～curing, being adjusted to thickness (height that is equivalent to dividing plate) thus is 400 μ m.Then, paste to do carve glue, expose～etching, preparation has formed the mask of the dividing plate pattern of line length 50 μ m, space 400 μ m, spacing 250 μ m thus.Then, remove redundance, form the partition shape of regulation, form desirable banded dividing plate through sandblast.
Prepare 2 kinds of different image display mediums of charged characteristic and optical reflectivity (white particles group A and black particles group B) respectively, it is in the following drying receptacle of 40%RH or 40%RH that flanged substrate (counter substrate) is moved to humidity, at first, with particle group A as the 1st particle group, by the nozzle that is arranged on the container internal upper part it is dispersed in the container, be dispersed in the unit on the substrate that is arranged at the container bottom, thus particle filled composite group A.
Then, with particle group B as the 2nd kind of particle group, by another nozzle that is arranged on the container internal upper part it is dispersed in the container, is dispersed in the unit on the substrate that is arranged at the container bottom and (has filled particle group A), overlap thus on the particle group A and fill.
Making the filling configuration amount of particle group A and particle group B is identical weight, and the cumulative volume occupation rate of two particle group between the substrate of 2 substrates of can fitting is adjusted into 26vol%.
Then, be filled another substrate of substrate superimposed layer that is configured in the unit in the particle group, substrate periphery is bonding with epoxy adhesive, enclose the particle group simultaneously, the preparation image shows with dull and stereotyped.
" evaluation of Presentation Function "
Show that to the image of making has been installed the image display device with dull and stereotyped applies the voltage of 250V, current potential is reversed, carry out the demonstration of black～white thus repeatedly.With regard to contrast than and the reflection density of white when showing carry out the evaluation of Presentation Function, use the reflected image densimeter respectively in the early stage, 10000 times back, 100000 times are measured after repeatedly repeatedly.Reflection density when herein, contrast reflection density/white when being defined as contrast ratio=black display shows.
＜embodiment 81 〉
Prepare particle group (particle group A, particle group B) as 2 kinds of image display mediums.
Particle group A is prepared as follows: add carbon black (MA100: Mitsubishi Chemical's (strain) system) 4 weight portions in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), charged controlling agent BONTRON N07 (Orient chemistry (strain) system) 2 weight portions, carry out mixing after, pulverize with jet pulverizer, the primary particle of making is applied hot pressing, thereby under 140 ℃ with its sealing, make sheet material, above-mentioned sheet material is added hot-stretch with drawing machine, obtain the sheet material that thickness is 8 μ m.Above-mentioned stretched sheet is broken imperceptibly, re-use Surfusion system (SFS-03: Japanese Pneumatic industry (strain) system), be under 450 ℃ the condition, to make the flinders surface that small fusion take place at hot blast temperature, obtain the flattened round particle.The particle group A of preparation is that negative charging, mean grain size are the flattened round black particles group of 9.4 μ m.
Particle group B is prepared as follows: add titanium dioxide 10 weight portions, charged controlling agent BONTRON E89 (Orient chemistry (strain) system) 2 weight portions in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), carry out mixing after, the method that employing order is identical with the above-mentioned particle group A of preparation is prepared.The particle group B of preparation is that Positively chargeable, mean grain size are the flattened round white particles group of 9.0 μ m.
Use has been installed the image made from above-mentioned particle group and has been shown with dull and stereotyped image display device, carries out the evaluation of Presentation Function.The result is as shown in table 8.
＜embodiment 82 〉
Particle group A is prepared as follows: add carbon black (MA100: Mitsubishi Chemical's (strain) system) 4 weight portions, charged controlling agent BONTRON N07 (Orient chemistry (strain) system) 2 weight portions in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), carry out mixing after, carry out crushing and classification with jet pulverizer and prepared.The particle group A of preparation is that negative charging, mean grain size are the black particles group of 9.0 μ m.
It is the flattened round white particles group of 9.0 μ m that particle group B uses Positively chargeable, the mean grain size of preparation among the embodiment 81.
Use has been installed the image made from above-mentioned particle group and has been shown that the image display device with flat board carries out the evaluation of Presentation Function.The result is as shown in table 8.
＜embodiment 83 〉
Particle group A uses the negative charging of preparation among the embodiment 81, mean grain size is the flattened round black particles group of 9.4 μ m, particle group B uses the Positively chargeable that is prepared as follows, mean grain size is the spherical white particles group of 8.5 μ m: the AIBN (azoisobutyronitrile) of dissolving 0.5 weight portion in metering system tert-butyl acrylate monomer 80 weight portions and methacrylic acid 2-(diethylamino) ethyl ester monomer 20 weight portions, dispersion is processed into oil loving titanium dioxide 20 weight portions with coupling agent, the liquid that obtains is suspended in 0.5% surfactant (lauryl sodium sulfate) aqueous solution of 10 times of amounts, polymerization, filter, after the drying, use grader (MDS-21 Japan's Pneumatic industry (strain) system) to be prepared.
Use has been installed the image made from above-mentioned particle group and has been shown that the image display device with flat board carries out the evaluation of Presentation Function.The result is as shown in table 8.
＜comparative example 81 〉
Particle group A is prepared as follows: the AIBN (azoisobutyronitrile) of dissolving 0.5 weight portion and as containing metal azo compound (BONTRONS34:Orient chemistry (strain) system) 5 weight portions of the charged controlling agent of negative charging in styrene monomer, disperse carbon black (MA100: Mitsubishi Chemical's (strain) system) 3 weight portions again as black pigment, make that the liquid that obtains suspends, polymerization in 0.5% surfactant (lauryl sodium sulfate) aqueous solution of 10 times of amounts, after filtration, the drying, use grader (MDS-2: Japanese Pneumatic industry (strain) system) prepared.The particle group A of preparation is that mean grain size is the spherical black particles group of negative charging of 8.9 μ m.
Particle group B uses the Positively chargeable that is prepared as follows, mean grain size is the spherical white particles group of 8.5 μ m: the AIBN (azoisobutyronitrile) of dissolving 0.5 weight portion in metering system tert-butyl acrylate monomer 80 weight portions and methacrylic acid 2-(diethylamino) ethyl ester monomer 20 weight portions, dispersion is processed into oil loving titanium dioxide 20 weight portions with coupling agent, the liquid that obtains is suspended in 0.5% surfactant (lauryl sodium sulfate) aqueous solution of 10 times of amounts, polymerization, filter, after the drying, use grader (MDS-2: Japanese Pneumatic industry (strain) system) prepared.
Use has been installed the image of being made by above-mentioned particle group and has been shown that the image display device with flat board carries out the evaluation of Presentation Function.The result is as shown in table 8.
Table 8
Embodiment 81 Embodiment 82 Embodiment 83 Comparative example 81
The shape of particle group A (white) Flattened round Flattened round Spherical Spherical
The shape of particle group B (black) Flattened round Spherical Flattened round Spherical
Initial stage white reflection density (%) 42 42 38 38
Initial stage contrast ratio 8.2 8.2 7.9 7.9
10000 back repeatedly white reflection densities (%) 42 42 36 36
10000 back repeatedly contrast ratios 8.0 7.9 7.6 6.8
100000 back repeatedly white reflection densities (%) 40 38 34 34
100000 back repeatedly contrast ratios 7.8 7.7 7.4 6.2
As shown in Table 8, the white reflection density of embodiment 81, embodiment 82 of particle group A (white) being made flattened round is higher in the early stage, and conversion shows that the reduction degree of the reduction degree of its white reflection density of back and contrast ratio is all less repeatedly.In addition, particle group B (black) being made the embodiment 83 of flattened round compares with the embodiment 81, the embodiment 82 that particle group A (white) are made flattened round, the white reflection density at initial stage is low, even after conversion showed repeatedly, the reduction degree of the reduction degree of its white reflection density and contrast ratio was also less.And the initial stage white reflection density of comparative example 81 that particle group A (white), particle group B (black) all do not make flattened round is low, and the reduction degree of the white reflection density after conversion shows repeatedly and the reduction degree of contrast ratio are higher.That is, preferably making at least one group in the particle group is flattened round particle group, and especially preferably making the white particles group is flattened round particle group.
＜the 9 embodiment that invention relates to 〉
Show with dull and stereotyped by the image that obtains in following benchmark evaluation embodiment and the comparative example.
" image shows with dull and stereotyped preparation "
At first, prepare electroded substrate (7cm * 7cm), making on substrate is the flange of 400 μ m highly, forms banded dividing plate.
Form flange as described below.At first prepare thickener:, prepare SiO as inorganic particle 2, Al 2O 3, B 2O 3, Bi 2O 3And the glass powder that obtains of potpourri fusion, cooling, the pulverizing of ZnO, as resin, prepare thermosetting epoxy resin, be 12000cps with solvent furnishing viscosity, make thickener.Then, thickener is coated on the ready substrate, under 150 ℃ it is heating and curing, carry out above-mentioned coating～curing repeatedly, being adjusted to thickness (height that is equivalent to dividing plate) thus is 400 μ m.Then, paste to do carve glue, expose～etching, prepared to form the mask of the dividing plate pattern of line length 50 μ m, space 400 μ m, spacing 250 μ m thus.Then, remove redundance, form the partition shape of regulation, form desirable banded dividing plate through sandblast.
Prepare 2 kinds of different image display mediums of color and charged characteristic (particle group A and particle group B) respectively, it is in the following drying receptacle of 40%RH or 40%RH that flanged substrate (counter substrate) is moved to humidity, at first, with particle group A as the 1st particle group, by the nozzle that is arranged on the container internal upper part it is dispersed in the container, be dispersed in the unit on the substrate that is arranged at the container bottom, thus particle filled composite group A.
Then, with particle group B as the 2nd kind of particle group, by another nozzle that is arranged on the container internal upper part it is dispersed in the container, is dispersed in the unit on the substrate that is arranged at the container bottom and (has filled particle group A), overlap thus on the particle group A and fill.
Making the filling configuration amount of particle group A and particle group B is identical weight, and the cumulative volume occupation rate of two particle group between the substrate of 2 substrates of can fitting is adjusted into 25vol%.
Then, be filled another substrate of substrate superimposed layer that is configured in the unit in the particle group, substrate periphery is bonding with epoxy adhesive, enclose the particle group simultaneously, the preparation image shows with dull and stereotyped.
" evaluation of Presentation Function "
Show that to the image of making has been installed the image display device with dull and stereotyped applies the voltage of 250V, current potential is reversed, carry out the demonstration of black～white thus repeatedly.At contrast than and the reflection density of white when showing carry out the evaluation of Presentation Function, respectively in the early stage, 10000 times back, 100000 times use the reflected image densimeter to measure in the back repeatedly repeatedly.Reflection density when herein, contrast reflection density/white when being defined as contrast ratio=black display shows.
＜embodiment 91 〉
Prepare particle group (particle group A, particle group B) as 2 kinds of image display mediums.
Particle group A is prepared as follows: add carbon black (MA100: Mitsubishi Chemical's (strain) system) 4 weight portions, charged controlling agent BONTRON N07 (Orient chemistry (strain) system) 2 weight portions in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), carry out mixing after, carry out crushing and classification with jet pulverizer and prepared.The particle group A that makes is that negative charging, mean grain size are the black particles group of 8.1 μ m.Being sample again with a part amplifies when observing with microscope, observes the particle that particle diameter surpasses 10 μ m.
Particle group B is prepared as follows: add titania 10 weight portions, charged controlling agent BONTRON E89 (Orient chemistry (strain) system) 2 weight portions in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), carry out mixing after, carry out crushing and classification with jet pulverizer and prepared.The particle group B of preparation is that Positively chargeable, mean grain size are the white particles group of 9.7 μ m.Being sample again with a part amplifies when observing with microscope, observes the particle that particle diameter is lower than 8 μ m.
Use to have installed to show, estimate Presentation Function with dull and stereotyped image display device with the image of above-mentioned particle group as image display medium.The result is as shown in table 9.
＜embodiment 92 〉
Particle group A is prepared as follows: add carbon black (MA100: Mitsubishi Chemical's (strain) system) 4 weight portions in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), charged controlling agent BONTRON N07 (Orient chemistry (strain) system) 2 weight portions, carry out mixing after, carry out crushing and classification with jet pulverizer, re-using grader (MDS-2: Japanese Pneumatic industry (strain) system) is that (over cut) classification that makes progress of 10 μ m or the particle more than the 10 μ m is prepared to particle diameter.The particle group A that makes is that negative charging, mean grain size are the black particles group of 7.4 μ m.Being sample again with a part amplifies when observing with microscope, does not observe the particle that particle diameter surpasses 10 μ m.
Particle group B is prepared as follows: add titania 10 weight portions, charged controlling agent BONTRON E89 (Orient chemistry (strain) system) 2 weight portions in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), carry out mixing after, carry out crushing and classification with jet pulverizer, re-using grader (MDS-2: Japanese Pneumatic industry (strain) system) is that 8 μ m or the particle diameter below the 8 μ m carry out downwards that (under cut) classification is prepared to particle diameter.The particle group B that makes is that Positively chargeable, mean grain size are the white particles group of 9.8 μ m.Being sample again with a part amplifies when observing with microscope, does not observe the particle that particle diameter is lower than 8 μ m.
Use the dull and stereotyped image display device of making as image display medium with above-mentioned particle group of image demonstration has been installed, estimate Presentation Function.The result is as shown in table 9.
＜embodiment 93 〉
It is that the mean grain size that 10 μ m or the above particle classification of 10 μ m obtain is the black particles group of 7.4 μ m that particle group A uses negative charging, the particle diameter of preparation among the embodiment 92.
Particle group B is prepared as follows: in metering system tert-butyl acrylate monomer 80 weight portions and methacrylic acid 2-(diethylamino) ethyl ester monomer 20 weight portions, dissolve the AIBN (azoisobutyronitrile) of 0.5 weight portion, dispersion is processed into oil loving titania 20 weight portions with coupling agent, the liquid that obtains is suspended in 0.5% surfactant (lauryl sodium sulfate) aqueous solution of 10 times of amounts, polymerization, filter, after the drying, use grader (MDS-2: Japanese Pneumatic industry (strain) system), be that 8 μ m or the particle below the 8 μ m carry out downward classification and prepared to particle diameter.The particle group B of preparation is that Positively chargeable, mean grain size are the spherical white particles group of 9.6 μ m.Being sample again with a part amplifies when observing with microscope, does not observe the particle that particle diameter is lower than 8 μ m.
Use has been installed the image of making as image display medium with above-mentioned particle group and has been shown with dull and stereotyped image display device, estimates Presentation Function.The result is as shown in table 9.
＜embodiment 94 〉
Particle group A is prepared as follows: add carbon black (MA100: Mitsubishi Chemical's (strain) system) 4 weight portions, charged controlling agent BONTRON N07 (Orient chemistry (strain) system) 2 weight portions in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), carry out mixing after, carry out crushing and classification with jet pulverizer and prepared.The particle group A of preparation is that negative charging, mean grain size are the black particles group of 5.2 μ m.
Particle group B is prepared as follows: add titania 10 weight portions, charged controlling agent BONTRON E89 (Orient chemistry (strain) system) 2 weight portions in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), carry out mixing after, carry out crushing and classification with jet pulverizer and prepared.The particle group B of preparation is that Positively chargeable, mean grain size are the white particles group of 11.3 μ m.
Use has been installed the image of making as image display medium with above-mentioned particle group and has been shown with dull and stereotyped image display device, estimates Presentation Function.The result is as shown in table 9.
＜comparative example 91 〉
Particle group A is prepared as follows: add carbon black (MA100: Mitsubishi Chemical's (strain) system) 4 weight portions, charged controlling agent BONTRON N07 (Orient chemistry (strain) system) 2 weight portions in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), carry out mixing after, carry out crushing and classification with jet pulverizer and prepared.The particle group A of preparation is that negative charging, mean grain size are the black particles group of 9.5 μ m.
Particle group B is prepared as follows: add titania 10 weight portions, charged controlling agent BONTRON E89 (Orient chemistry (strain) system) 2 weight portions in acrylated polyurethane resin EAU53B (Asia industry (strain) system)/IPDI class crosslinking chemical Excel Hardner HX (Asia industry (strain) system), carry out mixing after, carry out crushing and classification with jet pulverizer and prepared.The particle group B of preparation is that Positively chargeable, mean grain size are the white particles group of 8.2 μ m.
Use has been installed the image of making as image display medium with above-mentioned particle group and has been shown with dull and stereotyped image display device, estimates Presentation Function.The result is as shown in table 9.
Table 9
Embodiment 91 Embodiment 92 Embodiment 93 Implement 94 Comparative example 91
The mean grain size Ddark of deep dark particle group A (black) (μ m) 8.1 7.4 7.4 5.2 9.5
The mean grain size Dbright of shallow light tone particle group B (white) (μ m) 9.7 9.8 9.6 11.3 8.2
Dbright/Ddark 1.20 1.32 1.30 2.2 0.86
Stage division Deep dark particle group A Crushing and classification Crushing and classification+upwards classification Crushing and classification+upwards classification Crushing and classification Crushing and classification
Shallow light tone particle group B Crushing and classification Crushing and classification+classification downwards Crushing and classification+classification downwards Crushing and classification Crushing and classification
Initial stage white reflection density (%) 38 42 40 33 27
Initial stage contrast ratio 5.2 6.0 5.7 5.0 4.9
10000 back repeatedly white reflection densities (%) 36 41 38 31 26
10000 back repeatedly contrast ratios 5.1 5.8 5.6 4.9 4.7
100000 back repeatedly white reflection densities (%) 33 38 36 27 22
100000 back repeatedly contrast ratios 4.8 5.5 5.2 4.4 3.8
As shown in Table 9, relation for mean grain size, the white reflection density of the embodiment 91 of Ddark＜Dbright, embodiment 92, embodiment 93 and embodiment 94 is higher in the early stage, after conversion showed repeatedly, the reduction degree of the reduction degree of its white reflection density and contrast ratio was also all lower.In addition, re-using embodiment 92 and the embodiment 93 that grader (MDS-2: Japanese Pneumatic industry (strain) system) carried out upwards classification/classification downwards behind crushing and classification compares with the embodiment 91 of the classification that make progress/downward classification, the white reflection density height at initial stage, after conversion showed repeatedly, the reduction degree of the reduction degree of its white reflection density and contrast ratio was also lower.And, the pass of mean grain size is Dbright/Ddark＞2 among the embodiment 94, therefore white reflection density in the early stage, conversion shows that its white reflection density of back reduces the reduction degree aspect of degree and contrast ratio repeatedly, obtain being better than the result of comparative example 91, but this result omits the result inferior to the embodiment 91～93 of the relation that satisfies Dbright/Ddark＜2.And the initial stage white reflection density of comparative example 91 that the relation of mean grain size does not satisfy Ddark＜Dbright is low, after conversion shows repeatedly, and the reduction degree height of the reduction degree of its white reflection density and contrast ratio.
＜the 10 embodiment that invention relates to 〉
At first, said ratio shown in the according to the form below 10, carry out mixing with the twin shaft mixing roll following material, obtain potpourri, described material is: as the PBT (east beautiful (strain) system " Toraycon1401X31 ") of base resin, as the MgO (refreshing island chemistry (strain) system " STARMAGL-10 ") of metal oxide, as the C/B (DEGUSSA society system " SPECIAL BLACK-4 ") of pigment.Melting temperature is 240 ℃.Then, it is broken to carry out micro mist with jet pulverizer, obtains as the embodiment 101 of example of the present invention and the particle of embodiment 103.
The proportioning shown in the according to the form below 10 similarly, use is as the PBT of base resin (east beautiful (strain) system " Toraycon 1401X31 "), as the dolomol (reagent of Japanese grease (strain) system is pure) of fatty acid metal salts, as the C/B (rising sun CARBON (strain) makes " N-660 ") of pigment, adopt the method identical, be made as the particle of the embodiment 102 of example of the present invention with said method.In addition, in order to compare, proportioning shown in the according to the form below 1, use is as the PBT of base resin (east beautiful (strain) system " Toraycon 1401X31 "), as the C/B (DEGUSSA society system " SRECIALBLACK-4 ") of pigment, do not use metal oxide, do not use fatty acid metal salts yet, adopt the method identical to obtain the particle of comparative example 101 with said method.
Measure the particle diameter of particle in the embodiment 101～103 obtain and the comparative example 101 as stated above, adopt following method simultaneously, measure ejection (blow-off) carried charge of particle.The result is as shown in table 10.Need to prove the following mensuration of ejection carried charge.That is, ejection measuring principle and method are as described below.In the ejection method, in the cylindrical vessel of net is hanged up at two ends, put into the mixture of powder (being also referred to as the particle group) and carrier, be blown into gases at high pressure, powder is separated with carrier, only spray (blowing out) powder from mesh from an end.At this moment, on the carrier residual have with powder take outer carried charge equivalent of container and opposite carried charge out of.Then, whole electric fluxes of above-mentioned charge generation are collected in faraday's case, under this state, capacitor are charged.Measure the current potential at capacitor two ends, by Q=CV (C: condenser capacity, V: the voltage at capacitor two ends) obtain the quantity of electric charge Q of powder.
As ejection body of powder electrification amount determining device, use the TB-200 of CHEMICAL society of Toshiba system.Among the present invention,, use the F963-2535 of Powder-tech society system, at first measure the electric density (unit: μ C/g), calculate surface charge density (unit: μ C/m of particle per unit weight by mean diameter of obtaining in addition and proportion as carrier 2).Mean diameter adopts said method to measure, particularly, use Mastersizer2000 (Malvern Instruments Ltd.) mensuration machine, in nitrogen stream, drop into the particle group, measure with subsidiary parsing software (based on the software of the volume reference distribution of adopting the Mie theory), proportion uses Shimadzu Seisakusho Ltd.'s system picnometer (trade name: Multivolume densitometer H1305) measure.
In addition, to the embodiment 101～103 that obtains and the black particles with Positively chargeable of comparative example 101, use white particles (to use TiO as pigment with negative charging 2), preparation is the image display panel of black demonstration in vain, applies the voltage of 150V between electrode, and the conversion Show Color uses MINOLTA to make reflective liquid crystal system measurement white reflectivity, black reflection rate.Then, obtain contrast by The above results.The result is as shown in table 10.Need to prove in the table 10, judge that contrast is to be labeled as zero more than 1.0 or 1.0 as each routine display performance, being labeled as of contrast less than 1.0 *.
Table 10
Embodiment 101 Embodiment 102 Embodiment 103 Comparative example 101
Base resin PBT(90wt％) PBT(90wt％) PBT(85wt％) PBT(95wt％)
Metal oxide MgO(5wt％) MgO(5wt％)
Fatty acid metal salts Dolomol (5wt%) Dolomol (5wt%)
Pigment C/B(5wt％) C/B(5wt％) C/B(5wt％) C/B(5wt％)
Melting temperature (℃) 240 240 240 240
Particle diameter (μ m) 10 10 10 10
Carried charge (μ C/m 2) +55.3 +40.2 +84.8 +7.1
The transfer test contrast 1.2 1.2 1.3 0.4
Display performance is judged ○ ○ ○ ×
As shown in Table 10, the embodiment 101 that has cooperated metal oxide and embodiment 103 and the embodiment 102 that cooperated fatty acid metal salts with do not use metal oxide, do not use the comparative example 101 of fatty acid metal salts to compare yet, charged quantitative change is big, its result serves as reasons and uses the image display medium of above-mentioned particle to prepare the image display panel, can obtain high conversion performance.
Industrial applicability
As shown in the above description, according to the 1st invention of the present invention, the core of white particles has the total reflectivity more than 70% or 70% at the interface of core and outer layer segment, outer layer segment is made of the resin bed that the particulate of sneaking into high-index material in one or more layers at least low-index material obtains, therefore by having the core that shows high total reflectivity, can improve the briliancy rate of white. Utilize the white powder fluid of the 1st white particles that invention relates to of the present invention also can obtain identical effect.
As shown in the above description, the 2nd invention of the present invention relates to the particle group that is made of 3 kinds of particles that the 3rd kind of particle of adding in 2 kinds of different nearly spherical particles of charged characteristic obtained and encloses the image demonstration flat board for preparing between 2 substrates as image display medium, particle becomes each other and is difficult to aggegation and adheres to, and the durability that image shows improves.
As shown in the above description, according to the 3rd invention of the present invention, preferably use by DIELECTRIC CONSTANTSrBe εrThe particle that≤5.0 low-dielectric megohmite insulant consists of even the therefore particle of identical polar also is difficult to form interparticle aggegation piece, can carry out good image with showing.
As shown in the above description, according to the 4th invention of the present invention, make the surface-coated Chinese white that adhesive arranged, be preferably titanium oxide pigments aggegation or granulation, import a large amount of micro-bubbles in inside, can increase substantially thus white particles or utilize the covering power (reflectivity) of the white powder fluid of this white particles.
As shown in the above description, according to the 5th invention of the present invention, making one of 2 kinds of different particles of the charged characteristic that uses in the image display medium more than at least 2 kinds or 2 kinds is not have concavo-convex nearly spherical particle (for example polymer particles) on the surperficial macroscopic view for having concavo-convex particle (for example sized particles), another particle on the surperficial macroscopic view, make the surface state different (the 1st embodiment) of 2 kinds of particles, perhaps, making one of 2 kinds of different particles of the charged characteristic that uses in the image display medium more than at least 2 kinds or 2 kinds is not have concavo-convex nearly spherical particle (for example polymer particles) on the surperficial macroscopic view and be attached with on charged polarity and the surperficial macroscopic view not exist the different particulate of concavo-convex particle as the 3rd kind of particle (the 2nd embodiment) for having concavo-convex particle (for example sized particles), another kind of particle on the surperficial macroscopic view, particle is become each other be difficult to aggegation and adhere to, the durability that image shows improves.
As shown in the above description, according to the 6th invention of the present invention, in as the resin of matrix, fill Chinese white and hollow-particle, therefore utilize the covering effect of hollow-particle, can improve the whiteness (white reflectivity) of white particles (or powder fluid).
As shown in the above description, according to the 7th invention of the present invention, the heat-curing resin as the base resin of particle uses the heat cross-linking reaction to form can improve heat resistance thus, and the result can not show at image adhere to aggegation with flat board.
As shown in the above description, according to the 8th invention of the present invention, at least one in the different 2 kinds of particles of the charged characteristic that uses as image display medium and optical reflectivity is the flat circular particle, therefore mobile and when being arranged in the display base plate surface, particle is seamlessly arranged each other easily, interparticle gap tails off, so the contrast of image improves. In addition, the different 2 kinds of particles of the charged characteristic that uses as image display medium and optical reflectivity are during simultaneously as the flat circular particle, and particle becomes each other and is difficult to aggegation and adheres to, and the conflict when particle moves simultaneously relaxes, and the durability that image shows improves.
As shown in the above description, according to the 9th invention of the present invention, the particle diameter of deep dark particle group with Ddark represent, when the particle diameter of shallow light tone particle group represents with Dbright, the particle diameter relation of 2 kinds of particle groups that the color of using as image display medium is different with charged characteristic satisfies Ddark＜Dbright, therefore along the direction of an electric field between substrate towards each other opposite direction move, the contrast when being arranged in the display base plate surface is higher than above-mentioned particle diameter and concerns contrast when opposite.
According to the above description as can be known, the 1st embodiment and the 2nd embodiment that the 10th invention according to the present invention relates to, complexed metal oxide (MOx) (herein in the base resin of particle, M: metallic element, O: oxygen, the x:O/M ratio), or fatty acid metal salt compound (CmHnCOO) yMz (herein, M: metallic element, m, n, y, z are integer, 4＜m＜22), the control charging property, thus, even the atmosphere of having filled between the substrate of the image display medium that uses particle is dry environment, also can control charging property.
～the 10 image display device that invention relates to of the 1st invention of the invention described above is preferred for the display part of the removable machines such as notebook computer, PDA, mobile phone, portable terminal, the electronic paper such as e-book, electronic newspaper, the enlightenment such as billboard, poster, blackboard plate, the rewritten paper that replaces duplicator, printer media, the display part of desk-top electronic calculator, household appliances, Automobile Products etc., the card display parts such as some card, IC-card, the display part of e-advertising, electronics POP, electronics stock, electronic music, RF-ID machine etc.

Claims (12)

1. particle that is used for image display medium, it is characterized by, show with in the flat board at image, there is concavo-convex particle in one of 2 kinds of particles that charged characteristic that comprises in the image display medium more than at least 2 kinds or 2 kinds and optical reflectivity are different on the surperficial macroscopic view, another kind of for not having concavo-convex particle on the surperficial macroscopic view, this image shows with dull and stereotyped encloses image display medium more than at least 2 kinds or 2 kinds between the transparent counter substrate of at least one side, the 2 kind electrode pair described image display mediums different by current potential apply electric field, make image display medium move display image.
2. particle that is used for image display medium, it is characterized by, show with in the flat board at image, there is concavo-convex particle in one of 2 kinds of particles that charged characteristic that comprises in the image display medium more than at least 2 kinds or 2 kinds and optical reflectivity are different on the surperficial macroscopic view, another kind of concavo-convex for not existing on the surperficial macroscopic view, and the fine-grained particle of electrostatic adhesion on the surface, this image shows with dull and stereotyped encloses image display medium more than at least 2 kinds or 2 kinds between the transparent counter substrate of at least one side, the 2 kind electrode pair described image display mediums different by current potential apply electric field, make image display medium move display image.
3. the particle that is used for image display medium as claimed in claim 1 or 2, wherein, in the different 2 kinds of particles of charged characteristic and optical reflectivity, having concavo-convex particle on the surperficial macroscopic view is that resin mass is pulverized the particle that obtains.
4. as claimed in claim 1 or 2ly be used for the particle that image shows, wherein, in the different 2 kinds of particles of charged characteristic and optical reflectivity, having concavo-convex particle on the surperficial macroscopic view is to make the particulate brute force be attached to the master batch surface and the particle that obtains.
5. the particle that is used for image display medium as claimed in claim 4 wherein, when master batch and particulate are adhered to, adopts mechanical impact force.
6. the particle that is used for image display medium as claimed in claim 1 or 2, wherein, in the different 2 kinds of particles of charged characteristic and optical reflectivity, not having concavo-convex particle on the surperficial macroscopic view is the nearly spherical particle that the resin monomer polymerization obtains.
7. the particle that is used for image display medium as claimed in claim 1 or 2, wherein, in the different 2 kinds of particles of charged characteristic and optical reflectivity, not having concavo-convex particle on the surperficial macroscopic view is that the particle that will pulverize is exposed to the nearly spherical particle that makes its surface smoothing under the fusing point of this particle or the temperature more than the fusing point and obtain.
8. the particle that is used for image display medium as claimed in claim 2, wherein, in the different 2 kinds of particles of charged characteristic and optical reflectivity, the particulate that the surface does not exist concavo-convex particle surface to adhere on the macroscopic view have with described surperficial macroscopic view on do not have the charged opposite polarity polarity of concavo-convex particle, and behind the surface, do not change the charged polarity that does not have concavo-convex particle on the described surperficial macroscopic view.
9. the particle that is used for image display medium as claimed in claim 1 or 2, wherein, the mean grain size of 2 kinds of particles that charged characteristic and optical reflectivity are different is 0.5～50 μ m.
10. the particle that is used for image display medium as claimed in claim 1 or 2, wherein, there is not the mean grain size of the particulate of concavo-convex particle surface in electrostatic adhesion on surperficial macroscopic view be 20～200nm.
11. one kind is used the image of image display medium to show with dull and stereotyped, this image display medium uses as each described particle in the claim 1～10, wherein, be filled in the volume occupation rate of image display medium more than at least 2 kinds or 2 kinds between substrate in the scope of 5～70vol%.
12. an image display device is characterized by, this image display device has carried the described image of claim 11 and has shown with dull and stereotyped.
CNB2004800131801A 2003-04-02 2004-04-02 Particle used for image display medium, image display panel using same, and image display Expired - Fee Related CN100357819C (en)

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JP099342/2003 2003-04-02
JP2003099342 2003-04-02
JP102764/2003 2003-04-07
JP111516/2003 2003-04-16
JP150712/2003 2003-05-28
JP165353/2003 2003-06-10
JP183023/2003 2003-06-26
JP185243/2003 2003-06-27
JP189304/2003 2003-07-01
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TWI477873B (en) * 2012-02-16 2015-03-21 E Ink Holdings Inc Electrophoretic display film and electrophoretic display apparatus
JP6008685B2 (en) * 2012-10-12 2016-10-19 イー インク コーポレイション Display particle dispersion, display medium, and display device
JP6750245B2 (en) * 2016-02-19 2020-09-02 富士ゼロックス株式会社 Toner for developing electrostatic image, electrostatic image developer, toner cartridge, process cartridge, image forming apparatus, and image forming method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002139750A (en) * 2000-11-02 2002-05-17 Fuji Xerox Co Ltd Image display medium, image display device and image display method
CN1402068A (en) * 2001-08-28 2003-03-12 希毕克斯幻像有限公司 Improved electrophoresis display with high contrast, improved shear resistance and/or compressive property and local raised structure

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002139750A (en) * 2000-11-02 2002-05-17 Fuji Xerox Co Ltd Image display medium, image display device and image display method
CN1402068A (en) * 2001-08-28 2003-03-12 希毕克斯幻像有限公司 Improved electrophoresis display with high contrast, improved shear resistance and/or compressive property and local raised structure

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