CN1947058A - Particles for display medium, information display panel employing same, and information display - Google Patents
Particles for display medium, information display panel employing same, and information display Download PDFInfo
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- CN1947058A CN1947058A CN 200580012243 CN200580012243A CN1947058A CN 1947058 A CN1947058 A CN 1947058A CN 200580012243 CN200580012243 CN 200580012243 CN 200580012243 A CN200580012243 A CN 200580012243A CN 1947058 A CN1947058 A CN 1947058A
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Abstract
Particles constituting a display medium for use in an information display for displaying information such as an image by applying an electric field to the display medium sealed between opposing substrates at least one of which is transparent thereby moving the display medium. The particles are composed of composite particles where minor particles are buried in the surface layer of major particles while exposing the surfaces. Consequently, the particles constituting a display medium for use in an information display are capable of sustaining the initial display performance even at the time of inversion durability test without dissociating minor particles even through durability test where rewriting is repeated. Also provided are an information display panel employing such particles and an information display.
Description
Technical field
The present invention relates to message panel, the information display device of display medium particle and this particle of use, wherein said display medium particle is used for enclosing display medium between opposing substrates, display medium is applied electric field, make display medium move the information display device of information such as display image, at least one plate base is transparent in the wherein above-mentioned opposing substrates.
Background technology
In the past, the instead information display device of LCD (LCD) of the favourable information display device that causes technology such as color mode, hot mode, double-colored particle rotation mode with electrophoresis mode, electricity was proposed.
These prior aries are compared with LCD, have big field of view angle, the consumed power that can obtain near common printed matter little, have an advantage such as memory function, therefore consider its technology as the information display device that is applied to cheapness of future generation is just being expected to expand to aspects such as the demonstration of portable terminal client information, e-files.Especially recently proposed and to have made microcapsules by the dispersion liquid that dispersed particle and coloring solution are formed, and it has been configured between the opposing substrates and the electrophoresis mode that constitutes, and it has been expressed expectation.
Yet, in the electrophoresis mode,, thereby exist viscous resistance to cause the slow problem of response speed because of liquid owing to particle moves in liquid.In addition, also have following point: because the particle of high specific gravity such as titanium dioxide is dispersed in low-gravity solution, therefore, the particle of high specific gravity such as this titanium dioxide precipitates easily, is difficult to keep the stability of disperse state, and the repetition stability that image shows is poor.In addition, even make microcapsules, making cell size reach the microcapsules level, also only is to make above-mentioned shortcoming be difficult to show from the teeth outwards, but unresolved any substantive issue.
On the other hand, for the electrophoresis mode of utilizing the movement in solution, also proposed not use solution, conducting particles and charge transport layer are assembled in the part of substrate mode (for example, State of Zhao comes, other 3 people, " novel toner display device (I) ", on July 21st, 1997, Japanese iconology meeting annual general meeting (the 83rd) " Japan Hardcopy ' 99 " collection of thesis, reference is p.249-252).But, because because of charge transport layer being set even charge generation layer is set, and structure is complicated, and is difficult to consistently therefore also to have the problem of deficient in stability to the conducting particles iunjected charge.
As a method that solves above-mentioned variety of issue, known have such information display device: enclose population between opposing substrates, population is applied electric field, make particle move information such as display image, at least one plate base in the wherein above-mentioned opposing substrates is transparent.
As the employed particle of above-mentioned information display device, need have controlled to mobile and carried charge.Different with object of the present invention, as electrophoto-graphic toner, known following technology: be attached to coatingparticles by making seed (adjuvants such as titania, fumed particulate), thereby can improve flowability, and the may command carried charge.Yet, with the electrophoto-graphic toner of above-mentioned toner adjuvant attached type when acting on the display medium of above-mentioned information display device, because the thermal stress, the mechanical stress that work during the upset long duration test of the upset that shows in the information of carrying out repeatedly, occur that seed (adjuvant) breaks away from from the coatingparticles surface easily or seed is embedded to the phenomenon of coatingparticles inside fully.The problem that can not keep initial performance when having the upset long duration test thus.
Summary of the invention
The object of the invention is to address the above problem and a kind of display medium particle is provided and uses message panel, the information display device of this particle, and long duration test seed does not also break away from and can keep the information display device of initial performance when overturning long duration test even this display medium particle is used for overturning.
Display medium particle of the present invention is used for information display device as follows, this information display device is to enclose display medium between opposing substrates, display medium is applied electric field, make display medium move information such as display image, at least one plate base is transparent in the wherein above-mentioned opposing substrates, it is characterized in that this display medium particle is by so that the state that the seed sub-surface is exposed is buried the composite particle that seed forms underground constitutes in the top layer of coatingparticles.
In addition, as the preference of display medium particle of the present invention, make the particle diameter d of coatingparticles
0Particle diameter d with seed
1～nBe respectively 0.01＜d
0＜50 (μ m), 0.01＜d
1～n＜1.00 (μ m), and satisfy d
1～n/ d
0＜0.33, making with the undefined rate W that on average buries underground simultaneously is 0.05＜W＜0.95; W=1-((S-S
0φ
0)/∑ S
nφ
n), wherein, S is the surface area of composite particle unit volume, S
0Be the surface area of coatingparticles unit volume, S
nBe the surface area of seed subunit volume, when seed of burying underground is the n kind, the particle diameter d of each seed
1～n(d
1, d
2..., d
n) satisfy above-mentioned relation.
When the display medium that is used in message panel of the present invention is powder fluid described later, utilize above-mentioned display medium particle as the particulate material that constitutes powder fluid.In addition, message panel of the present invention as display medium, perhaps is adjusted to above-mentioned display medium particle powder fluid with above-mentioned display medium particle and uses.In addition, information display device of the present invention is equipped with above-mentioned message panel.
According to the present invention, by will be so that the state that the seed sub-surface is exposed is buried composite particle that seed forms underground as display medium in the top layer of coatingparticles, even overturn long duration test, particle can not break away from yet, and can keep initial characteristic when the upset long duration test yet.
Description of drawings
Fig. 1 (a) and (b) are the figure of an example that represent to use the message panel of particle of the present invention respectively.
Fig. 2 (a) and (b) are the figure of another example that represent to use the message panel of particle of the present invention respectively.
Fig. 3 (a) and (b) are the figure of another example that represent to use the message panel of particle of the present invention respectively.
Fig. 4 (a) and (b) are the figure of an example that represent to be used for the particle of display medium of the present invention respectively.
Fig. 5 is the SEM photo of particle shown in presentation graphs 4 (a) and (b).
Fig. 6 is used for illustrating the figure of an example that buries the method for seed at particle of the present invention in coatingparticles underground.
Fig. 7 is used for illustrating the figure of another example that buries the method for seed at particle of the present invention in coatingparticles underground.
Fig. 8 is the figure of an example of the shape in the next door of expression in the message panel of the present invention.
Embodiment
At first, to the basic structure of particle of the present invention as the message panels such as image that information display device had of the particle that constitutes display medium (population or powder fluid) is described.Message panel used in the present invention applies electric field to the display medium of enclosing between the 2 relative plate bases.Along the direction of an electric field that is applied in, charged be the charged display medium of electronegative potential by Coulomb force etc. towards the noble potential layback, in addition, charged be the charged display medium of noble potential by Coulomb force etc. towards the electronegative potential layback, these display mediums are because the variation of current potential direction of an electric field that conversion causes, and the moving direction of display medium is changed, come display message thus.Therefore, move equably, and can maintain and show when refreshing or the stability when showing continuously, need the design information display board in order to make display medium.Wherein, put on the power of display medium particle, except the power that attracts each other that forms by the Coulomb force between the particle, think the in addition crosslinked power of electric image power, intermolecular force, liquid between particle and electrode, the substrate, gravity etc.
The example of the message panel that information display device of the present invention uses is described according to Fig. 1 (a) and (b)～Fig. 3 (a) and (b).
In the example shown in Fig. 1 (a) and (b), at least the electric field that the display medium more than at least 2 kinds 3 (white display medium 3W that is made of population and the black display medium 3B that is made of population are shown here) that is made of the particle more than a kind respectively, have different colors and charged characteristic is applied corresponding to the outside from substrate 1,2, move along the direction vertical with substrate 1,2, make the observer can see black display medium 3B and carry out black display, or make the observer can see white display medium 3W and carry out white and show.In addition, in the example shown in Fig. 1 (b), on the example basis shown in Fig. 1 (a), also cancellate next door 4 for example is set between substrate 1,2 and the formation cell.
At Fig. 2 (a), (b) in the example shown in, make and constitute by the particle more than a kind at least respectively, display medium more than at least 2 kinds 3 (white display medium 3W that is made of population and the black display medium 3B that is made of population are shown here) with different colors and charged characteristic is corresponding to by applying the electric field that voltage produces being located at the electrode 5 on the substrate 1 and being located between the electrode 6 on the substrate 2, edge and substrate 1,2 vertical directions move, make the observer can see black display medium 3B and carry out black display, or make the observer can see white display medium 3W and carry out white and show.In addition, in the example shown in Fig. 2 (b), on the example basis shown in Fig. 2 (a), also cancellate next door 4 for example is set between substrate 1,2 and the formation cell.
In the example shown in Fig. 3 (a) and (b), make at least a kind of display medium 3 with color and charged characteristic (the white display medium 3W that is made of population is shown) that constitutes by the particle more than a kind at least respectively corresponding to by applying the electric field that voltage produces being located between electrode 5 on the substrate 1 and the electrode 6 here, move along the direction parallel with substrate 1,2, make the observer can see white display medium 3W and carry out white to show, or make the observer can see the color of electrode 6 or substrate 1 and the color of carrying out electrode 6 or substrate 1 shows.In addition, in the example shown in Fig. 3 (b), on the example basis shown in Fig. 3 (a), also cancellate next door 4 for example is set between substrate 1,2 and the formation cell.
At the white display medium 3W that uses the white display medium that constitutes by powder fluid to replace respectively to constitute by population, use the black display medium that constitutes by powder fluid to replace under the situation of the black display medium 3B that constitutes by population, more than explanation also can be suitable equally.
Fig. 4 (a) and (b) are the figure of an example that represent to be used for the particle of display medium of the present invention respectively, and Fig. 4 (a) represents its front view, and Fig. 4 (b) represents its sectional view.In the example shown in Fig. 4 (a) and (b), the particle 11 that is used for display medium of the present invention is characterised in that by so that the state that the seed sub-surface is exposed is embedded in the composite particle constituent particle 11 that the top layer of coatingparticles 12 forms with seed 13.In addition, represent that in this example seed 13 is examples of one deck, but its number of plies being not particularly limited, also can be the two-layer above number of plies.The SEM photo of the employed particle of display medium of the present invention in Fig. 5 shown in presentation graphs 4 (a) and (b).
In the particle that in display medium of the present invention, uses, seed 13 is embedded in the composite particle that forms in the top layer of coatingparticles 12 by the state that this particle is become expose with the seed sub-surface, in other words, by making this particle become the composite particle of the configuration/shape in the top layer that control depth of burying ground is embedded in seed 13 coatingparticles 12, can prevent that seed 13 when durable breaks away from.Consider on the one hand that from this if the depth of burying is too small, seed 13 can break away from from the surface of coatingparticles 12 sometimes when durable, on the other hand, if the depth of burying is excessive, then initial sometimes flowability diminishes, the poor performance of initially overturning.Therefore, preferably make with the undefined rate W that buries underground in 0.05～0.95 scope.
＜bury the definition of rate W underground 〉
If the surface area of composite particle, coatingparticles, seed unit volume separately (surface area by gas adsorption method etc. measure) is S, S
0, S
1(cm
-1), establishing coatingparticles, seed volume use level separately is φ
0, φ
1(φ
0+ φ
1=1) time, on average buries rate W underground by following formula (1) definition.
W＝1-((S-S
0φ
0)/S
1φ
1)……(1)
When the n seed particles used more than 2 kinds, the surface area per unit volume of establishing respectively separately is S
1, S
2... S
n(cm
-1), the volume use level of establishing separately is φ
1, φ
2φ
n(φ
0+ ∑ φ
n=1) time, on average buries rate W underground by following formula (2) definition.
W＝1-((S-S
0φ
0)/∑S
nφ
n)……(2)
An example of the condition when in addition, below expression is measured surface area with gas adsorption method.Operative installations: full-automatic gas adsorbance determinator Autosorb-1-C (manufacturing of Quantachrome society), control analysis software: AS1WIN (manufacturing of Quantachrome society), using gases: N
2, adsorption temp: 77K, pre-treatment condition: 60 ℃ * 10 hours, measure sample size: 0.2g, analytical approach: BET method.
In addition, in the employed particle of display medium of the present invention, the particle diameter of coatingparticles 12 and seed 13 is preferably the particle diameter d of coatingparticles 12
0At 0.1＜d
0In the scope of＜50 (μ m), the particle diameter d of seed 13
1～nAt 0.01＜d
1～nIn the scope of＜1.00 (μ m), and d
1～n/ d
0＜0.33.Wherein, if the particle diameter d of coatingparticles 12
0Be below the 0.1 μ m, then the cohesiveness between the particle strengthens, and drives the needed voltage of display medium and uprises, and is unsatisfactory as the particle that is used for display medium.If the particle diameter d of coatingparticles 12
0Be more than the 50 μ m, then show to go up to lack vividness, in addition, must increase substrate at interval, drive the required voltage of display medium and uprise, unsatisfactory as the particle that is used for display medium.In addition, if the particle diameter d of seed 13
1～nBe below the 0.01 μ m, then when showing the long duration test that refreshes repeatedly, seed 13 is embedded in coatingparticles 12 inside sometimes, if the particle diameter d of seed 13
1Be 1.00 μ m when above, then initial display medium flowability is little, shows that initially refresh performance is poor.In addition, if d
1～n/ d
0Be more than 0.33, then can produce condensed matter between seed or between the coatingparticles, the flowability of display medium diminishes, and initial demonstration refresh performance is poor.
In addition, in the particle that in display medium of the present invention, uses, for seed 13 being embedded in the method that becomes specified states in the coatingparticles 12, be not particularly limited the preferred method shown in Figure 7 that adopts under the situation that method shown in Figure 6 under the situation that expression buries one deck seed 13 underground or expression bury multilayer seed 13 underground.
When one deck seed shown in Figure 6 13 is set, using Henschel type mixer that ratio is according to the rules mixed the ready coatingparticles of being made up of for example thermoplastic resin 12 mixes with the powder that seed 13 forms, at first, pulverize seed 13, make it on the surface of coatingparticles 12, adhere to one deck, then by thermoplastic coatingparticles 12, antithetical phrase particle 13 applies along the center position of coatingparticles 12 and is pressed into acting force, makes the composite particle that seed 13 is embedded in the shape on coatingparticles 12 surfaces.
When burying multilayer seed son 13 underground, as shown in Figure 7, the composite particle that obtains with above-mentioned method shown in Figure 6 is as new coatingparticles 14, use Henschel type mixer mixes with the powder that seed 13 forms ratio masterbatch mix 14 according to the rules, at first, pulverize seed 13, make it on the surface of coatingparticles 12, adhere to more than one deck again, make coatingparticles 14 softening by heating then, antithetical phrase particle 13 applies along the center position of coatingparticles 14 and is pressed into acting force, makes the composite particle that seed 13 is embedded in the shape on coatingparticles 14 surfaces.
Below, each parts that constitute as the message panel of object of the present invention are described.
About substrate, at least one substrate is the transparent substrate 2 that can observe the color of display medium from the outside of display panel, and its suitable material is transmission of visible light height and the good material of thermotolerance.Substrate 1 can be transparent also can be opaque.Baseplate material is carried out illustrative words, can list polymer sheets such as poly terephthalic acid diethylester, polyethersulfone, tygon, polycarbonate, polyimide, esters of acrylic acid, or metal sheet such have a flexible material; And glass, quartz etc. do not have flexible inorganic sheet.The thickness of substrate is preferably 2～5000 μ m, further is suitably for 5～2000 μ m, if thin excessively, then is difficult to keep intensity, substrate distance homogeneity, if thicker than 5000 μ m, then is not suitable as slim information display panel.
About the electrode that is provided with corresponding to needs, be arranged on visual side and must be electrode 6 on the transparent substrate 2, it is formed by conductive material transparent and that can form pattern, as if illustration, can list metal species such as aluminium, gold, silver, copper; Electroconductive polymer classes such as ITO, indium oxide, zinc paste, polyaniline, polypyrrole, polythiophene can illustration vacuum evaporation, formation method such as coating.In addition,, be suitably for 3～1000nm, be preferably 5～400nm as long as the thickness of electrode can be guaranteed electric conductivity, not hinder transmitance.The material that is arranged on the electrode 5 on substrate 1 side and thickness etc. can be identical with above-mentioned electrode 6, but need not to be transparent.In addition, the external voltage input during this situation can overlapping direct current or interchange.
About the next door 4 that is provided with as required, its shape can be according to the kind of the display medium that is used to show, carry out suitably optimization setting, limited without exception, but the width in next door can be adjusted into 2～100 μ m, be preferably 3～50 μ m, and the height in next door can be adjusted into 10～500 μ m, be preferably 10～200 μ m.In addition, when forming the next door, can consider the both sides of the chest method that behind each self-forming rib on two substrates facing mutually, engages respectively; Only on the substrate of a side, form single rib method of rib.In the present invention, arbitrary method all is fit to use.
By the cell that the next door that is made of these ribs forms, as shown in Figure 8, to observe from the base plan direction, illustration has quadrilateral, triangle, wire, circle, hexagon; As its configuration, can clathrate, cellular or mesh-shape be arranged illustration.Reasonable is to dwindle as far as possible and divide suitable part (area of display booth frame part) from the visual next door cross-section of display surface one side, can increase the sharpness of information show state like this.Wherein, if the formation method of counter septum is carried out example, can enumerate silk screen print method, sand-blast, photoetching process, additive process, mould transfer printing.In these methods, be fit to adopt photoetching process, the mould transfer printing that uses etchant resist.
Below, describe with regard to the particle that is used for display medium of the present invention.Particle comprises coatingparticles 12 and seed 13, and can comprise charge control agent, colorant, inorganic additive etc. in as the resin of its principal ingredient as required samely.Below, resin, charge adjusting agent, colorant, other adjuvants are carried out illustration.
Example as resin, can list urethane resin, urea resin, acrylic resin, vibrin, acrylated polyurethane resin, acroleic acid polyurethane silicone resin, acroleic acid polyurethane fluororesin, acrylic acid fluororesin, silicone resin, silicon Acrylote ketone resin, epoxy resin, polystyrene resin, styrene acrylic resin, polyolefin resin, butyral resin, permalon, melmac, phenolics, fluororesin, polycarbonate resin, polysulfone resin, polyether resin, polyamide etc., also can mix more than 2 kinds.Particularly from the viewpoint of control with the bounding force of substrate, what be fit to is acrylated polyurethane resin, silicon Acrylote ketone resin, acrylic acid fluororesin, acroleic acid polyurethane silicone resin, acroleic acid polyurethane fluororesin, fluororesin, silicone resin.
For charge control agent, be not particularly limited, as negative charge controlling agent, can list oil-soluble dyes, quaternary ammonium compound, calixarene compound, boron-containing compound (benzoic acid boron complex), nitro imidazole derivatives of for example salicylic acid metal complex, containing metal azo dyes, containing metal (containing metallic ion or metallic atom) etc.As positive charge control agent, can list for example aniline black byestuffs, triphenyl methane compounds, quaternary ammonium compound, polyamino resin, imdazole derivatives etc.In addition, can also be with metal oxides such as ultra micron silicon dioxide, ultra micron titanium dioxide, ultra micron aluminium oxide; Nitrogenous ring compound such as pyridine and derivant or salt; The resins of various organic pigments, fluorine-containing, chlorine, nitrogen etc. etc. are as charge control agent.
As colorant, can use pigment, dyestuff various of all kinds as following illustrative organic or inorganic.
As black colorant, can use carbon black, cupric oxide, manganese dioxide, nigrosine, activated charcoal etc.
As blue colorant, the C.I. pigment blue 15 is arranged: 3, the part chloride of C.I. pigment blue 15, dark purple, cobalt blue, alkali blue lake, Victoria blue color lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue BC etc.
As red stain, have that colcother, cadmium red, red lead, mercuric sulphide, cadmium, permanent red 4R, lithol red, pyrazolone red, Wo Qiuge are red, 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.
As yellow colorants, chrome yellow, zinc yellow, cadmium yellow, yellow iron oxide, inorganic permanent yellow, nickel titanium yellow, navel orange Huang, S naphthol yellow S-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, peacock green color lake, final yellowish green G (final yellow green G) etc. are arranged.
As orange colorant, red chrome yellow, molybdate orange, permanent orange GTR, pyrazolone orange, fast orange (vulcan 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 paste, titanium dioxide, stibium trioxide, zinc sulphide etc. are arranged.
As extender pigment, be that ground barium sulfate, barium carbonate, clay, silicon dioxide, white carbon, talcum, aluminium oxide are white etc.In addition, as various dyestuffs such as alkalescence, acidity, dispersion, direct dyess, nigrosine, methylene blue, rose-red, quinoline yellow, ultramarine blue etc. are arranged.
As the example of mineral-type adjuvant, can enumerate that titanium dioxide, zinc paste, 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 purple, 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.
These pigment and mineral-type adjuvant can use separately or multiple being used in combination.Wherein, especially as the preferred carbon black of black pigment, as the preferred titanium dioxide of Chinese white.In addition, particle of the present invention, its mean grain size d (0.5) are preferably in 0.1～20 mu m range and be evenly distributed.If mean grain size d (0.5) greater than this scope, then lacks the sharpness on showing, if less than this scope, then the aggregation force between the particle becomes excessive, therefore can be to the mobile obstruction of bringing of display medium.
In addition, in the present invention, about the size distribution of each particle, the span of the size distribution shown in the following formula (Span) less than 5, preferred less than 3.
Span＝(d(0.9)-d(0.1))/d(0.5)
(wherein, d (0.5) is the grain diameter value of representing with μ m, 50% bigger in the particle than it, and 50% is littler than it; D (0.1) is the grain diameter value of representing with μ m, is 10% at the ratio of this particle below numerical value; D (0.9) is the grain diameter value of representing with μ m, is 90% at this particle below numerical value.)
By span is in the scope below 5, the size of each particle is even, can realize that uniform particle moves.
In addition, for the relation of each particle, the d (0.5) that importantly has the particle of minimum diameter in employed particle is below 50, is preferably below 10 with respect to the ratio of the d (0.5) of the particle with maximum gauge.Even if the size distribution span is little, also owing to be that the particle that charged characteristic differs from one another moves each other in the opposite direction, therefore what be fit to is that both sides' particle size is close, and both sides' particle can easily move according to equivalent round about, and this just requires above-mentioned scope.
In addition, above-mentioned size distribution and particle diameter can be tried to achieve by laser diffraction/scattering method etc.If to particle-irradiation laser as determination object, then can produce the light intensity distributions pattern of the diffraction/scattered light in space, because there are corresponding relation in this light intensity pattern and particle diameter, therefore can measure particle diameter and size distribution.
Wherein, particle diameter among the present invention and size distribution are distributed by volume reference and obtain.Specifically, can use Mastersizer2000 (Malvern InstrumentsLtd.) mensuration machine, in nitrogen stream, add particle, adopt subsidiary analysis software (based on the software of the volume reference distribution of using the Mie theory), measure particle diameter and size distribution.
The carried charge of particle obviously depends on its condition determination, as can be known in the information display panel carried charge of particle depend on the initial strip electric weight substantially, with the contacting of next door, with the contacting of substrate, along with the saturation value of the charged behavior of charge decay, the especially particle in elapsed time is a determinative.
People of the present invention have carried out the result that studies intensively, find can estimate the scope of the suitable charged characteristic value of the used particle of display medium by using identical carrier particle to measure the carried charge of particle in blowing out (blowoff) method.
Below, just for example powder fluid that uses as display medium of the present invention describes.In addition, about the title of the powder fluid that uses in the information display panel of the present invention, the applicant obtains the right of " electronics powder fluid (registered trademark): accession designation number 4636931 ".
" powder fluid " among the present invention is self not demonstrate both material of intermediateness mobile, that have fluid and particle properties concurrently by the power of the power of gas or liquid.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 the definition of particle is the object that negligible substantially size also has limited quality, (ball is kind: the physics dictionary) to be subjected to the influence of gravity.Wherein, also there is the special state that is called gas-solid fluidized bed body, liquid-solid liquid in the particle, if from base plate to particle jet flow gas, then particle is applied power upwards corresponding to gas velocity, when this power and gravitational equilibrium, be in the particle of the state that as fluid, can flow easily, be referred to as gas-solid fluidized bed body, similarly will utilize fluid to make its state that flows be called liquid-solid liquid (ordinary society: big encyclopaedia dictionary).Such gas-solid fluidized bed body or liquid-solid liquid are the states that utilizes gas stream or flow of liquid.In the present invention, clear and definite can produce the power that need not by the power of such gas or liquid, the material that self demonstrates mobile state specifically, it is defined as powder fluid.
Promptly, powder fluid among the present invention is identical with the definition of liquid crystal (the middle phase of liquid and solid), be the intermediateness that has particle and liquid two characteristics concurrently, demonstrate the utmost point feel bad above-mentioned gravity as particle characteristics influence and have the material of the special state of high fluidity.Such material can be under aerosol state, promptly can be in gas as obtaining in the stably floating dispersed system that solid shape or liquid material arranged of dispersed substance, in information display panel of the present invention, with solid shape material as dispersed substance.
As the information display panel of object of the present invention, between at least one side is the transparent substrate of facing mutually, be enclosed in the gas as dispersed substance stably floating solids aerosol state and demonstrate the powder fluid of high fluidity.Such powder fluid just can be easily under the applying of low-voltage stably moves under the effect of Coulomb force etc.
Employed powder fluid among the present invention, as mentioned above, be need not by the power of gas or liquid power, self just demonstrate both material of intermediateness mobile, that have fluid and particle properties concurrently.This powder fluid especially can be taked aerosol state, in information display panel of the present invention, floats to have under the state of solid shape material as dispersed substance in gas more stablely and uses.
The scope of aerosol state when preferably the apparent volume during powder fluid maximum floating is not floating more than 2 times, more preferably more than 2.5 times, be preferably especially more than 3 times.The upper limit is not particularly limited, and is preferably below 12 times.
If apparent volume 2 times when not floating during powder fluid maximum floating then are difficult to the control that shows, in addition, if greater than 12 times, operational inconvenience such as then take place that time in the powder fluid sealed in unit excessively float.In addition, maximum apparent volume when floating is measured according to as described below.That is, powder fluid put into to see through the closed container that powder fluid is observed, make the container local oscillation or fall, make maximum floating state, measure the apparent volume of this moment from outside of containers.Specifically, in the polypropylene system lidded container (trade name ア イ ボ one イ: ア ズ ワ Application (strain) is produced) of diameter (internal diameter) 6cm, high 10cm, powder fluid when not floating is put into the powder fluid that is equivalent to 1/5 volume, container is positioned in the oscillator, in the distance of 6cm, vibrated 3 hours with 3 reciprocal/sec.With the apparent volume of vibration after just having stopped as maximum the apparent volume when floating.
In addition, in the present invention, the time of the apparent volume of preferred powder fluid changes satisfies following formula.
V
10/V
5＞0.8
Wherein, V
5Expression begins the apparent volume (cm after 5 minutes when floating from maximum
3), V
10Expression is from the apparent volume (cm of the floating beginning of maximum after 10 minutes
3).In addition, the time of the apparent volume of information display device preferred powder fluid of the present invention changes V
10/ V
5Greater than 0.85, be preferably greater than 0.9 especially.Work as V
10/ V
5Be 0.8 when following, identical when using common so-called particle, can't guarantee high-speed response of the present invention, show the effect of the permanance of rewriting repeatedly.
In addition, the mean grain size (d (0.5)) that constitutes the particulate material of powder fluid is preferably 0.1～20 μ m, and more preferably 0.5～15 μ m is preferably 0.9～8 μ m especially.If, then be difficult to the control that shows less than 0.1 μ m; If greater than 20 μ m, then lack the sharpness that shows.In addition, it is identical with d (0.5) in the following size distribution span (Span) to constitute the mean grain size (d (0.5)) of particulate material of powder fluid.
Size distribution span less than 5 shown in the preferred following formula of particulate material of formation powder fluid, more preferably less than 3.
Size distribution span=(d (0.9)-d (0.1))/d (0.5)
Wherein, d (0.5) is the grain diameter value of representing with μ m, constitutes 50% bigger than it in the particulate material of powder fluid, and 50% is littler than it; D (0.1) is the grain diameter value of representing with μ m, is 10% at the ratio of the particulate material of this formation powder fluid below numerical value; D (0.9) is the grain diameter value of representing with μ m, is 90% at the particulate material of this formation powder fluid below numerical value.Be in the scope below 5 by the size distribution span that makes the particulate material that constitutes powder fluid, size is even, can realize that uniform display medium moves.
In addition, above-mentioned size distribution and particle diameter can be tried to achieve by laser diffraction/scattering method etc.If to powder fluid irradiating laser as determination object, then can produce the light intensity distributions pattern of the diffraction/scattered light in space, because there are corresponding relation in this light intensity pattern and particle diameter, therefore can measure particle diameter and size distribution.This particle diameter and size distribution are distributed by volume reference and obtain.Specifically, can use Mastersizer2000 (MalvernInstruments Ltd.) mensuration machine, in nitrogen stream, add powder fluid, adopt subsidiary analysis software (based on the software of the volume reference distribution of using the Mie theory), measure.
The manufacturing of powder fluid can be mixing with resin, charge control agent, colorant, other adjuvants of necessity, pulverize; Also can be polymerized by monomer; Can also apply existing particle with resin, charge control agent, colorant, other adjuvants.Below, resin, charge control agent, colorant, other adjuvants that constitute powder fluid are carried out illustration.
Example as resin, can enumerate urethane resin, acrylic resin, vibrin, polyurethane modified acrylic resin, silicone resin, nylon resin, epoxy resin, styrene resin, butyral resin, permalon, melmac, phenolics, fluororesin etc., can also mix more than 2 kinds.From the viewpoint of control with the bounding force of substrate, specially suitable is acrylated polyurethane resin, acroleic acid polyurethane silicone resin, acroleic acid polyurethane fluororesin, urethane resin, fluororesin.
As the example of charge control agent, when giving positive charge, can list quaternary ammonium compound, aniline black byestuffs, Synthesis of diaminodiphenyl, imdazole derivatives etc.; When giving negative charge, can list containing metal azo dyes, salicylic acid metal complex, nitro imidazole derivatives etc.
As colorant, can use pigment, dyestuff various of all kinds as following illustrative organic or inorganic.
As black colorant, can use carbon black, cupric oxide, manganese dioxide, nigrosine, activated charcoal etc.
As blue colorant, the C.I. pigment blue 15 is arranged: 3, the part chloride of C.I. pigment blue 15, dark purple, cobalt blue, alkali blue lake, Victoria blue color lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue BC etc.
As red stain, have that colcother, cadmium red, red lead, mercuric sulphide, cadmium, permanent red 4R, lithol red, pyrazolone red, Wo Qiuge are red, 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.
As yellow colorants, chrome yellow, zinc yellow, cadmium yellow, yellow iron oxide, inorganic permanent yellow, nickel titanium yellow, navel orange Huang, S naphthol yellow S-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, peacock green color lake, final yellowish green G (final yellow green G) etc. are arranged.
As orange colorant, red chrome yellow, molybdate orange, permanent orange GTR, pyrazolone orange, fast orange (vulcan 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 paste, titanium dioxide, stibium trioxide, zinc sulphide etc. are arranged.
As extender pigment, be that ground barium sulfate, barium carbonate, clay, silicon dioxide, white carbon, talcum, aluminium oxide are white etc.In addition, as various dyestuffs such as alkalescence, acidity, dispersion, direct dyess, nigrosine, methylene blue, rose-red, quinoline yellow, ultramarine blue etc. are arranged.
As the example of mineral-type adjuvant, can enumerate that titanium dioxide, zinc paste, 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 purple, 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.
These pigment and mineral-type adjuvant can use separately or multiple being used in combination.Wherein, especially as the preferred carbon black of black pigment, as the preferred titanium dioxide of Chinese white.
In addition, in the present invention, it is important that the gas of gap that the display medium between substrate is surrounded is managed, and it helps to improve exhibit stabilization.Specifically, for the humidity of the gas of gap, the relative humidity under 25 ℃ be 60%RH following, be preferably 50%RH following, more preferably be important below the 35%RH.
In Fig. 1 (a) and (b)～Fig. 3 (a) and (b), this gap is meant the gas part hermetic unit that occupies part (when the next door is set), information display panel that occupies part, next door 4, so-called display medium contact that deducts electrode 5,6, display medium 3 (population or powder fluid) from the part that is clipped in opposing substrates 1, substrate 2.
The gas of gap is so long as in above-mentioned humidity zone, its kind just without limits, what be fit to is dry air, drying nitrogen, dry argon gas, dry helium gas, dry carbon dioxide, dry methane etc.This gas must be enclosed under the condition that keeps its humidity in the information display panel, for example under the humidity environment of regulation, carry out the filling of display medium, the loading of display medium etc., in addition, apply in order to prevent that encapsulant, encapsulating method that moisture is invaded from the outside from being important.
Substrate in possessing the information display panel of information display device of the present invention and the interval between the substrate as long as display medium can move, can to keep contrast just passable, are adjusted into 10～500 μ m usually, are preferably 10～200 μ m.
The volume occupation rate of display medium is preferably 5～70% in the space between the substrate of facing mutually, and more preferably 5～60%.Under 70% the situation of surpassing, can be to the mobile generation obstacle of display medium, under the situation of less than 5%, it is unintelligible that contrast becomes easily.
Embodiment
Illustrate in greater detail the present invention below by embodiment and comparative example.But the present invention is not limited to following examples.
At first, as shown in the following Table 1, prepare by bury black track producing particle and the white particle that composite particle that 1 seed particles forms constitutes or only is made of the coatingparticles of not burying seed underground underground at a kind of coatingparticles.Coatingparticles is such according to match ratio shown in the following table 1, with twin shaft muller mixed-matrix resin and pigment, then, utilizes jet pulverizer to carry out particulate and pulverizes and make.When only by the coatingparticles constituent particle, with the gained particle as black track producing particle, white particle.
On the other hand, when forming the composite particle of coatingparticles and seed, according to such masterbatch mix of the match ratio shown in the table 1 and seed, drop into carbon mixer HFM-001C ((strain) エ ス エ system テ-manufacturing), under 50 ℃, the condition of 4000rpm, carry out handling in 120 minutes, seed is embedded on the surface of coatingparticles, make composite particle.Make the SUS sieve of the composite particle of gained by aperture 150 μ m, the particle that will pass through is as black track producing particle, white particle.
In addition, in table 1, use eastern レ (strain) to make ト レ コ Application 1401 * 31 as the PBT resin.Use the emerging product of space portion (strain) to make UBE nylon 1011FB as the PA resin.Use ト-ヨ-ス チ ロ-Le (strain) to make E-640 as the HIPS resin.Use デ グ サ society to make ス ペ シ ヤ Le Block ラ Star Network 4 as C/B.The イ ペ-Network CR-50 that uses the former industry of stone (strain) manufacturing is as TiO
2シ-ホ ス -the KE-P10 that uses (strain) Japanese catalyst manufacturing is as silicon dioxide microparticle.The エ Port ス -S that uses (strain) Japanese catalyst manufacturing is as the melamine resin particulate.Use the comprehensive ケ ミ ス ノ-MP300 of chemistry (strain) manufacturing that grinds as the PMMA resin particle.
Then, measure the particle diameter d of the coatingparticles that constitutes black track producing particle and white particle
0Particle diameter d with seed that uses the seed period of the day from 11 p.m. to 1 a.m
1, when using the seed period of the day from 11 p.m. to 1 a.m, calculate according to the surface area of trying to achieve and on average bury rate W underground simultaneously by above-mentioned surface area test method.In an embodiment, a kind of coatingparticles is buried underground 1 seed particles, the particle diameter of this coatingparticles (white or black) is d
0, the particle diameter of this seed (white or black) is d
1
Then, use ready black track producing particle and white particle, make the message panel that is used for information display device according to the method described above, evaluation as Presentation Function, measure initial show state contrast, the show state contrast after refreshing for 1000000 times, judge according to this result whether refresh permanance repeatedly good.The evaluation of Presentation Function is to make the current potential upset by apply 250V voltage to message panel, carries out the demonstration of black～white repeatedly.And measure initial and refresh contrast after the demonstration for 1000000 times.Contrast is the reflection density when utilizing the reflected image densimeter to measure black display and white to show, the reflection density the during reflection density during according to contrast=black display/white demonstration is tried to achieve.The results are shown in table 1.
[table 1]
| | | | Comparative example 1 | ||||||
| Black track producing particle | White particle | Black track producing particle | White particle | Black track producing particle | White particle | Black track producing particle | White particle | ||
| The cooperation of coatingparticles | Matrix resin | PBT | HIPS | PA | HIPS | PA | HIPS | PBT | HIPS |
| Matrix resin use level (weight %) | 95 | 50 | 95 | 50 | 95 | 50 | 95 | 50 | |
| C/B (black pigment) cooperates | 5 | 5 | 5 | 5 | |||||
| Content | Amount (weight %) | ||||||||
| TiO 2(Chinese white) use level (weight %) | 50 | ?50 | ?50 | 50 | |||||
| The seed subcategory | The melamine resin particulate | Silicon dioxide microparticle | The melamine resin particulate | ?- | The PMMA resin particle | - | - | ||
| The use level φ of coatingparticles 0 | 0.94 | 0.97 | 0.95 | ?1.00 | 0.92 | ?1.00 | 1.00 | 1.00 | |
| The use level of seed (treatment capacity) φ 1 | 0.06 | 0.03 | 0.05 | ?0.00 | 0.08 | ?0.00 | 0.00 | 0.00 | |
| Coatingparticles particle diameter d 0(μm) | 10.2 | 9.3 | 9.7 | ?9.3 | 9.7 | ?9.3 | 10.2 | 9.3 | |
| Seed seed footpath d 1(μm) | 0.24 | 0.11 | 0.24 | ?- | 0.10 | ?- | - | - | |
| d 1/d 0 | 0.024 | 0.012 | 0.025 | ?- | 0.010 | ?- | - | - | |
| On average bury rate W underground | 0.81 | 0.75 | 0.66 | ?- | 0.19 | ?- | - | - | |
| Initial contrast | 11.8 | 10.9 | 12.1 | 11.6 | |||||
| Refresh the back contrast for 1,000,000 times | 11.6 | 11.1 | 10.2 | 1.5 | |||||
| Permanance is judged | OK | OK | OK | NG | |||||
The result of table 1 shows: compare as the either party's who constitutes the black track producing particle group as display medium, white population comparative example 1 with not using composite particle, the composite particle that forms in the coatingparticles forms the black track producing particle group that constitutes as display medium, the carrying out of the embodiment 1～3 of the either party of population or both sides' particle shows that repeatedly the long duration test result who refreshes is good in vain by seed is embedded in.
Industrial applicibility
Use message panel that the information display device of particle of the present invention has, information display device to block the display part etc. of display parts, e-advertising, electronics POP, electronic shelf label, electronic price label, electronic music, RF-ID equipment applicable to the display parts such as the bulletin boards such as e-file, signboard, placard, blackboard, calculator, household appliances, automobile equipment, a note point card, IC-cards etc. such as the display part of the mobile devices such as notebook computer, PDA, mobile phone, portable terminal, e-book, electronic newspapers.
Claims (6)
1. display medium particle, it is the particle that is configured for the information display medium of information display device, this information display device is to enclose display medium between at least one plate base is transparent relative substrate, display medium is applied electric field, make display medium move information such as display image, it is characterized in that this display medium particle is embedded in the composite particle that forms in the top layer of coatingparticles by the state that exposes with the seed sub-surface with this seed and constitutes.
2. display medium particle according to claim 1 is characterized in that, makes the particle diameter d of coatingparticles
0Particle diameter d with seed
1～nBe respectively 0.1＜d
0＜50 (μ m), 0.01＜d
1～n＜1.00 (μ m), and satisfy d
1～n/ d
0＜0.33, making with the undefined rate W that on average buries underground simultaneously is 0.05＜W＜0.95;
W＝1-((S-S
0φ
0)/∑S
nφ
n)，
Wherein, S is the surface area of the unit volume of composite particle, S
0Be the surface area of the unit volume of coatingparticles, S
nIt is the surface area of the unit volume of seed.
3. display medium particle according to claim 1, wherein, display medium is a population.
4. display medium particle according to claim 1, wherein, display medium is a powder fluid.
5. a message panel is characterized in that, uses each described display medium particle in the claim 1～4.
6. an information display device is characterized in that, the described message panel of claim 5 is installed.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004115235 | 2004-04-09 | ||
| JP115235/2004 | 2004-04-09 | ||
| JP304186/2004 | 2004-10-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1947058A true CN1947058A (en) | 2007-04-11 |
| CN100432816C CN100432816C (en) | 2008-11-12 |
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ID=38045529
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005800122436A Expired - Fee Related CN100432816C (en) | 2004-04-09 | 2005-03-29 | Particles for display medium, information display panel employing same, and information display |
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08137416A (en) * | 1994-11-11 | 1996-05-31 | Fujikura Ltd | Color display device and color display method |
| EP0709713A3 (en) * | 1994-10-31 | 1997-03-26 | Fujikura Ltd | Electrically controlled color display device and method |
| JP2000035768A (en) * | 1998-07-16 | 2000-02-02 | Sekisui Chem Co Ltd | Spherical particulate and display device using the same |
| JP4135322B2 (en) * | 2001-02-07 | 2008-08-20 | 富士ゼロックス株式会社 | Image display medium, image forming method, image forming apparatus, and initialization apparatus |
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2005
- 2005-03-29 CN CNB2005800122436A patent/CN100432816C/en not_active Expired - Fee Related
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