CN100590685C - Particles for display media and information display panel using the particles - Google Patents
Particles for display media and information display panel using the particles Download PDFInfo
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- CN100590685C CN100590685C CN200710091040A CN200710091040A CN100590685C CN 100590685 C CN100590685 C CN 100590685C CN 200710091040 A CN200710091040 A CN 200710091040A CN 200710091040 A CN200710091040 A CN 200710091040A CN 100590685 C CN100590685 C CN 100590685C
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Abstract
In the particles (3B,3W) for display media (3) constituting the display media used for an information display panel, in which the display media having optical reflectance and charge characteristics are sealed between two substrates (1,2), at least one substrate being transparent, and, in which the display media, to which an electrostatic field is applied, are made to move so as to display information such as an image, the particles for display media having a substantially circular shape produced by a suspension polymerization of particle materials including monomer, wherein a part of the monomer is a cross-linking monomer and an amount of the cross-linking monomer is not less than 10 parts by weight and less than 50 parts by weight. By using the particles mentioned above, it is possible toobtain high heat resistance and low drive voltage (drive electric field).
Description
Technical field
The information display panel that the present invention relates to a kind of particle for display medium and use it, wherein, this particle for display medium has constituted the display medium that is used for information display panel, this information display panel is to enclose the display medium with optical reflectivity and charging property between transparent two substrates at least one side, by display medium being applied electric field display medium is moved, thus information such as display image.
Background technology
Traditionally, instead the information display device of liquid crystal (LCD) has proposed to adopt electrophoresis mode, electricity to cause the information display device of technology such as colored display mode, thermic mode, double-colored particle rotation mode.
These prior aries are compared with LCD, since have can obtain little with approaching big field angle, the power consumption of common printed thing, have an advantage such as memory function, therefore be considered to can be used for the technology of follow-on cheap information display device, can expect to apply it to portable terminal device with aspects such as information demonstration, Electronic Paper.Particularly the electrophoresis mode that proposes is recently expected very much, behind the dispersion liquid microencapsulation that will be made of discrete particles and coloring solution in this electrophoresis mode it is configured between the substrate of facing mutually.
Yet, in the electrophoresis mode, because particle swimming in liquid, thereby the slack-off problem of response speed that exists the viscous resistance by liquid to cause.In addition, because the particle dispersion that makes high specific gravity such as titanium dioxide is in low-gravity solution, thereby the easy sedimentation that becomes, be difficult to keep the stability of disperse state, have the problem of the repetition stability that shortage information shows.In addition,, make cell size reach the level of microcapsules, also just make above-mentioned shortcoming be difficult to show from the teeth outwards, but still do not solve the problem of any essence even carried out microencapsulation.
On the other hand, for the electrophoresis mode of utilizing the behavior in the solution, recently also begin to have proposed on the part of substrate, to pack into conductive particle and charge transport layer and do not use the scheme (for example with reference to non-patent literature 1) of solution.Yet this mode is owing to being provided with charge transport layer and charge generating layers makes structure complicated, and is difficult in conductive particle iunjected charge consistently, thereby also has the problem of the stability that lacks show state.
As a method that is used to solve above-mentioned variety of issue, known have a kind of information display panel, it is between at least one side is transparent two substrates, inclosure has the display medium of optical reflectivity and charging property, by display medium being applied electric field display medium is moved, thus information such as display image.This kind move display medium by electric field and the type of information such as display image information display panel in, from the positive negative characteristic of the charging property of giving display medium easily and being had and guarantee carried charge easily, using particle diameter is that the acrylic resin, methacrylic resin, styrene resin of 0.1～50 μ m is as the particle for display medium material.As its manufacture method,,, use the method for suspension polymerization more effective than comminuting method perhaps in order directly to obtain target grain size for simplification, the low power consuming of operation.In addition, when utilizing suspension polymerization to make resinous particle for display medium, take to use surfactant to carry out polymerization and obtain high molecular usually with the simple function monomer that the state of oil droplet is dispersed in the suspended solvents.
[non-patent literature 1] State of Zhao comes, other 3 people, " new い ト Na one デ イ ス プ レ イ デ バ イ ス (I) ", and on July 21st, 1999, Japanese iconology can annual conference (the 83rd) " Japan Hardcopy ' 99 ", p.249-252
Summary of the invention
The problem that invention will solve
When the particle for display medium that simple function monomer is as described above made as resin raw material is used for information display panel, can produce the problem that places high temperature following time not show.Its reason is, because high temperature, particle for display medium also can soften when the glass transition temperature Tg of its resin is following, becomes particle for display medium fusion adhesion and irremovable state can not show thereby become each other.And then also can produce following problem: in the situation of placing under the normal temperature after demonstration, the mobile required voltage (driving voltage) of the particle for display medium after the placement uprises.Its reason is that the resin that uses the simple function monomer to make has thermoplasticity usually, has therefore used the particle for display medium of this resin also can have creep properties at normal temperatures.Therefore, use in the information display panel that such particle for display medium makes, moving owing to adhering between the particle for display medium is obstructed of particle for display medium, the mobile required voltage (driving voltage) of the particle for display medium after consequently placing uprises.
As the solution of the problems referred to above, can consider to use for example cross-linkable monomer is used for molecule part or all and improved the resin of glass transition temperature Tg.But, when experience has confirmed such resin as the particle for display medium of desired application target, the ratio of cross-linkable monomer is when to a certain degree above in molecule, and the inversion driving characteristic of particle for display medium reduces, and then the display characteristic of information such as image also reduces.Therefore, for fear of the problem that thermotolerance is low and creep properties is such that aforesaid particle for display medium had and make its display characteristic that satisfies information such as image, in suitable scope, be important with the proportional control of the cross-linkable monomer in the molecule of particle for display medium.
The 1st purpose of the present invention is, by being set in the suitable scope, provide thermotolerance high and can reduce the particle for display medium of driving voltage (driving electric field) as the content of the cross-linkable monomer that is used as copolymerisable monomer of the raw-material part of particle for display medium.
The 2nd purpose of the present invention is to provide a kind of information display panel, and this information display panel uses above-mentioned particle for display medium and constitutes, and long lifetime aspect the permanance when being used for information display panel and display quality aspect excellence.
The method of dealing with problems
In order to realize above-mentioned the 1st purpose, information demonstration of the present invention is characterised in that with particle, this information demonstration has constituted the display medium that is used for information display panel with particle, this information display panel is enclosed display medium between at least one side is transparent two substrates, by display medium being applied electric field display medium is moved, thereby information such as display image, wherein, the roughly spheric grain that this particle for display medium forms for the particulate material suspension polymerization that will comprise monomer, the part of this monomer is a cross-linkable monomer, and the content of this cross-linkable monomer is more than 10 weight portions and less than 50 weight portions.
But the suitable example as particle for display medium of the present invention has the divinylbenzene of described cross-linkable monomer for copolymerization, when using monomer to carry out polymerization, the glass transition temperature Tg of its resin is more than 130 ℃, perhaps aggregates into the resin that does not observe glass transition temperature Tg; Other monomer that makes described cross-linkable monomer copolymerization is the monomer more than a kind that is selected from the multiple monomer that comprises acrylic monomer, methacrylic monomer and styrene monomer at least; The glass transition temperature Tg that constitutes the resin of described particle for display medium is more than 60 ℃; Use carrier and count 10～100 μ C/g with absolute value by the carried charge that blows out the described particle for display medium that method measures; Described particle for display medium is a particle as described below, promptly, the corona discharger that separates the arranged spaced of 1mm with particle surface is applied the voltage of 8KV and produces corona discharge, thereby when making surface charging, the maximal value of the surface potential after 0.3 second is greater than the particle of 300V; And the color of described particle for display medium is white and/or black.
In order to realize above-mentioned the 2nd purpose, information display panel of the present invention is characterised in that, at least one side is to enclose the display medium that comprises particle for display medium of the present invention more than at least a between transparent two substrates facing mutually, by the electric field that produces in the substrate display medium is moved, thus information such as display image.
The invention effect
Particle for display medium according to the invention described above, it has constituted the display medium that is used for information display panel, this information display panel is enclosed display medium between at least one side is transparent two substrates, by display medium being applied electric field display medium is moved, thereby information such as display image, the roughly spheric grain that forms for the particulate material suspension polymerization that will comprise monomer of this particle for display medium wherein, the part of this monomer is a cross-linkable monomer, the content of this cross-linkable monomer is more than 10 weight portions and less than 50 weight portions, thereby can confirm among the embodiment of explanation as described later that this particle for display medium becomes the thermotolerance height like that, and the low particle for display medium of driving voltage (driving electric field).
Information display panel according to the invention described above, being constituted as at least one side is to enclose the display medium that comprises particle for display medium of the present invention more than at least a between transparent two substrates facing mutually, by the electric field that produces in the substrate display medium is moved, thereby information such as display image, therefore, can confirm among Shuo Ming the embodiment as described later like that, become the long lifetime aspect the permanance when being used for information display panel and the information display panel of display quality excellence.
Description of drawings
The (a) and (b) of Fig. 1 are for representing the figure of an example of information display panel of the present invention respectively.
The (a) and (b) of Fig. 2 are for representing the figure of another example of information display panel of the present invention respectively.
The (a) and (b) of Fig. 3 are for representing the figure of the another example of information display panel of the present invention respectively.
Fig. 4 is the figure of an example of the next door shape of expression information display panel of the present invention.
Fig. 5 is the figure of mensuration main points of the surface potential of the expression particle for display medium that is used for information display panel of the present invention.
Symbol description
1,2 substrates
3 display mediums (particle swarm)
3W white display medium
3B black display medium
3Wa white particle for display medium
3Ba black display medium particle
4 next doors
5,6 electrodes
21 chucks
22 scorotron dischargers
23 surface potential meters
Embodiment
Below, based on accompanying drawing, be elaborated to being used to implement best mode of the present invention.
At first, the structure at the information display panel of the present invention that uses the display medium of being made up of particle for display medium of the present invention describes.In information display panel of the present invention, apply electric field to the display medium that is sealing between two substrates facing mutually.Along the direction of an electric field that is applied, charged display medium is subjected to the attraction of electric field force, Coulomb force etc., and these display mediums change moving direction according to the variation of direction of an electric field, thereby the information of realization image etc. shows.Therefore, information display panel must be designed to display medium move equably, and can keep repeatedly update displayed the time or the stability when continuing to show display message.At this, be applied to the power on the particle that constitutes display medium, except the power that attracts each other that produces by the Coulomb force between the particle, also have the Electronic Speculum image force, intermolecular force, liquid bridge power, gravity of itself and electrode, substrate etc.
Based on the (a) and (b) of (a) and (b)～Fig. 3 of Fig. 1, the example of the information display panel in the information display device that is attached to object of the present invention is described.
At Fig. 1 it (a), (b) in the example shown in, corresponding to from substrate 1, the electric field that 2 outside applies, to constitute by particle more than at least a kind, optical reflectivity display medium at least 2 kind or more 3 different (shown here is the white display medium 3W that constitutes of the particle swarm by white particle for display medium 3Wa and the black display medium 3B that is made of with the particle swarm of particle 3Ba the black display medium) and substrate 1 with charged characteristic, 2 vertically move, and make observer's visible black color display medium 3B and carry out black display, perhaps make the visible white display medium 3W of observer and carry out the white demonstration.In addition, in the example shown in Fig. 1 it (b), on the basis of example shown in Fig. 1 it (a), next door 4 for example is set to clathrate between substrate 1,2 and is formed with cell.In addition, in Fig. 1 it (b), omitted the next door that is positioned at the front side.
At Fig. 2 it (a), (b) in the example shown in, constitute by particle more than at least a kind, the different display medium more than at least 2 kinds 3 of optical reflectivity and charged characteristic (shown here is the white display medium 3W that constitutes of the particle swarm by white particle for display medium 3Wa and the black display medium 3B that is made of with the particle swarm of particle 3Ba the black display medium) is corresponding to by applying the electric field that voltage produces between the electrode 5 of being located at substrate 1 and the electrode 6 of being located at substrate 2, with substrate 1,2 vertically move, and make observer's visible black color display medium 3B and carry out black display, perhaps make the visible white display medium 3W of observer and carry out the white demonstration.In addition, in the example shown in Fig. 2 it (b), on the basis of example shown in Fig. 2 it (a), next door 4 for example is set to clathrate between substrate 1,2 and is formed with cell.In addition, in Fig. 2 it (b), omitted the next door that is positioned at the front side.
At Fig. 3 it (a), (b) in the example shown in, constitute by particle more than at least a kind, 1 kind of display medium 3 (shown here is the white display medium 3W that the particle swarm by white particle for display medium 3Wa constitutes) with optical reflectivity and charging property is corresponding to by applying the electric field that voltage produces between the electrode 5 of being located at substrate 1 and the electrode 6 of being located at substrate 2, edge and substrate 1,2 parallel directions move, make the visible white display medium 3W of observer and carry out the white demonstration, perhaps, make the color of visible electrode 6 of observer or substrate 1 and carry out the demonstration of the color of electrode 6 or substrate 1.In addition, in the example shown in Fig. 3 it (b), on the basis of the example shown in Fig. 3 it (a), next door 4 for example is set to clathrate between substrate 1,2 and is formed with cell.In addition, in Fig. 3 it (b), omitted the next door that is positioned at the front side.The electrode of substrate both can be located at the inboard of substrate, also can be arranged to imbed substrate inside.
Below, the particle for display medium that becomes feature of the present invention is elaborated.Particle for display medium of the present invention goes for the information display panel of (a) and (b) of (a) and (b)～Fig. 3 of Fig. 1, and its at least one side who constitutes display medium and be sealing into above-mentioned information display panel is between transparent two substrates.As this particle for display medium, use following material: it is the roughly spheric grain that the particulate material suspension polymerization that comprises monomer is formed, the part of this monomer is a cross-linkable monomer, and the content of this cross-linkable monomer is more than 10 weight portions and less than 50 weight portions.But as the cross-linkable monomer of described copolymerization, for example preferred the use as divinylbenzene with sufficient stable on heating resin.In addition, but the cross-linkable monomer of described copolymerization must be with the mixing ratio of q.s (promptly, more than content=10 weight portions and less than 50 weight portions) cooperate, when less than 10 weight portions, thermotolerance can be not enough, when 50 weight portions are above, owing to the excessively charged display characteristics such as contrast, permanance that make reduce.
In addition, be preferably as follows situation: but the cross-linkable monomer of above-mentioned copolymerization, and when using monomer to carry out polymerization, the glass transition temperature Tg of its resin is more than 130 ℃, perhaps aggregates into the resin that does not observe glass transition temperature Tg; Other monomer that makes above-mentioned cross-linkable monomer copolymerization is the monomer more than a kind that is selected from the multiple monomer that comprises acrylic monomer, methacrylic monomer and styrene monomer at least; The glass transition temperature Tg that constitutes the resin of above-mentioned particle for display medium is more than 60 ℃; Use carrier and count 10～100 μ C/g with absolute value by the carried charge that blows out the above-mentioned particle for display medium that method measures; Above-mentioned particle for display medium is a particle as described below, promptly, the corona discharger that separates the arranged spaced of 1mm with particle surface is applied the voltage of 8KV and produces corona discharge, thereby when making surface charging, the maximal value of the surface potential after 0.3 second is greater than the particle of 300V; And the color of above-mentioned particle for display medium is white and/or black.
According to particle for display medium of the present invention, the particle for display medium of information display panel of (a) and (b) that is used for (a) and (b)～Fig. 3 of Fig. 1 is to comprise the roughly spheric grain that the particulate material suspension polymerization of monomer forms, the part of this monomer is a cross-linkable monomer, the content of this cross-linkable monomer is more than 10 weight portions and less than 50 weight portions, therefore, can confirm among Shuo Ming the embodiment that as described later this particle for display medium becomes thermotolerance height and the low particle for display medium of driving voltage (driving electric field) like that.In addition, can confirm among Shuo Ming the embodiment as described later like that, use the information display panel of (a) and (b) of (a) and (b)～Fig. 3 of Fig. 1 of this particle for display medium to become the information display panel of permanance and display quality excellence.
Below, describe for each parts that constitute as information display panel of the present invention.
About substrate, at least one side's substrate is the transparent substrate that can observe the color of display medium from the device outside, and its suitable material is visible light transmittance height and the good material of thermotolerance.The back substrate that becomes the opposite side substrate can be transparent also can be opaque.Baseplate material is carried out illustrative words, can list polymer sheets such as polyethylene terephthalate, Polyethylene Naphthalate, polyethersulfone, tygon, polycarbonate, polyimide, acryl 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 unsuitable for making the situation of slim information display panel.
Form material as the electrode that is arranged on the electrode on the substrate as required, can metal species such as aluminium, silver, nickel, copper, gold be arranged illustration; Or conducting metal oxide class such as tin indium oxide (ITO), indium oxide, conductive tin oxide, antimony tin (ATO), electroconductive zinc oxide; Electroconductive polymer classes such as polyaniline, polypyrrole, polythiophene can suitably be selected to use.Formation method as electrode, can adopt by sputtering method, vacuum vapour deposition, CVD (chemical vapor deposition) method, rubbing method etc. to make above-mentioned illustrative material form the film like method of patterning, perhaps adopt by conductive agent being mixed into be coated with in solvent or the synthetic resin adhesive and form method of patterning.The electrode that is arranged on visual side (display surface side) substrate must be transparent, but the electrode that is arranged on the rear side substrate needs not to be transparent.No matter be which kind of situation, all be fit to the above-mentioned material that use can form pattern and have electric conductivity.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.Material, thickness that is arranged on the electrode on the rear side substrate etc. can be identical with the above-mentioned electrode that is arranged on the display surface side group plate, but need not to be transparent.In addition, the external voltage input during this situation can direct current or stack exchange.
For the next door that is arranged at substrate as required, its shape can suitably be carried out optimization according to the shape of the kind of the display medium that is used to show, the electrode that disposed and configuration and be set, 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 10～100 μ m, be preferably 10～50 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 1,2 of 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 formed cell in the next door that constitutes by these ribs, as shown in Figure 4, observe from the base plan direction, can quadrilateral, triangle, wire, circle, hexagon be arranged illustration, 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 cell frame part) from the visual next door cross-section of display surface one side, can increase the sharpness of demonstration like this.
At this,, then can list mould transfer printing, silk screen print method, sand-blast, photoetching process, additive process if the formation method of counter septum is carried out example.Arbitrary method all goes for being installed in the information display panel in the information display device of the present invention, but in the middle of these, is fit to adopt photoetching process, the mould transfer printing that uses etchant resist.
Particle method electronegative or positively charged is not limited, can use corona discharge method, electric charge injection method, rubbing manipulation etc. to make the charged method of particle.Use carrier and be preferably 10～100 μ C/g in absolute value by the carried charge that blows out the particle that method measures.When the absolute value of carried charge was lower than this scope, it is slow that the response speed of electric field change is latened, and storage property is step-down also.When the absolute value of carried charge was higher than this scope, strong excessively to the image force of electrode, substrate, though storage property is good, the display medium during the counter-rotating electric field moved the tracing ability variation.
Among the present invention, the mensuration of carried charge is following carries out.
＜blow out method measuring principle and assay method 〉
In blowing out method, in establishing the cylindrical vessel of net, two ends put into the mixture of particle and carrier, be blown into gases at high pressure with separating particles and carrier from an end, only blow out (blowing away) particle from the mesh of net.At this moment, carried charge equivalent of taking away outside container with particle and opposite carried charge residue in carrier.So, all be collected in the Faraday cylinder by the electric flux of this charge generation, only this part is charged to capacitor.Therefore, the current potential at the two ends by measuring capacitor, the following quantity of electric charge Q that tries to achieve particle.
Q=CV (C: condenser capacity, V: the voltage at capacitor two ends)
As blowing out particle carried charge determinator, the TB-200 that has used chemical company of Toshiba to make.Among the present invention, in measuring, the carried charge of tested particle uses the ferrite type carrier, but in information display panel, when the display medium that constitutes when the particle that for example is used in combination by Positively chargeable and these 2 kinds of display mediums of display medium of constituting by the particle of negative charging, when measuring the carried charge of the particle for display medium that constitutes each display medium, use the carrier of same kind.Specifically, the DFC100 WRINKLE (ferrite type that contains Mn-Mg) that use is same and iron powder industry (strain) is made measures the carried charge (μ C/g) of particle as carrier.
Particle be owing to must keep its charged particles, thereby to be preferably the volume intrinsic resistance be 1 * 10
10The insulativity particle that Ω cm is above, being preferably the volume intrinsic resistance especially is 1 * 10
12The insulativity particle that Ω cm is above.In addition, the slow particle of further preferably estimating of charge decay by the method for the following stated.
Promptly, measure the tested particle of surface configuration of using anchor clamps at the roller shape, and the corona discharger that separates the arranged spaced of 1mm with the particle surface that is disposed applied the voltage of 8KV and produce corona discharge, thereby make particle surface charged, measure and judge the variation of this surface potential.At this moment, importantly select the particle composition material to make, make the maximal value of the surface potential after 0.3 second, be preferably greater than 400V greater than 300V.
In addition, the mensuration of above-mentioned surface potential can be undertaken by device for example shown in Figure 5 (QEA company makes CRT2000).Under the situation of using this device, be fit to adopt following method to measure its surface potential, promptly, use chuck 21 to keep the axle both ends of the mensuration of the aforesaid roller shape that tested particle arranged in surface configuration with anchor clamps, the relative configures measurement units in interval that separates 1mm with above-mentioned tested particle surface, this measuring unit separates in predetermined distance and is arranged side by side small-sized scorotron discharger 22 and surface potential 23, make under the above-mentioned roller shape mensuration state static with anchor clamps, make above-mentioned measuring unit move to the other end from an end that is disposed at the roller shape and measures with the particle of chucking surface with fixing speed, the limit provides surface charge thus, and its surface potential is measured on the limit.In addition, measure environment and be made as 25 ± 3 ℃ of temperature, humidity 55 ± 5RH%.
Then, describe for the particle for display medium (the following particle that also claims) that constitutes display medium in the information display panel of the present invention.Particle for display medium can only directly be made of this particle for display medium and as display medium, perhaps mixes with other particle to constitute and as display medium.
In the particle, can in resin, comprise charge control agent, colorant, inorganic additive etc. as required as its major component.Below, example illustrates resin, charge control agent, colorant, other adjuvant.
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 (comprising 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 the resin of nitrogenous ring compound such as metal oxide, pyridine such as ultra micron silicon dioxide, ultra micron titanium dioxide, ultra micron aluminium oxide and derivant thereof or salt, various organic pigment, fluorine-containing, chlorine, nitrogen etc. etc. 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 cyan 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, 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, 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 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, ultramarine blue etc. are arranged.
As the example of mineral-type adjuvant, can list 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 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.Mix above-mentioned colorant, can make the particle for display medium of desired color.
In addition, particle for display medium of the present invention (the following particle that also claims), its mean grain size is preferably at the scope of 0.1～50 μ m, even and narrowly distributing.If mean grain size 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 as display medium.
In addition, in the present invention, about the size distribution of each particle for display medium, 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, and particle diameter is 10% at the ratio of this particle below numerical value; D (0.9) is the grain diameter value of representing with μ m, and particle diameter is 90% at the ratio of this particle below numerical value.)
By span being controlled in the scope below 5, the narrow size distribution of each particle can realize moving uniformly as display medium.
In addition, for the relation of each particle for display medium, the d (0.5) that importantly has the particle of minimum grain size 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 particle diameter.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 irradiating laser as determination object, then can produce the light intensity distributions pattern of the diffraction/scattered light on the space, because there are corresponding relation in this light intensity pattern and particle diameter, therefore can measure particle diameter and size distribution.
At this, 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 stream of nitrogen gas, drop into particle, use subsidiary analysis software (being distributed as the software on basis with the volume reference that adopts the Mie theory), measure particle diameter and size distribution.
In addition, to be applicable to by the display medium that particle for display medium constitutes in the gas space and drive under the situation of dry type information display panel of display medium, it is important that the gas of the gap of the encirclement display medium between substrate is managed, and it helps to improve exhibit stabilization.Specifically, for the humidity of the gas of gap, the relative humidity under 25 ℃ is that 60%RH is following, to be preferably below the 50%RH be important.
In the (a) and (b) of (a) and (b)～Fig. 3 of Fig. 1, this gap is meant gas part hermetic unit, that so-called display medium contacted of occupying part (when the next door is set), information display panel of occupying part, next door 4 that deducts electrode 5,6 (electrode is arranged at substrate when inboard), display medium 3 from be clipped in the substrate 1 faced mutually, part between the substrate 2.
The gas of gap is so long as in above-mentioned humidity range, 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 assembling of information display panel etc., in addition, apply in order to prevent that encapsulant, encapsulating method that moisture is invaded from the outside from being important.
Substrate and substrate distance in the information display panel of the present invention as long as display medium can move, can keep contrast, 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, to the mobile generation obstacle of display medium, under the situation of less than 5%, it is unintelligible that contrast becomes easily.
Embodiment
Below, embodiments of the invention and comparative example are shown, the present invention is further specified, but the present invention is not limited to following embodiment.For the information display panel of embodiment and comparative example, according to following standard, the dry air of particle below humidity 50%RH that estimate to use following method to make is sealed to the information display panel that forms in the space between the display panel substrate.
＜black display medium the Production Example 1 (black, styrene/divinylbenzene class, just charged) of particle 〉
The following acquisition of particle of just charged black display medium, promptly, use sand mill, in 94 parts by weight of styrene monomers (Northeast chemical reagent) and 6 weight portion divinylbenzenes (Northeast chemical reagent), disperse 3 weight portions as the nigrosine compound (BONTRON NO7:Orient Chemical manufacturings) of the charge control agent of Positively chargeable and 5 weight portions carbon black (goth black 5:Degussa manufacturing) as black pigment, dissolve 2 weight portion lauroyl peroxides (Peroyl L: Japanese grease manufacturing) again, the solution that obtains is thus suspended in the Purified Water that is added with the 0.5% polyoxyethylene alkyl ether sodium sulphate as surfactant (LATEMULE-118B: the flower king makes), after the polymerization, filter, dry, use grader (MDS-2:Nippon Pneumatic Mfg.) then, the scope that obtains particle diameter is 0.1～50 μ m, mean grain size is the particle 1 about 10 μ m.The glass transition temperature Tg of being measured by DSC is 75 ℃.
＜black display medium the Production Example 2 (black, styrene/divinylbenzene class, just charged) of particle 〉
As just charged black display medium particle, except styrene monomer being changed into 35 weight portions, divinylbenzene being changed into 65 weight portions, adopt the method same with particle 1, the scope that obtains particle diameter is that 0.1～50 μ m, mean grain size are the particle 2 about 10 μ m.Do not observe glass transition temperature Tg by DSC mensuration.
＜black display medium the Production Example 3 (black, styrene/divinylbenzene class, just charged) of particle 〉
As just charged black display medium particle, except styrene monomer being changed into 88 weight portions, divinylbenzene being changed into 12 weight portions, adopt the method same with particle 1, the scope that obtains particle diameter is that 0.1～50 μ m, mean grain size are the particle 3 about 10 μ m.The glass transition temperature Tg of being measured by DSC is 80 ℃.
＜black display medium the Production Example 4 (black, styrene/divinylbenzene class, just charged) of particle 〉
As just charged black display medium particle, except styrene monomer being changed into 76 weight portions, divinylbenzene being changed into 24 weight portions, adopt the method same with particle 1, the scope that obtains particle diameter is that 0.1～50 μ m, mean grain size are the particle 4 about 10 μ m.The glass transition temperature Tg of being measured by DSC is 85 ℃.
＜black display medium the Production Example 5 (black, styrene/divinylbenzene class, just charged) of particle 〉
As just charged black display medium particle, except styrene monomer being changed into 55 weight portions, divinylbenzene being changed into 45 weight portions, adopt the method same with particle 1, the scope that obtains particle diameter is that 0.1～50 μ m, mean grain size are the particle 5 about 10 μ m.The glass transition temperature Tg of being measured by DSC is 95 ℃.
The Production Example 1 of＜white particle for display medium (styrene/divinylbenzene class, negative charging in vain) 〉
As Chinese white, use the following material that obtains: (TIPAQUECR-50: the former industry manufacturing of stone) with respect to titanium dioxide is titante coupling agent (the Plenact KRTTS:Ajinomoto Fine-Techno.Co. of 1 weight % with titanium dioxide, the Inc manufacturing) being distributed to respect to titanium dioxide is in the methyl alcohol of 150 weight %, after the use paint shaker stirred 20 minutes, with 120 ℃ of heating 30 minutes and the broken material that obtains.
The following acquisition of negative charging white particle for display medium, promptly, 30 weight portions above-mentioned after coupling agent treatment titanium dioxide and 94 parts by weight of styrene monomers (Northeast chemical reagent) and 6 weight portion divinylbenzenes (Northeast chemical reagent) in dissolving 5 weight portions as the phenolic condensate of the charge control agent of negative charging (BONTRON E89:Orient chemistry is made), dissolve 2 weight portion lauroyl peroxides (Peroyl L: Japanese grease manufacturing) again, the solution that obtains is thus suspended in the Purified Water that is added with the 0.5% polyoxyethylene alkyl ether sodium sulphate as surfactant (LATEMUL E-118B: the flower king makes), after the polymerization, filter, dry, use grader (MDS-2:NipponPneumatic Mfg.) then, the scope that obtains particle diameter is 0.1～50 μ m, mean grain size is the particle 6 about 10 μ m.The glass transition temperature Tg of being measured by DSC is 75 ℃.
The Production Example 2 of＜white particle for display medium (styrene/divinylbenzene class, negative charging in vain) 〉
As negative charging white particle for display medium, except styrene monomer being changed into 35 weight portions, divinylbenzene being changed into 65 weight portions, adopt the method same with particle 6, the scope that obtains particle diameter is that 0.1～50 μ m, mean grain size are the particle 7 about 10 μ m.Do not observe glass transition temperature Tg by DSC mensuration.
The Production Example 3 of＜white particle for display medium (styrene/divinylbenzene class, negative charging in vain) 〉
As negative charging white particle for display medium, except styrene monomer being changed into 88 weight portions, divinylbenzene being changed into 12 weight portions, adopt the method same with particle 6, the scope that obtains particle diameter is that 0.1～50 μ m, mean grain size are the particle 8 about 10 μ m.The glass transition temperature Tg of being measured by DSC is 80 ℃.
The Production Example 4 of＜white particle for display medium (styrene/divinylbenzene class, negative charging in vain) 〉
As negative charging white particle for display medium, except styrene monomer being changed into 76 weight portions, divinylbenzene being changed into 24 weight portions, adopt the method same with particle 6, the scope that obtains particle diameter is that 0.1～50 μ m, mean grain size are the particle 9 about 10 μ m.The glass transition temperature Tg of being measured by DSC is 85 ℃.
The Production Example 5 of＜white particle for display medium (styrene/divinylbenzene class, negative charging in vain) 〉
As negative charging white particle for display medium, except styrene monomer being changed into 55 weight portions, divinylbenzene being changed into 45 weight portions, adopt the method same with particle 6, the scope that obtains particle diameter is that 0.1～50 μ m, mean grain size are the particle 10 about 10 μ m.The glass transition temperature Tg of being measured by DSC is 95 ℃.
＜experiment condition, evaluation method and evaluation result (with reference to table 1, table 2) 〉
Experiment condition: carry out heat resistant test (under 100 ℃ of atmosphere, placing 1.5 hours).At this moment, use the white particle for display medium of particle 9 in estimating with the panel counter-rotating of particle as the black display medium, use particle 4 to show black display medium particle in estimating as the panel counter-rotating of white particle for display medium.
Evaluation method: after above-mentioned heat resistant test,, carry out backing propeller test (voltage that per 1 μ m display panel substrate gap applies 2V carries out the driven nature test) with the information display panel drive unit of packing into.
Evaluation result: evaluation could reverse (have agranular fusion adhesion), contrast, permanance etc.
＜comparative example 1 〉
Use particle 1 as just charged black display medium particle, the result is as shown in table 1, obtains following evaluation result: could reverse: *; Contrast: can not estimate; Permanance: can not estimate.
＜comparative example 2 〉
Use particle 2 as just charged black display medium particle, the result is as shown in table 1, obtains following evaluation result: could reverse: zero; Contrast: zero; Permanance: *.
＜embodiment 1 〉
Use particle 3 as just charged black display medium particle, the result is as shown in table 1, obtains following evaluation result: could reverse: zero; Contrast: zero; Permanance: zero.Even if, also can reverse under non-reversible heat-resisting condition because the thermotolerance of resin is not enough in the past.
＜embodiment 2 〉
Use particle 4 as just charged black display medium particle, the result is as shown in table 1, obtains following evaluation result: could reverse: zero; Contrast: zero; Permanance: zero.Even if, also can reverse under non-reversible heat-resisting condition because the thermotolerance of resin is not enough in the past.
＜embodiment 3 〉
Use particle 5 as just charged black display medium particle, the result is as shown in table 1, obtains following evaluation result: could reverse: zero; Contrast: zero; Permanance: zero.Even if, also can reverse under non-reversible heat-resisting condition because the thermotolerance of resin is not enough in the past.
＜comparative example 3 〉
Use particle 6 as negative charging white particle for display medium, the result is as shown in table 2, obtains following evaluation result: could reverse: *; Contrast: can not estimate; Permanance: can not estimate.
＜comparative example 4 〉
Use particle 7 as negative charging white particle for display medium, the result is as shown in table 2, obtains following evaluation result: could reverse: zero; Contrast: *; Permanance: *.
＜embodiment 4 〉
Use particle 8 as negative charging white particle for display medium, the result is as shown in table 2, obtains following evaluation result: could reverse: zero; Contrast: zero; Permanance: zero.Even if, also can reverse under non-reversible heat-resisting condition because the thermotolerance of resin is not enough in the past.
＜embodiment 5 〉
Use particle 9 as negative charging white particle for display medium, the result is as shown in table 2, obtains following evaluation result: could reverse: zero; Contrast: zero; Permanance: zero.Even if, also can reverse under non-reversible heat-resisting condition because the thermotolerance of resin is not enough in the past.
＜embodiment 6 〉
Use particle 10 as negative charging white particle for display medium, the result is as shown in table 2, obtains following evaluation result: could reverse: zero; Contrast: zero; Permanance: zero.Even if, also can reverse under non-reversible heat-resisting condition because the thermotolerance of resin is not enough in the past.
In above-mentioned, zero expression is good, * expression is bad, △ represents bad a little
Table 1 black display medium particle embodiment and comparative example
(the white particle for display medium during counter-rotating is estimated as panel uses styrene/divinylbenzene=76/24, TiO
2=30phr)
1) 100 ℃ * 1.5hr rear panel backing propeller test (2V/ panel gap (μ m))
2) in the time of will adopting black display that Macbeth densimeter (SAKATA INX company make, RD-19) measures and the white optical concentration difference between showing to be made as R, with 10
RSpend as a comparison.
3) zero expression contrast is more than 5, * expression contrast less than 5
White particle for display medium embodiment of table 2 and comparative example
(the black display medium particle in estimating as panel counter-rotating, use styrene/divinylbenzene=76/24, carbon black=5phr)
1) 100 ℃ * 1.5hr rear panel backing propeller test (2V/ panel gap (μ m))
2) in the time of will adopting black display that Macbeth densimeter (SAKATA INX company make, RD-19) measures and the white optical concentration difference between showing to be made as R, with 10
RSpend as a comparison.
3) zero expression contrast is more than 5, * expression contrast less than 5
Industrial utilizability
Use is aobvious by the information of the display medium that particle for display medium of the present invention forms Show and use panel, be applicable to notebook-PC, PDA, portable phone, The display part of the removable machines such as hand-held terminal machine, the electricity such as e-book, electronic newspaper Sub-paper, the notice boards such as billboard, placard, blackboard, desk top computer, household electrical appliances The display part of product, Automobile Products etc., the card of some card (point card), IC-card etc. is aobvious Show section, e-advertising, electronics POP (Point of Presence, Point of Purchase Advertising), electronics price tag, electronics inventory tag, information board, electronic music, The display part of RF-ID machine etc.
Claims (7)
1. particle for display medium, it is characterized in that, it is used for information display panel, this information display panel is to enclose between transparent two substrates to comprise display medium described particle for display medium, that have optical reflectivity and charging property more than at least a at least one side, by display medium being applied electric field display medium is moved, thereby displays image information
This particle for display medium is the roughly spheric grain that the particulate material suspension polymerization that comprises monomer is formed, and the part of this monomer is a cross-linkable monomer, and the content of this cross-linkable monomer is that 12 weight portions are above and less than 50 weight portions,
When using described monomer to carry out polymerization, the glass transition temperature Tg of its resin is more than 130 ℃, perhaps aggregates into the resin that does not observe glass transition temperature Tg,
Wherein, but described cross-linkable monomer is the divinylbenzene of copolymerization.
2. particle for display medium according to claim 1, it is characterized in that other monomer that makes described cross-linkable monomer carry out copolymerization is the monomer more than a kind that is selected from the multiple monomer that comprises acrylic monomer, methacrylic monomer and styrene monomer at least.
3. particle for display medium according to claim 1 and 2 is characterized in that, the glass transition temperature Tg that constitutes the resin of described particle for display medium is more than 60 ℃.
4. particle for display medium according to claim 1 and 2 is characterized in that, uses carrier and counts 10～100 μ C/g by the carried charge that blows out the described particle for display medium that method (blow off method) measures with absolute value.
5. particle for display medium according to claim 1 and 2, it is characterized in that, described particle for display medium is a particle as described below: the corona discharger that separates the arranged spaced of 1mm with particle surface is applied the voltage of 8KV and produces corona discharge, thereby when making surface charging, the maximal value of the surface potential after 0.3 second is greater than 300V.
6. particle for display medium according to claim 1 and 2 is characterized in that, the color of described particle for display medium is white and/or black.
7. information display panel, it is characterized in that, at least one side is to enclose the display medium that comprises each described particle for display medium of claim 1～6 more than at least a between transparent two substrates facing mutually, by the electric field that produces in the substrate display medium is moved, thus displays image information.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6117368A (en) * | 1993-04-21 | 2000-09-12 | Copytele, Inc. | Black and white electrophoretic particles and method of manufacture |
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2007
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6117368A (en) * | 1993-04-21 | 2000-09-12 | Copytele, Inc. | Black and white electrophoretic particles and method of manufacture |
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