CN101100571A - Electrophoresis display electronic ink - Google Patents

Abstract

Electrophoretic display electronic ink consists of charge particle and transparent liquid wit stable dissolving function and suspended charge particle. The process is carried out by displaying electronic ink, dissolving and dispersing. The grain size reaches to 40-60 nm, display OD reaches above 3.16, it's not easy to aggregate and deposit. It has good storage performance and can be used for various electronic papers.

Description

Electrophoresis display electronic ink

Technical field

The present invention relates to information display technology fields, particularly flexible materials technique of display field such as image and literal, more properly describe, is to belong to electrophoresis display electronic ink, i.e. electrophoresis display electronic paper field.

Background technology

Electron display device (Electronic display device), the man-machine interface that it has often been said exactly (Man-Machine interface).Investigate from functional perspective, electron display device can be with the electrical signal of various electronic installations outputs, changes to people's vision to debate the light information of knowing.Find liquid crystal from Austrian Reinitzer in 1888, to fritz's Braun invention CRT monitor, so far, the history in more than 100 year has been experienced in the development of electronic console.Generally speaking, when optical signal takes light emission to show, be called initiatively demonstration or emission and show (active display/emissive display); And regulate the demonstration that incident light carries out by phenomenons such as reflection, scattering, interference, then be called as passive demonstration or non-emission and show (passive display/non-emissive display).It is generally acknowledged that Electronic Paper belongs to passive demonstration.

Current what occupy the market dominant position is liquid-crystal display, is ORGANIC ELECTROLUMINESCENCE DISPLAYS (OLED) what may compete with it in the recent period.Carry inconvenience, rely on electric energy, display device itself does not possess information storage function substantially, is the common defects of commercial various display devices.People expect a kind of display material that possesses paper and electron display device characteristic simultaneously always, and are promptly convenient and swift, economical and practical again.So the notion of Electronic Paper is just arisen at the historic moment.Document shows, the Sheridon of U.S. XEROX company is on international information display conference in 1977, screw electric paper display notion has been proposed first, and in United States Patent (USP) 5389945 (Sheridon, Writing system including paper-like digitallyaddressed media and addressing device therefor, February 14,1995) disclosed digitized, the display device of similar paper, i.e. Electronic Paper, and progressively form and the perfect notion of Electronic Paper: at first, Electronic Paper is a kind of electron display device, it is bistable state to the demonstration of image, promptly realizes showing applying under the condition of electric field, but after electric field removes, show still and keep, thereby Electronic Paper possesses information storage function, and energy-conservation.Because mainly being reflection-type, Electronic Paper shows that Lambert's law of reflection is followed in its reflection to light, so Electronic Paper has with great visual angle simultaneously.The 3rd, as electrode, can curl even folding, is easy to carry by the similar traditional paper of physical and mechanical properties by compliant conductive macromolecule membrane transistor (TFT) for Electronic Paper.

If ignore this feature of bistable state, the representative of active illuminating flexible display Electronic Paper is electroluminescent polymer (LED), under electric field action, polymkeric substance is launched color visible, effect and inorganic light-emitting diode match in excellence or beauty, but the manufacturing cost of organic LED is so high, to such an extent as to the active promoter Kodak of this technology also is and jointly exploitation of Japanese firm.Passive luminous electronic paper technology is a lot, as multistable state liquid srystal (Ernst Lueder, Roland Buerkle, Martin Muecke, Rucediger Klette, et.al.Flexible and bistable FLC and cholesteric displays on plasticsubstrates for mobile applications and smart cards, Journal of the SID7/1,1999 P29), be the main technique of display that is currently applied to e-book (E-BOOK).But liquid-crystal display be unable to do without backlight, otherwise the display effect that can't obtain, narrow visual angle also is one of its limitation.So comparatively speaking, electrophoresis showed has more advantage.

The Electronic Paper product technology relates to optics, chromatology, macromolecular material, electronics etc., belong to multidisciplinary synthesis class technology, wherein, conducting polymer composite is the prize-winning content of Nobel chemistry Prize in 2000, also be the forward position material that possible influence 21 century industrial technology development, product manufacture and various novel printing technique particularly inkjet technology are closely related.So electronic paper technology possesses frontier nature, comprehensive, suitable technical difficulty is arranged.

In order to make electric paper display, people have developed multiple principle type technique of display, also have a lot of new technologies to be expected to be applied to electric paper display and make.At present, what most possibly realize industrialization is that microcapsule electrophoresis display electronic paper and screw show Electronic Paper, and electric ink is its key part.

The electrophoresis image comprises laser electrophotography (D.S.Rimai; D.J.Quesnel; L.P.Demejo etc.Journal Imaging Science and Technology.Vol45, No.2, March/April, USP3145156,3384488,2940847) and electrophoresis image technique of display (ElectrophoreticImaging Display is called for short EPID).Electrophoresis image technique of display is at first delivered in 1973 by MAT, subsequently, and PHILIP (M.D Croucher, J.Harbour, M.Hopper, and M.L.Hair; Electrophoretic display:Materials as Related to Performance; 1981, Photographic Science And Engineering, V25, No.2, March/April, P80-86), XEROX (Andrew L.Dallsa, Electrophoretic Display Technology.IEEETransections on Electron Devices, Vol.ED-24, No.7, July 1977.P8273), (the Yoshinorl Toyashima of Tokyo University, Akira Takahashi, Hiroshi Nokeahi llda, etc.A New Imaging System Utilizing Photoelectrophoretic Behavior of TiO2, Photographic Science and Egineering[J], Vol 21, Number1, Jounary/February 1977.P294) has also carried out the applied research of this technology at the optics display image system in succession.

General electrophoretic display device (EPD) is micropartical to be dispersed in constitute colloid in the suspension liquid, and under the effect of charge control agent, particle is just having or negative charge, and has certain surface potential, and when this dispersed system was applied electric field, electrophoresis can take place charged particle.Like this, by adjusting strength of electric field, the charged particle that just allows to reflect or absorb certain color is to different electrode swimmings, and sees through the flexible and transparent electrode and constitute and show (Barrett Cosmiskey, J.D.Albert, Hidekazu Yoshizawa﹠amp; Joseph Jacobson, An electrophoretic ink for all-printed reflective electronic displays, Nature, vol394/16, July1998, P253-255).

The advantage of electrophoretic display device (EPD) is: (1) is as long as the control direction of an electric field just can be controlled demonstration; (2) the electrophoresis disclosing solution material is easy to get, and is with low cost; (3) the similar common printed product of display effect; (4) show that energy consumption is low; (5) has memory function.But experienced many year, the electrophoretic display device (EPD) formula development that never leads to a leap, reason is that there is open defect in the common electrical phoretic display: the electrophoretic particles in the colloid can very fast generation sedimentation, gathering or other problems, influences display effect and display life.In order to address this problem, people have carried out many explorations.The E-Ink electric ink electrophoresis disclosing solution of U.S. E-Ink Inc. exploitation, coat suspension with the smooth microcapsule of the spherical transparent of diameter 30-300 μ m, white adrift titanium dioxide scattering particulate in the suspension, these capsules are distributed in and constitute dispersion system in the tackiness agent, the electrophoresis microcapsule electric ink is coated with or is printed on the flexible transparent plastic electrode, has successfully developed the flexible EPID Electronic Paper of principle type.In January, 2002, it is Ink-In-Motion that 500 cover trade names have been arranged ^TMLaunch, be used for chain store and show.

The introducing of microcapsule is important breakthrough of electrophoretic display technology: (1) is these particles dispersed, confinement is in the capsule of limited bulk, make the diffusion of particulate and aggregation limited very among a small circle, solved the instability problem of long-term puzzlement electrophoresis showed to a certain extent; (2) capsule diameter is little of 30 μ m, can directly be printed on softness, the frivolous substrate, and be fixed by second layer transparent film, makes the E-Ink display thickness accomplish to have only the millimeter level; (3) pass through voltage-regulation reflected light particulate to electrode accumulative quantity, realize grey scale control; (4) the cost of material is low for E-Ink, and performance is relatively stable, and through switching tests repeatedly, effect is better.But the introducing of microcapsule does not fundamentally solve colo(u)rant dispersion particle aggregation and settlement issues, and this begin to improve so must constitute from ink by determining forming of electric ink itself.

The composition of general electrophoresis display electronic ink comprises: electrophoretic particles, electrophoresis suspensioning liquid, background dye, charge control agent (CCA), capsule material etc.

1 is used for the particle (electrophoretic particles) of display screen

Charged particle can be pigment dyestuff and mineral dye.Organic/inorganic pigment can be pure pigment or pigment lake, and scattering of light pigment, light absorbing pigment or high-visibility pigment also can be mixtures.These materials can scattered light, send electronics fluorescence, perhaps fluorescence, zinc sulphide when exciting (be subjected to alternating-electric field luminous) fluorescent particles (Albert for example, Electrophoretic displays with luminescent particlesand materials for making the same, USP6,300,932, October 9,2001), cadmium yellow, lithopone, iron oxide yellow, titan yellow, the titanium baryta yellow, the cadmium silver yellow, cadmium red, cadmium lithopone orange, the cadmium lithopone is red, the molybdic acid orange, red iron oxide, plumbous red, the silver orange, cadmium orange, amber, iron oxide brown, the zinc chrome cologne earth, chrome green, chromic oxide, cobalt green, turkey blue, the cobalt titanium is green, Prussian blue, cobalt blue, lapis lazuli, sky blue, cobalt aluminium cadmium indigo plant, cobalt violet, mineral violet, carbon black, iron black, ferromanganese is black, ferro-cobalt is black, copper-chrome black, copper chromium manganese black, titanium oxide is black, copper powder, aluminium powder, glass putty, zinc powder etc.These particles can pass through surface treatment, or combine with charge control agent, improve electric charge or dispersion stabilization.

The performance of electrophoretic particles, such as absorption, optics, electric charge, mobility, size shape, density, surface chemistry, stability, processibility etc., can improve by emulsification and microcapsulary, many dyestuffs or pigment can wrap in the capsule, improve the optical property of system.

Someone is at pigment variety, measure its ζ (abbreviation of ZETA) current potential, arrange according to the ZETA current potential order in non-polar solvent (dimethylbenzene), and estimate its alkalescence and acid strong and weak, (Zhou Chunlong, Mu Zhenyi write, pigment dyestuff structure, characteristic and application also to have listed relative order, Chemical Industry Press, in January, 2002 P225).United States Patent (USP) 5,380,362 disclose use Diarylide yellow PigmentYellow 14 and Pigment Yellow 55 these two kinds of pigment dyestuffs is dispersed in and constitutes dispersion system in the suspension, and uses OLOA-1200 as charge control agent.Although as seen the main structure body of these two pigment is identical, the electrophoresis showed performance has significant difference (BEVERLY FITZHENRY-RITZ, OpticalProperties of Electrophoretic Image Displays.IEEE TRANSACTIONS ONELECTRON DEVICES，VOL.ED-28，NO.6，JUNE1981)。Colour particles with different electrophoretic mobilities, high molecular dye for example, perhaps the dyes/pigments coating can be used as the electrophoresis liquid color grains.Other materials also has United States Patent (USP) 5,364,726 disclosed product pigment Hostaperm Pink E (HoechstCelanese Corporat ion) a and Lithol Scarlet (BASF), blue or green pigment Sudan Blue OS (BASF) and similar compound.

White particle generally is that 1-3 layer aluminium or Si oxide coat the titanium dioxide of handling, and palladium sulfide, kaolin, zinc oxide etc. are used in the document introduction that has.These ionic general character are refractive index, scattering coefficient height, and uptake factor is low.Titanium white rate of utilization the highest (USP6327072, December 4,2001 for Comiskey, et al.Microcellelectrophoretic displays).Ordinary titanium dioxide suspension is as showing that liquid has two kinds of shortcomings: can show two kinds of colors at most, and dull coloring; During two kinds of color conversion, titanium dioxide granule must move down the enough distances of action spot at electric field action.This needs the hundreds of millisecond, for Video Applications, and overlong time.

The advantage of titanium dioxide is whiteness height, technology maturation.Xerox Corporation (USP4285801, August 25,1981 for Chiang, Electrophoretic display composition) has once tested various types of titanium dioxide electrophoretic particles such as comprising R-100 in a large number.Because proportion is excessive, can't be in suspension stable suspersion, must coat (Swiss Patent Application No.1034-79 of Feb.2,1979) in the surface.Corresponding with it, (1999/363059,21DEC) microcapsule of having introduced the opaque silicon-dioxide of multi-hole type coat and use U.S. Patent application.Carter etc. are coated with the silicon-dioxide of aluminum oxide coating with tetramethylolmethane, be suspended in the sudan black diethyl phthalate solution, the electrophoresis disclosing solution that formation can be used repeatedly (Working fluids for electrophoretic imagedisplay devices, USP 4,093,534 June 6,1978).Perhaps Irgalite yellow 8GF (2Hydroxy 1 naphthaldehyde azine pigment produced by CIBA GEIGY (UK) Ltd) pigment is applied molecular weight and be 90,000 PVA, be suspended in the pentyl acetate sudan black solution and constitute electrophoresis liquid.

Nano particle utilizes nanoparticle dispersed and condensed state performance (United States Patent (USP) 6323989Jacobson; Joseph M. (Newton Centre, MA); Drzaic; Paul S. (Lexington, MA); Morrison; Ian D. (Acton, MA) .Electrophoretic displays usingnanoparticles.) also may realize electrophoresis showed, at present the product-free report.

United States Patent (USP) 6333754 discloses a kind of electrophoresis showed toner, in two kinds of particles, having a kind of is conductor, the extra electric field iunjected charge makes its motion, motion friction by conductive particles is charged, as long as electric field is constant, the iunjected charge of charged particle can be stablized maintenance, and the uniform and stable image that makes of particle charge keeps the certain period.

Japan Ricoh company discloses two kinds of color particles of multi-hole type and has shown in United States Patent (USP) 6400492, improve to show contrast.The microcapsule electrophoretic display device (EPD) can improve image stabilization, but uses dye solution look as a setting, and the background whiteness is low to be its critical defect.Taked following measure: (1) reduces the absorption (described by Philips Lab.in Conference Record of1980 Biennial Disp.Res.Conf.) of dyestuff on dispersion system pigment for this reason; (2) use lower concentration dyestuff (described by XeroxPaloAlto in Proc.SID, Vol.18,3/4,1977); (3) suitably optimizing dyestuff and pigment concentration (described by Matsushita Electric Works, Ltd.in Proc.SID, Vol.18, No.3/4,1977) under the Action of Surfactant.But display frame density and contrast are low.Japanese Laid-Open Patent Publication No.62-269124 has delivered without dye method for this reason, granule sealed in colourless conducting liquid two kinds of electrical different colours, because two kinds of particulate charges of different polarity attract colour mixtures, cause easily to show slow and cause visual contrast to reduce.Promptly use microcapsule to coat and show liquid, still can not avoid the problems referred to above.Japanese Laid-Open Patent Publication No.63-50886 uses the electrophoretic particles of electrical different colours of the same race, be dispersed in the high conductivity low-viscosity (mobile) liquid, show by different realization of the electrical particulate electrophoretic velocity of difference, and the particle aggregation of having avoided different electric charges to cause, but, when image repeats to show, owing to be difficult to the conversion of control with a kind of electrical different colours, so show the different colours difficulty simultaneously, and visual contrast is low.Japanese Patent PublicationKo-hyo No.8-510790 introduces and adds sterically hindered big material to system, is to avoid one of different electrically charged particle accumulative methods.But not very effective.In addition, Japanese Laid-Open PatentPublication No.10-149117 has delivered a kind of compound white particle, this particle is to mediate white resin by polyreaction on the white pigments surface, pulverize then, be dispersed in the dye solution with the pigment of another kind of color and use, owing to do not possess anti-congregational rate, can not avoid the problem of front.The porous grain type that Ricoh uses, comprise organic and inorganic and both meet material, even be distributed in the suspension, micropore still exists, good dispersity.

2 suspension

Suspension in the microcapsule mainly is chemically inert organic solvent, is the medium that charged particle moves about, and wherein contains extinction dyestuff, stablizer, antioxidant.E-inks suspension basic parameter in the microcapsule, comprise density, specific refractory power and solvability etc. [Chiang, Anne A. Electrophoreticdisplay composition, USP4285801, August 25,1981; P.Murau and B.Singer, The understanding and elimination of some suspension instabilities inan electrophoretic display, J.Appl.Phys.1978,49 (9): 4820]

Electronics profit suspension performance perameter table look-up 1

Project demand	Numerical value	Meaning
			Low-k	About 2
The specific resistance height	10 -15Ω-cm

Viscosity is low	Less than 5centistokes	Be convenient to particle motion
			The low toxicity low environment pollutes		Environmental protection
Water-soluble	Less than 10ppm
			Proportion	Greater than 1.5
Fusing point	More than 90 ℃
			Specific refractory power	Less than 1.2	Identical as far as possible with electrophoretic particles
Unreactiveness	Dissolve polymer not	Helping micropartical selects

Background colour dyestuff performance requriements: fast light, in suspension the dissolving, color is moderate, cost is low.General azo, anthraquinone and the triarylmethane compound dyestuff selected.The dyestuff that contains in the suspension is dissolved in suspension, but is not adsorbed in capsular other compositions.Be dissolved in the extinction dyestuff in the suspension, comprise black dyestuff, fluorescence dye, light-sensitive coloring agent (UV-irradiation becomes colourless or other colors), these dyestuffs also can be aggregated in and form solid absorption-type polymkeric substance on the shell.Known suitable dyes has: azo, oil red, Sudan red and sudan black series; Anthraquinone, solvent blue, Macrolex Blue series; Triarylmethane dyes, Michler ' s hydrol, Victoria Green WPB, Viola crystallina, Auramine O etc.

3 charge control agents and particle-stabilised dose

The theoretical explanation of electric charge control comprises the absorption of selectivity particle, prototropy and contact charging etc.Charge control agent is used to improve the electrophoretic characteristic of particle, and stablizer prevents that electrophoresis particle from condensing, and prevents these particle precipitations simultaneously.Charge control agent can be used in electrophoretic display device (EPD), non-aqueous coating and oil additives.

United States Patent (USP) 5498674 has been introduced positive charge control agent and negative charge controlling agent.Negative charge controlling agent has polyisobutenyl succinimide, dinonyl adipate (acid of naphthalene ester), polyethylene pyrimidine, pyrimidine, warm phosphatide, polyoxyethylene, polymethyl acrylic acid acid methyl esters, polyacrylamide etc.Positive charge control agent has polyisobutene dicarboxylic anhydride, copper naphthenate, zirconium caprylate, zinc octoate, calcium octoate, PVA, polyacrylic acid, polymethyl acrylic acid, polyvinyl chloride etc.

As previously mentioned, the method for several electron gain inks is arranged, the electrophoresis particle can be pigment dyestuff, the mineral dye of micron dimension, perhaps coats pigment dyestuff and the inorganic pigment granules of handling through microcapsule, also can be the semiconductor material particle of nanoscale.Comparatively speaking, increase with granularity, electrophoretic effects reduces.Relational expression between electrophoresis showed time of response and each influence factor:

$T=\frac{6\mathrm{\&pi;}{\mathrm{<figure-callout\; id="2"\; label="d"\; filenames="A20071012355500161.png"\; state="\{\{state\}\}">d</figure-callout>}}^2\mathrm{\&eta;}}{\mathrm{V\&zeta;\&epsiv;}}$

In the formula, d interelectrode distance, V voltage, η viscosity, ζ particle zeta current potential, T time of response, ε suspension specific inductivity.

As the electrophoresis disclosing solution of electric ink,, follow youth primary-Bill (Lambert-Beer ' s Law) law for absorption of incident light and transmission.Promptly

T _λi＝t _λ ^b

T _λi＝t _λ ^c

T _{λ i}Interior spectral transmittance, t _λInterior spectral transmittance on the b unit thickness (1cm); Liquid thickness, the c strength of fluid.Internal transmittance is the projection ratio of material internal.Promptly owing to change of refractive has been considered each surperficial spectral reflectance transmittance afterwards.

The optical phenomenon of incident beam body surface is by the performance decision of object itself.Generally body surface is divided into transparent, translucent and opaque three types, condition of surface difference, the rule difference that optical phenomenon is followed.

Be pigment dyestuff and mineral dye electric ink as mentioned above, the microcapsule electric ink of pigment dyestuff and mineral dye, primary products have been formed, but improve the stability and the response speed of electric ink, improve the diversity of electric ink electrophoresis showed color, remain the emphasis of industrialization technology research.Therefore provide a kind of electrophoretic particles littler, more stable, the abundant more electrophoresis display electronic ink of display color just becomes the problem that present technique field urgent need will solve.

Summary of the invention

It is littler to the purpose of this invention is to provide a kind of electrophoretic particles, more stable, and display color enriches more and can be at the electrophoresis display electronic ink of electrophoresis showed image under the low voltage.

Above-mentioned purpose of the present invention reaches by the following technical programs:

A kind of electrophoresis display electronic ink mainly comprises charged particle and the transparent liquid of stablizing the dissolving or the described charged particle that suspends, and it is characterized in that: described charged particle is a dyestuff.

A kind of optimal technical scheme is characterized in that: the type of described dyestuff, include but not limited to various matching stain, the metallized dyes that in solvent, have electric charge, even dispersed dye and cationic dyestuff.

A kind of optimal technical scheme is characterized in that: the consumption of described dyestuff is between the 1-20 weight % of electrophoresis showed ink gross weight, is best with the saturation concentration.

A kind of optimal technical scheme, it is characterized in that: described matching stain is a turmeric yellow (Acid Yellow) 117, turmeric yellow (Acid Yellow) 219, von Muller's indicator (Acid Orange) 3, von Muller's indicator (AcidOrange) 67, von Muller's indicator (Acid Orange) 171, Xylene Red (Acid Red) 37, Xylene Red (Acid Red) 87, Xylene Red (Acid Red) 88, Xylene Red (Acid Red) 111, Xylene Red Acid Red (114), Xylene Red (Acid Red) 12, turmeric yellow (Acid Red) 138 etc.

A kind of optimal technical scheme is characterized in that: described metallized dye, comprise that all dissolve in organic solvent, and particularly at low-pole, various coloured light metallized dyes of dissolved in non-polar organic solvent particularly.

A kind of optimal technical scheme is characterized in that: described metallized dye is orange (Orange)-10, orange (Orange)-09, red (Red)-04, red (Red)-35, red (Red)-06, red (Red)-95, red (Red)-10, red (Red)-16, palm fibre (Brown)-02, palm fibre (Brown)-05, blue (Blue)-03, blue (Blue)-06, green (Green)-20, green (Green)-575, black (Black)-04, black (Black)-20, black (Black)-55 Huangs (yellow-) 45k, yellow (Yellow)-20, yellow (Yellow)-57.

A kind of optimal technical scheme is characterized in that: described electrophoresis display electronic ink also comprises the interpolation material that can make described charged particle charged.

A kind of optimal technical scheme is characterized in that: described interpolation material is a charge control agent, and addition is as the criterion to obtain the maximum specific charge of electrophoresis material, and preferably its addition is 0.1-10 weight %.

A kind of optimal technical scheme is characterized in that: described charge control agent is acid or alkaline charge control agent.

A kind of optimal technical scheme is characterized in that: described alkaline charge control agent includes but not limited to basic solvent, for example various aminocompounds and derivative thereof, triethylamine for example, diethylamino, aniline, pyridine etc.; Can be various basic surface promoting agents, PIBI for example, various acyls (Asia) amine compound and derivative thereof.

A kind of optimal technical scheme is characterized in that: described transparent liquid is: with the identical or approaching organic solvent of electrophoresis suspended particle proportion, as ethanol, zellon, dimethylbenzene etc.

Beneficial effect:

Because dyestuff proportion is little, is easy to disperse or dissolve, the electric ink colour developing particle little (molecularity is main) that is made into, keeping quality is good, and with respect to other granules of pigments electrophoresis disclosing solutions, the comfort level of making improves greatly.This is the outstanding advantage of dyestuff electric ink contrast pigment dyestuff and mineral dye electric ink.

Electric ink blending process of the present invention is simple, the range of choice of dyestuff and transparent solvent system is big, the colour developing particle is little, good stability in electric ink preservation and the electrophoresis showed process, the display density height, the response voltage of demonstration requires low, in the certain voltage scope, repeated multiple times shows that no molecular structure of dye damages phenomenon in a large number and takes place.

Electrophoretic particles of the present invention is tiny of 40-60nm, shows that OD reaches more than 3.16, and keeping quality is good, is applicable to the Electronic Paper of various uses.

The present invention will be further described below in conjunction with drawings and Examples, but and do not mean that limiting the scope of the invention.

Description of drawings

Fig. 1 is the used electrophoresis chamber structural representation of the present invention.

Fig. 2 is the electric ink electrophoresis front and back density (X-Rite reflection densitometer test) of the used matching stain azogeramine of the present invention (C.I.Acid Red 1) with the mixed solvent preparation of ethanol and aniline.

Fig. 3 is the electric ink electrophoresis front and back density (X-Rite reflection densitometer test) of the used metallized dye solvent red 08 of the present invention (C.I.Solvent 08) with the alcohol solvent preparation.

Fig. 4 is the electric ink electrophoresis showed front and back picture of the used metallized dye solvent red 08 of the present invention (C.I.Solvent 08) with the alcohol solvent preparation.

Embodiment

Embodiment 1: the mixed solvent of matching stain azogeramine (C.I.Acid Red 1) and ethanol and aniline.

Acid red dye azogeramine (C.I.Acid Red 1) is dissolved in the mixing solutions of ethanol and aniline (mass ratio of ethanol and aniline is 3: 1), obtains the mixing solutions that concentration is 0.01mol/L.Acid red dye belongs to azoic dyestuff, and the per molecule dyestuff contains 2 sodium sulfonates, a hydroxyl.Aniline is the weakly alkaline solvent.In the mixed solvent of ethanol and aniline, the acid red dye particle has negative charge.This solution is injected electrophoresis chamber shown in Figure 1.

Electrophoresis chamber is made up of 2 layers of ITO conductive glass.ITO coating on glass inwardly, thickness is about 1mm between two sheet glass.The frame position sticks with glue agent and handles sealing.The glass surface that is positioned at the viewer front side only has the ITO coating at the position that needs display image through handling.All there is the ITO coating in the ito glass that is positioned at viewer's rear side.Electric ink injects electrophoresis chamber by the upper end tapping.With two ITO energisings, in the position that needs display image, the electric field that exists between the two-layer ITO makes the dyestuff generation electrophoresis in the electric ink.

Apply 2V voltage by constant voltage dc source between two ito glass electrodes, viewer's front side electrode is for just, and back electrode is for negative.Dyestuff generation electrophoresis.As shown in Figure 2, carry out density measurement with X-Rite inverse densometer, in the time, image position density OD rises to 1.98 by 1.55 at 15s.Other has sulfonic group is not only that the matching stain that has sulfonic group also electrophoresis can take place in specific solvent.Aniline is weakly alkaline as the charge control agent in this prescription.In theory, all Lewis bases can both serve as the charge control agent of matching stain.

Embodiment 2: matching stain Acid Black 1, pyridine and ethanol mixed solvent.

The 0.1g acid black dye is dissolved in the mixed solvent of 10ml pyridine and ethanol half and half, obtaining concentration is the mixing solutions of 10% (w/v) Acid Black 1 dyestuff.1 molecule Acid Black 1 dyestuff contains 2 sodium groups, an amino, a nitro, a hydroxyl.Pyridine is the weakly alkaline solvent.In pyridine, the acid red dye particle is because solvation is electronegative.This solution is injected electrophoresis chamber shown in Figure 1.Apply 2V voltage by constant voltage dc source between two ito glass electrodes, viewer's front side electrode is being for just, and back electrode is for negative, dyestuff generation electrophoresis.Can observe pictorial display.Apply reverse voltage, reverse electrophoresis takes place in dyestuff.

Embodiment 3: matching stain Acid Black 1, the mixed solvent of triethylamine and zellon.

The 0.1g acid black dye is dissolved in the mixed solvent of 10ml triethylamine and zellon half and half, obtaining concentration is the mixing solutions of 10% (w/v) Acid Black 1 dyestuff.1 molecule Acid Black 1 dyestuff contains 2 sodium groups, an amino, a nitro, a hydroxyl.Triethylamine is the weakly alkaline solvent.In triethylamine, the acid red dye particle is because solvation is electronegative.This solution is injected electrophoresis chamber shown in Figure 1.Apply 2V voltage by constant voltage dc source between two ito glass electrodes, viewer's front side electrode is being for just, and back electrode is for negative, dyestuff generation electrophoresis.Can observe pictorial display.Apply reverse voltage, reverse electrophoresis takes place in dyestuff.

Embodiment 4: matching stain Acid Black 1, the mixed solvent of diethylamino and dimethylbenzene.

The 0.1g acid black dye is dissolved in the mixed solvent of 10ml diethylamino and dimethylbenzene half and half, obtaining concentration is the mixing solutions of 10% (w/v) Acid Black 1 dyestuff.1 molecule Acid Black 1 dyestuff contains 2 sodium groups, an amino, a nitro, a hydroxyl.Diethylamino is the weakly alkaline solvent.In diethylamino, the acid red dye particle is because solvation is electronegative.This solution is injected electrophoresis chamber shown in Figure 1.Apply 2V voltage by constant voltage dc source between two ito glass electrodes, viewer's front side electrode is being for just, and back electrode is for negative, dyestuff generation electrophoresis.Can observe pictorial display.Apply reverse voltage, reverse electrophoresis takes place in dyestuff.

Embodiment 5: metallized dye solvent red 08 (C.I.Solvent 08), alcohol solvent.

Metallized dye solvent red 08 (C.I.Solvent 08) is dissolved in the ethanol, obtains the solution that concentration is 0.01ml/L.C.I.Solvent 08 is 1: 2 monoazo metalloid complex dyestuff, and each monoazo molecule has two hydroxyls.In ethanol, metallized dye solvent red 08 (C.I.Solvent08) is because solvation has negative electricity.This solution is injected electrophoresis chamber shown in Figure 1.Apply 2V voltage by constant voltage dc source between two ito glass electrodes, viewer's front side electrode is being for just, and back electrode is for negative, dyestuff generation electrophoresis.Carry out density measurement with Xrite inverse densometer, as shown in Figure 3, in 60S, image position density rises to 2.10 by 1.31.With the increase of voltage, the time of response can shorten.When two electrodes to electrophoresis chamber applied reverse voltage, reverse electrophoresis took place in dyestuff.In 2 minutes, image position density drops to 1.40 by 2.10, and pictorial display disappears.This electric ink good stability can show back and forth, and the gathering of no dyestuff or sedimentation phenomenon take place.

Left figure among Fig. 4 is that the solution that this example relates to injects the photo of taking behind the electrophoresis chamber shown in Figure 1.The picture of middle demonstration " seal institute " two words is that the electrophoresis chamber two-plate is applied 2V voltage, behind the dyestuff generation electrophoresis 60s, and the literal of demonstration.Right figure applies reverse 2V voltage to the electrophoresis chamber two-plate, dyestuff generation counterelectrophoresis 20s, the photo of the shooting that the display image disappearance is later.

All adopt the T10 digital camera of SONY with photographs, screening-mode is automatic, and light source is a daylight.

Embodiment 6: metallized dye solvent red 08 (C.I.Solvent 08), xylene solvent adds the poly-coral amber imide (PIBI) (U.S. Chevron Oronite) of charge control agent.

Metallized dye solvent red 08 (C.I.Solvent 08) is dissolved in the dimethylbenzene, obtains concentration and be the solution of 0.01ml/L and add dilution back charge control agent PIBI number droplet.Metallized dye solvent red 08 is the complex compound of azoic dyestuff.1 molecule monoazo-dyes has 2 hydroxyls and 1 nitro.Dimethylbenzene is non-polar solvent, and charge control agent PIBI is a Lewis base.The solubleness of metallized dye solvent red 08 in dimethylbenzene is very low, but after adding charge control agent PIBI, solubleness is greatly improved.Under the effect of charge control agent PIBI, dyestuff has negative charge.This solution is injected electrophoresis chamber shown in Figure 1.Apply 2V voltage by constant voltage dc source between two ito glass electrodes, viewer's front side electrode is being for just, and back electrode is for negative, dyestuff generation electrophoresis.Carry out density measurement with Xrite inverse densometer, in the time, image position density OD rises to 1.98 by 1.55 at 15S.Apply reverse voltage, reverse electrophoresis takes place in dyestuff.In time, image position density drops to 1.62 by 1.98 at 10S.

The step identical with above-mentioned enforcement 4 carried out following experiment:

Charge control agent is to the electrophoretic influence of metallized dye in table 2 xylene solvent,

Dyestuff	Dimethylbenzene	Dimethylbenzene+diethylamine	Dimethylbenzene+aniline	Dimethylbenzene+PIBI
					Metal complex indigo plant 06	×	○	×	○
Metal complex red 04	×	×	×	○

Metal complex Huang 20

×

×

×

×

Electrophoresis can not take place in the dyestuff the under * expression certain voltage in the system, illustrates that the charge control agent selection is improper, can't make electrophoresis material charged.Down together.

Electrophoresis can take place in the dyestuff under the zero expression certain voltage in the system.

The xylene solution concentration of dyestuff is 0.01mol/l, and the amount to the charge control agent of multiple adding in the process of the test is all tested

Charge control agent is to the electrophoretic influence of metallized dye in table 3 tetrachloroethylene solvent

Dyestuff	Stoste	Zellon+diethylamine	Zellon+aniline	Zellon+PIBI
					Metal complex indigo plant 06	×	○	○	○
Metal complex red 04	○	○	○	○
					Metal complex Huang 20	×	×	×	×

Variable density before and after the ethanolic soln generation electrophoresis of different concns (shown in seeing the following form) metal complex solvent red 08 (C.I.Solvent 08), voltage 2V, electrophoresis time 60S.See the following form 4.

Table 4

	0.002mol/L	0.004mol/L	0.006mol/L	0.008mol/L	0.001mol/L
						Before the electrophoresis	V：0.83	V：0.86	V：1.06	V：1.11	V：1.31
C：0.45	C：0.47	C：0.65	C：0.71	C：0.93
					M：1.95		M：2.08	M：2.75	M：2.90	M：2.72
Y：1.55	Y：1.55	Y：2.82	Y：3.01	Y：2.69
					Behind the electrophoresis		V：0.97	V：0.96	V：1.48	V：1.91	V：2.10
C：0.61	C：0.56	C：1.12	C：1.62	C：1.83
						M：2.00	M：2.23	M：2.70	M：2.81	M：3.30
Y：1.89	Y：2.00	Y：2.72	Y：2.76	Y：3.26

V represents gray scale density; The blue or green colour density of dividing of C; The M product divide colour density; The yellow colour density of dividing of Y.

The above results shows that dye strength is for the electrophoresis showed effect, and factors such as driving electric field voltage all can influence the electrophoresis showed effect.

Claims (10)

1, a kind of electrophoresis display electronic ink mainly comprises charged particle and the transparent liquid of stablizing the dissolving or the described charged particle that suspends, and it is characterized in that: described charged particle is a dyestuff.

2, electrophoresis display electronic ink according to claim 1 is characterized in that: described transparent liquid is ethanol, zellon or dimethylbenzene.

3, electrophoresis display electronic ink according to claim 1 is characterized in that: described electrophoresis display electronic ink also comprises the interpolation material that can make described charged particle charged.

4, electrophoresis display electronic ink according to claim 1 is characterized in that: the type of described dyestuff is included in matching stain, metallized dye, dispersed dye or the cationic dyestuff that has electric charge in the solvent.

5, electrophoresis display electronic ink according to claim 4, it is characterized in that: described matching stain is an acid yellow 11 7, turmeric yellow 219, von Muller's indicator 3, von Muller's indicator 67, von Muller's indicator 171, Xylene Red 37, acid red 87, acid red 88, azogeramine 11, azogeramine 14, azogeramine 2 or turmeric yellow 138.

6, electrophoresis display electronic ink according to claim 4 is characterized in that: described metallized dye is an orange-10, orange-09, red-04, red-35, red-06, red-95, red-10, red-16, brown-02, brown-05, blue-03, blue-06, green-20, green-575, black-04, black-20, deceive-55, yellow 45k, yellow-20 or yellow-57.

7, electrophoresis display electronic ink according to claim 4 is characterized in that: the consumption of described dyestuff is the 1-20 weight % of the gross weight of electric ink.

8, electrophoresis display electronic ink according to claim 3 is characterized in that: described interpolation material is a charge control agent, and its addition is 0.1-10 weight %.

9, electrophoresis display electronic ink according to claim 8 is characterized in that: described charge control agent is alkaline charge control agent.

10, electrophoresis display electronic ink according to claim 9 is characterized in that: described alkaline charge control agent is basic solvent or basic surface promoting agent.

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