CN100444015C - Liquid for electrophoretic display and display medium and display employing it - Google Patents

Abstract

A medium for electrophoretic display employing a liquid for electrophoretic display capable of changing the visual recognition state reversibly through action of an electric field, or the like, includes a liquid for electrophoretic display containing alkylpolyetheramine having a structural unit being represented by at least a specified structural formula, one kind or more of fine particles, a dispersant and a dispersion liquid medium where the fine particles contain those subjected to lipophilic surface treatment, and the liquid for electrophoretic display is encapsulated in a independent structure of microcapsule or cell. The electrophoretic display comprises a pair of substrates having a light transmitting electrode formed on at least one of them, and the electrophoretic display medium provided between the substrates. The electrophoretic display medium and the electrophoretic display employing the liquid for electrophoretic display have a high contrast on the display surface and provides a contrast display with high reliability even in the case of repetitive display while ensuring excellent response.

Description

Electrophoresis showed with liquid, use this electrophoresis showed display medium and display device with liquid

Technical field

The present invention relates to reversibly to change demonstration liquid that the electrophoresis showed of visible state uses, use display medium and the display device of this electrophoresis showed with liquid by effects such as electric fields.

Background technology

In recent years, be accompanied by the development of information instrument, the needs of the low consumption electrification of display device, slimming, flexibility etc. are increased to some extent, come into one's own with research, the exploitation of these display device that need adapt.

As one of this display device, the known electrophoretic display apparatus that has by inventions such as Harold D.Lees.This electrophoretic display apparatus has following formation, promptly be situated between and at least one disposed in opposite directions for 2 transparent electrode base boards by suitable dividing plate, between this electrode base board, fill and show liquid, form display board, above-mentioned demonstration liquid is particulate (pigment particles) is disperseed in being colored as the dispersion medium different with its color and to form.This display board is applied electric field, can obtain showing (for example with reference to patent documentation 1) at the transparency electrode face.

Be filled between this electrode base board electrophoresis showed with liquid by particulates such as titania (pigment particles), be dissolved with to be used to give and give adjuvants such as agent with spreading agents such as the dispersion medium of low-ks such as the dimethylbenzene of the dyestuff of this particulate color contrast, zellon, paraffin, silicone oil, surfactant and electric charge and constituted.By this electrophoresis showed is applied electric field with liquid, particulate in the demonstration liquid color of particulate occurs to the transparency electrode side shifting on display surface, and then by applying and this rightabout electric field, particulate moves to opposition side, the color of the dispersion medium that has occurred on display surface by dye coloring.

This electrophoretic display apparatus is the display device that can obtain required demonstration by the direction of control electric field, since have low cost, angle of visibility and common printed matter etc. same wide, power consumption is low, advantages such as Memorability that demonstration is arranged, so receive publicity as low-cost display device.

But, the demonstration liquid of the electrophoretic display apparatus of in this patent documentation 1 grade, being put down in writing, therefore inorganic pigment owing to generally being high index of refraction such as dispersed titanium dioxide in the dispersion medium of hydrophobicity that dissolving dye etc. is colored and low-k has following shortcoming: the contrast that the control difficulty of dispersion stabilization, aggegation etc. cause descends and repeats that display characteristic descends, display quality descends.In addition, owing to use dye solution, therefore also have because dyestuff is adsorbed in the shortcoming that surface of pigments etc. causes contrast decline.

Therefore, in order to address these problems etc., up to the present carried out One's name is legion for improving the exploitation of disperse system stabilization and display characteristic.

As the method that is used to improve dispersion stabilization, known for example have by dye coloring dispersion medium in used with titanate coupling agent and carried out in the system of surface-treated electrophoresis particle, add the technology (for example with reference to patent documentation 2) of sorbitan fatty acid ester surfactant.

Handle with quarternary ammonium salt compound, add the method (for example with reference to patent documentation 3) of surfactant afterwards again for one of also known in addition 2 kinds of electrophoresis particles that electriferous state is different.

On the other hand, as the method that is used to improve contrast, known have that for example to use surface of pigments be that the dyestuff of non-adsorbability is as being used for the painted dyestuff of dispersion medium (with reference to non-patent literature 1), reducing the dye strength (with reference to non-patent literature 2) of dispersion medium etc.

In addition, as preventing since on the display surface electrophoretic particle partially in the inhomogenous method of the demonstration that is caused, known have electrophoresis showed is enclosed in the method for utilizing as the demonstration particle in the microcapsules (for example with reference to patent documentation 4) with demonstration liquid.

But in the technology that above-mentioned patent documentation 2 is put down in writing, the effect of decentralized stabilization is insufficient, is not also obtaining on the effect of sufficient this point also existing problems on the contrast of display degree.

And in the technology that above-mentioned patent documentation 3 is put down in writing, not obtaining sufficient dispersion stabilization yet, effect is insufficient.

In the method for above-mentioned non-patent literature 1 and 2, do not solve the shortcoming that above-mentioned dye solution causes fully, also there is the problem in the practicality.

In the method for above-mentioned patent documentation 4, so it is same because the demonstration liquid of bag has utilized the coloured dye solution and the dispersion liquid of pigment particles in the institute with above-mentioned phenomenon, also insufficient aspect contrast.

Therefore, as the method for the problem that system had of the dispersion medium that solve to have used with dye coloring, known have an electrophoretic display apparatus that does not use dye solution.Known for example have at least one for 2 transparent cells that form by dividing plate that are situated between between the electrode in opposite directions in, be enclosed in the solution that is dispersed with the mutually different at least 2 kinds of electrophoretic particle of color harmony electrophoresis in the colourless dispersion medium and the electrophoretic display device (for example with reference to patent documentation 5) that obtains.

In the system that this solution that is dispersed with the mutually different 2 kinds of electrophoretic particle of color harmony electrophoresis (charged particles) is used with demonstration liquid as electrophoresis showed, interparticle aggegation becomes problem, as the method that is used to prevent this problem, knownly favourablely adjust solid that the interpolation of agent, the surface treatment of particle etc. the cause effect (for example with reference to patent documentation 6) of repelling each other with electric charge.

In addition, known have an electrophoretic display device (for example with reference to patent documentation 7) that has used the solution that is dispersed with the identical but mutually different at least 2 kinds of electrophoretic particle of color harmony electrophoretic velocity of electrophoresis in colourless dispersion medium.

Also known have in dispersion medium, contain in the electrophoresis showed of having implemented particle that surface-treated inside has the space and the pigment particles different with showing liquid (for example with reference to patent documentation 8) with this particle tone.

Also known have a technology (for example with reference to patent documentation 9) that wraps in the solution of the mutually different at least 2 kinds of electrophoresis particulates of color harmony electrophoresis in the microcapsules being dispersed with in colourless dispersion medium.

But, in the technology that above-mentioned patent documentation 5 is put down in writing and since the charged particles of different electrophoretic particle be just with negative combination, so between particulate, produced electric attraction, cause the aggegation of particulate, have thus dispersion stabilization descend, owing to colour mixture produces degradation problem under the contrast.

In the technology that above-mentioned patent documentation 6 is put down in writing, be difficult to prevent fully the cohesion of 2 kinds of electrophoretic particle, have the problem that can not realize good contrast.

And, even if the slow particulate of being put down in writing in the above-mentioned patent documentation 7 of translational speed, when near the electrode that is present in display surface,, just appear on the display surface sometimes because displacement is short, in addition, even owing between the particle that generally tone is identical, charged particles also has the distribution of different translational speeds, if therefore do not control so that they are not overlapping between the different particle of tone, then be difficult to obtain sufficient contrast, in this existing problems.

The inside of being put down in writing in above-mentioned patent documentation 8 has in the particle in space since the dispersion liquid medium to enter into the space medium, therefore the refractive index of particularly white particle descends, and is difficult to obtain sufficient contrast.

In the situation that above-mentioned patent documentation 9 is put down in writing, thereby the stability that also still has dispersion liquid can not be kept, because the aggegation that causes of electric attraction between the electrophoresis particulate and colour mixture takes place in microcapsules cause the problem that shows colour mixture.

Patent documentation 1: No. 3612758 communique of United States Patent (USP) (claims, embodiment etc.)

Patent documentation 2: specially permit No. 2733687 communique (claims, embodiment etc.)

Patent documentation 3: the spy opens flat 11-119704 communique (claims, embodiment etc.)

Non-patent literature 1:Philips Lab:Conference Record of 1980 BiennialDisp.Res.Conf.

Non-patent literature 2:XeroxPaloAlto:Proc.SID, Vol.183/4,1977.

Patent documentation 4: specially permit No. 2551783 communique (claims, embodiment etc.)

Patent documentation 5: the spy opens clear 62-269124 communique (claims, embodiment etc.)

Patent documentation 6: special table flat 8-5101190 communique (claims, embodiment etc.)

Patent documentation 7: the spy opens clear 63-50886 communique (claims, embodiment etc.)

Patent documentation 8: the open 2002-277903 communique (claims, embodiment etc.) of the U.S.

Patent documentation 9:WO98/03896 communique (claims, embodiment etc.)

Summary of the invention

The present invention is in view of above-mentioned problem and present situation etc. in the past, in advance with its solution, its purpose is to provide by improving the dispersion stabilization of electrophoresis showed with liquid, can realize the demonstration of high-contrast, when showing repeatedly, also can compare the also excellent electrophoresis showed liquid of demonstration, response, use display medium and the display device of this electrophoresis showed with liquid with high reliability.

The inventor etc. further investigate the problem of above-mentioned conventional art, found that: by when containing a kind or multiple particulate, spreading agent, dispersion liquid medium, also containing special component, can access as the electrophoresis showed of above-mentioned target with liquid, use display medium and the display device of this electrophoresis showed with liquid, thereby finish the present invention.

That is, the present invention is following (1)～(24)

(1) a kind of electrophoresis showed liquid, it is characterized in that, it contains the alkyl, polyether amine that has at least with structural unit shown in the following general formula (I), a kind or multiple particulate, spreading agent and dispersion liquid medium, and described particulate contains the particulate of being handled by the lipophilic surface.

[in the above-mentioned formula (I), R ₁Be saturated hydrocarbyl or unsaturated alkyl, R ₂Be (OCH ₂CH ₂) _X-H, R ₃Be (OCH ₂CH ₂) _y-H, x, y are positive number.]

(2) a kind of electrophoresis showed liquid, it is characterized in that it contains the alkyl, polyether amine that has at least with structural unit shown in the following general formula (I), has the polyoxyethylene propylene oxide block polymer with structural unit shown in the following general formula (II), a kind or multiple particulate and dispersion liquid medium.

[in the above-mentioned formula (I), R ₁Be saturated hydrocarbyl or unsaturated alkyl, R ₂Be (OCH ₂CH ₂) x-H, R ₃Be (OCH ₂CH ₂) y-H, x, y are positive number.]

OH(C ₂H ₄O)p(C ₃H ₆O)qH (II)

[in the above-mentioned formula (II), p, q are positive number.]

(3) as above-mentioned (2) described electrophoresis showed liquid, it further contains the acetylene-derivative that has with structural unit shown in the following general formula (III).

[in the above-mentioned formula (III), R ₄And R ₅Be saturated hydrocarbyl or unsaturated alkyl, R ₆Be OCH ₂CH (CH ₃)-or (OCH ₂CH ₂) m-OH.R ₇Be OCH ₂CH (CH ₃)-or (OCH ₂CH ₂) n-OH.M, n are 0 or positive number.Above-mentioned R ₆And R ₇Can be identical, also can be different.]

(4) as above-mentioned (2) or (3) described electrophoresis showed liquid, wherein the mean molecular weight of polyoxyethylene propylene oxide block polymer is 1000～4000.

(5) as each described electrophoresis showed liquid of above-mentioned (2)～(4), wherein the amount of ethylene oxide in the polyoxyethylene propylene oxide block polymer is 50 weight % or following.

(6) as each described electrophoresis showed liquid of above-mentioned (2)～(5), wherein the content of polyoxyethylene propylene oxide block polymer is with respect to showing that the liquid total amount is 0.01～30 weight %.

(7) as each described electrophoresis showed liquid of above-mentioned (3)～(6), wherein the HLB of acetylene-derivative be 10 or below.

(8) as each described electrophoresis showed liquid of above-mentioned (2)～(7), wherein particulate was handled by the lipophilic surface.

(9) as above-mentioned (1)～(8) each electrophoresis showed liquid, wherein the lipophilic surface handles and to be to use coupling agent to carry out.

(10) as above-mentioned (9) described electrophoresis showed liquid, wherein coupling agent is that to be selected from titanate esters be that coupling agent, aluminium are at least a kind among coupling agent, the silane series coupling agent.

(11) as each described electrophoresis showed liquid of above-mentioned (1)～(10), wherein the surface functionalities of the particulate of being handled by lipophilic surface group is alkoxy carbonyl.

(12) as each described electrophoresis showed liquid of above-mentioned (1)～(11), wherein the content of alkyl, polyether amine is 1.0～200 weight % with respect to particulate.

(13) as each described electrophoresis showed liquid of above-mentioned (1)～(12), wherein at least 1 of particulate kind is high molecular particle, organic pigment, the inorganic pigment that contains colorant.

(14) as above-mentioned (13) described electrophoresis showed liquid, the constituent that wherein contains the high molecular particle of colorant is that cross-linked acrylic acid is a resin.

(15) as each described electrophoresis showed liquid of above-mentioned (1)～(14), wherein the mean grain size of particulate is 0.05～20 μ m.

(16) as each described electrophoresis showed liquid of above-mentioned (2)～(15), wherein also further contain spreading agent.

(17) as each described electrophoresis showed liquid of above-mentioned (1)～(16), wherein spreading agent is that nonionic system or negative ion are surfactant.

(18) as each described electrophoresis showed liquid of above-mentioned (1)～(17), wherein the content of spreading agent is with respect to showing that the liquid total amount is 0.01～50 weight %.

(19) a kind of electrophoresis showed medium is characterized in that, each described electrophoresis showed of above-mentioned (1)～(18) is enclosed in the body of independent structures separately of microcapsules or cell with liquid.

(20) as above-mentioned (19) described electrophoresis showed medium, wherein filling electrophoresis showed with in the cell structure of liquid, to carrying out hydrophilicity-imparting treatment with electrophoresis showed with liquid electrodes in contact portion and cell portion, this hydrophilicity-imparting treatment is selected from ozone treatment, plasma treatment, corona treatment, UV Itro processing, sputter process, polymeric layer formation processing, inorganic layer formation processing, organic or inorganic mixolimnion formation processing.

(21) as above-mentioned (19) described electrophoresis showed medium, wherein the size of microcapsules is 10～200 μ m.

(22) as above-mentioned (19) or (21) described electrophoresis showed medium, wherein microcapsules have flexibility, and are difficult to produce the gap when arranging microcapsules.

(23) as above-mentioned (19)～(22) electrophoresis showed medium as described in each, wherein independently the volume of cell is 1 * 10 ^-9Cm ³～1 * 10 ^-3Cm ³

(24) a kind of electrophoretic display apparatus is characterized in that, it has a pair of substrate and is present in each described electrophoretic display medium of above-mentioned (19)～(23) between this substrate, is formed with one of at least optically transparent electrode in the described a pair of substrate.

According to the present invention, the contrast height of display surface can be provided, when showing repeatedly also can with high reliability compare the also excellent electrophoresis showed of demonstration, response with liquid, use the display medium and the display device of this electrophoresis showed usefulness liquid.

Description of drawings

Fig. 1 is the key diagram of the titanium oxide microparticle after with titanium coupling agent titania surface being handled.

Fig. 2 is for being enclosed in electrophoresis showed the synoptic diagram of the simple grain subtype embodiment in the structure that is formed by microcapsules with liquid.

Fig. 3 is for being enclosed in electrophoresis showed the synoptic diagram of two each embodiment of corpuscular type in the structure that is formed by microcapsules with liquid.

Fig. 4 is for being enclosed in electrophoresis showed the synoptic diagram of the routine embodiment in the structure that is formed by cell with liquid.

Fig. 5 is for being enclosed in electrophoresis showed the synoptic diagram of another the routine embodiment in the structure that is formed by cell with liquid.

Fig. 6 is for being enclosed in electrophoresis showed the synoptic diagram of another the routine embodiment in the structure that is formed by cell with liquid.

Fig. 7 is the schematic cross-section that is presented at the routine embodiment when having disposed microcapsules between electrode in opposite directions.

Fig. 8 is the schematic cross-section that is presented at the routine embodiment when having disposed cell structure sheet material in opposite directions between electrode.

Fig. 9 is the schematic cross-section that is presented at another the routine embodiment when having disposed cell structure sheet material in opposite directions between electrode.

Figure 10 is the synoptic diagram of electrophoresis showed with the electrophoretic display apparatus of the display medium of liquid that used enclosing of simple grain subtype in the structure that is made of microcapsules.

Figure 11 is the synoptic diagram of electrophoresis showed with the electrophoretic display apparatus of the display medium of liquid that used enclosing of two corpuscular types in the structure that is made of microcapsules.

Figure 12 is for showing the sectional view of a routine electrophoretic display apparatus user mode.

Symbol description

1 titanium oxide microparticle 2 black solvent of being handled by lipophilicity

3 capsule walls, 10 transparency electrodes

11 adhesive resin layers, 12 microcapsules

13 in opposite directions substrate 14 cells form sheet material

Embodiment

Below, with regard to each detailed description of the invention embodiments of the present invention.

Electrophoresis showed of the present invention is made of with liquid each electrophoresis showed that forms the 1st invention～the 3 invention with liquid.Specifically, the electrophoresis showed of this 1st invention is characterised in that with liquid, it contains the alkyl, polyether amine that has at least with structural unit shown in the following general formula (I), a kind or multiple particulate, spreading agent and dispersion liquid medium, and above-mentioned particulate contains the particulate of being handled by the lipophilic surface.

[in the above-mentioned formula (I), R ₁Be saturated hydrocarbyl or unsaturated alkyl, R ₂Be (OCH ₂CH ₂) x-H, R ₃Be (OCH ₂CH ₂) y-H, x, y are positive number.]

And the electrophoresis showed of this 2nd invention is characterised in that with liquid, and it contains the alkyl, polyether amine that has at least with structural unit shown in the following general formula (I), has the polyoxyethylene propylene oxide block polymer with structural unit shown in the following general formula (II), a kind or multiple particulate and dispersion liquid medium.Electrophoresis showed of this 3rd invention is characterised in that with liquid, and it further contains the acetylene-derivative that has with structural unit shown in the following general formula (III) in the above-mentioned the 2nd electrophoresis showed of inventing in liquid.

OH(C ₂H ₄O)p(C ₃H ₆O)qH (II)

[in the above-mentioned formula (II), p, q are positive number.]

[in the above-mentioned formula (III), R ₄And R ₅Be saturated hydrocarbyl or unsaturated alkyl, R ₆Be OCH ₂CH (CH ₃)-or (OCH ₂CH ₂) m-OH.R ₇Be OCH ₂CH (CH ₃)-or (OCH ₂CH ₂) n-OH.M, n are 0 or positive number.Above-mentioned R ₆And R ₇Can be the same or different.]

Employed alkyl, polyether amine is mainly as charge control agent in this 1st invention～the 3 invention, so long as the material of representing with structural formula shown in the above-mentioned general formula (I) gets final product, can list for example polyglycol lauryl amine, polyalkylene glycol alkyl (coconut palm) amine, polyglycol stearmide, polyalkylene glycol alkyl (tallow) amine, hydroxyethyl lauryl amine, polyalkylene glycol alkyl (deer fat) amine, polyalkylene glycol alkyl (suet) amine etc., so long as the material that is dissolved at least in the used dispersion liquid medium gets final product, be not limited to above-mentioned substance.

When using the alkyl, polyether amine be not included in the above-mentioned general formula (I) etc., the contrast of display surface reliability low, that show repeatedly is also low, response is also poor etc., so not preferred.

In addition, used alkyl, polyether amine can be distinguished separately, and (a kind) uses, also can make up two or more uses, suitably determine content according to its kind, but the preferred particulate of being handled by lipophilicity with respect to the surface of aftermentioned the 1st invention, perhaps, contain 1.0～200 weight % (following only be called " % "), more preferably 10～150% with respect to the particulate of the 2nd and the 3rd invention.

The content of this alkyl, polyether amine; if handle the particulate less than 1.0% of particulate or the 2nd invention, the 3rd invention with respect to the lipophilic surface of the 1st invention, then the effect of alkyl, polyether amine not have to embody, the contrast reliability low, demonstration repeatedly of display surface is also low, yet variation of response.On the other hand; surpass 200% if handle particulate or particulate with respect to the lipophilic surface, then since the electric conductivity of solvent rise, therefore reduced particulate move and contrast shows; and become owing to electrolysis etc. causes the key element of electrophoresis showed with the liquid autoclasia, so not preferred.

As employed particulate in this 1st invention～the 3 invention, can use the inorganic pigment particles, organic pigment particles, high molecular particle of for example coloured or colourless (white) etc., these can distinguish (a kind) use separately, perhaps mix two or more and use.

In this 1st invention, viewpoint from performance effect of the present invention, in used above-mentioned particulate, must contain the particulate of being handled by the lipophilic surface at least, if contain at least a kind of particulate of being handled by the lipophilic surface, except this particulate of being handled by the lipophilic surface, can also contain not by surface-treated particulate (inorganic pigment particles of coloured or colourless (white), organic pigment particles, high molecular particle etc.).

In this 1st invention, when not using the particulate of being handled by the lipophilic surface, show repeatedly and bad response that the stability of solution also reduces, and can not bring into play effect of the present invention.

And in this 2nd invention and the 3rd is invented, even if the particulate of being handled by the lipophilic surface not as described later, also can be brought into play effect of the present invention.

In this 1st invention～the 3 invention, above-mentioned " pigment particles " be meant with as the combination of the solvent of dispersion liquid medium in to the low and material that in solvent, can exist of dissolubility of solvent with the particle state that disperses.

As the inorganic pigment particles that can use, can list for example titania, zinc sulphide, lime carbonate, silicon dioxide, calcium silicate, white lead, zinc paste, lithopone, antimony oxide, porcelain earth, mica, barium sulphate, gloss white, alumina white, talcum, cadmium yellow, cadmium lithopone Huang, yellow iron oxide, titan yellow, the titanium baryta yellow, cadmium orange, cadmium lithopone orange, the molybdate orange, iron oxide red, lead orthoplumbate, vermilion, cadmium red, the cadmium lithopone is red, umber, brown iron oxide, zinc-iron, the chromium palm fibre, chrome green, chromium oxide, chrome green, cobalt green, turkey blue, cobalt titanate green, Prussian blue, cobalt blue, ultramarine, peace is blue in the match fine jade, cobalt aluminium chrome blue, cobalt violet, mineral violet, carbon black, iron black, the ferromanganese hydrochlorate is black, the ferro-cobalt hydrochlorate is black, copper-chrome black, copper chromium manganese black, black is titanium dioxide at a low price, aluminium powder, copper powder, lead powder, glass putty, zinc powder etc.

As operable organic pigment particles, can list for example permanent yellow, two diazonium Huangs, the condensation azophosphine, the naphthazine Huang, the isoindoline Huang, copper azomethine Huang, the quinophthalone Huang, the benzimidazolone Huang, nickel dioxime Huang, the yellow color lake of monoazo, dinitro aniline orange, pyrazolone orange, purple cyclic ketones orange, naphthol reds, toluidine red, permanent carmine, bright solid scarlet, pyrazolone red, the rhodamine 6G color lake, permanent red, lithol red, nation's C lake red CAN'T, C lake red CAN'T, bright famille rose, purplish red 10B, naphthol reds, quinoline a word used for translation ketone is deep red red, the condensation azophloxine, the naphthols famille rose, perylene scarlet, the condensation azo is scarlet, the benzimidazolone famille rose, the red perylene chestnut of the red perylene of anthraquinone, quinoline a word used for translation ketone chestnut, quinoline a word used for translation ketone is scarlet, quinoline a word used for translation ketone is red, diketopyrrolopyrrolecocrystals is red, the benzimidazolone palm fibre, phthalocyanine green, the Victoria blue color lake, phthalocyanine blue, solid forever sky blue, the alkali blue toner, indanthrene, rhodamine B lake, methyl violet color lake dioxazine violet, naphthols purple etc.

As operable high molecular particle, can use the formed high molecular particle of organic polymer that makes by by known method in the past, can list and for example utilize method of emulsion polymerization, the crystal seed emulsion polymerization, the emulsifier-free polymerization, dispersion copolymerization method, suspension polymerization, the crystal seed polymerization, utilize the method for crystal seed polymerization+polymerization shrinkage, method by the suspension polymerization of W/O/W emulsion mediation, utilize the method for the dry tack free of spray drying drop, by adding the crystal seed agglutination etc. that the electrolyte solids make the polymer emulsion aggegation, but be not limited to the material that makes by these methods.

As the material of high molecular particle, can the material of known polymeric material uses in the combination that is not dissolved in the transparent dispersion medium of using as electrophoresis showed with being selected from the past.As these examples, can list polystyrene, styrene-propene acid system, styrene-isoprene system, the divinyl benzene series, methyl methacrylate system, methacrylate ester, Jia Jibingxisuanyizhi system, ethyl acrylate system, n-butyl acrylate system, acrylic acid series, acrylic, acrylic rubber-methacrylate ester, ethene system, ethylene-acrylic acid system, nylon system, silicone-based, urethane system, melamine system, benzo guanamine system, phenol system, fluorine (zellon) is, vinylidene chloride, season pyridiniujm system, synthetic rubber, cellulose, cellulose acetate, shitosan, polymeric materials such as calcium alginate and by these polymeric materials being carried out the crosslinked polymeric material that the solvent resistance function is increased, the material that particularly contains cross-linked acrylic acid in the composition and be resin considers it is preferred from the solvent resistance aspect, but is not limited to these polymeric materials.

These high molecular particles can be by the particulate after dyestuff and the pigment coloring by known method, can list the method for for example before the synthetic high polymer particulate, using said method to make the painted back of monomer, in the manufacturing of high molecular particle, carry out method of colouring, carry out method of colouring etc. behind the manufacturing high molecular particle.

As other method, can also be in by the above-mentioned polymeric material that is synthesized in advance after physics disperse dyes, the pigment etc., pulverize until reaching desirable particle size and obtain,, be not limited to the material that obtains by these means as the high molecular particle that is colored.

In the present invention, the employed particulate of being handled by the lipophilic surface is to use lipophilic surface's treating agent etc. that the surface element of above-mentioned various particulates [coloured or colourless (white) inorganic pigment particles, organic pigment particles, high molecular particle etc.] has been carried out the particulate of handling.

As lipophilic surface's treating agent, can list for example coupling agent, pigment derivative, lipophilic surfactant etc., consider from dispersed, mobile aspect, especially preferably use coupling agent.

As the coupling agent that can use, for example can listing, silane series coupling agent, titanate esters are that coupling agent, aluminium are that coupling agent, zirconium are that coupling agent, zircoaluminate are that coupling agent, chromium are coupling agent, fluorine is a coupling agent etc. in addition.

As these various coupling agents, can list for example following material, but be not limited to these materials.

As titanate esters is coupling agent; can list for example isopropyl three isostearoyl titanate esters; isopropyl three stearoyl titanate esters; isopropyl three decoyl titanate esters; isopropyl dimethyl propylene thiazolinyl isostearoyl titanate esters; isopropyl three (dodecyl benzenesulfonyl) titanate esters; isopropyl stearoyl two propylene titanate esters; isopropyl three (dioctyl phosphate) titanate esters; isopropyl three cumyl benzene titanate esters; isopropyl three (dioctylphyrophosphoric acid ester) titanate esters; isopropyl three (positive amino-ethyl-amino-ethyl) titanate esters; two (dioctyl phosphite ester) titanate esters of tetra isopropyl; two (double tridecyl phosphite ester) titanate esters of four octyl groups; four (2; 2-two allyloxy methyl isophthalic acid-butyl) two (double tridecyl) phosphite ester titanate esters; dicumyl phenoxyethanoic acid ester titanate esters; two (dioctylphyrophosphoric acid ester) hydroxacetic acid ester titanate; two iso stearate ethene titanate esters; two (dioctylphyrophosphoric acid ester) ethene titanate esters; two (dioctylphyrophosphoric acid ester) diisopropyl titanate esters; positive metatitanic acid tetramethyl ester; positive tetraethyl titanate; positive metatitanic acid orthocarbonate; positive metatitanic acid tetra isopropyl tetra-ethyl ester; tetrabutyl titanate; poly(tributoxy titanium); positive metatitanic acid four isobutyl esters; 2-ethylhexyl titanate esters; the stearoyl titanate esters; tolyl titanate esters monomer; tolyl titanate esters polymkeric substance; diisopropoxy-two-(2, the 4-acetylacetonate) titanium (IV); diisopropyl-two-triethanolamine base titanate esters; the ethohexadiol titanate esters; lactic acid titanium ester; the acetoacetic ester titanate; two (diacetone dentate) titaniums of diisopropoxy; two (the three aluminium ethylate dentates) titaniums of two n-butoxies; dihydroxy lactyl-lactic acid dentate titanium; titanium-isopropoxy ethohexadiol acid esters; four n-butoxy titanium polymers; the tri-n-butoxytitanium monostearate polymkeric substance; butyltitanate dimer; the acetylacetonate titanium; poly-titanium acetylacetonate titanium; titanium ethohexadiol acid esters; titanium lactate salt ammonium salt; the ethyl lactate titanium; ammonification three titanium ethanolates; poly-hydroxyl titanium stearate etc.

As aluminium is coupling agent, can list for example acetyl group aluminum alkoxide diiso propoxide etc.

As silane series coupling agent, can list for example 3-aminopropyltriethoxywerene werene, 3-aminopropyl methyldiethoxysilane, 3-urea groups propyl-triethoxysilicane, 3-urea groups propyl trimethoxy silicane, the 3-TSL 8330,3-aminopropyl-3 (2-methoxyl-ethoxy-ethoxy) silane, N-methyl-3-TSL 8330, N-amino-ethyl-3-aminopropyl-trimethoxy silane, diamino silanes, N-amino-ethyl-3-aminopropyl methyl dimethoxysilane, triamido propyl group-trimethoxy silane, 3-amino-4,5-glyoxalidine propyl-triethoxysilicane, the 3-methacryloxypropyl trimethoxy silane, the 3-glycidoxypropyltrime,hoxysilane, 3-sulfydryl propyl-triethoxysilicane, 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl group methyl dimethoxysilane, the 3-chloropropyl triethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-chloropropylmethyldimethoxysilane, 3-cyano group propyl-triethoxysilicane, vinyl trichlorosilane, vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) silane, hexamethyldisilazane, N, two (trimethyl silyl) acetamides of O-, methyltrimethoxy silane, methyl triethoxysilane, ethyl trichlorosilane, the n-pro-pyl trimethoxy silane, the isobutyl trimethoxy silane, the amyl group trichlorosilane, octyltri-ethoxysilane, vinyl three ('beta '-methoxy ethoxy) silane, γ-methacryloxypropyl trimethoxy silane, N-β-(amino-ethyl) gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, N-phenyl-γ G-TSL 8330, phenyltrimethoxysila,e, phenyl triethoxysilane, methyl three (methacryloxy ethoxy) silane, methyl three (glycidoxypropyl) silane, the chain alkyl triethoxysilane, the tetramethylsilane hydrochlorate, tetraethyl-metasilicate, vinyl three (2-methoxy ethoxy) silane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, the 3-methacryloxypropyl trimethoxy silane, γ-(2-amino-ethyl) aminopropyl methyl dimethoxysilane.

In addition, also can list N-β-(N-vinyl benzyl amino-ethyl)-gamma-amino propyl trimethoxy silicane hydrochloride, vinyltriacetoxy silane, γ-anilino-propyl trimethoxy silicane, octadecyl dimethyl [3-(trimethoxysilyl) propyl group] ammonium chloride, γ-chloropropyl dimethyl dichlorosilane (DMCS), γ-methacryloxypropyl methyl dimethoxysilane, the trimethyl methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, tetramethoxy-silicane, tetraethoxysilane, methyl dimethoxysilane, methyldiethoxysilane, dimethylethoxysilane, dimethyl vinyl methoxy silane, dimethyl vinyl Ethoxysilane, methyl ethylene dimethoxy silane, the methyl ethylene diethoxy silane, the diphenyl diethoxy silane, the diphenyl diethoxy silane, trimethyl chlorosilane, dimethyldichlorosilane, methyl trichlorosilane, dimethyl dichlorosilane (DMCS), dimethylchlorosilane, the dimethyl vinyl chlorosilane, the methyl ethylene dichlorosilane, the methyl chloride disilane, tri-phenyl chloride, methyldiphenyl base chlorosilane, diphenyl dichlorosilane, dichloromethyl phenylsilane, phenyl trichlorosilane, the CMDMCS chloromethyl dimethyl chlorosilane hexamethyldisilazane, ring-type silazane potpourri, N, two (trimethyl silyl) ureas of N-, N-trimethyl silyl acetamide, dimethyl trimethyl silyl amine, diethyl trimethyl silyl amine, trimethyl-silyl-imidazole, N-trimethyl silyl phenylurea etc.

As zirconium is coupling agent, can list butylation zirconium, zirconium acetylacetonate, diacetone butylation zirconium, zirconium lactate, stearic acid butylation zirconium, four (triethanolamine) zirconate, tetra isopropyl zirconate etc.

As zirconium aluminate is coupling agent, can list nanmu and originally change into the ProductName A that company produces, C, C-1, F, M, M-1, S, APG, CPG, CPM, FPM, MPG, MPM and tetrapropyl zirconium aluminate etc.

As chromium is coupling agent, can list the compound of methacrylic acid chromium and chromium chloride etc.

As fluorine is coupling agent, can list trifluoro propyl trimethoxy silane, 17 trifluoro decyl trimethoxy silanes etc.

For above-mentioned each coupling agent, except can distinguishing (a kind) use separately, can also mix the back use by a plurality of (two or more) coupling agent.And also can implement to use the processing of a plurality of coupling agents by stages.

In above-mentioned various coupling agents, preferred titanate esters is that coupling agent, aluminium are coupling agent, silane series coupling agent, and this is because shown excellent more effect when using these coupling agents.

The surface treatment of being undertaken by coupling agent etc. of this 1st invention, not only with inorganic series pigments as object, also can be with the high molecular particle of organic system material, for example organic polymer system and organic system pigment particles etc. as object.In these parent particles, also comprise can and coupling agent between carry out the also indefinite material of existence at the active reaction position (for example hydroxyl) of coupling reaction.But for this parent particle, as mentioned above, when implementing coupling processing by various coupling agents, the character of surface of parent particle also can change along with the difference of coupling agent.

Its reason thinks, even if when reaction active groups does not exist, by coupling agent at the absorption of parent particle Surface Physical or dipping to the surface, also can realize the variation of character of surface.The so-called processing of being undertaken by coupling agent of the present invention also comprises the variation of above-mentioned character of surface.

Among the present invention,, can list ITT-2 TiO particularly as the particulate of being handled by the lipophilic surface ₂CR-50 (titanium dioxide, the mean grain size that daylight Chemicals company produces, handled with titanium coupling agent on the surface are about 0.4 μ m), ITT-7 TiO ₂(daylight Chemicals company produces TTO-S-3, the particulate titanium dioxide that handled with titanium coupling agent on the surface, mean grain size is about 0.05～0.1 μ m), (titanium industrial group produces KR-380, the titanium dioxide that handled with lipophilic surface's treating agent on the surface, mean grain size is about 0.5 μ m), (titanium industrial group produces KR-270, the titanium dioxide that handled with lipophilic surface's treating agent on the surface, mean grain size is about 0.4 μ m), (the former industry of stone company produces with Tipaque CR-50, become the titanium dioxide of hydrophilic surface, mean grain size is about 0.4 μ m) (as aluminium is coupling agent with coupling agent, silane series coupling agent) particle of handling etc.

Figure 1 shows that the titanium oxide microparticle (ITT-2TiO that titania surface was handled with titanium coupling agent ₂CR-50).

In this 1st invention, the dispersiveness of dispersion medium and mobile viewpoint are considered from improving for the above-mentioned particulate of being handled by the lipophilic surface, special preferred surface functional group is the particulate of alkoxy carbonyl.In order to make this surface functionalities group have alkoxy carbonyl, for example can be undertaken by as described below, from three isostearic acid propyl ester titaniums, remove isopropyl, and titanium combines with the hydroxyl of powder surface as titanium coupling agent.

The various particulates of above-mentioned formation have been to use as the particulate of this 1st invention～the 3 invention, with with the relation of the display medium that is constituted, can use the material of various particle diameters, wherein from bringing into play display characteristic better, showing the viewpoint of the effect of Memorability and dispersion stabilization, preferred use mean grain size is the particulate of 0.05～20 μ m, is preferably the particulate that mean grain size is 0.1～10 μ m especially.

If the mean grain size deficiency of this particulate 0.05 μ m, then occur by particulate Brownian movement caused extends influence, and display characteristic descends, the aggegation tendency strengthens, so dispersed system becomes unstable.On the other hand,, then be easy to generate the sedimentation of particulate, become the essential factor that demonstration Memorability and dispersion stabilization are worsened if mean grain size surpasses 20 μ m.

Used particulate among the present invention, from the viewpoint of further performance effect of the present invention, the particulate of being handled by the lipophilic surface is with respect to the particulate total amount at least, preferably contain 10% or more than, more preferably contain 20～100%.

The total content of particulate is preferably 3～50% with respect to the electrophoresis disclosing solution total amount, and more preferably 5～35%.

This particulate contain quantity not sufficient 3%, then contrast shows the difficulty that becomes fully; If surpass 50% on the other hand, then cause interference between the particulate etc., translational speed and response speed reduce, and be therefore not preferred.

For example, when using white and deceiving 2 kinds of particulates, can be 3%～50% scope, and can carry out the mode of sufficient contrast black-and-white display that the ratio that changes the black and white particulate is used according to the total amount of two kinds of particles.

Spreading agent as in this 1st invention can use habitual various spreading agents, surfactant, high molecular surfactant.

Object lesson as the surfactant of spreading agent, can list following nonionic is that surfactant, negative ion are that surfactant, kation are that surfactant, both sexes are surfactant, high molecular type surfactant etc., but is not limited to these materials.

As nonionic is surfactant, polyoxyethylene thiazolinyl nonylphenyl ether is for example arranged, polyoxyethylene thiazolinyl dinonyl phenol ether, polyoxyethylene thiazolinyl octyl phenol ether, polyoxyethylene thiazolinyl styrenated phenol ether, the polyoxyethylene bisphenol-A, polyoxyethylene thiazolinyl nonylplenyl ether, polyoxyethylene octylphenyl ether, polyoxyalkylenes alkylphenol ethers such as nonyl phenol ethoxylate, polyoxyethylene thiazolinyl castor oil, the polyoxyalkylene block polymkeric substance, polyoxyethylene thiazolinyl cetyl ether, polyoxyethylene thiazolinyl lauryl ether, polyoxyethylene base oil ether, polyoxyethylene thiazolinyl octadecyl ether, the poly-polyoxyalkylene ethers that waits, the polyoxyalkylene diols of single pure type, the polyoxyalkylene diols of diol type, the polyoxyalkylene diols of triol type, single alcohol is the poly alkylene glycol of block type, glycol is the poly alkylene glycol of block type, glycolss such as the poly alkylene glycol of random, the octyl phenol ethoxylate, the oleyl alcohol ethoxylate, straight chain primary alcohol ethoxylate and linear secondary ethoxylates such as lauryl alcohol ethoxylate, alkylol ethers such as polynuclear phenol ethoxylate, polyoxyethylene thiazolinyl rosin ester, polyoxyethylene thiazolinyl lauryl, polyoxyethylene base oil ester, polyoxyalkylene alkyl esters such as polyoxyethylene thiazolinyl stearyl, Span-20, sorbitan monopalmitate, sorbitan monostearate, the sorbitan dilaurate, the sorbitan dipalmitate, the sorbitan distearate, sorbitan sesquialter laurate, sorbitan sesquialter palmitate, the sorbitan sesquistearate, sorbitan monooleate, the sorbitan dioleate, Span-83, sorbitan fatty acid ester classes such as sorbitan trioleate, the polyoxyethylene Span-20, the polyoxyethylene sorbitan monopalmitate, the polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan dilaurate, polyoxyethylene sorbitan dipalmitate, polyoxyethylene sorbitan distearate, polyoxyethylene sorbitan sesquialter laurate, polyoxyethylene sorbitan sesquialter palmitate, polyoxyethylene sorbitan ester classes such as polyoxyethylene sorbitan sesquistearate, saturated fatty acid methyl ester, the unsaturated fatty acid methyl esters, the saturated fat acid butyl ester, the unsaturated fat acid butyl ester, the saturated fatty acid stearyl, the unsaturated fatty acid stearyl, the saturated fatty acid monooctyl ester, the unsaturated fatty acid monooctyl ester, the stearic acid macrogol ester, the oleic acid macrogol ester, fatty acid esters such as polyglycol ester abietate, stearic acid, oleic acid, palmitic acid, lauric acid, the amide compound class of fatty acids such as myristic acid and these fatty acid, lauric monoethanolamide, senior fatty monoethanol amide classes such as coconut fatty acid diglycollic amide, higher fatty acid diglycollic amide class, the polyoxyethylene stearic amide, coconut diethanolamide (1-2 type/1-1 type), amide compound class and alkanolamide classes such as alkyl-alkyl alkylolamides.

In addition, can also list (CH with R- ₂CH ₂O) mH (CH ₂CH ₂O) nH, R-NH-C ₃H ₆-NH ₂[R=oil base, octyl group, dodecyl, myristyl, cetyl, octadecyl etc. or the higher fatty acid that obtains from coconut, tallow, soybean etc.] represented alkanol amine is with R-NH ₂[R=oil base, octyl group, dodecyl, myristyl, cetyl, octadecyl etc. or from coconut, tallow, the higher fatty acid that soybean etc. obtain] represented primary amine class, with R1R2-NH[R1 and R2 is oil base, octyl group, dodecyl, myristyl, cetyl, octadecyl etc. or from coconut, tallow, the higher fatty acid that soybean etc. obtain] represented secondary amine class, with R1R2R3-N[R1, R2 and R3 are oil base, octyl group, dodecyl, myristyl, cetyl, octadecyl etc. or from coconut, tallow, the higher fatty acid that soybean etc. obtain] represented tertiary amines, various synthesizing is higher alcohols and various natural series higher alcohols etc.

As negative ion is surfactant, can list for example special fatty acid soap, metal carboxylates such as rosin soap, the castor oil sulfuric acid, the sulfuric ester sodium salt of lauryl alcohol, the sulfuric ester amine salt of lauryl alcohol, natural alcohol sulfuric ester sodium salt, alcohol such as higher alcohol sulfate sodium salt are the sulfuric ester amine salt of sulfuric ester salt and lauryl alcohol, the sulfuric ester sodium salt of lauryl alcohol, the sulfuric ester amine salt of synthetic senior alcohol ether, the sulfuric ester sodium salt of synthetic senior alcohol ether, alkyl, polyether sulfuric ester amine salt, alkyl, polyether sulfuric ester sodium salt, natural alcohol EO (oxirane) adds architectonical sulfuric ester amine salt, natural alcohol EO (oxirane) adds architectonical sodium sulfovinate salt, synthol EO (oxirane) adds architectonical sulfuric ester amine salt, synthol EO (oxirane) adds architectonical sodium sulfovinate salt, alkylphenol EO (oxirane) adds architectonical sulfuric ester amine salt, alkylphenol EO (oxirane) adds architectonical sodium sulfovinate salt, polyoxyethylene thiazolinyl nonylplenyl ether sulfuric ester amine salt, polyoxyethylene thiazolinyl nonylplenyl ether sulfuric ester sodium salt, polyoxyethylene Quito ring phenyl ether sulfuric ester amine salt, sulfuric ester salts such as polyoxyethylene Quito ring phenyl ether sulfuric ester sodium salt, various alkyl allyl sulphonic acid amine salt, various alkyl allyl sulphonic acid sodium salts, the naphthalene sulfonic acids amine salt, naphthalene sulfonate salt, various benzene sulfonamide amine acid salts, various alkyl benzene sulphonate sodium salts, Sulfonateses such as naphthalene sulfonic acid condensate, polyoxyethylene thiazolinyl nonylplenyl ether sulfonic amine salt, polyoxyethylene thiazolinyl nonylplenyl ether sulfonate sodium, the special allyl ether sulfonic amine salt of polyoxyethylene thiazolinyl, the special allyl ether sulfonate sodium of polyoxyethylene thiazolinyl, polyoxyethylene thiazolinyl tridane base ether sulfonic acid amine salt, polyoxyethylene thiazolinyl tridane base ether sulfonic acid sodium salt, polyoxyethylene thiazolinyl alkyl ether sulfonic amine salt, polyoxyalkylenes such as polyoxyethylene thiazolinyl alkyl ether sulfonate sodium are Sulfonates, dialkyl sulfosuccinate succinate amine salt, dialkyl sulfosuccinate succinate sodium salt, many ring phenyl polyethoxy sulfosuccinate amine salt, many ring phenyl polyethoxy sulfosuccinic acid ester sodium salts, polyoxyethylene thiazolinyl alkyl ether sulfosuccinic acid monoesters amine salt, sulfosuccinate ester salt classes such as polyoxyethylene thiazolinyl alkyl ether sulfosuccinic acid monoesters sodium salt, alkyl phosphate, the alkoxyalkyl phosphate, high alcohol phosphate, higher alcohol phosphate, alkylphenol type phosphate, aromatic phosphoric ester, the polyoxyalkylene alkyl phosphate, phosphoric acid esters such as polyoxyalkylene alkyl allyl ether phosphate and phosphoric acid salt etc.

As kation is surfactant, can list for example with R-N (CH ₃) ₃X[R=octadecyl, cetyl, lauryl, oil base, dodecyl, coconut, soybean, tallow etc./X is halogen, amine etc.] represented alkyl trimethyl amine is that quaternary ammonium salt, tetramethyl amine are quaternary ammonium salts such as salt, tetrabutyl amine salt, with (RNH ₃) (CH ₃COO) [R=octadecyl, cetyl, lauryl, oil base, dodecyl, coconut, soybean, tallow etc.] represented acetic acid salt, lauryl dimethyl benzyl ammonium salt (halogen, amine salt etc.), octadecyl dimethyl benzyl ammonium salt (halogen, amine salt etc.), dodecyl dimethyl benzyl ammonium salt benzyl amine such as (halogen, amine salt etc.) are quaternary ammonium salt, with R (CH ₃) N (C ₂H ₄O) mH (C ₂H ₄O) nX[R=octadecyl, cetyl, lauryl, oil base, dodecyl, coconut, soybean, tallow etc./X is halogen, amine etc.] represented polyoxyalkylene is quaternary ammonium salt etc.

As both sexes is surfactant, and can list for example various betaine type amphoteric surfactants, various imidazoline is surfactant, Beta-alanine type surfactant, the poly-amino-ethyl glycine hydrochloride of poly-octyl group etc.

Operable in the present invention high molecular type surfactant, with respect to molecular weight (number-average molecular weight, following identical) is low molecular weight substance about hundreds of, be the big polymkeric substance of molecular weight, except contain be commonly referred to as macromolecule (polymkeric substance) and molecular weight be about 10000 or above polymkeric substance, also comprise molecular weight and be 10000 or following and be commonly referred to as the low polymer of oligomer.

As high molecular type surfactant, can list following negative ion is that high molecular type surfactant, kation are that high molecular type surfactant, nonionic are high molecular type surfactant etc.

As negative ion is high molecular type surfactant, can list formaldehyde condensation products, polyacrylic acid sodium carbonate, polyocarboxy acid type anion active agent, polyacrylic acid amide partial hydrolystate, acrylamide acrylic acid sodium carbonate multipolymer, alginic acid sodium carbonate of for example styrene-maleic anhydride copolymer, alkene copolymer-maleic anhydride, naphthalenesulfonate condensation compound, naphthalene sulfonate etc.

As kation is high molecular type surfactant, can list for example polyethyleneimine, polyvinyl imidazole quinoline ketone, aminoalkyl (methyl) acrylate-acrylamide copolymer, polyacrylic acid amide Mannich modifier, shitosan etc.

As nonionic is high molecular type surfactant, can list the oligomer modifier, poly-hydroxy fatty acid, poly-hydroxy fatty acid modifier, poly--1 of oligomer, the hydroxy fatty acid of multipolymer, polyacrylamide, polycarboxylic-acid compound, the hydroxy fatty acid of for example polyvinyl alcohol (PVA), polyoxyethylene ether-ether, the hard ester acid of 2-hydroxyl, N-polyoxyalkylene polyene polyamine, starch etc.

In the spreading agent of the present invention, preferably especially use the positive negative charging that is difficult to microparticle surfaces to produce harmful effect, electrophoresis showed also be difficult to produce dysgenic nonionic system when wrapping in microcapsules in the liquid or negative ion is a surfactant, nonionic is or negative ion is a high molecular surfactant.

These spreading agents can use a kind, also can make up two or more and use, and its content is suitably determined by used particulate, solvent species, still, with respect to the electrophoresis disclosing solution total amount, is preferably 0.01～50.0% especially, and more preferably 1～30%.

If this spreading agent contain quantity not sufficient 0.01%, then be difficult to guarantee the sufficient dispersion stabilization of disperse system; On the other hand, if surpass 50%, then the electric conductivity of dispersion liquid medium uprise, the viscosity increased of disperse system etc., display characteristic is produced harmful effect, so not preferred.

As operable dispersion liquid medium among the present invention, for example can use usually employed various types of materials in the electrophoresis showed.

Specifically, as fragrant family hydrocarbon, can list benzene, toluene, dimethylbenzene, ethylbenzene, benzene derivatives such as dodecyl benzene, phenyl xylyl ethane, 1,1-xylyl ethane, 1,2-xylyl ethane, 1,2-two (3,4-3,5-dimethylphenyl ethane) (BDMF) wait diallyl chain alkane derivatives, alkyl naphthalene derivants such as diisopropyl naphthalene, single isopropyl biphenyl, isopropyl biphenyl, alkyl biphenyl derivants such as isopentyl biphenyl, with various ratio hydrogenations the terphenyl derivant, triallyl bismethane derivants such as dibenzyl toluene, the benzyl naphthalene derivant, the phenylene oxide derivant, the diallyl alkylene derivative, the allyl indan derivative, the polybiphenyl derivant, naphthene series hydrocarbon etc.

In addition; can also list hexane; cyclohexane; kerosene; isopar; aliphatic hydrocarbons such as paraffin series hydrocarbon; chloroform; triclene; zellon; trifluoro-ethylene; tetrafluoroethene; methylene chloride; halogenated hydrocarbons such as bromoethane; tricresyl phosphate; trioctyl phosphate; octyl diphenyl phosphate; phosphoric acid esters such as tricyclohexyl phosphate; dibutyl phthalate; dioctyl phthalate; dilauryl phthalate; phthalates such as dicyclohexyl phthalate; butyl oleate; the diethylene glycol dibenzoate; di-n-octyl sebacate; dibutyl sebacate; dioctyl adipate; trioctyl trimellitate; citric acid acetyl group triethyl; the maleic acid monooctyl ester; dibutyl maleate; carboxylic acid esters such as ethyl acetate; chlorinated paraffin; N; N-dibutyl-2-butoxy-uncle's 5-octyl group aniline etc., but be not limited to these materials.

And, in the present invention, can distinguish and use these dispersion liquid media separately, perhaps they are mixed two or more and use.Dispersion medium especially preferably uses the solvent of specific inductive capacity low (5.0 or following), preferably selects according to the mode identical with the proportion of particulate.

The content of these dispersion liquid media suitably determines according to used particulate and spreading agent kind, is 25～85% with respect to the electrophoresis disclosing solution total amount especially preferably, more preferably 30～60%.

If this dispersion liquid medium contain quantity not sufficient 25%, then the viscosity of solution uprises, response speed descends; On the other hand, if surpass 85%, then can not show sufficient contrast, so not preferred.

Among the present invention, can dissolve various oil-soluble dyes to above-mentioned dispersion liquid medium and carry out painted the use.At this moment, as operable dyestuff, can list following substances, but the present invention is not limited to these materials.

As operable dyestuff, its representative for example can list spirit black (SB, SSBB, AB), nigrosine (SA, SAP, SAPL, EE, EEL, EX, EXBP, EB), oil yellow (105,107,129,3G, GGS), the oil orange (201, PS, PR), solid forever orange, oil red (5B, RR, OG), oil is scarlet, oil-bound distemper red 312, the purple #730 of oil, transparent blue RR, fluorescence green G, oil palm (GR, 416), sudan black X60, glossy dark green (502, BG), oil blue (613,2N, BOS), glossy black (HBB, 860, BS), Oil Yellow (1101,1105,3108,4120), the molten orange (3209 of oil, 3210), oil red (1306,1355,2303,3304,3306,3320), the molten pink 2310N of oil, typophor brown (2402,3405), solvent blue (3405,1501,1603,1605,1607,2606,2610), Oil Violet (1701,1702), nigrosine (1802,1807,3804,3810,3820,3830) etc.

These dyestuffs are preferably selected and can be used with the material that used particulate compares the color of demonstration, also can use two or more to carry out the color adjustment.

The electrophoresis showed of this 1st invention contains the alkyl, polyether amine that has at least with structural unit shown in the above-mentioned general formula (I), above-mentioned a kind or multiple particulate, spreading agent and dispersion liquid medium with liquid, and above-mentioned particulate contains the particulate of being handled by the lipophilic surface, in the scope of not damaging effect of the present invention, can contain any composition that is useful on electrophoresis showed usefulness liquid in right amount.

Any composition as using can list ultraviolet light absorber, antioxidant, light stabilizer, thermal stabilizer, antibacterial mildew inhibitor etc.

Electrophoresis showed of this 1st invention can prepare by carrying out following processing with liquid: after above-mentioned a kind or multiple particulate, spreading agent and the dispersion liquid medium that will have alkyl, polyether amine with structural unit shown in the above-mentioned general formula (I) at least, contains the particulate handled by the lipophilic surface mixes stirring, use no medium process for dispersing, wet type ball mill etc. such as ultrasonic dispersing to use the process for dispersing etc. of medium to carry out various dispersion treatment, thereby make.In addition, as required, in order to control the granularity of particulate, the classification that can also practice the centrifuging principle handles, carry out the method that granularity is adjusted with filtration method etc.

The electrophoresis showed of basis the 1st invention that constitutes like this is with in the liquid, contain the alkyl, polyether amine that has at least with structural unit shown in the above-mentioned general formula (I), a kind or multiple particulate, spreading agent and dispersion liquid medium, and above-mentioned particulate contains the particulate of being handled by the lipophilic surface, by using such material, the contrast height of display surface can be provided, also can compare the also excellent material of demonstration, response when showing repeatedly with high reliability.

Electrophoresis showed of this 2nd invention is characterised in that with liquid it contains the alkyl, polyether amine that has at least with structural unit shown in the above-mentioned general formula (I), has the polyoxyethylene propylene oxide block polymer with above-mentioned general formula (II) institute formula structural unit, a kind or multiple particulate and dispersion liquid medium.

OH(C ₂H ₄O)p(C ₃H ₆O)qH (II)

[in the above-mentioned formula (II), p, q are positive number]

The material that the employed polyoxyethylene propylene oxide block polymer dispersiveness that is particulate in this 2nd invention, electrophoresis showed increase with the ageing stability of liquid, so long as the material of representing with structural formula shown in the above-mentioned general formula (II) gets final product, from dissolubility to the low-k solvent, preferred mean molecular weight is 1000～4000 polyoxyethylene propylene oxide block polymer, more preferably the amount of ethylene oxide in the polyoxyethylene propylene oxide block polymer is 50 weight % or following, and special optimization ethylene oxide amount is 5～30 weight %.

Specifically, as operable polyoxyethylene propylene oxide block polymer, (mean molecular weight is 1250 can to list the Pronon 102 that Nof Corp. produces, amount of ethylene oxide is 20 weight %), (mean molecular weight is 1670 to Pronon 104, amount of ethylene oxide is 40 weight %), (mean molecular weight is 2220 to Pronon 201, amount of ethylene oxide is 10 weight %), (mean molecular weight is 3300 to Pronon 204, amount of ethylene oxide is 40 weight %), (mean molecular weight is 10000 to Pronon 208, amount of ethylene oxide is 80 weight %) etc. among at least a kind (a kind, two or more), so long as the material that is dissolved at least in the dispersion medium gets final product, be not limited to these.

The content of these polyoxyethylene propylene oxide block polymers is preferably 0.01～30% with respect to showing the liquid total amount, and more preferably 0.01～10%.

If this polyoxyethylene propylene oxide block polymer contain quantity not sufficient 0.01%, then the dispersiveness of particulate descends, electrophoresis showed is with the ageing stability variation of liquid; On the other hand, if surpass 30%, then display performances such as contrast are produced harmful effect, so not preferred.

The electrophoresis showed of this 2nd invention electrophoresis showed liquid phase ratio of liquid and above-mentioned the 1st invention, owing to used the polyoxyethylene propylene oxide block polymer of above-mentioned characteristic, the material that therefore can use a kind or multiple particulate not handled by the lipophilic surface, even do not use spreading agent, also can bring into play effect of the present invention.

Except the polyoxyethylene propylene oxide block polymer of above-mentioned characteristic, electrophoresis showed of this 2nd invention has alkyl, polyether amine with structural unit shown in the above-mentioned general formula (I), a kind or multiple particulate, dispersion liquid medium, spreading agent, surfactant or high molecular type surfactant, colorant (dyestuff) and waits each composition and each content and the above-mentioned the 1st electrophoresis showed of inventing to use in the liquid used each composition identical with employed in the liquid, so omits its explanation.In this 2nd invention,, the particulate of being handled by the lipophilic surface can be used, spreading agent can also be contained in addition as optimal way.

Electrophoresis showed of this 2nd invention contains the alkyl, polyether amine that has at least with structural unit shown in the above-mentioned general formula (I), has the polyoxyethylene propylene oxide block polymer with above-mentioned general formula (II) institute formula structural unit, a kind or multiple particulate and dispersion liquid medium with liquid, in the scope of not damaging effect of the present invention, can contain any composition that is useful in the electrophoresis showed usefulness liquid in right amount.

Any composition as using can list ultraviolet light absorber, antioxidant, light stabilizer, thermal stabilizer, antibacterial mildew inhibitor etc.

Electrophoresis showed of this 2nd invention can prepare by carrying out following processing with liquid: will have alkyl, polyether amine with structural unit shown in the above-mentioned general formula (I) at least, have polyoxyethylene propylene oxide block polymer with above-mentioned general formula (II) institute formula structural unit, after a kind or multiple particulate and dispersion liquid medium mix stirring, use no medium process for dispersing, wet type ball mill etc. such as ultrasonic dispersing to use the process for dispersing etc. of medium to carry out various dispersion treatment, thereby make.In addition, as required, in order to control the granularity of particulate, the classification that can also practice the centrifuging principle is handled, is carried out the method that granularity is adjusted with filtration method.

The electrophoresis showed of basis the 2nd invention that constitutes like this is with containing the alkyl, polyether amine that has at least with structural unit shown in the above-mentioned general formula (I) in the liquid, having the polyoxyethylene propylene oxide block polymer with above-mentioned general formula (II) institute formula structural unit, a kind or multiple particulate and dispersion liquid medium, by using such material, the contrast height of display surface can be provided, also can compare the also excellent material of demonstration, response when showing repeatedly with high reliability.

Electrophoresis showed of this 3rd invention is characterised in that with liquid, and it contains the alkyl, polyether amine that has at least with structural unit shown in the above-mentioned general formula (I), have polyoxyethylene propylene oxide block polymer with structural unit shown in the above-mentioned general formula (II), have the acetylene-derivative with structural unit shown in the following general formula (III), a kind or multiple particulate and dispersion liquid medium.

[in the above-mentioned formula (III), R ₄And R ₅Be saturated hydrocarbyl or unsaturated alkyl, R ₆Be OCH ₂CH (CH ₃)-or (OCH ₂CH ₂) m-OH.R ₇Be OCH ₂CH (CH ₃)-or (OCH ₂CH ₂) n-OH.M, n are 0 or positive number.Above-mentioned R ₆And R ₇Can be the same or different.]

The acetylene-derivative that uses in this 3rd invention material that to be electrophoresis showed increase with the durability and the reliability of liquid so long as the material of representing with structural formula shown in the above-mentioned general formula (III) gets final product, can list for example acetylenediol derivant [R ₄And R ₅Be isobutyl, R ₆And R ₇Be-OH base (m, n are 0)], the ethylene oxide adduct [R of acetylenediol derivant ₄And R ₅Be isobutyl, R ₆(OCH ₂CH ₂) m-OH and R ₇Be (OCH ₂CH ₂) n-OH, m, n are positive number], the propylene oxide adduct [R of acetylenediol derivant ₄And R ₅Be isobutyl, R ₆And R ₇Be (OCH ₂CHCH ₃-) and the potpourri of these derivants and organic solvent (ethylene glycol, dipropylene glycol monomethyl ether), these separately (a kind) use, perhaps mix two or more and use.

Specifically (comprise situation about using among the aftermentioned embodiment), can list commercially available Surfynol 104[acetylenediol derivant, R ₄And R ₅Be isobutyl, R ₆And R ₇For-OH base (m, n is 0), HLB is 4], the potpourri of Surfynol 104E[Surfynol 104 (50 weight %) and ethylene glycol (50 weight %), HLB is 4], the potpourri of Surfynol 104DPM[Surfynol104 (50 weight %) and dipropylene glycol monomethyl ether (50 weight %), HLB is 4], oxirane (20%) addition product of Surfynol 420[Surfynol 104, HLB be 4], SurfynolDF-110D[acetylenediol, HLB be 4], Olfin B[acetylene alcohol, HLB be 10 or following] (above produce for a day letter chemical industrial company) etc.

Preferably with the HLB of the acetylene-derivative shown in the above-mentioned general formula (III) be 10 or below, more preferably 2～5.By using this HLB is 10 or following acetylene-derivative, can further improve the compatibility of particulate to electrophoresis disclosing solution, and display characteristic becomes better repeatedly.

During acetylene-derivative not to be covered, not enough in using above-mentioned general formula (III) to the compatibility of electrophoresis disclosing solution, and not have to find fully repeatedly the effect of display characteristic raising, so not preferred.

The content of these acetylene-derivatives is preferably 0.01～10.0% with respect to showing the liquid total amount, and more preferably 0.05～5.0%.

If this acetylene-derivative contain quantity not sufficient 0.01%, then do not have the effect of finding fully that repeatedly display characteristic improves; On the other hand,, then cause the viscosity rising of electrophoresis disclosing solution etc., sometimes electrophoretic characteristic is produced harmful effect if surpass 10.0%.

Electrophoresis showed of this 3rd invention has further contained the acetylene-derivative of above-mentioned characteristic with the electrophoresis showed liquid phase ratio of liquid and above-mentioned the 2nd invention.

Except the acetylene-derivative of above-mentioned characteristic, electrophoresis showed of this 3rd invention with employedly in the liquid have alkyl, polyether amine, have polyoxyethylene propylene oxide block polymer with structural unit shown in the above-mentioned general formula (II) with structural unit shown in the above-mentioned general formula (I), a kind or multiple particulate, dispersion liquid medium, spreading agent, surfactant or high molecular type surfactant, colorant (dyestuff) wait each composition and each content and above-mentioned the 1st invention and the 2nd electrophoresis showed of inventing use in the liquid used each composition identical, so omit its explanation.In this 3rd invention,, the particulate of being handled by the lipophilic surface can be used, spreading agent can also be contained in addition as optimal way.

Electrophoresis showed of this 3rd invention contains the alkyl, polyether amine that has at least with structural unit shown in the above-mentioned general formula (I), has polyoxyethylene propylene oxide block polymer with above-mentioned general formula (II) institute formula structural unit, has the acetylene-derivative with structural unit shown in the above-mentioned general formula (III), a kind or multiple particulate and dispersion liquid medium with liquid, in the scope of not damaging effect of the present invention, can contain any composition that is useful in the electrophoresis showed usefulness liquid in right amount.

Any composition as using can list ultraviolet light absorber, antioxidant, light stabilizer, thermal stabilizer, antibacterial mildew inhibitor etc.

Electrophoresis showed of this 3rd invention can prepare by carrying out following processing with liquid: will have alkyl, polyether amine with structural unit shown in the above-mentioned general formula (I) at least, have polyoxyethylene propylene oxide block polymer with above-mentioned general formula (II) institute formula structural unit, have acetylene-derivative with structural unit shown in the above-mentioned general formula (III), after a kind or multiple particulate and dispersion liquid medium mix stirring, use no medium process for dispersing, wet type ball mill etc. such as ultrasonic dispersing to use the process for dispersing etc. of medium to carry out various dispersion treatment, thereby make.In addition, as required, in order to control the granularity of particulate, the classification that can also practice the centrifuging principle is handled, is carried out the method that granularity is adjusted with filtration method.

The electrophoresis showed of basis the 3rd invention that constitutes like this is with containing the alkyl, polyether amine that has at least with structural unit shown in the above-mentioned general formula (I) in the liquid, have polyoxyethylene propylene oxide block polymer with above-mentioned general formula (II) institute formula structural unit, having the acetylene-derivative with structural unit shown in the above-mentioned general formula (III), a kind or multiple particulate and dispersion liquid medium, by using such material, the contrast height of display surface can be provided, also can high reliability compare the also excellent material of demonstration, response when showing repeatedly.

In addition, electrophoresis showed of the present invention is characterised in that with medium the electrophoresis showed that above-mentioned the 1st invention～the 3 is invented each is enclosed in the body of independent structures separately of microcapsules or cell with liquid.

Fig. 2 and Fig. 3 are for being enclosed in electrophoresis showed simple grain subtype in the structure that is made of microcapsules and each embodiment of two corpuscular types with liquid.

Fig. 2 be for being colored as with oil-soluble dyes in the solution of black, and proportioning is dispersed with Titanium particles or the electrophoresis showed of the Titanium particles handled by lipophilicity has been carried out the material of microencapsulation with urea-formaldehyde resin with liquid according to the rules.Graphical sysmbol 1 is the white particle of positively charged (titanium dioxide), and 2 is black solvent, and 3 is capsule wall.

Fig. 3 for will be in dispersion medium with the regulation proportioning be dispersed with Titanium particles or reached by the Titanium particles that lipophilicity was handled in be surrounded by the acrylic acid series copolymer crosslinked particle of carbon black electrophoresis showed carried out the material of microencapsulation with urethane-urea resin with liquid, graphical sysmbol 4 is the white particle of positively charged (titanium dioxide), 5 are charged black particles not the acrylic acid series polymeric compounds crosslinked particle of carbon black (in be surrounded by), 6 are not painted solvent, and 7 is capsule wall.

Fig. 4～Fig. 6 is for being enclosed in each embodiment in the structure that is made of cell with electrophoresis showed with liquid, illustrated the pattern of each cell respectively.In addition, Fig. 7～Fig. 9 has illustrated the sectional view when disposing microcapsules or cell structure sheet material in opposite directions between electrode respectively, among Fig. 7～Fig. 9, graphical sysmbol 10 is a transparency electrode, 11 is adhesive resin layer, 12 is microcapsules, and 13 are substrate in opposite directions, and 14 is that cell forms sheet material (also identical among Figure 10, Figure 11).

Electrophoresis showed of the present invention can be prepared from by normally used situ aggregation method, interfacial polymerization, agglutination etc. with employed microcapsules in the medium, can list polyurethane, poly-urea, poly-urea-polyurethane, urea-formaldehyde resin, melamine-formaldehyde resin, polyamide, polyester, poly-sulfanilamide (SN), polycarbonate, poly-sulfinate, epoxy resin, acrylate, methacrylate, ethyl acetate, gelatin etc. as the cyst material of microcapsules this moment.

Electrophoresis showed of the present invention is preferably about 10～200 μ m with the particle diameter that shows employed microcapsules in the particle.

If the particle diameter deficiency of these microcapsules 10 μ m then can not fully obtain contrast sometimes; On the other hand, if surpass 200 μ m, then can produce not increase and apply the inconvenience that voltage just can not get abundant response speed, so not preferred.

The granularity of microcapsules is preferably concentrated as far as possible and is certain distribution.If inhomogeneous, then produce the demonstration inequality, display characteristic reduces.

Electrophoresis showed of the present invention employed microcapsules in the display medium, in order to interleave the fashionable space that do not produce to the subsidiary electrode in opposite directions of display device between microcapsules at least, preferred capsule has the flexibility that high density is arranged.

Thus, the ratio that shows the zone not have effect is become considerably less, contrast increases, and microcapsules also carry out the face contact to electrode in opposite directions simultaneously, is difficult to produce show inequality, can access the electrophoretic display apparatus with high-quality display characteristic.

In addition, because microcapsules have flexibility, physical strength also increases as a result, and the characteristic when microcapsules are arranged in demonstration with electrode by rubbing method etc. also improves.

Be coated with electrophoresis showed of the present invention with employed coating fluid during employed microcapsules in the medium to electrode of substrate, can use water-dispersion type resin system bonding agent, dissolution with solvents type resin system bonding agent etc., but in order to arrange microcapsules equably to base plate coating the time, preferred microcapsules are to the favorable dispersibility of coating fluid.

Also preferably contact equably mutually between the microcapsules in drying steps does not hinder microcapsules and carries out the face contact in final drying steps.

Electrophoresis showed of the present invention is with in the display medium, as Fig. 4～shown in Figure 6, in being enclosed in electrophoresis showed by the formed constituting body of the cell of independently cutting apart with liquid, in filling the structure of electrophoresis showed with the cell of liquid, from the compatibility aspect of control with electrophoresis particle, preferably to carrying out hydrophilicity-imparting treatment with electrophoresis showed with liquid electrodes in contact portion and cell portion, this water wettability is handled and is selected from ozone treatment, plasma treatment, corona treatment, UV Itro handles, sputter process, polymeric layer forms to be handled, inorganic layer forms to be handled, the organic or inorganic mixolimnion forms to be handled.

As ozone treatment, contact with ozone molecule by making the cell sheet material, be purpose to import functional groups (hydrophilic radical) such as hydroxyl peroxy, hydroxyl, carbonyl, make the cell sheet surface be exposed to ozone, carry out hydrophilicity-imparting treatment thus.As process for exposing, can list the method for maintenance stipulated time in the atmosphere that ozone exists, in streams of ozone, expose the method for stipulated time etc., but be not particularly limited.

As plasma treatment, above-mentioned cell sheet material is placed in the container that contains air, oxygen, nitrogen, carbon dioxide, argon, neon etc., undertaken by being exposed to the plasma that produces by glow discharge, to import functional groups (hydrophilic radical) such as the carboxylic acid group contain aerobic, nitrogen etc., carbonyl, amino in cell sheet surface portion is purpose, the discharge type that plasma produces has direct-current discharge, low frequency discharge, radiowave discharge, microwave discharge etc., but is not particularly limited.Contain the aspect of the water wettability functional group of oxygen atom from importing, be preferably that air plasma is handled, oxygen plasma treatment.

As corona treatment, can pass through etc. by in producing the electric field of corona discharge, making above-mentioned cell sheet material, the inner surface portion of cell sheet material is carried out hydrophilicity-imparting treatment.

Handle as UV Itro, be to be that at least one fuel gas flame of 10～100 ℃ modifier compound blows attached processing (the silicon oxidation flame is handled, the titanium oxidizing flame is handled, aluminium oxidizing flame handle) to above-mentioned cell sheet material, the inner surface portion of cell sheet material is carried out hydrophilicity-imparting treatment by containing at least one modifier compound of being selected among alkyl silane cpd, alkoxysilane compound containing trialkylsilyl group in molecular structure, alkyl titanium compound, alkoxy titanium compound, alkyl aluminum compound, the alkoxy aluminum compound, preferably containing boiling point.Flame temperature when blowing attached handle is that 500～1500 ℃, processing time are about 0.1～100 second.

In addition, can also pass through sputter process, polymeric layer formation processing, inorganic layer formation processing, organic or inorganic mixolimnion formation processing, to carrying out hydrophilicity-imparting treatment with liquid electrodes in contact portion and cell portion with electrophoresis showed.

With in the display medium, as Fig. 4～shown in Figure 6, in being enclosed in electrophoresis showed by the material in the structure of independently cutting apart that cell constituted with liquid, the volume of the cell of independently cutting apart is preferably 1 * 10 in electrophoresis showed of the present invention ^-9Cm ³～1 * 10 ^-3Cm ³

If this volume less than 1 * 10 ^-9Cm ³, then be easy to generate demonstration decrease of contrast etc.; On the other hand, if the volume of cell surpasses 1 * 10 ^-3Cm ³, then easily causing aggegation in each little chamber interior, generation shows unequal bad.

The electrophoresis showed of the present invention that constitutes like this is wrapped in the liquid in microcapsules or the cell and the electrophoresis showed display medium that forms has been realized the contrast height of display surface, also can have been compared the also characteristic of excellence of demonstration, response with high reliability when showing repeatedly with showing.

Electrophoretic display apparatus of the present invention is characterised in that, the electrophoretic display medium that it has a pair of substrate and is present in the above-mentioned formation between this substrate, and in the above-mentioned a pair of substrate is optically transparent electrode one of at least.

As electrophoretic display apparatus of the present invention, can list for example following 1)～6) scheme, but electrophoretic display apparatus of the present invention is not limited to these.

1) a kind of electrophoretic display apparatus, its a pair of demonstration that will be provided with electrode at the substrate single face is situated between with base material and electrode surface is disposed in opposite directions and is formed the space by dividing plate, in this space, fill electrophoresis showed liquid of the present invention, and at least one is shown with base material for be provided with the base material of transparency electrode at the single face of transparency carrier.

2) a kind of electrophoretic display apparatus, its demonstration that the substrate single face is provided with electrode with base material on, Jie makes insulation film form the space in opposite directions by dividing plate, fills electrophoresis showed of the present invention with showing liquid in this space, and makes and show with at least one of base material and insulation film for transparent.

3) a kind of electrophoretic display apparatus, its a pair of demonstration that will be provided with electrode at the substrate single face is situated between with base material and electrode surface is disposed in opposite directions and is formed the space by dividing plate, in this space, fill electrophoresis showed of the present invention demonstration particle, and at least one is shown with base material for be provided with the base material of transparency electrode at the transparency carrier single face.

4) a kind of electrophoretic display apparatus, its demonstration that the substrate single face is provided with electrode with base material on, Jie makes insulation film form the space in opposite directions by dividing plate, fills electrophoresis showed of the present invention with showing particle in this space, and makes and show with at least one of base material and insulation film for transparent.

5) a kind of electrophoretic display apparatus, its demonstration that is provided with transparent or opaque electrode on the transparent or opaque substrate single face with base material on, electrophoresis showed of the present invention is coated with bonding agent with medium.

6) a kind of electrophoretic display apparatus, its a pair of demonstration that will be provided with electrode at the substrate single face is situated between with base material and electrode surface is disposed in opposite directions and is formed the space by dividing plate, and then independently divided in this space by walls such as clathrates be in the space of cell, fill electrophoresis showed liquid of the present invention, and at least one is shown with base material for be provided with the base material of transparency electrode at the transparency carrier single face.

In this display device, the volume of the preferred above-mentioned cell of independently being cut apart is 1 * 10 ^{- 9}Cm ³～1 * 10 ^-3Cm ³

Figure 10 is an electrophoretic display apparatus, and it has used the simple grain subtype electrophoresis showed of Fig. 2 is enclosed in by in the formed structure of microcapsules and the display medium that obtains with liquid.Figure 11 is an electrophoretic display apparatus, and it has used two corpuscular type electrophoresis showed of Fig. 3 are enclosed in by in the formed structure of microcapsules and the display medium that obtains with liquid.

Figure 12 is that (D1 is that the ito glass electrode of 1100 μ m is the dividing plate sheet material of 500 μ m and the synoptic diagram of electrophoretic display apparatus when applying voltage as electrode, used thickness (D2) in opposite directions D3), and d1 and d2 are the thickness (0.15 μ m) of ito thin film with thickness.

In the electrophoretic display apparatus of the present invention, except above-mentioned microcapsule-type, can also be clipped in opposite directions between electrode accommodating the film like sheet material with a plurality of cells of electrophoresis showed with liquid.

This accommodates the formation method of electrophoresis showed with the liquid sheet material, can be processed to form fine cell on thin-film sheet by application, photoetching process, the various print process of various UV laser processing technologys, is made thus.

The electrophoretic display apparatus of the present invention of Gou Chenging has been realized the contrast height, also can have been compared demonstration with high reliability when showing repeatedly like this, the characteristic that response is also excellent.

Embodiment

Then, describe the present invention in detail by embodiment and comparative example, but the present invention is not limited to the following stated.

(preparation, this 1st invention of liquid of embodiment 1～19 and comparative example 1～6, electrophoresis showed)

The mixing of each embodiment shown in the following table 1 and comparative example is formed, used beaded glass to disperse 60 minutes, preparation electrophoresis showed liquid with the coating rocker.

(A-1～A-8, (((E-1～E-6) uses following substances to used particulate for D-1～D-4), alkyl, polyether amine etc. for C-1～C-3), spreading agent for B-1～B-2), dyestuff, dispersion liquid medium.

Particles A:

A-1:ITT-2 TiO ₂CR-50 (production of daylight Chemicals company), the titanium dioxide that handled with titanium coupling agent on the surface, mean grain size is about 0.4 μ m

A-2:ITT-7 TiO ₂TTO-S-3 (production of daylight Chemicals company), the particulate titanium dioxide that handled with titanium coupling agent on the surface, mean grain size is about 0.05～0.1 μ m

A-3:KR-380 (production of titanium industrial group), the titanium dioxide that handled with lipophilic surface's treating agent on the surface, mean grain size is about 0.5 μ m

A-4:KR-270 (production of titanium industrial group), the titanium dioxide that handled with lipophilic surface's treating agent on the surface, mean grain size is about 0.4 μ m

A-5:Technopolymer MBX-20 White (ponding changes into product industrial group and produces), the PMMA toner, mean grain size is about 20 μ m

A-6:Tipaque CR-50 (production of the former industry of stone company) becomes the titanium dioxide of hydrophilic surface, and mean grain size is about 0.4 μ m

A-7:Tipaque CR-50 (production of the former industry of stone company), the particle of handling with Plenact AL-M (Ajinomoto company produce, aluminium be coupling agent) (mean grain size is about 0.4 μ m)

A-8:Tipaque CR-50 (production of the former industry of stone company), the particle of handling with KBE-503 (silicon dioxide company of SHIN-ETSU HANTOTAI produce, silane series coupling agent) (mean grain size is about 0.4 μ m)

Particles B:

B-1:Rubcouleur 220 (MD) Black (refine big day industrial group's production, acrylic copolymer colored beads), mean grain size are about 10 μ m

Tri-iron tetroxide, the mean grain size that handled with titanium coupling agent on B-2:ITT-2BLACK BL-100 (production of daylight Chemicals company), surface are about 0.25 μ m

Colorant (dyestuff):

Oil blue N (production of the pure medicine of dyestuff and light company)

Dispersion liquid medium C:

C-1: dimethylbenzene

C-2: standard paraffin H (production of Nippon Oil(Nippon Mitsubishi Oil) chemical company)

C-3: day stone Isosol 400 (productions of Nippon Oil(Nippon Mitsubishi Oil) chemical company)

Spreading agent D:

D-1: sorbitan monooleate

D-2: sorbitan trioleate

D-3:NIKKOL DDP-2 (production of daylight Chemicals company, negative ion are surfactant)

D-4: oleic acid

Alkyl, polyether amine E:

E-1:Nymeen L-201 (Nof Corp.'s production), hydroxyethyl lauryl amine

E-2:Nymeen L-202 (Nof Corp.'s production), polyglycol lauryl amine

E-3:Nymeen S-202 (Nof Corp.'s production), polyglycol octadecylamine

E-4:Nymeen T ₂-202 (Nof Corp.'s productions), polyalkylene glycol alkyl (tallow) amine

E-5:DT-203 (Nof Corp.'s production), polyoxyethylene allylic alkylation (tallow) Pn

E-6: trioctylphosphine amine

Table 1

(mixing unit: weight %, total amount are 100)

Used the following making of electrophoretic display medium of resulting each electrophoresis showed usefulness liquid in the above-mentioned table 1, by following each evaluation method, estimated white display surface reflectivity, visual assessment white display surface, the reflectivity of painted display surface, the painted display surface of visual assessment, particulate aggegation and adhere to, response, contrast.

The evaluation of physical property result of these electrophoretic display mediums is shown in following table 2.

(having used the making of electrophoresis showed) with the electrophoretic display medium of liquid

As the substrate that is provided with electrode at single face, use single face to be formed with the glass substrate (thickness is 1.1mm) of 0.15 μ m nesa coating (ITO film), Jie is disposed in opposite directions by a pair of dividing plate that is about 500 μ m with this glass substrate, forms cell.

In this space, the electrophoresis showed of preparation in the above-mentioned table 1 is gone into fluid-tight, make electrophoretic display medium thus.

(evaluation of physical property of electrophoretic display medium)

For the embodiment that makes by said method and each electrophoretic display medium of comparative example, Jie by the electrode of medium apply+200V or-voltage of 200V makes it electrophoresis, use MSC-5N (Suga testing machine company produces, below identical), measure the reflectivity of formed white or painted display surface.

Simultaneously, visual assessment white shows and painted demonstration, the aggegation of particle and the evaluation of attachment state, and the evaluation of contrast ratio is undertaken by following method.

(visual assessment white shows and painted demonstration)

The whiteness of the white display surface that shows for applying voltage and the color depth of painted display surface carry out visual observations, press commentary price card standard and carry out sensory evaluation.

The standard of visual assessment white display surface:

Zero: white

△: be with color slightly

*: color is very heavy

The standard of the painted display surface of visual assessment:

Zero: bright, color is strong

△: have slightly and turn white

*: turn white

(evaluation of the aggegation of particle and attachment state and response)

The aggegation of particle and to the following evaluation of adhering to of electrode surface: with the interval in 1 second alternately apply 100 times+200V or-voltage of 200V, switch show after, the tonal variation of visualization display part and state, following commentary price card standard is estimated.

In addition, also estimate for switching the corresponding response that changes that shows according to following evaluation criterion with voltage.

The aggegation of particle and the evaluation criterion of attachment state

Zero: almost do not have aggegation and adhere to

△: aggegation is slightly arranged and adhere to

*: aggegation takes place and adhere to

The evaluation criterion of response:

Zero: change rapidly

△: react that some is slow

*: delay of response

(evaluation of contrast ratio)

Contrast is such as obtaining down: apply+200V or-voltage of 200V, a visual display portion is shown as white, aim at focus at the outermost display surface, after shine-vertically being subjected to light measurement white reflection through 45, apply with initial opposite polarity-200V or+voltage of 200V, visual display portion as painted demonstration, is similarly measured painted reflectivity, obtain from their ratio (reflectivity of the reflectivity of white display surface/painted display surface).

By above-mentioned table 2 result as can be known, the electrophoresis showed medium of the embodiment 1～19 of the scope of the invention, compare with medium with the electrophoresis showed of scope of the invention comparative example 1～6 outward, the reflectivity excellence of white display surface and painted display surface, the white demonstration of range estimation and the tone of painted demonstration are also excellent, and do not have the aggegation of particulate and adhere to response and contrast excellence.

Then, make the electrophoresis showed device of microcapsule-type (MC) and sheet type (S) by following method, estimated with above-mentioned each evaluation method white display surface the white display surface of reflectivity, visual assessment, the reflectivity of painted display surface, the painted display surface of visual assessment, particulate aggegation and adhere to, response, contrast.

The evaluation of physical property of these electrophoretic display apparatus the results are shown in following table 3.

Microcapsule-type embodiment 1

(1) the electrophoresis showed preparation of liquid

The dispersion liquid for preparing 100g according to the mixing ratio of the foregoing description 2 records.

(2) microencapsulation

The gum arabic solution of the 5 weight % of the aqueous gelatin solution of the 5 weight % of 200g and 200g is mixed while stirring, be warming up to 50 ℃, use the pH regulator to 9.0 of sodium hydrate aqueous solution solution.The electrophoresis showed dispersion liquid that the limit adds above-mentioned (1) is slowly stirred on the limit in this aqueous solution, the preparation emulsion type.

Then, under the stirring condition of regulation, use aqueous acetic acid that pH is reduced to 4.0, behind the formation gelatin/gum arabic agglutinant layer, in about 30 minutes, be cooled to about 5 ℃.

Add 10g formaldehyde 35% aqueous solution then, be warming up to 50 ℃, implement about 2 hours curing reaction, the slurry of preparation microcapsules.

The mean grain size of gained microcapsules is 80 μ m.

(3) device is estimated

With with respect to resulting microcapsules slurry in 1 part above-mentioned (2), the water-based urethane is that binder solution is that 1.5 parts ratio is mixed, and uses the dressing coating machine to be coated with on the ito transparent electrode of PET base material, and is fully dry under 50 ℃ drying condition.

Should show with cell to be connected in opposite directions on the electrode base board, carry out vacuum pressing-combining, make display device, implementation evaluation according to the mode that makes electrode interbody spacer in opposite directions become 60 μ m.

Microcapsule-type embodiment 2

(1) the electrophoresis showed preparation of liquid

The dispersion liquid for preparing 100g according to the mixing ratio of the foregoing description 9 records.

(2) microencapsulation

After in above-mentioned dispersion liquid (1), dissolving the hexamethylene diisocyanate (HDI) of 10g, the aqueous gelatin solution that under the stirring condition of regulation, adds 300g 5 weight % immediately, the preparation emulsion type, with temperature maintenance at 35 ℃, continue to stir after 2 hours, the temperature of system is cooled to 5 ℃.

Then, with NaOH with pH regulator to 9.0 after, add 10g glutaraldehyde 25% aqueous solution, system temperature is risen to 50 ℃, with finishing encapsulated reaction in about 2 hours.

The mean grain size of gained microcapsules is 90 μ m.

(3) device is estimated

With with respect to resulting microcapsules slurry in 1 part above-mentioned (2), the water-based silicon that the specific inductive capacity that contains ormal weight is adjusted material is that binder solution is that 2 parts ratio is mixed, use the dressing coating machine on the ito transparent electrode of PET base material, to be coated with, fully dry under 50 ℃ drying condition.

Should show with cell to be connected in opposite directions on the electrode base board, carry out vacuum pressing-combining, make display device, implementation evaluation according to the mode that makes electrode interbody spacer in opposite directions become 60 μ m.

Microcapsule-type embodiment 3

(1) the electrophoresis showed preparation of liquid

The dispersion liquid for preparing 100g according to the mixing ratio of the foregoing description 10 records.

(2) microencapsulation

After in above-mentioned dispersion liquid (1), dissolving the biuret body of 10g HDI, the PVA aqueous solution that under the stirring condition of regulation, adds 300g 5 weight % immediately, the preparation emulsion type, with temperature maintenance at 60 ℃, continue to stir after 3 hours, with NaOH with pH regulator to 9.0 after, add 10g glutaraldehyde 25% aqueous solution, system temperature is risen to 50 ℃, with finishing encapsulated reaction in about 2 hours.

The mean grain size of gained microcapsules is 75 μ m.

(3) device is estimated

With with respect to resulting microcapsules slurry in 1 part above-mentioned (2), the PVA that the specific inductive capacity that contains ormal weight is adjusted material is that binder solution is that 2 parts ratio is mixed, use the dressing coating machine on the ito transparent electrode of PET base material, to be coated with, fully dry under 50 ℃ drying condition.

Should show with cell to be connected in opposite directions on the electrode base board, carry out vacuum pressing-combining, make display device, implementation evaluation according to the mode that makes electrode interbody spacer in opposite directions become 60 μ m.

Sheet type embodiment 1

(1) the electrophoresis showed preparation of liquid

The dispersion liquid for preparing 100g according to the mixing ratio of the foregoing description 2 records.

(2) sheet type is accommodated the baffle plate device evaluation of ink

Form at as shown in Figure 9 usefulness size pattern on the sheet material of pattern and fill electrophoretic ink, with the ito transparent electrode electrode in opposite directions of PET base material on this sheet material of configuration, make display device, implementation evaluation.

By above-mentioned table 3 result as can be known, use in the device in the electrophoresis showed of microcapsule-type (MC) and sheet type (S), the reflectivity excellence of white display surface and painted display surface, the white demonstration of range estimation and the tone of painted demonstration are also excellent, and do not have the aggegation of particulate and adhere to response and contrast excellence.

(preparation, this 2nd invention of liquid of embodiment 20～25 and comparative example 7～11, electrophoresis showed)

The mixing of each embodiment shown in the following table 4 and comparative example is formed, used beaded glass to disperse 60 minutes, preparation electrophoresis showed liquid with the coating wobbler.

(E) such as used particulate (A-1, B-1), colorant (dyestuff), dispersion liquid medium (C-1, C-4), polyoxyethylene propylene oxide (POEOP) block polymer F, spreading agent (D-2), alkyl, polyether amine uses following substances.

Particulate:

A-1::ITT-2TiO ₂Titanium dioxide, the mean grain size that handled with titanium coupling agent on CR-50 (production of daylight Chemicals company), surface are about 0.4 μ m

B-1:Rubcouleur 220 (MD) Black (refine big day industrial group's production, acrylic copolymer colored beads), mean grain size are about 10 μ m

Colorant (dyestuff): oil blue N (producing) with the pure medicine of light company

Dispersion liquid medium C:

C-1: dimethylbenzene

C-4: day stone Hisol SAS296 (production of Nippon Oil(Nippon Mitsubishi Oil) chemical company, diallyl alkane)

Polyoxyethylene propylene oxide (POEOP) block polymer F:

F-1:Pronon 102 (mean molecular weight is 1250, amount of ethylene oxide is 20 weight %, Nof Corp. produce)

F-2:Pronon 104 (mean molecular weight is 1670, amount of ethylene oxide is 40 weight %, Nof Corp. produce)

F-3:Pronon 201 (mean molecular weight is 2220, amount of ethylene oxide is 10 weight %, Nof Corp. produce)

F-4:Pronon 204 (mean molecular weight is 3300, amount of ethylene oxide is 40 weight %, Nof Corp. produce)

F-5:Pronon 208 (mean molecular weight is 10000, amount of ethylene oxide is 80 weight %, Nof Corp. produce)

Spreading agent D:

D-2: sorbitan trioleate

E such as alkyl, polyether amine:

E-1:Nymeen L-201 (Nof Corp.'s production), hydroxyethyl lauryl amine

E-3:Nymeen S-202 (Nof Corp.'s production), polyglycol octadecylamine

E-5:DT-203 (Nof Corp.'s production), polyoxyethylene allylic alkylation (tallow) Pn

E-6: trioctylphosphine amine

Make by the method identical and to have used in the above-mentioned table 4 each electrophoresis showed of gained with the electrophoretic display medium of liquid with the foregoing description 1 etc., by above-mentioned each evaluation method, estimated white display surface reflectivity, visual assessment white display surface, the reflectivity of painted display surface, the painted display surface of visual assessment, particulate aggegation and adhere to, response, contrast, simultaneously, the aggegation of the particulate after having estimated 50 ℃, 1M (1 month) and preserve by following evaluation method and adhere to response, contrast.

The evaluation of physical property result of these electrophoretic display mediums is shown in following table 5.

[aggegation of the particulate after 50 ℃, 1M (1 month) are preserved and adhere to the evaluation method of response, contrast]

The embodiment 20～25 that will make with said method and each electrophoretic display medium of comparative example 7～11 50 ℃ preserve 1M (1 month) after, with the aggegation of above-mentioned each evaluation method evaluation particulate with adhere to response, contrast.

Result by above-mentioned table 5 is as can be known clear and definite, the electrophoresis showed medium of the embodiment 20～25 of the scope of the invention, compare with medium with the electrophoresis showed of scope of the invention comparative example 7～11 outward, the reflectivity excellence of white display surface and painted display surface, the white demonstration of range estimation and the tone of painted demonstration are also excellent, and do not have the aggegation of particulate and adhere to, response and contrast excellence, simultaneously, even if behind 50 ℃ of preservation 1M (1 month), also do not have the aggegation of particulate and adhere to, response and contrast are also excellent.

Then, make the electrophoresis showed device of microcapsule-type (MC) and sheet type (S) by following method, estimated with above-mentioned each evaluation method white display surface reflectivity, visual assessment white display surface, the reflectivity of painted display surface, the painted display surface of visual assessment, particulate aggegation and adhere to, response, contrast, and the aggegation of the particulate after having estimated 50 ℃, 1M (1 month) and preserving and adhere to the evaluation method of response, contrast.

The evaluation of physical property of these electrophoretic display apparatus the results are shown in following table 6.

Microcapsule-type embodiment 4

(1) the electrophoresis showed preparation of liquid

The dispersion liquid for preparing 100g according to the mixing ratio of the foregoing description 20 records.

(2) microencapsulation

The aqueous gelatin solution of 200g 5 weight % and the Arabic gum aqueous solution of 200g 5 weight % are mixed while stirring, be warming up to 50 ℃, use the pH regulator to 9.0 of sodium hydrate aqueous solution solution.The electrophoresis showed dispersion liquid that the limit adds above-mentioned (1) is slowly stirred on the limit in this aqueous solution, the preparation emulsion type.

Then, under the stirring condition of regulation, use aqueous acetic acid that pH is reduced to 4.0, behind the formation gelatin/gum arabic agglutinant layer, in about 30 minutes, be cooled to about 5 ℃.

Add 10g formaldehyde 35% aqueous solution then, be warming up to 50 ℃, implement about 2 hours curing reaction, the slurry of preparation microcapsules.

The mean grain size of gained microcapsules is 80 μ m.

(3) device is estimated

With with respect to resulting microcapsules slurry in 1 part above-mentioned (2), the water-based urethane is that binder solution is that 1.5 parts ratio is mixed, and uses the dressing coating machine to be coated with on the ito transparent electrode of PET base material, and is fully dry under 50 ℃ drying condition.

Should show with cell to be connected in opposite directions on the electrode base board, carry out vacuum pressing-combining, make display device, implementation evaluation according to the mode that makes electrode interbody spacer in opposite directions become 60 μ m.

Microcapsule-type embodiment 5

(1) the electrophoresis showed preparation of liquid

The dispersion liquid for preparing 100g according to the mixing ratio of the foregoing description 21 records.

(2) microencapsulation

After in above-mentioned dispersion liquid (1), dissolving 10g hexamethylene diisocyanate (HDI), the aqueous gelatin solution that under the stirring condition of regulation, adds 300g 5 weight % immediately, the preparation emulsion type, with temperature maintenance at 35 ℃, continue to stir after 2 hours, the temperature of system is cooled to 5 ℃.

Then, use NaOH with pH regulator to 9.0 after, add 10g glutaraldehyde 25% aqueous solution, system temperature is risen to 50 ℃, with finishing encapsulated reaction in about 2 hours.

The mean grain size of gained microcapsules is 90 μ m.

(3) device is estimated

With with respect to resulting microcapsules slurry in 1 part above-mentioned (2), the water-based silicon that the specific inductive capacity that contains ormal weight is adjusted material is that binder solution is that 2 parts ratio is mixed, use the dressing coating machine on the ito transparent electrode of PET base material, to be coated with, fully dry under 50 ℃ drying condition.

Should show with cell to be connected in opposite directions on the electrode base board, carry out vacuum pressing-combining, make display device, implementation evaluation according to the mode that makes electrode interbody spacer in opposite directions become 60 μ m.

Microcapsule-type embodiment 6

(1) the electrophoresis showed preparation of liquid

The dispersion liquid for preparing 100g according to the mixing ratio of the foregoing description 22 records.

(2) microencapsulation

After in above-mentioned dispersion liquid (1), dissolving the biuret body of 10g HDI, the PVA aqueous solution that under the stirring condition of regulation, adds 300g 5 weight % immediately, the preparation emulsion type, with temperature maintenance at 60 ℃, continue to stir after 3 hours, with NaOH with pH regulator to 9.0 after, add 10g glutaraldehyde 25% aqueous solution, system temperature is risen to 50 ℃, with finishing encapsulated reaction in about 2 hours.

The mean grain size of gained microcapsules is 75 μ m.

(3) device is estimated

With with respect to resulting microcapsules slurry in 1 part above-mentioned (2), the PVA that the specific inductive capacity that contains ormal weight is adjusted material is that binder solution is that 2 parts ratio is mixed, use the dressing coating machine on the ito transparent electrode of PET base material, to be coated with, fully dry under 50 ℃ drying condition.

Should show with cell to be connected in opposite directions on the electrode base board, carry out vacuum pressing-combining, make display device, implementation evaluation according to the mode that makes electrode interbody spacer in opposite directions become 60 μ m.

Sheet type embodiment 2

(1) the electrophoresis showed preparation of liquid

The dispersion liquid for preparing 100g according to the mixing ratio of the foregoing description 23 records.

(2) sheet type is accommodated the baffle plate device evaluation of ink

Form at as shown in Figure 9 usefulness size pattern on the sheet material of pattern and fill electrophoretic ink, with the ito transparent electrode electrode in opposite directions of PET base material on this sheet material of configuration, make display device, implementation evaluation.

Result by above-mentioned table 6 is as can be known clear and definite, the electrophoresis showed of microcapsule-type (MC) and sheet type (S) is with in the device, the reflectivity excellence of white display surface and painted display surface, the white demonstration of range estimation and the tone of painted demonstration are also excellent, and do not have the aggegation of particulate and adhere to response and contrast excellence, simultaneously, even if 50 ℃ preserve 1M (1 month) after, do not have the aggegation of particulate yet and adhere to, response and contrast be excellence also.

(preparation, this invention greatly of liquid of embodiment 26～30 and reference example 1～5, electrophoresis showed)

The mixing of each embodiment shown in the following table 7 and reference example is formed, used beaded glass to disperse 60 minutes, preparation electrophoresis showed liquid with the coating wobbler.

(G-1～G-2), polyoxyethylene oxypropylene (POEOP) block polymer F, spreading agent D, alkyl, polyether amine E use following substances for used particulate (A-1, B-1), colorant (dyestuff), dispersion liquid medium (C-1, C-4), acetylene-derivative.

Particles A:

A-1:ITT-2 TiO ₂CR-50 (production of daylight Chemicals company), the titanium dioxide that handled with titanium coupling agent on the surface, mean grain size is about 0.4 μ m

B-1:Rubcouleur 220 (MD) Black (refine big day industrial group's production, acrylic copolymer colored beads), mean grain size is about 10 μ m

Colorant (dyestuff): oil blue N (producing) with the pure medicine of light company

Dispersion liquid medium C:

C-1: dimethylbenzene

C-4: day stone Hisol SAS296 (production of Nippon Oil(Nippon Mitsubishi Oil) chemical company, diallyl alkane)

Acetylene-derivative G:

G-1:Surfynol 104DPM (HLB is 4, believes that a chemical industrial company produces day)

G-2:Surfynol DF110D (HLB is 3, believes that a chemical industrial company produces day)

Polyoxyethylene propylene oxide (POEOP) block polymer F:Pronon 102 (mean molecular weight is 1250, amount of ethylene oxide is 20 weight %, Nof Corp. produce)

Spreading agent D: sorbitan trioleate

Alkyl, polyether amine E:Nymeen L-201 (Nof Corp.'s production), hydroxyethyl lauryl amine

Make the electrophoretic display medium that has used each electrophoresis showed usefulness liquid of gained in the above-mentioned table 7 by following method, estimated the reflectivity of white display surface by above-mentioned each evaluation method, the reflectivity of visual assessment white display surface and painted display surface, the painted display surface of visual assessment, the aggegation of particulate and adhering to, response, contrast, simultaneously, estimated by following evaluation method and to have shown number of times repeatedly (1000 times, 5000 times, 10000 times) after display characteristic (aggegation and adhering to, contrast), and by above-mentioned evaluation method estimate 50 ℃, the aggegation of the particulate after 1M (1 month) preserves and adhering to, response, contrast.

The evaluation of physical property result of these electrophoretic display mediums is shown in following table 8.

(having used the making of electrophoresis showed) with the electrophoretic display medium of liquid

As the substrate that is provided with electrode at single face, use single face to be formed with the glass substrate (thickness is 1.1mm) of 0.15 μ m nesa coating (ITO film), Jie is disposed in opposite directions by a pair of dividing plate that is about 100 μ m with this glass substrate, forms cell.In order to see the hydrophilicity-imparting treatment effect of electrode of substrate, use forms cell to the substrate that glass substrate has carried out ozone treatment and UV Itro processing in the experiment of a part.Ozone treatment is to be 20g/m with the ozone concentration to above-mentioned resulting glass substrate ³Carry out 60 minutes ozone treatment (the Ozonizer OS-IN of Mitsubishi, Mitsubishi Electric Corporation produce).And UV Itro handles and to be to use that to contain 0.0001 mole of %, boiling point be that tetramethylsilane and 0.00001 mole of %, boiling point of 27 ℃ is the fuel gas of 122 ℃ tetramethoxy-silicane, and the silicon oxidation flame that glass substrate was implemented 0.5 second is handled.

In this space, enclose the prepared electrophoresis showed liquid of above-mentioned table 7, make electrophoretic display medium thus.

[evaluation method of display characteristic (aggegation, contrast) repeatedly]

The evaluation of display characteristic is carried out aggegation and contrast repeatedly, and the show state that is following commentary price card standard when implementing 1000 times, 5000 times, 10000 times is estimated.

Evaluation criterion:

Zero: compare no change with A-stage

△: find a part on electrode aggegation and adhere to, contrast has decline slightly

*: aggegation and adhere to seriously, contrast significantly descends

Result by above-mentioned table 8 is as can be known clear and definite, the electrophoresis showed medium of the embodiment 26～30 of the scope of the invention, compare with medium with the electrophoresis showed of reference example 1～5, the reflectivity excellence of white display surface and painted display surface, the white demonstration of range estimation and the tone of painted demonstration are also excellent, and do not have the aggegation of particulate and adhere to, response and contrast excellence, simultaneously, for 1000 times, 5000 times, 10000 times display characteristic repeatedly, do not have aggegation yet and adhere to, contrast is also excellent, and, even if behind 50 ℃ of preservation 1M (1 month), also do not have the aggegation of particulate and adhere to, response and contrast are also excellent.

Then, make the electrophoresis showed device of microcapsule-type (MC) and sheet type (S) by following method, estimated the reflectivity of white display surface with above-mentioned each evaluation method, visual assessment white display surface, the reflectivity of painted display surface, the painted display surface of visual assessment, the aggegation of particulate and adhering to, response, contrast, show number of times repeatedly (1000 times, 5000 times, 10000 times) after display characteristic (aggegation and adhering to, contrast), and 50 ℃ have been estimated, the aggegation of the particulate after 1M (1 month) preserves and adhere to response, the evaluation method of contrast.

The evaluation of physical property of these electrophoretic display apparatus the results are shown in following table 9.

Microcapsule-type embodiment 7

(1) the electrophoresis showed preparation of liquid

The electrophoresis showed liquid for preparing 100g according to the mixing ratio of the foregoing description 27 records.

(2) microencapsulation

The aqueous gelatin solution of 200g 5 weight % and the Arabic gum aqueous solution of 200g 5 weight % are mixed while stirring, be warming up to 50 ℃, use the pH regulator to 9.0 of sodium hydrate aqueous solution solution.The electrophoresis showed dispersion liquid that the limit adds above-mentioned (1) is slowly stirred on the limit in this aqueous solution, the preparation emulsion type.

Then, under the stirring condition of regulation, use aqueous acetic acid that pH is reduced to 4.0, behind the formation gelatin/gum arabic agglutinant layer, in about 30 minutes, be cooled to about 5 ℃.

Add 10g formaldehyde 35% aqueous solution then, be warming up to 50 ℃, implement about 2 hours curing reaction, the slurry of preparation microcapsules.

The mean grain size of gained microcapsules is 80 μ m.

(3) device is estimated

With with respect to resulting microcapsules slurry in 1 part above-mentioned (2), the water-based urethane is that binder solution is that 1.5 parts ratio is mixed, and uses the dressing coating machine to be coated with on the ito transparent electrode of PET base material, and is fully dry under 50 ℃ drying condition.

Should show with cell to be connected in opposite directions on the electrode base board, carry out vacuum pressing-combining, make display device, implementation evaluation according to the mode that makes electrode interbody spacer in opposite directions become 60 μ m.

Sheet type embodiment 3

(1) the electrophoresis showed preparation of liquid

The electrophoresis showed liquid for preparing 100g according to the mixing ratio of the foregoing description 2 records.

(2) sheet type is accommodated the baffle plate device evaluation of ink

As shown in Figure 9, be spaced apart on the cell sheet material of 80 μ m forming pattern and cell on the ito transparent electrode of PET base material by photoetching process with the size pattern, fill electrophoresis disclosing solution, dispose electrode in opposite directions, by UV cure adhesive (UV3400, East Asia synthetic chemistry company produce, following identical) make the sheet material change display device, make display device, implementation evaluation.

Sheet type embodiment 4

(1) the electrophoresis showed preparation of liquid

The electrophoresis showed liquid for preparing 100g according to the mixing ratio of the foregoing description 28 records.

(2) sheet type is accommodated the baffle plate device evaluation of ink

As shown in Figure 9, form pattern by laser processing method and thickness is on the polyimide system cell sheet material of 50 μ m with the size pattern, fill electrophoresis disclosing solution, dispose electrode in opposite directions, by the UV curing adhesive make the sheet material change display device, make display device, implementation evaluation.

Sheet type embodiment 5

In above-mentioned sheet type embodiment 3, with formed the ito transparent electrode of cell pattern and in opposite directions electrode carry out ozone treatment [the Ozonizer OS-IN of Mitsubishi, Mitsubishi Electric Corporation produce, be 20g/m with the ozone concentration ³Handled 60 minutes] after, fill electrophoresis disclosing solution, make display device.

Sheet type embodiment 6

In above-mentioned sheet type embodiment 4, with ito transparent electrode, cell sheet material, electrode carries out filling electrophoresis disclosing solution after UV Itro handles in opposite directions, makes display device.

Result by above-mentioned table 9 is as can be known clear and definite, the electrophoresis showed of microcapsule-type (MC) and cabinet type (S) is with in the device, the reflectivity excellence of white display surface and painted display surface, the white demonstration of range estimation and the tone of painted demonstration are also excellent, and do not have the aggegation of particulate and adhere to, response and contrast excellence, simultaneously, for 1000 times, 5000 times, 10000 times display characteristic repeatedly, do not have aggegation yet and adhere to, contrast is also excellent, and, even if 50 ℃ preserve 1M (1 month) after, do not have the aggegation of particulate yet and adhere to, response and contrast be excellence also.

In sum, like this electrophoresis showed of the present invention of Gou Chenging with liquid, used display medium and the display device of this electrophoresis showed with liquid, because the electrophoresis showed dispersion stabilization excellence of liquid, therefore realized the demonstration of high-contrast, when showing repeatedly, also can compare demonstration with high reliability, response is also excellent, therefore applicable to as portable display device such as information terminal, electronics price tag, e-books.

Claims (28)

1. electrophoresis showed liquid, it is characterized in that, it contains the alkyl, polyether amine that has at least with structural unit shown in the following general formula (I), 1 kind or multiple particulate, spreading agent and dispersion liquid medium, and described particulate contains the particulate of being handled by the lipophilic surface, wherein, the content of described alkyl, polyether amine is 1.0～150 weight % with respect to the described particulate of being handled by the lipophilic surface, at least a kind of described particulate for containing the high molecular particle of colorant, organic pigment or inorganic pigment, described lipophilic surface handles and is to use coupling agent to carry out

In the above-mentioned formula (I), R ₁Be saturated hydrocarbyl or unsaturated alkyl, R ₂Be (OCH ₂CH ₂) x-H, R ₃Be (OCH ₂CH ₂) y-H, x be 0 or positive number, y be positive number.

2. electrophoresis showed liquid, it is characterized in that, it contains the alkyl, polyether amine that has at least with structural unit shown in the following general formula (I), has the polyoxyethylene propylene oxide block polymer with structural unit shown in the following general formula (II), a kind or multiple particulate and dispersion liquid medium, wherein, the content of described alkyl, polyether amine is 1.0～150 weight % with respect to described particulate; The mean molecular weight of described polyoxyethylene propylene oxide block polymer is 1000～4000, and its content is with respect to showing that the liquid total amount is 0.01～30 weight %, and the amount of ethylene oxide in the polymkeric substance is 50 weight % or following; At least a kind of particulate is high molecular particle, organic pigment or the inorganic pigment that contains colorant,

In the above-mentioned formula (I), R ₁Be saturated hydrocarbyl or unsaturated alkyl, R ₂Be (OCH ₂CH ₂) x-H, R ₃Be (OCH ₂CH ₂) y-H, x be 0 or positive number, y be positive number,

OH(C ₂H ₄O)p(C ₃H ₈O)qH (II)

In the above-mentioned formula (II), p, q are positive number.

3. electrophoresis showed liquid as claimed in claim 2, wherein particulate was handled by the lipophilic surface, and this lipophilic surface handles and is to use coupling agent to carry out.

4. electrophoresis showed liquid as claimed in claim 1, wherein coupling agent is that to be selected from titanate esters be that coupling agent, aluminium are at least a kind among coupling agent, the silane series coupling agent.

5. electrophoresis showed liquid as claimed in claim 3, wherein coupling agent is that to be selected from titanate esters be that coupling agent, aluminium are at least a kind among coupling agent, the silane series coupling agent.

6. electrophoresis showed liquid as claimed in claim 1, wherein the surface functionalities of the particulate of being handled by lipophilic surface group is alkoxy carbonyl.

7. electrophoresis showed liquid as claimed in claim 3, wherein the surface functionalities of the particulate of being handled by lipophilic surface group is alkoxy carbonyl.

8. electrophoresis showed liquid as claimed in claim 1, the constituent that wherein contains the high molecular particle of colorant are that cross-linked acrylic acid is a resin.

9. electrophoresis showed liquid as claimed in claim 2, the constituent that wherein contains the high molecular particle of colorant are that cross-linked acrylic acid is a resin.

10. electrophoresis showed liquid as claimed in claim 1, wherein the mean grain size of particulate is 0.05～20 μ m.

11. electrophoresis showed liquid as claimed in claim 2, wherein the mean grain size of particulate is 0.05～20 μ m.

12. electrophoresis showed liquid as claimed in claim 2 wherein also further contains spreading agent.

13. electrophoresis showed liquid as claimed in claim 1, wherein spreading agent is that nonionic system or negative ion are surfactant.

14. electrophoresis showed liquid as claimed in claim 12, wherein spreading agent is that nonionic system or negative ion are surfactant.

15. electrophoresis showed liquid as claimed in claim 1, wherein the content of spreading agent is with respect to showing that the liquid total amount is 0.01～50 weight %.

16. electrophoresis showed liquid as claimed in claim 12, wherein the content of spreading agent is with respect to showing that the liquid total amount is 0.01～50 weight %.

17. an electrophoresis showed medium is characterized in that, the described electrophoresis showed of claim 1 is enclosed in the body of independent structures separately of microcapsules or cell with liquid.

18. an electrophoresis showed medium is characterized in that, the described electrophoresis showed of claim 2 is enclosed in the body of independent structures separately of microcapsules or cell with liquid.

19. electrophoresis showed medium as claimed in claim 17, wherein filling electrophoresis showed with in the cell structure of liquid, to carrying out hydrophilicity-imparting treatment with electrophoresis disclosing solution electrodes in contact portion and cell portion, this hydrophilicity-imparting treatment is selected from ozone treatment, plasma treatment, corona treatment, UV Itro processing, sputter process, polymeric layer formation processing, inorganic layer formation processing, organic or inorganic mixolimnion formation processing.

20. electrophoresis showed medium as claimed in claim 18, wherein filling electrophoresis showed with in the cell structure of liquid, to carrying out hydrophilicity-imparting treatment with electrophoresis disclosing solution electrodes in contact portion and cell portion, this hydrophilicity-imparting treatment is selected from ozone treatment, plasma treatment, corona treatment, UV Itro processing, sputter process, polymeric layer formation processing, inorganic layer formation processing, organic or inorganic mixolimnion formation processing.

21. electrophoresis showed medium as claimed in claim 17, wherein the size of microcapsules is 10～200 μ m.

22. electrophoresis showed medium as claimed in claim 18, wherein the size of microcapsules is 10～200 μ m.

23. electrophoresis showed medium as claimed in claim 17, wherein microcapsules have flexibility, and are difficult to produce the gap when arranging microcapsules.

24. electrophoresis showed medium as claimed in claim 18, wherein microcapsules have flexibility, and are difficult to produce the gap when arranging microcapsules.

25. electrophoresis showed medium as claimed in claim 17, wherein independently the volume of cell is 1 * 10 ^-9Cm ³～1 * 10 ^-3Cm ³

26. electrophoresis showed medium as claimed in claim 18, wherein independently the volume of cell is 1 * 10 ^-9Cm ³～1 * 10 ^-3Cm ³

27. an electrophoretic display apparatus is characterized in that, it has a pair of substrate and is present in the described electrophoretic display medium of claim 17 between this substrate, is formed with one of at least optically transparent electrode in the described a pair of substrate.

28. an electrophoretic display apparatus is characterized in that, it has a pair of substrate and is present in the described electrophoretic display medium of claim 18 between this substrate, is formed with one of at least optically transparent electrode in the described a pair of substrate.

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