CN102246094B - Bicolored particles having improved display performance - Google Patents

Abstract

Disclosed are bicolored particles which exhibit excellent rotation performance when a voltage is applied thereto, in particular, particles having a color combination other than the combination of black and white, wherein high rotation performance can be achieved when a voltage is applied thereto. The bicolored particles are resin spherical particles, each having an appearance colored roughly half and half in two different colors. The bicolored particles are characterized in that one roughly hemisphere of each bicolored particle contains a conductive white pigment forming a ground color, and the other roughly hemisphere is colored in an arbitrary color other than the ground color.

Description

Improved the double-colored particle of display performance

Technical field

The present invention relates to double-colored particle and image display device.More specifically, the present invention relates to be suitable as the rotary-type image display device of particle display element double-colored particle and comprise this particle as the rotary-type image display device of the particle of display element.

Background technology

The display packing of image is varied.CRT (Braun tube), PDP (plasma display), LCD (liquid crystal display), FED (field-emitter display) are for example arranged.

CRT is by making the electron ray that is formed by the electronics convergence scan the display device that makes fluorescent material luminous to fluorescent material.PDP encloses the rare gas of high pressure in being clipped in two interelectrode zones with luminescent coating, this rare gas is applied voltage and makes it produce the next luminous display device of ultraviolet ray.LCD is the light transmission liquid crystal that makes from backlight, the device that makes by this polarized state of light change to show according to the orientation of liquid crystal.FED is released into electronics in vacuum, makes the collision of electronics and fluorophor and makes its luminous display device.

Except above-mentioned display device, the particle that will be divided in addition two kinds of colors is configured in insulating resin and makes this display packing of the rotary-type demonstration of particle of this double-colored particle rotation.In this display packing, make the particle with two or more color regions be scattered in the light transmission supporting masses such as silicon rubber in the mode that rotates freely, clamp this light transmission supporting mass and apply voltage with electrode, making by this specific color region of all particles towards same direction.The reason that realizes said method is the charged characteristic difference of each color region of particle.In addition, if make the proportion of each color region of particle consistent, the verticity of particle improves.In addition, consistent by making proportion, once applying particle after voltage towards be fixed as this towards, even cut off the power supply that is used for executing alive device, this state also can continue (being referred to as memory characteristic).Therefore, the rotary-type demonstration of particle is electrically good display packing of province.On the other hand, in the method, because the rotation of particle needs the time, so rotary-type demonstration is not suitable for the fast-changing display device of image such as demonstrations such as the display device that shows dynamic menu.But due to above-mentioned memory characteristic, the rotary-type demonstration of particle is suitable for the still frames such as display text, picture, can expect its application in so-called electronic paper etc.

As the particle that uses in the rotary-type demonstration of this particle, various particles have been developed.For example, disclosed in patent documentation 1 (the clear 64-42683 communique of Japanese Patent Laid-Open) and to use waxy substance as the particle that is formed by this material and pigment, dyestuff of main material.

Disclosed in patent documentation 2 (Japanese patent laid-open 11-352421 communique) and formed the hemisphere of small ball of white with glass, titanium dioxide, zinc paste, zirconia, aluminium oxide etc. as material, made the painted particle that gets of this hemisphere with TiC etc. by sputtering method etc.

Disclosed the twin color ball that applies black material on the glass bead of titania and get being filled with in patent documentation 3 (Japanese Patent Laid-Open 2000-122103 communique).

Patent documentation 1: the clear 64-42683 communique of Japanese Patent Laid-Open

Patent documentation 2: Japanese patent laid-open 11-352421 communique

Patent documentation 3: Japanese Patent Laid-Open 2000-122103 communique

The announcement of invention

But the particle that discloses in these patent documentations is mainly white/black double-colored particle, for the particle of in addition color combination, and the verticity of particle (rotational speed) deficiency when applying voltage, but it is agnogenio.

The object of the present invention is to provide the good double-colored particle of the verticity of particle when applying voltage, the high verticity when particularly realizing applying voltage in the particle of the color combination beyond white/black color combination.

The inventor finds, hemispherical portion by a kind of color of the formation that makes double-colored particle (background color) contains the electric conductivity Chinese white, even the high verticity in the time of also realizing applying voltage in the particle of the color combination beyond white/black color combination, thereby completed the present invention.

Namely, double-colored particle of the present invention is the resinous double-colored particle that each spherical particle roughly is divided into two kinds of different colours in appearance, it is characterized in that, the approximate hemisphere of described double-colored particle contains the electric conductivity Chinese white, thereby the formation background color, the approximate hemisphere of all the other of described double-colored particle is coloured to the random color except described background color.

The electric conductivity Chinese white for example can be processed the method for giving electric conductivity to Chinese white by the conductive material that use is selected from antimony oxide/tin ash, indium oxide/tin ash and make.

Consist of the powder resistance rate of the electric conductivity Chinese white that mixes in the approximate hemisphere of background color of described double-colored particle usually in the scope of 1～100 Ω cm.

Like this double-colored particle that specific inductive capacity is high and interhemispheric specific inductive capacity there are differences of the approximate hemisphere of background color apply voltage the time verticity high.

Be coloured to the approximate hemisphere of the random color except described background color for example by chromatic colour dyestuff or chromatic colour pigment coloring, at this moment, the approximate hemispherical portion that is coloured to the random color except described background color contains chromatic colour dyestuff or chromatic colour pigment.

Consider the rotation efficiency of particle, the mean grain size of described double-colored particle represents usually in the scope of 30～200 μ m with volume reference.

In addition, double-colored particle of the present invention is suitable as the display element of the rotary-type image display device of particle.the rotary-type display device of particle of the present invention is by contain in the mode of freely rotating the rotary-type image display device of particle that the insulating resin of double-colored particle forms between pair of electrodes, it is characterized in that, described double-colored particle is the resinous double-colored particle that each spherical particle roughly is divided into two kinds of different colours in appearance, the approximate hemisphere of described double-colored particle contains the electric conductivity Chinese white, thereby formation background color, the approximate hemisphere of all the other of described double-colored particle is coloured to the random color except described background color, by being applied to described interelectrode voltage, described double-colored particle rotates in described insulating resin.

In the rotary-type image display device of described particle, be better that described double-colored particle swims in the mode of freely rotating and soaks in the insulativity liquid that is contained in described insulating resin.

In the rotary-type image display device of described particle, the voltage that is applied between described pair of electrodes is better in the scope of 50～300V.

By the present invention, can provide the verticity of the particle when applying voltage good double-colored particle, particularly verticity good white/the double-colored particle of color combination beyond black color combination, and comprise this double-colored particle as the rotary-type image display device of the particle of display element.

The simple declaration of accompanying drawing

Fig. 1 means the first microchannel of being used for transferring painted external phase in the manufacture method of the double-colored particle of putting down in writing in Japanese Patent Laid-Open 2004-197083 communique and for the manufacture of the schematic diagram of the second microchannel of double-colored particle and the figure that represents the formation of double-colored particle.

Fig. 2 means the schematic diagram of the example of a kind of mode that forms painted external phase in the manufacture method of the double-colored particle of putting down in writing in Japanese Patent Laid-Open 2004-197083 communique.

Fig. 3 means a kind of figure of mode of the manufacture method of the double-colored particle of putting down in writing in Japanese Patent Laid-Open 2004-197083 communique.

The best mode that carries out an invention

The below is to double-colored particle of the present invention and comprise this double-colored particle and be elaborated as the rotary-type image display device of the particle of display element.

[double-colored particle of the present invention]

Double-colored particle of the present invention is the resinous double-colored particle that each spherical particle roughly is divided into two kinds of different colours in appearance.The approximate hemisphere of this double-colored particle contains the electric conductivity Chinese white, and the Chinese white take this electric conductivity Chinese white as the main body composition consists of background color.And the approximate hemisphere of all the other of this double-colored particle is coloured to the random color except described background color.

That is, double-colored particle of the present invention is made of irritability zone and painted areas, and described irritability zone is half zone of a pact in particle, contain the electric conductivity Chinese white, described painted areas is the remaining approximately zone of half, does not contain the electric conductivity composition, but contains coloured material.

Pact half the irritability zone that forms a particle of double-colored particle of the present invention is formed by resin, this resin contain the powder resistance rate usually at 1～100 Ω cm, better be electric conductivity Chinese white in the scope of 1～30 Ω cm.This irritability is better to be formed with cross-linked structure in the zone.

In this irritability zone, the content of electric conductivity Chinese white with respect to general assembly (TW) 100 weight portions of electric conductivity Chinese white and resin usually at 1～10 weight portion, better be in the scope of 2～5 weight portions.By containing the electric conductivity Chinese white with this amount, pact half the zone that accounts for double-colored particle demonstrates electric conductivity, and demonstrates high-k.

Irritability in this double-colored particle zone and the potential difference (PD) that contains between the painted areas of coloured material become the driving force that the of the present invention double-colored particle that is placed between pair of electrodes and the voltage that puts on electrode are rotated accordingly.

The irritability zone of containing the electric conductivity Chinese white usually reflects the color of electric conductivity Chinese white and is white in color, but also can make it painted in the scope of the characteristic of not damaging this irritability zone.For example, if with irritability area coloring yellowly, the background color of double-colored particle of the present invention is yellow.That is, in double-colored particle of the present invention, the composition of characteristic that determines to account for approximately the irritability zone of half is the electric conductivity Chinese white, due to this electric conductivity Chinese white this as white, therefore the original background color of double-colored particle of the present invention be white.Therefore, also the background color of this double-colored particle can be adjusted into white or light color to the random color of dark color or black.Above-mentioned characteristic is can be by the characteristic of the double-colored particle of the present invention realized with the electric conductivity Chinese white in the irritability zone, and in the situation that the conductive carbon black of use black etc. as conductive material, can't carry out by the stack of above-mentioned color the adjustment of background color.

In the double-colored particle of the invention described above, can be freely the irritability zone is carried out painted, remaining approximately half the painted areas that therefore consists of double-colored particle can suitably be selected according to the color in irritability zone.In general, by with the opposite color of the color in irritability zone or with it approximate color come paintedly, form image and become distincter.

Ratio about the resin in painted areas and coloured material, as long as the consumption of coloured material can make the color in irritability zone see through painted areas and appear, total amount 100 weight portions with respect to resin and coloured material, the consumption of coloured material in the scope of 1～70 weight portion, is better in the scope of 2～50 weight portions usually.

This painted areas is formed by resin and the coloured material that is dispersed or dissolved in this resin.Better that this painted areas also similarly is formed with cross-linked structure with the irritability zone.

Of the present invention double-colored particle with said structure can be by the whole bag of tricks manufacturing, and the manufacture method of double-colored particle of the present invention can roughly be divided into three types usually.Particularly, can roughly be divided into microchannel method (for example with reference to Japanese Patent Laid-Open 2004-197083 communique), the method for dripping (for example with reference to Japanese Patent Laid-Open 2004-199022 communique) and comminuting method (for example with reference to Japanese Patent Laid-Open 2004-294628 communique).The below describes these methods.

(microchannel method)

This microchannel method is divided the painted external phase 6 of the two kinds of colors of coordinating as shown in Figure 1 in the first interior handover in microchannel 1, make it continuously or spue successively off and on to the second microchannel 2 that the mobility media flow is arranged.There is the insoluble relation of O/W or W/O between described painted external phase and described mobility medium, becomes spherical particle 12 ' because of surface tension when the painted external phase that therefore spues flows in the second microchannel.And, this painted external phase contains resin or monomer whose, resin or monomer whose are by being spued in painted external phase and being carried out UV irradiation and/or heating during spheroidizing and polymerizing curable, by this, can be made into the resinous double-colored particle that each spherical particle roughly is divided into two kinds of different colours in appearance.

＜painted external phase 〉

Described painted external phase is divided the two kinds of colors of coordinating, and this two-phase all contains resin or painted material and other any compositions such as monomer whose, dyestuff or pigment.In double-colored particle of the present invention, the phase (background color phase) that is approximate hemisphere that consists of background color contains coloured material and electric conductivity Chinese white, and this electric conductivity Chinese white is used for giving the approximate hemisphere of formation background color with electric conductivity.The phase that is approximate hemisphere (beyond background color any form and aspect) that is coloured to random color except background color contains any coloured material except background color.Any form and aspect beyond described background color phase and background color can be mixed and obtain by the composition that contains with them.

(resin or monomer whose)

As described resin, but exemplified by acrylic resinoid, styrene resin, vinyl resins, vinyl chloride resin, vinyl acetate esters resin etc. as described monomer, can exemplify the monomer that can form described resin.

The concrete example of described monomer is as described below.

As principal monomer used in the present invention, can exemplify (methyl) acrylic monomer, styrene monomer and vinyl monomer.

Example as described (methyl) acrylic monomer, can exemplify the alkyl acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) acrylic acid cycloalkyl esters such as (methyl) cyclohexyl acrylate, the ester of (methyl) acrylic acid such as isobornyl acrylate and bicyclic alcohols, (methyl) acrylic acid aryl ester classes such as (methyl) phenyl acrylate, (methyl) benzyl acrylate.

As the example of described styrene monomer, can exemplify styrene, methyl styrene, dimethyl styrene, trimethylbenzene ethene, ethyl styrene, diethylbenzene ethene, triethylbenzene ethene, propylstyrene, butylstyrene, hexyl benzene ethene, heptyl benzene ethene, octyl group styrene, fluorobenzene ethene, chlorostyrene, bromstyrol, Dowspray 9,1-chloro-4-methyl-benzene, nitrostyrolene, acetylbenzene ethene, methoxy styrene, α-methyl styrene, vinyltoluene, sodium p styrene sulfonate.

As the example of described vinyl monomer, can exemplify vinyl acetate, propionate, vinyl propionate, isobutyric acid vinyl acetate, trimethylace tonitric vinyl acetate, vinyl caproate, tertiary ethylene carbonate, vinyl laurate, stearic acid vinyl ester, vinyl benzoate, p-tert-butyl benzoic acid vinyl acetate, vinyl salicylate.

As the example of other monomer used in the present invention, can exemplify vinylidene chloride, chlorohexane vinyl carboxylates, Beta-methyl acryloxy ethyl hydrogen phthalic ester, perfluoroethylene, perfluoropropene, vinylidene, vinyltrimethoxy silane, vinyltriethoxysilane.

In addition, in order to improve the dispersiveness of coloured material in monomer, perhaps in order to adjust the specific inductive capacity of each hemisphere that consists of double-colored particle, can and with the monomer that has at least a functional group in molecule, described functional group is for example carboxyl, amide group, amino, hydroxyl, epoxy radicals, itrile group.

Example as the monomer that has carboxyl in molecule, can exemplify acrylic acid, methacrylic acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, maleic acid, fumaric acid, iso-crotonic acid, norbornene dicarboxylic acids, dicyclo [2 as unsaturated carboxylic acid, 2,1] hept-2-ene"-5,6-dicarboxylic acid etc.In addition, as their derivant, can exemplify maleic anhydride, itaconic anhydride, citraconic anhydride, tetrabydrophthalic anhydride, dicyclo [2,2,1] hept-2-ene"-5,6-dicarboxylic anhydride, carboxylic acid halides, these compounds also can exemplify the example for the monomer that has carboxyl in molecule.

example as the monomer that has amide group in molecule, can exemplify the acrylamide as the vinyl monomer of amide-containing, Methacrylamide, the N-methylol methacrylamide, N-methoxy ethyl Methacrylamide, N-butoxymethyl Methacrylamide, N, the N-DMAA, N, N-dimethylaminopropyl acrylamide, acrylamide analog derivative and (methyl) acrylic amides such as N-methylol (methyl) acrylamide and diacetone acrylamide such as N methacrylamide, the amino hexyl succinimide of 6-, 2-amino-ethyl succinimide.

as the example that has amino monomer in molecule, can exemplify as (methyl) acrylic-amino ethyl ester that contains amino vinyl monomer, (methyl) acrylic acid propyl group amino ethyl ester, dimethylaminoethyl methacrylate, (methyl) acrylic-amino propyl ester, methacrylic acid phenyl amino ethyl ester, the alkyl esters derivant of the acrylic or methacrylic acid such as methacrylic acid cyclohexyl amino ethyl ester, N-vinyl diethylamine, the vinylamine analog derivatives such as N-acetyl group vinylamine, allylamine, the methyl-prop enamine, the propylamine derivants such as N-methyl-prop enamine, the aminobenzene vinyl such as p-aminophenyl ethene.

As the example of the monomer that has hydroxyl in molecule, can exemplify the addition product of monoesters, lactone and (methyl) 2-Hydroxy ethyl acrylate of (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid and polypropylene glycol or polyglycol.

example as the monomer that has epoxy radicals in molecule, can exemplify (methyl) glycidyl acrylate, single ethylene oxidic ester and the 2-glycidyl ester of maleic acid, single ethylene oxidic ester and the 2-glycidyl ester of fumaric acid, single ethylene oxidic ester and the 2-glycidyl ester of crotonic acid, single ethylene oxidic ester and the 2-glycidyl ester of tetrahydrophthalic acid, single ethylene oxidic ester and the 2-glycidyl ester of itaconic acid, the tricarboxylic single ethylene oxidic ester of butylene and 2-glycidyl ester, single ethylene oxidic ester and the 2-glycidyl ester of citraconic acid, single ethylene oxidic ester and the alkyl glycidyl ester of the dicarboxylic acid such as single ethylene oxidic ester of allyl succinic acid and 2-glycidyl ester, alkyl glycidyl ester to the styrene carboxylic acid.

As the example of the monomer that has itrile group in molecule, can exemplify vinyl cyanide, methacrylonitrile.

In the present invention, can use separately a kind of above-mentioned monomer, perhaps also the multiple above-mentioned combination of monomers more than 2 kinds can be used.

Above-mentioned resin can obtain by making corresponding monomer polymerization.For example by being spued in described painted external phase and carrying out UV irradiation and/or heating during spheroidizing, solidify when monomer or resin are spherical because surface tension becomes, become the resin cured matter with spherical-like morphology.

(electric conductivity Chinese white)

Any conductive material that described electric conductivity Chinese white for example is selected from antimony oxide/tin ash, indium oxide/tin ash by use is processed the method for giving electric conductivity to Chinese white and is obtained, be used for giving consist of background color approximate hemisphere with electric conductivity.As described Chinese white, can exemplify for example titanium dioxide, zinc paste.

Here, process and specifically to refer to spherical Chinese white (for example titanium dioxide) as core, carry out the operation of coating or dipping with described conductive material.Chinese white is in the situation of titanium dioxide, and titanium dioxide can be both that rutile-type can be also Detitanium-ore-type.In addition, described coating or dipping are by carrying out Chinese white and conductive material with wet method or dry mixed.The electric conductivity Chinese white that obtains is as mentioned above also sold on market.Such as also using with commercially available electric conductivity Chinese whites such as trade name ET-500W (the former industry of stone (the former industry of stone) Co., Ltd.'s system).

In the present invention, consisting of the Chinese white of electric conductivity Chinese white and the amount of lining material or impregnated material can suitably set, the weight ratio of Chinese white and lining material or impregnated material (Chinese white: lining material or impregnated material) is set in the scope of 95: 5～70: 30 usually, be better to be set in 90: 10～scope of 80: 20 in.By use lining material or impregnated material in above-mentioned scope, can give Chinese white with good electric conductivity.

The particle diameter of electric conductivity Chinese white is generally 0.10～5 μ m, preferably 0.10～0.5 μ m.

The powder resistance rate of electric conductivity Chinese white is generally 1～100 Ω cm, preferably 1～30 Ω cm.

In the present invention, also above-mentioned electric conductivity Chinese white can be mixed use with the Chinese white of processing without electric conductivity.

(coloured material)

As described coloured material, can exemplify netrual colour dyestuff, netrual colour pigment, chromatic colour dyestuff, chromatic colour pigment.

Particularly can exemplify: black ... Olesolol Fast Black, BONJET BLACK CW-1, Solvent Black 27 contain 5% Cr (3 valency), pigment black (Pigment Black) 7;

Water colour, redness ... VALIFAST RED 3306, Olesolol Fast RED BL, Solvent RED 8 contain 5.8% Cr (3 valency), Permanent Carmain FBB02-JP;

Blue ... Kayaset Blue, Solvent Blue 35, cyanines blue (Cyanine Blue);

Yellow ... VALIFAST YELLOW 4120, Oil Yellow 129, Solvent Yellow 16, Solvent Yellow 33, Disperse Yellow 54, PV Fast Yellow H2G;

Lemon yellow ... Piast Yellow 8005;

Green ... Oil Green 502, Opias Green 502, Solvent Green 3,

Magenta ... VALIFAST PINK 2310N, Plast RED D-54, Plast RED 8355, Plast RED 8360, Plast Vioiet 8850, Disperse Violet 28, Solvent RED 149, Solvent RED 49, Solvent RED 52, Solvent RED 218 contain 4% Cr (3 valency);

Cyan ... VALIFAST BLUE 2610, VALIFAST BLUE 2606, Oil BLUE 650, Plast BLUE 8580, Plast BLUE 8540, Oil BLUE 5511, Solvent Blue 70 contain 4%Cu;

Orange ... Oil Orange 201, VALIFAST ORANGE 3210, Solvent Orange 70, Kayaset Orange G;

Brown ... VALIFAST BROWN 2402, Solvent Yellow 116, Kayaset Flavine FG etc.

In addition, as the example of coloured material, also can exemplify, Lumogen F Orange green such as solvent blue, solvent red, solvent orange, solvent etc.

in addition, as described coloured material, also can exemplify for example curare bases, the perylene class, dicyano is vinyl-based, azo, the quinophthalone class, amino pyrazoles, the methine class, the dicyano imidazole class, the indoaniline class, the dyestuff of commonly using in the note taking liquid such as phthalocyanines, leuco dye as electrothermal sensitive recording paper or temperature sensitive coloured material, and rhodamine B stearate (red No. 215), tetrachloro-tetrabromfluorescein's (red No. 218), eosin (red No. 223), soudan III (red No. 225), dibromofluorescein (orange No. 201), diiodofluorescein (orange No. 206), fluorescein (yellow No. 201), quinoline yellow SS (yellow No. 204), the green SS of quinizarin (green No. 202), the purple SS (No. 201, purple) of zaurine, medicinal scarlet red (red No. 501), oil red XO (red No. 505), orange SS (orange No. 403), yellow AB (yellow No. 404), yellow OB (yellow No. 405), the tar class dyestuff that the blue B of the Sudan (blue No. 403) etc. uses in cosmetics.

These dyestuffs can use separately or mix more than 2 kinds and use; As the example of coloured material, also can exemplify as required various direct dyess, acid dyes, basic-dyeable fibre, azo dyes, chemically-reactive dyes, fluorescent dye and fluorescer, they can also be dispersed in described (methyl) acrylic monomer.

For example also can use permanent yellow DHG, Lionol Yellow 1212B, Si Mule fast yellow (Symuler Fast Yellow) 4400, pigment Yellow 12 as yellow uitramarine;

Paratonere 57:1, Lionol Red 6B-4290G, Irgalite Rubine 4BL, Fastogen SuperMagenta RH as magenta pigment;

Lionol Blue 7027, Fastogen Blue BB, Cromophtal Blue 4GNP as green pigment;

Carbon black, Black Pearls 430, iron oxide red, ultramarine as black pigment;

As the various inorganic pigments such as the titanium white that does not have electric conductivity of Chinese white, zinc sulphide, zinc paste, alumina white, calcium carbonate and organic pigment etc.

In the present invention, consist of the phase (background color phase) that is approximate hemisphere of background color and be coloured to total amount that being of random color except background color be similar to coloured material contained in (background color any form and aspect in addition) mutually of hemisphere that the described resin in mutually and total amount 100 weight portions of monomer whose are generally 0.1～50 weight portion with respect to each, preferably 2～40 weight portions.When representing with volume fraction, preferably 1～20%.

(polymerization initiator)

In the present invention, be better to make any the form and aspect beyond background color phase and background color contain polymerization initiator.

Particularly, described polymerization initiator is used for making the described monomer that will be polymerized as resin more easily begin polyreaction, is better to make painted external phase contain polymerization initiator in the present invention.

As polymerization initiator, can exemplify persulfates such as potassium persulfate, ammonium persulfate, the superoxide such as benzoyl peroxide, lauroyl peroxide, the azo-compounds such as azoisobutyronitrile etc.The polymerization initiator that preferably uses during as painted or polymerization, can exemplify for example as 2 of azo polymerization initiator, 2 '-azo two (2-methyl propionitrile), 2,2 '-azo two (2-methylbutyronitrile), 2,2 '-azo two (2,4-methyl pentane nitrile), 2,2 '-azo two (2-cyclopropyl propionitrile), 1,1 '-azo two (cyclohexane-1-formonitrile HCN), 2, two (2 Methylpropionic acid) dimethyl esters of 2 '-azo.

It is 0.01～5 weight portion that the consumption of these polymerization initiators is generally with respect to every 100 described monomers of weight portion, is better 0.5～2 weight portion.

As other polymerization initiator, for example can exemplify the existing known acetophenone class as Photoepolymerizationinitiater initiater, acetophenone, 2 for example, 2-diethoxy acetophenone, to dimethylamino acetyl benzene, *-methoxy acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2-hydroxyl-2-cyclohexyl acetophenone;

Ketone, for example benzophenone, 2-chloro benzophenone, p, p '-two chloro benzophenone, p, p '-two (diethylamino) benzophenone, N, N '-tetramethyl-4,4 '-diamido benzophenone (Michler's keton), 4-(2-hydroxyl-oxethyl) phenyl (2-hydroxyl-2-propyl group) ketone;

Benzoin ethers, for example benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether, benzil dimethyl ketal, benzoylbenzoic acid ester, α-acyl group oxime ester, thioxanthene ketone.

As thermal decomposition type polymerization initiator, can exemplify for example peroxyesters, organic peroxide class, organic hydroperoxide class, organic peroxy ketal class and azo-compound class.

As described peroxyesters, can exemplify for example own ester of peroxide neopentanoic acid uncle, the peroxide neodecanoic acid tert-butyl ester, t-butyl peroxybenzoate, peroxidating-own ester of 2 ethyl hexanoic acid uncle, the own ester of peroxide neodecanoic acid, peroxide neodecanoic acid cumyl ester, peroxidating-2 ethyl hexanoic acid-1,1,3,3-tetramethyl butyl ester.

As described organic peroxide class, can exemplify for example dicumyl peroxide, di-t-butyl peroxide, tert-butyl peroxide cumyl, dilauroyl peroxide, dibenzoyl peroxide, diacetyl peroxide, didecanoyl peroxide, the different nonanoyl of peroxidating two, peroxidating-2-methyl valeryl.

As described organic hydroperoxide class, can exemplify for example t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethyl-2,5-two hydroperoxy hexanes, p-methane hydroperoxide, di-isopropylbenzene hydroperoxide.

As described organic peroxy ketal class, for example can exemplify 1, two (the uncle's hexyl peroxies)-3 of 1-, 3,5-trimethyl-cyclohexane, 1, two (the uncle's hexyl peroxy) cyclohexanes, 1 of 1-, 1-bis(t-butylperoxy)-3,3, the 5-trimethyl-cyclohexane.

As described azo-compound class, for example can exemplify 2,2 '-azoisobutyronitrile, 2,2 '-azo two-(2, the 4-methyl pentane nitrile), 2,2 '-azo two (cyclohexanenitriles), 1,1 '-azo two (cyclohexane-1-formonitrile HCN), 2-phenylazo-4-methoxyl-2,4-methyl pentane nitrile, 2,2 '-azo-bis-iso-dimethyl.

These polymerization initiators can use separately a kind, also can be used in combination more than 2 kinds.

(multi-functional monomer)

In the present invention, mix the multi-functional monomer more than two senses in any form and aspect that can be beyond background color phase and background color, make principal monomer or other monomer reaction used in itself and the invention described above.

Example as the multi-functional monomer more than described two senses, can exemplify diacrylate class, triacrylate class, the tetraacrylate class of (gathering) aklylene glycol, perhaps (gather) dimethylacrylate class, trimethyl acrylic ester class, the tetramethyl esters of acrylic acid of aklylene glycol.

as their example, can exemplify ethylene glycol bisthioglycolate (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, diethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, 1, 1, 1-trihydroxy methyl ethane diacrylate, 1, 1, 1-trihydroxy methyl ethane triacrylate, 1, 1, 1-trihydroxy methyl propane triacrylate, N hydroxymethyl acrylamide, 1, 9-nonanediol diacrylate, 2-butyl-2-ethyl-1, the ammediol diacrylate.

The above multi-functional monomer of described two senses is used for introducing cross-linked structure at described resin.Cross-linked structure is not essential, but has cross-linked structure by double-colored particle, in the rotary-type image display device of following particle of the present invention, even the insulativity liquid of silicone oil and so on contacts with double-colored particle of the present invention, double-colored particle of the present invention can because of insulativity liquid swelling, can not make in the double-colored insulativity liquid that swims in insulative resin particle-stabilisedly yet.

The consumption of this multi-functional monomer is generally 10～90 weight portions in monomer 100 weight portions that will become described resin.In addition, about multi-functional monomer, also can only use multi-functional monomer, make its polymerization and form cross-linked structure, with the polymkeric substance of multi-functional monomer as the resin in double-colored particle of the present invention.

(other any composition)

As other contained any composition in described painted external phase (being any the form and aspect beyond background color phase and background color), can exemplify UV sensitizer, band controling agent, pigment dispersing agent, thermal stabilizer, conductive agent, antiseptic, surface tension adjusting agent, defoamer, rust preventive, antioxidant, near infrared absorbent, ultraviolet light absorber, fluorescer, fluorescer etc.

Described UV sensitizer is the composition that uses for the effect of having given play to better described Photoepolymerizationinitiater initiater, as its example, can exemplify n-butylamine, triethylamine, tri-n-butyl phosphine etc.

Described purposes with controling agent is as follows: contain this band controling agent by making any the form and aspect beyond described background color phase and/or background color, can regulate the charged characteristic of each approximate hemisphere of the double-colored particle of gained, improve the verticity of the double-colored particle when applying voltage.Here, as the example with controling agent, can exemplify slaine, copper phthalocyanine sulfonamide, hydrocarbon black, metal naphthenate, 4-hydroxyl naphthalene-quaternary ammonium salts such as 1-sulfonic acid benzyl tributyl ammonium of the simple substance of styrene acrylic base polymer, Calixarene Derivatives, hindered amine, azines, salicylic acid metal complex, phenolic condensate, lecithin, paramagenta, nigrosine class dyestuff, alkoxylated amines, alkylamide, phosphorus and tungsten and compound, molybdic acid chelate pigment, fluorine class activator, hydrophobic silica, monoazo dyes etc.The band controling agent also can double as coloured material, and coloured material also can double as the band controling agent.

Consumption with controling agent is generally 0.05～5 weight portion with respect to monomer 100 weight portions that will become described resin, preferably 0.5～2 weight portion.

＜mobility medium 〉

In the method for microchannel mobility medium used as mentioned above, be and described painted external phase between have the medium of the relation of O/W or W/O.In other words, the mobility medium is medium as described below: itself does not dissolve painted external phase, and painted external phase is spherical, and therefore painted external phase can freely distortion in this mobility medium.

As the mobility medium, can exemplify the polyvinyl alcohol water solution, carboxymethyl cellulose aqueous solution, the Carboxymethyl Cellulose aqueous solution that for example make polyvinyl alcohol (PVA) be dissolved in ion exchange water and get.Because painted external phase mostly is greatly the phase (O phase) of oiliness, so as the mobility medium, the phase (W phase) of preferred water-based.

The manufacture method of＜double-colored particle 〉

In microchannel method as an example of the method that forms double-colored particle of the present invention, as shown in Figure 1, the painted external phase 6 of dividing the two kinds of colors of coordinating in the first interior handover in microchannel 1 makes it continuously or spues successively off and on to the second microchannel 2 that the mobility media flow is arranged.There is insoluble relation between described painted external phase and described mobility medium, namely forms O/W or W/O state and exist.When flowing, the painted external phase that therefore, spues becomes spherical particle 12 ' because of surface tension in the second microchannel.And, this painted external phase contains resin or monomer whose, resin or monomer whose are by being spued in painted external phase and being carried out UV irradiation and/or heating during spheroidizing and polymerizing curable, by this, usually can form the solidfied material of resin, thereby generate the double-colored particle that each spherical particle roughly is divided into two kinds of different colours in appearance.

In the method, the microchannel is superfine, its flow path width is in the situation of hundreds of microns left and right, and the viscosity of the fluid (painted external phase) that flows is therein occupied an leading position, and therefore having becomes the tendency of laminar condition under the condition below 1000 at Reynolds number.Coordinate two kinds of colors too even painted external phase is divided, divide the painted external phase of the two kinds of colors of coordinating that the tendency of transferring with the STATIC CORRECTION USING APPROXIMATE LAYER stream mode is arranged, therefore, can be used as external phase easily handover in the first microchannel that two kinds of colors can not mix.

Speed when painted external phase is transferred in the first microchannel depends on viscosity, surface tension, density, fluidity (polar group) of painted external phase etc., usually can be with the flow velocity of flow F1=0.01～10ml/hr, better be that the flow velocity of 0.01～5ml/hr is suitably transferred or spues to the second microchannel.

In addition, the flow F2 ml/hr of the mobility medium that flows in the second microchannel is as long as when the painted external phase that is spuing flows in the scope of spheroidizing, be not particularly limited, be generally the flow velocity of flow F2=1～100ml/hr, better be the flow velocity of 1～50ml/hr.

The throughput ratio that represents with F2/F1 can be considered the fluidity such as the fluid viscosity, density, surface tension of growing amount, mean grain size and particle monodispersity, painted external phase and the mobility medium of the double-colored particle that wish is made and suitably set.

The painted external phase that spues to the second microchannel is spuing under the state of two kinds of colors that minute coordinates, is disperseing, spherical particle occuring in the handover process, and the resin in this painted external phase that spues or monomer whose are by UV irradiation and/or heating and polymerizing curable.Because the spherical shape of the painted external phase that spues after spheroidizing is stable, so in this polymerizing curable, even polymerizing curable fully in the process that painted external phase does not flow in this second microchannel is suitably carrying out polymerizing curable under the UV irradiation and/or under heating in other container of the double-colored particle accumulator tank of conduct that also can be being arranged at the second microchannel system outside.

Exposure during irradiation UV is generally 300～1500mJ/cm ², the heating-up temperature during heating is generally the temperature of 60～100 ℃, and be 20～120 minutes heat time heating time.

For the painted external phase 6 in the first double-colored phase of the interior handover in microchannel 1 [6a/6b], for example in the mode shown in Fig. 2 (a), the liquid that double-colored phase [6a/6b] is supplied to the first microchannel is flowed into port.As shown in Fig. 2 (a), the liquid in the first microchannel 1 flows into the port, and the 3rd microchannel 3 and the 4th microchannel 4 are engaged in the mode that forms the V font.By the 3rd microchannel and the 4th microchannel to the first interior supply background color in microchannel 1 mutually with background color beyond any form and aspect 6a and 6b, in the painted external phase 6 of the first double-colored phase of the interior formation in microchannel 1 [6a/6b].In mode shown in this Fig. 2 (a), form the 3rd microchannel 3 of V font and the 4th microchannel 4 and be better be arranged to the first microchannel 1 in the same plane.In addition, the angle theta 5=90 of the formation V font at place, this junction ± 80 ° is better angle theta 5=90 ± 60 °.

In addition, also can will divide the painted external phase of the two kinds of colors of coordinating to be supplied to the first microchannel in the mode shown in Fig. 2 (b).In mode shown in Fig. 2 (b), for example engage the 3rd microchannel 8 at the position midway of the first microchannel 1 of transferring form and aspect 6b, make angle (or angular aperture) θ 6 with the transfer direction of form and aspect 6b in the scope of acute angle.And, by supplying with form and aspect 6a by the 3rd microchannel 8, can be in the painted external phase 6 of the first double-colored phase of the interior formation in microchannel 1 [6a/6b].

Double-colored particle of the present invention can also be made in mode shown in Figure 3.The liquid of the second microchannel 2 of the liquid outflow port of the first microchannel 1 and tubular flows into port and engages along coaxial rectilinear direction each other, and in described the second microchannel 2, mobility medium 7 is mobile with the flow F of the regulation that represents with units/ml/hr.

Both sides near the same plane this connecting portion, two sides microchannel 5a, 5b engage with the second microchannel 2 along the transfer direction of the painted external phase 6 in the first microchannel, and its angle theta 3 and θ 4 are respectively in the scope of 45 ± 5～40 °.

As shown in Figure 3, locate to be nipped off by the mobility medium 7 of being supplied with by two sides microchannel 5a, 5b at this front port as first microchannel 1 of junction (or connecting portion) (liquid outflow port) in the painted external phase 6 of the double-colored phase [6a/6b] of the first microchannel 1 interior handover and take out and spue to the second microchannel 2, thereby form the spherical compound 12 ' of painted external phase 6.

The angle theta 3 that microchannel, two sides becomes with the first microchannel and θ 4 are better θ 3=θ 4, and in addition, in above-mentioned Fig. 3, this angle theta 3 and θ 4 are interior acute angles of scope of 45 ± 5～40 °.Though not shown, also this angle theta 3 and θ 4 can be made as right angle or obtuse angle more than 90 °.

As the shape of the vertical incision of above-mentioned the first microchannel～the 3rd microchannel and microchannel, side, can exemplify for example circular, ellipse and quadrilateral (square, rectangle, trapezoidal).The angle of the microfabrication when using starting material such as glass plate, plastic plate to form the microchannel of above-mentioned shape is as the shape of the vertical incision of microchannel, preferred quadrilateral (square, rectangle).The otch of these microchannels is in the situation of rectangle (or rectangle), be better the long limit of this otch in the scope of 0.5～500 μ m, the minor face of this otch is in the scope of 0.5～500 μ m.The lower limit that is more preferably the length on each limit is 1 μ m.

(sessile drop method)

In sessile drop method, the second drop of any form and aspect beyond making the first drop of being background color and having background color contacts in air or in liquid and forms a drop, it is contacted and moment solidifies with reactant liquor, thereby makes double-colored particle of the present invention.

As making described the first drop and the painted coloured material of the second drop, can use the coloured material identical with coloured material used in the method for described microchannel.In sessile drop method, in the method for microchannel composition used, also can use the amines such as 1,6-hexane diamine, sodium alginate, sodium carboxymethyl cellulose, polyvinyl alcohol (PVA) as the composition that contains of described the first drop and the second drop, their can and the reaction of described reactant liquor.In addition, the first drop contains the electric conductivity Chinese white.As described the first drop and the second drop contain arbitrarily composition, also can mix charge control agent or band controling agent.

＜the method for formation drop in air or in liquid 〉

At first, the method that forms drop in air is described.Described the first drop and the second drop can be by being formed with for example spray nozzle, inkjet nozzle ejection by the liquid (first liquid and second liquid) that composition forms that contains separately.

Then, the method that forms drop in liquid is described.Described the first drop and the second drop can form to the liquid that does not dissolve first liquid and second liquid by first liquid and second liquid are spued.For example, first liquid and second liquid are in the situation of hydrophilic liquid, they can be spued to the non-hydrophilic solvent of for example wet goods.

＜reactant liquor 〉

As described reactant liquor, can exemplify the acid such as multivalent cation, borax, hydrochloric acid such as isocyanates such as the acyl chlorides such as sebacoyl chloride, TDI, lime chloride.They can suitably be selected according to the composition of formed the first drop and the second drop.

The manufacture method of＜double-colored particle 〉

As mentioned above, for example contact in air with the second drop by the first drop made from inkjet nozzle ejection and form a drop.As long as described reactant liquor is prepared in the position in this droplets fall, drop just can contact and instantaneous solidification with reactant liquor.Make thus double-colored particle of the present invention.

(comminuting method)

In comminuting method, the layer that will be formed by thermoplastic resin background color composition (A) and form duplexer (C) by the thermoplastic resin coloured composition (B) that is coloured to the random color beyond background color, by the impact of the point-like on the direction substantially vertical with lamination surface, this duplexer (C) is pulverized and obtained crushing piece, to this crushing piece heating, thereby make double-colored particle of the present invention.In comminuting method, spherical because described crushing piece need to be deformed into by heating, so must be thermoplastic resin as the resin of the resin that consists of double-colored particle.

Thermoplastic resin as using in described thermoplastic resin background color composition (A) and described thermoplastic resin coloured composition (B) can use known thermoplastic natural resin or synthetic resin.

Particularly, can use the natural resins such as pentaerythritol ester such as rosin, rosin, dammar (dammar), the acrylic monomer polymerization that can use in the method for described microchannel or copolymerization and the synthetic resin such as acrylic resin, styrene-(methyl) acrylate copolymer, styrene-(methyl) acrylic copolymer, polystyrene, maleic acid resin, Polyvinylchloride, polyester, thermoplastic polyurethane.

Above-mentioned resene can use separately or mix more than 2 kinds and use.But, in comminuting method, make to pulverize after the duplexer that is formed by described thermoplastic resin and make its panelization, then make its particlized by heating, so preferably have the flexibility that is adapted to crush force and glass temperature at the resin more than 60 ℃.

The manufacture method of＜duplexer (C) 〉

Method as making duplexer (C) can exemplify for example following methods.

(1) after coating on matrix contains the coating (A1) of thermoplastic resin background color composition (A) and makes its drying, stacked coating contains the coating (B1) of thermoplastic resin coloured composition (B), dry rear stacked rubbing method from matrix stripping.

(2) after being sprayed at coating (A1) on matrix and making its drying, spray coatings (B1), dry after from the method for matrix stripping.

The method that (3) will be extended with warm-up mill etc. by thermoplastic resin background color composition (A) and the overlapping plate object that forms of thermoplastic resin coloured composition (B) or ingot.

Need solvent in these methods, as solvent, can exemplify alcohols, ester class, ketone, dibasic alcohol ethers, binary alcohol esters class and diatomic alcohol ether acid ester class etc.

The manufacture method of＜double-colored particle 〉

In comminuting method, by the impact of the point-like on the direction substantially vertical with lamination surface, described duplexer (C) is pulverized and obtained crushing piece, to this crushing piece heating.

The impact of described point-like applies with impact, this impact has such as needle-like or taper etc. can apply to the narrow and small area of point-like the shape of shock, is made by the material of the shock of above size such as the breakdown strength that can apply duplexer (C) such as steel or stainless steel etc.

Described substantially vertical direction is particularly vertical direction ± 15 °.

Utilize the described son that impacts duplexer (C) is applied the impact of the point-like on the direction substantially vertical with lamination surface and it is pulverized, to the crushing piece heating of gained.More specifically, utilize hot blast etc. that crushing piece is heated to the fusing initial temperature of the thermoplastic resin that in thermoplastic resin contained in thermoplastic resin background color composition (A) or thermoplastic resin coloured composition (B), the fusing initial temperature is higher above and make its melting.Crushing piece changes into just spherical because the surface tension of thermoplastic resin is spherical, the crushing piece after spheroidizing is carried out cooling, thereby obtain double-colored particle.

(double-colored particle of the present invention)

The of the present invention double-colored particle of making by for example said method is formed by resin, each spherical particle roughly is divided into two kinds of different colours in appearance, the approximate hemisphere of this double-colored particle contains the electric conductivity Chinese white, thereby the formation background color, the approximate hemisphere of all the other of this double-colored particle is coloured to the random color except described background color.

As mentioned above, in double-colored particle of the present invention, the specific inductive capacity of the approximate hemisphere of its background color has very big-difference with the specific inductive capacity that is coloured to the approximate hemisphere of the random color except background color, and therefore the charged characteristic of above-mentioned each approximate hemisphere has very big-difference.Therefore, double-colored particle of the present invention apply voltage the time the verticity of particle good, particularly for existing verticity deficiency white/the double-colored particle of color combination beyond black color combination also can realize high verticity.

The mean grain size of double-colored particle of the present invention represents common in the scope of 30～200 μ m with volume reference, be better in the scope of 70～150 μ m.The double-colored particle of mean grain size in this scope easily rotates when applying voltage.The deviation of particle diameter with uniformity coefficient Cv value representation, usually below 20%, is better below 5%, is more preferably below 3%.

Described mean grain size can as described belowly be adjusted.

Adopt in the situation of microchannel method, by the restriction of the quantitative limitation that spues, nozzle, the restriction of resin viscosity etc., the mean grain size of the double-colored particle of gained reduces.

Adopt in the situation of sessile drop method, such as making in the situation of the first drop and the second drop with the ejection such as spray nozzle, by reducing the aperture of nozzle, the particle diameter of two kinds of drops reduces, so consequently, the particle diameter of double-colored particle also reduces.In sessile drop method, with the sodium alginate of reactant liquor reaction etc. to be dissolved in solvent the form of solution use, therefore described the first drop and the second drop also comprise solvent.If make double-colored particle and dry, described solvent evaporation, less before the evaporation of particle diameter ratio solvent.Therefore, by the concentration of the composition beyond the solvent of regulating the first drop and the second drop, the mean grain size of the double-colored particle of capable of regulating.

Adopt in the situation of comminuting method, impact of the impact by will apply point-like is made by pin and is tied up the pencil thing that forms and the density of adjusting pin, can control the size of the double-colored particle of gained.That is, change the density of pin and after obtaining double-colored particle, measure its particle diameter, can determine by this to obtain efficiently the density of the pin of required particle diameter.The relation of the density of particle diameter and pin is subject to utilizing the impact of the size of impacting the sub crushing piece that cracks.

[the rotary-type image display device of particle]

As mentioned above, double-colored particle of the present invention apply voltage the time verticity good, therefore be suitable as the display element of the rotary-type image display device of particle.

comprising double-colored particle of the present invention is by contain in the mode of freely rotating the rotary-type image display device of particle that the insulating resin of double-colored particle forms between pair of electrodes as the rotary-type display device of the particle of display element, it constitutes: described double-colored particle is the resinous double-colored particle that each spherical particle roughly is divided into two kinds of different colours in appearance, the approximate hemisphere of described double-colored particle contains the electric conductivity Chinese white, thereby formation background color, the approximate hemisphere of all the other of described double-colored particle is coloured to the random color except described background color, by being applied to described interelectrode voltage, described double-colored particle rotates in described insulating resin.

The rotary-type image display device of particle of the present invention is generally chip shape, can be via following operation manufacturing.

(1) preparation is dispersed with the operation of the compositions of thermosetting resin of double-colored particle of the present invention;

(2) make its heat curing after this compositions of thermosetting resin is coated base material, thereby make the operation of the insulativity transparent resin sheet material that is dispersed with described double-colored particle;

(3) make this sheet material swelling in insulativity liquid by this insulation transparent resin sheet be impregnated in, the mode that encases with the double-colored particle that will be dispersed in inside forms the vacuole of insulativity liquid, thereby makes the operation of the display member that is formed with described vacuole;

(4) in the operation of the two sides of this display member multilayer electrode member.

As the thermoset resin that uses in the compositions of thermosetting resin in operation (1), so long as insulativity and the transparency all good resin get final product, be not particularly limited, can preferably use and make the two-solution curing type organic siliconresin that has flexibility when showing sheet material.Below, describe as the rotary-type image display device of the particle of thermoset resin using the two-solution curing type organic siliconresin.

Compositions of thermosetting resin acquisition as described below: according to the condition that the containing ratio of double-colored particle of the present invention is 40～60 volume %, it is mixed the two-solution curing type organic siliconresin, then mix with stirring machine.If the containing ratio of this double-colored particle is less than 40 volume %, the covering property deficiency of the demonstration sheet material of gained, the display characteristic of image display device worsens sometimes.On the other hand, if more than 60 volume %, amount of resin is not enough, thereby is difficult to sometimes compositions of thermosetting resin is coated base material equably when making sheet material.

Described compositions of thermosetting resin can be coated base material by known customary way.The viscosity of this compositions of thermosetting resin is usually up to 5000～10000mPas, as the coating process that is suitable for said composition, can exemplify lithographic plate coating machines such as ring rod coating (ワ イ ヤ バ Yi Tu work), spreader coating, rotary coating, in addition also can exemplify knife type coater, comma doctor knife coater, mould and be coated with the continous way coating machines such as machine, lip coating machine etc.

About base material used this moment, as long as normal use the at can the temperature as the curing of the thermoset resin of subsequent handling the time is not particularly limited the polyethylene terephthalate of preferred intensity and excellent size stability (PET).

The coating thickness of compositions of thermosetting resin is better 2～4 times of the mean grain size that represents with volume reference of double-colored particle of the present invention.If less than 2 times, not only can be because of oversize grain etc. when coating substrate former thereby easily produce crawling, and also the covering property of the demonstration sheet material of gained may be not enough.Otherwise if greater than 4 times, double-colored particle through-thickness is arranged in multilayer, thereby shows that the reflectivity of sheet material descends, and display quality may worsen.

The filming heating of described compositions of thermosetting resin made its curing.Solidify is better to carry out at high as far as possible temperature in the scope of glass temperature of thermoplastic resin used in being no more than double-colored particle.

The thermosetting paint film of described compositions of thermosetting resin is peeled off from base material, obtained being dispersed with the insulativity transparent resin sheet material of double-colored particle of the present invention.Be dispersed in this insulativity transparent resin sheet material double-colored particle with solidify after the matrix resin driving fit, can not rotate even therefore apply electric field yet.So, this insulativity transparent resin sheet material be impregnated in insulativity liquid, make the solidfied material swelling of described compositions of thermosetting resin, can form by this around double-colored particle the vacuole of this insulativity liquid abrim.

The insulativity liquid that uses must be able to make the thermoset resin swelling after curing, and can not make any dissolving or swelling in the resin that uses in the induction region of double-colored particle of the present invention and painted areas.As such insulativity liquid, can exemplify silicone oil, high-grade aliphatic ester, polyene hydrocarbyl ether, isoalkane, fluorinated polyether as an example.

Thermoset resin is in the situation of described organic siliconresin, and what can be preferably used as insulativity liquid is silicone oil.Because the compatibility of silicone oil and organic siliconresin is good, so although can make organic siliconresin solidfied material swelling, can not make any resin dissolves or the swelling used in described irritability zone and painted areas.

As silicone oil, can use such as methyl phenyl silicone, dimethyl polysiloxane etc.The viscosity of silicone oil under 25 ℃ is better below 100mPas.If viscosity is higher than 100mPas, the rotation of the double-colored particle in vacuole is difficult, and the response speed of demonstration may descend.If improve electric field intensity in order to make up this deficiency, the tendency of the problems such as power consumption increase required when producing image switching etc. is arranged.The proportion of silicone oil is the proportion close with the proportion of double-colored particle preferably.

Condition when impregnated in the insulativity transparent resin sheet material that is dispersed with double-colored particle in insulativity liquid depends on the thermoset resin that uses and the kind of insulativity liquid, the state of cure of thermoset resin.Above-mentioned thermoset resin is the two-solution curing type organic siliconresin, and insulativity liquid is in the situation of silicone oil, and at room temperature the dipping by 10～24 hours forms vacuole usually.This time can shorten by improving as much as possible the temperature that insulativity transparent resin sheet material be impregnated in insulativity liquid, but in the scope of the glass temperature of the resin that must use in not higher than double-colored particle.

Then, at the two sides of the sheet display member that obtains by said method multilayer electrode layer, thereby obtain the rotary-type image display device of particle of the present invention.For this reason, as long as the stacked one side at base material as substrate is provided with the pellet electrode member of electrode layer on the two sides of this sheet display member, for example simultaneously be provided with the plastic sheeting of electrode layer.At this moment, may not make the face driving fit of electrode surface and the sheet display member of this substrate, also can make face and this sheet display member driving fit of opposition side of the electrode surface of this substrate.In order to prevent between this sheet display member and this substrate etc. that spilling of insulativity liquid appears in the place, and the blocking-up ambient atmos, the single or multiple lift plastic sheeting with barrier properties for gases is clipped in wherein.

As the base material that is used for stacked described electrode layer, can use film or sheet material and the glass plate etc. of the plastics such as vinylidene chloride, vinyl chloride, tygon, polypropylene, polyethylene terephthalate.Electrode layer can use the paper tinsel of aluminium, copper, metal that nickel constant resistance value is low or the film that forms by evaporation or sputter, perhaps also can use the transparent electrode thin film of tin indium oxide (ITO), antimony tin (ATO), tin oxide etc. etc.

In the rotary-type image display device of particle of the present invention that gets by the two sides that this electrode layer is laminated in described sheet display member, at least the electrode layer of the observation side of device, be used for the base material of multilayer electrode layer and the plastic sheeting that uses as required etc. must be all transparent.This is because if opaque, can't see the image that device shows.

Can use bonding agent or double-sided adhesive sheet etc. when the multilayer board of the two sides of sheet display member.At this moment, also must be according to the condition selection material of the transparency that can not affect the observation side that shows sheet material.

In the rotary-type image display device of particle of the present invention that obtains by said method, be generally 50～500V, the voltage in the scope of 50～300V preferably by applying between the electrode to this substrate, can make the double-colored particle rotation in the insulativity liquid in the solidfied material that swims in compositions of thermosetting resin.

And, in the rotary-type image display device of particle of the present invention, described thermoset resin (insulativity and the transparency are good) contains double-colored particle of the present invention in the mode of freely rotating, and the verticity of the double-colored particle when therefore applying voltage is good, thereby can realize showing rapidly.

In addition, if the proportion of the approximate hemisphere of the background color of double-colored particle is roughly the same with the proportion of the approximate hemisphere that is coloured to the random color except background color (calling painted approximate hemisphere arbitrarily in the following text), the center of double-colored particle is center or the close center of ball, and double-colored particle easily rotates.And after applying voltage and making the rotation of double-colored particle, double-colored particle can not cause the demonstration of display device to change because gravity rotates yet, and can give play to memory characteristic.Although proportion has difference to a certain degree, because the viscosity of the insulativity liquid such as silicone oil produces constraining force to double-colored particle, therefore the unordered rotation of double-colored particle is suppressed, and the rotary-type image display device of particle of the present invention has memory characteristic usually.

Carry out as mentioned above in the situation of proportion coupling, the proportion coupling of the approximate hemisphere of background color and any painted approximate hemisphere for example can as described belowly be carried out.

The approximate hemisphere of background color of the present invention contains the electric conductivity Chinese white.Therefore, the proportion of the approximate hemispherical portion of background color is arranged than any heavier tendency of painted approximate hemisphere.

Therefore, by the content that reduces electric conductivity Chinese white contained in the approximate hemisphere of background color or the content that increases the lighter composition of other proportion contained in the approximate hemisphere of background color, can alleviate the proportion of the approximate hemisphere of background color.

On the other hand, for any painted approximate hemisphere, content by increasing the heavier coloured material of proportion or in the situation that can not impact the color of painted approximate hemisphere arbitrarily and contain the heavier proportion adjusting agent of proportion can increase the weight of the proportion of painted approximate hemisphere arbitrarily.As described proportion adjusting agent, for example in the situation that any painted approximate hemisphere is black, can exemplify magnetic iron ore etc.

By mating as mentioned above the approximate hemisphere of background color and the proportion of painted approximate hemisphere arbitrarily, the verticity in the time of can obtaining applying voltage is good and can be as the double-colored particle of the display element of the rotary-type image display device of particle with memory characteristic.

In the rotary-type image display device of the particle of the invention described above, even as the double-colored particle of its display element white/the double-colored particle of color combination beyond black color combination, verticity is also good, and by certain adjustment, therefore also have memory characteristic, can expect the application in electronic paper etc.

Embodiment

The present invention will be described in more detail by the following examples, but the present invention is not limited thereto.

[preparation of reactive solution A-1]

Make titanium white as 30 weight portions of coloured material (Ishihara Sangyo Kaisha, Ltd.'s system: the electric conductivity titanium of CR-50-2) He 5 weight portions (Ishihara Sangyo Kaisha, Ltd.'s system: ET-500W) be dispersed in trimethylolpropane triacrylate (TMPTA) as the methyl methacrylate (MMA) of 20 weight portions of the monomer that forms resin and 80 weight portions with bowl mill.The dissolving conduct is with the quaternary ammonium salt (4-hydroxyl naphthalene-1-sulfonic acid benzyl tributyl ammonium) of 0.5 weight portion of controling agent in the gained mixed liquor, dissolve again the own ester of peroxide neodecanoic acid as 5 weight portions of thermal polymerization, obtain painted external phase reactive solution A-1.

Described electric conductivity titanium ET-500W is that spherical titanium dioxide take rutile-type is as core and by the material of tin ash and antimony pentaoxide coating, in the electric conductivity Chinese white, the weight of titania is 83%, the weight of tin ash is 10%, the weight of antimony pentaoxide is 4%, the particle diameter of electric conductivity Chinese white is 0.2～0.3 μ m, and the powder resistance rate under the pressure of 9.8MPa is 2～5 Ω cm.The powder resistance rate is as described below to be calculated: carry out press molding and make coupons with the condition of the 9.8MPa powder to the electric conductivity Chinese white, resistance value under pressurized state between the up and down of mensuration coupons, the thickness of determination test sheet, calculate the volume resistance value according to thickness and the sectional area of the resistance value that records and test film simultaneously.

[preparation of reactive solution A-2]

Make as 6 weight portion cyanines of coloured material blue (elite industry in large day (industry of refining large day) Co., Ltd.'s system) with bowl mill and be dispersed in the 20 weight portion MMA and 80 weight portion TMPTA as the monomer that forms resin.The dissolving conduct is with salicylic acid metal complex (east chemical industry (オ リ エ Application ト chemical industry) Co., Ltd.'s system: BONTRON E-84) of 1 weight portion of controling agent in the gained mixed liquor, dissolve again the own ester of peroxide neodecanoic acid as 5 weight portions of thermal polymerization, obtain painted external phase reactive solution A-2.

[embodiment 1]

Then, 88% saponified polyvinyl alcohol of dissolving 1 weight portion in 100 weight portion ion exchange waters is with its mobility medium B as water-based.

with the micro-channel device shown in Fig. 2 (a) (θ 5=90 °), described solution A-1 and A-2 are converged, it is transferred to (θ 3=45 ° of micro-channel device shown in Figure 3, θ 4=45 °) the first microchannel, then, from microchannel, side 5a, these three streams of 5b and the first microchannel intersect first microchannel of center of the microchannel that forms and with the amount that amounts to 1ml/hr, described solution A-1 and A-2 are spued to the mobility medium B that flows with the amount of 20ml/hr in the microchannel, side of its both sides, then make in its PTFE tube that flow to bore 1mm and pass through simultaneously in 70 ℃ of tepidariums, thereby carry out polymerizing curable.

By above operation, obtain the consistent double-colored particle of particle diameter of white/blue.The mean grain size that represents take volume reference of this double-colored particle is as 100 μ m, and the CV value is 2%.

The confirmation of the display performance of the double-colored particle of gained is as described below to be carried out.

The above-mentioned double-colored particle of 6g is well dispersed in the two-solution curing type organic siliconresin, it is coated on the PET base material, make it become long 200mm * wide 200mm * high 0.3mm after solidifying end, complete curing in 80 ℃ of times with 10 hours, obtain containing the resin sheet of particle.

Then, the gained resin sheet is peeled off from the PET base material, silicone oil (viscosity: 2mPas), dipping is 15 hours, thus the vacuole that obtains that double-colored particle is encased by silicone oil and can freely rotate in organic siliconresin.

The glass plate that has the ITO electrode with the coated processing in surface is clamped across laminated plastics the organic siliconresin that this comprises vacuole, thereby makes electronic paper.

The evaluation of＜particle verticity 〉

According to the condition that produces the potential difference (PD) of 100V between electrode, described electronic paper is applied voltage, make the orientation of double-colored particle unified.By the positive and negative counter-rotating of the applying method that makes interelectrode voltage, thereby make double-colored particle counter-rotating.Confirm the Reversion of the double-colored particle of this moment, the population (in 200) of counter-rotating has occured in counting.Have counter-rotating occured more than 150 be denoted as zero, the number of counter-rotating be less than 150 be denoted as *, be shown in following table 1.The size of affirming score is approximately in the square scope of 1mm.Mean value with N=5 is estimated.

The evaluation of＜particle response performance 〉

According to the condition that produces the potential difference (PD) of 100V between electrode, described electronic paper is applied voltage, make the orientation of double-colored particle unified.By the positive and negative counter-rotating of the applying method that makes interelectrode voltage, thereby make double-colored particle counter-rotating.At this moment, instrumentation is until the time till can't confirming the particle that rotation has occured.The size of affirming score is approximately in the square scope of 1mm, estimates with the mean value of N=5.

The evaluation of＜aberration 〉

According to the condition that produces the potential difference (PD) of 100V between electrode, described electronic paper is applied voltage, make the positive and negative counter-rotating of applying method of interelectrode voltage, thereby make double-colored particle counter-rotating.Measure double-colored particle and be arranged in by this aberration when single direction.Measure to use the TC-8600A processed of Tokyo electricity look Co., Ltd. ((have) East capital Electricity look).The results are shown in following table 1.

[embodiment 2～6, comparative example 1～2]

Except the composition of the painted external phase of change as shown in table 1 with reactive solution A-1 and A-2, make similarly to Example 1 double-colored particle and electronic paper, carry out similarly to Example 1 the evaluation of particle verticity and particle response performance and the evaluation of aberration.The results are shown in table 1.The evaluation of particle response performance is only carried out embodiment 1 and comparative example 1.Consequently, the required time of the counter-rotating of the double-colored particle of embodiment 1 is 1/3rd of the required time of the double-colored particle counter-rotating of comparative example 1.That is, the speed reversal of the double-colored particle of embodiment 1 is 3 times of speed reversal of the double-colored particle of comparative example 1.

In following table 1, " part " expression weight portion.

Shown in abbreviation in upper table 1 etc. thes contents are as follows.

IBXA ... isobornyl acrylate

EGDMA ... ethylene glycol dimethacrylate

CR-50-2 ... the titanium white of Ishihara Sangyo Kaisha, Ltd.'s system

PV Fast Yellow H2G ... the yellow coloring material of Japan's Clariant (Network ラ リ ア Application ト ジ ヤ パ Application) Co., Ltd.'s system

R-980 ... the titanium white of Ishihara Sangyo Kaisha, Ltd.'s system

ET-500W ... the electric conductivity Chinese white of Ishihara Sangyo Kaisha, Ltd.'s system

Electroconductive zinc oxide ... plain boiled water chemical industry (Ha Network ス イ テ Star Network) Co., Ltd.'s system

Cyanines are blue ... the industry of refining in large day (industry of refining large day) Co., Ltd.'s system: 4920

Permanent Carmain FBB02-JP ... the red colored material of Japan Clariant Co., Ltd. system

1,9-ND-A ... 1,9-nonanediol diacrylate

BMA ... butyl methacrylate

NPA ... neopentylglycol diacrylate

BEPGA ... 2-butyl-2-ethyl-1,3-PD diacrylate

CR-58 ... the titanium white of Ishihara Sangyo Kaisha, Ltd.'s system

KA-20 ... the titanium white of titanium industry (industry of チ タ Application) Co., Ltd.'s system

The explanation of symbol

1 first microchannel

2 second microchannels

3 the 3rd microchannels

4 the 4th microchannels

5a, microchannel, 5b side

6 painted external phases

7 mobility media

8 the 3rd microchannels

The spew of 10 painted external phases

11 ' the spew of spheroidizing gradually

12 ' double-colored particle

Claims (7)

1. double-colored particle, this double-colored particle is the resinous double-colored particle that each spherical particle roughly is divided into two kinds of different colours in appearance, it is characterized in that,

The approximate hemisphere of described double-colored particle contains the electric conductivity Chinese white, thereby consists of background color,

The approximate hemisphere of all the other of described double-colored particle is coloured to the random color except described background color,

Consist of the powder resistance rate of the electric conductivity Chinese white that mixes in the approximate hemisphere of background color of described double-colored particle in the scope of 1～100 Ω cm.

2. double-colored particle as claimed in claim 1, it is characterized in that, consist of contained electric conductivity Chinese white in the approximate hemisphere of background color of described double-colored particle and be the conductive material that is selected from antimony oxide/tin ash, indium oxide/tin ash by use and Chinese white is processed given the pigment that electric conductivity is made.

3. double-colored particle as claimed in claim 1, is characterized in that, the approximate hemisphere that is coloured to the random color except described background color contains chromatic colour dyestuff or chromatic colour pigment.

4. double-colored particle as claimed in claim 1, is characterized in that, the mean grain size of described double-colored particle is illustrated in the scope of 30～200 μ m with volume reference.

5. rotary-type image display device of particle, this device is formed by the insulating resin that contains double-colored particle in the mode of freely rotating between pair of electrodes, it is characterized in that,

Described double-colored particle is the resinous double-colored particle that each spherical particle roughly is divided into two kinds of different colours in appearance,

The approximate hemisphere of described double-colored particle contains the electric conductivity Chinese white, thereby consists of background color,

The approximate hemisphere of all the other of described double-colored particle is coloured to the random color except described background color,

Consist of the powder resistance rate of the electric conductivity Chinese white that mixes in the approximate hemisphere of background color of described double-colored particle in the scope of 1～100 Ω cm,

By being applied to described interelectrode voltage, described double-colored particle rotates in described insulating resin.

6. the rotary-type image display device of particle as claimed in claim 5, is characterized in that, described double-colored particle swims in the mode of freely rotating and soaks in the insulativity liquid that is contained in described insulating resin.

7. the rotary-type image display device of particle as claimed in claim 5, is characterized in that, is applied to voltage between described pair of electrodes in the scope of 50～300V.

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