CN100432817C - Method for producing electrophoretic particles, electrophoretic dispersion solution, micro-capsule, electrophoresis display device and electronic machine - Google Patents

Method for producing electrophoretic particles, electrophoretic dispersion solution, micro-capsule, electrophoresis display device and electronic machine Download PDF

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CN100432817C
CN100432817C CNB2006100737009A CN200610073700A CN100432817C CN 100432817 C CN100432817 C CN 100432817C CN B2006100737009 A CNB2006100737009 A CN B2006100737009A CN 200610073700 A CN200610073700 A CN 200610073700A CN 100432817 C CN100432817 C CN 100432817C
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polymerism
electrophoresis particle
base
surfactant
electrophoresis
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CN1854873A (en
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山本均
川濑健夫
宫林利行
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E Ink Corp
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Seiko Epson Corp
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Abstract

A method for producing electrophoretic particles includes dispersing particles having a charge on the surfaces thereof in an polar dispersion medium; adding a first polymerizable surfactant including a first polar group having a polarity opposite to the charge of the surfaces of the particles, a hydrophobic group, and a polymerizable group to the polar dispersion medium and mixing the liquid; adding a second polymerizable surfactant including a second polar group, a hydrophobic group, and a polymerizable group to the polar dispersion medium and emulsifying the mixture; and adding a polymerization initiator to induce polymerization reaction, thereby preparing electrophoretic particles in which the particles are coated with an organic polymer. In the method, the charge polarity and the amount of charge of the electrophoretic particles are controlled by setting the polarity of the second polar group included in the second polymerizable surfactant, and at least one condition of the number of the second polar groups in second polymerizable surfactant, the valence of the second polymerizable surfactant, and the molar amount of the second polymerizable surfactant added.

Description

The manufacture method of electrophoresis particle, electrophoresis dispersion, micro-capsule, electrophoretic display apparatus and e-machine
Technical field
The present invention relates to manufacture method, electrophoresis dispersion, micro-capsule, electrophoretic display apparatus and the e-machine of electrophoresis particle.
Background technology
As everyone knows, when electric field action had disperseed the dispersed system of particulate in liquid, particulate moved (swimming) in liquid under the effect of Coulomb force usually.This phenomenon is called electrophoresis, and in recent years, the electrophoretic display apparatus that utilizes electrophoresis showed information needed (image) just is being subjected to people and is paying close attention to (for example, patent documentation 1) as a kind of novel display device.
This electrophoretic display apparatus has stopping that memory under the state of impressed voltage shows and the characteristic at wide visual angle, also has characteristics such as low power consumption and high-contrast demonstration.
In addition,, compare, also have the advantage that does not stimulate eyes with light emitting-type display device such as cathode-ray tube (CRT) because electrophoretic display apparatus is non-light emitting-type display device.
In patent documentation 1, a kind of electrophoretic display apparatus with following structure is disclosed, promptly between a pair of transparency electrode, the micro-capsule of being filled by pigmented fluids with insulativity and charged particle in clamping.
When adding voltage between a pair of transparency electrode at this electrophoretic display apparatus, charged particle moves towards a lateral electrode in pigmented fluids according to the direction of the electric field that produces between electrode.Thus, the observer can see the color of charged particle and/or the color of pigmented fluids.
Thus, if the electrode of one or both sides is carried out composition, to its added voltage, can show required information by control.
Yet existing electrophoretic display apparatus generally is by selecting to use the charged particle of required electriferous state to operate.In addition, also pay its electric charge, but the kind of coupling agent that is suitable for and polymkeric substance is limited by coating coupling agent and polymkeric substance etc. at particle surface.Therefore, be difficult under any circumstance the electriferous state of charged particle is controlled at required scope.
This is owing to be difficult to control due to the electriferous state of particle, thereby a kind of method that can easily the electriferous state of particle be controlled at required scope of expectation exploitation at present.
Patent documentation 1 spy opens the 2002-202534 communique
Summary of the invention
The present invention aims to provide a kind of electrophoresis particle manufacture method that can easily make the electrophoresis particle with required electriferous state, contain electrophoresis dispersion by the manufacture method high reliability electrophoresis particle that make, that electriferous state is controlled of this electrophoresis particle, inside comprises the micro-capsule of this electrophoresis dispersion, and high reliability electrophoretic display apparatus and e-machine with this micro-capsule.
Content by following (1)～(13) has realized purpose of the present invention.
(1) a kind of manufacture method of electrophoresis particle: disperseing the surface to have in the aqueous liquid dispersion of particle of electric charge, add and to have with the 1st polymerism surfactant of the 1st polar group, hydrophobicity base and the polymerism base of the opposite polarity on aforementioned particles surface and mix, add the 2nd polymerism surfactant and emulsification then with the 2nd polar group, hydrophobicity base and polymerism base, add polymerization initiator then and produce polyreaction, coat aforementioned particles by organic polymer, wherein:
By setting the polarity of aforementioned the 2nd polar group that aforementioned the 2nd polymerism surfactant had, and at least 1 condition in the addition of the molecular weight of quantity, the valence mumber of aforementioned the 2nd polar group, aforementioned the 2nd polymerism surfactant of aforementioned the 2nd polar group and aforementioned the 2nd polymerism surfactant in aforementioned the 2nd polymerism surfactant, to control the charged polarity and the carried charge of aforementioned electrophoresis particle.
(2) manufacture method of the electrophoresis particle of above-mentioned (1) record, wherein: aforementioned particles obtains by the raw material particle is paid electric charge.
(3) manufacture method of the electrophoresis particle of above-mentioned (1) or (2) record, wherein: aforementioned particles is that main material constitutes with pigment or dyestuff.
(4) manufacture method of the electrophoresis particle of each record in above-mentioned (1) to (3), wherein: the hydrophobicity base that aforementioned the 1st polymerism surfactant and aforementioned the 2nd polymerism surfactant are had contains at least a group that is selected from alkyl and the aryl respectively.
(5) manufacture method of the electrophoresis particle of each record in above-mentioned (1) to (4), wherein: the polymerism base that aforementioned the 1st polymerism surfactant and aforementioned the 2nd polymerism surfactant are had is the unsaturated alkyl of free redical polymerization.
(6) manufacture method of the electrophoresis particle of above-mentioned (5) record; wherein: the unsaturated alkyl of described free redical polymerization is for being selected from vinyl, allyl, acryloyl group, methacryl, propenyl, 1; 1-ethenylidene and 1, in the 2-ethenylidene at least a kind.
(7) manufacture method of the electrophoresis particle of each record in above-mentioned (1) to (6), wherein: the 2nd polar group that aforementioned the 2nd polymerism surfactant is had is the cationic base, and this cationic base is selected from a kind in primary amine cation radical, secondary amine cation radical, tertiary amine cation radical and the quaternary ammonium cation base.
(8) manufacture method of the electrophoresis particle of each record in above-mentioned (1) to (6), wherein: the 2nd polar group that aforementioned the 2nd polymerism surfactant is had is the anionic property base, this anionic property base is for being selected from sulfonic acid anion base (SO 3 -), sulfinic acid anion base (RSO 2 -: R is alkyl or phenyl or its modifier of carbon number 1～12) and carboxylate anion's base (COO -) in a kind.
(9) a kind of electrophoresis dispersion, wherein: contain a kind of electrophoresis particle of making by the manufacture method of the electrophoresis particle of each record in above-mentioned (1) to (8) at least.
(10) a kind of micro-capsule, wherein: electrophoresis dispersion and the inner capsule body that comprises this electrophoresis dispersion inside with above-mentioned (9) record.
(11) a kind of electrophoretic display apparatus, wherein: electrophoresis dispersion with transparency carrier, the subtend substrate of facing this transparency carrier and above-mentioned (9) between aforementioned transparency carrier and aforementioned subtend substrate record.
(12) a kind of electrophoretic display apparatus, wherein: micro-capsule with transparency carrier, the subtend substrate of facing this transparency carrier and above-mentioned (10) between aforementioned transparency carrier and aforementioned subtend substrate record.
(13) a kind of e-machine, wherein: electrophoretic display apparatus with above-mentioned (11) or (12) record.
Description of drawings
Fig. 1 is the mode chart in longitudinal profile of the electrophoretic display apparatus of expression the 1st embodiment.
Fig. 2 is the mode chart of the operation principles of expression electrophoretic display apparatus shown in Figure 1.
Fig. 3 is the mode chart of the manufacture method of explanation electrophoresis particle of the present invention.
Fig. 4 is the partial enlarged drawing of the dispersion of nano-particles state that produced in the aqueous liquid dispersion of presentation graphs 3 (c), and the partial enlarged drawing of a kind of form of the electrophoresis particle of presentation graphs 3 (d).
Fig. 5 is the partial enlarged drawing of other disperse staties of the particle that produced in the aqueous liquid dispersion of presentation graphs 3 (c), and the partial enlarged drawing of the another kind of form of the electrophoresis particle of presentation graphs 3 (d).
Fig. 6 is the mode chart in longitudinal profile that shows the electrophoretic display apparatus of the 2nd embodiment.
Fig. 7 is the mode chart in longitudinal profile that shows the electrophoretic display apparatus of the 3rd embodiment.
Fig. 8 is the mode chart in longitudinal profile that shows the electrophoretic display apparatus of the 4th embodiment.
Fig. 9 is the side view that expression is applied to e-machine of the present invention embodiment in the Electronic Paper.
Figure 10 is the figure that expression e-machine of the present invention is applied to the embodiment in the display.
Figure 11 is the part enlarged drawing of the dispersion of nano-particles state that produced in the aqueous liquid dispersion of displayed map 3 (c).
Figure 12 is the part enlarged drawing of structure of the electrophoresis particle of displayed map 3 (d).
Reference numeral
1 ... the 1st substrate, 2 ... the 2nd substrate, 3 ... the 1st electrode, 4 ... the 2nd electrode, 5 ... electrophoresis particle, 6 ... dispersion medium, 7 ... spacing body, 71 ... confined space, 72 ... the gap, 73 ... the next door, 10 ... electrophoresis dispersion, 20 ... electrophoretic display apparatus, 40 ... micro-capsule, 41 ... jointing material, 50 ... particle, 50a ... the raw material particle, 50b ... silicon oxide layer, 60,60 ' ... organic polymer, 61,61 ', 61 " ... the 1st polymerism surfactant; 62 ... the 2nd polymerism surfactant, 70 ... hydrophobic region, 80 ... polymerization initiator, 90 ... aqueous liquid dispersion, 611,611 ', 611 " ... the 1st polar group, 621 ... the 2nd polar group; 612; 612 '; 612 ", 622 ... the hydrophobicity base, 613,613 ', 613 "; 623 ... polymerism base, 64 ... electric charge, 600 ... Electronic Paper; 601 ... main body, 602 ... display unit, 800 ... display, 801 ... main part, 802a, 802b ... conveying cylinder is right, 803 ... hole portion, 804 ... transparency glass plate, 805 ... insert mouth, 806 ... portion of terminal, 807 ... socket, 808 ... controller, 809 ... operating portion
Embodiment
With reference to the accompanying drawings, manufacture method, electrophoresis dispersion, micro-capsule, electrophoretic display apparatus and the e-machine to electrophoresis particle of the present invention describes.
＜the 1 embodiment 〉
At first, the 1st embodiment 1 to electrophoretic display apparatus of the present invention describes.
Fig. 1 is the longitudinal diagram of the 1st embodiment of expression electrophoretic display apparatus of the present invention, and Fig. 2 is the synoptic diagram of the operation principles of expression electrophoretic display apparatus shown in Figure 1.In addition, below for convenience of explanation, with the upside among Fig. 1 and Fig. 2 as " on ", downside is described as D score.
Electrophoretic display apparatus 20 shown in Figure 1 has the 1st substrate 1 that is provided with the 1st electrode 3, the 2nd substrate 2 that is provided with the 2nd electrode 4 of facing the 1st electrode 3, is located at the electrophoresis dispersion 10 between these the 1st substrates 1 and the 2nd substrate 2.Next coming in order describe the formation of each several part.
The 1st substrate 1 and the 2nd substrate 2 are made of the parts of sheet (tabular) respectively, have to support and protect the various functions of components that are arranged at therebetween.
Each substrate 1,2 can be respectively to have in the member of flexible parts, hard any one, preferably has flexible member.Have flexible substrate 1,2 by use, can obtain to have flexible electrophoretic display apparatus 20, that is, can obtain for example to help making up the electrophoretic display apparatus 20 of Electronic Paper.
In addition, when employing has flexible parts as each substrate 1,2 o'clock, as its constituent material, can enumerate for example tygon respectively, polypropylene, polyolefin such as ethylene-vinyl acetate copolymer, improved polyalkene, (for example nylon 6 for polyamide, nylon 46, nylon 66, NYLON610, nylon 612, nylon 11, nylon 12, nylon 6-12, nylon 6-66), TPI, liquid crystal polymers such as aromatic polyester, polyphenylene oxide, polyphenylene sulfide, polycarbonate, polymethylmethacrylate, polyethers, polyetheretherketone, polyetherimide, poly-acetal, phenylethylene, polyvinyl chloride, polyurethanes, polyesters, polyamide-based, polybutadiene, the using trans-polyisoprene class, fluororubber, various thermoplastic resins such as haloflex class etc. or based on their multipolymer, mixture, polymer alloies etc. can use mixing more than a kind or 2 kinds in them.
The average thickness of this substrate 1,2 can wait suitably and set according to constituent material, purposes respectively, and there is no particular limitation, still, when employing has flexible material, about preferred 20～500 μ m, more preferably about 25～250 μ m, further about preferred 50～150 μ m.The flexibility of electrophoretic display apparatus 20 and the coordination between the intensity can be realized like this, the miniaturization (particularly slimming) of electrophoretic display apparatus 20 can also be realized simultaneously.
Face in aftermentioned electrophoresis dispersion 10 sides of these substrates 1,2 promptly, at the lower surface of the 1st substrate 1 and the upper surface of the 2nd substrate 2, is respectively equipped with the 1st electrode 3 and the 2nd electrode 4 that are stratiform (membranaceous).
When between the 1st electrode 3 and the 2nd electrode 4, adding voltage, between them, just produce electric field, this electric field action is on electrophoresis particle 5.
In the present embodiment, the 1st electrode 3 is made as public electrode, the 2nd electrode is made as the absolute electrode (pixel capacitors) that is divided into rectangular (ranks shape), the 1st electrode 3 and 1 the 2nd electrode 4 superposed part constitute 1 pixel.In addition, the 1st electrode 3 also can similarly be divided into a plurality of with the 2nd electrode 4.
As each electrode 3,4 constituent material, as long as be respectively the material that has electric conductivity in fact, just be not particularly limited, for example, can enumerate: copper, aluminium, nickel, cobalt, platinum, gold, silver, molybdenum, tantalum or contain their metal materials such as alloy, carbon black, carbon nano-tube, carbon class materials such as fullerene, polyacetylene, polypyrrole, polythiophene, polyaniline, poly-(to phenylene), poly-(to phenylene vinylidene), poly-fluorenes, polycarbazole, electron conduction macromolecular materials such as polysilane or derivatives thereof are at polyvinyl alcohol (PVA), polycarbonate, polyethylene oxide, polyvinyl butyral, polyvinylcarbazole, disperseed NaCl in the matrix resins such as vinyl acetate, LiClO 4, KCl, H 2O, LiCl, LiBr, LiI, LiNO 3, LiSCN, LiCF 3SO 3, NaBr, NaI, NaSCN, NaClO 4, NaCF 3SO 3, KI, KSCN, KClO 4, KCF 3SO 3, NH 4I, NH 4SCN, NH 4ClO 4, NH 4CF 3SO 3, MgCl 2, MgBr 2, MgI 2, Mg (NO 3) 2, MgSCN 2, Mg (CF 3SO 3) 2, CaBr 2, CaI 2, CaSCN 2, Ca (ClO 2) 2, Ca (CF 3SO 3) 2, ZnCl 2, ZnI 2, ZnSCN 2, Zn (ClO 4) 2, Zn (CF 3SO 3) 2, CuCl 2, CuI 2, CuSCN 2, Cu (ClO 4) 2, Cu (CF 3SO 3) 2The ion conducting polymer material of isoiony material, is mixed tin-oxide (FTO), the tin-oxide (SnO of fluorine at indium tin oxide (ITO) 2), various conductive materials such as indium oxide electroconductive oxides such as (IO) material, can use a kind in them or be used in combination more than 2 kinds.
In addition, as the constituent material of each electrode 3,4, also can use respectively not have and mix conductive materials such as gold, silver, nickel, carbon (electroconductive particle) in the material of electric conductivity and added the various compound substances of electric conductivity at for example glass material, elastomeric material, macromolecular material etc.
Object lesson as this compound substance, for example can enumerate, the conducting rubber that in elastomeric material, has mixed conductive material, the conductive adhesive or the conducting resinl that in adhesive composites such as epoxies, carbamates, acrylic compounds, have mixed conductive material, polyolefin, Polyvinylchloride, polystyrene, ABS resin, nylon (polyamide), ethylene vinyl acetate copolymer, polyester, acrylic resin, epikote, mixed electroconductive resin of conductive material etc. in the matrix resin such as carbamate resinoid.
The thickness (on average) of kind electrode 3,4 can suitably be set according to constituent material, purposes etc. respectively, and there is no particular limitation, about preferred 0.05～10 μ m, more preferably about 0.05～5 μ m.
In addition, in each substrate 1,2 and each electrode 3,4, the substrate and the electrode (in the present embodiment, being the 1st substrate 1 and the 1st electrode 3) that are disposed at the display surface side adopt the material with light transmission respectively, that is, preferably be essentially the material of transparent (water white transparency, colored transparent or translucent).Like this, just can be more easily by the visual state of recognizing the electrophoresis particle 5 in the electrophoresis dispersion 10 described later, the information (image) that shows by electrophoretic display apparatus 20 just.
In addition, each electrode 3,4 except the monomer by foregoing material constitutes the electrode of single layer structure, also can be successively lamination the electrode of multilayer laminated structure of multiple material.That is, each electrode 3,4 can be respectively the single layer structure that for example is made of ITO, also can be the double-deck rhythmo structure of ITO layer and polyaniline layer.
In addition, near the sidepiece of electrophoretic display apparatus 20, between the 1st substrate 1 and the 2nd substrate 2, be provided with the spacing body 7 of function with the interval that limits the 1st electrode 3 and the 2nd electrode 4.
In the present embodiment, this spacing body 7 is set to surround the mode of the periphery of electrophoretic display apparatus 20, and it also has as the function that marks off the containment member of confined space 71 between the 1st substrate 1 and the 2nd substrate 2.
Constituent material as spacing body 7, for example can enumerate epikote, various stupaliths such as various resin materials such as acrylic resin, carbamate resinoid, melamine resinoid, phenolic resinoid and monox, aluminium oxide, titanium dioxide etc., can use a kind in them or be used in combination more than 2 kinds.
The average thickness of this spacing body 7, promptly there is no particular limitation for the distance of 1,2 of substrates (distance between substrate), still, about preferred 10～500 μ m, more preferably about 20～100 μ m.
In addition, spacing body 7 has more than the structure that is limited to the periphery that is set to surround electrophoretic display apparatus 20, for example, also a plurality of spacing bodies 7 can be equipped on specific interval near the sidepiece of electrophoretic display apparatus 20.At this moment, the gap that utilizes other encapsulant (sealing material) to seal between the spacing body 7 gets final product.In addition, spacing body 7 also can omit.
In seal cavity 71 (inner space of unit), holding (filling) has electrophoresis dispersion 10.Like this, electrophoresis dispersion 10 just directly contacts with the 2nd electrode 4 with the 1st electrode 3.
This electrophoresis dispersion 10 is by disperseing (outstanding turbid) to form in dispersion medium 6 at least a kind of electrophoresis particle 5.
As electrophoresis dispersion 10, roughly can be divided into the form of in dispersion medium 6, disperseing a kind of electrophoresis particle, the form of the multiple electrophoresis particle different with disperse properties in dispersion medium 6 can be used a kind of arbitrarily.
The dispersion of electrophoresis particle 5 in dispersion medium 6 can be adopted a kind in paint shaker method, ball milling method, meida mill method, ultrasonic dispersing method, the dispersed with stirring method etc., or make up more than 2 kinds and carry out by for example.
The present invention relates to a kind of manufacture method of special this electrophoresis particle 5.
In addition, see explanation described later for details about electrophoresis particle 5 and manufacture method thereof.
As dispersion medium 6, the preferred medium that uses with comparison high-insulativity, for example can enumerate various water (distilled water, pure water, ion exchange water, RO water etc.), methyl alcohol, ethanol, isopropyl alcohol, butanols, octanol, ethylene glycol, diglycol, alcohols such as glycerine, methyl cellosolve, ethyl cellosolve, cellosolve classes such as ethylene glycol monophenyl ether, methyl acetate, ethyl acetate, butyl acetate, ester classes such as ethyl formate, acetone, methyl ethyl ketone, metacetone, methyl isobutyl ketone, methyl isopropyl Ketone, ketones such as cyclohexanone, pentane, normal hexane, aliphatic hydrocarbons such as octane, cyclohexane, alicyclic hydro carbons such as methylcyclohexane, benzene, toluene, dimethylbenzene, hexyl benzene, heptyl benzene, octyl group benzene, nonyl benzene, decyl benzene, undecyl benzene, dodecyl benzene, tridane, myristyl benzene etc. has the arene of chain alkyl, methylene chloride, chloroform, phenixin, 1, halogenated hydrocarbons such as 2-ethylene dichloride, pyridine, pyrazine, furans, the pyrroles, thiophene, heteroaromatic classes such as methyl pyrrolidone, acetonitrile, propionitrile, nitriles such as vinyl cyanide, N, dinethylformamide, N, amide-types such as N-dimethyl acetamide, carboxylate and other various oils etc., it can use separately, or uses as potpourri.
In addition, according to the present invention, for the electrophoresis particle 5 that obtains required electriferous state, the range of choice of employed dispersion medium 6 can be expanded.
In addition, in dispersion medium 6 (electrophoresis dispersion 10), in case of necessity, also can add various adjuvants such as spreading agent, lubricant, stabilizing agent such as the charged controlling agent that constitutes by particles such as electrolyte, surfactant, metallic soap, resin material, elastomeric material, oils, varnish (varnish), compounds, titanium class coupling agent, aluminium class coupling agent, silanes coupling agent.
In addition, in dispersion medium 6, in case of necessity, can also dissolve various dyestuffs such as anthraquinone dyes, azo dyes, indigoid dye, triphenylmethane dye, pyrazoline ketone dyestuff, stibene class dyestuff, diphenylmethyl alkanes dyestuff, xanthone class dyestuff, alizarin class dyestuff, acridine dye, quinone imides dyestuff, thiazoles dyestuff, methylene dye, nitro class dyestuff, nitrous base class dyestuff.
In this electrophoretic display apparatus 20, when add voltage between the 1st electrode 3 and the 2nd electrode 4, then produce electric field between them, electrophoresis particle 5 just carries out electrophoresis towards one of them electrode respectively.
For example, the particle that has a positive charge in use is during as electrophoresis particle 5, and when the 2nd electrode 4 was made as positive potential, then shown in Fig. 2 (A), electrophoresis particle 5 concentrated on the 1st electrode 3 to the 1st electrode 3 side shiftings.So, when (display surface side) observes electrophoretic display apparatus 20 from the top, just can see the color of electrophoresis particle 5.
Otherwise when the 2nd electrode 4 was made as negative potential, shown in Fig. 2 (B), electrophoresis particle 5 concentrated on the 2nd electrode 4 to the 2nd electrode 4 side shiftings.So, when (display surface side) observes electrophoretic display apparatus 20 from the top, just can see the color of dispersion medium 6.
Therefore, rerum natura by suitably controlling electrophoresis particle 5 (for example color, positive and negative, carried charge (quantity of electric charge) etc.), electrode 3 and 4 polarity, the potential difference (PD) between the electrode 3,4 etc., by on the display surface side of electrophoretic display apparatus 20, the color combinations of the color of electrophoresis particle 5 and dispersion medium 6 can show required information (image).
As previously mentioned, electrophoresis particle 5 can form by the particle that is had electric charge by the organic polymer clad surface.
Particularly in the present invention, by using the organic polymer coating particles, the electric charge with required polarity and carried charge can be paid electrophoresis particle 5.Thus, can prevent effectively that the material that does not need (not wanting) from adhering to (absorption) because of carelessness on the surface of electrophoresis particle 5.Like this, can stablize the surface potential of electrophoresis particle 5, stablize the electrophoretic characteristic of electrophoresis particle 5 in dispersion medium 6.Thereby can promote the characteristic (display characteristic) of electrophoretic display apparatus 20.
In addition, the proportion of electrophoresis particle 5 be preferably set to the proportion of dispersion medium 6 about equally.Like this, even stop between the electrode 3,4 after the impressed voltage, electrophoresis particle 5 also can be trapped on the certain position in the dispersion medium 6 for a long time.That is, electrophoretic display apparatus 20 shown information can keep for a long time.
In addition, about preferred 0.1～10 μ m of the mean grain size of electrophoresis particle 5, more preferably about 0.1～7.5 μ m, about preferred especially 0.2～0.5 μ m.
The mean grain size of electrophoresis particle 5 is controlled in the aforementioned range, can keeps the dispersiveness of electrophoresis particle 5 in dispersion medium 6 preferably, effectively prevent cohesion mutually between the electrophoresis particle 5.
In addition, usually electrophoresis particle is meant following a kind of particle, and it has mean distance (electrophoretic mobility) that plus or minus electric charge, response external electric field move obviously greater than non-electrophoresis particle in dispersion liquid in dispersion liquid.
Manufacture method according to electrophoresis particle of the present invention, in the polymkeric substance that electrophoresis particle 5 is had, the 2nd polar group is positioned at its outside, it is the aqueous liquid dispersion side, at least 1 condition in polarity by setting the 2nd polar group that the 2nd polymerism surfactant had, the 2nd polymerism surfactant in the addition of the molecular weight of the valence mumber of the quantity of the 2nd polar group, the 2nd polar group, the 2nd polymerism surfactant and the 2nd polymerism surfactant, the charged polarity and the carried charge of control electrophoresis particle 5.
Particularly, charged polarity and carried charge that for example can following control electrophoresis particle 5.
(A) in the manufacture process of aftermentioned electrophoresis particle 5, the polarity of the 2nd polar group that is had by the 2nd polymerism surfactant that will add is set at plus or minus, the charged polarity of the electrophoresis particle 5 that finally obtains can be controlled to be plus or minus respectively.
(B) in the manufacture process of aftermentioned electrophoresis particle 5, the quantity of the 2nd polar group that is had by the 2nd polymerism surfactant that increase to add can increase the carried charge of the electrophoresis particle 5 that finally obtains.
(C) in the manufacture process of aftermentioned electrophoresis particle 5,, can increase the carried charge of the electrophoresis particle 5 that finally obtains by the 2nd bigger polymerism surfactant of valence mumber that uses the 2nd polar group.
(D) in the manufacture process of aftermentioned electrophoresis particle 5, by using the 2nd bigger polymerism surfactant of molecular weight, because the ratio of the polarity of the 2nd polar group part reduces with respect to nonpolarity part, therefore can reduce the carried charge of the electrophoresis particle 5 that finally obtains.
(E) in the manufacture process of aftermentioned electrophoresis particle 5,, can increase the carried charge of the electrophoresis particle 5 that finally obtains by increasing the addition of the 2nd polymerism surfactant that is added.
Above by setting (A), (B), (C), (D) and (E) at least 1 condition, can obtain the bigger electrophoresis particle of electrophoretic mobility 5.Therefore, by using the bigger electrophoresis particle of this electrophoretic mobility 5, can promote the characteristic (display characteristic) of electrophoretic display apparatus 20.
This electrophoresis particle 5 can followingly be made.Manufacture method to electrophoresis particle 5 describes below.
Fig. 3 is the mode chart of the manufacture method of explanation electrophoresis particle of the present invention, Fig. 4 (a) is the partial enlarged drawing of the dispersion of nano-particles state that produced in the aqueous liquid dispersion of presentation graphs 3 (c), and Fig. 4 (b) is a kind of partial enlarged drawing of form of the electrophoresis particle of presentation graphs 3 (d).
Also have, Fig. 5 (a) is the partial enlarged drawing that expression comes from other disperse staties of the particle that is produced in the aqueous liquid dispersion of Fig. 3 (c), and Fig. 5 (b) is the partial enlarged drawing of another kind of form of the electrophoresis particle of presentation graphs 3 (d).
The manufacture method of electrophoresis particle of the present invention comprises following operation, [1] particle 50 is scattered in operation in the aqueous liquid dispersion 90, [2] in aqueous liquid dispersion 90, add electric charge 64 opposite polarity the 1st polar groups 611 that have with particle 50, the operation that the 1st polymerism surfactant 61 of hydrophobicity base 612 and polymerism base 613 mixes, [3] in aqueous liquid dispersion 90, add and have the 2nd polar group 621, the operation of the 2nd polymerism surfactant 62 emulsifications of hydrophobicity base 622 and polymerism base 623, [4] in aqueous liquid dispersion 90, add polymerization initiator 80 and produce polyreaction, obtain the operation of the electrophoresis particle 5 that formed by organic polymer 60 coating particles 50, [5] reclaim the operation of electrophoresis particle 5 and the operation of (6) dry electrophoresis particle 5 from aqueous liquid dispersion 90.
Below by enumerating the dispersion of nano-particles state that is produced in the aqueous liquid dispersion 90, aforementioned each operation is described.The disperse state of the electrophoresis dispersion of wherein, below enumerating comprises the content of supposition.
[1] at first, the particle 50 that the surface is had an electric charge 64 is scattered in the aqueous liquid dispersion 90.
Constituent material as particle 50, as long as its surface has electric charge 64, there is no particular limitation, for example can enumerate pigment, dyestuff, resin etc., can use wherein a kind, perhaps make up more than 2 kinds and use (for example containing the resin of pigment or dyestuff etc.).These materials are because the surface has electric charge 64, and its dispersed good in aqueous liquid dispersion 90 is applicable to the constituent material of particle 50.
As pigment, there is no particular limitation, for example can enumerate, white color system inorganic pigments such as titanium dioxide, barium sulphate, zinc paste, zinc white are arranged; Yellow system has, organic pigments such as azo ligands salts such as condensation azo-compound class, benzimidazolone azophosphine such as insoluble azo-compound class, color development phthalein Huang, flavanones condensations such as (flavanthrone) condensed ring class, hansa yellow, S naphthol yellow S, nitro compound and pigment yellow such as inorganic pigment such as yellow iron oxide, cadmium yellow, titan yellow, chrome yellow, yellow lead or colour-fast Huang; Having of Yellow Red preferably can be enumerated inorganic pigments such as molybdate orange; Or organic pigments such as condensation condensed ring class such as azo complexing salt such as benzimidazolone azo orange and Perynone orange, having of red colour system, quinacridone pigments such as condensation condensed ring class, Cinquacia red Y and Hostabarm red such as condensation azo-compound class, thioindigo bordeaux such as insoluble azo-compound classes such as dissolubility azo-compound class, naphthol reds such as dyeing color lake class, C lake red CAN'T such as inorganic pigment such as iron oxide red and cadmium red or madder lake, color development phthalein are scarlet, permanent red and colour-fast organic pigments such as azo pigment such as red; Having of violet, organic pigments such as condensation condensed ring class such as dyeing color lake class, dioxazine violet such as inorganic pigment such as manganese violet or rhodamine color lake; Blue system has, organic pigments such as indanthrone class, alkali blue such as phthalocyanines, indanthrone indigo plant such as inorganic pigment such as barba hispanica, ultramarine, cobalt blue and celeste blue or phthalocyanine blue; Green system has, organic pigments such as phthalocyanines such as nitroso compound class, phthalocyanine green such as azo complexing salt, naphthol green and naphthol green such as emerald green, chrome green, chromium oxide and inorganic pigment such as emerald green or nickel chromium triangle azophosphine; Black system has, organic pigments such as inorganic pigment such as carbon black, titanium are black, iron oxide black or nigrosine etc.These pigment particles can use separately, also can two or more mixing use.Black series pigments particles such as the pigment particles of preferred white system, carbon black, titanium be black in these pigment particles.
In addition, when using Titanium particles, there is no particular limitation for its kind, so long as generally be used for the titanium dioxide of white color system pigment, for example rutile-type or Detitanium-ore-type etc. any all can, consider because the photocatalytic activity of titanium dioxide produces the situations such as colour mixture of colorant, the rutile-type that the preferred light catalytic activity is lower, for the further photocatalytic activity that reduces, can implement Si processing, Al processing, Si-Al processing, Zn-Al processing etc. to iron oxide.
As dyestuff, there is no particular limitation, as yellow based dye, can enumerate oil yellow 3G azo-compound classes such as (manufacturings of オ リ エ Application ト chemical company); As the Yellow Red dyestuff, can enumerate colour-fast orange G azo-compound classes such as (BASF AG's manufacturings); As blue based dye, can enumerate Macrolex Blue RR anthraquinone classes such as (manufacturings of バ イ エ Le company); As green based dye, can enumerate Sumiplast Green G anthraquinones such as (sumitomo chemical company systems) class; As dark brown based dye, can enumerate oil palm GR azo-compound classes such as (オ リ エ Application ト chemical company systems); As the red colour system dyestuff, can enumerate oil red 5303 (this chemical company system is arranged) and oil red 5B azo-compound classes such as (オ リ エ Application ト chemical company systems); As the violet dyestuff, can enumerate oily purple #730 anthraquinone classes such as (オ リ エ Application ト chemical company systems); As the black based dye, can enumerate the potpourri etc. of the oil red XO (カ Application ト-chemical company's system) of the Macrolex Blue FR (バ イ エ Le corporate system) of oil-soluble carbon black X60 azo-compound classes such as (BASF AG's systems) or anthraquinone class and azo-compound class.These dyestuffs can only use a kind, also can more than 2 kinds and use.
As resin, for example can enumerate polyolefin polymers, poly-halogenated hydrocarbon polymkeric substance (halogenatedolefin), polyester polymer, polyurethane polymer, polystyrene base polymer, acrylic polymers, epoxide polymer, melamine base polymer, urea base polymer etc.So-called herein polymkeric substance not only means homopolymer, but also comprises the multipolymer with other monomer copolymerization of a small amount of copolymerization.These polymer particles may be used alone, two or more kinds can also be used.
Also have, in above-mentioned material, particularly, preferably constitute with pigment or dyestuff position main material as the constituent material of particle 50.Pigment and dyestuff mostly have electric charge on the surface, himself present multiple color, thereby the electrophoresis particle 5 and the electrophoretic display apparatus 20 that contain particle 50 can show higher contrast ratio.
Aqueous liquid dispersion 90 for example can suitably use various water such as distilled water, ion exchange water, pure water, ultrapure water, RO water separately, perhaps with water as principal ingredient, mix the aqueous liquid dispersion 90 that various lower alcohols such as methyl alcohol, ethanol obtain.
In addition, as the constituent material of particle 50, except above-mentioned, for example can use the material that obtains by the processing of implementing to pay the raw material particle charging etc.At this moment, except aforementioned various constituent materials, also can use the material that does not contain electric charge in fact.As this processing can enumerate make the raw material particle for example adsorb couplant, surfactant etc. have the method for the compound of polarity.
[2] then, shown in Fig. 3 (a), in aqueous liquid dispersion 90, add to have and mix with the 1st polymerism surfactant 61 of electric charge 64 opposite polarity the 1st polar groups 611, hydrophobicity base 612 and the polymerism base 613 of particle 50.
At this moment, the addition of the 1st polymerism surfactant 61 is, the scope of 0.5～2.0 times of mole of the total mole number (amount [mol/g] of the polar group with electric charge 64 of weight (the g) * particle 50 of=employed particle 50) of the polar group with electric charge 64 of calculating according to the consumption of particle 50, the more preferably scope of 0.8～1.2 times of mole.If addition is at 0.5 times more than the mole, then can combine securely by ionic link with particle 50 with electric charge 64, thus easily encapsulated.On the other hand, if addition then can reduce the generation that is not adsorbed on the 1st polymerism surfactant 61 on the particle 50 at 2 times below the mole, prevent not with the polymer particle of particle 50 as core substance
The generation of (i.e. the particle that only forms) by polymkeric substance.
In addition, in case of necessity, can be to the aqueous liquid dispersion ultrasound wave of 90 irradiation stipulated times.Can control the configuration that is present in particle 50 the 1st polymerism polymerism surfactant 61 on every side so very to heavens.
Specifically, when particle 50 had negative charge 64, the polymeric surfactant that can use cationic was as the 1st polymerism surfactant 61.Otherwise when particle 50 had positive charge 64, the polymeric surfactant that can use anionic property was as the 1st polymerism surfactant 61.
Below operable cationic and anionic surfactant among the present invention are elaborated.
As the cationic base that the polymerism surfactant of cationic has, can enumerate for example primary amine cation radical, secondary amine cation radical, tertiary amine cation radical, quaternary ammonium cation base, sulphur cation radical, pyridylium base etc.
Wherein, as the cationic base, preferably be selected from a kind in primary amine cation radical, secondary amine cation radical, tertiary amine cation radical, the quaternary ammonium cation base.
As the hydrophobicity base that the polymerism surfactant of cationic has, preferably comprise at least a in alkyl and the aryl.
As the polymerism base that the polymerism surfactant of cationic has, the unsaturated alkyl of preferred free redical polymerization.
In addition, in the unsaturated alkyl of free redical polymerization, preferably be selected from vinyl, allyl, acryloyl group, methacryl, propenyl, 1,1-ethenylidene and 1, in the 2-ethenylidene a kind.Wherein preferred especially acryloyl group, methacryl.
As the example of the polymerism surfactant of cationic, can enumerate cationic acrylic acid derivative of putting down in writing in the special fair 4-65824 communique etc.As the object lesson of the polymerism surfactant of cationic, can enumerate dimethylaminoethyl acrylate methyl amido ethyl methyl esters chloride, dimethylaminoethyl acrylate methyl amido benzyl ethyl ester chloride, methacryloxyethyl trimethyl ammonium chloride, diallyl dimethyl ammonium chloride, 2-hydroxy-3-methyl acryloxy oxypropyl trimethyl ammonium chloride etc.
In addition, polymerism surfactant as cationic, can use the commercially available prod, for example ア Network リ エ ス テ Le DMC (Mitsubishi's レ イ ヨ Application (strain)), ア Network リ エ ス テ Le DML60 (Mitsubishi's レ イ ヨ Application (strain)), C-1615 (the first industrial pharmacy (strain)) etc.
The polymerism surfactant of above-named cationic can use individually, perhaps uses the potpourri more than 2 kinds.
On the other hand, the anionic property base as the polymerism surfactant of anionic property has preferably is selected from sulfonic acid anion base (SO 3 -), sulfinic acid anion base (RSO 2 -: R is alkyl or phenyl or its modifier of carbon number 1～12) and carboxylate anion (COO -) in waiting a kind.
As the hydrophobicity base that the polymerism surfactant of anionic property has, can use the same hydrophobicity base of hydrophobicity base that is had with the ionic polymerism surfactant of aforementioned male.
As the polymerism base that the polymerism surfactant of anionic property has, can use the same polymerism base of polymerism base that is had with the ionic polymerism surfactant of aforementioned male.
As the example of the polymerism surfactant of anionic property, can enumerate, in the public clear 49-46291 communique of spy, special fair 1-24142 communique and the special anionic property allyl deriv of putting down in writing in the clear 62-104802 communique of opening; Open the anionic property propenyl derivatives of putting down in writing in the clear 62-221431 communique in the spy; The spy opens the anionic property acrylic acid derivative of putting down in writing in clear 62-34947 communique and the clear 55-11525 communique of Te Kai; The negative ion derivatives from itaconic acid of putting down in writing in special public clear 46-34898 communique and the clear 51-30284 communique of Te Kai etc.
As the object lesson of the polymerism surfactant of this anionic property, preferably as general formula (31):
Figure C20061007370000191
[in the formula, R 21And R 31Be respectively the alkyl of hydrogen atom or carbon number 1～12 independently, Z 1For carbon-carbon single bond or-CH 2-O-CH 2-shown in alkyl, m is 2～20 integer, X is-SO 3M 1Shown base, M 1Be alkaline metal, ammonium salt or alkanolamine.]
Shown compound, or as general formula (32)
Figure C20061007370000192
[in the formula, R 22And R 32Be respectively the alkyl of hydrogen atom or carbon number 1～12 independently, D be carbon-carbon single bond or-CH 2-O-CH 2-shown in alkyl, n is 2～20 integer, Y is-SO 3M 2Shown base, M 2Be alkaline metal, ammonium salt or alkanolamine.]
Polymerism surfactant shown in the aforementioned formula (31) is disclosed in the spy and opens in flat 5-320276 communique and the flat 10-316909 communique of Te Kai.By R in the adjustment type (31) 21Kind and the value of X, can make the quantity of electric charge of the electric charge 64 that its corresponding particle 50 had.Suc as formula the polymerism surfactant shown in (31), can enumerate the compound shown in the following formula (310) as preferably, specifically can enumerate the compound shown in the following formula (31a)～(31d).
Figure C20061007370000201
[in the formula, R 31, m and M 1Identical with the compound shown in the formula (31)]
Figure C20061007370000202
Figure C20061007370000211
Asahi Denka Kogyo K. K ア デ カ リ ア ソ-プ SE-10N is in the compound shown in the formula (310), M 1Be NH 4, R 31Be C 9H 19, the compound of m=10.Asahi Denka Kogyo K. K ア デ カ リ ア ソ-プ SE-20N is in the compound shown in the formula (310), M 1Be NH4, R 31Be C 9H 19, the compound of m=20.
In addition, the anionic property base that has as the polymerism surfactant of anionic property, preferably general formula (33) for example:
[in the formula, p is 9 or 11 integer, and q is 2～20 integer, and A is-SO 3M 3Shown base, M 3Be alkaline metal, ammonium salt or alkanolamine.]
Shown compound.Suc as formula the polymerism surfactant of the anionic property shown in (33), can enumerate following compound as preferably,
Figure C20061007370000213
[in the formula, r is 9 or 11, and s is 5 or 10]
Polymerism surfactant as aforementioned anionic property also can use the commercially available prod.For example can enumerate the ア Network ア ロ Application KH series of Di-ichi Kogyo Seiyaku Co., Ltd. (ア Network ア ロ Application KH-5, ア Network ア ロ Application KH-10) etc.ア Network ア ロ Application KH-5 is in the compound shown in the following formula, and r is 9, and s is that 5 compound and r are 11, and s is the potpourri of 5 compound.ア Network ア ロ Application KH-10 is in the compound shown in the following formula, and r is 9, and s is that 10 compound and r are 11, and s is the potpourri of 10 compound.
In addition, as the polymerism surfactant of the anionic property that uses among the present invention, preferably use the compound shown in the following formula (34).
Figure C20061007370000221
[in the formula, R is the alkyl of carbon number 8～15, and n is 2～20 integer, and X is-SO 3Base shown in the B, B are alkaline metal, ammonium salt or alkanolamine.]
Polymerism surfactant as aforementioned anionic property also can use the commercially available prod.As the commercially available prod, for example can enumerate the ア デ カ リ ア ソ-プ SR series of Asahi Denka Kogyo K. K (ア デ カ リ ア ソ-プ SR-10, SR-20, R-1025) (above is trade name) etc.ア デ カ リ ア ソ-プ SR series is that B represents NH in above-mentioned general formula (34) 4Compound, wherein SR-10 is the compound of n=10, SR-20 is the compound of n=20.
In addition, as the polymerism surfactant of anionic property, the compound shown in the preferred following formula (A).
[in the formula, R 4Be the alkyl of hydrogen atom or carbon number 1～12, I is 2～20 number, M 4Be alkaline metal, ammonium salt or alkanolamine.]
Polymerism surfactant as above-mentioned anionic property also can use the commercially available prod.As the commercially available prod, for example can enumerate the ア Network ア ロ Application HS series (ア Network ア ロ Application HS-10, HS-20 and HS-1025) (above is trade name) that Di-ichi Kogyo Seiyaku Co., Ltd. makes etc.
In addition,, for example can enumerate the alkyl allyl sulfosuccinic acid sodium salt shown in the general formula (35) as the polymerism surfactant of the anionic property that uses among the present invention.
Figure C20061007370000231
Polymerism surfactant as above-mentioned anionic property also can use the commercially available prod.As the commercially available prod, for example can enumerate, the エ レ ミ ノ-Le JS-2 of Sanyo Chemical Industries, Ltd., it is in above-mentioned general formula (35), the compound of m=12.
In addition,, for example can enumerate the methacryloxy polyoxyalkylene sulfuric ester sodium salt shown in the general formula (36) as the polymerism surfactant of the anionic property that uses among the present invention.In the following formula, n is 1～20.
Figure C20061007370000232
Polymerism surfactant as above-mentioned anionic property also can use the commercially available prod.As the commercially available prod, for example can enumerate, the エ レ ミ ノ-Le RS-30 of Sanyo Chemical Industries, Ltd., it is in above-mentioned general formula (36), the compound of n=9.
In addition,, for example can enumerate the compound shown in the general formula (37) as the polymerism surfactant of the anionic property that uses among the present invention.
Figure C20061007370000241
Polymerism surfactant as above-mentioned anionic property also can use the commercially available prod.The Antox MS-60 of for example Japanese emulsifying agent Co., Ltd..
The polymerism surfactant of the anionic property of more than enumerating can use separately, also can use the potpourri more than 2 kinds.
In addition, organic polymer 60 more preferably contains the constitutional repeating unit of being derived by hydrophobic monomer.
This hydrophobic monomer contains hydrophobicity base and polymerism base at least in its molecular structure.Owing to contain this hydrophobic monomer, can realize the hydrophobicity of organic polymer 60 and the lifting of polymerism.Can realize the lifting of the physical strength and the permanance of organic polymer 60 thus.
Wherein, as the hydrophobicity base, can enumerate at least a kind the group that comprises in aliphatic alkyl, ester ring type alkyl and the aromatic hydrocarbyl.
As aliphatic alkyl, can enumerate methyl, ethyl, propyl group etc., as the ester ring type alkyl, can enumerate cyclohexyl, dicyclopentenyl, two cyclopentyl, isobornyl etc., as aromatic hydrocarbyl, can enumerate benzyl, phenyl, naphthyl etc.
In addition,, be the unsaturated alkyl of free redical polymerization thing, can enumerate being selected from vinyl, allyl, acryloyl group, methacryl, propenyl, 1,1-ethenylidene and 1, in the 2-ethenylidene a kind as the polymerism base.
As the concrete example of hydrophobic monomer, can enumerate styrene derivatives such as styrene, methyl styrene, dimethyl styrene, chlorostyrene, dichlorostyrene, bromstyrol, p-chloromethyl styrene, divinylbenzene; Monofunctional acrylates such as methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid butoxy ethyl ester, benzyl acrylate, phenyl acrylate, acrylic acid phenoxy ethyl, cyclohexyl acrylate, acrylic acid two ring pentyl esters, acrylic acid two cyclopentene esters, acrylic acid two cyclopentene 2-ethoxyethyl acetates, tetrahydrofurfuryl acrylate, isobornyl acrylate; Methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, methacrylic acid 2-Octyl Nitrite, methacrylic acid butoxy methyl esters, benzyl methacrylate, the methacrylic acid phenylester, the methacrylic acid phenoxy ethyl, cyclohexyl methacrylate, methacrylic acid two cyclopentyl esters, methacrylic acid dicyclopentenyl ester, methacrylic acid two cyclopentene 2-ethoxyethyl acetates, tetrahydrofurfuryl methacrylate, simple function methacrylates such as isobornyl methacrylate; Allyl benzene, propionic acid allyl-3-cyclohexyl, 1-allyl-3, allyl compounds such as 4-dimethoxy benzene, acetate allyl phenoxy group ester, acetate allyl phenyl ester, allyl cyclohexane, polybasic carboxylic acid allyl ester; Fumaric acid, maleic acid, itaconic acid and ester class thereof; N-substituted maleimide amine, cycloolefin etc. have the monomer of free-radical polymerised base.Can suitably select to satisfy the hydrophobic monomer of above-mentioned requirements characteristic, its addition can at random determine.
And then organic polymer 60 preferably contains the constitutional repeating unit of being derived by cross-linkable monomer and/or by the constitutional repeating unit of the monomer derived shown in the following general formula (1).
General?formula(1)
Figure C20061007370000251
[wherein, R 1Be hydrogen atom or methyl, R 2Be the tert-butyl group, ester ring type alkyl, aromatic hydrocarbyl or heterocyclic radical.M is 0～3 integer, and n is 0 or 1 integer.]
Organic polymer 60 has formed more fine and close cross-linked structure by containing the constitutional repeating unit of being derived by cross-linkable monomer in polymkeric substance, thereby can improve the physical strength of electrophoresis particle 5.
Organic polymer 60 is by containing the constitutional repeating unit by the monomer derived shown in the general formula (1), by the aforementioned R as " large volume " base 2Base, the molecular change of organic polymer 60 must be difficult to bending, and promptly the motility of molecule is limited, thereby the physical strength of organic polymer 60 improves.In addition, owing to there is the aforementioned R of " large volume " base in the organic polymer 60 2Base, the solvent resistance of electrophoresis particle 5 becomes good.In general formula (1), as R 2Shown ester ring type alkyl can be enumerated for example naphthenic base, cycloalkenyl group, isobornyl, two cyclopentyl, dicyclopentenyl, adamantyl, tetrahydrofuran base etc.
Object lesson as cross-linkable monomer; be selected from vinyl for having more than 2; allyl; acryloyl group; methacryl; propenyl; 1; 1-ethenylidene and 1; the compound of the unsaturated alkyl in the 2-ethenylidene more than a kind; for example can enumerate; glycol diacrylate; diethylene glycol diacrylate; triethylene glycol diacrylate; tetraethylene glycol diacrylate; polyethyleneglycol diacrylate; allyl acrylate; two (acrylyl oxy-ethyl) hydroxyethyl isocyanuric acid ester; hexane diacid two (acryloxy neopentyl glycol) ester; 1; the 3-butanediol diacrylate; 1; the 6-hexanediyl ester; neopentylglycol diacrylate; propylene glycol diacrylate; polypropyleneglycol diacrylate; 2-hydroxyl-1; 3-two propylene acyloxy propane; 2; 2-two [4-(acryloyl-oxy) phenyl] propane; 2; 2-two [4-(acryloyl-oxy base oxethyl) phenyl] propane; 2; 2-two [4-(acryloxy diethoxy) phenyl] propane; 2; 2-two [4-(acryloxy polyethoxy) phenyl] propane; the hydroxy new pentane acid neopentylglycol diacrylate; 1; the 4-butanediol diacrylate; two cyclopentyl diacrylates; dipentaerythritol acrylate; dipentaerythritol monohydroxy five acrylate; two (trimethylolpropane) tetraacrylate; pentaerythritol triacrylate; the tetrabromobisphenol A diacrylate; the triglycerin diacrylate; trimethylolpropane triacrylate; three (acrylyl oxy-ethyl) isocyanuric acid ester; ethylene glycol dimethacrylate; diethylene glycol dimethacrylate; triethylene glycol dimethacrylate; tetraethylene glycol dimethacrylate; polyethylene glycol dimethacrylate; the propylene glycol dimethylacrylate; polypropylene glycol dimethacrylate; 1; the 3-butanediol dimethylacrylate; 1; the 4-butanediol dimethylacrylate; 1; the 6-hexanediol dimethacrylate; neopentylglycol dimethacrylate; 2-hydroxyl-1; 3-dimethyl allene acyloxy propane; 2; 2-two [4-(methacryloxypropyl) phenyl] propane; 2; 2-two [4-(methacryloxy ethoxy) phenyl] propane; 2; 2-two [4-(methacryloxy diethoxy) phenyl] propane; 2,2-two [4-(methacryloxy ethoxy polyethoxy) phenyl] propane; the tetrabromobisphenol A dimethylacrylate; two cyclopentane base dimethylacrylates; dipentaerythritol hexamethyl acrylate; the glycerine dimethylacrylate; the hydroxy new pentane acid neopentylglycol dimethacrylate; dipentaerythritol monohydroxy pentamethyl acrylate; two (trimethylolpropane) tetramethyl acrylate; pentaerythritol acrylate trimethyl; pentaerythrite tetramethyl acrylate; the triglycerin dimethylacrylate; trimethylol-propane trimethacrylate; three (methylacryoyloxyethyl) isocyanuric acid ester; allyl methacrylate; divinylbenzene; diallyl phthalate; diallyl p phthalate; properties of diallyl isophathalate; diglycol diallyl carbonic ester etc.
The isobornyl methacrylate against weather
Figure C20061007370000271
The isobornyl acrylate against weather
Figure C20061007370000272
94 ℃ of homopolymer Tg
The dicyclopentenyl acrylate is paid the acryl resin stickability
Homopolymer Tg120 ℃
Figure C20061007370000273
Dicyclopentenyl methacrylated reagent patience
Figure C20061007370000274
Dicyclopentenyl oxygen base ethyl propylene acid esters is paid stickability
Figure C20061007370000275
Two cyclopentyl acrylate agent of low hygroscopicity
Against weather
Figure C20061007370000276
Homopolymer Tg120 ℃
Dicyclopentenyl oxygen base ethyl-methyl acrylate chemistry reagent patience
Figure C20061007370000281
Two cyclopentyl-methyl acrylate agent of low hygroscopicity
Figure C20061007370000282
Tg107 ℃ of metering system tert-butyl acrylate homopolymer
Figure C20061007370000283
Tg54 ℃ of benzyl methacrylate homopolymer
Tg66 ℃ of cyclohexyl methacrylate homopolymer
Tg60 ℃ of tetrahydrofurfuryl methacrylate homopolymer
Figure C20061007370000286
[3] then, shown in Fig. 3 (b), in aqueous liquid dispersion 90, add the 2nd polymerism surfactant 62 emulsifications with the 2nd polar group 621, hydrophobicity base 622 and polymerism base 623.
At this moment, be selected from
(A) polarity of the 2nd polar group 621 that had of the 2nd polymerism surfactant 62 of Jia Ruing,
(B) quantity of the 2nd polar group 621 in the 2nd polymerism surfactant 62,
(C) valence mumber of the 2nd polar group 621,
(D) molecular number of the 2nd polar group 621,
(E) addition of the 2nd polymerism surfactant 62, condition in, set (A), and (B), at least 1 condition among (C), (D), (E), can control the charged polarity and the carried charge of the electrophoresis particle 5 that finally obtains.
In addition, the addition of the 2nd polymerism surfactant 62 is, the scope about 1～10 times of mole of the 1st polymerism surfactant 61 that adds in aforementioned operation [2], the more preferably scope about 1～5 times of mole.If addition can carry out the control of the carried charge of electrophoresis particle 5 more accurately at 1 times more than the mole, improve the display performance of electrophoretic display apparatus 20.On the other hand, if addition at 10 times below the mole, then can suppress to be unfavorable for the generation of hydrophilic monomer of the formation of organic polymer 60, thereby can prevent generations beyond the electrophoresis particle 5, that do not have the polymer particle of core substance.
In addition, in case of necessity, can be to the aqueous liquid dispersion ultrasound wave of 90 irradiation stipulated times.Can control the configuration that is present in particle 50 the 2nd polymerism surfactant 62 on every side so very to heavens.
As the 2nd polymerism surfactant 62, can use and the same material of aforementioned the 1st polymerism surfactant 61.
[4] then, shown in Fig. 3 (c), in aqueous liquid dispersion 90, add polymerization initiator 80 and produce polyreaction.Thus, shown in Fig. 3 (d), obtain organic polymer 60 coating particles 50 and the electrophoresis particle 5 of formation.
At this moment polymerization can be carried out as follows, and where necessary, the temperature (temperature of polymerization initiator 80 activation) by the temperature that makes aqueous liquid dispersion 90 heats up and reaches regulation adds polymerization initiator 80, makes polymerization initiator 80 activation, polymerization in aqueous liquid dispersion 90.
As polymerization initiator 80, preferred water-soluble polymerization initiator can be enumerated potassium persulfate, ammonium persulfate, sodium peroxydisulfate, 2,2-azo two (2-methyl propione amidine) dihydrochloride or 4,4-azo two (4-cyanopentanoic acid) etc.
Wherein, when in the aqueous liquid dispersion 90 of above-mentioned explanation be polymerized to emulsion polymerization the time, infer that the mechanism of action of the 1st polymerism surfactant 61 and each monomer is as follows.In addition, below for aforementioned operation [1], be to describe in the situation that adds hydrophobic monomer.
At first, electric charge 64 absorption the 1st polymerism surfactant 61 that particle 50 is had, the irradiation ultrasound wave, add hydrophobic monomer then, add the 2nd polymerism surfactant 62, the irradiation ultrasonic Treatment is present in the 1st polymerism surfactant 61 around the particle 50 and the configuration of monomer and is controlled to heavens by the utmost point, is formed on the state that outermost layer the 1st polar group 611 is arranged towards aqueous liquid dispersion 90.By emulsion polymerization, keep this state of highly controlling then, conversion of monomer is an organic polymer 60, obtains the electrophoresis particle 5 of present embodiment.
By said method, can reduce generation as the water-soluble oligomer and the polymkeric substance of accessory substance.Thus, can reduce the viscosity of the aqueous liquid dispersion 90 that has disperseed gained electrophoresis particle 5, make high precision filtration etc. refining step is easier and carry out.
Above-mentioned polyreaction can be carried out in the reaction vessel that ultrasonic generator, stirring machine, reflux condenser, tap funnel and temperature regulator are housed.
In the polyreaction, the rising temperature reaches the fracture temperature of the polymerization initiator 80 that adds in the reaction system (aqueous liquid dispersion 90), makes polymerization initiator 80 fractures, produces the initiating agent free radical.Unsaturated group and the unsaturated group of monomer, the initiated polymerization thus of this each polymerism surfactant 61,62 of initiating agent free radical attack.
Can be by for example with the method that polymerization initiator 80 adds in the reaction system, water-soluble polymerization initiator 80 is dissolved in the aqueous solution that forms in the pure water is added drop-wise in the reaction vessel and implements.At this moment, the interpolation of polymerization initiator 80 can be passed through, and in the aqueous liquid dispersion 90 that is heated to activation temperature, adding contains the aqueous solution of polymerization initiator 80 and carries out once, in batches or continuously.In addition, also can be after 80s at the interpolation polymerization initiator, heating aqueous liquid dispersion 90 arrives the temperature that makes polymerization initiator 80 activation.
As previously mentioned, among the present invention, preferably use water miscible polymerization initiator, and it is dissolved in aqueous solution that pure water obtains is added drop-wise in the aqueous liquid dispersion 90 in the reaction vessel as polymerization initiator 80.Thus, polymerization initiator 80 fractures of interpolation produce the initiating agent free radical, the polymerism base of each polymerism surfactant 61,62 of its attack or the polymerism base of polymerizable monomer, thereby initiated polymerization.The kind that polymerization temperature and polymerization reaction time can employed polymerization initiators 80 and the kind of polymerizable monomer are and different, and those skilled in the art can be according to selecting suitable polymerizing condition set.
As previously mentioned, the activation of the polymerization initiator 80 in the reaction system can be undertaken by the polymerization temperature that makes aqueous liquid dispersion 90 be warming up to regulation.Polymerization temperature is preferably in 60～90 ℃ scope.Polymerization time is preferably in 3～10 hours scope.
The electrophoresis particle 5 that as above obtains is formed by organic polymer 60 coating particles 50.
Herein, according to Fig. 4, in the manufacture process of the electrophoresis particle 5 that as above makes, the mechanism of action that each polymerism surfactant and each monomer are shown is described in detail.
After being added to the 1st polymerism surfactant 61 in the aqueous liquid dispersion 90, the 1st polar group 611 of the electric charge 64 that particle 50 has and the 1st polymerism surfactant 61 combines by ionic link.By combination, the opposite polarity that both had is cancelled each other.In addition, the 1st hydrophobicity base 612 of the 1st polymerism surfactant 61 is relative with the hydrophobicity base 622 of the 2nd polymerism surfactant 62, the 2nd polar group 621 of the 2nd polymerism surfactant 62 is arranged towards aqueous liquid dispersion 90 sides, forms the micelle shape structure shown in Fig. 4 (a).If carry out polyreaction in this state, then form the organic polymer 60 shown in the Fig. 4 (b) that keeps aforementioned structure on particle 50 surfaces.That is to say that the configuration of the polymerism surfactant 61,62 that exists around the particle 50 before the polyreaction is controlled to heavens by the utmost point.Thus, by emulsion polymerization, keeping under this state of highly controlling, polymerism surfactant 61,62 and each conversion of monomer are organic polymer 60.Thereby the structure of the electrophoresis particle 5 that the manufacture method by electrophoresis particle of the present invention is made is by high Control of Precision.
In addition, according to Fig. 5, an example of other mechanism of action that each polymerism surfactant and each monomer are shown describes.
Shown in Fig. 5 (a), the 1st polar group 611 of the 1st polymerism surfactant 61 is arranged towards the particle 50 with negative charge 64, by strong ionic link absorption.Thus, by hydrophobic interaction, the hydrophobicity base 622 and the polymerism base 623 of the hydrophobicity base 612 of the 1st polymerism surfactant 61 and polymerism base 613 and the 2nd polymerism surfactant 62 face one another, the 2nd polar group 621 promptly is positioned at the direction away from particle 50 towards the direction that has aqueous liquid dispersion 90.
In addition, the surface of particle 50 is when having with the negative charge 64 of specific density by the chemical bond combination, between negative charge 64, also have hydrophobic region 70, remaining the 1st polymerism surfactant 61 " hydrophobicity base 612 " and polymerism base 613 " towards this hydrophobic region 70.Thus, the 2nd polymerism surfactant 62 is according to making its 2nd polar group 621 in the face of above-mentioned remaining the 1st polymerism surfactant 61 " the 1st polar group 611 " mode dispose.By hydrophobic interaction, these the 1st polymerism surfactants 61,61 " each hydrophobicity base 612,612 " and polymerism base 613,613 " face one another with the hydrophobicity base 622 and the polymerism base 623 of the 2nd polymerism surfactant 62; the 2nd polar group 621 promptly is positioned at the direction away from particle 50 towards the direction that exists of aqueous liquid dispersion 90.
If in the aqueous liquid dispersion 90 of above-mentioned disperse state, add for example polymerization initiator 80, by making the 1st polymerism surfactant 61,61 " and each polymerism base 613,613 of the 2nd polymerism surfactant 62 ", 623 polymerizations, then shown in Fig. 5 (b), make the electrophoresis particle 5 that forms by organic polymer 60 ' coating particles 50.
Each above-mentioned polymerism surfactant 61,62 is in polymerization system, electric charge 64 that particle 50 is had and the 1st polar group 611 of the 1st polymerism surfactant 61 are by the ionic link combination, arrange towards the aqueous liquid dispersion side at the 2nd polar group 621 of outermost layer the 2nd polymerism surfactant 62 thus, form micelle shape structure, be formed with organic polymer 60 by polyreaction, the configuration of the monomer that exists around the particle 50 before the emulsion polymerization influence near the polarized state the particle 50 after the polymerization, we can say can with high degree of accuracy control.Consequently, the electrophoresis particle 5 that finally obtains is provided with the 2nd polar group 621 in its outside, its charge polarity that has depends on the charged polarity of the 2nd polar group 621, and its carried charge depends on the quantity of the 2nd polar group 621 in the 2nd polymerism surfactant 62, the valence mumber of the 2nd polar group 621, the molecular weight of the 2nd polymerism surfactant 62 and the addition of the 2nd polymerism surfactant 62.In other words, by setting these factors, can control the charged polarity and the carried charge of electrophoresis particle 5.
In addition, in above-mentioned polyreaction, the compound shown in above-mentioned each polymerism surfactant, hydrophobic monomer, cross-linkable monomer, the above-mentioned general formula (1) and other known polymerizable monomer can use respectively more than a kind or 2 kinds.
In addition, the above-mentioned emulsion polyreaction is owing to use ionic polymerism surfactant, even do not use emulsifying agent, the emulsified state that contains the mixed liquor of starting monomer also often is good.Thereby the use of emulsifying agent is optional, and where necessary, can use and be selected from known negative ion system, nonionic system, kation is at least a in the emulsifying agent.
Give one example below, based on Figure 11 and Figure 12, to the Titanium particles handled through Si as particle 50, the material that uses aforementioned formula (31b) is as polymerism surfactant 61,61 ', when using hydrochloride aqueous solution (hydrochloric acid) as the dispersion medium of aqueous liquid dispersion 90, the formed disperse state of polymerism surfactant describes.
Figure 11 is the part enlarged drawing that is presented at the dispersion of nano-particles state that forms in the aqueous liquid dispersion of Fig. 3 (c), and Figure 12 is the part enlarged drawing of structure of the electrophoresis particle of displayed map 3 (d).
Particle 50 shown in Figure 11 has raw material particle 50a that is made of titanium dioxide and the monox (SiO that coats this raw material particle 50a surface 2) layer 50b.Thus, on the surface of silicon oxide layer 50b, expose O (oxygen) atom that combines with the Si atom of monox and with the covalently bound H of this oxygen atom
(hydrogen) atom, promptly hydroxyl (OH).
In addition, polymerism surfactant 61,61 ' has polar group 611,611 ', hydrophobicity base 612,612 ' and polymerism base 613,613 '.
In addition, simplified the chemical formula of the polymerism surfactant shown in the aforementioned formula (31b) herein, with XSO 3Na represents.Wherein, X represents SO 3Hydrocarbon part beyond the Na.
In the dispersion medium of aqueous liquid dispersion 90, add particle 50 and polymerism surfactant 61,61 ', following reaction then takes place:
HCl+H 2O→H 3O ++Cl -…(a)
SiOH+H 3O ++XSO 3Na?Cl -→SiO -H ++H ++XSO 3 -+H 2O+Na +Cl -…(b)
Generate H +(proton) combines by the O atom of the hydroxyl on the Si atom of coordination bond and monox.This proton makes the surface of particle 50 have positive charge 64 by the H atom in the hydroxyl.
In addition, XSO 3Na ionization in aqueous liquid dispersion 90 produces sulfonic group (polar group 611).This sulfonic group and positive charge 64 face one another arrangement by electrostatic attraction.
And then, cohesion mutually between a plurality of alkyl phenyls of adjacency (hydrophobicity base 612).
By the effect of above-mentioned each base, polymerism surfactant 61 is with the mode orientation on coating particles 50 surfaces, and it is right to form the ion coupling.
And then, in the outside of the alkyl phenyl (hydrophobicity base 612) that forms the right polymerism surfactant 61 (the 1st polymerism surfactant) of ion coupling, other polymerism surfactant 61 ' (the 2nd polymerism surfactant) with hydrophobicity base 612 ' is to arrange in the face of the mode of hydrophobicity base 612 and hydrophobicity base 612 '.Thus, formation micelle shape structure as shown in figure 11.
In the aqueous liquid dispersion 90 of above-mentioned disperse state, add polymerization initiator, then polymerization reaction take place between the polymerism base that had of a plurality of each polymerism surfactant 61,61 ' of adjacency 613,613 '.
, be example as the situation of polymerization initiator herein, polyreaction is described in detail to use ammonium persulfate.
If add ammonium persulfate in hydrotropism's dispersion liquid 90, the then O-O in the ammonium persulfate (oxygen-oxygen) bond rupture forms free radical.A reaction of 2 shared electron centerings of the formation pi-electron of each vinyl (polymerism base 613,613 ') in this free radical and the polymerism surfactant 61,61 '.Thus, another in the pi-electron becomes unpaired electron, becomes free radical.The reaction of the pi-electron of the vinyl of this free radical and adjacency when generating new free radical, forms cross-linked structure between these polymerism surfactants 61,61 '.By carry out above-mentioned reaction chainly, each vinyl polymerization materialization as shown in figure 12, forms the organic polymer 60 on coating particles 50 surfaces.Thus, obtain electrophoresis particle 5.
[5] then, in case of necessity, from aqueous liquid dispersion 90, reclaim electrophoresis particle 5.
As recovery method, can enumerate various filter methods such as high precision filtration, nanofiltration, secondary filter, cake filtration, reverse osmosis, can use wherein a kind or make up more than 2 kinds, especially preferably use high precision to filter.
It is a kind of method that fine particle is filtered that high precision is filtered (ultrafilte), is a kind of filter method that is suitable for electrophoresis particle 5.
[6] then, in case of necessity, dry electrophoresis particle 5.
The drying of electrophoresis particle 5 can be passed through for example freeze drying, aeration-drying, dry tack free, the various drying means such as drying, pneumatic conveying drying, spray drying, vacuum drying, infrared drying, radio-frequency drying, ultrasound wave drying, the broken drying of micro mist that flow, and preferably carries out freeze drying.
In the freeze drying, carry out drying from solid distillation for gas, thereby original shape and function exerts an influence in the organic polymer 60 that can not had electrophoresis particle 5 substantially, and organic polymer 60 is carried out drying by making aqueous liquid dispersion 90.
Freeze-drying method to electrophoresis particle 5 describes below.
At first, to cooling off, it is freezed by filtering the electrophoresis particle 5 that from aqueous liquid dispersion 90, takes out.Contained aqueous liquid dispersion 90 becomes solid in the electrophoresis particle 5 thus.
As chilling temperature, get final product so long as aqueous liquid dispersion 90 freezes following temperature, there is no particular limitation, preferably about-100 ℃～-20 ℃, more preferably-80～-40 ℃ about.If chilling temperature is higher than the said temperature scope, then aqueous liquid dispersion 90 can not solidify fully sometimes.On the other hand, if chilling temperature is lower than the said temperature scope, then the curing of aqueous liquid dispersion 90 does not have bigger effect yet.
Then, to reducing pressure around the electrophoresis particle 5 that freezes.Can reduce the boiling point of aqueous liquid dispersion 90 thus, make aqueous liquid dispersion 90 distillations.
Pressure during decompression is according to the composition of aqueous liquid dispersion 90 and different, below preferably about 100Pa, more preferably from about below the 10Pa.If the pressure during decompression then can be guaranteed the distillation of aqueous liquid dispersion 90 more in aforementioned range.
In addition, be accompanied by the distillation of aqueous liquid dispersion 90, the pressure around the electrophoresis particle 5 rises, thereby in freeze drying, carries out exhaust continuously by off-gas pump etc., preferably pressure is maintained certain value.Can suppress the rising of pressure like this, prevent that the distillation efficient of aqueous liquid dispersion 90 from reducing.
The freeze drying of electrophoresis particle 5 can as above be carried out.
＜the 2 embodiment 〉
Below the 2nd embodiment of electrophoretic display apparatus is described.
Fig. 6 is the mode chart in longitudinal profile of the electrophoretic display apparatus of the 2nd embodiment.In addition, below for convenience of explanation, with the upside among Fig. 6 as " on ", downside is described as D score.
Electrophoretic display apparatus to the 2nd embodiment describes below, and for identical item, its explanation will be omitted.
As shown in Figure 6, in the electrophoretic display apparatus 20 of the 2nd embodiment, except between the 1st electrode 3 and the 2nd electrode 4, be provided with the micro-capsule 40 of a plurality of inclosure electrophoresis dispersions 10, beyond the peripheral part of these micro-capsules 40 supply jointing material 41, the electrophoretic display apparatus 20 of all the other and aforementioned the 1st embodiment is identical.
Micro-capsule 40 is arranged on (gap between the inner face of the inner face of transparency carrier 1 and subtend substrate 2) between transparency carrier 1 and the subtend substrate 2 with horizontal mode individual layer ground (thickness direction is not overlappingly one by one in turn) side by side, contacts with the 2nd electrode 4 with the 1st electrode 3 respectively.In addition, in the present embodiment, 2 the 2nd electrodes 4 with respect to adjacency are provided with 1 micro-capsule 40.Being micro-capsule 40 is provided with in the mode across 2 the 2nd electrodes 4 of adjacency.
Constituent material as micro-capsule 40, be not particularly limited, for example can enumerate, various resin materials such as the compound substance of gum arabic and gelatin, carbamate resinoid, melamine resinoid, urea resin, epoxy resin, polyamide, polyethers can use wherein a kind or are used in combination more than 2 kinds.
In addition, manufacture method (with the method in the electrophoresis dispersion 10 inclosure micro-capsules 40) as micro-capsule 40, be not particularly limited, for example can use, various microencapsulation methods such as interfacial polymerization, situ aggregation method, phase separation method (or coacervation), interphase precipitate method, spray drying process.And, according to constituent material of micro-capsule 40 etc., described microencapsulation method is suitably selected to get final product.
The preferably basic homogeneous of the size of this kind micro-capsule 40.Like this, electrophoretic display apparatus 20 can be brought into play better display performance.In addition, for example can utilize filtration method, density difference stage method to wait and obtain the evenly micro-capsule 40 of size.
The size of micro-capsule 40 (mean grain size) is not particularly limited, usually, and about preferred 10～150 μ m, more preferably about 20～100 μ m.
At these micro-capsule 40 inner electrophoresis dispersions 10 of enclosing.
Jointing material 41 is for for example fixing micro-capsule 40 or guarantee that the purposes such as insulativity between the electrode 3,4 provide.The permanance of electrophoretic display apparatus 20 and reliability are further improved.
In this jointing material 41, can suitably use the resin material that compatibility (connecting airtight property) is good and insulativity is good with each electrode 3,4 and micro-capsule 40.
As this resin material, be not particularly limited, for example can enumerate, tygon, Polyvinylchloride, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polypropylene, ABS resin, polymethyl methacrylate resin, vestolit, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, the vinyl chloride acrylate multipolymer, vinyl chloride methacrylic acid, vinyl chloride-acrylonitrile copolymer, ethylene-vinyl alcohol-vinyl chloride copolymer, propylene-vinyl chloride copolymer, permalon, vinyl acetate resin, polyvinyl alcohol (PVA), tygon acetal formaldehyde, thermoplastic resins such as cellulosic resin, poly-formamide resin, polyacetal, polycarbonate, the Polyethylene Terephthalates, poly-terephthalic acids butanediol ester, polyphenylene oxide, polysulfones, the inferior acid amides of polyamide, PABM, polyethersulfone, PPSU, polyarylate, the grafting polyphenylene oxide, polyetheretherketone, macromolecular compounds such as polyetherimide, teflon, the polyvinyl fluoride propylene, tetrafluoroethene-perfluor alcoxyl ethylene copolymer, ethylene-tetrafluoroethylene copolymer, Kynoar, polychlorotrifluoroethylene, fluorine-type resins such as fluororubber, silicone resin, silicones such as silicone rubber, in addition, also has methacrylic acid-styrol copolymer, polybutylene, MBSs etc. can use wherein a kind or are used in combination more than 2 kinds.
In addition, jointing material 41 preferred its specific inductive capacity is made as with the specific inductive capacity of aforementioned dispersion medium 6 equate substantially.Therefore, in adhesives 41, preferred for example add 1,2-butylene glycol, 1, specific inductive capacity correctivess such as alcohols such as 4-butylene glycol, ketone, carboxylate.
By the electrophoretic display apparatus 20 of described the 2nd embodiment, can realize effect and the effect same with aforementioned the 1st embodiment.
＜the 3 embodiment 〉
The 3rd embodiment to electrophoretic display apparatus describes below.
Fig. 7 is the mode chart in longitudinal profile of the electrophoretic display apparatus of the 3rd embodiment.
Electrophoretic display apparatus to the 3rd embodiment describes below, but only with the aforementioned the 1st and the difference of the electrophoretic display apparatus of aforementioned the 2nd embodiment be that the center describes, for identical item, its explanation will be omitted.
As shown in Figure 7, in the electrophoretic display apparatus 20 of the 3rd embodiment, between the absolute electrode that is divided into the 2nd rectangular electrode 4, be provided with next door 73, confined space 71 is divided into littler gap 72, and electrophoresis dispersion 10 with supply in this gap 72, in addition, the electrophoretic display apparatus 20 of all the other and aforementioned the 1st embodiment is identical.
By the electrophoretic display apparatus 20 of described the 3rd embodiment, can realize and same effect and the effect of the aforementioned the 1st and the 2nd embodiment.
＜the 4 embodiment 〉
Below the 4th embodiment of electrophoretic display apparatus is described.
Fig. 8 is the mode chart in longitudinal profile of the electrophoretic display apparatus of the 4th embodiment.In addition, below for convenience of explanation, with the upside among Fig. 8 as " on ", downside is described as D score.
Electrophoretic display apparatus to the 4th embodiment describes below, but is that the center describes with the difference with the electrophoretic display apparatus of aforementioned the 1st, the 2nd and the 3rd embodiment only, and for identical item, its explanation will be omitted.
In the electrophoretic display apparatus 20 of the 4th embodiment, except the structure of the 1st electrode 3 and the 2nd electrode 4 (configuration etc.) was different, the electrophoretic display apparatus 20 of all the other and aforementioned the 3rd embodiment was identical.
That is, as shown in Figure 8, in the electrophoretic display apparatus 20 of the 4th embodiment, on the 2nd substrate 2, with the 1st electrode 3 and the 4 overlapping settings of the 2nd electrode of size greater than the 2nd electrode 4.
In addition, in the present embodiment, be white as electrophoresis particle 5, the 2 substrates 2 to use electronegative black (coloured) particle, the 2nd electrode 4 is that an example describes for the situation of black (coloured).
In above-mentioned electrophoretic display apparatus 20, if the 2nd electrode 4 is made as positive potential, then electrophoresis particle 5 converges to the 2nd electrode 4 to the 2nd electrode 4 side shiftings.
Otherwise if the 2nd electrode 4 is made as negative potential, then electrophoresis particle 5 converges on this part to the 1st electrode 3 side shiftings of not blocked by the 2nd electrode 4.
Thus, as shown in Figure 8, by the combinations of polarities of the 2nd electrode 4, when from the top (display surface side) can see respectively when seeing electrophoretic display apparatus 20, in the gap 72 in left side, the left side is owing to the color of electrophoresis particle 5 shows black, and the right side is owing to the color display white of the 2nd substrate 2, in the gap 72 on right side, because the color of electrophoresis particle 5 and the color of the 2nd electrode 4, integral body presents black.
In addition, in above-mentioned electrophoretic display apparatus 20, even after stopping to the 1st electrode 3 and 4 energisings of the 2nd electrode, in the gap 72 in left side, because the electrostatic force that lap produced (gravitation) of the 1st electrode 3 and the 2nd electrode 4, electrophoresis particle 5 keeps with the state that is attracted by the 1st electrode 3, in the gap 72 on right side, because the electrostatic force that lap produced (repulsion) of the 1st electrode 3 and the 2nd electrode 4, electrophoresis particle 5 keeps by the state of the 1st electrode 3 repulsions.
In addition, in above-mentioned electrophoretic display apparatus 20, be added in the size of the voltage on the electrode 3,4, alive time etc. by adjusting, can be controlled at the amount of movement of the electrophoresis particle 5 between the part that the 2nd electrode 4 and the 1st electrode 3 do not block by the 2nd electrode 4, realize that multi-level gray scale shows.
By the electrophoretic display apparatus 20 of described the 4th embodiment, can realize and same effect and the effect of aforementioned the 1st, the 2nd and the 3rd embodiment.
＜e-machine 〉
Electrophoretic display apparatus 20 as implied above can be packed in the various e-machines.Below the e-machine of the present invention that is provided with electrophoretic display apparatus 20 is described.
" Electronic Paper "
The embodiment that e-machine of the present invention is applied in the Electronic Paper describes below.
Fig. 9 is the stereographic map that expression is applied to e-machine of the present invention embodiment in the Electronic Paper.
Electronic Paper 600 shown in Figure 9 has main body 601, the display unit 602 that is made of the rewritten thin slice identical with flexibility with the texture of paper.
In this Electronic Paper 600, display unit 602 is made of foregoing electrophoretic display apparatus 20.
" display "
Below, the embodiment that e-machine of the present invention is applied in the display describes.
Figure 10 is the figure that expression e-machine of the present invention is applied to the embodiment in the display.Wherein, Figure 10 (a) is a sectional view, (b) is vertical view.
Display shown in Figure 10 (display device) 800 is provided with main part 801, is located at Electronic Paper 600 on this main part 801 in the mode that can freely dismantle with respect to this main body 801.In addition, the structure of this Electronic Paper 600 as previously mentioned, that is, identical with structure shown in Figure 10.
Main part 801 forms the insertion mouth 805 that can insert Electronic Paper 600 at its sidepiece (being the right side among Figure 10).In addition, be provided with two groups of conveying cylinders in inside to 802a, 802b.In the time of in Electronic Paper 600 is passed insertion mouthful 805 insertion main parts 801, Electronic Paper 600 just is arranged in the main part 801 under being transferred the state of cylinder to 802a, 802b clamping.
In addition, form the hole portion 803 of rectangle, in this hole portion 803, embed transparency glass plate 804 in the display surface side (being the paper front side among Figure 10 (a)) of main part 801.Like this, from the outside of main part 801, just can see the Electronic Paper 600 of being located at state in the main part 801.That is, in this display 800, see the Electronic Paper 600 of being located at state in the main part 801, constitute display surface with this by transparency glass plate 804.
In addition, the direction of insertion leading section (being the left side among Figure 10) in Electronic Paper 600 is provided with portion of terminal 806, in the inside of main part 801, is provided with socket 807, and it is connected with portion of terminal 806 under the state that Electronic Paper 600 is arranged in the main part 801.On this socket 807,809 energisings are connected with operating portion with controller 808.
In the aforementioned display device 800, Electronic Paper 600 is arranged in the main part 801 in the mode that can freely dismantle, and it also can portably use under the state that unloads from main part 801.
In addition, in the aforementioned display device 800, Electronic Paper 600 is made of foregoing electrophoretic display apparatus 20.
In addition, e-machine of the present invention is not limited to the application in the said apparatus, for example, can enumerate TV, video tape recorder, automobile navigation apparatus, pager, electronic notebook, counter, electronic newspaper, word processor, PC, workstation, videophone, the POS terminal of the type of finding a view, monitor direct viewing type, have the machine of touch-type panel etc., in the display part of these various e-machines, can use electrophoretic display apparatus 20 of the present invention.
Abovely according to illustrated each embodiment electrophoretic display apparatus of the present invention and e-machine are illustrated, still, the present invention is not limited to these.
In addition, electrophoretic display apparatus of the present invention can be the device that will select in each embodiment after any content (feature) more than 2 kinds makes up.
Embodiment
Below specific embodiments of the invention are described.
1. the manufacturing of electrophoresis particle
(embodiment 1)
[1] at first the TiO 2 particles (the former industry corporate system of stone is made " CR-90 ") of mean grain size 0.3 μ m is disperseed (aqueous liquid dispersion) in water, obtain dispersion liquid.In addition, the TiO 2 particles surface has positive electricity.
[2] then, in this dispersion liquid, add the polymerism surfactant (the 1st polymerism surfactant) of the anionic property shown in the following chemical formula (38), under hyperacoustic irradiation, stir, obtain mixed liquor.
Figure C20061007370000401
[3] then, the diallyl dimethyl ammonium chloride salt (the 2nd polymerism surfactant of cationic) of the polymerism surfactant equimolar amounts of adding and anionic property stirs under hyperacoustic irradiation in this mixed liquor, obtains emulsion.
[4] then, in this emulsion, add sodium peroxydisulfate (polymerization initiator), stir, obtain comprising the mixed liquor by the electrophoresis particle that forms around the organic polymer cladding titanium dioxide particle, in addition, the condition of this moment is, temperature: 70 ℃, mixing time: 5 hours.
[5] then, from mixed liquor, reclaim electrophoresis particle by the high precision filtration.
[6] then, the electrophoresis particle that obtains of vacuum drying.In addition, cryodesiccated condition is as follows.
Chilling temperature :-45 ℃
Pressure: 9Pa
(embodiment 2)
Except the polymerism surfactant that uses the anionic property shown in the aforementioned chemical formula (38) replaced the diallyl dimethyl ammonium chloride salt, all the other and previous embodiment 1 similarly obtained electrophoresis particle.
(embodiment 3)
Except the polymerism surfactant of the anionic property shown in the aforementioned chemical formula (38) that adds 2 times of molar weights, all the other and previous embodiment 2 similarly obtain electrophoresis particle.
(embodiment 4)
Except the polymerism surfactant that uses the anionic property shown in the following chemical formula (39) replaced the polymerism surfactant of the anionic property shown in the aforementioned chemical formula (38), all the other and previous embodiment 2 similarly obtained electrophoresis particle.
Figure C20061007370000411
(embodiment 5)
Except the polymerism surfactant that uses the anionic property shown in the following chemical formula (40) replaced the polymerism surfactant of the anionic property shown in the aforementioned chemical formula (38), all the other and previous embodiment 2 similarly obtained electrophoresis particle.
Figure C20061007370000412
(embodiment 6)
Except the polymerism surfactant that uses the anionic property shown in the following chemical formula (41) replaced the polymerism surfactant of the anionic property shown in the aforementioned chemical formula (38), all the other and previous embodiment 2 similarly obtained electrophoresis particle.
Figure C20061007370000413
(embodiment 7)
Except the polymerism surfactant that uses the anionic property shown in the following chemical formula (42) replaced the polymerism surfactant of the anionic property shown in the aforementioned chemical formula (38), all the other and previous embodiment 2 similarly obtained electrophoresis particle.
Figure C20061007370000421
2. estimate
The electrophoresis particle that obtains among each embodiment is measured its surperficial Zeta-potential respectively.
The result shows that the charged polarity of each electrophoresis particle of the electrophoresis particle of embodiment 1 and embodiment 2～7 is different.That is, the electrophoresis particle of embodiment 1 is for just, and any in each electrophoresis particle of embodiment 2～7 is all electronegative.
In addition, the carried charge of the electrophoresis particle of embodiment 1 is different with the TiO 2 particles monomer.
And then the carried charge of each electrophoresis particle of embodiment 2～7 is also different respectively.
These results show, has the polarity of the 2nd polar group by changing the 2nd polymerism surfactant that in aforementioned operation [3], adds, and at least 1 condition in the addition of the molecular weight of the valence mumber of the composition of the quantity of the 2nd the 2nd polar group in the polymerism surfactant, the 2nd polar group, the 2nd polar group, the 2nd polymerism surfactant and the 2nd polymerism surfactant, can control the charged polarity and the carried charge of the electrophoresis particle that obtains.

Claims (19)

1. the manufacture method of an electrophoresis particle, the 1st polymerism surfactant that is to use the surface to have the particle of positive charge and has the 1st polar group, the 1st hydrophobicity base, the 1st polymerism base, manufacturing wherein, has with the be covered method of electrophoresis particle of described particle of organic polymer:
In the polarity dispersion medium, disperse described particle and prepare the 1st operation of dispersion liquid;
In described dispersion liquid, add multiple described the 1st polymerism surfactant, make described multiple the 1st polymerism surface active agent ionization, form ionically bonded the 2nd operation by described the 1st polar group with negative charge and surface with described particle of positive charge;
Add polymerization initiator in described dispersion liquid, a plurality of described polymerism base that described multiple the 1st polymerism surfactant is had reacts to each other, and forms the 3rd operation of described organic polymer,
And, between described the 2nd operation and described the 3rd operation, also have and in described dispersion liquid, add multiple the 2nd polymerism surfactant, make the operation of described multiple the 2nd polymerism surface active agent ionization,
Described multiple the 2nd polymerism surfactant has the 2nd polar group, the 2nd hydrophobicity base, the 2nd polymerism base separately, and described the 2nd hydrophobicity base of described the 2nd polymerism surfactant is relative with described the 1st hydrophobicity base of described the 1st polymerism surfactant.
2. the manufacture method of electrophoresis particle according to claim 1, wherein,
Described the 2nd polar group of described the 2nd polymerism surfactant has negative charge.
3. the manufacture method of electrophoresis particle according to claim 1, wherein,
Described the 2nd polar group of described the 2nd polymerism surfactant has positive charge.
4. the manufacture method of electrophoresis particle according to claim 2, wherein,
The surface negative charge amount of described organic polymer is by the addition control of described the 2nd polymerism surfactant.
5. the manufacture method of electrophoresis particle according to claim 3, wherein,
The positive surface charge amount of described organic polymer is by the addition control of described the 2nd polymerism surfactant.
6. the manufacture method of electrophoresis particle according to claim 1, wherein,
Described the 1st hydrophobicity base contains at least one in alkyl and the aryl.
7. the manufacture method of electrophoresis particle according to claim 1, wherein,
Described the 1st polymerism base be can free radical polymerization unsaturated alkyl.
8. the manufacture method of electrophoresis particle according to claim 7, wherein,
Described unsaturated alkyl that can free radical polymerization is selected from vinyl, allyl, acryloyl group, methacryl, propenyl, 1,1-ethenylidene and 1, in the 2-ethenylidene a kind.
9. the manufacture method of electrophoresis particle according to claim 1, wherein,
Described the 2nd polar group is the cationic base, and described cationic base is a kind that is selected from primary amine cation radical, secondary amine cation radical, tertiary amine cation radical and the quaternary ammonium cation base.
10. the manufacture method of electrophoresis particle according to claim 1, wherein,
Described the 2nd polar group is the anionic property base, and this anionic property base is for being selected from sulfonic acid anion base-SO 3 -, sulfinic acid anion base-RSO 2 -, and carboxylate anion-COO -In a kind, described sulfinic acid anion base-RSO 2 -In R be the alkyl or phenyl and the modifier thereof of carbon number 1～12.
11. the manufacture method of an electrophoretic display apparatus, wherein,
Have operation that forms a plurality of micro-capsules and the operation that on substrate, disposes described a plurality of micro-capsules,
Each self-contained electrophoresis particle of described a plurality of micro-capsule, described electrophoresis particle is by each the described manufacture method manufacturing in the claim 1 to 10.
12. the manufacture method of an e-machine, wherein,
Have the operation that forms electrophoretic display apparatus and the operation of described electrophoretic display apparatus be set at main part,
Described electrophoretic display apparatus is by the described manufacture method manufacturing of claim 11.
13. an electrophoresis particle, wherein,
Comprise Titanium particles, the silicon oxide layer of the described titanium dioxide of lining and the organic polymer of the described silicon oxide layer that is covered,
At a plurality of protons of the surface configuration of described silicon oxide layer, described organic polymer contains a plurality of the 1st polar groups, described a plurality of the 1st polar groups and described a plurality of proton ionic bonding,
And described organic polymer has a plurality of the 1st hydrophobicity bases, described a plurality of the 1st polar groups between described a plurality of the 1st hydrophobicity bases and described a plurality of proton,
And described organic polymer has a plurality of the 2nd hydrophobicity bases, described a plurality of the 1st hydrophobicity bases between described a plurality of the 2nd hydrophobicity bases and described a plurality of the 1st polar group,
And described organic polymer has a plurality of the 2nd polar groups, and described a plurality of the 2nd hydrophobicity bases are between described a plurality of the 2nd polar groups and described a plurality of the 1st hydrophobic group.
14. electrophoresis particle according to claim 13, wherein,
Described a plurality of the 1st polar group has negative charge separately, and described a plurality of the 2nd polar groups have negative charge.
15. electrophoresis particle according to claim 13, wherein,
Described a plurality of the 1st polar group has negative charge separately, and described a plurality of the 2nd polar groups have positive charge.
16. electrophoresis particle according to claim 14, wherein,
The carried charge of the surface negative charge of described organic polymer is by the quantity control of described a plurality of the 2nd polar groups.
17. electrophoresis particle according to claim 15, wherein,
The carried charge of the positive surface charge of described organic polymer is by the quantity control of described a plurality of the 2nd polar groups.
18. an electrophoretic display apparatus, wherein,
Substrate with a plurality of micro-capsules and the described a plurality of micro-capsules of mounting, described a plurality of micro-capsules contain each described electrophoresis particle in the claim 13 to 17 separately.
19. an e-machine, wherein,
Have described electrophoretic display apparatus of claim 18 and the main part that described electrophoretic display apparatus is set.
CNB2006100737009A 2005-04-19 2006-04-19 Method for producing electrophoretic particles, electrophoretic dispersion solution, micro-capsule, electrophoresis display device and electronic machine Active CN100432817C (en)

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