JP2009031329A - Electrophoretic colored particle, manufacturing method of electrophoretic colored particle, electrophoretic colored particle dispersion liquid, image display medium and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide electrophoretic colored particles, a manufacturing method thereof and an image display device. <P>SOLUTION: An organic pigment is surface-treated by reaction of a silane compound represented by general formula (I), a silane compound having a polymerizable group represented by general formula (II) or general formula (III) and a polymerizable monomer represented by general formula (IV) or general formula (V). In the general formulas (I) to (V), R<SP>1</SP>denotes a fluorine atom containing alkyl group, a fluorine atom containing aryl group or a fluorine atom containing aralkyl group, X denotes a methoxy group, an ethoxy group or a chlorine atom, R<SP>2</SP>denotes a hydrogen atom or a methyl group, Y denotes a methoxy group or an ethoxy group, n denotes an integer of 1 to 20, R<SP>3</SP>denotes a hydrogen atom or a methyl group, R<SP>4</SP>denotes an alkyl group or an aralkyl group and R<SP>5</SP>denotes an alkyl group, an aryl group or an aralkyl group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to electrophoretic colored particles, a method for producing electrophoretic colored particles, an electrophoretic colored particle dispersion, an image display medium, and an image display device.

  Conventionally, display technologies such as Twisting Ball Display (two-color particle rotation display), electrophoresis, magnetophoresis, thermal rewritable media, and liquid crystal with memory properties have been proposed as repetitively rewritable sheet-like image display media. Has been.

  The electrophoretic display technology, which is one of the above display technologies, is a display device in which conductive colored particles and white particles are sealed between opposing electrode substrates, via a charge transport layer provided on the inner surface of the electrode of the non-display substrate. Electric charges are injected into the conductive colored particles, and the charged conductive colored particles move to the display substrate side facing the non-display substrate by an electric field between the electrode substrates, and the conductive colored particles are displayed on the display side substrate. This is a display technique for displaying an image based on the contrast between conductive colored particles and white particles utilizing adhesion to the inside.

  By the way, in the said display technique, the electroconductive coloring particle which moves between board | substrates is enclosed between board | substrates in the state disperse | distributed to the dispersion medium. Therefore, it is necessary to use particles having good dispersibility. In addition, a charging property that can sufficiently cope with the applied voltage is required.

  As a method for improving the dispersibility and chargeability of the conductive colored particles, for example, a polymer of 1% by weight or more and 15% by weight or less of the pigment is chemically bonded to the pigment particles, or crosslinked around the polymer. A method is disclosed (for example, see Patent Document 1).

  In addition, electrophoretic particles having a polymer graft chain formed on the particle surface are disclosed (for example, see Patent Document 2).

  Furthermore, (a) acrylic acid ester, methacrylic acid ester, or styrene derivative, (b) radical polymerizable group-containing polysiloxane macromonomer, (c) silicon-containing resin obtained by copolymerization with radical polymerizable group-containing alkoxysilane And (d) microparticles made of a silicon-containing compound obtained by cohydrolyzing tetraalkoxysilane are disclosed as electrophoretic particles (see, for example, Patent Document 3).

Charged electrophoretic particles (see, for example, Patent Document 4) used for electrophoretic display elements whose surfaces are coated with a fluorinated (meth) acrylate polymer, monomers having a fluoro group at the end, and those having 8 or more carbon atoms at the end An electrophoretic colored particle (for example, Patent Document 5) that is coated with a copolymer with a monomer having an alkyl group and has a ζ potential value of −50 mV or less is also disclosed.
Special table 2004-526210 gazette JP-A-5-173193 JP 2005-30936 A JP 2005-352423 A JP 2006-18026 A

In order to realize electrophoretic display, in addition to improving the dispersibility of the particles in the dispersion medium, the electrophoretic speed can be precisely controlled for each particle type (color) with a dispersed particle size of submicron order. Electrophoretic particles are required.
However, it has been generally difficult to obtain particles having a particle size of submicron or less and exhibiting high dispersion stability in an insulating solvent, particularly in silicone oil.

  Accordingly, an object of the present invention is to provide electrophoretic colored particles that exhibit high dispersion stability and that are easy to control chargeability, a method for producing electrophoretic colored particles, an electrophoretic colored particle dispersion, an image display medium, and An image display device is provided.

  The above problem is solved by the following means. That is,

  The invention according to claim 1 is a silane compound represented by the following general formula (I), a silane compound having a polymerizable group represented by the following general formula (II) or general formula (III), and the following general formula An electrophoretic colored particle characterized by being an organic pigment surface-treated by a reaction with a polymerizable monomer represented by (IV) or general formula (V).

General formula ^(I): R 1 -SiX ₃

In general formula (I), R ¹ represents a fluorine atom-containing alkyl group, a fluorine atom-containing aryl group, or a fluorine atom-containing aralkyl group, and X represents a methoxy group, an ethoxy group, or a chlorine atom.

Formula ^{_{(II): CH 2 = CR}} 2 COO (CH 2) n SiY 3

In general formula (II), R ² represents a hydrogen atom or a methyl group, Y represents a methoxy group or an ethoxy group, and n represents an integer of 1-20.

Formula _{(III): CH 2 = CH-} (A) m -SiZ 3
In general formula (III), A represents a divalent aliphatic residue or aromatic residue, and these substituents represented by A may further have a substituent. Z represents a methoxy group, an ethoxy group or a chlorine atom, and m represents 0 or 1.

Formula ^{_{(IV): CH 2 = CR}} 3 COOR 4

In general formula (IV), R ³ represents a hydrogen atom or a methyl group. R ⁴ represents an alkyl group or an aralkyl group, and these substituents represented by R ⁴ may further have a substituent.

Formula _{(V): CH 2 = CH} -R 5

In general formula (V), R ⁵ represents an aryl group or a heterocyclic group, and these substituents represented by R ⁵ may further have a substituent.

  In the invention according to claim 2, in the surface treatment, at least after the surface treatment with the silane compound having a polymerizable group represented by the general formula (II) or the general formula (III), the general formula (IV The electrophoretic colored particles according to claim 1, wherein the electrophoretic colored particles are surface-treated with a polymerizable monomer represented by formula (V).

  The invention according to claim 3 is characterized in that the organic pigment is at least one selected from the group consisting of phthalocyanine pigments, quinacridone pigments, and azo pigments. The electrophoretic colored particles described.

Invention of Claim 4 makes an organic pigment a silane compound represented by the following general formula (I), a silane compound having a polymerizable group represented by the following general formula (II) or general formula (III), And a polymerizable monomer represented by the following general formula (IV) or general formula (V):
At least after the surface treatment with the silane compound having a polymerizable group represented by the general formula (II) or the general formula (III), the polymerizable unit represented by the general formula (IV) or the general formula (V) is used. It is a method for producing electrophoretic colored particles, wherein the surface treatment is performed with a monomer.

General formula ^(I): R 1 -SiX ₃

In general formula (I), R ¹ represents a fluorine atom-containing alkyl group, a fluorine atom-containing aryl group, or a fluorine atom-containing aralkyl group, and X represents a methoxy group, an ethoxy group, or a chlorine atom.

Formula ^{_{(II): CH 2 = CR}} 2 COO (CH 2) n SiY 3

In general formula (II), R ² represents a hydrogen atom or a methyl group, Y represents a methoxy group or an ethoxy group, and n represents an integer of 1-20.

Formula _{(III): CH 2 = CH-} (A) m -SiZ 3
In general formula (III), A represents a divalent aliphatic residue or aromatic residue, and these substituents represented by A may further have a substituent. Z represents a methoxy group, an ethoxy group or a chlorine atom, and m represents 0 or 1.

Formula ^{_{(IV): CH 2 = CR}} 3 COOR 4
In general formula (IV), R ³ represents a hydrogen atom or a methyl group. R ⁴ represents an alkyl group or an aralkyl group, and these substituents represented by R ⁴ may further have a substituent.

Formula _{(V): CH 2 = CH} -R 5
In general formula (V), R ⁵ represents an aryl group or a heterocyclic group, and these substituents represented by R ⁵ may further have a substituent.

In the invention according to claim 5, the surface treatment with the silane compound represented by the general formula (I) is performed.
(1) Simultaneously with the surface treatment with the silane compound having a polymerizable group represented by the general formula (II) or the general formula (III),
(2) Simultaneously with the surface treatment with the polymerizable monomer represented by the general formula (IV) or the general formula (V),
(3) After the surface treatment with the polymerizable monomer represented by the general formula (IV) or the general formula (V),
5. The method for producing electrophoretic colored particles according to claim 4, wherein the method is performed so as to satisfy at least one of them.

  The invention according to claim 6 is an electrophoresis in which the electrophoretic colored particles according to any one of claims 1 to 3 are dispersed in a light-transmitting dispersion medium. Coloring particle dispersion.

The invention according to claim 7 is a pair of substrates disposed opposite to each other, at least one of which has translucency,
The electrophoretic colored particle dispersion according to claim 6 injected between the pair of substrates;
An image display medium comprising:

The invention according to claim 8 provides:
The electrophoretic colored particle dispersion contains a plurality of types of electrophoretic colored particles,
8. The image display medium according to claim 7, wherein each of the electrophoretic colored particle groups has different voltage absolute values necessary for moving in accordance with an electric field, and exhibits different color development properties. It is.

  The invention according to claim 9 is characterized in that each electrophoretic colored particle group has a voltage range necessary for moving in accordance with an electric field, and the voltage range is different from each other. 8. The image display medium according to 8.

The invention according to claim 10 is the image display medium according to any one of claims 7 to 9,
Voltage applying means for applying a voltage between the pair of substrates of the image display medium;
It is an image display apparatus characterized by having.

According to the present invention, it is possible to provide an electrophoretic colored particle, an electrophoretic colored particle dispersion liquid that exhibits high dispersion stability and whose chargeability can be easily controlled, and a method for producing the same.
Further, according to the present invention, an image display medium and an image display device that are excellent in displayability and reliability can be obtained.

  Hereinafter, embodiments of the present invention will be described.

(Electrophoretic colored particles)
The electrophoretic colored particles according to the first embodiment include a silane compound represented by the following general formula (I), a silane compound having a polymerizable group represented by the following general formula (II) or general formula (III), And an organic pigment surface-treated by reaction of a polymerizable monomer represented by the following general formula (IV) or general formula (V).

General formula ^(I): R 1 -SiX ₃

In general formula (I), R ¹ represents a fluorine atom-containing alkyl group, a fluorine atom-containing aryl group, or a fluorine atom-containing aralkyl group, and X represents a methoxy group, an ethoxy group, or a chlorine atom.

Formula ^{_{(II): CH 2 = CR}} 2 COO (CH 2) n SiY 3

In general formula (II), R ² represents a hydrogen atom or a methyl group, Y represents a methoxy group or an ethoxy group, and n represents an integer of 1-20.

Formula _{(III): CH 2 = CH-} (A) m -SiZ 3

  In general formula (III), A represents a divalent aliphatic residue or aromatic residue, and the substituent represented by A may further have a substituent. Z represents a methoxy group, an ethoxy group or a chlorine atom, and m represents 0 or 1.

Formula ^{_{(IV): CH 2 = CR}} 3 COOR 4

In general formula (IV), R ³ represents a hydrogen atom or a methyl group. R ⁴ represents an alkyl group or an aralkyl group, and these substituents represented by R ⁴ may further have a substituent.

Formula _{(V): CH 2 = CH} -R 5

In general formula (V), R ⁵ represents an aryl group or a heterocyclic group, and the substituent represented by R ⁵ may further have a substituent.

In the electrophoretic colored particles according to the present embodiment, the surface of the organic pigment particle is a silane compound represented by the general formula (I) having fluorine in the molecule, the general formula (II) having the polymerizable group, or the general formula It is modified with a polymer compound chain formed by the reaction of the silane compound represented by (III) and the polymerizable monomer represented by the general formula (IV) or general formula (V).
The electrophoretic colored particles thus obtained have improved dispersibility in a nonpolar solvent, and the dispersion particle size can be reduced, the dispersion stability can be freely controlled, and the chargeability can be freely controlled. As a result, it is possible to realize the atomization of electrophoretic colored particles necessary for realizing one-pixel multicolor display and control of the electrophoretic properties of each color.
Hereinafter, each composition will be described.

<Silane compound represented by formula (I)>
General formula ^(I): R 1 -SiX ₃

In general formula (I), R ¹ represents a fluorine atom-containing alkyl group, a fluorine atom-containing aryl group, or a fluorine atom-containing aralkyl group.

The group represented by R ¹ in formula (I) is preferably an alkyl group having 2 or more carbon atoms, and more preferably an alkyl group having 8 to 20 carbon atoms.
Specific examples include an ethyl group, a propyl group, a butyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group.

Of the hydrogen atoms of the alkyl group represented by R ¹ in the general formula (I), the number of hydrogen atoms substituted by fluorine atoms may be one or more, preferably three or more, More preferably, it is 10 or more and 20 or less.

Examples of the fluorine atom-containing alkyl group represented by R ¹ in the general formula (I) include a trifluoromethyl group, a 3,3,3-trifluoropropyl group, and a tridecafluoro-1,1,2,2 -Tetrahydrooctyl group, etc. are mentioned.

  In general formula (I), X represents a methoxy group, an ethoxy group, or a chlorine atom. X is preferably a methoxy group or an ethoxy group in consideration of the reactivity of the silane compound.

  Specific examples of the silane compound represented by the general formula (I) are shown below, but are not limited to the following specific examples.

-Specific examples of silane compounds represented by formula (I)-
Trifluoromethyltriethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltrichlorosilane, 3,3,3-trifluoropropyltrimethoxysilane, (pentafluorophenyl) triethoxysilane, (tridecafluoro-1, 1,2,2-tetrahydrooctyl) trimethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) tri Chlorosilane.

Among the silane compounds represented by the general formula (I), the case where R ¹ is a fluorine atom-containing alkyl group having 2 or more carbon atoms and 3 or more fluorine atoms is preferable from the viewpoint of improving dispersibility. Specifically, 3,3,3-trifluoropropyltrimethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl) trimethoxysilane, (tridecafluoro-1,1,2,2- Tetrahydrooctyl) triethoxysilane, and the like, more preferably, R ¹ is a linear fluorine atom-containing alkyl group having 8 to 20 carbon atoms and 10 or more fluorine atoms. (Tridecafluoro-1,1,2,2-tetrahydrooctyl) trimethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl) Triethoxysilane.

<Silane compound having a polymerizable group represented by formula (II)>
Formula ^{_{(II): CH 2 = CR}} 2 COO (CH 2) n SiY 3

In general formula (II), R ² represents a hydrogen atom or a methyl group.
In general formula (II), Y represents a methoxy group or an ethoxy group.
In general formula (II), n represents an integer of 1 or more and 20 or less, preferably an integer of 1 or more and 3 or less, more preferably 3.

  Specific examples of the polymerizable monomer represented by the general formula (II) are shown below, but are not limited to such specific compounds.

-Specific examples of polymerizable monomers represented by formula (II)-
Acryloxypropyltrimethoxysilane, acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane.

<Silane compound having a polymerizable group represented by formula (III)>
Formula _{(III): CH 2 = CH-} (A) m -SiZ 3

  In general formula (III), A represents a divalent aliphatic residue or aromatic residue.

  Examples of the aliphatic residue include a methylene group, 1,2-ethylene group, 1,3-propylene group, 1,6-hexamethylene group, and the like.

  Examples of the aromatic residue include m-phenylene group, p-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 1,8-naphthylene group, 2,7-naphthylene group and the like. Preferably, it is a p-phenylene group.

In the general formula (III), Z represents a methoxy group, an ethoxy group or a chlorine atom, and Z is preferably a methoxy group or an ethoxy group.
In general formula (III), m represents 0 or 1.

  Specific examples of the silane compound having a polymerizable group represented by the general formula (III) will be given below, but are not limited to such specific examples.

  Vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 4-butenyltriethoxysilane, 6-hexenyltriethoxysilane, 7-octenyltrimethoxysilane, p-styryl Triethoxysilane.

<Polymerizable monomer represented by general formula (IV)>
Formula ^{_{(IV): CH 2 = CR}} 3 COOR 4

In general formula (IV), R ³ represents a hydrogen atom or a methyl group.
In general formula (IV), R ⁴ represents an alkyl group or an aralkyl group.

The alkyl group represented by R ⁴ in the general formula (IV) may be any of a linear, branched, or cyclic alkyl group, preferably an alkyl group having 1 to 20 carbon atoms. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms.
Specific examples include a methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, 2-ethylhexyl group, octyl group, decyl group, dodecyl group, octadecyl group and the like.

The aralkyl group represented by R ⁴ in the general formula (IV) is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 10 carbon atoms.
Specific examples include a benzyl group, a phenethyl group, and a 3-phenylpropyl group.

The alkyl group and aralkyl group represented by R ⁴ in the general formula (IV) may further have a substituent. Examples of such a substituent include a hydroxyl group, an alkoxy group, an optionally substituted amino group, a quaternary ammonium group, a fluorine atom, a chlorine atom, and an organosiloxane residue.

When R ⁴ in the general formula (IV) is an alkyl group substituted with an amino group, the amino group is preferably a secondary or tertiary amino group substituted with an alkyl group.

  Specific examples of the polymerizable monomer represented by the general formula (IV) are shown below, but are not limited to such specific compounds.

-Specific examples of polymerizable monomers represented by formula (IV)-
Methyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n-dodecyl methacrylate, octadecyl methacrylate, 2-ethoxyethyl acrylate, 2 -Ethoxyethyl acrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 3,3,4,4,5,5,6,6,7 , 7,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylate, (3-methacryloxypropyl) polydimethylsiloxane.

<Polymerizable monomer represented by formula (V)>
Formula _{(V): CH 2 = CH} -R 5

In general formula (V), R ⁵ represents an aryl group or a heterocyclic group, and these substituents represented by R ⁵ may further have a substituent.

The aryl group represented by R ⁵ in the general formula (V) preferably has 6 to 20 carbon atoms, and specifically includes, for example, a phenyl group, an m-methylphenyl group, and a p-methylphenyl group. , P-chloromethylphenyl group, 1-naphthyl group, 2-naphthyl group, and the like.

Specific examples of the heterocyclic group represented by R ⁵ in the general formula (V) include 2-vinylpyridine, 4-vinylpyridine, N-vinylpyrrolidone and the like.

  Specific examples of the polymerizable monomer represented by the general formula (V) are given below, but the invention is not limited to such specific compounds.

  Styrene, 3-methylstyrene, 4-methylstyrene, 4-chloromethylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene.

<Organic pigment>
Organic pigment particles are used as the particles constituting the electrophoretic colored particles of the present invention.
Organic pigments include phthalocyanine pigments, quinacridone pigments, anthraquinone pigments, perylene pigments, isocindolinone pigments, azo pigments, polycondensed azo pigments, metal complex azo pigments, pyranthrone pigments, dioxazine pigments Organic pigments such as perylene pigments can be used.

Preferred organic pigments are phthalocyanine pigments, quinacridone pigments, anthraquinone pigments, perylene pigments, and azo pigments.
It is preferable to apply a phthalocyanine pigment as a cyan color, a quinacridone pigment as a magenta color, and an azo pigment as a yellow color, and a phthalocyanine pigment is more preferable from the viewpoint of efficient surface treatment.

  Specifically, the organic pigment particles are disazo yellow, condensed azo yellow, rhodamine 6G lake, anthraquinonyl red, perylene red, perylene maroon, quinacridone maroon, quinacridone scarred, quinacridone magenta, phthalocyanine green, phthalocyanine blue. , Rhodamine B lake, dioxazine violet, naphthol violet, and the like.

The average particle diameter of the organic pigment particles is preferably 10 nm or more and 1000 nm or less, more preferably 50 nm or more and 500 μm or less, and further preferably 100 nm or more and 300 μm or less.
The average particle diameter of the organic pigment refers to a value measured by a laser scattering method.

<Other ingredients>
In addition to the organic pigment, the electrophoretic colored particles can contain a compounding material.
As another compounding material, for example, a charge control agent is used for the purpose of adjusting the charge amount of the electrophoretic colored particles obtained. As the charge control agent, known materials used for toner materials for electrophotography can be used. For example, cetylpyridyl chloride, BONTRON P-51, BONTRON P-53, BONTRON E-84, BONTRON E-81 (above, Quaternary ammonium salts such as Orient Chemical Industries), salicylic acid metal complexes, phenol condensates, tetraphenyl compounds, metal oxide fine particles, and metal oxide fine particles surface-treated with various coupling agents.
In the present embodiment, electrophoretic colored particles having a controlled charge amount can be obtained without using a charge control agent, but may be used for the purpose of adjusting charge characteristics, for example.

<Surface treatment method>
The organic pigment (including other compounding materials as necessary) includes a silane compound represented by the general formula (I), a polymerizable group represented by the general formula (II) or the general formula (III). Surface treatment is carried out by the reaction of at least three compounds of the silane compound having and the polymerizable monomer represented by the general formula (IV) or the general formula (V).

  Hereinafter, the “silane compound represented by the general formula (I)” is referred to as “first surface treatment agent”, and “the silane having a polymerizable group represented by the general formula (II) or the general formula (III)”. “Compound” is referred to as “second group surface treatment agent”, and “polymerizable monomer represented by general formula (IV) or general formula (V)” is referred to as “third group surface treatment agent”. An explanation may be given.

The organic pigment is preferably surface-treated with at least a second group of surface treatment agents and then surface-treated with a third group of surface treatment agents.
In this surface treatment method, the second group of surface treatment agents functions as a so-called silane coupling agent, and the hydroxyl group and various polar groups present on the surface of the organic pigment and the -SiY ₃ portion (Y Methoxy group or ethoxy group), and as a result, a second group of surface treatment agents are introduced on the surface of the organic pigment. Since there is a polymerizable group in the residue part of the introduced second group of surface treatment agents, this part reacts with the polymerizable group of the third group of surface treatment agents, resulting in a polymer on the surface of the organic pigment. A compound chain is formed.

Further, the -SiZ ₃ portion of the first group of surface treatment agents reacts with hydroxyl groups and various polar groups present on the surface of the organic pigment, or in the second group of surface treatment agents introduced into the organic pigment particles. It reacts with Y (Y is a methoxy group or an ethoxy group).

Therefore, the surface treatment with the surface treatment agent preferably satisfies any of the following (1) to (3).
(1) After the surface treatment with the first group of surface treatment agents and the second group of surface treatment agents, the surface treatment is performed with the third group of surface treatment agents.
(2) After performing the surface treatment with the second group of surface treatment agents, the surface treatment is performed with the first group of surface treatment agents and the third group of surface treatment agents.
(3) After performing the surface treatment with the second group of surface treatment agents, the third group of surface treatments is performed, and then the first group of surface treatment agents is performed with the surface treatment.

  By such surface treatment, the organic pigment after the surface treatment is improved in dispersibility in a non-polar solvent, the dispersed particle size is reduced, high dispersion stability is exhibited, and chargeability can be freely controlled. It becomes.

  In the surface treatment of the organic pigment, the ratio of the surface treatment agent of the first group is preferably 1% by mass or more and 100% by mass or less, more preferably 10% by mass or more and 100% by mass or less with respect to the organic pigment. preferable.

In the surface treatment of the organic pigment, the ratio of the surface treatment agent of the second group is preferably 1% by mass or more and 100% by mass or less, and more preferably 10% by mass or more and 100% by mass or less with respect to the organic pigment. preferable.
In the surface treatment of the organic pigment, the ratio of the surface treatment agent of the third group is preferably 10% by mass or more and 1000% by mass or less, and more preferably 100% by mass or more and 1000% by mass or less with respect to the organic pigment. preferable.

  The average particle diameter of the electrophoretic colored particles after the surface treatment is preferably 50 μm or more and 1000 μm or less, and more preferably 100 μm or more and 500 μm or less.

(Electrophoretic colored particle dispersion)
The electrophoretic colored particle dispersion according to the second embodiment is obtained by dispersing the electrophoretic colored particles according to the first embodiment in a light-transmitting dispersion medium. Hereinafter, the electrophoretic colored particle dispersion may be referred to as “particle dispersion”.

The dispersion medium is preferably an insulating liquid.
Specific examples of the insulating liquid include tridecane, hexadecane, octadecane, kerosene, paraffin, isoparaffin, mineral oil, silicone oil, and mixtures thereof.

  Among the above dispersion media, silicone oil is most preferable from the viewpoints of safety, environmental load, and the like.

Specifically, silicone oils having hydrocarbon groups bonded to siloxane bonds (for example, dimethyl silicone oil, diethyl silicone oil, methyl ethyl silicone oil, methyl phenyl silicone oil, diphenyl silicone oil, etc.), modified silicone oil ( For example, fluorine-modified silicone oil, amine-modified silicone oil, carboxyl-modified silicone oil, epoxy-modified silicone oil, alcohol-modified silicone oil, and the like.
Among these silicone oils, dimethyl silicone oil is particularly desirable from the viewpoints of high safety, chemical stability, good long-term reliability, and high electrical resistivity.

  The viscosity of the silicone oil is desirably 0.1 mPa · s or more and 20 mPa · s or less, and more desirably 0.1 mPa · s or more and 2 mPa · s or less in an environment at a temperature of 20 ° C. By setting the viscosity within the above range, the moving speed of the electrophoretic colored particles, that is, the display speed can be improved. In addition, Tokyo Keiki B-8L type | mold viscosity meter is used for the measurement of this viscosity.

  In the electrophoretic colored particle dispersion liquid, the content of the electrophoretic colored particles according to the first embodiment is not particularly limited as long as it is a concentration at which a desired hue can be obtained. It is more preferably from 0.01% by mass to 10% by mass, and more preferably from 0.1% by mass to 5% by mass from the viewpoint of maintaining color developability and dispersion stability in the device.

<Other ingredients>
The electrophoretic colored particle dispersion may contain other compounding materials.
As other compounding materials, for example, an external additive may be used for the purpose of adhering to the surface of the electrophoretic colored particles obtained. The color of the external additive is preferably transparent so as not to affect the color of the electrophoretic colored particles.

  The external additive is preferably added after the surface treatment.

  As the external additive, inorganic particles such as metal oxides such as silicon oxide (silica), titanium oxide, and alumina are used. In order to adjust the charging property, fluidity, and environment dependency of the particles, they may be surface-treated with a coupling agent or silicone oil.

  Coupling agents include positively chargeable ones such as aminosilane coupling agents, aminotitanium coupling agents, nitrile coupling agents, and silanes that do not contain nitrogen atoms (consisting of atoms other than nitrogen). There are negatively charged ones such as coupling agents, titanium-based coupling agents, epoxy silane coupling agents, and acrylic silane coupling agents. Similarly, silicone oil includes positively chargeable ones such as amino-modified silicone oil, dimethyl silicone oil, alkyl-modified silicone oil, α-methylsulfone-modified silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, fluorine-modified. Examples include negatively chargeable ones such as silicone oil. These are selected according to the desired resistance of the external additive.

Among such external additives, well-known hydrophobic silica and hydrophobic titanium oxide are preferable. In particular, TiO (OH) ₂ described in JP-A-10-3177 and a silane compound such as a silane coupling agent are used. The titanium compound obtained by the reaction with is suitable. As the silane compound, any of chlorosilane, alkoxysilane, silazane, and a special silylating agent can be used. This titanium compound is produced by reacting TiO (OH) ₂ produced in a wet process with a silane compound or silicone oil and drying it. Since it does not pass through the firing step of several hundred degrees, a strong bond between Ti is not formed, there is no aggregation, and the particles are almost primary particles. Furthermore, since the silane compound or silicone oil reacts directly with TiO (OH) ₂ , the treatment amount of the silane compound or silicone oil can be increased, and the charging characteristics can be controlled by adjusting the treatment amount of the silane compound. And the chargeability imparted is also significantly improved over that of conventional titanium oxide.

  The primary particles of the external additive are generally 5 nm to 100 nm, preferably 10 nm to 50 nm, but are not limited thereto.

  The mixing ratio of the external additive and the electrophoretic colored particles is appropriately adjusted based on the balance between the particle diameter of the electrophoretic colored particles and the particle diameter of the external additive. If the amount of the external additive added is too large, a part of the external additive is liberated from the surface of the electrophoretic colored particles and this adheres to the surface of the other electrophoretic colored particles, thereby obtaining desired charging characteristics. Disappear. In general, the amount of the external additive is 0.01 parts by mass or more and 3 parts by mass or less, more preferably 0.05 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of the electrophoretic colored particles. .

  If necessary, an acid, an alkali, a salt, a dispersion stabilizer, a stabilizer for the purpose of preventing oxidation or ultraviolet absorption, an antibacterial agent, an antiseptic, and the like may be added to the obtained particle dispersion.

  For the obtained particle dispersion, as a charge control agent, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, a fluorosurfactant, a silicone surfactant, a metal Soap, alkyl phosphate esters, succinimides and the like may be added.

Charge control agents include ionic or nonionic surfactants, block or graft copolymers composed of a lipophilic part and a hydrophilic part, polymers such as cyclic, star-like or dendritic polymers (dendrimers) Examples thereof include compounds having a chain skeleton, metal complexes of salicylic acid, metal complexes of catechol, metal-containing bisazo dyes, tetraphenylborate derivatives, and the like.
More specific examples of the ionic and nonionic surfactants are as follows. Nonionic activators include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, And fatty acid alkylolamide. Examples of the anionic surfactant include alkylbenzene sulfonate, alkylphenyl sulfonate, alkyl naphthalene sulfonate, higher fatty acid salt, sulfate of higher fatty acid ester, sulfonic acid of higher fatty acid ester, and the like. Examples of the cationic surfactant include primary to tertiary amine salts and quaternary ammonium salts. These charge control agents are preferably 0.01% by weight or more and 20% by weight or less, and particularly preferably 0.05% by weight or more and 10% by weight or less based on the solid content of the electrophoretic colored particles.

  Further, for example, the obtained particle dispersion may be diluted with a solvent (a solvent containing an emulsion as necessary) or an additive (for example, an emulsifier) may be added as necessary.

  The electrophoretic colored particle dispersion according to this embodiment is used for an electrophoretic image display medium, a liquid toner of a liquid developing electrophotographic system, and the like. In particular, since the obtained particle dispersion liquid is a highly safe, chemically stable and long-term reliable silicone oil, it can be used as it is without being replaced by another dispersion medium. In addition, the dispersion stability of the electrophoretic colored particles can be applied to each field while maintaining good dispersion stability.

(Image display medium and image display device)
The image display medium according to the third embodiment includes a pair of translucent substrates, at least one of which is translucent, and the electrophoretic colored particle dispersion according to the second embodiment is interposed between a pair of substrates disposed to face each other. Liquid is being injected.
The image display device according to the fourth embodiment includes the image display medium according to the third embodiment and voltage applying means for applying a voltage between a pair of substrates in the image display medium.

  FIG. 1 is a schematic configuration diagram illustrating an example of an image display device according to a fourth embodiment. The image display device 10 according to the fourth embodiment uses the electrophoretic colored particle dispersion according to the second embodiment as a particle dispersion including the dispersion medium 50 and the particle group 34 of the image display medium 12 according to the third embodiment. It is a form to apply. For this reason, the image display apparatus according to the fourth embodiment (the image display medium according to the third embodiment) has excellent display properties and reliability.

  As shown in FIG. 1, the image display device 10 according to the fourth embodiment includes an image display medium 12, a voltage application unit 16, and a control unit 18. The control unit 18 is connected to the voltage application unit 16 so as to be able to exchange signals.

  The control unit 18 includes a CPU (Central Processing Unit) that controls the operation of the entire apparatus, a RAM (Random Access Memory) that temporarily stores various data, and a program indicated by a control program and a processing routine for controlling the entire apparatus. The microcomputer includes a ROM (Read Only Memory) in which various programs are stored in advance.

  The image display medium 12 corresponds to the image display medium of the present invention, the image display apparatus 10 corresponds to the image display apparatus of the present invention, and the voltage application unit 16 corresponds to the voltage application means of the image display apparatus of the present invention. To do.

  The voltage application unit 16 is electrically connected to the front electrode 40 and the back electrode 46. In this embodiment, the case where both the front electrode 40 and the back electrode 46 are electrically connected to the voltage application unit 16 will be described. However, one of the front electrode 40 and the back electrode 46 is grounded. The other may be connected to the voltage application unit 16.

  The voltage application unit 16 is a voltage application device for applying a voltage to the front electrode 40 and the back electrode 46, and applies a voltage according to the control of the control unit 18 between the front electrode 40 and the back electrode 46.

  Hereinafter, the image display medium 12 will be described in detail.

  As shown in FIG. 1, the image display medium 12 includes a display substrate 20 serving as an image display surface, a rear substrate 22 that faces the display substrate 20 with a gap, and holds these substrates at a predetermined interval. And the back substrate 22 are configured to include a gap member 24 that partitions the plurality of cells, and a particle group 34 enclosed in each cell.

  The cell indicates a region surrounded by the display substrate 20, the back substrate 22, and the gap member 24. A dispersion medium 50 is enclosed in this cell. Particle groups 34 (details will be described later) are dispersed in the dispersion medium 50 and move between the display substrate 20 and the back substrate 22 in accordance with the electric field strength formed in the cell.

  The gap member 24 is provided so as to correspond to each pixel when an image is displayed on the image display medium 12, and cells are formed so as to correspond to each pixel, so that the image display medium 12 is provided for each pixel. You may comprise so that a color display is attained.

  A plurality of types of particle groups 34 having different colors are dispersed in the dispersion medium 50 of the image display medium 12. The plurality of types of particle groups 34 are particles that are electrophoresed between the substrates, and the absolute value of the voltage required to move in accordance with the electric field is different for each color particle group.

  As the particles of the plurality of types of particle groups 34 having different absolute values of voltages necessary for movement according to the electric field, for example, in the electrophoretic colored particles according to the first embodiment, for example, chargeability It can be obtained by mixing electrophoretic colored particles having different charge amounts, for example, by changing the type and addition amount of the control agent.

  Here, the content (% by mass) of the particle group 34 with respect to the total mass in the cell is not particularly limited as long as a desired hue can be obtained, and the content is adjusted by the thickness of the cell. This is effective as the image display medium 12. That is, in order to obtain a desired hue, the content may be small when the cell is thick, and the content may be increased when the cell is thin. Generally, it is 0.01 mass% or more and 50 mass% or less.

  Hereinafter, each component of the image display medium 12 will be described.

  The display substrate 20 has a configuration in which a surface electrode 40 and a surface layer 42 are sequentially laminated on a support substrate 38. The back substrate 22 has a structure in which a back electrode 46 and a surface layer 48 are sequentially laminated on a support substrate 44.

  Examples of the support substrate 38 and the support substrate 44 include glass and plastics such as polycarbonate resin, acrylic resin, polyimide resin, polyester resin, epoxy resin, and polyether sulfone resin.

  For the back electrode 46 and the surface electrode 40, oxides such as indium, tin, cadmium and antimon, composite oxides such as ITO, metals such as gold, silver, copper and nickel, organic conductive materials such as polypyrrole and polythiophene, etc. May be used. These can be used as a single layer film, a mixed film or a composite film, and are formed by vapor deposition, sputtering, coating, or the like. Moreover, the thickness is normally 100 angstroms or more and 2000 angstroms or less according to the vapor deposition method and the sputtering method. The back electrode 46 and the front electrode 40 are formed in a desired pattern, for example, a matrix shape or a stripe shape that enables passive matrix driving, by a conventionally known means such as etching of a conventional liquid crystal display element or a printed circuit board.

  Further, the surface electrode 40 may be embedded in the support substrate 38. Similarly, the back electrode 46 may be embedded in the support substrate 44. In this case, since the material of the support substrate 38 and the support substrate 44 may affect the charging characteristics and fluidity of each electrophoretic colored particle of the particle group 34, the composition of each electrophoretic colored particle of the particle group 34. It selects suitably according to etc.

  The back electrode 46 and the front electrode 40 may be separated from the display substrate 20 and the back substrate 22 and disposed outside the image display medium 12. In this case, since the image display medium 12 is sandwiched between the back electrode 46 and the surface electrode 40, the inter-electrode distance between the back electrode 46 and the surface electrode 40 increases, and the electric field strength decreases. In order to obtain a desired electric field strength, it is necessary to devise measures such as reducing the thickness of the support substrate 38 and the support substrate 44 of the image display medium 12 and reducing the distance between the support substrate 38 and the support substrate 44.

  In the above description, the case where both the display substrate 20 and the back substrate 22 are provided with the electrodes (the front electrode 40 and the back electrode 46) has been described.

  In order to enable active matrix driving, the support substrate 38 and the support substrate 44 may include a TFT (thin film transistor) for each pixel. The TFTs are preferably formed not on the display substrate but on the back substrate 22 because wiring can be easily laminated and components can be easily mounted.

  In addition, when the image display medium 12 is a simple matrix drive, the configuration of an image display device 10 including the image display medium 12 to be described later can be simplified. When the active matrix drive using TFTs is used, a simple matrix is used. Display speed is faster than driving.

  When the surface electrode 40 and the back electrode 46 are formed on the support substrate 38 and the support substrate 44, respectively, the electrodes between the electrodes that cause breakage of the surface electrode 40 and the back electrode 46 and adhesion of each particle of the particle group 34 are obtained. In order to prevent the occurrence of leakage, it is preferable to form a surface layer 42 and / or a surface layer 48 as a dielectric film on each of the surface electrode 40 and the back electrode 46 as necessary.

  As the material for forming the surface layer 42 and / or the surface layer 48, polycarbonate, polyester, polystyrene, polyimide, epoxy, polyisocyanate, polyamide, polyvinyl alcohol, polybutadiene, polymethyl methacrylate, copolymer nylon, ultraviolet curable acrylic resin Fluorine resin or the like may be used.

  In addition to the insulating material described above, an insulating material containing a charge transport material may be used. Inclusion of a charge transport material improves the chargeability of the electrophoretic colored particles by injecting the charge into the electrophoretic colored particles, and the electrophoretic properties when the charge amount of the electrophoretic colored particles becomes extremely large Effects such as leakage of the charge of the colored particles and stabilization of the charge amount of the electrophoretic colored particles can be obtained.

Examples of the charge transport material include a hydrazone compound, a stilbene compound, a pyrazoline compound, and an arylamine compound that are hole transport materials. Further, a fluorenone compound, a diphenoquinone derivative, a pyran compound, zinc oxide, or the like, which is an electron transport material, may be used. Further, a self-supporting resin having a charge transporting property may be used.
Specific examples thereof include polyvinyl carbazole and polycarbonate obtained by polymerization of a specific dihydroxyarylamine and bischloroformate described in US Pat. No. 4,806,443. Since the dielectric film may affect the charging characteristics and fluidity of the electrophoretic colored particles, it is appropriately selected according to the composition of the electrophoretic colored particles. Since the display substrate which is one of the substrates needs to transmit light, it is preferable to use a transparent one of the above materials.

  The gap member 24 for holding the gap between the display substrate 20 and the back substrate 22 is formed so as not to impair the transparency of the display substrate 20, and is made of a thermoplastic resin, a thermosetting resin, an electron beam curable resin, a photocuring agent. It is made of resin, rubber, metal or the like.

  The gap member 24 includes a cell type and a particle type. An example of the cellular type is a net. Since the net is easy to obtain, inexpensive, and has a relatively uniform thickness, it is useful when manufacturing an inexpensive image display medium 12. The net is not suitable for displaying a fine image, and is preferably used for a large image display apparatus that does not require high resolution. Other cellular spacers include a sheet with holes in a matrix by etching, laser processing, etc. In this sheet, the thickness, hole shape, hole size, etc. are compared to the net. Easy to adjust. For this reason, the sheet is used for an image display medium for displaying a fine image, and is effective in further improving the contrast.

The gap member 24 may be integrated with any one of the display substrate 20 and the back substrate 22, and the support substrate 38 or the support substrate 44 is etched, laser processed, or using a prefabricated mold, The support substrate 38 or the support substrate 44 having the cell pattern of any size and the gap member 24 are produced by printing or the like.
In this case, the gap member 24 can be fabricated on either the display substrate 20 side, the back substrate 22 side, or both.

  The gap member 24 may be colored or colorless, but is preferably colorless and transparent so as not to adversely affect the display image displayed on the image display medium 12, and in this case, for example, polystyrene, polyester, acrylic, etc. A transparent resin or the like may be used.

  The particulate gap member 24 is preferably transparent, and glass particles are also used in addition to transparent resin particles such as polystyrene, polyester or acrylic.

  In the image display medium 12, insulating particles 36 are enclosed in each cell. The insulating particles 36 are different in color and insulative particles from the particle group 34 enclosed in the same cell, and have a gap through which each electrophoretic colored particle of the particle group 34 can pass. The rear substrate 22 and the display substrate 20 are arranged along a direction substantially orthogonal to the opposing direction. Further, between the insulating particles 36 and the back substrate 22 and between the display substrate 20 and the insulating particles 36, each electrophoretic colored particle of the particle group 34 included in the same cell is connected to the back substrate 22. The space | interval of the grade which can be laminated | stacked in the direction facing the display substrate 20 is provided.

  That is, the electrophoretic colored particles of the particle group 34 are moved from the back substrate 22 side to the display substrate 20 side or from the display substrate 20 side to the back substrate 22 side through the gaps of the insulating particles 36. As the color of the insulating particles 36, for example, white or black is preferably selected so as to be a background color.

  Insulating particles 36 include spherical particles of benzoguanamine / formaldehyde condensate, spherical particles of benzoguanamine / melamine / formaldehyde condensate, spherical particles of melamine / formaldehyde condensate, (Nippon Shokubai Co., Ltd. poster), titanium oxide-containing crosslinking Spherical particles of polymethyl methacrylate (MBX-white manufactured by Sekisui Plastics Co., Ltd.), spherical particles of crosslinked polymethyl methacrylate (Kemisnow MX manufactured by Soken Chemical Co., Ltd.), particles of polytetrafluoroethylene (Lublon L manufactured by Daikin Industries, Ltd.) , Shamrock Technologies Inc. SST-2), fluorocarbon particles (CF-100 manufactured by Nippon Carbon, CFGL, CFGM manufactured by Daikin Industries), silicone resin particles (Tospearl manufactured by Toshiba Silicone Co., Ltd.), polyester containing titanium oxide Particles (Nippon Paint Bilucia PL1000 White T), acid Titanium-containing polyester acrylic particles (manufactured by NOF Corporation Konagi No181000 white), silica spherical particles (Ube-Nitto Kasei Ltd. Haipureshika), and the like. Without limitation to the above, a white pigment such as titanium oxide may be mixed and dispersed in a resin, and then pulverized and classified to a desired particle size.

  Since these insulating particles 36 are provided between the display substrate 20 and the back substrate 22 as described above, the insulating particles 36 are 1/50 of the length of the cell in the facing direction between the display substrate 20 and the back substrate 22. The volume average primary particle size is 1/5 or less, and the content is preferably 1% by volume or more and 50% by volume or less with respect to the volume of the cell.

  The size of the cell in the image display medium 12 is closely related to the resolution of the image display medium 12, and the smaller the cell, the higher the resolution display medium can be made. Usually, the size is about 10 μm to 1 mm. is there.

  In order to fix the display substrate 20 and the back substrate 22, fixing means such as a combination of bolts and nuts, a clamp, a clip, and a substrate fixing frame can be used. Also, fixing means such as an adhesive, heat melting, and ultrasonic bonding can be used.

  The image display medium 12 includes a bulletin board that can store and rewrite images, a circulation version, an electronic blackboard, an advertisement, a signboard, a flashing sign, an electronic paper, an electronic newspaper, an electronic book, and a document sheet that can be shared with a copier / printer. Can be used for etc.

  In the image display medium 12, different colors are displayed by changing the applied voltage (V) applied between the display substrate 20 and the back substrate 22.

  In the image display medium 12, by moving according to the electric field formed between the display substrate 20 and the back substrate 22, each cell corresponding to each pixel of the image display medium 12 corresponds to each pixel of the image data. Colors can be displayed.

  Here, in the image display medium 12, as described above, as shown in FIG. 2, the electrophoretic colored particles move in accordance with the electric field when electrophoresis is performed between the substrates for each particle group 34 having different color developability. The absolute value of the voltage required to do so is different. The voltage ranges necessary for moving the electrophoretic colored particles are different for each particle group 34 having different color developability. In other words, the absolute value of the voltage has the voltage range, and the voltage range is different for each color of the particle group 34.

  In this embodiment, as the particle group 34 enclosed in the same cell of the image display medium 12, as shown in FIG. 1, a magenta magenta particle group 34M, a cyan cyan particle group 34C, In the following description, the three-color particle group 34 including the yellow-colored yellow particle group 34Y is enclosed.

  The magenta magenta magenta particle group 34M, the cyan cyan particle group 34C, and the yellow color yellow particle group 34Y are magenta magenta as absolute values of voltages when the three color particle groups start moving. In the following description, it is assumed that the particle group 34M is | Vtm |, the cyan cyan particle group 34C is | Vtc |, and the yellow yellow particle group 34Y is | Vty |. In addition, the absolute value of the maximum voltage for moving almost all of the three color particle groups including the magenta particle group 34M, the cyan cyan particle group 34C, and the yellow yellow particle group 34Y of each color particle group 34. In the following description, it is assumed that the magenta magenta particle group 34M is | Vdm |, the cyan cyan particle group 34C is | Vdc |, and the yellow yellow particle group 34Y is | Vdy |.

  The absolute values of Vtc, −Vtc, Vdc, −Vdc, Vtm, −Vtm, Vdm, −Vdm, Vty, −Vty, Vdy, and −Vdy described below are | Vtc | <| Vdc | <| Description will be made assuming that the relationship is Vtm | <| Vdm | <| Vty | <| Vdy |.

  Specifically, as shown in FIG. 2, for example, all the particle groups 34 are charged with the same polarity, and the absolute value of the voltage range necessary to move the cyan particle group 34C | Vtc ≦ Vc ≦ Vdc | (Vtc Absolute value of a value between Vtm and Vdm), absolute value of voltage range necessary to move the magenta particle group 34M | Vtm ≦ Vm ≦ Vdm | (absolute value of a value between Vtm and Vdm), and yellow particles The absolute value of the voltage range necessary to move the group 34M | Vty ≦ Vy ≦ Vdy | (the absolute value of the value between Vty and Vdy) is set to be large without overlapping in this order. Yes.

  Further, in order to independently drive the particle groups 34 of the respective colors, the absolute value | Vdc | of the maximum voltage for moving almost all the cyan particle groups 34M is the absolute value of the voltage range necessary for moving the magenta particle group 34M. Value | Vtm ≦ Vm ≦ Vdm | (the absolute value of the value between Vtm and Vdm) and the absolute value of the voltage range necessary to move the yellow particle group 34M | Vty ≦ Vy ≦ Vdy | (Vty to Vdy The absolute value of the value between) is set smaller. Further, the absolute value | Vdm | of the maximum voltage for moving almost all of the magenta particle group 34M is equal to the absolute value | Vty ≦ Vy ≦ Vdy | (Vty to Vdy) of the voltage range necessary for moving the yellow particle group 34M. Is set to be smaller than the absolute value).

  That is, in this embodiment, the voltage groups necessary for moving the color particle groups 34 are set so as not to overlap, so that the particle groups 34 for each color are independently driven.

The “voltage range necessary for moving the particle group 34” means the voltage necessary for the particle to start moving and the change in display density even if the voltage and voltage application time are further increased from the start of movement. It shows the voltage range until it disappears and the display density is saturated.
The “maximum voltage required to move almost all the particle groups 34” means that even if the voltage and the voltage application time are further increased from the start of the movement, the display density does not change and the display density is saturated. Indicates voltage.
Further, “almost all” means that there is a variation in the characteristics of the particle groups 34 of the respective colors, so that some of the characteristics of the particle groups 34 are different to the extent that they do not contribute to the display characteristics. That is, even if the voltage and the voltage application time are further increased from the start of the movement described above, the display density does not change and the display density is saturated.
“Display density” is the color density on the display surface side measured with the optical density (Optical Density = 0D) reflection densitometer X-rite's reflection densitometer. Apply a voltage and gradually change this voltage in the direction of increasing the measured concentration (increase or decrease the applied voltage) to saturate the concentration change per unit voltage, and in that state, adjust the voltage and voltage application time. Even when the density is increased, the density does not change, and the density is shown when the density is saturated.

  In the image display medium 12 according to the present embodiment, a voltage is applied from 0 V between the front substrate 20 and the rear substrate 22 to gradually increase the voltage value of the applied voltage, and the voltage is applied between the substrates. When the voltage exceeds + Vtc, the display density starts to change due to the movement of the cyan particle group 34C in the image display medium 12. Further, when the voltage value is increased and the voltage applied between the substrates becomes + Vdc, the change in display density due to the movement of the cyan particle group 34 in the image display medium 12 stops.

  When the voltage value is further increased and the voltage applied between the front substrate 20 and the rear substrate 22 exceeds + Vtm, a change in display density due to the movement of the magenta particle group 34M starts to appear in the image display medium 12. When the voltage value is further increased and the voltage applied between the front substrate 20 and the rear substrate 22 becomes + Vdm, the change in display density due to the movement of the magenta particle group 34M in the image display medium 12 stops.

  Further, when the voltage value is increased and the voltage applied between the substrates exceeds + Vty, a change in display density due to the movement of the yellow particle group 34Y starts to appear in the image display medium 12. When the voltage value is further increased and the voltage applied between the substrates becomes + Vdy, the change in display density due to the movement of the yellow particle group 34Y in the image display medium 12 stops.

  On the other hand, if the negative electrode voltage is applied from 0 V to the substrate between the front substrate 20 and the rear substrate 22 to gradually increase the absolute value of the voltage, and the absolute value of the voltage −Vtc applied between the substrates is exceeded. In the image display medium 12, the display density starts to change due to the movement of the yellow particle group 34C between the substrates. Further, when the absolute value of the voltage value is increased and the voltage applied between the front substrate 20 and the rear substrate 22 becomes −Vdc or more, the change in display density due to the movement of the cyan particle group 34 </ b> C in the image display medium 12. Stops.

  When the negative voltage is further applied by increasing the absolute value of the voltage value, and the voltage applied between the front substrate 20 and the rear substrate 22 exceeds the absolute value of −Vtm, magenta in the image display medium 12. A change in display density due to the movement of the particle group 34M begins to appear. When the absolute value of the voltage value is further increased so that the voltage applied between the front substrate 20 and the rear substrate 22 becomes −Vdm, the display density changes due to the movement of the magenta particle group 34M in the image display medium 12. Stop.

  When the absolute value of the voltage value is further increased to apply a negative voltage, and the voltage applied between the front substrate 20 and the rear substrate 22 exceeds the absolute value of -Vty, yellow is displayed on the image display medium 12. Changes in the display density begin to appear due to the movement of the particle group 34Y. When the absolute value of the voltage value is further increased so that the voltage applied between the substrates becomes −Vdy, the change in display density due to the movement of the yellow particle group 34C in the image display medium 12 stops.

  In other words, in the present embodiment, as shown in FIG. 2, the voltage applied between the substrates is within the range of −Vtc to Vtc (voltage range | Vtc | or less). 22 is applied between the substrate and the particle group 34 (the cyan particle group 34C, the magenta particle group 34M, and the yellow particle group 34Y) to the extent that the display density of the image display medium 12 changes. It can be said that no movement has occurred. When a voltage higher than the absolute value of the voltage + Vtc and the voltage −Vtc is applied between the substrates, a change occurs in the display density of the image display medium 12 for the cyan particle group 34C among the three color particle groups 34. The display density starts to change for a certain degree of particle movement, and when a voltage equal to or higher than the absolute value | Vdc | of the voltage −Vdc and the voltage Vdc is applied, the display density per unit voltage does not change.

  Further, when a voltage is applied between the front substrate 20 and the rear substrate 22 such that the voltage applied between the substrates is in the range of −Vtm to Vtm (voltage range | Vtm | or less), It can be said that there is no movement of the particles of the magenta particle group 34M and the yellow particle group 34Y to the extent that the display density of the image display medium 12 changes. When a voltage higher than the absolute value of the voltage + Vtm and the voltage −Vtm is applied between the substrates, the magenta particle group 34M and the magenta particle group 34M in the yellow particle group 34Y have the display density of the image display medium 12. The display density per unit voltage starts to change to such an extent that the particles move to the extent that the change occurs, and when a voltage equal to or higher than the absolute value | Vdm | of the voltage −Vdm and the voltage Vdm is applied, the change in the display density changes. No longer occurs.

  Further, when a voltage is applied between the front substrate 20 and the rear substrate 22 so that the voltage applied between the substrates is within the range of −Vty to Vty (voltage range | Vty | or less), the image It can be said that there is no movement of the particles of the yellow particle group 34Y to the extent that the display density of the display medium 12 changes. When a voltage greater than the absolute value of the voltage + Vty and the voltage -Vty is applied between the substrates, the yellow particle group 34Y starts to move particles to the extent that the display density of the image display medium 12 changes. When the display density starts to change and a voltage equal to or higher than the absolute value | Vdy | of the voltage −Vdy and the voltage Vdy is applied, the display density does not change.

  Next, with reference to FIG. 3, the mechanism of particle movement when an image is displayed on the image display medium 12 of the present invention will be described.

  For example, the image display medium 12 will be described assuming that the yellow particle group 34Y, the magenta particle group 34M, and the cyan particle group 34C described with reference to FIG.

  In the following, the voltage applied between the substrates that is larger than the absolute value of the voltage necessary for the particles constituting the yellow particle group 34Y to start moving and less than or equal to the maximum voltage of the yellow particle group 34Y is referred to as “large voltage”. The voltage applied between the substrates that is larger than the absolute value of the voltage necessary for the particles constituting the magenta particle group 34M to start moving and is equal to or less than the maximum voltage of the magenta particle group 34M is referred to as “medium voltage”. The voltage applied between the substrates that is larger than the absolute value of the voltage required for the particles constituting the cyan particle group 34C to start moving and below the maximum voltage of the cyan particle group 34C is referred to as a “small voltage”. To do.

  Further, when a higher voltage is applied between the substrates on the display substrate 20 side than the back substrate 22 side, the respective voltages are referred to as “+ large voltage”, “+ medium voltage”, and “+ small voltage”, respectively. . Further, when a higher voltage is applied to the back substrate 22 side than the display substrate 20 side, the respective voltages are referred to as “−large voltage”, “−medium voltage”, and “−small voltage”, respectively. I will explain.

  As shown in FIG. 3A, if all of the magenta particle group 34M, the cyan particle group 34C, and the yellow particle group 34Y as all the particle groups are positioned on the back substrate 22 side in the initial state, When “+ large voltage” is applied between the display substrate 20 and the back substrate 22 from the state, the magenta particle group 34M, the cyan particle group 34C, and the yellow particle group 34Y are displayed on the display substrate 20 side as all particle groups. Move to. In this state, even if the voltage application is canceled, each particle group does not move while adhering to the display substrate 20 side, and subtractive color mixing (magenta) by the magenta particle group 34M, the cyan particle group 34C, and the yellow particle group 34Y. In this case, the black color is displayed by the subtractive color mixture of cyan and yellow. (See FIG. 3B).

  Next, when “−medium voltage” is applied between the display substrate 20 and the back substrate 22 from the state of FIG. 3B, the magenta particle group 34 </ b> M among the particle groups 34 of all colors and cyan The particle group 34 </ b> C moves to the back substrate 22 side. Therefore, since only the yellow particle group 34Y is attached to the display substrate 20 side, yellow display is performed (see FIG. 3C).

  Further, when “+ small voltage” is applied between the display substrate 20 and the back substrate 22 from the state of FIG. 3C, the magenta particle group 34M and the cyan particle group 34C moved to the back substrate 22 side. The cyan particle group 34C moves to the display substrate 20 side. For this reason, the yellow particle group 34Y and the cyan particle group 34C are attached to the display substrate 20 side, and green is displayed by the subtractive color mixture of yellow and cyan (see FIG. 3D).

  3B, when a “−small voltage” is applied between the display substrate 20 and the back substrate 22, the cyan particle groups 34C of all the particle groups 34 move to the back substrate 22 side. To do. For this reason, since the yellow particle group 34Y and the magenta particle group 34M are attached to the display substrate 20 side, red display is performed by additive mixing of cyan and magenta (see FIG. 3I).

  On the other hand, when “+ medium voltage” is applied between the display substrate 20 and the back substrate 22 from the initial state shown in FIG. 3A, all the particle groups 34 (magenta particle group 34M, cyan particle group 34C) are applied. , And the yellow particle group 34Y), the magenta particle group 34M and the cyan particle group 34C move to the display substrate 20 side. For this reason, the magenta particle group 34M and the cyan particle group 34C adhere to the display substrate 20 side, so that blue is displayed by the subtractive color mixing of magenta and cyan (see FIG. 3E).

When a “−small voltage” is applied between the display substrate 20 and the back substrate 22 from the state of FIG. 3E, the magenta particle group 34M and the cyan particle group 34C adhering to the display substrate 20 side. Among them, the cyan particle group 34C moves to the back substrate 22 side.
Therefore, only the magenta particle group 34M is attached to the display substrate 20 side, so that a magenta color is displayed (see FIG. 3F).

When a “−large voltage” is applied between the display substrate 20 and the back substrate 22 from the state of FIG. 3F, the magenta particle group 34M adhering to the display substrate 20 side is moved to the back substrate 22 side. Moving.
For this reason, since nothing is adhered to the display substrate 20 side, white is displayed as the color of the insulating particles 36 (see FIG. 3G).

  When a “+ small voltage” is applied between the display substrate 20 and the back substrate 22 from the initial state shown in FIG. 3A, all the particle groups 34 (magenta particle group 34M, cyan particle group) are applied. 34C and the yellow particle group 34Y), the cyan particle group 34C moves to the display substrate 20 side. For this reason, the cyan particle group 34C adheres to the display substrate 20 side, so that a cyan color is displayed (see FIG. 3H).

Further, when a “−large voltage” is applied between the display substrate 20 and the back substrate 22 from the state shown in FIG. 3I, all the particle groups 34 appear on the back surface as shown in FIG. Moving to the substrate 22 side, white display is performed.
Similarly, when a “−large voltage” is applied between the display substrate 20 and the back substrate 22 from the state shown in FIG. 3D, all the particle groups 34 are formed as shown in FIG. Moving to the back substrate 22 side, white display is performed.

  Thus, in the present embodiment, by applying a voltage according to each particle group 34 between the substrates, the desired particles are selectively moved according to the electric field due to the voltage, so that a color other than the desired color can be obtained. The particles can be prevented from moving in the dispersion medium 50, color mixing with a color other than the desired color is suppressed, and color display is performed while image quality deterioration of the image display medium 12 is suppressed. In addition, if the absolute value of the voltage required for each particle group 34 to move according to the electric field is different from each other, even if the voltage ranges necessary for moving according to the electric field overlap with each other, clear color display is possible. However, when the voltage ranges are different from each other, color mixing is further suppressed and color display is realized.

  Further, by dispersing the three color particle groups 34 of cyan, magenta, and yellow in the dispersion medium 50, cyan, magenta, yellow, blue, red, green, and black can be displayed, and white insulation can be displayed. The white particles can be displayed by the active particles 36, and a desired color display can be performed.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited by such an Example.

[Example 1]
(Production of electrophoretic colored particle dispersion (cyan))
In a 50 ml sample bottle, 40 g of glass beads (diameter 1 mm), phthalocyanine blue (Pigment Blue 15: 3), 1.0 g, 20 ml of toluene, 0.5 g of 3-methacryloxypropyltrimethoxysilane, and (Tridecafluoro- 0.5 g of 1,1,2,2-tetrahydrooctyl) triethoxysilane was added and shake-dispersed for 1 hour using a paint shaker (manufactured by Toyo Seiki).

The obtained pigment paste was diluted with 100 ml of dimethyl silicone oil (trade name: KF96L-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.), and a 200 ml four-necked flask equipped with a thermometer, stirring blade, nitrogen introducing tube, and reflux tube was attached. Then, 5 g of 2-ethylhexyl methacrylate and 0.02 g of 2,2′-azobis (isobutyronitrile) were added, and stirring was continued at 80 ° C. for 5 hours.
After standing to cool, the solvent was removed by centrifugal sedimentation, washed repeatedly with dimethyl silicone oil (trade name: KF96L-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.), and then dimethyl silicone oil (trade name: KF96L-2cs, Shin-Etsu Chemical Co., Ltd.). 100 ml) was added, and dispersion treatment was carried out for 10 minutes in an ultrasonic bath to obtain an electrophoretic colored particle dispersion.

  When the particle size distribution of the electrophoretic colored particles in the electrophoretic colored particle dispersion was measured by a laser scattering method (LA-300, manufactured by Horiba, Ltd.), the average particle diameter (median diameter) was 0.3 μm. .

The electrophoretic colored particle dispersion is placed in a cell for optical measurement (made of polystyrene, 12.5 × 12.5 × 45 mm), and two copper electrodes are opposed to each other with a glass plate having a thickness of 1 mm as a spacer. Installed. When a DC voltage of 1000 V was applied between both electrodes, the electrophoretic colored particles moved to the negative electrode side.
The moving speed of the electrophoretic colored particles was measured by moving image analysis using a microscope (VHX-100 manufactured by Keyence Corporation), and found to be 1.0 mm / s.

[Example 2]
(Production of electrophoretic colored particle dispersion (magenta))
In a 20 ml sample bottle, 12 g of glass beads (diameter 1 mm), 1.0 g of quinacridone magenta (Pigment Red 122), 5 ml of toluene, 0.5 g of 3-methacryloxypropyltrimethoxysilane, and (tridecafluoro-1,1 , 2,2-tetrahydrooctyl) triethoxysilane (0.5 g) was added and shake-dispersed for 1 hour using a paint shaker (manufactured by Toyo Seiki).

  The obtained pigment paste was diluted with 100 ml of dimethyl silicone oil (trade name: KF96L-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.), and a 200 ml four-necked flask equipped with a thermometer, stirring blade, nitrogen introducing tube, and reflux tube was attached. 4.8 g of 2-ethylhexyl methacrylate, 0.2 g of 2- (dimethylamino) ethyl methacrylate, and 0.02 g of 2,2′-azobis (isobutyronitrile) were added, and the mixture was stirred at 80 ° C. under a nitrogen stream. Stirring was continued for an hour.

  After standing to cool, the solvent was removed by centrifugal sedimentation, washed with dimethyl silicone oil (trade name: KF96L-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.), and then dimethyl silicone oil (trade name: KF96L-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.). 20 ml was added, and the dispersion treatment was performed for 10 minutes in an ultrasonic bath to obtain an electrophoretic colored particle dispersion.

  When the particle size distribution of the electrophoretic colored particles in the electrophoretic colored particle dispersion was measured by a laser scattering method, the average particle diameter (median diameter) was 0.6 μm.

When a DC voltage of 1000 V was applied to the electrophoretic colored particle dispersion liquid between the electrodes in the optical measurement cell in the same manner as in Example 1, the particles moved to the negative electrode side.
It was 5.0 mm / s when the moving speed of this particle | grain was measured by the moving image analysis by a microscope (VHX-100 by Keyence Corporation).

[Example 3]
In a 50 ml sample bottle, 40 g of glass beads (diameter 1 mm), 1.0 g of phthalocyanine blue (Pigment Blue 15: 3), 20 ml of toluene, 0.5 g of 3-methacryloxypropyltrimethoxysilane, and (Tridecafluoro-1 , 1,2,2-tetrahydrooctyl) triethoxysilane (0.5 g) was added and shake-dispersed for 1 hour using a paint shaker (manufactured by Toyo Seiki).

  The obtained pigment paste was diluted with 100 ml of dimethyl silicone oil (trade name: KF96L-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.), and a 200 ml four-necked flask equipped with a thermometer, stirring blade, nitrogen introducing tube, and reflux tube was attached. 2-ethylhexyl methacrylate 4.0 g, 3-methacryloxypropyl polydimethylsiloxane (trade name: Silaplane FM-0721, manufactured by Chisso Corporation) 1.0 g, 2- (dimethylamino) ethyl methacrylate 1.0 g, and 0.02 g of 2,2′-azobis (isobutyronitrile) was added and stirring was continued at 80 ° C. for 5 hours.

  After standing to cool, the solvent was removed by centrifugal sedimentation, washed with dimethyl silicone oil (trade name: KF96L-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.), and then dimethyl silicone oil (trade name: KF96L-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.). 20 ml was added, and the dispersion treatment was performed for 10 minutes in an ultrasonic bath to obtain an electrophoretic colored particle dispersion.

  When the particle size distribution of the electrophoretic colored particles in the electrophoretic colored particle dispersion was measured by a laser scattering method, the average particle diameter (median diameter) was 0.3 μm.

  Further, the moving speed of the electrophoretic colored particles in this electrophoretic colored particle dispersion was measured in the same manner as in Example 1. The results are shown in Table 1.

[Example 4]
In a 50 ml sample bottle, 40 g of glass beads (diameter 1 mm), 1.0 g of pigment yellow 74, 20 ml of toluene, 0.5 g of 3-methacryloxypropyltrimethoxysilane, and (tridecafluoro-1,1,2, 2-Tetrahydrooctyl) triethoxysilane (0.5 g) was added, and the mixture was shaken and dispersed for 1 hour using a paint shaker (manufactured by Toyo Seiki).

  The obtained pigment paste was diluted with 100 ml of dimethyl silicone oil (trade name: KF96L-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.), and a 200 ml four-necked flask equipped with a thermometer, stirring blade, nitrogen introducing tube, and reflux tube was attached. 2-ethylhexyl methacrylate 5.0 g, 3-methacryloxypropyl polydimethylsiloxane) (trade name: Silaplane FM-0721, manufactured by Chisso Corporation) 1.0 g, 2- (dimethylamino) ethyl methacrylate 0.1 g, Then, 0.02 g of 2,2′-azobis (isobutyronitrile) was added and stirring was continued at 80 ° C. for 5 hours.

  After standing to cool, the solvent was removed by centrifugal sedimentation, washed with dimethyl silicone oil (trade name: KF96L-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.), and then dimethyl silicone oil (trade name: KF96L-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.). 20 ml was added, and the dispersion treatment was performed for 10 minutes in an ultrasonic bath to obtain an electrophoretic colored particle dispersion.

  When the particle size distribution of the electrophoretic colored particles in the electrophoretic colored particle dispersion was measured by a laser scattering method, the average particle diameter (median diameter) was 0.5 μm.

  Further, the moving speed of the electrophoretic colored particles in this electrophoretic colored particle dispersion was measured in the same manner as in Example 1. The results are shown in Table 1.

[Example 5]
In a 50 ml sample bottle, 40 g of glass beads (diameter 1 mm), 1.0 g of quinacridone magenta (Pigment Red 122), 20 ml of toluene, 0.5 g of 3-methacryloxypropyltrimethoxysilane, and (tridecafluoro-1,1 , 2,2-tetrahydrooctyl) triethoxysilane (0.5 g) was added and shake-dispersed for 1 hour using a paint shaker (manufactured by Toyo Seiki).

  The obtained pigment paste was diluted with 100 ml of dimethyl silicone oil (trade name: KF96L-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.), and a 200 ml four-necked flask equipped with a thermometer, stirring blade, nitrogen introducing tube, and reflux tube was attached. 2-ethylhexyl methacrylate 4.5 g, 3-methacryloxypropyl polydimethylsiloxane) (trade name: Silaplane FM-0721, manufactured by Chisso Corporation) 1.0 g, 2- (dimethylamino) ethyl methacrylate 0.5 g, Then, 0.02 g of 2,2′-azobis (isobutyronitrile) was added and stirring was continued at 80 ° C. for 5 hours.

  After standing to cool, the solvent was removed by centrifugal sedimentation, washed with dimethyl silicone oil (trade name: KF96L-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.), and then dimethyl silicone oil (trade name: KF96L-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.). 20 ml was added, and the dispersion treatment was performed for 10 minutes in an ultrasonic bath to obtain an electrophoretic colored particle dispersion.

  When the particle size distribution of the electrophoretic colored particles in the electrophoretic colored particle dispersion was measured by a laser scattering method, the average particle diameter (median diameter) was 0.4 μm.

  Further, the moving speed of the electrophoretic colored particles in this electrophoretic colored particle dispersion was measured in the same manner as in Example 1. The results are shown in Table 1.

[Example 6]
In a 50 ml sample bottle, 40 g of glass beads (diameter 1 mm), 1.0 g of phthalocyanine blue (Pigment Blue 15: 3), 20 ml of toluene, 0.5 g of 3-methacryloxypropyltrimethoxysilane, and (Tridecafluoro-1 , 1,2,2-tetrahydrooctyl) triethoxysilane (0.5 g) was added and shake-dispersed for 1 hour using a paint shaker (manufactured by Toyo Seiki).

  The obtained pigment paste was diluted with 100 ml of dimethyl silicone oil (trade name: KF96L-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.), and a 200 ml four-necked flask equipped with a thermometer, stirring blade, nitrogen inlet tube, and reflux tube was attached. Then, 5.0 g of 2,2,2-trifluoroethyl methacrylate and 0.02 g of 2,2′-azobis (isobutyronitrile) were added, and stirring was continued at 80 ° C. for 5 hours.

  After standing to cool, the solvent was removed by centrifugal sedimentation, washed with dimethyl silicone oil (trade name: KF96L-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.), and then dimethyl silicone oil (trade name: KF96L-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.). 20 ml was added, and the dispersion treatment was performed for 10 minutes in an ultrasonic bath to obtain an electrophoretic colored particle dispersion.

  When the particle size distribution of the electrophoretic colored particles in the electrophoretic colored particle dispersion was measured by a laser scattering method, the average particle diameter (median diameter) was 0.6 μm.

  Further, the moving speed of the electrophoretic colored particles in this electrophoretic colored particle dispersion was measured in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 1]
In a 50 ml sample bottle, 40 g of glass beads (diameter 1 mm), 1.0 g of phthalocyanine blue (Pigment Blue 15: 3), 20 ml of toluene, and 0.5 g of 3-methacryloxypropyltriethoxysilane are used, and a paint shaker is used. And shaken for 1 hour.
The obtained pigment paste was diluted with 100 ml of dimethyl silicone oil (trade name: KF96L-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.), and a 200 ml four-necked flask equipped with a thermometer, stirring blade, nitrogen introducing tube, and reflux tube was attached. Then, 2 g of 2-ethylhexyl methacrylate and 0.02 g of 2,2′-azobis (isobutyronitrile) were added, and stirring was continued at 80 ° C. for 5 hours.
After standing to cool, the solvent was removed by centrifugal sedimentation, washed with dimethyl silicone oil (trade name: KF96L-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.), and then dimethyl silicone oil (trade name: KF96L-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.). ) 100 ml was added, and dispersion treatment was performed for 10 minutes in an ultrasonic bath to obtain an electrophoretic colored particle dispersion.

The particle size distribution of the electrophoretic colored particles in this electrophoretic colored particle dispersion was measured by a laser scattering method (LA-300 manufactured by Horiba, Ltd.), and the average particle diameter (median diameter) was 5.1 μm. .
Further, the moving speed of the electrophoretic colored particles in this electrophoretic colored particle dispersion was measured in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 2]
In a 50 ml sample bottle, 40 g of glass beads (diameter 1 mm), 1.0 g of quinacridone magenta (Pigment Red 122), 20 ml of toluene, 0.5 g of 3-methacryloxypropyltriethoxysilane are placed for 1 hour using a paint shaker. Dispersed with shaking.
The obtained pigment paste was diluted with 100 ml of dimethyl silicone oil (trade name: KF96L-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.), and a 200 ml four-necked flask equipped with a thermometer, stirring blade, nitrogen introducing tube, and reflux tube was attached. Then, 1.8 g of 2-ethylhexyl methacrylate, 0.2 g of 2- (dimethylamino) ethyl methacrylate, and 0.02 g of 2,2′-azobis (isobutyronitrile) were added, and the mixture was stirred at 80 ° C. for 5 hours under a nitrogen stream. Stirring was continued.

  After standing to cool, the solvent is removed by centrifugal sedimentation, and after washing with toluene, 100 ml of dimethyl silicone oil (trade name: KF96-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.) is added, and dispersion treatment is performed for 10 minutes in an ultrasonic bath. An electrophoretic colored particle dispersion was obtained.

When the particle size distribution of the electrophoretic colored particles in the electrophoretic particle dispersion was measured by a laser scattering method, the average particle diameter (median diameter) was 44 μm.
Further, the moving speed of the electrophoretic colored particles in this electrophoretic colored particle dispersion was measured in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 3]
(Production of electrophoretic colored particle dispersion)
(Production of electrophoretic colored particle dispersion (cyan))
In a 50 ml sample bottle, 40 g of glass beads (diameter 1 mm), 1.0 g of quinacridone magenta (Pigment Red 122), 20 ml of toluene, 0.5 g of 3-methacryloxypropyltriethoxysilane, and tridecafluoro-1,1, 0.5 g of 2,2-tetrahydrooctyltriethoxysilane was added and shake-dispersed for 1 hour using a paint shaker (manufactured by Toyo Seiki).

  After removing the solvent by centrifugal sedimentation and repeatedly washing with toluene, 20 ml of dimethyl silicone oil (trade name: KF96-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.) is added, and the dispersion treatment is performed for 10 minutes in an ultrasonic bath, and electrophoresis is performed. Colored particle dispersion was obtained.

When the particle size distribution of the electrophoretic colored particles in the electrophoretic colored particle dispersion was measured by a laser scattering method (LA-300 manufactured by Horiba, Ltd.), the average particle size (median diameter) was 2.5 μm.
Further, the moving speed of the electrophoretic colored particles in this electrophoretic colored particle dispersion was measured in the same manner as in Example 1. The results are shown in Table 1.

  In the table, “---” means that no measurement is performed.

  From the above results, the average particle diameter (median diameter) of the electrophoretic colored particles in the electrophoretic colored particle dispersions obtained in Examples 1 to 6 was on the order of submicrons. It can be seen that the dispersion stability is excellent as compared with the electrophoretic coloring average particle diameter in the electrophoretic coloring particle dispersions obtained in Comparative Examples 1 to 3 being on the order of microns.

[Example 7]
(Production of electrophoretic display element)
1 g of the electrophoretic colored particle dispersion (cyan) obtained in Example 1, and 1 g of the electrophoretic colored particle dispersion (magenta) obtained in Example 2, dimethyl silicone oil (trade name: KF96L-2cs, 2 g of Shin-Etsu Chemical Co., Ltd.) and 0.5 g of titanium oxide powder (average particle size 10 μm) as white particles were mixed to prepare a mixed dispersion of colored particles and white particles.

  On the other hand, an ITO glass substrate of length × width × thickness 40 mm × 30 mm × 1.1 mm was placed as the first electrode so that the conductive film surface was the upper surface, and the center was cut out as a spacer into a 10 mm × 10 mm square. (Length x width x thickness 30 mm x 30 mm x 0.5 mm silicone rubber sheet) is placed, and the mixed dispersion is put into a central square gap. From this, the second electrode is vertically x width x thickness 40 mm. An ITO glass substrate of × 30 mm × 1.1 mm was placed so that the ITO film surface was the lower surface, and was crimped and sealed using a clip from above and below to produce an electrophoretic display element.

  Using the electrophoretic display element produced above, a DC voltage of 500 V was applied between both electrodes so that the second electrode side was a positive electrode. The two kinds of colored particles in the dispersion were all moved to the first electrode side on the lower surface by voltage application, and the upper surface of the display element was white.

  Next, when a DC voltage of 100 V was applied between both electrodes so that the first electrode became a positive electrode, only the magenta particles moved to the second electrode side, and the upper surface of the display element changed to reddish purple.

  Next, when a DC voltage of 500 V is applied between both electrodes so that the first electrode becomes a positive electrode, cyan particles move to the second electrode side, forming a color mixture with magenta particles, and a display element The upper surface of the blue turned purple.

  Next, when a DC voltage of 100 V is applied between both electrodes so that the second electrode becomes a positive electrode, only magenta particles move to the first electrode side, and only cyan particles remain on the upper surface of the display element. And turned blue.

[Example 8]
(Production of electrophoretic display element)
1 g of electrophoretic colored particle dispersion (cyan) obtained in Example 4, 1 g of electrophoretic colored particle dispersion (magenta) obtained in Example 2, and electrophoretic colored particles obtained in Example 4 1 g of a dispersion (yellow), 3 g of dimethyl silicone oil (trade name: KF96L-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.), and 0.75 g of titanium oxide powder (average particle size: 10 μm) as white particles are mixed to give colored particles and A mixed dispersion of white particles was prepared.

  On the other hand, an ITO glass substrate of length × width × thickness 40 mm × 30 mm × 1.1 mm was placed as the first electrode so that the conductive film surface was the upper surface, and the center was cut out as a spacer into a 10 mm × 10 mm square. Place a silicone rubber sheet of length x width x thickness 30 mm x 30 mm x 0.5 mm, put the above mixed dispersion in the central square gap, and from this top as the second electrode length x width x thickness 40 mm x An ITO glass substrate having a size of 30 mm × 1.1 mm was placed so that the ITO film surface was the lower surface, and was crimped and sealed using clips from above and below to produce an electrophoretic display element.

  Using the electrophoretic display element produced above, a DC voltage of 500 V was applied between both electrodes so that the second electrode side was a positive electrode. The two kinds of colored particles in the dispersion were all moved to the first electrode side on the lower surface by voltage application, and the upper surface of the display element was white.

  Next, when a DC voltage of 50 V was applied between both electrodes so that the first electrode became a positive electrode, only cyan particles moved to the second electrode side, and the upper surface of the display element changed to blue.

Next, when a DC voltage of 150 V is applied between the electrodes so that the first electrode becomes a positive electrode, the magenta particles move to the second electrode side and form a color mixture with the cyan particles. The upper surface of the blue turned purple.
Next, when a DC voltage of 50 V is applied between both electrodes so that the second electrode becomes a positive electrode, only cyan particles move to the first electrode side, and only magenta particles remain on the upper surface of the display element. It turned reddish purple.

  Next, when a DC voltage of 500 V was applied between both electrodes so that the first electrode became a positive electrode, cyan particles and yellow particles moved to the second electrode side, and cyan particles and magenta particles The yellow particles formed a mixed color, and the upper surface of the display element changed to black.

Next, when a DC voltage of 50 V is applied between both electrodes so that the second electrode becomes a positive electrode, only cyan particles move to the first electrode side, and only magenta particles and yellow particles are display elements. The mixture remained on the upper surface of the film to form a mixed color and turned orange.
Next, when a DC voltage of 150 V is applied between the electrodes so that the second electrode becomes the positive electrode, only the magenta particles move to the first electrode side, and only the yellow particles remain on the upper surface of the display element. Turned yellow.
Next, when a DC voltage of 50 V is applied between both electrodes so that the first electrode becomes a positive electrode, only cyan particles move to the second electrode side, forming a color mixture with yellow particles, and displaying The top surface of the device turned green.

[Comparative Example 4]
(Production of electrophoretic display element)
The electrophoretic colored particle dispersion (cyan) obtained in Comparative Example 1 and the electrophoretic colored particle dispersion (magenta) obtained in Comparative Example 2 were used in the same manner as in Example 8 except that An electrophoretic display element was produced.

  Using the electrophoretic display element produced above, a DC voltage of 500 V was applied between both electrodes so that the second electrode side was a positive electrode. Some of the cyan particles and most of the magenta particles in the dispersion moved to the first electrode side by application of voltage, but the other colored particles were left on the upper surface of the display element and exhibited a bluish purple color.

Next, a 100 V DC voltage was applied between both electrodes so that the first electrode became a positive electrode, but no significant change was observed in the color of the display element.
Next, when a DC voltage of 500 V was applied between both electrodes so that the first electrode became a positive electrode, some of the colored particles left on the lower surface moved to the second electrode side, and the upper surface of the display element was The color changed to a slightly strong purple of red, but no clear change was seen.
Next, a 100 V DC voltage was applied between both electrodes so that the second electrode became a positive electrode, but no significant change was observed in the color of the display element.

It is a schematic block diagram of the image display apparatus which concerns on 4th Embodiment. It is a diagram which shows typically the relationship between the voltage to apply and the moving amount (display density | concentration) of particle | grains. It is explanatory drawing which shows typically the relationship between the voltage aspect applied between the board | substrates of an image display medium, and the movement aspect of particle | grains.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Image display apparatus 12 Image display medium 16 Voltage application part 20 Display substrate 22 Back substrate 24 Gap member 34 Particle group 34C Cyan particle group 34Y Yellow particle group 34M Magenta particle group 36 Insulating particle 38 Support substrate 40 Surface electrode 42 Surface layer 44 Support substrate 46 Back electrode 48 Surface layer 50 Dispersion medium

Claims (10)

Silane compound represented by the following general formula (I), silane compound having a polymerizable group represented by the following general formula (II) or general formula (III), and the following general formula (IV) or general formula (V) An electrophoretic colored particle which is an organic pigment surface-treated by a reaction with a polymerizable monomer represented by the formula:
General formula ^(I): R 1 -SiX ₃
[In General Formula (I), R ¹ represents a fluorine atom-containing alkyl group, a fluorine atom-containing aryl group, or a fluorine atom-containing aralkyl group, and X represents a methoxy group, an ethoxy group, or a chlorine atom. ]
Formula ^{_{(II): CH 2 = CR}} 2 COO (CH 2) n SiY 3
[In General Formula (II), R ² represents a hydrogen atom or a methyl group, Y represents a methoxy group or an ethoxy group, and n represents an integer of 1-20. ]
Formula _{(III): CH 2 = CH-} (A) m -SiZ 3
[In General Formula (III), A represents a divalent aliphatic residue or aromatic residue, and these substituents represented by A may further have a substituent. Z represents a methoxy group, an ethoxy group or a chlorine atom, and m represents 0 or 1. ]
Formula ^{_{(IV): CH 2 = CR}} 3 COOR 4
[In General Formula (IV), R ³ represents a hydrogen atom or a methyl group. R ⁴ represents an alkyl group or an aralkyl group, and these substituents represented by R ⁴ may further have a substituent. ]
Formula _{(V): CH 2 = CH} -R 5
[In General Formula (V), R ⁵ represents an aryl group or a heterocyclic group, and these substituents represented by R ⁵ may further have a substituent. ]   In the surface treatment, at least after the surface treatment with the silane compound having a polymerizable group represented by the general formula (II) or the general formula (III), the surface treatment is represented by the general formula (IV) or the general formula (V). The electrophoretic colored particles according to claim 1, wherein the electrophoretic colored particles are surface-treated with a polymerizable monomer.   3. The electrophoretic colored particle according to claim 1, wherein the organic pigment is at least one selected from the group consisting of a phthalocyanine pigment, a quinacridone pigment, and an azo pigment. Organic pigments include silane compounds represented by the following general formula (I), silane compounds having a polymerizable group represented by the following general formula (II) or general formula (III), and the following general formula (IV) or general A method for producing electrophoretic colored particles that is surface-treated by reaction with a polymerizable monomer represented by formula (V),
At least after the surface treatment with the silane compound having a polymerizable group represented by the general formula (II) or the general formula (III), the polymerizable unit represented by the general formula (IV) or the general formula (V) is used. A method for producing electrophoretic colored particles, wherein the surface treatment is performed with a polymer.
General formula ^(I): R 1 -SiX ₃
[In General Formula (I), R ¹ represents a fluorine atom-containing alkyl group, a fluorine atom-containing aryl group, or a fluorine atom-containing aralkyl group, and X represents a methoxy group, an ethoxy group, or a chlorine atom. ]
Formula ^{_{(II): CH 2 = CR}} 2 COO (CH 2) n SiY 3
[In General Formula (II), R ² represents a hydrogen atom or a methyl group, Y represents a methoxy group or an ethoxy group, and n represents an integer of 1-20. ]
Formula _{(III): CH 2 = CH-} (A) m -SiZ 3
[In general formula (III), A represents a divalent aliphatic residue or aromatic residue, and these substituents represented by A may further have a substituent. Z represents a methoxy group, an ethoxy group or a chlorine atom, and m represents 0 or 1. ]
Formula ^{_{(IV): CH 2 = CR}} 3 COOR 4
[In General Formula (IV), R ³ represents a hydrogen atom or a methyl group. R ⁴ represents an alkyl group or an aralkyl group, and these substituents represented by R ⁴ may further have a substituent. ]
Formula _{(V): CH 2 = CH} -R 5
[In General Formula (V), R ⁵ represents an aryl group or a heterocyclic group, and these substituents represented by R ⁵ may further have a substituent. ] Surface treatment with the silane compound represented by the general formula (I)
(1) Simultaneously with the surface treatment with the silane compound having a polymerizable group represented by the general formula (II) or the general formula (III),
(2) Simultaneously with the surface treatment with the polymerizable monomer represented by the general formula (IV) or the general formula (V),
(3) After the surface treatment with the polymerizable monomer represented by the general formula (IV) or the general formula (V),
The method for producing electrophoretic colored particles according to claim 4, wherein the method is performed so as to satisfy at least one of them.   An electrophoretic colored particle dispersion, wherein the electrophoretic colored particles according to any one of claims 1 to 3 are dispersed in a light-transmitting dispersion medium. A pair of substrates disposed opposite to each other, at least one of which has translucency;
The electrophoretic colored particle dispersion according to claim 6 injected between the pair of substrates;
An image display medium comprising: The electrophoretic colored particle dispersion contains a plurality of types of electrophoretic colored particles,
8. The image display medium according to claim 7, wherein each of the electrophoretic colored particle groups has different voltage absolute values necessary for moving in accordance with an electric field, and exhibits different color development properties. .   9. The image display medium according to claim 8, wherein each of the electrophoretic colored particle groups has a voltage range necessary for moving in accordance with an electric field, and the voltage ranges are different from each other. The image display medium according to any one of claims 7 to 9,
Voltage applying means for applying a voltage between the pair of substrates of the image display medium;
An image display device comprising:

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