JP2003096191A - Image displaying medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dye capable of coloring a nonpolar organic solvent, particularly a highly insulating dispersing medium such as a silicone oil and the like, and an improved electrophoretic image displaying medium by utilizing the same. SOLUTION: The quinacridone derivative compound bears in the molecule both a group represented by general formula (I) (wherein the phenyl group may bear a substituent group) and a group represented by general formula (V) (wherein n is a natural number; and R is an alkyl group).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel polydimethylsiloxane group-substituted quinacridone compound containing a polydimethylsiloxane group and a heterocyclic group containing two nitrogen atoms in the ring, a polydimethylsiloxane group and two nitrogen atoms. Novel polydimethylsiloxane group-substituted indigo compound having heterocyclic group contained in ring, and novel polydimethylsiloxane group-substituted diketopyrrolopyrrole derivative having polydimethylsiloxane group and heterocyclic group having two nitrogen atoms in ring The present invention relates to a compound and a novel isoindolinone derivative compound having a polydimethylsiloxane group and a heterocyclic group containing two nitrogen atoms in the ring, and using these novel compounds,
The present invention relates to an electrophoretic image display medium capable of reversibly changing the visible state by moving charged white or colored particles by the action of an electric field.

[0002]

2. Description of the Related Art Conventionally, CRTs and liquid crystal displays have been used as terminals for displaying so-called images such as characters, still images and moving images. These can display and rewrite image data and character data instantly, but it is difficult to carry the device around all the time, eyes are tired during long-term work, and it is impossible to display when the power is off. There is also a drawback. On the other hand, when a character or a still image is distributed or stored as a document or the like, it is widely used as a so-called hard copy recorded on a paper medium by a printer. Hard copy is easier to read than the display, less tired,
You can read it freely. Further, it has a feature that it is lightweight and can be freely carried. However, the hard copy is discarded after being used and is recycled, but it requires a lot of labor and cost, which causes a problem in resource saving.

There is a great need for a rewritable, paper-like display medium having the advantages of both of these displays and hard copy.
Bistable cholesteric liquid crystals, electrochromic elements, electrophoretic elements and the like have been attracting attention as a display medium having a reflective and bright display and having a memory property. Among them, the one using the electrophoretic element has the display quality,
It is excellent in terms of power consumption during display operation, and is disclosed in, for example, Japanese Patent Laid-Open No. 5-173194, Japanese Patent No. 2612472, and the like. In the electrophoretic display medium, a dispersion liquid in which a plurality of electrophoretic particles having a color different from the color of the dispersion medium are dispersed in a colored dispersion medium is enclosed between a pair of transparent electrodes. Electrophoretic particles have an electric charge on the surface in the dispersion medium, and when a voltage opposite to the electric charge of the electrophoretic particles is applied to one of the transparent electrodes, the electrophoretic particles are deposited there and the color of the electrophoretic particles is observed. When a voltage in the same direction as the charge of the electrophoretic particles is applied, the electrophoretic particles move to the opposite side, and the color of the dispersion medium is observed. This allows display.

Generally, a nonpolar organic solvent is used as a dispersion medium used in an electrophoretic display medium. Among them, paraffin hydrocarbons and silicone oils are preferable because they have high insulating properties and display responsiveness due to migration of charged particles.
On the other hand, it is required to dissolve the dye in order to color these solvents. And, for example, many conventional organic solvent-soluble dyes have good solubility in polar organic solvents such as alcohols and esters, but are difficult to dissolve in paraffin hydrocarbons and silicone oils. Therefore, there is a problem that the coloring of the dispersion medium is insufficient and the contrast ratio when the display medium is displayed and when it is not displayed is small.

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a dye capable of coloring a non-polar organic solvent, especially a dispersion medium having a high insulating property such as silicone oil, and an electrophoretic image display improved by using the dye. To provide the medium. That is, the first object of the present invention is to provide a novel compound having a high coloring ability in a non-polar solvent by having both a group which is a coloring component and a group having a high affinity with a non-polar solvent. A second object of the present invention is to provide an electrophoretic image display medium having good contrast by using a compound having a high coloring ability for the nonpolar solvent for coloring the nonpolar solvent. The third object of the present invention is to provide an electrophoretic image display medium having a good contrast and a highly transparent colored state by virtue of the compatibility of the non-polar solvent and the compound, and thus having a higher contrast. In addition, the fourth object of the present invention is to increase the solubility of the compound in the non-polar solvent by containing a polar compound compatible with the non-polar solvent in the dispersion liquid, and to improve the contrast. By that is to provide a good electrophoretic image display medium, a fifth object of the present invention, a non-polar solvent is a silicone oil,
An object of the present invention is to provide an image display medium that is highly safe, chemically stable, and has a long-term reliability. Furthermore, a sixth object of the present invention is to provide a dispersion medium having a volume resistivity of 1 × 10 ^9. Ω
It is to provide an image display medium having a high insulating property and effectively obtaining an electric field required for migration of particles by having a size of cm or more.

[0006]

Means for Solving the Problems The above-mentioned problems are (1) the group represented by the following general formula (I) of the present invention.

[0007]

[Chemical 9] (However, the phenyl group may have a substituent) and a group represented by the following general formula (V)

[0008]

[Chemical 10] (However, n is a natural number and R is an alkyl group) both in the molecule, a quinacridone derivative compound, (2) "a group represented by the following general formula (II)"

[0009]

[Chemical 11] (However, the phenyl group may have a substituent) and a group represented by the following general formula (V)

[0010]

[Chemical 12] (However, n is a natural number and R is an alkyl group) both in the molecule, an indigo derivative compound ”,
(3) "Group represented by the following general formula (III)

[0011]

[Chemical 13] (Wherein X ₁ and X ₂ each represent an aryl group) and a group represented by the following general formula (V)

[0012]

[Chemical 14] (Wherein, n is a natural number and R is an alkyl group) both in the molecule, (diketopyrrolopyrrole derivative compound) (4) "group represented by the following general formula (IV)

[0013]

[Chemical 15] (However, the phenyl group may have a substituent) and a group represented by the following general formula (V)

[0014]

[Chemical 16] Are both present in the molecule.

Further, the above-mentioned problem is (5) of the present invention, "at least one or both of the two conductive layers which are light-transmissive and which are arranged with a desired interval are provided with at least white or colored particles and non-polar particles. Solvent, any one of claims 1 to 4.
And (6) "the quinacridone derivative compound, the indigo derivative compound, the diketopyrrolopyrrole derivative compound, or the isoindolinone derivative. The compound is compatible with a non-polar solvent, the image display medium according to the above item (5), (7) "containing a polar compound compatible with the non-polar solvent in the dispersion liquid". (8) The image display medium according to item (5) or (6), characterized in that the nonpolar solvent is silicone oil. The image display medium according to any one of items (7), and (9), wherein the dispersion medium has a volume resistivity of 1 × 10 ⁹ Ω · cm or more. The image according to any one of item (8) It is achieved by 示媒 body "image display medium according to any one of claims 5 to 9".

The present invention will be described in detail below. The non-polar solvent-colorable compound of the present invention is obtained by adding a polydimethylsiloxane group compatible with a non-polar solvent such as silicone oil represented by the above general formula (V) to quinacridone which is (i) a colored organic pigment. (Ii)
Obtained by adding a polydimethylsiloxane group compatible with a non-polar solvent such as silicone oil represented by the general formula (V) to indigo which is a colored organic pigment, and (iii) a diketo which is a colored organic pigment Obtained by adding a polydimethylsiloxane group compatible with a non-polar solvent such as silicone oil represented by the above general formula (V) to pyrrolopyrrole, and (iv) an isoindolinone-based colorant organic pigment. It can be obtained by adding a polydimethylsiloxane group compatible with a nonpolar solvent such as silicone oil represented by the above general formula (V) to the pigment.

As a method for producing a pigment derivative by modifying an organic pigment, an organic pigment having a> C═O group and a> NH group conjugated in a molecule is dissolved in an aprotic polar solvent in the presence of a strong base. However, a method for producing a pigment derivative by reacting with a functional group capable of causing an electrophilic addition reaction is disclosed in JP-A No. 9-12916 and Coloring Materials Society, Vol. 70, No. 5, pp. 308-314.

The quinacridone, indigo, diketopyrrolopyrrole and isoindolinone pigments used in the present invention have> C═O groups and> NH groups which are conjugated in the molecule, and they are prepared according to the above method. It is possible to produce the desired pigment derivative.

On the other hand, the polydimethylsiloxane group represented by the general formula (V) has a high affinity with a nonpolar solvent, and the compound having the polydimethylsiloxane group is easily dissolved or mixed in the nonpolar solvent. That is, the quinacridone, indigo, diketopyrrolopyrrole, and isoindolinone pigments are capable of addition reaction with a compound having both a polydimethylsiloxane group represented by the above general formula (V) and a functional group capable of causing an electrophilic addition reaction. It has been found that the quinacridone derivative compound produced thereby is easily soluble or miscible in a nonpolar solvent. It was also found that an electrophoretic image display medium using a non-polar solvent colored with the quinacridone derivative compound has good response to a driving electric field and good display contrast. Further, they have found that the indigo derivative compound is easily dissolved or mixed in a nonpolar solvent. Further, they have found that the diketopyrrolopyrrole derivative compound is easily dissolved or mixed in a nonpolar solvent. Furthermore, they have found that the isoindolinone pigment derivative compound is easily dissolved or mixed in a nonpolar solvent.

It was also found that an electrophoretic image display medium using a non-polar solvent colored with the quinacridone derivative compound has a good response to a driving electric field and a good display contrast. Further, they have found that an electrophoretic image display medium using a nonpolar solvent colored with the indigo derivative compound has good responsiveness to a driving electric field and good display contrast. Further, they have found that an electrophoretic image display medium using a nonpolar solvent colored with the diketopyrrolopyrrole derivative compound has good response to a driving electric field and good display contrast. Furthermore, it has been found that an electrophoretic image display medium using a nonpolar solvent colored with the isoindolinone pigment derivative compound has good response to a driving electric field and good display contrast. The present invention is based on the above findings.

The present invention will be described in more detail below. [Synthesis of the 4 New Compounds] The quinacridone derivative of the novel compound of the (i) type of the present invention is prepared by dissolving quinacridone in an aprotic polar solvent in the presence of a strong base to give a compound of the above general formula (V). It is a derivative obtained by adding a compound having both the polydimethylsiloxane group shown and a functional group capable of causing an electrophilic addition reaction. The quinacridone used for the synthesis of the novel quinacridone derivative compound of the present invention is quinacridone which is unsubstituted or has a substitutable site of the phenyl group.

A novel compound of the second type (ii) of the present invention, an indigo derivative, is prepared by dissolving indigo in an aprotic polar solvent in the presence of a strong base to give a polydimethylsiloxane group represented by the general formula (V) and a parent compound. It is a derivative obtained by adding a compound having both a functional group capable of causing an electron addition reaction. The indigo used in the first embodiment is an indigo that is unsubstituted or has a substitutable site of the phenyl group.

A novel compound of the third (iii) type of the invention,
The diketopyrrolopyrrole derivative is prepared by dissolving diketopyrrolopyrrole in an aprotic polar solvent in the presence of a strong base, and adding the polydimethylsiloxane group represented by the general formula (V) and a functional group capable of causing an electrophilic addition reaction together. It is a derivative obtained by adding a compound having. Any diketopyrrolopyrrole pigment having a diketopyrrolopyrrole skeleton portion is used.

The isoindolinone derivative of the novel compound of the fourth type (iv) of the present invention is prepared by dissolving an isoindolinone pigment in an aprotic polar solvent in the presence of a strong base and is represented by the above general formula (V). It is a derivative obtained by adding a compound having both a polydimethylsiloxane group and a functional group capable of causing an electrophilic addition reaction. An optional isoindolinone-based pigment having the skeleton portion is used.

Specific examples of the strong base to be present in the reaction include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and lithium hydroxide, and alkali metal hydroxides such as potassium methoxide, potassium butoxide and sodium ethoxide. An alkoxide etc. can be mentioned.

Examples of the compound having both the polydimethylsiloxane group represented by the general formula (V) and the functional group capable of causing an electrophilic addition reaction include polydimethylsiloxane having a terminal modified with a functional group capable of causing an electrophilic addition reaction. To be Specific examples of these include one-terminal modified silicones such as vinyl polydimethyl siloxane, methacryloxypropyl polydimethyl siloxane, and polydimethylsiloxypropyl glycidyl ether.

As the aprotic polar solvent, known aprotic polar solvents can be used, and for example, dimethyl sulfoxide, dimethylformamide, tetramethylurea, acetonitrile and the like can be used. In order to improve the solubility of a compound having both a strong base, a polydimethylsiloxane group represented by the general formula (V) and a functional group capable of causing an electrophilic addition reaction in an aprotic polar solvent, the aprotic polar A solvent other than the solvent can be added. Examples of these solvents include protic polar solvents such as methanol, ethanol and propanol, and nonpolar solvents such as toluene and xylene.

In the synthesis of (i) the novel quinacridone derivative compound of the present invention, quinacridone is dissolved in an aprotic polar solvent to which a strong base is added. To this is added a compound having both a polydimethylsiloxane group represented by the general formula (V) and a functional group capable of causing an electrophilic addition reaction, and the mixture is heated and stirred to give quinacridone and the polydimethylsiloxane group represented by the general formula (V) and the parent group. A compound having both a functional group capable of causing an electron addition reaction causes an addition reaction.
After completion of the reaction, an aqueous solution of acid is added for neutralization, the reaction solvent is removed, washed with water, and dried to obtain the novel quinacridone derivative of the present invention.

In the synthesis for (ii) the novel indigo derivative compound of the present invention, indigo is dissolved in an aprotic polar solvent to which a strong base is added. A polydimethylsiloxane group represented by the general formula (V) and a compound having both a functional group capable of causing an electrophilic addition reaction are added thereto, and the mixture is heated and stirred to give indigo and the polydimethylsiloxane group represented by the general formula (V) and the parent group. A compound having both a functional group capable of causing an electron addition reaction causes an addition reaction. After completion of the reaction, an aqueous solution of acid is added for neutralization, the reaction solvent is removed, washed with water, and dried to obtain the novel indigo derivative of the present invention.

In the synthesis of (iii) the novel diketopyrrolopyrrole derivative compound of the present invention, diketopyrrolopyrrole is dissolved in an aprotic polar solvent to which a strong base is added. A compound having both a polydimethylsiloxane group represented by the general formula (V) and a functional group capable of causing an electrophilic addition reaction is added thereto, and the mixture is heated and stirred to give diketopyrrolopyrrole and the polydimethylsiloxane represented by the general formula (V). A compound having both a group and a functional group capable of causing an electrophilic addition reaction undergoes an addition reaction. After completion of the reaction, an aqueous solution of acid is added for neutralization, the reaction solvent is removed, washed with water, and dried to obtain the novel diketopyrrolopyrrole derivative of the present invention.

In the synthesis of (iv) the novel isoindolinone derivative compound of the present invention, the isoindolinone pigment is dissolved in an aprotic polar solvent containing a strong base.
A compound having both a polydimethylsiloxane group represented by the general formula (V) and a functional group capable of causing an electrophilic addition reaction is added thereto, and the mixture is heated and stirred to give an isoindolinone pigment and the polydimethyl group represented by the general formula (V). A compound having both a siloxane group and a functional group capable of causing an electrophilic addition reaction undergoes an addition reaction. After completion of the reaction, an aqueous solution of acid is added for neutralization, the reaction solvent is removed, washed with water, and dried to obtain the novel isoindolinone derivative of the present invention.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION [Image Display] An example of the image display according to the first embodiment of the image display of the present invention will be described with reference to FIG. In FIG. 1, (1) and (2)
Is a conductive layer, at least one of which is light transmissive. As the conductive layer, metal such as Al, Ag, Ni, Cu, ITO, Sn, etc.
A transparent conductor such as O ₂ , ZnO, or Al is formed into a thin film by a sputtering method, a vacuum deposition method, a CVD method, a coating method, or a conductive agent is mixed with a solvent or a synthetic resin binder and applied. Used. Examples of the conductive agent include cationic polyelectrolytes such as polymethylbenzyl trimethyl chloride and polyallyl polymethyl ammonium chloride, anionic polyelectrolytes such as polystyrene sulfonate and polyacrylate, and zinc oxide and tin oxide having electronic conductivity. Indium oxide fine powder or the like is used.
The conductive layer may be thick enough to have a self-holding function itself, or the conductive layer may be provided on a substrate (not shown) having a self-holding function, and in any case, it can be preferably used. The conductive layers (1) and (2) may be layers exhibiting anisotropic conductivity, or layers having a pattern-like or multi-dot-like segment having a conductive portion penetrating in the thickness direction. May be. In either case, if a power supply electrode is brought into contact with a part of the conductive layers (1) and (2), an electric field can be generated between the conductive layers (1) and (2), so that white or colored particles ( 3) can move reliably. Since it is sufficient to prepare a voltage applying means between the conductive layers (1) and (2) for displaying, it is easy.

In FIG. 1, (3) is white to colored particles. As the simplest example, solid particles of a metal oxide such as silicon dioxide, aluminum oxide and titanium oxide can be used. As the black colorant, for example, carbon black, aniline black, furnace black, lamp black and the like can be used. Examples of cyan colorants that can be used include phthalocyanine blue, methylene blue, Victoria blue, methyl violet, aniline blue, and ultramarine blue. Examples of magenta colorants include rhodamine 6G lake,
Dimethylquinacridone, Watching Red, Rose Bengal, Rhodamine B, Alizarin Lake, etc. can be used. As the yellow colorant, for example, chrome yellow, benzidine yellow, Hansa yellow, naphthol yellow, molybdenum orange, quinoline yellow, tartrazine and the like can be used. Alternatively, it is possible to use a dispersion or mixture of the above metal oxide and colorant in at least a binder resin which is insoluble in a solvent serving as a dispersion medium. As the binder resin, all of known thermoplastic resins and thermosetting resins which are insoluble in a silicone oil solvent can be used, but a non-adhesive material is particularly preferably used.
As a direct example of such a resin, a polyester resin,
Examples thereof include polystyrene, poly (p-chlorostyrene), styrene such as polyvinyltoluene, and homopolymers of substitution products thereof. The amount of the metal oxide or colorant that can be used is 0.1 to 300 parts by weight, preferably 1 to 100 parts by weight, based on 100 parts by weight of the binder resin.

In FIG. 1, (4) is a dispersion medium. The dispersion medium is composed of at least a non-polar solvent, and a surfactant or the like may be added as necessary in order to control the dispersibility of the dispersed particles. As the non-polar solvent used for the dispersion medium of the present invention, pentane, hexane, heptane, octane, nonane, decane, dodecane, ligroin, solvent naphtha (commercially available from Exxon H, G, L, K Or an aliphatic hydrocarbon solvent such as Ciel Sekiyu Co., Ltd., etc.), an aromatic hydrocarbon solvent such as toluene, xylene, benzene, or alkylbenzene, and a silicone oil. These solvents may be used alone or in combination of two or more. (I) the novel quinacridone derivative compound, (ii) the novel indigo derivative compound, (iii) the novel diketopyrrolopyrrole derivative compound of the present invention in the above non-polar solvent.
And / or (iv) a novel isoindolinone derivative compound is added to obtain a colored dispersion medium.

The combination of the nonpolar solvent and the compound in the second embodiment (2) of the image display of the present invention differs depending on the nonpolar solvent used. Examples of the non-polar solvent that can be used in this case include the non-polar solvents described above. Depending on the type of the non-polar solvent, (i) the novel quinacridone derivative compound, (ii) the novel indigo derivative compound, and (iii) the novel diketo according to the present invention. Pyrrolopyrrole derivative compound and / or (i
v) The number of n in the group represented by the general formula (V) in the novel isoindolinone derivative compound and the type of the alkyl group of R are suitably selected.

The compound compatible with the non-polar solvent used in the third embodiment of the image display of the present invention is the compound in the first embodiment of the present invention and the non-polar solvent. It is preferable to use a substance which assists the compatibility of the above, and is capable of dissolving the compound in the first embodiment (1) of the present invention and soluble or miscible in a nonpolar solvent. Examples of these substances include ethers, esters, alcohols, ketones, amides and the like. The mixing ratio of such other solvent is 100
It is about 0.1 to 10 parts by weight with respect to parts by weight.

The silicone oil used in the fourth embodiment of the image display of the present invention is a dialkyl silicone oil represented by the following general formula (VI); cyclic polydialkylsiloxane or cyclic polyalkylphenylsiloxane; Examples thereof include alkylphenyl siloxane. In addition, higher fatty acid modified silicone oil, methyl chlorinated phenyl silicone oil, alkyl modified silicone oil, methyl hydrogen silicone oil, amino modified silicone oil, epoxy modified silicone oil and the like can be used.

[0038]

[Chemical 17] [However, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R
₈ -CnH ₂ n + 1 represents the (n = 1~20), these may be the same or different. x is 0 or an integer of 1 or more. When the dialkyl silicone oil represented by the general formula (VI) is used, there is an advantage that the temperature during polymerization can be freely selected. Of these, use of dimethylpolysiloxane is advantageous. The silicone oil represented by the general formula (VI) preferably has a viscosity at 25 ° C. of 0.01 to 1,000,000 cs (centistokes). In addition or in the general formula (V
It is preferable to use the one having x of 1 to 20,000 in I).

Further, when a cyclic polydialkyl siloxane or a cyclic polyalkyl phenyl siloxane is used, the resin obtained has a drying property of the polymerization solvent, so that especially the coating property of the resin is improved and gloss is exhibited. Is advantageous to.
When an alkylphenyl siloxane (particularly, it is desirable to use methylphenyl silicone oil) is used, the solubility is improved by introducing a phenyl group (5 to 50 mol%), so that the dispersion stability of the resin solution is improved. It is advantageous to raise. Specific examples of these various silicone oils are as follows.

Examples of (A) dialkyl silicone oil:

[0041]

[Table 1]

(B) Examples of cyclic polydialkyl siloxane and cyclic polyalkyl phenyl siloxane (contents of phenyl groups are 5, 10, 20, 50 mol%): cyclic polydimethyl siloxane, cyclic polymethyl phenyl siloxane, cyclic poly Diethyl siloxane, cyclic polyethylphenyl siloxane, cyclic polydibutyl siloxane, cyclic polybutylphenyl siloxane, cyclic polydihexyl siloxane, cyclic polyhexyl phenyl siloxane, cyclic polydilauryl siloxane, cyclic polymethyl chlorophenyl siloxane, cyclic poly distearyl siloxane, cyclic polymethyl Bromphenyl siloxane.

Examples of (C) alkylphenyl silicone oils:

[0044]

[Table 2]

Commercially available examples of these silicone oils are KF-96L [0.65, manufactured by Shin-Etsu Chemical Co., Ltd.].
1.0, 1.5, 2.0 centistokes (cs)],
KF-96 [10, 20, 30, 50, 500, 100
0,3000 (cs)], KF-56, KF-58, K
F-54, etc., and Toshiba Silicone Co., Ltd.
Made TSF451 series, TSF456 series, T
SF410, 411, 440, 4420, 484, 48
3,431,433 series, THF450 series,
TSF404, 405, 406, 451-5A, 451
-10A, 437 series, TSF440, 400, 4
01, 4300, 4445, 4700, 4450, 47
02, 4730 series, TSF 434, 4600 series, and Toray Dow Corning Silicone Co., Ltd.
Manufactured by SH-200 and the like.

In the fifth embodiment of the image display body of the present invention, the volume resistivity of the dispersion medium is 1 × 10 ⁹ Ω · c.
It is preferably m or more. If the volume resistivity of the dispersion medium is less than 1 × 10 ⁹ Ω · cm, it becomes difficult to generate an electric field necessary for the electrophoresis of particles between the conductive layers (1) and (2) in FIG. As a result, a malfunction occurs. In order to prepare the dispersion liquid of the present invention, the above components may be mixed and dispersed in a silicone oil solvent. in this case,
A ball mill, a sand mill, an attritor or the like may be used as the dispersing means. The order of mixing is not particularly limited.

[0047]

EXAMPLES The present invention will be described in more detail by way of examples. However, the present invention is not limited to the following examples. All parts used in the following examples are parts by weight.

[Synthesis Example of Novel Compound] (Example 1) [Preparation of quinacridone derivative] Dimethyl sulfoxide 50 was placed in a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser.
Parts, xylene 50 parts, potassium-tert-butoxide 2.2 parts, and quinacridone 6.2 parts were taken and heated to 60 ° C. A compound having the following structure (made by Gelest)
20 copies,

[0049]

[Chemical 18] Was added dropwise over 1 hour. 6 more at this temperature after dropping
The reaction was allowed to stir for hours. 1.0 mol after completion of reaction
Then, 20 parts of an aqueous solution of hydrochloric acid / L was added to precipitate a reaction product, and the reaction solvent was removed. After further washing with water, it was dried to obtain an oily product.

(Example 2) [Preparation of quinacridone derivative] Dimethyl sulfoxide 50 was placed in a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser.
Parts, xylene 50 parts, potassium-tert-butoxide 2.2 parts, and quinacridone 6.2 parts were taken and heated to 60 ° C. A compound having the following structure (made by Gelest)
20 copies,

[0051]

[Chemical 19]

(Example 3) [Preparation of indigo derivative] 50 parts of dimethyl sulfoxide were placed in a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser.
50 parts xylene, potassium-tert-butoxide 2.
2 parts and 5.2 parts of indigo were taken and heated to 60 ° C. 20 parts of a compound having the following structure (made by Gelest),

[0053]

[Chemical 20] Was added dropwise over 1 hour. 6 more at this temperature after dropping
The reaction was allowed to stir for hours. 1.0 mol after completion of reaction
Then, 20 parts of an aqueous solution of hydrochloric acid / L was added to precipitate a reaction product, and the reaction solvent was removed. After further washing with water, it was dried to obtain an oily product.

(Example 4) [Preparation of indigo derivative] 50 parts of dimethyl sulfoxide were placed in a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser.
50 parts xylene, potassium-tert-butoxide 2.
2 parts and 5.2 parts of indigo were taken and heated to 60 ° C. 20 parts of a compound having the following structure (made by Gelest),

[0055]

[Chemical 21] Was added dropwise over 1 hour. 6 more at this temperature after dropping
The reaction was allowed to stir for hours. 1.0 mol after completion of reaction
Then, 20 parts of an aqueous solution of hydrochloric acid / L was added to precipitate a reaction product, and the reaction solvent was removed. After further washing with water, it was dried to obtain an oily product.

(Example 5) [Preparation of diketopyrrolopyrrole derivative] In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 50 parts of dimethyl sulfoxide, 50 parts of xylene and 2.2 parts of potassium tert-butoxide were prepared. Part, diketopyrrolopyrrole pigment (C.I.
I. Pigment Red 255) 5.8 parts, 60 ° C
Heated to. The compound of the following structure (Gelest)
20),

[0057]

[Chemical formula 22] Was added dropwise over 1 hour. 6 more at this temperature after dropping
The reaction was allowed to stir for hours. 1.0 mol after completion of reaction
Then, 20 parts of an aqueous solution of hydrochloric acid / L was added to precipitate a reaction product, and the reaction solvent was removed. After further washing with water, it was dried to obtain an oily product.

(Example 6) [Preparation of diketopyrrolopyrrole derivative] In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 50 parts of dimethyl sulfoxide, 50 parts of xylene and 2.2 parts of potassium-tert-butoxide were prepared. Part, diketopyrrolopyrrole pigment (C.I.
I. Pigment Red 254) 7.1 parts, 60 ° C
Heated to. The compound of the following structure (Gelest)
20),

[0059]

[Chemical formula 23] Was added dropwise over 1 hour. 6 more at this temperature after dropping
The reaction was allowed to stir for hours. 1.0 mol after completion of reaction
Then, 20 parts of an aqueous solution of hydrochloric acid / L was added to precipitate a reaction product, and the reaction solvent was removed. After further washing with water, it was dried to obtain an oily product.

(Example 7) [Preparation of isoindolinone derivative] In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 50 parts of dimethyl sulfoxide, 50 parts of xylene, and 2.2 parts of potassium-tert-butoxide. , C.I. I. Pigment Yellow 109 13.1 parts was taken and heated to 60 ° C. 20 parts of a compound having the following structure (made by Gelest),

[0061]

[Chemical formula 24] Was added dropwise over 1 hour. 6 more at this temperature after dropping
The reaction was allowed to stir for hours. 1.0 mol after completion of reaction
Then, 20 parts of an aqueous solution of hydrochloric acid / L was added to precipitate a reaction product, and the reaction solvent was removed. After further washing with water, it was dried to obtain an oily product.

(Example 8) [Preparation of isoindolinone derivative] In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 50 parts of dimethyl sulfoxide, 50 parts of xylene and 2.2 parts of potassium-tert-butoxide. , C.I. I. Pigment Yellow 110 1
2.8 parts were taken and heated to 60 ° C. 20 parts of a compound having the following structure (made by Gelest),

[0063]

[Chemical 25] Was added dropwise over 1 hour. 6 more at this temperature after dropping
The reaction was allowed to stir for hours. 1.0 mol after completion of reaction
Then, 20 parts of an aqueous solution of hydrochloric acid / L was added to precipitate a reaction product, and the reaction solvent was removed. After further washing with water, it was dried to obtain an oily product.

[Image Display Medium] (Example 9) 5 parts of the quinacridone derivative obtained in Example 1 and 5 parts of titanium oxide were added to 95 parts of isoparaffin hydrocarbon (Isopar H, Exxon Chemical Co.) and dispersed by a ball mill. A dispersion was prepared. The volume resistivity at 20 ° C. of the dispersion medium obtained by adding 5 parts of the quinacridone derivative obtained in Example 1 to 95 parts of the above isoparaffinic hydrocarbon was determined by AC impedance measurement to be 3.2 × 1.
It was 0 ¹⁰ Ω · cm. Next, a space is created by sandwiching a 250 μm-thick polyester film having a 1 cm □ opening between two ITO electrode-attached substrates. The dispersion liquid was enclosed in the space. When -200 V was applied to the upper ITO electrode, the titanium oxide particles were immediately electrodeposited on the upper electrode and appeared white when viewed from the upper substrate surface. Then +20 on the upper electrode
When 0 V was applied, the titanium oxide particles moved to the lower electrode, and when viewed from the upper substrate side, the colored state due to the color of the quinacridone derivative was clearly seen.

(Example 10) [Image display medium] Dimethyl silicone oil (SH200 1cs, Toray Dow Corning Silicone Co., Ltd.) 9
To 4 parts, 5 parts of the quinacridone derivative obtained in Example 2, 1 part of ethyl laurate, and 5 parts of titanium oxide were added and dispersed by a ball mill to prepare a dispersion liquid. The quinacridone derivative 5 obtained in Example 2 was added to 94 parts of the above silicone oil.
And the volume resistivity of the dispersion medium to which 1 part of ethyl laurate was added at 20 ° C. was found to be 1.1 × 10 ¹⁰ Ω · cm by AC impedance measurement. Next, an opening of 1 cm □ was provided between two substrates with ITO electrodes 250
A space is created by sandwiching a μm thick polyester film. The dispersion liquid was enclosed in the space. -20 for the upper ITO electrode
When 0 V was applied, the titanium oxide particles were immediately electrodeposited on the upper electrode and looked white from the upper substrate surface. Next, when +200 V was applied to the upper electrode, the titanium oxide particles moved to the lower electrode, and when viewed from the upper substrate side, a colored state due to the color of the quinacridone derivative was clearly seen.

(Example 11) [Image display medium] 5 parts of the indigo derivative obtained in Example 3 and 5 parts of titanium oxide were added to 95 parts of isoparaffin hydrocarbon (Isopar H manufactured by Exxon Chemical Co.) and dispersed by a ball mill. A dispersion was prepared. The volume resistivity at 20 ° C. of a dispersion medium obtained by adding 5 parts of the indigo derivative obtained in Example 3 to 95 parts of the above isoparaffinic hydrocarbon was determined by AC impedance measurement to be 1.9 × 10.
It was ¹⁰ Ω · cm. Next, a space is created by sandwiching a 250 μm-thick polyester film having a 1 cm □ opening between two ITO electrode-attached substrates. The dispersion liquid was enclosed in the space. When -200V is applied to the upper ITO electrode,
The titanium oxide particles were immediately electrodeposited on the upper electrode and appeared white when viewed from the upper substrate surface. Then + 200V to the upper electrode
When was applied, the titanium oxide particles moved to the lower electrode, and when viewed from the upper substrate side, the colored state due to the color of the indigo derivative was clearly seen.

(Example 12) [Image display medium] Dimethyl silicone oil (SH200 1cs, Toray Dow Corning Silicone Co., Ltd.) 9
To 4 parts, 5 parts of the indigo derivative obtained in Example 4, 1 part of ethyl laurate, and 5 parts of titanium oxide were added and dispersed by a ball mill to prepare a dispersion liquid. The volume resistivity at 20 ° C. of the dispersion medium obtained by adding 5 parts of the indigo derivative obtained in Example 4 and 1 part of ethyl laurate to 94 parts of the above silicone oil was determined by AC impedance measurement.
It was 8.7 × 10 ¹⁰ Ω · cm. Next, two ITO
A 250 μm-thick polyester film having an opening of 1 cm □ is sandwiched between the substrates with electrodes to form a space. The dispersion liquid was enclosed in the space. When -200 V was applied to the upper ITO electrode, the titanium oxide particles were immediately electrodeposited on the upper electrode and appeared white when viewed from the upper substrate surface. Next, when +200 V was applied to the upper electrode, the titanium oxide particles moved to the lower electrode, and when viewed from the upper substrate side, the colored state due to the color of the indigo derivative was clearly seen.

(Example 13) [Image display medium] 5 parts of the diketopyrrolopyrrole derivative obtained in Example 5 and 5 parts of titanium oxide were added to 95 parts of isoparaffinic hydrocarbon (Isopar H manufactured by Exxon Chemical Co.), and the mixture was mixed with a ball mill. Dispersion was performed to prepare a dispersion liquid. In addition, the dispersion medium obtained by adding 5 parts of the diketopyrrolopyrrole derivative obtained in Example 5 to 95 parts of the above isoparaffin hydrocarbon is 20 ° C.
Was determined from AC impedance measuring volume resistivity at, was ^{1.4 × 10 1 0 Ω · cm} . Then 2
An opening of 1 cm □ was provided between two ITO electrode substrates 2
A space is created by sandwiching a 50 μm thick polyester film.
The dispersion liquid was enclosed in the space. On the upper ITO electrode
When 200 V was applied, the titanium oxide particles were immediately electrodeposited on the upper electrode and appeared white when viewed from the upper substrate surface. Next, when +200 V was applied to the upper electrode, the titanium oxide particles moved to the lower electrode, and when viewed from the upper substrate side, a colored state due to the color of the diketopyrrolopyrrole derivative was clearly seen.

(Example 14) [Image display medium] Dimethyl silicone oil (SH200 1cs, Toray Dow Corning Silicone Co., Ltd.) 9
To 4 parts, 5 parts of the diketopyrrolopyrrole derivative obtained in Example 6, 1 part of ethyl laurate and 5 parts of titanium oxide were added and dispersed by a ball mill to prepare a dispersion liquid. The volume resistivity at 20 ° C. of a dispersion medium prepared by adding 5 parts of the diketopyrrolopyrrole derivative obtained in Example 6 and 1 part of ethyl laurate to 94 parts of the above-mentioned silicone oil was determined by AC impedance measurement. It was 0.2 × 10 ¹⁰ Ω · cm. Next, a space is created by sandwiching a 250 μm-thick polyester film having a 1 cm □ opening between two ITO electrode-attached substrates. The dispersion liquid was enclosed in the space. Upper part I
When -200 V was applied to the TO electrode, the titanium oxide particles were immediately electrodeposited on the upper electrode and looked white when viewed from the upper substrate surface. Next, when +200 V was applied to the upper electrode, the titanium oxide particles moved to the lower electrode, and when viewed from the upper substrate side, a colored state due to the color of the diketopyrrolopyrrole derivative was clearly seen.

(Example 15) [Image display medium] 5 parts of the isoindolinone derivative obtained in Example 7 and 5 parts of titanium oxide were added to 95 parts of isoparaffinic hydrocarbon (Isopar H manufactured by Exxon Chemical Co.) and dispersed by a ball mill. To prepare a dispersion liquid. The volume resistivity at 20 ° C. of the dispersion medium obtained by adding 5 parts of the isoindolinone derivative obtained in Example 7 to 95 parts of the above isoparaffin hydrocarbon was 9.1 × 10 ^{10 as} determined by AC impedance measurement. It was Ω · cm. Then two I
250μ with 1cm □ opening between the substrates with TO electrodes
Create a space by sandwiching m thick polyester film. The dispersion liquid was enclosed in the space. -200 for the upper ITO electrode
When V was applied, the titanium oxide particles were immediately electrodeposited on the upper electrode and appeared white when viewed from the upper substrate surface. Next, when +200 V was applied to the upper electrode, the titanium oxide particles moved to the lower electrode, and when viewed from the upper substrate side, a colored state due to the color of the isoindolinone derivative was clearly seen.

Example 16 [Image display medium] Dimethyl silicone oil (SH200 1cs, Toray Dow Corning Silicone Co., Ltd.) 9
4 parts of the isoindolinone derivative 5 obtained in Example 8
Part, ethyl laurate 1 part and titanium oxide 5 parts were added and dispersed by a ball mill to prepare a dispersion liquid. The volume resistivity at 20 ° C. of a dispersion medium obtained by adding 5 parts of the isoindolinone derivative obtained in Example 8 and 1 part of ethyl laurate to 94 parts of the above-mentioned silicone oil was determined by AC impedance measurement. It was 5 × 10 ¹⁰ Ω · cm.
Next, a space is created by sandwiching a 250 μm-thick polyester film having a 1 cm □ opening between two ITO electrode-attached substrates. The dispersion liquid was enclosed in the space. When -200 V was applied to the upper ITO electrode, the titanium oxide particles were immediately electrodeposited on the upper electrode and appeared white when viewed from the upper substrate surface. Next, when +200 V was applied to the upper electrode, the titanium oxide particles moved to the lower electrode, and when viewed from the upper substrate side, a colored state due to the color of the isoindolinone derivative was clearly seen.

[0072]

As is apparent from the detailed and specific description above, according to the present invention as defined in claim 1, a nonpolar solvent is obtained by modifying the carbonyl group of quinacridone with a group containing dimethylpolysiloxane. Because the affinity of
A dye capable of coloring a non-polar solvent can be obtained. Further, according to the invention of claim 2, since the affinity with a nonpolar solvent is increased by modifying the carbonyl group of indigo with a group containing dimethylpolysiloxane, a dye capable of coloring the nonpolar solvent is obtained. be able to. Further, claim 3
According to the invention described, the diketopyrrolopyrrole> NH
Since the affinity with a nonpolar solvent is increased by modifying the group with a group containing dimethylpolysiloxane, a dye capable of coloring the nonpolar solvent can be obtained. Further, according to the invention of claim 4, the affinity with a nonpolar solvent is increased by modifying the> NH group of the isoindolinone pigment with a group containing dimethylpolysiloxane. Therefore, the nonpolar solvent is colored. Possible dyes can be obtained. According to the present invention of claim 5, a dispersion medium having a low light transmittance can be obtained by adding a compound having a high coloring ability to the non-polar solvent to the non-polar solvent, so that an electrophoretic image display medium having a good contrast can be obtained. Can be obtained. Further, according to the present invention of claim 6, since the nonpolar solvent and the compound are compatible with each other, a colored state with good color development and high transparency can be obtained. Therefore, an electrophoretic image display medium having better contrast. Is obtained. Further, according to the present invention of claim 7, the inclusion of a polar compound compatible with the non-polar solvent in the dispersion increases the solubility of the compound in the non-polar solvent, resulting in a better contrast of electricity. An electrophoretic image display medium is obtained. According to the present invention of claim 8, since the non-polar solvent is silicone oil, it is highly safe and chemically stable, so that an image display medium having long-term reliability can be obtained. Furthermore, according to the present invention of claim 9, the volume resistivity of the dispersion medium is 1 × 10 ⁹ Ω · cm.
By the above, the insulating property between the conductive layers is increased and the electric field required for the migration of particles is effectively obtained, so that an image display medium having good responsiveness can be obtained.

[Brief description of drawings]

FIG. 1 is a sectional view schematically showing an example of an image display medium according to the present invention.

[Explanation of symbols]

1 Conductive layer 2 Conductive layer 3 White or colored particles 4 dispersion medium

Continuation of front page (51) Int.Cl. ⁷ identification code FI theme code (reference) C09B 69/10 C09B 69/10 B G02F 1/167 G02F 1/167

Claims (9)

[Claims] 1. A group represented by the following general formula (I): (However, the phenyl group may have a substituent) and a group represented by the following general formula (V): (Wherein n is a natural number and R is an alkyl group) both in the molecule, a quinacridone derivative compound. 2. A group represented by the following general formula (II): (However, the phenyl group may have a substituent) and a group represented by the following general formula (V): (However, n is a natural number and R is an alkyl group) in the molecule, an indigo derivative compound. 3. A group represented by the following general formula (III): (However, X ₁ and X ₂ each represent an aryl group) and a group represented by the following general formula (V): (Wherein n is a natural number and R is an alkyl group) both in the molecule, a diketopyrrolopyrrole derivative compound. 4. A group represented by the following general formula (IV): (However, the phenyl group may have a substituent) and a group represented by the following general formula (V): (However, n is a natural number and R is an alkyl group) in the molecule, an isoindolinone derivative compound. 5. At least white or colored particles, a non-polar solvent, between two conductive layers, at least one of which or both of which are light-transmissive, disposed at desired intervals,
An image display medium comprising a dispersion liquid containing the compound according to any one of items 1 to 4. 6. The image according to claim 5, wherein the quinacridone derivative compound, the indigo derivative compound, the diketopyrrolopyrrole derivative compound, or the isoindolinone derivative compound is compatible with a nonpolar solvent. Display medium. 7. The dispersion according to claim 5, wherein the dispersion contains a polar compound compatible with a non-polar solvent.
The image display medium according to. 8. The image display medium according to claim 5, wherein the non-polar solvent is silicone oil. 9. The volume resistivity of the dispersion medium is 1 × 10 ⁹ Ω · c.
The image display medium according to claim 5, wherein the image display medium has a length of m or more.