JP2014209137A - Colored liquid and colored composition in separate liquid state - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored liquid prepared by adding a dye as a colorant to a non-polar solvent, which is to be used for a device employing an electrowetting system or an electrofluidic system and which is excellent in separation property from a polar solvent, and to provide a colored composition in a separate liquid state using the colored liquid.SOLUTION: The colored liquid is to be used for a device employing an electrowetting system or an electrofluidic system in which a color or brightness is modulated by moving or deforming a liquid by an external electric field. The colored liquid comprises a non-polar solvent, a dye, and a resin (P) having a polar group and a siloxy group.

Description

  The present invention relates to a modulation method for moving a liquid using an external electric field, and more particularly to a coloring liquid used for an electrowetting device or an electrofluidic device, and a separate liquid coloring composition.

  A modulation method for moving a liquid using an external electric field has been studied as an image display device or an optical element such as an optical shutter, an optical pickup device, and a liquid optical lens. Typical examples of these modulation methods include an electroosmosis method, an electrophoretic method, an electrofluidic method, and an electrowetting method.

  Among them, the electrowetting method has been studied as an image display device that does not consume power because it has a high contrast ratio and a wide viewing angle and does not require a front light or a backlight. As described in Patent Documents 1 and 2, the principle is based on a concept called “electrocapillary”. By applying or not applying voltage, droplets made of colored liquid existing in non-colored liquid are enlarged or reduced. (Alternatively, a colored image is formed by enlarging or reducing droplets made of a non-colored liquid present in the colored liquid.)

Such a liquid composed of a separated liquid non-colored liquid and a colored liquid (hereinafter referred to as a separated liquid colored liquid) needs to be separated, that is, not miscible, and therefore generally a nonpolar solvent such as silicone oil, A polar solvent such as water, alcohol or ethylene glycol is used, and a colorant is added to any of them.
For example, as an example of adding a colorant in a polar solvent, Patent Document 3 discloses an ionic liquid containing a room temperature molten salt in which a cation and an anion are combined in a polar solvent, a carboxyl group, a hydroxyl group, and a carbonyl group. In addition, it is disclosed that a colored liquid to which a self-dispersing pigment having a functional group such as a sulfone group, a hydroxyl group, or a phosphoric acid group is added is used. Patent Document 4 discloses the use of a colored liquid having a specific electric conductivity and ionic radius obtained by adding a pigment or a dye to a polar solvent having a specific viscosity and surface tension.
Further, as an example of adding a colorant in a nonpolar solvent, Patent Document 5 discloses that an organic pigment and / or an inorganic pigment, a solvent soluble or solvent dispersible in a nonpolar solvent such as decane, decalin or tetralin. It is disclosed to use a polymer dispersant and a colored liquid to which an aldehyde resin or a ketone resin is added.

JP-A-10-39800 Japanese Patent Laid-Open No. 10-74055 JP 2008-203282 A WO2011 / 017446 gazette Special table 2011-510336 gazette

  An object of the present invention is a colored liquid for use in an electrowetting or electrofluidic device in which a coloring agent as a coloring agent is added to a nonpolar solvent, and is excellent in separability from a polar solvent. And a separate liquid coloring composition using the same.

  The present inventors have found that the above problem can be solved by adding a resin having a polar group and a siloxy group to a nonpolar solvent.

  That is, the present invention relates to a colored liquid used in an electrowetting method or an electrofluidic device that modulates color or brightness by moving or deforming the liquid by an external electric field. And a colored liquid containing a resin (P) having a polar group and a siloxy group.

  Moreover, this invention provides the isolation | separation liquid coloring composition containing the coloring liquid of the said description and the polar solvent which is not miscible with the said coloring liquid.

  The present invention also provides use of the above-described colored liquid as a colorant for generating an image in a light modulation type device that modulates color or brightness by moving or deforming the liquid by an external electric field. To do.

  According to the present invention, it is possible to provide a separation liquid coloring composition which is excellent in separability between a colored nonpolar solvent and a polar solvent and is useful as an electrowetting or electrofluidic device.

(Nonpolar solvent)
The nonpolar solvent used in the colored liquid of the present invention is not particularly limited as long as it is a nonpolar solvent usually used in electrowetting devices and electrofluidic devices, and known ones can be used. Specifically, for example, non-aqueous linear and / or branched or cyclic alkane having 4 to 30 carbon atoms, preferably pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, Cyclopentane, cyclohexane, cycloheptane, cyclooctane, methylcyclohexane, particularly preferably decane, tetradecane, undecane and dodecane or mixtures of these in any ratio; linear and / or branched and / or cyclic Haloalkanes having 1 to 30 carbon atoms, preferably dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorocyclohexane, and their positional isomers; aromatic compounds having 6 to 22 carbon atoms, preferably Benzene Ene, xylene, mesitylene, or a mixture of these in any ratio; or hydrogenated aromatic compounds having 10 to 22 carbon atoms, preferably tetralin, cis-decalin and trans-decalin, or any ratio thereof A mixture of cis-decalin and trans-decalin;

Aromatic compounds having 6 to 22 halogenated carbon atoms, preferably chlorobenzene, fluorobenzene, dichlorobenzene or difluorobenzene, trichlorobenzene or trifluorobenzene, chloronaphthalene or fluoronaphthalene, and their positional isomers; linear And / or branched and / or cyclic alcohols having 4 to 22 carbon atoms, preferably butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, benzyl alcohol, phenylethanol, cyclopen Butanol, cyclohexanol, cycloheptanol, or cyclooctanol, and their positional isomers; linear and / or branched and / or cyclic ethers, Preferably, diethyl ether, dipropyl ether, tert-butyl methyl ether, tert-amyl methyl ether, tert-amyl ethyl ether, dimethoxyethane, diethoxyethane, diglyme, triglyme, furan, tetrahydrofuran, tetrahydromethylfuran, dioxolane, Tetrahydrothiophene, tetrahydropyran, dioxane, methoxybenzene, methylthiobenzene, ethoxybenzene, and their positional isomers;

Linear and / or branched and / or cyclic ketones, preferably acetone, trichloroacetone, butanone, pentanone, hexanone, heptanone, octanone, nonanone, cyclopentanone, cyclohexanone, acetophenone, acetylacetone, and their positions Isomers;
Linear and / or branched and / or cyclic nitroalkanes, preferably nitromethane, nitroethane, nitrocyclohexane, and their positional isomers;
Nitroaromatic compounds having 6 to 22 carbon atoms, preferably nitrobenzene; linear and / or branched and / or cyclic amines, preferably tert-butylamine, diaminoethane, diethylamine, triethylamine, tributylamine, pyrrolidine , Piperidine, morpholine, N-methylaniline, and N, N-dimethylaniline and their positional isomers; hexamethyldisilane, diphenyldimethylsilane, chlorophenyltrimethylsilane, phenyltrimethylsilane, phenethyltris (trimethylsiloxy) silane, phenyl Tris (trimethylsiloxy) silane, polydimethylsiloxane, tetraphenyltetramethyltrisiloxane, poly (3,3,3-trifluoropropylmethylsiloxane), 3,5,5 -Triphenylnonamethylpentasiloxane, 3,5-diphenyloctamethyltetrasiloxane, 1,1,5,5-tetraphenyl-1,3,3,5-tetramethyl-trisiloxane, hexamethylcyclotrisiloxane, etc. Silicone oil of hydrofluoroether, chlorodifluoromethane, 1,1,1,2-tetrafluoroethane, pentafluoroethane, difluoromethane, trifluoromethane, 1,1,1,2,3,3,3-heptafluoro Propane, 1,1-difluoroethane, 1,1,1,3,3,3-hexafluoropropane, octafluoropropane, or mixtures of any of the above solvents are included.
Among these, decane, dodecane, tetradecane, decalin, tetralin, polydimethylsiloxane, a mixture thereof, or a substance containing these substances as a main component is particularly preferable.

(Dye)
Examples of the coloring matter used in the present invention include pigments and dyes. In the present invention, it is preferable to use a pigment from the viewpoint of weather resistance and the like. As the pigment, known and commonly used organic pigments or inorganic pigments can be used. Moreover, the pigment | dye formed by coat | covering the said pigment with resin can also be used.

  Examples of organic pigments include perylene / perinone compound pigments, quinacridone compound pigments, phthalocyanine compound pigments, anthraquinone compound pigments, phthalone compound pigments, dioxazine compound pigments, isoindolinone compound pigments, and isoindoline compounds. Examples thereof include pigments, diketopyrrolopyrrole compound pigments, insoluble azo compound pigments, soluble azo compound pigments, condensed azo compound pigments, and aniline black pigments. Specific examples of the organic pigment are as follows, for example.

Examples of perylene / perinone compound pigments include C.I. I. PigmentViolet 29, C.I. I. Pigment Red 123, 149, 178, 179, C.I. I. Pigment Black 31, 32, C.I. I. Pigment Orange 43 and the like.
Examples of quinacridone compound pigments include C.I. I. Pigment Violet 19, 42, C.I. I. Pigment Red 122, 202, 206, 207, 209, C.I. I. Pigment Orange 48, 49 and the like.
Examples of the phthalocyanine compound pigment include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, C.I. I. Pigment Green 7, 36 and the like.
Examples of the anthraquinone compound pigment include C.I. I. Pigment Blue 60, C.I. I. Pigment Yellow 24, 108, C.I. I. Pigment Red 168, 177, C.I. I. Pigment Orange 40 and the like.
Examples of the phthalone compound pigment include C.I. I. And pigments such as Pigment Yellow 138.
Examples of the dioxazine compound pigment include C.I. I. Pigment Violet 23, 37, and the like.
Examples of isoindolinone compound pigments include C.I. I. Pigment Yellow 109, 110, 173, C.I. I. Pigment Orange 61 and the like.
Examples of isoindoline-based compound pigments include C.I. I. Pigment Yellow 139, 185, C.I. I. Pigment Orange 66, C.I. I. Pigment Brown 38 and the like.
Examples of the diketopyrrolopyrrole compound pigment include C.I. I. Pigment Red 254, 255 and the like.

Examples of insoluble azo compound pigments include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 17, 55, 73, 74, 81, 83, 97, 130, 151, 152, 154, 156, 165, 166, 167, 170, 171, 172, 174, 175, 176, 180, 181, 188, C.I. I. Pigment Orange 16, 36, 60, C.I. I. Pigment Red5, 22, 22, 31, 112, 146, 150, 171, 175, 176, 183, 185, 208, 213, C.I. I. PigmentViolet 43, 44, C.I. I. Pigment Blue 25, 26 and the like.
Examples of the soluble azo compound pigment include C.I. I. Pigment Red 53: 1, 57: 1, 48 and the like.
Examples of the condensed azo compound pigment include C.I. I. Pigment Yellow 93, 94, 95, 128, 166, C.I. I. Pigment Orange 31C. I. Pigment Red 144, 166, 214, 220, 221, 242, 248, 262, C.I. I. Pigment Brown 41, 42 and the like.
Examples of the aniline black pigment include C.I. I. Pigment Black 1.

  Examples of inorganic pigments include titanium oxide, zinc sulfide, lead white, zinc white, lithbon, antimony white, basic lead sulfate, basic lead silicate, barium sulfate, calcium carbonate, gypsum, silica, carbon black, iron black. , Titanium black, cobalt violet, vermillion, molybdenum orange, red lead, bengara, chrome lead, cadmium yellow, zinc chromate, yellow ocher, chromium oxide, ultramarine, bitumen, cobalt blue and the like.

  In the present invention, when the device is to be displayed in black and white, carbon black or titanium black is used as a pigment.

  Examples of the dye include C.I. I. Acid Black 1, 2, 7, 16, 17, 24, 26, 28, 31, 41, 48, 52, 58, 60, 63, 94, 107, 109, 112, 118, 119, 121, 122, 131, 155, 156; C.I. I. Acid Yellow 1, 3, 4, 7, 11, 12, 13, 14, 17, 18, 19, 23, 25, 29, 34, 38, 40, 41, 42, 42, 76, 78, 79, 99, 111, 114, 116, 122, 135, 142, 161, 172; I. Acid Orange 7, 8, 10, 19, 20, 24, 28, 33, 41, 45, 51, 56, 64; C.I. I. Acid Red 1, 4, 6, 8, 13, 14, 15, 18, 19, 21, 26, 27, 30, 32, 34, 35, 37, 40, 42, 44, 51, 52, 54, 57, 80, 82, 83, 85, 87, 88, 89, 92, 94, 97, 106, 108, 110, 111, 114, 115, 119, 129, 131, 133, 134, 135, 143, 143: 1, 144, 152, 154, 155, 172, 176, 180, 184, 186, 187, 249, 254, 256, 289, 317, 318; I. Acid Violet 7, 11, 15, 34, 35, 41, 43, 49, 51, 75; C.I. I. Acid Blue 1, 7, 9, 15, 22, 23, 25, 27, 29, 40, 41, 43, 45, 49, 51, 53, 55, 56, 59, 62, 78, 80, 81, 83, 90, 92, 93, 102, 104, 111, 113, 117, 120, 124, 126, 138, 145, 167, 171, 175, 183, 229, 234, 236, 249; I. Acid Green 3, 9, 12, 16, 19, 20, 25, 27, 41, 44; C.I. I. Acid dyes such as Acid Brown 4 and 14,

C. I. Basic Black 2.8; C.I. I. Basic yellow 1, 2, 11, 12, 14, 21, 32, 36; I. B. Basic Orange 2, 15, 21, 22; C.I. I. Basic Red 1, 2, 9, 12, 13, 37; I. B. Basic violet 1, 3, 7, 10, 14; I. Basic blue 1, 3, 5, 7, 9, 24, 25, 26, 28, 29; I. Basic green 1, 4; basic dyes such as basic brown 1 and 12,

C. I. Direct Black 2, 4, 9, 11, 14, 17, 19, 22, 27, 32, 36, 38, 41, 48, 49, 51, 56, 62, 71, 74, 75, 77, 78, 80, 105, 106, 107, 108, 112, 113, 117, 132, 146, 154, 168, 171, 194; C. Direct Yellow 1, 2, 4, 8, 11, 12, 24, 26, 27, 28, 33, 34, 39, 41, 42, 44, 50, 51, 58, 72, 85, 86, 87, 88, 98, 100, 110, 127, 135, 141, 142, 144; C.I. I. Direct orange 6, 8, 10, 26, 29, 41, 49, 52, 102; C.I. I. Direct Red 1, 2, 4, 8, 9, 11, 13, 15, 17, 20, 23, 24, 28, 31, 33, 37, 39, 44, 46, 47, 48, 51, 59, 62, 63, 73, 75, 77, 80, 81, 83, 84, 85, 87, 89, 90, 94, 95, 99, 101, 108, 110, 145, 189, 197, 220, 224, 225, 226, 227, 230, 250, 254, 256, 257; I. Direct violet 1, 7, 9, 12, 35, 48, 51, 90, 94; I. Direct Blue 1, 2, 6, 8, 15, 22, 25, 34, 69, 70, 71, 72, 75, 76, 78, 80, 81, 82, 83, 86, 90, 98, 106, 110, 110, 120, 123, 158, 163, 165, 192, 193, 194, 195, 196, 199, 200, 201, 202, 203, 207, 218, 236, 237, 239, 246, 258, 287; Direct Green 1, 6, 8, 28, 33, 37, 63, 64; C.I. I. Direct dyes such as direct brown 1A, 2, 6, 25, 27, 44, 58, 95, 10, 101, 106, 112, 173, 194, 195, 209, 210, 211,

C. I. Reactive black 1, 3, 5, 6, 8, 12, 14; I. Reactive yellow 1, 2, 3, 13, 14, 15, 17; I. Reactive Blue 2, 5, 7, 16, 20, 24; Reactable Red 6, 7, 11, 12, 15, 17, 21, 23, 24, 35, 36, 42, 63, 66, 84, 184; C . I. Reactive violet 2, 4, 5, 8, 9; I. Reactive Blue 2, 5, 7, 12, 13, 14, 15, 17, 18, 19, 20, 21, 25, 27, 28, 37, 38, 40, 41; C.I. I. Reactive dyes 5, 7; reactive dyes such as Reacteve Brown 1, 7, 16, etc.

C. I. Food black 1, 2; C.I. I. Food yellow 3, 4, 5; C.I. I. Food Red 2, 3, 7, 9, 14, 52, 87, 92, 94, 102, 104, 105, 106; C.I. I. Food violet 2; C.I. I. Food Blue 1, 2; I. Examples include food dyes such as Food Green 2 and 3.

(Dye: blending amount)
The amount of the dye added to the nonpolar solvent is preferably in the range of 1 to 50% by weight, more preferably in the range of 2 to 10% by weight.

(Resin having a polar group and a siloxy group (P))
The resin (P) having a polar group and a siloxy group used in the present invention can be used without any problem as long as it is a resin having a polar group and a siloxy group (Si—O—).

  For example, (1) A commercially available dimethyl silicone (polydimethylsiloxane, etc.), methylhydrogen silicone, methylphenyl silicone (tetraphenyltetramethyltrisiloxane, etc.), etc. Reactive such as epoxy groups, cycloaliphatic epoxy groups, methacryl groups, mercapto groups, carboxyl groups, hydroxy groups (including polyether groups terminated by hydroxy groups, carbinol groups, phenol groups, silanol groups, etc.) Examples thereof include reactive silicone oil into which a polar group has been introduced. Examples of commercially available products include reactive modified silicone oils manufactured by Shin-Etsu Chemical Co., Ltd.

  (2) Reactive silicone oil in which a reactive polar group is introduced into the side chain or terminal of the straight silicone oil of (1), various compounds having a group capable of reacting with the reactive polar group, Examples thereof include modified silicone oils obtained by reacting various polymers. Specifically, for example, the modified silicone oil as described in (1) above is reacted with (i) a polyurethane having an isocyanate group at the terminal, (ii) the polyester having a hydroxy group at the terminal is reacted, Alternatively, (iii) (meth) acrylate (meth) acrylate having various reactive groups such as (meth) acrylic acid, glycidyl (meth) acrylate, methacryloyloxyethyl isocyanate and the like is subjected to radical copolymerization reaction with a general-purpose radical reactive monomer (meth) It can be obtained by reacting with an acrylic copolymer pendant with an acryloyl group, a glycidyl group or an isocyanato group.

,
Moreover, it is good also as a copolymer which copolymerized the monomer which has a siloxy group. For example, (3) a (meth) acryloyl group obtained by reacting (meth) acrylic acid with a reactive silicone oil in which a reactive polar group is introduced at the side chain or terminal of the straight silicone oil of (1). And an acrylic copolymer having a polar group and a siloxy group, which is obtained by radical copolymerization reaction of a silicone oil having a general-purpose radical-reactive monomer.

  Further, for example, (4) a vinyl monomer containing a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon bond and a general-purpose radical reactive monomer are subjected to a radical copolymerization reaction to obtain an acrylic copolymer. An acrylic copolymer having a polar group and a siloxy group obtained by mixing the silanol group and / or hydrolyzable silyl group with a general-purpose silane compound as necessary and subjecting it to a hydrolytic condensation reaction.

  Specific examples of the vinyl monomer containing a silanol group and / or hydrolyzable silyl group used in the above (4) include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinyltri ( 2-methoxyethoxy) silane, vinyltriacetoxysilane, vinyltrichlorosilane, 2-trimethoxysilylethyl vinyl ether, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (Meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrichlorosilane and the like can be mentioned. Among these, vinyltrimethoxysilane and 3- (meth) acryloyloxypropyltrimethoxysilane are preferable because the hydrolysis reaction can easily proceed and by-products after the reaction can be easily removed.

  Examples of the general-purpose silane compound used in the above (4) include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, and iso-butyl. Various organotrialkoxysilanes such as trimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane, diphenyldimethoxy Various diorganodialkoxysilanes such as silane, methylcyclohexyldimethoxysilane or methylphenyldimethoxysilane; methyltrichlorosilane, ethyltrichlorosilane Emissions, phenyl trichlorosilane, vinyl trichlorosilane, dimethyl dichlorosilane, chlorosilane such as diethyl dichlorosilane or diphenyl dichlorosilane and the like. Of these, organotrialkoxysilanes and diorganodialkoxysilanes that can easily undergo a hydrolysis reaction and easily remove by-products after the reaction are preferable.

  Moreover, there is no limitation in particular as said general purpose radical reactive monomer used by said (2)-(4), It is possible to use a well-known monomer. Vinyl monomers can also be copolymerized. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate; aralkyl (meth) acrylates such as benzyl (meth) acrylate and 2-phenylethyl (meth) acrylate; cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; 2-methoxy Ω-alkoxyalkyl (meth) acrylates such as ethyl (meth) acrylate and 4-methoxybutyl (meth) acrylate; dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate Rate,

Aromatic vinyl monomers such as styrene, p-tert-butylstyrene, α-methylstyrene and vinyltoluene; vinyl acetates such as vinyl acetate, vinyl propionate, vinyl pivalate and vinyl benzoate; methyl crotonate Alkyl esters of crotonic acid such as ethyl crotonate; dialkyl esters of unsaturated dibasic acids such as dimethyl malate, di-n-butyl malate, dimethyl fumarate and dimethyl itaconate; α-olefins such as ethylene and propylene Fluoroolefins such as vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene and chlorotrifluoroethylene; alkyl vinyl ethers such as ethyl vinyl ether and n-butyl vinyl ether; cyclopentyl vinyl ether, cyclo Cycloalkyl vinyl ethers such as hexyl vinyl ether; tertiary amide group-containing monomers such as N, N-dimethyl (meth) acrylamide, N- (meth) acryloylmorpholine, N- (meth) acryloylpyrrolidine, N-vinylpyrrolidone, etc. Can be mentioned.

  Further, the radical copolymerization reaction method in (2) to (4) is not particularly limited to a solvent or a polymerization initiator, and the vinyl polymer segment (a2) can be obtained by a known method. . For example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-) can be obtained by various polymerization methods such as bulk radical polymerization, solution radical polymerization, and non-aqueous dispersion radical polymerization. Dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), tert-butylperoxypivalate, tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, di- It can be obtained using a polymerization initiator such as tert-butyl peroxide, cumene hydroperoxide, or diisopropyl peroxycarbonate.

  In addition, in the hydrolysis condensation reaction in (4), a part of the hydrolyzable group is hydrolyzed under the influence of water or the like to form a hydroxyl group, and then between the hydroxyl groups or between the hydroxyl group and the hydrolyzable group. It refers to a condensation reaction that proceeds. The hydrolysis-condensation reaction can be performed by a known method, but a method in which the reaction is advanced by supplying water and a catalyst in the production process is simple and preferable. Examples of the catalyst used include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate and acetic acid; inorganic bases such as sodium hydroxide and potassium hydroxide; tetraisopropyl titanate , Titanates such as tetrabutyl titanate; 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), 1 Compounds containing various basic nitrogen atoms, such as 1,4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine, dimethylbenzylamine, monoethanolamine, imidazole, 1-methylimidazole; Tetramethylammonium salt, tetrabutylammonium salt, dilauryldimethylammonium Quaternary ammonium salts having chloride, bromide, carboxylate or hydroxide as a counter anion; dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetylacetate Examples thereof include tin carboxylates such as narate, tin octylate and tin stearate. A catalyst may be used independently and may be used together 2 or more types.

  The amount of the catalyst to be added is not particularly limited, but generally it is preferably used in the range of 0.0001 to 10% by weight with respect to the total amount of each compound having the silanol group or hydrolyzable silyl group. , More preferably in the range of 0.0005 to 3% by weight, and particularly preferably in the range of 0.001 to 1% by weight.

The amount of water to be supplied is preferably 0.05 mol or more with respect to 1 mol of the silanol group or hydrolyzable silyl group of each compound having the silanol group or hydrolyzable silyl group, The above is more preferable, and particularly preferably 0.5 mol or more.
These catalyst and water may be supplied collectively or sequentially, or may be supplied by previously mixing the catalyst and water. The reaction temperature at this time is suitably in the range of 0 ° C to 150 ° C, and preferably in the range of 20 ° C to 100 ° C. The reaction can be carried out under any conditions of normal pressure, increased pressure, or reduced pressure. Moreover, you may remove the alcohol and water which are the by-products which can be produced | generated in the said hydrolysis-condensation reaction by methods, such as distillation, as needed.

  The polar group preferably has an amino group, a carboxyl group, an epoxy group, a mercapto group, a carbinol group, a hydroxyl group and the like from the viewpoint of the affinity of the pigment. Of these, an amino group, a carboxyl group, a mercapto group, and a hydroxyl group are preferable, and an amino group is more preferable.

  Among the above-mentioned resins (P) having a polar group and a siloxy group, an acrylic copolymer having a siloxy group is preferable because it is well-familiar with the pigment and easy molecular design according to the pigment to be used. Among them, an acrylic copolymer having a siloxy group and having a dialkylamino group, and an acrylic copolymer having a siloxy group and having a benzene ring or an aromatic group are preferable.

  The molecular weight of the resin having a polar group and a siloxy group is preferably in the range of 1000 to 70000, more preferably in the range of 3000 to 40000, in terms of weight average molecular weight.

  Although the addition amount of the resin (P) having the polar group and the siloxy group with respect to the dye varies depending on the dye, it is preferable to increase the addition amount as the dye has a smaller average particle diameter. Specifically, the range of 10 to 200% by mass with respect to the pigment is preferable, and the range of 30 to 150% by mass is particularly preferable. If the amount used is too small, sufficient stability of the dye may not be obtained, whereas if it is too large, aggregation of the dyes may occur.

(Living anion polymerized resin (PL))
The resin (P) having a polar group and a siloxy group was obtained by subjecting a polymerizable monomer containing a polymerizable monomer (A) having a siloxy group to living anion polymerization in the presence of a polymerization initiator (C). It is preferable to contain resin (PL).
Although there are various living anion methods, in the present invention, it is preferable to use a microreactor having a flow channel capable of mixing a plurality of liquids. Specifically, the first polymerizable monomer and the polymerization initiator (C) are introduced into the flow path in the microreactor and subjected to living anion polymerization to form an intermediate polymer, and the intermediate A polymer and a second polymerizable monomer are introduced into the microreactor, and in the microreactor, the polymerizable monomer having the siloxy group at the growth terminal of the intermediate polymer is subjected to living anion polymerization, And a second step of forming a block copolymer. In order to obtain the resin (P) used in the present invention, as at least one of the first polymerizable monomer and the second polymerizable monomer, a polymerizable monomer having a siloxy group (A ). Specific embodiments will be described in detail below.

(Method for producing living anion polymerized resin (PL))
The method for producing a resin (PL) obtained by living anion polymerization of a polymerizable monomer containing a polymer (A) having a siloxy group used in the present invention in the presence of a polymerization initiator (C) includes the following: There are two aspects.

  In the first aspect, a microreactor including a flow channel capable of mixing a plurality of liquids is used, and a polymerizable monomer containing a polymerizable monomer (A) having a siloxy group and a polymerization initiator (C Is introduced into the flow path in the microreactor and is subjected to living anionic polymerization to obtain a polymer. In this first embodiment, the polymerizable monomer (A) having a siloxy group alone or the polymerizable monomer having a siloxy group (A ) And other polymerizable monomer (B) other than the polymerizable monomer (A) having a siloxy group may be used in combination.

On the other hand, the second embodiment uses a microreactor having a flow path capable of mixing a plurality of liquids, and transfers the first polymerizable monomer and the polymerization initiator (C) to the flow path in the microreactor. Introducing the living anion polymerization to form an intermediate polymer, introducing the intermediate polymer and the second polymerizable monomer into the microreactor, and in the microreactor, the intermediate polymer A second step of forming a block copolymer by subjecting the polymerizable monomer having a siloxy group to living anion polymerization at a growth terminal of the polymer to form a block copolymer, and the first polymerizable monomer and the second In this method, a polymer is obtained by containing a polymerizable monomer (A) having a siloxy group in at least one of the polymerizable monomers.
That is, it is sufficient that the polymerizable monomer used in the first step and the polymerizable monomer used in the second step contain the polymerizable monomer (A) having a siloxy group. As the polymerizable monomer to be used, other polymerizable monomers (B) other than the polymerizable monomer (A) having a siloxy group described later can be used.

  Examples of the siloxy group that the polymerizable monomer (A) has include a dialkylsiloxy group, a diphenylsiloxy group, a trialkylsiloxy group, a triphenylsiloxy group, and the like. Specific examples of the dialkylsiloxy group and the trialkylsiloxy group Examples include dimethylsiloxy group and trimethylsiloxy group. The siloxy group also includes a polydimethylsiloxane chain that is a polydialkylsiloxane chain in which a dialkylsiloxy group such as a dimethylsiloxy group is repeated.

  Specific examples of the polymerizable monomer (A) include compounds represented by the following general formula (1) having a trialkylsiloxy group or a triphenylsiloxy group, a dialkylsiloxy group or a diphenylsiloxy group. Examples thereof include a compound represented by the following general formula (2) having a repeated dialkylsiloxane chain or diphenylsiloxane chain.

(In the formulas (1) and (2), R ¹ represents an alkyl group having 1 to 4 carbon atoms or phenyl, R ² represents a hydrogen atom or methyl group, and R ³ represents a hydrogen atom or 1 to 1 carbon atoms. And m and n represent the number of repeating units, m is in the range of 1 to 1000 on average, and n is an integer of 1 to 3).

  Examples of commercially available 3-tris (trimethylsiloxy) silylpropyl methacrylate corresponding to the above general formula (1) include “Silaplane TM-0701” and “Silaplane TM-0701T” manufactured by JNC Corporation. Moreover, as a commercial item of the compound which has a dimethylsiloxane chain corresponding to the said General formula (2), "Silaplane FM-0711", "Silaplane FM-0721", and "Silaplane FM-0725" by JNC Corporation are available. "X-222-2404", "X-22-8201", "X-22-174DX", "X-22-2426" manufactured by Shin-Etsu Chemical Co., Ltd. and the like.

  On the other hand, as other polymerizable monomer (B) other than the polymerizable monomer having a siloxy group, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate, t-butyl (meth) acrylate, isopropyl (meth) acrylate, and isobutyl (meth) acrylate; aromatic (meth) acrylates such as benzyl (meth) acrylate; glycidyl (Meth) acrylate having an epoxy group such as (meth) acrylate; (meth) acrylate having an alkylamino group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate; Meta) Acrylamide compounds such as rilamide, N, N-dimethylacrylamide, N-methylol (meth) acrylamide, isopropylacrylamide and diacetone acrylamide; vinylpyridine compounds such as 2-vinylpyridine, 4-vinylpyridine and naphthylvinylpyridine; methoxypolyethylene glycol Alkyl polyalkylene glycol mono (meth) acrylates such as mono (meth) acrylate and methoxypolypropylene glycol mono (meth) acrylate; Fluorine (meth) acrylates such as perfluoroalkylethyl (meth) acrylate; Styrene and styrene derivatives (p- Dimethylsilyl styrene, (p-vinylphenyl) methyl sulfide, p-hexynyl styrene, p-methoxy styrene, p-tert-butyl Aromatic vinyl compounds such as methylsiloxystyrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, α-methylstyrene), vinylnaphthalene, vinylanthracene, 1,1-diphenylethylene; methyl (meta ) Acrylate, ethyl (meth) acrylate, t-butyl methacrylate, n-butyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, epoxy (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylene glycol tetra (meth) acrylate, 2-hydroxy-1,3-diaacryloxypropane, 2,2-bis [ -(Acryloxymethoxy) phenyl] propane, 2,2-bis [4- (acryloxyethoxy) phenyl] propane, dicyclopentenyl (meth) acrylate tricyclodecanyl (meth) acrylate, tris (acryloxyethyl) isocyanate (Meth) acrylate compounds such as nurate and urethane (meth) acrylate; 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1 Conjugated dienes such as 1,3-hexadiene and 1,3-cyclohexadiene. These other polymerizable monomers can be used alone or in combination of two or more.

  Further, the alkyl group in the perfluoroalkylethyl methacrylate is not particularly limited, and specific examples of perfluoroalkylethyl methacrylate include 2- (perfluorobutyl) ethyl methacrylate and 2- (perfluorohexyl) ethyl. Methacrylate, 2- (perfluorooctyl) ethyl methacrylate and the like.

  In the present invention, “(meth) acrylate” refers to one or both of methacrylate and acrylate.

  In the method for producing a polymer according to the first aspect, the polymerizable monomer (A) having a siloxy group is used by using only the polymerizable monomer (A) having a siloxy group as a raw material of the polymer. Is obtained. In addition to the polymerizable monomer (A) having a siloxy group, the polymerizable monomer (B) is also used in combination with the polymerizable monomer (A) having the siloxy group and the polymerizable monomer. A random copolymer with the body (B) is obtained.

  On the other hand, in the method for producing a polymer according to the second embodiment, a block polymerizable copolymer is obtained by using a single polymerizable monomer for each of the first polymerizable monomer and the second polymerizable monomer. A polymer can be produced. For example, as the first polymerizable monomer, only one type of the polymerizable monomer (B) is used, and as the second polymerizable monomer, a polymerizable monomer having a siloxy group ( By using only A), an AB type block copolymer can be produced.

  In the method for producing a polymer according to the second aspect, a plurality of types of polymerizable monomers are used as the first polymerizable monomer and the second polymerizable monomer. A copolymer having a plurality of different polymer blocks can be obtained.

  In the method for producing a polymer according to the second aspect, in addition to the polymerization reaction in the first step and the polymerization reaction in the second step, the intermediate polymer obtained in the second step, and the first step And a polymerizable monomer of a different type from the polymerizable monomer used in the second step is introduced into the microreactor, and the third polymerizable property is added to the growth terminal of the intermediate polymer obtained in the second step. A ternary block copolymer may be formed by performing a third step of forming a block copolymer by subjecting the monomer to living anion polymerization.

  In the living anion polymerization in the first and second aspects, in addition to the polymerizable monomer and the polymerization initiator, lithium chloride, lithium perchlorate, N, N, N ′, N ′ -The presence of one or more additives selected from the group consisting of tetramethylethylenediamine and pyridine makes it possible to perform living anionic polymerization, which usually needs to be performed at a low temperature, in a temperature range that can be industrially produced. Here, these additives are polymerization initiators for ester bonds existing in the structure of the polymerizable monomer used in the first aspect or the second aspect or the structure of the polymer obtained by the polymerization reaction ( It is thought that it has a function to prevent nucleophilic reaction of anion). The amount of these additives used can be adjusted as appropriate according to the amount of the polymerization initiator. However, since the polymerization reaction rate is increased and the molecular weight of the resulting polymer can be easily controlled, the polymerization is initiated. 0.05-10 mol is preferable with respect to 1 mol of agent, and 0.1-5 mol is more preferable.

  In the second aspect, at least one of the polymerization reaction in the first step and the polymerization reaction in the second step, lithium chloride, lithium perchlorate, N, N, N ′, N′-tetra One or more additives selected from the group consisting of methylethylenediamine and pyridine can be present, but the additive is present only in the polymerization reaction in the first step and only in the polymerization reaction in the second step. Alternatively, it may be present in the polymerization reaction in both the first step and the second step.

  The polymerizable monomer, the polymerization initiator, and the additive are preferably diluted or dissolved using an organic solvent and introduced into the microreactor as a solution.

  Examples of the organic solvent include hydrocarbon solvents such as pentane, octane, cyclohexane, benzene, toluene, xylene, decalin, tetralin, and derivatives thereof; diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, 1, Examples include ether solvents such as 2-dimethoxyethane, diethylene glycol dimethyl ether and diglyme. These organic solvents can be used alone or in combination of two or more.

  As the concentration of the polymerizable monomer in the organic solvent solution, the production amount of the polymer per unit time becomes good, and the heat of the polymerization reaction can be efficiently removed. L, the same shall apply hereinafter) is preferred, a range of 0.05 to 3M is more preferred, and a range of 0.1 to 2M is particularly preferred.

  As the polymerization initiator, organic lithium can be used. For example, methyllithium, ethyllithium, propyllithium, butyllithium (n-butyllithium, sec-butyllithium, iso-butyllithium, tert-butyllithium, etc.) ), Alkyllithium such as pentyllithium and hexyllithium; alkoxyalkyllithium such as methoxymethyllithium and ethoxymethyllithium; α-methylstyryllithium; 1,1-diphenylhexyllithium and 1,1-diphenyl-3-methylpentryl Diarylalkyllithium such as lithium and 3-methyl-1,1-diphenylpentyllithium; alkenyllithium such as vinyllithium, allyllithium, propenyllithium and butenyllithium; ethynyllithium Alkynyl lithium such as butynyl lithium, pentynyl lithium and hexynyl lithium; aralkyl lithium such as benzyl lithium and phenylethyl lithium; aryl lithium such as phenyl lithium and naphthyl lithium; 2-thienyl lithium, 4-pyridyl lithium, 2- Heterocyclic lithium such as quinolyl lithium; alkyl lithium magnesium complex such as tri (n-butyl) magnesium lithium and trimethylmagnesium lithium; Among these, alkyl lithium is preferable because the polymerization reaction can be efficiently advanced, and n-butyl lithium and sec-butyl lithium are preferable among them. In addition, n-butyllithium is more preferable because it is easily available industrially and has high safety. These polymerization initiators can be used alone or in combination of two or more.

  Further, as described above, these polymerization initiators are preferably diluted or dissolved using an organic solvent and introduced into the microreactor as a solution. Examples of the organic solvent used include solubility of the polymerization initiator and Tetrahydrofuran (THF) is preferred because of its high solvation with respect to the counter cation and high polymerization rate.

  Moreover, it is preferable to introduce diphenylethylene or a derivative thereof (hereinafter abbreviated as “diphenylethylene etc.”) into the microreactor together with organic lithium which is a polymerization initiator. By using diphenylethylene or the like, it becomes a bulky polymerization initiator due to the phenyl group, so that the activity of the polymerization initiator can be weakened, so when using a (meth) acrylate monomer as a polymerizable monomer, There is an advantage that side reaction can be suppressed and living anionic polymerization can be appropriately controlled. In addition, even if diphenylethylene etc. introduce | transduce into a microreactor separately from organic lithium which is a polymerization initiator, and mix in a microreactor, it mixes with organic lithium which is a polymerization initiator beforehand, diphenylethylene etc. and organic After forming a reaction product with lithium, it may be introduced into a microreactor.

  The concentration of the polymerization initiator in the organic solvent solution is such that the polymerization reaction can proceed efficiently, and precipitation of insoluble substances during the polymerization that causes clogging of the microreactor flow path can be suppressed. The range of 001 to 1M is preferable, the range of 0.002 to 0.75M is more preferable, the range of 0.01 to 0.5M is more preferable, and the range of 0.02 to 0.2M is particularly preferable.

  Further, in the second aspect of the method for producing the resin (PL), the intermediate polymer obtained in the first step is brought into contact with the polymerizable monomer (A) having a siloxy group in the second step, and living An anionic polymerization reaction is carried out, and the intermediate polymer is preferably introduced into the microreactor in the form of a solution dissolved in an organic solvent.

  The microreactor used in the method for producing the resin (PL) is provided with a flow channel capable of mixing a plurality of liquids, but preferably has a heat transfer reaction vessel provided with a flow channel, and has a microtubule inside. What has a heat-conductive reaction container in which the flow path was formed is more preferable, and what has a heat-conductive reaction container which laminated | stacked the heat-conductive plate-shaped structure in which the several groove part was formed in the surface is especially preferable.

  The living anion polymerization reaction in the production of the resin (PL) can be carried out at a temperature of −78 ° C. or lower, which is the reaction temperature in the conventional batch method, in both the first and second aspects. It can also be performed at a temperature of −40 ° C. or higher, which is a feasible temperature, and can be performed at −28 ° C. or higher. A reaction temperature of −40 ° C. or higher is preferable because a polymer can be produced using a cooling device having a simple structure, and the production cost can be reduced. Moreover, it is preferable that the temperature is −28 ° C. or higher because a polymer can be produced using a cooling device having a simpler configuration, and the production cost can be greatly reduced.

  A micromixer is mentioned as a channel which can mix a plurality of liquids with which a microreactor used for manufacture of the resin (PL) is provided. As this micromixer, it is possible to use a commercially available micromixer, for example, a microreactor equipped with an interdigital channel structure, a single mixer manufactured by Institute, Futur, Microtechnique Mainz (IMM), and Caterpillar mixer; Microglass reactor manufactured by Microglass; Cytos manufactured by CPC Systems; YM-1 and YM-2 mixer manufactured by Yamatake Corporation; Mixing tee and tee (T-shaped connector) manufactured by Shimadzu GLC; Examples include IMT chip reactor; Toray Engineering Development Micro-High Mixer, etc., any of which can be used in the present invention.

  Furthermore, as a preferred form of the micromixer system, a process plate having a flow path for a polymer and a process plate having a flow path for a polymerization initiator are stacked one above the other, and the two fluids are combined at the flow path outlet. It is preferable to combine a mixer and a micromixer having a flow path through which the fluid after joining passes.

  The reaction channel described in the above formation method is a combination of at least two members and the space formed between the members is used as the reaction channel. It may be used as a reaction channel. The flow rate of flowing the flow path is such that the Reynolds number in the reaction vessel of the fluid containing the polymerizable monomer, the polymerization initiator, and the additive is continuously controlled at 2 to 300, so that the polymerizable monomer Further, the mixing property of the fluid containing the polymerization initiator and the additive is further enhanced by the turbulent flow effect, whereby the production can be performed more efficiently.

  Here, by controlling the movement of the fluid in the flow path with a value larger than Reynolds number 2, the mixing property of the fluid containing the polymerizable monomer, the polymerization initiator, and the additive is not remarkably deteriorated. It is preferable because it is possible to prevent the problem that the production efficiency is deteriorated without causing a reaction in a short time, and the reaction is completed without increasing the residence time. Further, it is difficult to control the Reynolds number to be over 300.

  The Reynolds number in the present invention is calculated according to the following formula (1).

Reynolds number = (D × u × ρ) / μ (1)
Here, D (inner diameter of the flow path), u (average flow velocity), ρ (fluid density), and μ (fluid viscosity).

As the reaction apparatus used in the method for producing the resin (PL), a reaction apparatus in which a flow path is installed in a heat transfer reaction vessel is preferable, and a micro-tubular flow path can be quickly controlled. This is preferable. As the microtubular channel, a channel having a void size with a channel cross-sectional area of 0.1 to 4.0 mm ² is preferable for controlling the polymerization reaction temperature. In the present invention, “cross section” means a cross section perpendicular to the flow direction in the flow path, and “cross sectional area” means the area of the cross section.

  The cross-sectional shape of the channel is a square, a rectangle including a rectangle, a polygon including a trapezoid, a parallelogram, a triangle, a pentagon, etc. (a shape with rounded corners, a high aspect ratio, ie including a slit shape) It may be a star shape, a semicircle, a circle including an ellipse, or the like. The cross-sectional shape of the channel need not be constant.

  The method for forming the reaction channel is not particularly limited, but in general, the member (X) having a plurality of grooves on the surface is laminated and bonded to the other surface (Y) on the surface having the grooves. And is formed as a space between the member (X) and the member (Y).

  The channel may further be provided with a heat exchange function. In that case, for example, a groove for flowing the temperature adjusting fluid is provided on the surface of the member (X), and another member is bonded or laminated on the surface provided with the groove for flowing the temperature adjusting fluid. What is necessary is just to fix. In general, a member (X) having a groove on the surface and a member (Y) provided with a groove for flowing a temperature-controlled fluid include a surface provided with a groove, and a surface provided with a groove of another member. A flow path may be formed by fixing the opposite surface, and a plurality of these members (X) and members (Y) may be fixed alternately.

  At this time, the groove formed on the member surface may be formed as a so-called groove lower than the peripheral portion thereof, or may be formed between the walls standing on the member surface. The method of providing the groove on the surface of the member is arbitrary, and for example, methods such as injection molding, solvent casting method, melt replica method, cutting, etching, photolithography (including energy beam lithography), and laser ablation can be used.

  The layout of the flow paths in the member may be in the form of a straight line, a branch, a comb, a curve, a spiral, a zigzag, or any other arrangement according to the purpose of use.

  The flow path is, for example, a mixing field, an extraction field, a separation field, a flow rate measurement unit, a detection unit, a liquid storage tank, a membrane separation mechanism, a connection port to the inside or outside of the device, a tangential line, a development path for chromatography or electrophoresis Further, it may be connected to a part of the valve structure (portion surrounding part), a pressurizing mechanism, a depressurizing mechanism or the like.

  The outer shape of the member need not be particularly limited, and can take a shape according to the purpose of use. The shape of the member may be, for example, a plate shape, a sheet shape (including a film shape, a ribbon shape, etc.), a coating film shape, a rod shape, a tube shape, and other complicated shapes. External dimensions such as thickness are preferably constant. The material of the member is arbitrary, and may be, for example, a polymer, glass, ceramic, metal, semiconductor, or the like.

  As described above, the reaction apparatus used in the method for producing the resin (PL) is preferably a reaction apparatus in which a flow path is installed in a heat transfer reaction vessel, and may be a tube immersed in an oil bath or a water bath. good. Furthermore, as a reaction apparatus comprising a heat transfer reaction vessel in which a channel is formed, a reaction apparatus having a structure in which a heat transfer plate-like structure having a plurality of grooves formed on the surface is laminated can be used.

  Examples of such a reaction apparatus include an apparatus in which the channel (hereinafter sometimes simply referred to as “microchannel”) is provided in a member used as a chemical reaction device.

  Hereinafter, a schematic configuration example of a microreactor provided with a flow channel in a preferable form used in the production of the resin (PL) will be described with reference to FIGS. 1 and 2.

  In the chemical reaction device 1, a plurality of first plates (2 in FIG. 1) and second plates (3 in FIG. 1) having the same rectangular plate shape in FIG. Configured. Each one first plate is provided with a flow path (4 in FIG. 1; hereinafter referred to as a reaction flow path) (hereinafter, the plate provided with the reaction flow path is referred to as a process plate). Further, the second plate is provided with a temperature control fluid channel (6 in FIG. 1; hereinafter referred to as a temperature control channel) (hereinafter, the plate provided with the temperature control channel is referred to as a temperature control plate). ). And as shown in FIG. 2, those supply ports and discharge ports are distributed and arranged in each region of the end surface 1b, 1c, side surface 1d, 1e of the device for chemical reaction 1, and in these regions, the polymerizable monomer The joint part 32 which consists of the connector 30 and the joint part 31 for flowing the fluid (alpha) containing a body, a polymerization initiator, and an additive, and the temperature control fluid (gamma) is each connected.

  Via these joints, a fluid α containing a polymerizable monomer, a polymerization initiator, and an additive is supplied from the end surface 1b, discharged to the end surface 1c as a fluid β, and a temperature-controlled fluid γ is supplied from the side surface 1e. And is discharged to the side surface 1d. The planar view shape of the device for chemical reaction 1 is not limited to the rectangular shape as shown in the figure, and may be a square shape or a rectangular shape having a longer distance between the side surfaces 1d and 1e than between the end surfaces 1b and 1c.

(Other additives)
In the colored liquid of the present invention, surfactants, dispersants, wetting agents, thickeners, preservatives, viscosity stabilizers, grinding aids, fillers, precipitation preventions are also included within the range not impairing the effects of the present invention. Additives such as an agent, a photoprotective agent, an antioxidant, a biocide, a deaerator / antifoaming agent, a foaming inhibitor, and a baking inhibitor may be added. It is desirable to keep these to such an extent that the conductivity is not increased. For example, usable surfactants include polyalkylene glycols and derivatives thereof. Examples of the dispersant include polyamide, polyester, polyacrylate, polyvinylazolidones, polystyrene, polyepoxide, polyurethane, and polyvinyl halogen.

(Method for producing colored liquid)
The colored liquid of the present invention can be obtained by a known method for producing a pigment dispersion. As an example, the pigment, the resin having a polar group and a siloxy group, a nonpolar solvent, and a mixture to which the additive is added as necessary are dispersed by using a normal disperser such as a bead mill. be able to. Moreover, after preparing a high concentration dispersion (mill base) using an ordinary dispersing machine such as a bead mill in advance, it can be adjusted by further mixing and stirring to a desired viscosity with a nonpolar solvent and diluting. The timing of addition of the additive can be selected as appropriate before or after dispersion depending on the type.

  When the pigment is a pigment, the stirring / dispersing device for dispersing the pigment includes, for example, an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a disperse mat, and SC. Various commonly known dispersers such as a mill and a nanomizer can be used.

  The relative permittivity of the colored liquid thus obtained is preferably less than 25. Moreover, the response speed in switching of light modulation can be improved when the viscosity is low. For this purpose, the viscosity of the colored liquid is preferably less than 300 mPa · s, more preferably less than 100 mPa · s at 25 ° C.

(Polar solvent)
The separated liquid coloring composition of the present invention contains the coloring liquid and a polar solvent that is immiscible with the coloring liquid.
Non-miscible polar solvents include water, glycol, alcohol, polyol, ether, ester, ketone, acetal, ketal, lactone, carbonate, lactam, urethane (carbamate), urea, pyrrolidine, pyrrolidone, sulfone, sulfoxide, amide, etc. Yes, specifically, for example, water, methanol, ethanol, isopropanol, n-propanol, 1,2-propanediol, 1,3-propanediol, ethylene glycol, triethylene glycol, tetraethylene glycol, glycerin, 1,4 -Butylene glycol, diethylene glycol, dipropylene glycol, ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 1,2-cyclohexane carbonate, glycerin carbonate Dimethyl carbonate, diethyl carbonate, acetone, acetophenone, pyridine, dimethyl malonic acid, diacetone alcohol, hydroxypropyl carbamate, β-hydroxyethyl carbamate, formamide, N-methylformamide, dimethylformamide, N-methylacetamide, dimethylacetamide, dimethyl sulfoxide , Sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, acetoacetone, cyclohexanone, ethyl acetoacetate, ethyl-L-lactic acid, pyrrole, N-methylpyrrole, N-ethylpyrrole, 4H-pyran-4-one, 1,3-dimethyl-2-imidazolidinone, morpholine, N-ethylmorpholine, N-formylmorpholine, β-propio Lactone, β-valerolactone, β-hexalactone, γ-butyrolactone, γ-valerolactone, γ-hexalactone, γ-heptalactone, γ-octalactone, γ-nonalactone, γ-decalactone, δ-valerolactone, δ -Hexalactone, delta-heptalactone, delta-octalactone, delta-nonalactone, delta-decalactone, and any combination thereof.

These polar solvents preferably exhibit a higher dielectric constant than the colored liquid. For the purpose of imparting a higher relative dielectric constant, an electrolyte such as a salt that undergoes ion dissociation in a polar solvent can be added. The ion may be a cation or an anion. Specifically, for example, pyrazoline, 2-imidazoline, pyrazole, imidazoline-2-thione, 1,2,3-thiazole, 1,2,4-thiazole, IH-tetrazole, oxazoline, 5-oxazolone, isoxazole, oxazole 2-thiazoline, isothiazole, thiazole, 1,2,3-oxadiazo, ie 1,2,4-oxadiazo, ie 1,2,5-oxadiazo, ie 1,3,4-oxadiazole, 1,3 , 4-thiadiazole, LH-pyridin-2-one, piperazine, pyrididine, 1,2,3-triazine, 1,2,4-triazine, oxazine, thiomorpholine, oxadiazine, oxathiazone, indoline, indole, carbazole, indazole, Benzimidazole, quinoxaline, Salts containing cations such as phthalazine, 1,5-naphthyridine, phenazine, benzothiazole, 2H-l 1,4-benzoxazine, phenoxazine, phenothiazine and the like can be used.
The addition amount can be appropriately selected according to a desired relative dielectric constant. For example, it can be used within a range of 10% by weight or less.

(Dye)
The polar solvent may be colored as necessary. The dye is not particularly limited as long as it is used as a colorant, and organic pigments, inorganic pigments and the like used as the above-mentioned dyes can be used.
When used as a device, it is preferable to select a dye having a color different from the color used for the nonpolar solvent. Among them, those having high color purity and color density and high transparency are preferable. Further, a liquid colored cyan (C), magenta (M), yellow (Y), green or white as necessary, and black (K) using a modified pigment using a black pigment as the colored liquid. It is possible to display a full-color image by using a colored liquid introduced into a pixel of an electrowetting device.

  In addition, the polar solvent includes a surfactant, a dispersant, a wetting agent, a thickening agent, a preservative, a viscosity stabilizer, a grinding aid, a filler, and a suspending agent as long as the effects of the present invention are not impaired. Additives such as a photoprotective agent, an antioxidant, a biocide, a deaerator / antifoaming agent, a foaming inhibitor, and a baking inhibitor may be added. For example, usable surfactants include anionic surfactants such as alkyl sulfonates, alkyl benzene sulfonates, and alkyl carboxylates, cationic surfactants such as alkyl ammonium salts and alkyl pyridinium salts, and polyalkylene glycols. And nonionic surfactants such as derivatives thereof and the like, but are not limited thereto.

(Electrowetting device)
The colored liquid of the present invention can be suitably used for an electrowetting device that moves the colored liquid using an external electric field. In particular, those using a pigment as the coloring matter are excellent in light resistance and the like. Above all, the use of the device in an image display device and the excellent separation of the colored liquid and the polar solvent that is immiscible with the colored liquid, which is the effect of the present invention, can maximize the stable driving of the device over a long period of time. preferable.
An example of an electrowetting device that can use the non-conductive colored liquid will be given. That is, a display space is provided between the layers provided with electrodes, and the display space is filled with the separated liquid coloring composition containing the colored liquid and a polar solvent that is immiscible with the colored liquid. ing.
The layer on the display side of the display space is a transparent layer through which the colored liquid can be seen, while the layer on the non-display side is a light scattering layer, and the display side space is applied when voltage is applied to the colored liquid. Further, the colored liquid is moved by an electrowetting phenomenon, or the surface area on the display side is increased for color display.

  When a light scattering molecule is blended in the polar solvent to form a light scattering fluid, the light scattering layer may not be disposed on the non-display side layer.

Specifically, an upper layer on the display side, an intermediate layer made of a light scatterer having a through hole, and a lower layer are provided, and the upper space on the display side, the intermediate layer and the lower layer are provided between the upper layer and the intermediate layer. A lower space is provided between the layers, and the lower space, the through-hole, and the upper space are used as a liquid storage section including a sealed communication channel. The liquid storage part is filled with the separated liquid coloring composition containing the colored liquid and a polar solvent that is immiscible with the colored liquid. The upper and lower spaces are provided with colored liquid passages communicating with each other through the through holes, and the colored liquid is caused to flow into and out of the display-side upper space by an electrowetting method with or without application of voltage to the colored liquid.
A colored image is displayed without transmitting light at the time of inflow, and light is transmitted at the time of outflow, and white display is performed by light scattering of the light scatterer, that is, display is performed by modulating the brightness of the passing light.

The device has a two-terminal structure in which an electrode is arranged on the upper layer and an electrode is arranged on the inner surface of the through hole, the two terminals are connected via a switch, and the switch is turned on / off to turn the display side The colored liquid is allowed to flow into the upper space to display a colored image, and the colored fluid is allowed to flow out of the upper space to switch to the white scattering screen. Alternatively, a three-terminal structure may be used instead of the two-terminal structure.
In the three-terminal structure, an upper electrode is provided on the upper surface or / and the lower surface of the upper space, a lower electrode is provided on the upper surface or / and the lower surface of the lower space, and a common electrode disposed along the inner surface of the through hole of the white scattering sheet is provided, An upper side power supply circuit and a lower side power supply circuit connected to the common electrode and the upper electrode, and connected to the common electrode and the lower electrode and provided with circuit opening / closing means, respectively. The circuit opening / closing means may be alternately opened / closed to switch the inflow / outflow of the colored liquid to / from the upper space.
With this three-terminal structure, the colored liquid flows into and out of the upper space by alternately opening and closing the upper power circuit and the lower power circuit, so that the speed of the colored liquid flowing into and out of the upper space can be increased quickly. It can be carried out.

Regardless of the configuration of the device, a dielectric layer may be disposed on the side of the electrode that contacts the colored liquid. The dielectric layer preferably contains, for example, parylene or alumina oxide, and the layer thickness is preferably about 1 to 0.1 μm.
In addition, when a water repellent film that becomes a hydrophilic layer is laminated on the surface of the dielectric layer and the water repellent film is in contact with the colored liquid, the colored liquid can be moved at high speed or the surface area can be increased or decreased. It can be suitable as a moving image display.

  The device divides the display space for each pixel by a partition wall, and the colored liquid used for each pixel is a colored liquid of R, G, or B or a liquid of C, M, Y, or K. The color liquid is introduced into the display space and spreads to display a full-color image, and the color liquid is moved at a high speed to display a full-color moving image.

  The device may be configured to form a color filter of any one of R, G, B or C, M, Y, K before and after light passes through the display space, and further perform light modulation. it can.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited to the following Example at all. In the following examples, g and% are in terms of mass.

<Micromixer used in Examples>
The microreactor used in the examples includes a micromixer made of a T-shaped pipe joint and a tube reactor connected downstream of the micromixer. As the micromixer, a special order product manufactured by Sanko Seiki Kogyo Co., Ltd. was used (it is possible to request the manufacture based on the description in the Examples and obtain an equivalent product). Note that the micromixer used in this example has a part of the first introduction path, the second introduction path, and the flow path in which these are merged, and any of them is included in the micromixer. The inner diameter is the same. Therefore, hereinafter, these inner diameters are collectively referred to as “the inner diameter of the micromixer”.

[Method for measuring number average molecular weight and weight average molecular weight]
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymers obtained in the examples were measured by gel permeation chromatography (GPC) method under the following conditions.

Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%)
Standard sample: A calibration curve was prepared using the following standard polystyrene.

(Standard polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation

[Measurement method of residual monomer amount]
The polymer solutions obtained in Examples and Comparative Examples were measured under the following conditions using gas chromatography (“GC-2014F type” manufactured by Shimadzu Corporation) to determine the amount of residual monomers.
Column: Wide bore capillary column manufactured by Shimadzu Corporation Detector: FID (hydrogen flame ionization detector)
Column temperature: 70-250 ° C
Injection volume: 1 μL (tetrahydrofuran diluted solution)

(Resin Synthesis Method 1: Preparation of Resin (PL-1) Having Polar Group and Siloxy Group)
The following four types of solutions were prepared.
(1) Polymerizable monomer (0.5 M) solution having an alkylamino group In a 300 mL eggplant flask substituted with argon gas, dimethylaminoethyl methacrylate (hereinafter abbreviated as “DMAMA”) 18 using a syringe. .9 g (20.2 mL) and 219.8 mL of THF were collected and stirred to prepare 240 mL of a 0.5 M solution of DMAMA.
(2) DPhLi (0.1M) solution (polymerization initiator solution)
In a 300 mL eggplant flask replaced with argon gas, 2.7 g (2.7 mL) of diphenylethylene and 141.6 mL of THF were collected using a syringe, and then cooled by being immersed in a container immersed in ice water. After cooling, 5.8 mL of a 2.6 M hexane solution of n-butyllithium was collected using a syringe and stirred to prepare 150 mL of a 0.1 M solution of DPhLi.
(3) TM-0701 (0.5M) solution In a 300 mL eggplant flask substituted with argon gas, a polymerizable monomer having a trialkylsiloxy group using a syringe ("Silaplane TM-0701" manufactured by JNC Corporation) In the above general formula (1), R ¹ and R ² are methyl groups and n is 3; hereinafter abbreviated as “TM-0701”.) TM-0701 55.0 g (59.1 mL) Then, 200.1 mL of THF was collected and stirred to prepare 260 mL of a 0.5 M solution of TM-0701.
(4) MeOH (0.33 M) solution In a 100 mL eggplant flask substituted with argon gas, 0.53 g (0.64 mL) of MeOH and 49.4 mL of THF were collected using a syringe and stirred to obtain 0.33 M of MeOH. 50 mL of the solution was prepared.

  Next, a block copolymer was prepared by living anionic polymerization of DMAMA and TM-0701 by the following operation. Three syringe pumps (“Syringe Pump Model 11 Plus” manufactured by Harvard) were added to a microreactor device equipped with a micromixer composed of two T-shaped saddle joints and a tube reactor connected downstream of the micromixer. The 50 mL gust syringe that sucked each of the three types of solutions obtained above was set in the syringe pump. First, from the upstream side of a reactor composed of a micromixer with a diameter of 250 μm and a tube reactor with an inner diameter of 1 mm and a length of 100 cm, the DMAMA solution and the DPhLi solution are 2.0 mL / min and 2.0 mL / min, respectively. By sending the solution, living anionic polymerization of DMAMA was performed to obtain a solution of DMAMA polymer. Next, the obtained DMAMA polymer solution and TM-0701 solution were added at 2.0 mL / min from the upstream side of the reactor composed of a micromixer having a heel joint diameter of 500 μm and a tube reactor having an inner diameter of 1 mm and a length of 400 cm. The living anion copolymerization of DMAMA and TM-0701 was performed by feeding the solution at a rate of. Polymerization reaction is stopped by putting the obtained polymer solution into a container containing a predetermined amount of MeOH solution, and a resin having a polar group and a siloxy group which is a block copolymer of DMAMA and TM-0701 ( A solution of PL-1) was obtained. The reaction temperature was adjusted to −28 ° C. by burying the entire microreactor in a constant temperature layer. A simplified reaction procedure for preparing PL-1 is shown in FIG.

  From the amount of residual monomers in the obtained polymer solution, the DMAMA reaction rate (polymer pass-through rate) was 99.6%, and the TM-0701 reaction rate (polymer pass-through rate) was 99.5%. . Moreover, the number average molecular weight (Mn) of the obtained polymer was 6,701, the weight average molecular weight (Mw) was 8,569, and dispersity (Mw / Mn) was 1.28.

(Resin synthesis methods 2 to 4: Preparation of resin (PL-2 to 4) having a polar group and a siloxy group)
A resin having a polar group and a siloxy group (PL) is prepared by performing living anion polymerization in the same manner as in the resin synthesis method 1 except that the type, concentration and supply rate of the polymerizable monomer are changed to the conditions shown in Table 1. -2) to (PL-4) were obtained. The polymerizable monomer “FM-0711” used in the resin synthesis methods 3 and 4 is a polymerizable monomer having a polydimethylsiloxane chain (“Silaplane FM-0711” manufactured by JNC Corporation, the above general formula In (2), a compound in which R ¹ and R ² are a methyl group, R ³ is a butyl group, m is 10 on average, and n is 3; hereinafter abbreviated as “FM-0711”. ).

(Resin synthesis method 5: Preparation of resin (PL-5) having polar group and siloxy group)
The following three types of solutions were prepared.
(1) DMAMA / FM-0711 (0.3M) mixed solution In a 300 mL eggplant flask substituted with argon gas, DMAMA 7.1 g (7.6 mL), FM-071145.0 g (46.9 mL) and 95.6 mL of THF was collected and stirred to prepare 150 mL of a mixed solution in which the concentrations of DMAMA and FM-0711 were each 0.3 M.
(2) DPhLi (0.1M) solution (polymerization initiator solution)
In a 100 mL eggplant flask substituted with argon gas, 1.3 g (1.2 mL) of diphenylethylene and 66.1 mL of THF were collected using a syringe, and then cooled by being immersed in a container immersed in ice water. After cooling, 2.7 mL of a 2.6 M hexane solution of n-butyllithium was collected using a syringe and stirred to prepare 70 mL of a 0.1 M solution of DPhLi.
(3) MeOH (0.33M) solution In a 100 mL eggplant flask substituted with argon gas, 0.53 g (0.64 mL) of MeOH and 49.4 mL of THF were collected using a syringe and stirred to obtain 0.33 M of MeOH. 50 mL of the solution was prepared.

  Next, a random copolymer was prepared by living anionic polymerization of DMAMA and FM-0711 by the following operation. Two syringe pumps (“Syringe Pump Model 11 Plus” manufactured by Harvard) were installed in a microreactor device equipped with a micromixer consisting of two T-shaped saddle joints and a tube reactor connected downstream of the micromixer. A 50 mL gust syringe that sucked the two types of solutions obtained above was set in the syringe pump. From the upstream of the reactor composed of a micromixer with a joint diameter of 250 μm and a tube reactor with an inner diameter of 1 mm and a length of 400 cm, the DMAMA / FM-0711 mixed solution is 2.7 mL / min and the DPhLi solution is 2 mL / min. Living anionic polymerization of DMAMA and FM-0711 was performed by feeding and mixing. A polymerization reaction is stopped by charging the obtained polymer solution into a container containing a predetermined amount of MeOH solution, and a resin having a polar group and a siloxy group, which is a random copolymer of DMAMA and FM-0711 ( A solution of PL-5) was obtained. The reaction temperature was adjusted to −28 ° C. by burying the entire microreactor in a constant temperature layer. In addition, the simplified reaction procedure of resin (PL-5) which has a polar group and a siloxy group is shown in FIG.

  From the amount of residual monomer in the solution of the obtained resin (PL-5) having a polar group and a siloxy group, the DMAMA reaction rate (polymer pass-through rate) is 100%, and FM-0711 reaction rate (polymer pass-through rate). ) Was 99%. Moreover, the number average molecular weight (Mn) of the obtained polymer was 8,508, the weight average molecular weight (Mw) was 10,800, and dispersity (Mw / Mn) was 1.27. From these results, it was confirmed that a random copolymer having a narrow molecular weight distribution was obtained.

(Resin synthesis method 6: Preparation of resin (PL-6) having a polar group and a siloxy group)
Resin having a polar group and a siloxy group (PLL) by operating in the same manner as Resin Synthesis Method 5 except that the type, concentration, and supply rate of the polymerizable monomer were changed to the conditions shown in Table 1 to perform living anion polymerization. -6) was obtained.

Example 1
In a 30 ml polyethylene bottle, 1 g of carbon black (MA-8; manufactured by Mitsubishi Chemical Corporation), 1 g of a resin having a polar group and a siloxy group (PL-1), straight silicone oil (KF-96-) as a nonpolar solvent 2cs; manufactured by Shin-Etsu Chemical Co., Ltd.) 8 g and 0.5 g zirconia beads 60 g were added and dispersed with a paint conditioner for 120 minutes to obtain a colored liquid (J1).

(Examples 2 to 6)
In the same manner as in Example 1 except that the resin (PL-1) having a polar group and a siloxy group in Example 1 was changed to resins (PL-2) to (PL-6) having a polar group and a siloxy group, Colored liquids (J2) to (J6) were obtained.

(Comparative Example 1)
In a 30 ml polyethylene bottle, 1 g of carbon black (MA-8; manufactured by Mitsubishi Chemical Corporation), 1 g of Solsperse 17000 (manufactured by Lubrizol), straight silicone oil (KF-96-2cs; Shin-Etsu Chemical) 8 g and 0.5 mm zirconia beads 60 g were added and dispersed with a paint conditioner for 120 minutes to obtain a colored liquid (H1).

(Example 7)
Using ethylene glycol as a polar solvent, a 10 ml vial was charged with 5 g of ethylene glycol and 0.5 g of the colored liquid (J1) obtained in Example 1, and the vial was shaken and stirred 10 times. A separated liquid coloring composition (J7) was obtained.

(Examples 8 to 12, Comparative Example 2)
For the colored liquids (J2) to (J6) obtained in Examples 2 to 6 and the colored liquid (H1) obtained in Comparative Example 1, the separated liquid colored composition (J8) to (J12), a separated liquid coloring composition (H2) was obtained.

(Separation confirmation method of separated liquid coloring composition)
On the slide glass, a few drops of the separated liquid coloring composition (A) were put with a dropper, and a cover glass was put on the drop to prepare a measurement sample. This was observed at a magnification of 200 times with a microscope “System Microscope BX51” manufactured by OLYMPUS.

The separability was evaluated in five stages according to the following criteria. The results are shown in Table 1.
5: The interface between ethylene glycol and the colored liquid is clear and no coloration to ethylene glycol is observed.
4: The interface between ethylene glycol and the colored liquid is clear, and ethylene glycol is slightly colored.
3: The interface between ethylene glycol and the colored liquid is somewhat unclear, and no coloration to ethylene glycol is observed.
2: The interface between ethylene glycol and the colored liquid is somewhat unclear, and ethylene glycol is slightly colored.
1: The interface between ethylene glycol and the colored liquid is unclear and does not separate.

  As a result, in Examples 7 to 12 using a resin having a polar group and a siloxy group, a colored liquid excellent in separability from a polar solvent or the like was obtained in any case.

It is a schematic structural example of the microreactor provided with the flow path of the preferable form used by manufacture of the said resin (PL). It is a schematic structural example of the microreactor provided with the flow path of the preferable form used by manufacture of the said resin (PL). The reaction path | route in manufacture of resin PL-1 and PL-2 is shown. The reaction path | route in manufacture of resin PL-3-PL-6 is shown.

1: Microreactor 2: First plate 3: Second plate 4: Reaction flow path 6: Temperature control flow path 30: Connector 31: Joint part 32: Joint part 1b: Supply port 1c: Discharge port 1d: Supply port 1e: Discharge port α: Fluid containing polymerizable monomer, polymerization initiator, additive β: Fluid γ: Temperature control fluid M1: Microreactor device M2: Microreactor device

Claims (8)

A colored liquid for use in an electrowetting or electrofluidic device that modulates color or brightness by moving or deforming the liquid by an external electric field, comprising a nonpolar solvent, a dye, a polar group, and A colored liquid comprising a resin (P) having a siloxy group. The resin (P) having the polar group and the siloxy group is a living anion polymerized polymerizable monomer containing the polymerizable monomer (A) having a siloxy group in the presence of a polymerization initiator (C). The coloring liquid according to claim 1 which is resin (PL). The colored liquid according to claim 1 or 2, wherein the resin (PL) is a living anion-polymerized resin (PL) using a microreactor having a flow channel capable of mixing a plurality of liquids. The living anionic polymerization is a first step in which a first polymerizable monomer and a polymerization initiator (C) are introduced into a flow path in a microreactor to perform living anionic polymerization to form an intermediate polymer; An intermediate polymer and a second polymerizable monomer are introduced into the microreactor, and in the microreactor, the polymerizable monomer having the siloxy group at the growth terminal of the intermediate polymer is subjected to living anion polymerization. A second step of forming a block copolymer, wherein at least one of the first polymerizable monomer and the second polymerizable monomer is a polymerizable monomer having a siloxy group (A The coloring liquid in any one of Claims 1-3 containing. The colored liquid according to claim 1, wherein the pigment is titanium black or carbon black. A separated liquid coloring composition comprising the colored liquid according to claim 1 and a polar solvent that is immiscible with the colored liquid. The coloring liquid according to any one of claims 1 to 5, as a colorant for generating an image in a light modulation type device that modulates color or brightness by moving or deforming the liquid by an external electric field use. The use according to claim 7, wherein the modulation method is an electrowetting method or an electrofluidic method.

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