TW200811249A - Organic pigment nano-particle dispersion, its producing method, and ink-jet ink, colored photosensitive resin composition, photosensitive resin transcription material containing it, and color filter, liquid crystal display device, CCD device using it - Google Patents

Abstract

The purpose of the present invention is provided a color filter with high contrast by using organic pigment nano-particle, and a liquid crystal display device and CCD device with excellent display property containing it. Specifically, the present application provides organic pigment nano-particle dispersion and its use, which the contrast of liquid crystal display device, the display property and display unevenness could be improved simultaneously. Provided is an organic pigment nano-particle dispersion, wherein it is characterized in that in the organic pigment dispersion consisting of nano-particle containing organic pigment, the content of alkali or alkaline-earth metal family in the said dispersion is controlled in the range of 0.001 ppm to 500 ppm.

Description

200811249 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to organic pigment nanoparticle dispersions and their use. More specifically, it relates to an organic pigment nanoparticle dispersion which defines a concentration of an alkali and/or an alkaline earth metal, in particular, an organic pigment nanoparticle dispersion which exhibits uneven display of a liquid crystal display device, and a use thereof A photosensitive resin composition, a color filter, a CCD device, and a liquid crystal display device.

[Prior Art] Pigments have vivid color tone, high tinting strength, light resistance, etc., and are widely used in most fields. Among these pigments, in general, those who are practically important are generally fine particles. It is obtained by preventing the aggregation of the pigment by miniaturization, and obtaining a vivid color tone and high coloring power. However, when the pigment is finely refined by a physical method such as salt honing, the dispersion of the pigment mostly exhibits high viscosity. For this reason, when the pigment dispersion liquid is prepared in an industrial scale, it becomes difficult to take it out from the disperser of the pigment dispersion liquid, and it cannot be conveyed by a line, and further gelatinizes during storage. In order to obtain a pigment dispersion liquid or a color-sensitive photosensitive composition which is excellent in fluidity and dispersibility, it is known that surface treatment of an organic pigment is carried out (for example, refer to Patent Documents 1 and 2), and various types of use are used. A dispersing agent (for example, refer to Patent Documents 3 and 4). Further, a method of obtaining a reprecipitation method using particles by injecting a sample dissolved in a good solvent into a poor solvent has been described in detail in Patent Documents 5 and 6. When such a pigment is used, for example, in the case of forming a colored image using a colored photosensitive composition, the layer formed by the colored photosensitive composition is generally thin, and it is required to represent a thin thickness and a high coloring concentration. Therefore, it is necessary to disperse the organic pigment in a state of high or uniform fineness in, for example, an organic solvent. However, the present state of the art does not provide a pigment dispersion or a composition thereof which satisfies such requirements and has excellent dispersibility, fluidity and the like.

Further, a general commercially available pigment is honed and dispersed by ceramic beads to be used as a pigment dispersion. A pigment dispersion liquid, a pigment dispersion paste, or a use for controlling the sodium or sodium concentration of such a person has been proposed. These color filters (Patent Document 7). These are mostly those who directly use commercially available pigments. However, there is no record of the formation of nanometer particleizers by molding. On the other hand, "the liquid crystal display device has demanded higher performance in recent years." In general, there are many problems that should be solved. For example, it is desirable to use a system in which the organic pigment is a nanometer-sized particle in order to increase the optical density. The nanoparticle formation of the organic pigment of the pigment dispersion contributes to the improvement of the contrast of the color filter for the liquid crystal display device. However, there is a problem that the display performance (display durability) is lowered for a long time or the display is not caused by the cause φ. Among these, in particular, it is desirable to improve the color filter display unevenness analysis for a liquid crystal display device which is one of the important performances. However, an effective solution is not obtained in the current situation. Even in the color filter of Patent Document 7, the problem cannot be solved, and it is impossible to achieve both improvement in high contrast and display unevenness when used as a color filter for a liquid crystal display device. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Laid-Open Patent Publication No. 2003-336001 (Patent Document 7) Japanese Laid-Open Patent Publication No. JP-A No. 7-1989 No.

An object of the present invention is to provide a contrast-control color filter using an organic pigment nanoparticle dispersion and a liquid crystal display device having excellent display characteristics, and a CCD device, particularly an improved liquid crystal display device, which can improve display characteristics. And the use of organic pigment nanoparticle dispersions which are unevenly displayed and their use. Means for Solving the Problems The above problems were achieved by the following means. (1) An organic pigment nanoparticle dispersion characterized in that the content of the alkaline earth metal in the dispersion is controlled to be 0.001 ppm to 500 ppm in the organic pigment dispersion of the nanoparticle containing the organic pigment. . (2) The organic pigment nanoparticle dispersion according to (1), wherein the content of the alkali or the soil-based metal is 0.01 ppm to 350 ppm. (3) The organic pigment nanoparticle dispersion according to (1) or (2), wherein the nanoparticle dispersion of the organic pigment contains a molecular compound having a mass average molecular weight of 1,000 or more. (4) The organic pigment nanoparticle dispersion according to (3), wherein the polymer compound is represented by the following formula (1), 200811249

[wherein, R1 represents a (m + n)-valent linking group, R2 represents a single bond or a divalent linking group, and A1 represents a group having an acidic group and a basic nitrogen.

a group consisting of an atomic group, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxyalkyl group, an epoxy group, an isocyanate group, and a hydroxyl group A monovalent organic group or a monovalent organic group containing an organic dye structure which may have a substituent or a heterocyclic ring. In the formula, η A1 systems are available! Same or different. m represents a number from 1 to 8, η represents a number from 2 to 9, and m + n is satisfied from 3 to 10. Ρ1 represents a polymer compound residue]. (5) The organic pigment nanoparticle dispersion according to (1) to (4), wherein the pigment in the pigment dispersion is a pyrrolopyrrole pigment. (6) The organic pigment nanoparticle dispersion according to any one of (1) to (5), wherein the organic pigment nanoparticle dispersion is an inkjet ink. (7) A process for producing an organic pigment nanoparticle dispersion according to any one of (1) to (6), which comprises: a solution of an organic pigment dissolved in a good solvent, and a good solvent A step of mixing the organic pigment as a solvent of the poor solvent and precipitating the organic pigment into fine particles having a nanometer size. (8) The method for producing a dispersion of an organic pigment nanoparticle according to (7), wherein the method for producing the nanoparticle dispersion comprises a step of depositing fine particles of a nanometer size and then concentrating the dispersion. (9) A colored photosensitive resin composition containing at least an organic pigment nanoparticle dispersion, a binder, a monomer or a low polymer, photopolymerization of any one of (1) to (6) 200811249 Heuristics or photopolymerization heuristics. (10) A photosensitive resin transfer material characterized in that a photosensitive resin layer containing at least the colored photosensitive resin composition described in (9) is provided on a temporary support. (11) A color filter characterized in that the coloring photosensitive resin composition described in (9) and/or the photosensitive resin transfer material described in (1) are used.

Made with material. (12) A liquid crystal display device characterized by comprising the color filter described in (11). (1.3) The liquid crystal display device according to (12), wherein the display device is a VA method. (14) A CCD device characterized by comprising the color filter described in (11). EFFECTS OF THE INVENTION The organic pigment nanoparticle dispersion of the present invention has a small particle diameter of the organic pigment nanoparticle contained therein, and is small in particle size change over a long period of time. Further, the organic pigment nanoparticle dispersion of the present invention can provide an organic pigment nanoparticle dispersion and an inkjet ink for a color filter which exhibits greatly improved display characteristics such as display durability and display unevenness. Further, the method for producing an organic pigment nanoparticle dispersion of the present invention can efficiently produce the above-described excellent organic pigment nanoparticle dispersion. Moreover, the colored photosensitive resin composition of the present invention, the photosensitive resin transfer material, and the inkjet ink system using the above-described excellent dispersion exhibit stability. Further, by using the colored photosensitive resin composition, the photosensitive resin transfer material, or the ink jet ink, it is possible to provide a color filter which exhibits excellent display characteristics with stable quality. Further, the color filter of the present invention provides a liquid crystal display device which is highly contrast-oriented and whose display characteristics are greatly improved. In addition, the liquid crystal display device and the CCD device of the present invention are excellent in display characteristics such as display durability and display unevenness. [Embodiment]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. [Organic Pigment] The organic pigment used in the preparation of the organic pigment nanoparticle of the present invention is not particularly limited as long as it can be formed by the re-precipitation method, and may be used singly or in plural. Combine users. There is no limitation on the hue of the organic pigment system, such as hydrazine, phenanthone, quinophthalone, quinophthalone oxime, hydrazine, fluorenone ketone, benzimidazolone, diazo condensate, diazo, azo , standard reduction blue 'phthalocyanine, triarylcarbyl, dioxan, aminoguanidine, diketopyrrolopyrrole, thiopurine, isoindolin, isoindolinone, dermozone dye or different Suitable and blue ketone compound pigments, or mixtures thereof, and the like. More specifically, for example, bismuth compound pigments such as CI Pigment Red 190 (cl number 71140), CI·Pigment Red 224 (C.I_ No. 71127), C.l_ Pigment Violet 29 (CI No. 71129) , CI·Pigment Orange 43 (CI number 711〇5), or 茈_丨. Pigment Red 194 ((} 丄 number 71100), etc. oxime compound pigment, CI·Pigment Violet 19 (CI·No. 730000), CI ·Pigment Violet 42, CI Pigment-10-200811249 Red 122 ((:·Ι.No. 7391 5), C"·Pigment Red 192, CI Pigment Red 202 (C.I_ No. 73907), 〇_1_Pigment Red 207 (〇_1. No. 73900, 73906), or C_l_Pigment Red 209 (C. 丨·No. 73905) quinacridone compound pigment, CI Pigment Red 206 (CI·No. 73900/73920), C”·Pigment Hydrazine compound pigment such as quinacridone quinone compound pigment such as orange 48 (CI number 73900/73920) or CI·Pigment orange 49 (C"·number 73900/73920), CI Pigment Yellow 147 (CI number 60645) , · ketone ketone compound pigment such as CI·Pigment Red 168 (CI number 59300), C_l. Pigment 0 Brown 25 (〇.丨. No. 12510), 〇丄Pigment Violet 32 (〇.丨_No. 12517), 〇.1· Pigment Yellow 180(( .1. No. 21290), (}. 丨 _ pigment yellow 181 ((:. 丨. number 1 1 777), C" · Pigment Orange 62 (CI · number 1 1 775), or CI Pigment Red 1 85 ( CI·No. 1 251 6) Benzimidazolone compound pigment, CI Pigment Yellow 93 (C·丄 number 2 0 71 0), C, Ί_Pigment Yellow 94 (C·丨_number 20048), C·I Pigment Yellow 95 (〇_1. No. 200 34), 0_丨. Pigment Yellow 128 (0丄 number 20037), CI Pigment Yellow 166 (C"·Number 20035), CI·Pigment Orange 34 (C)·Number 21115), C"·Pigment Orange 13 (CI number 21110), CI Φ Pigment Orange 31 (C_I. No. 20050), CI Pigment Red 144 (0·Ι_No. 20735), C.l_ Pigment Red 166 (C"_ No. 20730), CI·Pigment Red 220 (C′′·No. 20055), CI·Pigment Red 221 (CI·No. 20065), CI Pigment Red 242 (C_丨·No. 20067), C”·Pigment Red 248, CI Pigment red 262, or a diazo condensed compound pigment such as CJ_Pigment Brown 23 (CI number 20060), C". Pigment Yellow i3 (C·丨·No. 21100), CI Pigment Yellow 83 (C)·No. 21108 ), or a diazo compound pigment such as CI·Pigment Yellow 188 (C”_No. 21 094), C丄Pigment Red 187 (C) _I·Number 1 2486) , CI Pigment Red 170 (CI·Number 1 2475), C”·Pigment Yellow 74 (C”. No. 200811249 11714), CI·Pigment Yellow 150 (C·丨·No. 48545), CI Pigment Red 48 (C" _ number 1 5865), CI Pigment Red 53 (CI number 1 5585), Cl Pigment Orange 64 (C" number 12760), or CI·Pigment Red 247 (C_J. number)

15915) azo compound pigment, 〇.1. Pigment blue 60 ((:.1. No. 69 80 0), etc. Standard reduced blue compound pigment, (:.1_Pigment Green 7 (().1. 74260), CI Pigment Green 36 (CI number 74265), Pigment Green 37 (CI number 74255), Pigment Blue 16 (CI number 741 00), C_l·Pigment Blue 75 (CI number 74160: 2), or Triaryl carboxy key such as phthalocyanine compound pigment such as 15 (CI number 74160), C"·Pigment blue 56 (CI number 42800), or C·丨·Pigment blue 61 (CI number 42 765:1) Compound pigment, C.|·Pigment Violet 2 3 (C"_ number 51319), or dipyridose compound pigment such as CI Pigment Violet 37 (CI number 51345), CL Pigment Red 1 77 (CI number 65300), etc. Amine hydrazine compound pigment, C_L Pigment Red 254 (C_I_ number 56110), CI Pigment Red 2 5 5 (C · I · number 5 6 1 0 5 0 ), C · I Pigment Red 2 6 4, C. I · Pigment Red 272 (CI·No. 561 1 50), C_l·Pigment Orange 71, or a diketopyrrolopyrrole compound pigment such as CI·Pigment Orange 73, CI Pigment Red 88 (CJ·No. 7 3 3 1 2) Etctosulfate compound pigment, c J Pigment Yellow 1 3 9 (C · I. No. 5 6 2 9 8 ), C. I · Pigment Orange 6 6 (C · I number 4 8 2 1 0 ), etc. 化合物 Compound pigment, CI Pigment Yellow 1〇9 (C_l • number 56284), or c_l·pigment orange β 1 (C _ I · number 1 1 2 9 5 ) Temple of the different π-pyrotropone compound pigment, c · | · Pigment Orange 40 (CI number 59700), or It is a dermozone dye compound pigment such as cl·pigment red 216 (CI· number 59710), or a heterogeneous and chloroketone compound pigment such as c_丨·Pigment Violet 31 (60010). Among them, quinacridone S pigment, monoketone, and compound pigment, bis [| oxime compound pigment, phthalocyanine compound pigment, or azo compound pigment is better, diketone-12-200811249 pyrrolopyrrole compound pigment or two The disgusting compound pigment is preferred. Hereinafter, the diketopyrrolopyrrole compound pigment or the dioxo compound pigment will be described in further detail. C·丨.PR· 2 54, 255, 264 are representative pyrrolopyrrole compounds

The pigment has a suitable absorption region because the color purity of the red pixel constituting the color filter is improved, and since the color reproduction region is enlarged, the color filter is tried to be used. However, conventional pigments cannot cope with the requirements of color purity or contrast. Even if it is obtained by the method of inkjet ink, bead dispersion, or salt honing described in JP-A-2003-336001, a good color filter cannot be obtained. According to the production method of the present invention, nano-sized pyrrolopyrrole compound pigment fine particles can be obtained in a state where the particle size distribution is steep. Further, when the pigment fine particles are used in a color filter, the desired color purity and high contrast can be achieved, and the light resistance is excellent, and the occurrence of the folded matter can be suppressed. On the other hand, the liquid crystal display device having the color filter is excellent in black compactness and redness, and display unevenness is suppressed. In the above-mentioned diketopyrrolopyrrole compound pigment, C_LP_R.254 (compound represented by the following formula (Z)), 255 (compound represented by the following formula (W)), and 264 (the following formula) The compound represented by (V) is preferred, and C.LP.R.254 is more preferable from the viewpoint of absorption spectrum. Further, all of the commercially available persons such as Irgaphor Red B-CF, Cromophtal DPP Red BO, Irgazin DPP Red BO, and Microlen DPP RED BP can be used for C.I.P.R.254. C.丨.P.R.255 can be used with Cromophtal Coral

Red C, Irgazin DPP Red 5G, etc. C.I.P.R_264 can be used Ho st apepermRubi n D3BLP26 15, Irgazin DPP Rubin TR -13- 200811249

V /|\

Next, the dioxic compound pigment will be described. In recent years, as a coloring agent for blue pixels of color filters, C.I_P_B.15:6 is often used, and the color purity of the color filter can be extracted. However, a light source such as a cold cathode tube, which is often used for a light source of a liquid crystal display device, emits a little light on the long-wave side 0 of the blue light-emitting peak, and thus the chromaticity is inferior to NTSC. This problem can be improved by adding (e.g., about 5%) C·丨·Ρ·V· 2 3, 3 7 as a representative dioxic compound pigment. However, although the color filter of the high color purity is expected to improve the contrast and improve the display characteristics, the conventional bead dispersion method or the salt honing method is not satisfactory. According to the production method of the present invention, a dioxin compound pigment having a particle size distribution of a nano-sized pigment can be obtained. Further, it is also possible to form a dispersion containing fine particles of an anthraquinone compound pigment which is excellent in stability over time. -14 - 200811249 For this reason, the color filter system using it has high color purity and high contrast, and is excellent in light resistance. Further, the liquid crystal display device having the color filter is used, and the blackness and blueness are excellent in reproducibility and displayability, and display unevenness is suppressed. In addition, C_I_P.V_23 can use Cromofine Violet RE, Fastgen Super Violet BBL, Helio Fast Violet EB,

Microlith Violet RL-WA, Sanyo FastViolet BLD, etc. are available to consumers. 〇.1.卩^.37 can make 甩(^〇阳(^1^3 1^〇1818, 1^1〇1*〇11 than Violet B-A and other commercials.

In the production of the organic pigment nanoparticle of the present invention (hereinafter, simply referred to as "organic nanoparticle"), a solid solution of two or more kinds of organic pigments or organic pigments may be used in combination. [Production of Organic Nanoparticles] Next, a method of producing organic nanoparticles will be described. In the present invention, the organic nanoparticle is a solvent which is compatible with the above-mentioned good solvent and which is a poor solvent with respect to the organic pigment by dissolving the organic pigment in the organic pigment solution of the good solvent (hereinafter, the solvent is called It is produced by mixing [lean solvent for organic pigments] or simply "lean solvent" (hereinafter, this method is also called "re-precipitation method", and contains a dispersion of organic nanoparticles obtained at this time. Also known as "organic nanoparticle re-sinking"). Here, the "good solvent" is a solvent having a large solubility in an organic pigment, and the "lean solvent" is a solvent having a small solubility in an organic pigment. The good solvent and the poor solvent used in the present invention are required to have sufficient solubility of the organic pigment in order to form the organic pigment nanoparticle, and the solvents satisfying the requirements can be used in combination with each other. The poor solvent of the organic pigment is not particularly limited as long as it is compatible or homogeneously mixed with a good solvent for dissolving the organic pigment -15 - 200811249. The solubility of the poor solvent organic pigment of the organic pigment is preferably 0.02% by mass or less, preferably 0.01% by mass or less. The organic pigment has no particular lower limit for the solubility of the poor solvent, but it is actually 0.000001% by mass or more in consideration of the organic pigment generally used. The solubility can also be the solubility in the case of dissolution in the presence of an acid or a base. Further, the compatibility between the good solvent and the poor solvent or the uniform mixing property is preferably 30% by mass or more, and preferably 50% by mass or more based on the amount of the solvent dissolved in the poor solvent. The amount of the good solvent to be dissolved in the poor solvent is not particularly limited, and may actually be mixed with each other at an arbitrary ratio of I. Examples of the poor solvent include an aqueous solvent (for example, water, hydrochloric acid, aqueous sodium hydroxide solution), an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, an aromatic solvent, a carbon disulfide solvent, an aliphatic solvent, and a nitrate compound. The solvent, the halogen compound solvent, the ester compound solvent, the ionic liquid, a mixed solvent thereof, and the like are preferably an aqueous solvent, an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, an ester compound solvent, or a mixture thereof. Aqueous solvent, alcohol compound solvent or ester compound solvent is preferred. The solvent of the alcohol compound is, for example, methanol, ethanol, isopropanol, n-propanol or 1-methoxy-2-propanol. The solvent of the ketone compound is, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone. Examples of the ether compound solvent include dimethyl ether, diethyl ether, tetrahydrofuran and the like. The aromatic solvent is exemplified by benzene, toluene and the like. The aliphatic compound solvent is, for example, hexane or the like. The nitronium compound solvent is, for example, acetonitrile or the like. Examples of the halogen compound solvent are, for example, a dichlorocarbyl group or a trichloroethylene. The solvent of the ester compound is, for example, ethyl acetate, ethyl lactate or 2-(1-methoxy)propyl acetate. The ionic liquid system is -16- 200811249, for example, 1-butyl-3-methylimidazole key and PF, a salt or the like. Next, a good solvent for dissolving an organic pigment will be described. The organic solvent to be used for dissolving the good solvent is not particularly limited as long as it can be dissolved or uniformly mixed with the above-mentioned poor solvent. The solubility of the organic pigment in the solubility of the organic pigment in the good solvent is 0.2% by mass.

The above is preferably 5% by mass or more. The solubility of the organic pigment in the good solvent is not particularly limited, and is generally 50% by mass or less in consideration of the organic pigment generally used. The solubility can also be the solubility in the case of being dissolved in the presence of an acid or a base. The preferred range of compatibility or uniform mixing of the poor solvent with the good solvent is as described above. Examples of the solvent include aqueous solvents (for example, water, hydrochloric acid, aqueous sodium hydroxide), alcohol compound solvents, guanamine compound solvents, ketone compound solvents, ether compound solvents, aromatic solvent, carbon disulfide solvent, and aliphatic solvent. , a nitrate compound solvent, a yam compound solvent, a halogen compound solvent, an ester compound solvent, an ionic liquid, a mixed solvent thereof, an aqueous solvent, an alcohol compound solvent, a ketone compound solvent, an ether oxime compound solvent, an arsenic compound solvent An ester compound solvent, a guanamine compound solvent, or a mixture thereof, preferably an aqueous solvent, an alcohol compound solvent, an ester compound solvent, an arsenic compound solvent or a guanamine compound solvent, an aqueous solvent, an arsenic compound solvent or hydrazine. The amine compound solvent is more preferred, and the Yafeng compound solvent or the guanamine compound solvent is particularly preferred. Examples of the hydrazine compound solvent include dimethyl hydrazine, diethyl hydrazine, hexamethylene fluorene, and cyclobutyl hydrazine. The guanamine compound solvent is, for example, N,N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-i-i-diketanone , 2 _ pyrrolidone, ε-caprolactam, formamide, N--17- 200811249 methyl formamide, acetamide, N-methyl acetamide, hydrazine, hydrazine-dimethyl ethene Indoleamine, hydrazine-methyl propylamine, hexamethylphosphonium triamine, and the like. Further, the organic pigment is dissolved in the concentration of the organic pigment solution of the good solvent, and the conditions at the time of dissolution are preferably in the range of the saturated concentration of the organic solvent to about 1/100. The conditions for the preparation of the organic pigment solution are not particularly limited, and a range from atmospheric pressure to subcritical and supercritical conditions can be selected. The temperature under normal pressure is preferably -1 0~1 50 °c, preferably -5~1 30 °c, and 〇~1 〇〇 °C is particularly good.

The organic pigment of the present invention must be uniformly dissolved in a good solvent, and it may be dissolved in an acidic or alkaline state. In the case of a pigment having a base which can be largely dissociated in the molecule, it is basic, but it is acidic when it is not present in the base which can be dissociated, and a nitrogen atom which is easy to add a proton in the molecule. For example, quinophthalone, diketopyrrolopyrrole, and a diazo condensed pigment are dissolved in an acidic state by a basic or phthalocyanine pigment. Examples of the base used in the case of alkaline dissolution include an inorganic base such as lithium hydroxide, sodium hydroxide, potassium hydroxide, hydroxide or cesium hydroxide, or a trialkylamine or diazo. An organic base such as a dicycloundecene (DBU) or a metal alkoxide is preferably an inorganic base. The amount of the base to be used is not particularly limited as long as the amount of the pigment can be uniformly dissolved, but in the case of an inorganic base, it is preferably 10 to 30 mole equivalents relative to the organic pigment, more preferably 1 〇 ~25 molar equivalents, and more preferably 1. 0 to 20 molar equivalents. The organic base is preferably 1.0 to 100 mole equivalents, more preferably 5 to 0 to 100 mole equivalents, still more preferably 20 to 100 mole equivalents, based on the organic pigment. The acid used in the case of being dissolved in acid is sulfuric acid, hydrochloric acid, or -18 - 200811249 is an inorganic acid such as phosphoric acid, or acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, or difluoromethanesulfonic acid. The organic acid is preferred, and is preferably an inorganic acid. Very good is sulfuric acid. The amount of the acid to be used is such that the amount of the organic pigment can be uniformly dissolved without particular limitation, but it is more than the case where the excess amount of the base is used. Regardless of the inorganic acid and the organic acid, it is preferably 3 to 5 moles equivalent to the organic pigment, more preferably 10 to 500 moles, and more preferably 3 to 2 moles. .

When a base or an acid is mixed with an organic solvent and used as a good solvent for an organic pigment, 'the alkali or the acid is completely dissolved, so that a certain amount of water or a base or an acid for a lower alcohol or the like can have a high solubility. The solvent is added to the organic solvent. The amount of water or lower alcohol is preferably 50% by mass or less and 30% by mass based on the total amount of the organic pigment solution. /. The following are preferred. Specifically, water, methanol, ethanol, n-propanol, isopropanol, butanol or the like can be used. When the organic pigment nanoparticles are produced, that is, when the organic nanoparticles are precipitated and formed, the conditions of the poor solvent are not particularly limited, and the range from normal pressure to subcritical and supercritical conditions can be selected. The temperature under normal pressure is preferably -30 to 00 ° C, preferably -1 to 60 ° C, and preferably 0 to 30 ° C. When the organic pigment solution and the lean solvent are mixed, either one of them may be added and mixed, and the organic pigment solution may be added to the poor solvent to be mixed, and it is preferred that the poor solvent is stirred. The stirring speed is preferably 1 0 0 ~ 1 0 0 0 0 r p m is preferably 1 5 0 〜 8 0 0 0 r p m is preferably, 2 0 0 ~ 6 0 0 0 r p m is particularly preferable. The addition system may or may not use a pump. Further, it may be added to the liquid or may be added externally, and it is preferably added in a liquid. The mixing ratio of the organic pigment solution to the poor solvent (organic nanoparticle re-sinking -19-200811249 ratio of good solvent/lean solvent ratio) is preferably 1/50 ~ 2/3, 1/40~1/ 2 is better, 1/20 to 3/8 is particularly good. The concentration of the organic nanoparticle re-sinking liquid is not particularly limited as long as the organic nanoparticle can be produced, and it is preferably in the range of 1 〇 to 40 00 mg with respect to 1 〇〇〇 ml of the organic solvent of the dispersion solvent. More preferably, it is in the range of 20 to 30000 mg, and particularly preferably in the range of 50 to 25,000 mg.

Further, the modulation scale of the organic nanoparticle formation is not particularly limited, and the preparation amount of the poor solvent is preferably 1 to 2 000 L, and the modulation scale of 50 to 1 000 L is preferable. . Regarding the particle diameter of the organic nanoparticle, there is a method of expressing the average size of the group by the number of measurement methods, but the more commonly used one is the mode diameter indicating the largest distribution, and the central point corresponding to the integral distribution curve. The median diameter, various average diameters (quantity average, length average, area average, weight average, volume average, etc.) and the like are not particularly limited in the present invention, and the average particle diameter is referred to as a number average diameter. The average particle diameter of the organic nanoparticles (primary particles) is a nanometer size, and the average particle diameter is preferably 1 ηηι to 1 μηι, preferably 1 to 200 nm, more preferably 2 to 100 nm, and particularly preferably 5 to 80 nm. Further, the particles formed by the production method of the present invention may be crystalline particles or amorphous particles, or a mixture thereof. Further, the index indicating the monodispersity of the particles is not particularly limited in the present invention, and the ratio (?v / ?) of the volume average particle diameter (Mv) to the number average particle diameter (Mn) is used. The monodispersity of the particles (primary particles) contained in the organic nanoparticle dispersion liquid for the method of concentrating the organic nanoparticle, that is, the Μν/Μη is preferably 1.0 to 2.0, and preferably 1.0 to 1-8. 1.0Μ.5 is especially good -20-

200811249 Determination of the particle size of organic nanoparticles, such as display, gravimetric method, light scattering method, light interception method, electrical resistance method, sound dynamic light scattering method, microscopic method, dynamic light scattering method is a special microscope The microscope of the method is, for example, a scanning electron microscope or a crystal microscope. The particle measuring device by the dynamic light scattering method is a Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd., and a DLS-7000 series of the Otsuka electronic public light scattering photometer. [Regulations of alkali or alkaline earth metal concentration] Improvement of the color reproduction area or brightness of the liquid crystal display device The image quality of the image reproduced in the CCD of the digital camera is improved. For this purpose, color filters generally use organic pigments which are more optically intensive than inorganic pigments. However, in the production of organic pigments, the incorporation of alkali metal compounds such as sodium and potassium cannot be avoided, and in the process of dispersing agents, additives such as surface treatment agents, and dispersions of dispersion media, there are also alkali metal compounds, as the case may be calcium. Impurities such as metals such as ruthenium. Further, since an acid is used in the formation of particles, a base to be used as a solvent or an alkali metal salt or an alkaline earth metal salt which is inevitably formed therein may remain in the present invention, and the pigment is dispersed. The amount of the alkali or alkaline earth gold in the product, which is called a base, is set in the following range. The method of controlling the base is not particularly limited, and the base is generally washed and removed as a compound by water to be reduced to a desired level. In addition to this, it is preferred to use an organic solvent-soluble method which is compatible with water. The alkali and/or micromirror method in the pigment nanoparticle dispersion of the present invention. For the over-type electric power, for example: the brake, or the system is used in the process of lifting the cylinder, the alkaline earth and the alkali produced by the use of the sub-genus and the reaction genus (the following range of water-soluble concentration agent to the soil-like gold - 21- 200811249 The genus of genus is 0 001 ~ 500ppm, 〇. 〇 1~350ppm is better, 0. 01~250ppm is particularly good. When it exceeds 50oppm, the display unevenness when making liquid crystal display device is unbearable, forming A bad grade, on the other hand, less than 0.001 ppm is very troublesome on the cost side and practically inappropriate. [Dispersant]

In the production method of the present invention, it is preferred to contain a dispersant each time the organic nanoparticle dispersion is prepared. The step of containing the dispersing agent is not particularly limited, and it is preferred to add a dispersing agent to either or both of the organic pigment solution and the poor solvent. Further, the dispersant solution may be added to the other two liquids when the organic nanoparticles are formed. It is also possible to use a pigment particle or a pigment particle which has been surface-treated in advance by a dispersing agent, or a surface treatment which promotes adsorption of the dispersing agent. The dispersant system (1) rapidly adsorbs to the surface of the precipitated pigment to form fine nanoparticles, and (2) has a function of preventing such particles from undergoing another aggregation. The dispersing agent which can be used is, for example, an anionic, cationic, diionic, nonionic or pigment derivative of a low molecular or high molecular dispersing agent. Further, the molecular weight of the polymer dispersant may be any one as long as it can be uniformly dissolved in the solution, and is preferably a molecular weight of 1,000 to 2,000,000, preferably 5,000 to 1,100,000, more preferably 10,000 to 500,000, and more preferably 1,0,000. ~100, 〇〇〇 is especially good. Specific examples of the polymer dispersant include polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene glycol, polypropylene glycol, polypropylene decylamine, and vinyl alcohol-vinyl acetate copolymerization. , polyvinyl alcohol-partial methylallate, polyvinyl alcohol-partial butyralate, vinyl pyrrolidone-vinyl acetate-22- 200811249 ester copolymer, polyethylene oxide/propylene oxide block Copolymer, polyacrylate, polyvinyl sulfate, poly(4-vinylpyridinium) salt, polyamine, polyallylamine salt, condensed naphthalenesulfonate, cellulose derivative, starch derivative, and the like. Further, natural polymers such as alginate, gelatin, albumin, casein, arbor gum, toluene gum, and lignosulfonate can also be used. Among them, polyvinylpyrrolidone is preferred. These polymers may be used alone or in combination of two or more. These dispersants can be used singly or in combination. The dispersant used for pigment dispersion is described in detail on pages 29 to 46 of "Pigment Dispersion Safety Quantification and Surface Treatment Technology and Evaluation" (Chemical Information Association, issued in December 2001). Examples of the anionic dispersant (anionic surfactant) include N-fluorenyl-indole-alkyl taurate, a fatty acid salt, an alkyl sulfate, an alkylbenzenesulfonate, and an alkylnaphthalenesulfonate. An acid salt, a dialkyl sulfosuccinate, an alkyl phosphate salt, a naphthalenesulfonic acid formalin condensate, a polyoxyethylene alkyl sulfate salt, and the like. Among them, especially fluorenyl-fluorenyl-hydrazine-alkyl taurates are preferred. The fluorenyl-fluorenyl-hydrazinyl taurate is preferably Φ as described in the specification of Japanese Patent Laid-Open No. 3-2730. These anionic dispersing agents can be used singly or in combination of two or more. The cationic dispersant (cationic surfactant) contains a quaternary ammonium salt, an alkoxylated polyamine, an aliphatic amine polyglycol ether, an aliphatic amine, and is induced by an aliphatic amine and an aliphatic alcohol. Amines and polyamines, imidazolines induced by fatty acids, and salts of such cationic materials. These cationic dispersing agents may be used singly or in combination of two or more. The two-ionic dispersing agent contains, in the molecule, a dispersing agent having an anionic group portion of the above anionic dispersing agent and a cationic group portion having a cationic dispersing agent in the molecule. -23- 200811249 Nonionic dispersing agents (nonionic surfactants) include, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters. , polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, and the like. Among them, polyoxyethylene alkyl aryl ether is preferred. These nonionic dispersing agents may be used singly or in combination of two or more.

The pigment derivative type dispersant is defined as a pigment derivative type dispersant which is produced by chemically modifying its main structure, which is induced by an organic pigment as a affi substance, or pigmented by a chemically modified pigment precursor. A pigment derivative-type dispersant obtained by the reaction. For example, a sugar-containing pigment derivative-type dispersant, a piperidinyl-based pigment derivative-type dispersant, a naphthalene or anthracene-inducing pigment derivative-type dispersant, and a pigment derivative having a functional group transmissive to a main structure of a pigment through a methylene group Material type dispersant, pigment main structure chemically modified by polymer, pigment derivative type dispersant having sulfonic acid group, pigment derivative type dispersing agent having sulfonamide group, pigment derivative type dispersion having ether group An agent or a pigment derivative-type dispersant having a carboxylic acid group, a carboxylate group or a carboxamide group. In the production method of the present invention, it is preferred to coexist with an amine-based pigment dispersant when producing an organic pigment solution dissolved in a good solvent. Here, the amine group may include a primary amino group, a secondary amino group, and a tertiary amino group, and the number of the amine groups may be one or plural. A pigment derivative compound having a substituent having an amine group introduced into the pigment skeleton, or a polymer compound having a monomer having an amine group as a polymerization component may be used. The examples are described in, for example, JP-A-2000-239554, JP-A-2003-96329, JP-A-2001-31885, JP-A-H05-339949, JP-A-5-72943--24-200811249 Compounds, etc., are not subject to these restrictions. The dispersing agent having an amine group used in the production method of the present invention is not limited thereto, and may be selected from compounds represented by the following formulas (D1), (D3), and (D4). At least one. < 1 · Compound represented by the formula (D 1 ) > Formula (D I)

A—N==N—X—Y

In the formula (D1), A represents a component which forms an azo dye together with X-oxime. The above A may be arbitrarily selected as long as it is a compound which forms an azo dye after coupling with a heavy-key compound. The specific examples of the above A are as follows, but the present invention is not limited thereto.

CHgOOCHCONI

Cl type 1 - 1

<Q>-cochconh - Equation 1 - 3

-25- 200811249 〇5c

In the formula (D1), X represents a group of a divalent linking group selected from a single bond or a structural formula represented by the following formulas (1) to (v).

^^CONH— Formula (i) CONH-Formula (ii) so2nh—Formula (iii) -〇-S02IMH- _^.〇_ Formula (iv) Formula (v) In the formula (D1), Y represents the following In the formula (D 2 ) "(GONH-Z-NR^) in the formula (D 2 ) represented by the formula (D2), Z represents a lower-grade stretching base. 2 is represented by _((^2)1)-', but the b is an integer of 1 to 5, preferably 2 or 3. In the formula (D2), -NR21 represents a lower alkylamino group or a 5- to 6-membered saturated heterocyclic group containing a nitrogen atom. In the case where the -NR21 represents a lower alkylamino group, it means that r is an integer of 1 to 4, preferably 1 or 2. On the other hand, the -nR21 is a 5- to 6-membered saturated heterocyclic group containing a nitrogen atom, and a heterocyclic group represented by the following structural formula is preferred. -26- 200811249

In the above formula (D2), Z and -NR21 each may have a lower alkyl group or an alkoxy group as a substituent. In the above formula (D2), a represents 1 or 2, and is preferably represented by 2. Specific examples of the compound represented by the above formula (D 1 ) are shown below, but the present invention is not limited by the specific examples. -27- 200811249

2.

COCH3 i〇fcH-N= OCH3

CONHiGH^N^HB^ CONHCCH^sNiCaHs^ 3.

9〇ci NHCOOH CONH{CH2)3N(C2Hsfe

〇K

khXC^hQ( OONHiCH^NfCgH^g CONH(CH2)2N{C2H5)2 5· Η \_Z»QQNH(CH2)3M<C2H5)2 6. com{CH2)2ti{c^2 CONH(CH2)2N( C2H5)2

CONHH^J CON H(QH points 3N (〇2啦2 COHH(Oi2)M〇2»Bi2 -28 - 200811249

8 K

C〇ch3 MHCOCH-N=N

So2nh CONH(CH2)3N(C2H6^ CONH(CHa)〇N(C2H5)2 9.

〇K

9〇ch5 coop-»= H NHi

CONH

CONHCCH^sNCCaH^ CONHiCHANiCsHsh

CONHiCH^NtCzH^ CONHCCH^aNtCgHefo

CONH C〇m{CH^H(〇2^2 CONHiCH^NtCa^ 2.

CONHiCH^NCCHgJa €0ΝΗ(0Η2)3Ν(0Η3)2 3 /30^ H NHC〇tH-f4=^H〇)-CONH OCHg

CONHiCH^) o CONHCCHg^ -29- 14.200811249

Cl

jDCH3 (p〇Ch NHCOCH-N=l

pONHiCMa):

CONHiCHa)

5 -

dcH3 C pONH(CHa);

CONH(CH2)aN 6.

CONH(CHa)3N

CONH(CHe)aN

H 〇=«(

H NHCOCH-N=NHi]>-

18. S'

H

NHC〇0h-N=IsH^J CONH(CH2)4N(C2H5)2 COMH(CH2)4N(C2H5)2 19· a

Nhcoch-n=m-(Qkconh-^^ €ONH(CH2)sN(CH3}2 CONH(CH2)5N(CH3)2 30- 200811249

It is synthesized by the method described in JP-A-2000-239554. <2. Compound represented by the formula (D3)>

General formula (D3)

The Q system is selected from the group consisting of an anthraquinone compound dye, an azo compound dye, a phthalocyanine compound dye, a quinophthalone compound dye, a dioxin compound dye, an alizarin pyrimidine compound dye, an anthrone compound dye, and an indanthrone compound. Pigment, flavanone compound pigment, dermoside compound pigment, fluorenone-31- 200811249 compound pigment, quinone compound pigment, and organic pigment residue of thioindigo compound pigment, among which azo compound dye 'or two It is preferred that the argon compound pigment is a good azo compound dye.

The Xi series is not -C〇-, -CONH-Y2·, -SO2NH-Y2-, or CH2NHCOCH2NH-Y2-, and -CO-, -CONH-Y2- is preferred.丫2 represents an alkylene group or an extended aryl group which may have a substituent, and particularly preferably a phenyl group, a methylphenyl group or a hexyl group, and a phenyl group is preferred.

R11 and R12 are each independently substituted or unsubstituted, or r i i and R12 may form a heterocyclic group containing at least a nitrogen atom. Among them, a methyl group, an ethyl group, a propyl group or a pyridyl group containing a nitrogen atom is preferred, and an ethyl group is preferred. Y1 represents -N Η _ or -Ο -. Ζ1 represents a hydroxyl group or a group represented by the formula (D3a), and the case of ^nmi Z! may be -NH-XrQ. Ml represents an integer from 1 to 6, preferably 2 to 3. 〇1 represents an integer from 1 to 4, preferably 1 to 2.

General formula (D 3 a

R 11

—Y3-(CH2)-N 12

R In the formula (D3a), 丫3 represents -NH· or -0-, and the mi, ρ^, and Ri2 systems have the same meanings as those in the formula (D3). More specifically, the compound represented by the formula (D3) is represented by, for example, the following formula. -32- 200811249

Further, in the general formulae (D3_1) to (D3-6), Q, ml, n1, Ru, and R12 have the same meanings as those in the formula (D3). Specific examples of the compound represented by the formula (D3) are listed below, but the present invention is not limited thereto. -33- 200811249 In addition, the Cu-Pc system in the formula represents copper phthalocyanine (a)

Cu-Pc- (b) SO^NH hQ-nw ah T /C2H5 nh(ch2)3n, g2h5 C2H5 c2h5 1~3

CH2NHCOCH2NH"^^-NH

NH(CH2)3N; C2H5 NH(CH2)3N: /C2H5 (c) NHCOCHCOCH3 ^H(c NH(CH2)3N; ,CaH5 C2H5

NH(CH2)3I n^c2h5 C2H5 (d)

IS^N points no2CCcOH

CONH-H〇^NH-fNTNH(CH2)3N /C2H5 (e) N々N丫 /C2H5 nh“ch2)3N\ C2H5 c2h5

Cu-Pc- •CONH(CH2)2NH·

0-(CHa)2N; 'c2h5 NH.(CH2)3N, 'C4H9 c4h9 •34- 200811249

The compound represented by the formula (D3) is, for example, reacted with an amine compound having R12 and an alcohol compound having R12, and a halogenated tri-nized compound, and reacting the dye compound with the obtained intermediate. Can get. In addition, the description of the specification of the special fair No. 5-72 943 can also be referred to. <3. Pigment Dispersant Containing Graft Copolymer> In the method for producing an organic nanoparticle of the present invention, a graft copolymer having an amine group and an ether group is contained, and may be appropriately selected if necessary. Dispersing agent for other ingredients. The above graft copolymer is obtained by containing at least an amine group and an ether group, and may contain other monomers or the like as a copolymer unit. The weight average molecular weight (M w) of the above graft copolymer is preferably from -35 to 200811249 3000 to 1,000, and preferably from 5,000 to 50,000. When the weight average molecular weight (Mw) is less than 3,000, the aggregation of the organic nanoparticles cannot be prevented and the viscosity _ rises. When the viscosity exceeds 1 〇〇 〇〇, the solubility in the organic solvent is insufficient, and the viscosity is increased. Further, the weight average molecular weight is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography method (carrier: tetrahydrofuran). The above graft copolymer contains at least: (i) a polymerizable low polymer having an ethylenically unsaturated double bond at the terminal, (ii) a monomer having an amine group and an ethylenically unsaturated double bond, and (Hi) having The ether-based polymerizable monomer may be used as a copolymer unit, and if necessary, (iv) another monomer may be contained as a copolymerization unit. The content of the above graft copolymer in the copolymer unit, (i) the polymerizable low polymer is preferably from 15 to 98% by mass, preferably from 25 to 90% by mass, based on the amine group. The amount of the polymer is preferably from 1 to 40% by mass, preferably from 5 to 30% by mass, and the polymerizable monomer having an ether group of (Hi) is preferably from 1 to 70% by mass, preferably from 5 to 60% by mass. When the content of the polymerizable low polymer is less than 15% by mass, the stereo repulsion effect as a dispersing agent cannot be obtained, and aggregation of the organic nanoparticles can not be prevented. When the content exceeds 98% by mass, the above nitrogen-containing monomer The proportion is reduced and the adsorption capacity for the organic nanoparticle is lowered, and the dispersibility is insufficient. When the content of the nitrogen-containing monomer is less than 1% by mass, the adsorption ability of the organic nanoparticles is lowered, and the dispersibility is insufficient. When the content is more than 40% by mass, the ratio of the polymerizable low polymer is decreased, and the ratio is not obtained. As a dispersing effect of the dispersing agent, aggregation of the organic nanoparticles is not sufficiently prevented. The content of the above polymerizable monomer having an ether group is less than 1 mass. /. In the case of producing a color filter or the like, the imaging suitability is insufficient. When the color filter is more than 70% by mass, the ability to use -36-200811249 as a dispersant is lowered. Γ») Polymeric low polymer The polymerizable low polymer (hereinafter referred to as "macromonomer") is a low polymer containing a group having an ethylenically unsaturated double bond at the terminal. In the above polymerizable low polymer of the present invention, it is preferred that the one having the ethylenically unsaturated double bond is contained only in one of the both ends of the low polymer.

In general, the above low polymer may have, for example, at least one selected from the group consisting of alkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, styrene, acrylonitrile, vinyl acetate, and butadiene. Among the homopolymers or copolymers formed by the body, among them, a homopolymer or copolymer of an alkyl (meth)acrylate, polystyrene or the like is preferable. In the present invention, these oligomeric compounds may be substituted with a substituent, and the substituent is not particularly limited, and examples thereof include a halogen atom and the like. The group having the above ethylenically unsaturated double bond is preferably, for example, a (meth) acrylonitrile group, a vinyl group or the like, and among these, a (meth) acrylonitrile group is particularly preferable. In the present invention, among the above polymerizable low polymers, a low polymer represented by the following formula (E 6 ) is particularly preferable. :::...:: 〇S1 :::.-·:: .. -.:::.:Γ\:: Η2〇=(ίϊ—G—0—F Produce a S-(CH2-Order —Η •1 · ...:::.::. . . . -- ^ Formula: (E6) In the above formula (E6), R61 and R63 represent a hydrogen atom or a methyl group. R62 represents a carbon. The alkylene group substituted with the alcoholic hydroxyl group of 1 to 8 is preferably an alkyl group having a carbon number of 2 to 4 - 37 to 200811249. Y6 represents a phenyl group, a phenyl group having a carbon number of 1 to 4 alkyl groups, or COOR64 (herein, R64 means an alkyl group which may be substituted with an alcoholic hydroxyl group or a halogen of 1 carbon number, a phenyl group, or an arylalkyl group having 7 to 10 carbon atoms), a phenyl group or a -COOR64 (here, R64 is preferably an alkyl group which may be substituted with an alcoholic hydroxyl group having a carbon number of 44, and q is 20 to 200.

Specific examples of the above polymerizable low polymer are poly-2-hydroxy(methyl)propionic acid ethyl ester, polystyrene, poly(methyl)methyl acrylate, poly-(methyl)propionic acid n-butyl ester, Isobutyl poly-(meth)acrylate, copolymers of these, and a polymer having a (meth)acrylonitrile group bonded to the terminal of the molecule are preferred. The polymerizable low polymer may be a commercially available product or may be a suitable compound. The commercially available product is, for example, a sheet-end methacryl-based polystyrene low polymer (Mn = 6000, trade name: AS). -6, East Asia Synthetic Chemical Industry Co., Ltd.), sheet end methacryloyl thiolated polymethyl methacrylate low polymer (Mn = 6000, trade name: AA_6, manufactured by East Asia Synthetic Chemical Industry Co., Ltd.) ), terminal methacryloyl fluorenated poly-n-butyl acrylate low polymer (Mn = 6000, trade name: AB-6, manufactured by East Asia Synthetic Chemical Industry Co., Ltd.), terminal methacryloyl thiolation Polymethyl methacrylate/methacrylic acid 2_ hydroxyethyl ester low polymer (Μη = 70Ό0, trade name: AA-71 4, manufactured by East Asia Synthetic Chemical Industry Co., Ltd.), sheet end methacryloyl fluorenylation polymerization Butyl methacrylate / 2-hydroxyethyl methacrylate low polymer (Mn = 7000, trade name • 707S, manufactured by East Asia Synthetic Chemical Industry Co., Ltd.), methacrylic acid thiolated polymethyl group 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate low polymerization (Μ η = 7000, trade name: A Y- 7 0 7 S, A Y- 7 1 4 S, manufactured by the East Asian Synthetic Chemical Industry Co., Ltd.). Preferred examples of the above polymerizable low polymer in the present invention are exemplified by -38 to 200811249, such as a polymer selected from alkyl (meth)acrylate, and copolymerization of alkyl (meth)acrylate and polystyrene. At least one low polymer of the material having a number average molecular weight of from 1 000 to 20,000 and having a (meth) acrylonitrile group at the end. (M) Amino group-containing monomer The above-described amine group-containing single system is preferably at least one selected from the group consisting of the compounds represented by the following formula (E2). R21

In the above formula (E2), R21 represents a hydrogen atom or a methyl group. R22 represents an alkylene group having 1 to 8 carbon atoms. Among them, an alkylene group having preferably 1 to 6 carbon atoms and an alkylene group having 2 to 3 carbon atoms are particularly preferred. X2 represents -N(R23)(R24) and -R25N(R26)(R27). Here, R23 and R24 represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. R25 represents an alkylene group having 1 to 6 carbon atoms, and R26 and R27 represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group. In the above, R23 and R24 of -N(R23)(R24) are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R25 of -R25-N(R26)(R27) is preferably The alkylene group having 2 to 6 carbon atoms is preferred, and the R26 and R27 are preferably an alkyl group having 1 to 4 carbon atoms. M2 and n2 represent 1 or 〇, and m2 = 1 and n2 = 1, or m2 = 1 and n2 = 0 (i.e., corresponding to the monomers represented by the following general formulae (E3), (E4)) . In the present invention, among the monomers represented by the above formula (E2), at least one selected from the group consisting of any of the following formulae (E3) and (E4) is preferred. -39- 200811249

In the above formula (E4), R41 is synonymous with R21. X4 is synonymous with X2, -N(R43)(R44) (here, R43 and R44 are synonymous with R23 and R24), or -R45_N(R46)(R47) (here, R45, R46 and R47 are respectively It is better to synonymous with R25, R26 and R27).

Specific examples of the monomer represented by the above formula (E2) include, for example, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, diisopropyl (meth) acrylamide, Di-n-butyl (meth) acrylamide, di-isobutyl (meth) acrylamide, morpholino (meth) acrylamide, piperene B (meth) acrylamide, N -methyl-2-piperidinyl (meth) acrylamide and N,N-methylphenyl (meth) acrylamide (above (meth) acrylamide); 2-(N, N -Dimethylamino)ethyl(meth)acrylamide, 2-(N,N-diethylamino)ethyl(meth)acrylamide,3·(Ν,Ν-diethyl Amino)propyl(meth)acrylamide, 3-(N,N-dimethylamino)propyl(meth)acrylamide, 1-(N,N-dimethylamino)- 1,1-dimethylmethyl(meth)acrylamide, 6-(N,N-diethylamino)hexyl(methyl) acrylamide (above aminoalkyl (meth) propylene oxime) Amines and the like are preferred. -40-200811249 (Polymerizable monomer having an ether group) The polymerizable single system having an ether group is preferably at least one selected from the group consisting of monomers represented by the following formula (E1).

Rir i=C-C-(C (4) 2 1 1 :E::_ 1 ) ::::

In the above formula (E1), R11 represents a hydrogen atom or a methyl group. The r12 series represents an alkylene group having 1 to 8 carbon atoms. Among them, an alkylene group having 1 to 6 carbon atoms is preferred, and an alkylene group having 2 to 3 carbon atoms is more preferred. X1 represents -OR13 or -〇C〇R14. Here, R13 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a phenyl group substituted with an alkyl group having 1 to 18 carbon atoms. R14 represents an alkyl group having 8 carbon atoms. Further, m3 means 2 to 200, 5 to 100 is preferable, and 1 〇 to 1 〇〇 is particularly preferable. The polymerizable monomer having an ether group is not particularly limited as long as it has an ether group and is polymerizable, and may be appropriately selected from usual, and may, for example, be polyethylene glycol mono(meth)acrylate. , polypropylene glycol mono(meth)acrylate, polyethylene glycol polypropylene glycol mono(meth)acrylate, polybutanediol monomethacrylate, etc., which may be commercially available or suitable Synthesizer. The commercially available product is, for example, methoxypolyethylene glycol methacrylate (trade name: NK ester M-40G, M-90G, M-230G (above, manufactured by Toago Chemical Co., Ltd.); Name: Bremer PME-100, PME-200, PME-400, PME-1000, PME-2000, PME-4000 (above, manufactured by Nippon Oil & Fats Co., Ltd.), polyethylene glycol monomethacrylate ( Product name: Bremer PE-90, PE-200, PE-350, manufactured by Nippon Oil & Fats Co., Ltd., polypropylene glycol monomethacrylate (trade name: Bremer-41-200811249 PP-500, PP-800 , ΡΡ·1 000, manufactured by Sakamoto Oil Co., Ltd.), polyethylene glycol polypropylene glycol monomethacrylate (trade name: Bremer 70PEP-3 70B, manufactured by Sakamoto Oil Co., Ltd.), Polyethylene B Glycol polycondensation butanediol monomethacrylate (trade name: Bremer 55PET-800, manufactured by Nippon Oil & Fats Co., Ltd.), polypropylene glycol polybutanediol monomethacrylate (trade name: Bremer NHK) -5050, manufactured by Nippon Oil & Fats Co., Ltd.). (iv) other monomers

The above-mentioned graft copolymer may further include the above other monomers as a copolymer unit, and the other single system is not particularly limited, and may be appropriately selected depending on the purpose thereof, and examples thereof include an aromatic vinyl compound (for example, styrene, Α-methyl styrene and vinyl toluene), alkyl (meth) acrylate (for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate and (a) (isobutyl acrylate), alkyl aryl (meth) acrylate (eg, benzyl (meth) acrylate), glycidyl (meth) acrylate, vinyl carboxylic acid (eg, vinyl acetate and Vinyl propionate), ethylene cyanide (for example, (meth)acrylonitrile and α-chloroacrylonitrile), and aliphatic conjugated dienes (for example, 1,3-butadiene and isoprene) , (meth)acrylic acid, and the like. Among these, an unsaturated carboxylic acid, an alkyl (meth)acrylate, an alkylaryl (meth)acrylate, and an ethyl phthalate are preferable. The content of the other monomer in the above graft copolymer is preferably, for example, 5 to 70% by weight. When the content is less than 5% by weight, the physical properties of the coating film cannot be controlled, and when it exceeds 7% by weight, the ability as a dispersing agent cannot be sufficiently exhibited. Preferred specific examples of the above graft copolymer are, for example: (11) 3-(anthracene, dimethylamino) propyl acrylamide/polyethylene glycol-(-42- 200811249 methyl)acrylic acid Ester/terminal methacryl oxime poly(methyl) acrylate copolymer, (1 2) 3-(N,N-dimethylamino) propyl decylamine / polyethylene glycol one (A Acrylate/terminal methacryl oxime polystyrene copolymer, (13) 3-(N,N-dimethylamino)propyl acrylamide/polyethylene glycol mono(meth)acrylic acid Ester/methyl (meth) acrylate end methacryl oxime polystyrene copolymer,

(14) 3-(N,N-Dimethylamino)propyl acrylamide/polyethylene glycol mono(meth)acrylate/terminal methacryl thiolated methyl (meth) acrylate and methyl Copolymer of 2-hydroxyethyl acrylate copolymer, (15) 3-(N,N-dimethylamino)propyl acrylamide/polyethylene glycol mono(meth)acrylate/terminal methyl Copolymer of acrylylated methyl methacrylate and 2-hydroxyethyl methacrylate copolymer, (16) 3-(N,N-dimethylamino)propyl acrylamide/polyethylene glycol Copolymer of mono(meth)acrylate/terminal methacryloyl methacrylate methyl methacrylate and 2-hydroxyethyl methacrylate copolymer, (17) 3-(anthracene, fluorenyl-dimethylamino group ) propyl acrylamide / polypropylene glycol mono (meth) acrylate / terminal methacryl oxime polymethyl (meth) acrylate copolymer, (18) 3- (Ν, Ν-dimethylamino) Propyl acrylamide/polyethylene glycol polypropylene glycol mono(meth)acrylate/terminal methacrylic acid poly(methyl) acrylate copolymer, (1 9) 3-(Ν,Ν-dimethyl Aminopropyl) propyl acrylamide/polyethylene glycol Glycol mono(meth)acrylate/terminal methacrylic acid poly(methyl) acrylate copolymer, '-43- 200811249 (20 )3-( N,N-dimethylamino)propyl Acrylamide/polypropylene glycol polybutane diol-(meth) acrylate/terminal methacryl oxime poly(methyl) acrylate copolymer, and the like. Among them, a compound represented by the following formula (D4) is preferred, and (11), (14), and (18) are preferred. In the formula (D4), Me represents a methyl group. Formula (D4) -CHvCH-

CONHC3H6NMe2 j \ C02(C2H40)23Mea, , b :1>4 = 15:20:65 (weight ratio)

CH? CH〇-C-

CH C〇2C2H4S-|CH2*C

C02Me/60 The above graft copolymer is obtained by forming a component of each of the above copolymer units, for example, by radical polymerization in a solvent. In the radical polymerization, a radical polymerization initiator can be used, and a lock transfer agent (for example, 2-hydrothioethanol and dodecanethiol) can be further used. For the pigment dispersant containing the graft copolymer, reference is also made to the description of JP-A-2001-31 885.

In order to further improve the uniform dispersibility and storage stability of the pigment particles, the content of the dispersant is preferably in the range of 0 1 to 1 0 0 parts by mass, more preferably 1 to 500 parts by mass, based on 1 part by mass of the pigment. The range is more preferably 5 to 20 parts by mass. When the amount is less than 1 part by mass, the dispersion stability of the organic nanoparticle may not be observed. Further, the dispersing agent may be used singly or in combination of plural kinds. [Manufacturing Apparatus] A preferred embodiment of a manufacturing apparatus for forming organic nanoparticles in the manufacturing method of the present invention will be described. The present invention is not limited by the definition of -44-200811249. (Manufacturing Apparatus Example 1) Fig. 1-1 is a schematic view showing a manufacturing apparatus as an embodiment of the present invention. The organic pigment solution in the first to the first embodiment is continuously supplied into the container 11 through the supply pipe 14. Here, the container 11 contains a poor solvent 1 1 a, and a large amount of the poor solvent is continuously convected by stirring. Fig. 1 - 2 is a schematic view of a manufacturing apparatus used as another more preferable aspect of the present invention, and a mixing chamber (a stirring area) 13 is provided in the container 11 of the manufacturing apparatus of the first to the first aspect. The mixing chamber 13 is disposed under the liquid surface of the poor solvent, and the interior thereof is filled with the poor solvent. Further, a large amount of the poor solvent in the reaction vessel 1 is caused by the stirring action in the mixing chamber 13, so that the inside of the mixing chamber 13 is continuously cut from the lower side (the direction of the arrow in the figure). It produces convection. Fig. 1-3 is an enlarged partial cross-sectional view showing, in a schematic manner, a mixing chamber 13 as an embodiment of the manufacturing apparatus of Figs. 1-2. The organic pigment solution is supplied from the supply pipe 14 to the mixing chamber 13 . The mixing chamber 13 is composed of a housing 17 of a straight rectangular tube having a constant cross-section, the upper end of the housing 17 is an open end (opening), and the lower end is provided with a circular hole 18 and the mixer In the case of the poor solvent system in the 1st and the outside of the stirring field (in the case of the composition in the figure, a large amount of the solvent 11 a, the field other than the mixing chamber 13 is outside the stirring field, also referred to as a stirring outside field) The poor solvent is formed by connecting each other. The organic pigment solution supply pipe 14 is disposed in a wall constituting the lower end of the casing 17 and opens toward the circular hole. Further, a stirring blade 1 2 is provided in the mixer 1 3, and a rotating shaft 15 is attached to the stirring blade, and is rotated by the motor cymbal 6. By the rotation of the agitating blades 12, the lean solvent passes through the circular holes 18 and moves from the bottom to the upper side of -45-200811249 toward the mixer 13 to make it circulate frequently. The agitating blades 12 provided in the mixing chamber 13 described above must produce a desired mixing strength in the mixing chamber. This mixed strength is estimated to be an important operational factor for the size of droplets (droplets) at the time of mixing of the organic pigment solution. Further, the stirring blade 12 is selected to have a larger particle formed by combining the organic pigment particles generated in the mixing space with the other organic pigment particles, and being exposed to the mixing chamber 13 In the organic pigment solution, it is preferred that the organic pigment particles are quickly extracted and rapidly discharged to the outside of the mixing chamber 13 so as to form large particles without generating large particles. ^ The agitating blade 12 can be used in any form to achieve the above object, for example, a turbine type, a fan turbine type, or the like can be used. Further, it is preferable that the casing 17 is constituted by a square cylinder as described above. By doing so, the flow created by the stirring blade 1 2 disturbs the square of the casing 1 7 and does not require an attachment such as a baffle to further improve the mixing effect. Fig. 1-4 is another embodiment of the manufacturing apparatus of Fig. 1-2, which is a mixture of two stirring blades in the mixing chamber (mixing mixing blade 19a, discharging agitating blade 1 9b) An enlarged view of the enlarged part of the device. By providing two such agitating blades', the ability to control the mixing strength and the ability to discharge the generated organic pigment particles out of the mixer can be selected, and the mixing intensity and circulation amount can be independently set to the desired state. . (Manufacturing Apparatus Example 2) Fig. 2 is a cross-sectional view showing another embodiment of the manufacturing method used in the manufacturing method of the present invention, in the manufacturing apparatus-46-200811249. In Fig. 2, the organic pigment solution and the poor solvent medium are continuously supplied into the stirring tank 21a by the supply pipes 24a, 24b, respectively. The organic pigment particles formed in the agitation tank 2 1 a are retained in the agitation tank _ 21 a to combine with other organic pigment particles to form larger particles, which are exposed to the supply from the supply tubes 24 a, 2 4 b In the organic pigment solution, the produced organic pigment particle dispersion is quickly extracted from the discharge pipe 23 so as to form large particles without generating large particles.

Fig. 3 is a cross-sectional view showing still another embodiment of the apparatus used in the manufacturing method of the present invention. In the manufacturing apparatus of FIG. 3, the stirring apparatus 50 is provided in the cylindrical shape of the liquid discharge port 36 which has the two liquid supply ports 32 and 33 which flow the organic pigment solution and the poor solvent respectively, and the mixed liquid which discharges the stirring process. The agitation tank 38 and the pair of agitating blades 41 and 42 which are driven by the rotation in the agitation tank 38 to control the stirring state of the liquid in the agitation tank 38. The agitation tank 38 is composed of a cylindrical groove body 9 that faces the center axis in the vertical direction, and a sealing plate 40 that blocks the upper and lower open ends of the groove body 39 to form a groove wall. Further, the agitation vessel 38 and the tank body 39 are formed of a non-magnetic material excellent in magnetic permeability. The two liquid supply ports 32, 33 are provided at positions close to the lower end of the tank body 39, and the liquid discharge port 36 is provided at a position close to the upper end of the tank body 39. Then, the pair of agitating blades 41 and 42 are disposed apart from each other in the upper and lower ends of the agitating grooves 38, and are rotationally driven in opposite directions. Each of the agitation blades 41, 42 constitutes a magnetic air coupling C with an outer magnet 46 disposed on the outer side of the groove wall (sealing plate 40) of the agitation blades 41, 42 respectively. That is, each of the agitating blades 41 and 42 is connected to the respective outer magnets 46 by magnetic force, and each of the outer magnets - 47 - 200811249 stones 46 is rotationally driven by independent motors 48 and 49 to perform reverse rotation operations. The pair of agitating blades 41 and 42 disposed opposite each other in the groove 38 are formed by the arrow (X) of the broken line in FIG. 3 and the arrow (γ) of the solid line forming a different tendency in the groove 38. Stir the flow. Therefore, the agitation flow formed by each of the agitation blades 41 and 42 collides with each other due to the difference in the flow direction, and the groove 38 generates a high-speed turbulent flow in the promotion tank 38, and even if the flow in the groove 38 is prevented from being fixed, even in the agitation. When the rotation of the blades 4 1 and 42 is increased, the rotation of the agitating blades 41 and 42 is prevented from rotating to form a cavity, and the inner circumferential surface of the agitation tank 38 can be prevented from being insufficiently subjected to the agitation. The so-called unsuitable occurrence of a flowing fixed flow in the groove 38 occurs. Therefore, the processing speed can be easily increased by the rotation of the high-speed stirring blades 41 and 42, and at this time, the flow of the liquid in the groove 38 can be prevented from being fixed, and the liquid which is insufficiently stirred and mixed can be discharged, thereby preventing the deterioration of the processing quality. . Further, since each of the stirring blades 41 and 42 in the stirring tank 38 is coupled to the motors 48 and 49 disposed outside the stirring tank 38 by the magnetic air coupling C, it is not necessary to insert the rotating shaft into the groove wall of the stirring tank 38. Since the agitation tank 38 can form a closed container structure in which the rotating shaft has no insertion portion, f is prevented from agitating the dense seed liquid to the granules. The material of the material begins with the quality of the material, and the material of the machine is opened. The machine is made up of a machine, and it is made of a quilt. The material is made from acre, and the low price is available for this. It is also used within the scope of the application. In the square, the square borrows the m _ , the amount, and mixes the 48--liquid stream and stirs the -4 >/ method. It is thought that the 8 Λ 连 产 产 常 常 常 常 常 常 常 常 常 , , , , , , , , , , , , , , , , , , 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经The liquid m is not dissolved in the liquid solution, and is mixed with the lean and poorly sealed. When the product is finished at the end of 200811249, the solubility of the organic material of the dispersion can be fixed, and the monodisperse organic pigment particles can be stably produced. In the tank, the liquid flow is fixed, and the organic pigment particle dispersion liquid which is insufficiently stirred and mixed is discharged, and impurities such as a lubricating fluid (sealing liquid) for rotating the shaft are prevented from being mixed into the solution in the tank, whereby the order can be further stably produced. Dispersed organic pigment particles. (Production apparatus example 3) Another manufacturing embodiment of the apparatus used in the production method of the present invention will be described as a manufacturing method in which a blade having a shearing force is used for stirring. The shearing force is the shearing force of the droplets (microdroplets) generated by the stirring blade and the organic pigment solution mixed with the poor solvent. The shape of the stirring portion that can be used in the present invention is as long as high shear can be performed. The form of the force is not particularly limited, but generally, for example, a stir blade, a turbine blade, a spiral blade, a Pfau die blade, or the like, preferably a dissolver blade, a rotatable turbine portion, and the like It is preferable to provide a stirring, emulsification, and dispersing machine for the stirring portion formed by the baffle portion having a slight Φ point gap around the fixed portion. The dissolver blade is a special stirring blade having a function capable of forming a high shear force. Fig. 4-1 is a front view schematically showing one example, and the drawing substitute photo is shown in Fig. 4-2. Further, it is also possible to use a turbine unit that can be rotated as shown in Fig. 5. A device for agitating, emulsification, and dispersing a device having a small amount of a gap between the baffle portions and a baffle portion that is fixed in the vicinity thereof, for example, Physcotron manufactured by Microtec Nition Co., Ltd., and 200811249 manufactured by Special Machine Chemical Co., Ltd. Τ·κ homogenizing mixer, ULTRA-TURRAX manufactured by Nippon Steel Co., Ltd. The stirring speed is different depending on the viscosity, temperature, type of surfactant or addition amount of the poor solvent, but only 1 〇〇. 1 〇〇〇0 rp m is better, 1 5 0~8 0 0 0 r p'm is better, 2 0 0-6 0 0 rpm is particularly good. If the number of rotation is too low, the stirring effect cannot be Give full play, and if it is too high, bubbles will be trapped in the poor solvent.

In the method for producing an organic nanoparticle of the present invention, the organic nanoparticle dispersion can be produced on a commercial scale by a desalination and concentration, or a concentrated liquid suitable for inkjet ink. Hereinafter, the concentration method will be described. The concentration method is not particularly limited as long as it is a concentrated organic nanoparticle liquid. For example, a mixed extraction solvent is added to the organic nanoparticle dispersion, and the organic nanoparticle is extracted by concentration in the extraction solvent phase, and filtered. a method of filtering the concentrated nanoparticle liquid of the concentrated extract; a method of concentrating the organic nanoparticle by centrifugation; a method of desalting and concentration by filtering over Φ; and sublimating the solvent by vacuum freeze drying Concentration method; a concentration method of drying the solvent by heating or even under reduced pressure is preferred. Or use such combinations, etc. is particularly good. The concentration of the organic nanoparticles after concentration is preferably 1 to 1% by mass, more preferably 5 to 1.0% by mass, and particularly preferably 1 to 10,000% by mass. Hereinafter, a method of concentrated extraction will be described. The extraction solvent used in the concentrated extraction is not particularly limited, but is not substantially mixed with a dispersion solvent (for example, an aqueous solvent) of the organic nanoparticle dispersion (in the present invention, substantially no mixing means compatibility) The low is preferably -50-1111, the dissolved amount is preferably 50% by mass or less, and more preferably 30% by mass or less. There is no particular lower limit for the amount of the solution, and it is actually 1% by mass or more in consideration of the solubility of the usual solvent. It is preferred to form a solvent at the interface after mixing and standing. Further, the extraction solvent is preferably a solvent in which the organic nanoparticles are redispersed in an extraction solvent without causing weak agglomeration (a floc which can be redispersed even if a high breaking force such as honing or high-speed stirring is not applied). . If it is in such a state, it does not cause a strong agglomeration which changes the particle size, and the organic nanoparticle for the purpose of wetting the solvent is wetted, and it is easy to remove the dispersion solvent such as water by filter filtration or the like. good. The extraction solvent is preferably an ester compound solvent, an alcohol compound solvent, an aromatic solvent or an aliphatic compound solvent, an ester compound solvent, an aromatic solvent or an aliphatic solvent, and particularly preferably an ester compound solvent. The ester compound solvent is, for example, 2-(1-methoxy)propyl acetate, ethyl acetate or ethyl lactate. The alcohol compound solvent is, for example, n-butanol or isobutanol. Examples of the aromatic compound solvent include benzene, toluene, xylene, and the like. The aliphatic compound solvent is, for example, η-hexane or cyclohexane. Further, the extraction solvent Φ medium may be a pure solvent formed from the above preferred solvent, or may be a mixed solvent composed of a plurality of solvents. The amount of the extraction solvent is not particularly limited as long as it can extract the organic nanoparticles, but it is preferable to use a small amount of the organic solvent. When it is represented by a volume ratio, when the organic nanoparticle dispersion liquid is set to 1 Torr, the extraction solvent to be added is preferably in the range of 1 to 1 Torr, more preferably in the range of 10 to 90, and 20 to 80. The range is particularly good. When too much is too concentrated, it takes a lot of time. When the amount is too small, the extraction is insufficient and the nanoparticles are left in the dispersion solvent. -51- 200811249 After the extraction solvent is added, it is preferred to mix and mix in such a manner as to sufficiently contact the dispersion. A general method can be used for stirring and mixing. The temperature at which the mixed extraction solvent is added is not particularly limited, but preferably 1 to 1 〇 〇 °c and preferably 5 to 60 ° C is preferable. Any apparatus can be used as long as it is desirable to carry out the addition and mixing of the extraction solvent in each step, and for example, it can be carried out using a separatory funnel type apparatus.

The method used in, for example, desalting/concentration of a silver halide emulsion can be applied depending on the case of exceeding cerium. Research Disclosure No. 1 0208 (1 972), No. 1 3 1 22 (1 975), and Nο"6 351 (1 977) are known. For the pressure difference or flow rate that is important for the operating conditions, please refer to the characteristic curve described in the book "Using the Membrane Utilization Technology Operation Manual" (1978) and ρ2 75, which is designed to deal with organic nanoparticle dispersions. In the above, it is necessary to find the optimum conditions for inhibiting particle agglutination. Further, in addition to the method of dispersing the solvent due to the membrane permeation, there is a batch type in which the constant volume type and the discontinuity of the solvent are continuously added, and the constant volume type in which the desalination treatment time is relatively short is preferable. The solvent thus replenished may be pure water obtained by ion exchange or distillation, and the pure solvent may be mixed with a dispersant or a poor solvent of the dispersant, or may be directly added to the organic nanoparticle dispersion. Fig. 6 shows an example of the configuration of a device for performing ultrafiltration. In the sixth embodiment, as shown in the figure, the apparatus has a storage tank 81 for accommodating organic nanoparticles, a circulation pump 82 for circulating the dispersion in the storage tank 81, and a pump 82 for circulation. The by-produced inorganic salt in the dispersion is removed into the excess enthalpy module 83 which is permeable to water. The permeate system returns the separated dispersion to the storage tank 81 again, and repeats the same operation until the deuterated inorganic salt is removed to achieve the intended purpose. Further, the device is provided with a supplementary pure water measuring flow meter 84 for use in a certain amount of supplement-52-200811249 as pure water for the solvent lost by the permeated water, and is provided for determining the amount of pure water replenishment. The permeate water metering flow meter 85. Further, a pump 86 for cleaning in the reverse direction for introducing water for diluting the permeate water is provided. The ultrafiltration membrane system has been assembled as a module, such as a flat plate type, a spiral type, a cylindrical type, a hollow fiber type, and a hollow fiber type, such as Asahi Kasei Co., Ltd., Daisei Chemical Co., Ltd., Toray Co., Ltd. It is commercially available from Nitto Denko Electric Co., Ltd., but it is preferably a spiral type or a hollow type from the viewpoint of total membrane area or detergency. Further, the classification molecular weight of the critical enthalpy index which can form a permeable membrane component must be determined according to the molecular weight of the dispersing agent to be used, and it is preferably 5, 0.001 or more and 50,000 or less, and 5,000 or more and 15,000 or less. Better. In order to separate the dispersion solvent and the concentrated extract of the organic nanoparticle dispersion, it is preferred to filter with a filter. The device for filter filtration is, for example, a device that can be used for pressure filtration. Preferred filters include, for example, a nano filter, a super filter, and the like. Filtration by a filter removes the residual dispersion solvent, and further concentrates the organic nanoparticles in the concentrated extract to form a concentrated nanoparticle liquid. The method of freeze-drying is not particularly limited, and any method that the manufacturer may utilize may be used. For example, a refrigerant direct expansion method, a repetitive freezing method, a heat medium circulation method, a triple heat exchange method, an indirect heating freezing method, preferably a refrigerant direct expansion method, an indirect heating freezing method, and more preferably an indirect heating freezing method. In any of the above methods, it is preferred to perform freeze-drying after performing the pre-freezing. The conditions for pre-freezing are not particularly limited, but the freeze-dried sample must be generally frozen. The apparatus for indirect heating and freezing method is preferably, for example, a small freeze-53-200811249 dryer, an FTS freeze dryer, a LYOVAC freeze dryer, an experimental freeze dryer, a freeze dryer for research, and a triple heat exchange vacuum freeze-drying. Machine, single-cooling freeze dryer, HULL freeze dryer, preferably small freeze dryer, experimental freeze dryer, freeze dryer for research, single-cooling freeze dryer, more preferably small freeze dryer, Single cooling freeze dryer.

The freeze-drying temperature is not particularly limited, and is, for example, -190 to -4 ° C, preferably -1 2 0 to · 20 ° C, more preferably -8 0 to -60 ° (: left and right. Freeze-dried The pressure is not particularly limited, and the manufacturer may suitably select, for example, 0.1 to 35 Pa, preferably 1 to 15 Pa, more preferably 5 to 10 Pa. The freeze drying time is, for example, 2 to 48 hours. Preferably, the temperature is from 6 to 36 hours, more preferably from about 16 to 26 hours, but these conditions are suitable for the manufacturer. For the freeze-drying method, for example, the preparation machine technical operation manual: preparation machinery technology research conference, Local Library, P.120-129 (September 2000); Vacuum Handbook: Japan Vacuum Technology Co., Ltd., OM, ρ· 32 8-331 (1992); Freeze and Dry Research Conference志: Imo filial piety, N 〇 · 15 , p _ 8 2 (1 9 6 5 ), etc. The following is a description of centrifugation. • Centrifugal separator used for concentration of organic nanoparticles separated by centrifugation As long as it is capable of dispersing organic nanoparticle particles (or organic nanoparticle concentrate extract) Any of the devices for sedimentation of the organic nanoparticles may be used. The centrifugal separator may be, for example, a widely used device, and may have, for example, a function of a crude distillation (a function of absorbing a liquid layer during rotation and a function outside the discharge system). Or a continuous centrifugal separator that continuously discharges solids, etc. The centrifugal separation conditions are preferably centrifugal force (indicating a centrifugal acceleration of several times -54-200811249 by gravity acceleration) 50 to 10000, preferably 100 to 8000, preferably 15 0 to 60 00 is particularly preferable. The temperature at the time of centrifugation is preferably -10 to 80 ° C, preferably -5 to 70 ° C, and preferably 0 to 60 ° C depending on the solvent type of the dispersion. Describes drying.

The apparatus used in the concentration of the organic nanoparticles to be dried under reduced pressure is not particularly limited as long as it evaporates the solvent of the organic nanoparticle dispersion (or organic nanoparticle concentrated extract). For example, a vacuum dryer and a rotary pump which are widely used, or a device which can be heated and reduced in pressure while stirring a solution, and a device which can be continuously dried by passing the liquid through a tube which is heated and decompressed can be used. The heating and decompression drying temperature is preferably 30 to 230 ° C, preferably 35 to 200 ° C, and particularly preferably 40 to 180 ° C. The pressure at the time of pressure reduction is preferably 100 to 1,000,000 Pa, preferably 300 to 90,000 Pa, and particularly preferably 500 to 80,000 Pa. According to the concentration method as described above, the organic nanoparticle can be more efficiently concentrated from the organic nanoparticle dispersion. In the concentration ratio, for example, when the concentration of the nanoparticles in the organic nanoparticle dispersion forming the raw material is 1 Φ, the concentration in the concentrated organic nanoparticle paste is preferably concentrated to about 100 to 3000 times, more preferably It is about 500~2000 times. [Micro-dispersion] According to the production method of the present invention, organic nanoparticles having an aggregated state can be finely dispersed by, for example, concentration, etc. (In the present invention, fine dispersion means that the dispersion is improved. Dispersion of particle agglutination). The organic nanoparticle contained in the organic nanoparticle liquid concentrated by the above extraction solvent, centrifugation, drying, or the like is usually concentrated by condensation. In this case, in order to perform rapid filter filtration -55 - 200811249 and obtain a good dispersion state, it is preferable to be a floc which can be agglomerated at a redispersible degree. Next, the polymer compound which can be preferably used in the production method of the present invention is described in detail (the "polymer compound" of the present invention is preferably an organic compound having a mass average molecular weight of not more than 1,000, and there is no particular upper limit. Actually, the mass average molecular weight is 50% or less, preferably 1,000,000 or less, more preferably 50,000 or less.

The polymer compound which can be preferably used in the production method of the present invention is preferably a polymer compound having a mass average molecular weight of 1,000 or more and a polymer compound represented by the following formula (1). ___ 逋 (1)

In the above formula (1), A1 represents a non-acid group, a group having a basic nitrogen atom, a urea group, a carbamate group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, and an alkoxy group. An alkyl group, an epoxy group, an isocyanate group, and a monovalent organic group having a group selected from a trans group, or a monovalent organic group containing an organic dye structure which may have a substituent or a hetero ring. The η A1 lines may be the same or different. Specifically, the A1 system is not particularly limited, and the above-mentioned "monovalent organic group having an acidic group" has, for example, a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate group, A monovalent organic group such as a boronic acid group. Moreover, the above-mentioned "monovalent organic group having a group having a basic nitrogen atom" is, for example, a monovalent organic group having an amine group (-NH2) and a substituted imido group (_NHR8, -56-200811249-NR9R1G) The monovalent organic group (herein, R8, R9, and R1Q each independently represent a fluorenyl group having 1 to 20 carbon atoms, an aryl group having 6 or more and 20 or less carbon atoms, and an aralkyl group having 7 or more and 30 or less carbon atoms) A monovalent organic group having a mercapto group represented by the following formula (a1): In the formula (a1), Ra1 and Ra2 each independently represent an alkyl group having a carbon number of 20 and a carbon number of 6 or more and 20 or less. An aryl group, an aralkyl group having 7 or more and 30 or less carbon atoms, and a monovalent organic group having a mercapto group represented by the following formula (a2): In the formula (a2), Ra3 and Ra4 each independently represent a carbon number An alkyl group of 1 to 20, an aryl group having 6 or more and 20 or less carbon atoms, an aromatic group having 7 or more and 30 or less carbon atoms, and the like.

The above-mentioned "monovalent organic group having a ureido group" is, for example, -NHCONHR15 (here, R15 represents a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more and 20 or less carbon atoms, and a carbon number; 7 or more and 30 or less aralkyl groups).

The above-mentioned "monovalent organic group having a urethane group" is, for example, -NHCOOR16 or -〇CONHR17 (here, R16 and R17 each independently represent an alkyl group having a carbon number of 2, and a carbon number of 6 or more and 20 The following aryl group, an aralkyl group having 7 or more and 30 or less carbon atoms, and the like. The above "group containing a group having a coordinating oxygen atom" is exemplified by a group having a acetyl ketone ligand group, a group having a crown ether, and the like. The "group having a hydrocarbon group of 4 or more carbon atoms" is, for example, an alkyl group having 4 or more carbon atoms (for example, an octyl group or a dodecyl group) or an aryl group having 6 or more carbon atoms (for example, a phenyl group, a naphthyl group, etc.). An aralkyl group having a carbon number of 7 or more (e.g., benzyl group, etc.), etc. -57-200811249. At this time, there is no upper limit on the carbon number, and it is preferably 30 or less. The above "a group having an alkoxy group and a decyl group" is, for example, a group having a trimethoxyalkyl group, a triethoxyalkyl group or the like. The above "epoxy group-containing group" is, for example, a group having a glycidyl group or the like. The above "isocyanate group-containing group" is, for example, a 3-isocyanatepropyl group or the like. The above "group having a hydroxyl group" is, for example, a 3-hydroxypropyl group or the like.

In the above, the above-mentioned A1 is preferably a monovalent organic group selected from the group consisting of an acidic group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms, and the above organic dye structure or heterocyclic ring system. It is not particularly limited, and more specifically, the organic dye structure is, for example, a phthalocyanine compound, an insoluble azo compound, an azo lake compound, an anthraquinone compound, a quinone ketone compound, a dioxine A cultivating compound, a diketopyrrolopyrrole compound, a hydrazine compound, an anthrone compound, an indanthrone compound, a yellow ketone ketone compound, an anthrone compound, an anthraquinone compound, a sulfonium compound, and the like. Further, the heterocyclic ring is exemplified by, for example, thiophene, furan, hydrazine, pyrrole, pyrroline, lysine B, bis-dioxane, pyridoxine, pyridoxine, pyridoxine, imipenem, B. Anthraquinone, chemodiazole, triazole, thiadiazine, pyran, pyridine, piperidine, dioxane, miso, sorghum, pyrimidine, piperazine, triterpene, trimethylthioaldehyde, isoporphyrin, Isoindolinone, benzimidazolone, amber imine, phthalimide, naphthyl imine, hydantoin, hydrazine, quinone, azole, print, mark, Hey. Further, the above-mentioned organic dye structure or heterocyclic ring may have a substituent, and the substituent -58- 200811249 is an alkyl group having a carbon number of 20 such as a methyl group or an ethyl group, and a carbon number of 6 or more such as a phenyl group or a naphthyl group. An aryl group of 16 having a carbon number of 1 to 6 such as a methoxy group, an ethoxy group or the like having a carbon number of 1 to 6 such as a group, an amine group, an anthracenyl group, a sulfonylamino group, an N-thioguanamine group or an ethoxylated group. Alkoxy group having 1 to 6 carbon atoms, a halogen atom such as chlorine or bromine; alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group; A carbonate group or the like of a third butyl carbonate or the like. Further, the above A1 is preferably a monovalent organic group represented by the following formula (4).

In the above formula (4), B 1 is selected from an acidic group and has an alkalinity.

a group of a nitrogen atom, a urea group, a carbamate group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxyalkyl group, an epoxy group, an isocyanate group, and a hydroxyl group, or An organic dye structure or a heterocyclic ring having a substituent; R18 represents a single bond or an a1 valent organic or inorganic linking group. A1 represents 1 to 5, and a 1 B 1 system may be different or different. The B1 system is synonymous with the above A1 in the formula (4), and the preferred embodiment is also the same. The above organic dye structure or heterocyclic ring system is, for example, a phthalocyanine compound, an insoluble azo compound, or an azo lake (Αζσ lake) compound. , anthraquinone compound, quinophthalone compound, dioxan compound, diketopyrrolopyrrole compound, azide compound, anthrone compound, indanthrone compound, flavanone compound, anthrone compound, phenanthrene compound An organic dye structure such as a thioindigo compound, such as thiophene, furan, hydrazine, pyrrole, pyrroline, pyrrolidine, dioxane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, 59- 200811249 Oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, porphyrin, hydrazine, pyrimidine, piperidine, tri-nral, trimeric methyl aldehyde, isoporphyrin , isoindolinone, benzimidazolone, amber imine, phthalimide, naphthyl imine, hydantoin, quinone, quinoline, carbazole acridine, acridone Heterocycles such as hydrazine. Further, the above-mentioned organic dye structure or heterocyclic ring may have a substituent, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group, and an aryl group having 16 carbon atoms such as a phenyl group or a naphthyl group. a hydroxyl group having 1 to 6 carbon atoms such as a hydroxyl group, an amine group, a carboxyl group, a sulfonylamino group, a N-sulfinylamino group or an ethoxycarbonyl group; and a carbon number of 1 to 6 such as a methoxy group or an ethoxy group; a halogen atom having an alkoxy group, a chlorine atom or a bromine group, an alkoxycarbonyl group having a carbon number of 2 to 7 such as a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group; a cyano group; a third butyl carbonate; Carbonate groups and the like. R18 represents a single bond or a bond of a1+1 valence, and a1 represents b. The linking group R18 contains 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, one to 50 oxygen atoms, one to 200 hydrogen atoms, and one to 20 sulfur atoms. The base formed may be unsubstituted or substituted. It is preferable that the R1 8 system has a φ machine connection base. Specific examples of R18 include, for example, the following structural units or a combination of the structural units. -60- 200811249 -Bu g--0-一s一一一一一4!——%——-έ- —— (t-1) (t-2) (t-3) (t-4) ( T-5) (t-6) (t-7) (t-8) (t-9) (t-10) (t-11) (t-12) u Vis-上-七- (t-13 ) (t-14) (t -15) (t-16) (t-17) (t -18) (t-19)

(t-20)

G~ -S=6- hc=c- (t-21) (t - 22) (t-23) (t-24) -C (t-25) 4 (t-26) (t-27) ( T-28) (t-29) (t-30) (t-31) (t-32) (t-33) (t-34) In the case where R1 8 has a substituent, the substituent is, for example, a An alkyl group having 1 to 20 carbon atoms such as a group or an ethyl group; an aryl group having 6 to 16 carbon atoms such as a phenyl group or a naphthoquinone group; a hydroxyl group, an amine group, a carboxyl group, a sulfonylamino group, and an N-thioguanamine group. Ethoxylated

An alkoxy group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group, a halogen atom such as chlorine or bromine, a methoxycarbonyl group or an ethoxycarbonyl group; An alkoxycarbonyl group having 2 to 7 carbon atoms such as a cyclohexyloxycarbonyl group, or a carbonate group such as a cyano group or a tributyl carbonate. In the above formula (1), R1 represents a (m + n)-valent linking group. The m + n system is full 3 to 1 0. The (m + n) valent linking group represented by the above R1 contains 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 2 〇〇. The hydrogen atom and the base of 0 to 20 sulfur atoms may be unsubstituted, and may further have a substituent at -61-200811249. It is preferred that R1 is an organic linking group. Specific examples of R1 include, for example, the structural unit of the above (t-1) to (t-34) or a group composed of the structural unit (which can form a ring structure). In the case where R1 has a substituent, the substituent is, for example, an alkyl group having a carbon number of 20 such as a methyl group or an ethyl group, an aryl group having a carbon number of 6 to 16 such as a phenyl group or a naphthyl group, a hydroxyl group or an amine group, a methoxy group having 1 to 6 carbon atoms such as a carboxyl group, a sulfonylamino group, an N-thioguanamine group or an ethoxylated group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group; a halogen atom such as bromine, a methoxyl group, an ethoxy group, an alkoxycarbonyl group having a carbon number of 2 to 7 such as a cyclohexyloxycarbonyl group, or a carbonic acid such as a cyano group or a t-butyl carbonate. Ester group and the like. R2 represents a single bond or a divalent linking group. R2 contains 1~1〇〇 of carbon atoms, 〜1~1〇 of nitrogen atoms, ~~50 oxygen atoms, 1~200 hydrogen atoms, and 〜20 sulphur The base formed by an atom may be unsubstituted or may have a substituent. It is preferred that R2 is an organic linking group. Specific examples of R2 include, for example, the structural unit of the above-mentioned 3, 4, 7-18, 22-26, 32, and 34, or a combination of the structural unit.

In the case where R2 has a substituent, the substituent is, for example, an alkyl group having a carbon number of 1 to 20 such as a methyl group or an ethyl group, a aryl group having a carbon number of 6 to 16 such as a naphthyl group, a hydroxyl group or an amine group. a carboxyl group having a carbon number of a carboxyl group, a sulfonylamino group, an N-thioguanamine group or an ethoxylated group, an alkoxy group having a carbon number of 1 to 6 such as a methoxy group or an ethoxy group, chlorine or bromine An alkoxycarbonyl group having a carbon number of 2 to 7 such as a halogen atom such as a methoxyl group, an ethoxylate group or a cyclohexyloxycarbonyl group, or a carbonate group such as a cyano group or a t-butyl carbonate. . In the above formula (1), m represents 1 to 8. The m system is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 to 2. -62-

200811249 In addition, η represents 2 to 9. The η system is preferably 2 to 8 and 2 to 7 is preferred and preferably 3. In the above formula (1), Ρ1 represents a polymer compound residue (referred to as a polymer skeleton), and can be selected from a general polymer or the like according to the purpose. Among the polymers, especially when forming a polymer skeleton, a polymer or a copolymer selected from a base monomer, an ester polymer, an ether-based polyurethane polymer, a guanamine polymer, or an epoxy a polymer oxygen polymer, and the like, or a copolymer (for example, an ether/polyurethane copolymer, a polymer of a polyether/vinyl monomer, etc. (may be a random copolymer) At least one of the groups formed by the block copolymer and the graft copolymer is preferably selected from the group consisting of a vinyl polymer or a copolymer, an ester polymer, an ether polymer, and an amine polymer. Preferably, the group of the modified material or the copolymer is preferably a polymer or a copolymer of a vinyl monomer, and the polymer is preferably soluble in an organic solvent. When the affinity is low, for example, when it is used as a pigment dispersant, the affinity of the medium is weak, and it is impossible to ensure a dispersion which is dispersed and stabilized. Among the polymer compounds represented by the above formula (1), the polymer compound represented by the following (2) is preferable. -6 is a special one, which is also composed of a copolymer of a vinyl compound and a polyfluorene. The copolymer of any of the monomers is at least one of a solvent and a dispersion.

-63- 200811249 In the above formula (2), A2 is synonymous with A1 of the above formula (1), and specific preferred embodiments thereof are also the same, and specific examples of the structure of the organic dye are phthalocyanine compounds and even Azo lake compound, anthraquinone compound, diB oxo compound, diketopyrrolopyrrole compound, etc. are preferred, and the heterocyclic ring is imidazole, triazole, pyridine, piperidine, porphyrin, and three tillage. , isoporphyrin, isoindolinone, benzimidazolone, benzothiazole, amber imine, phthalimide, naphthyl imine, hydantoin, quinone, quinoline, Carbazole, acridine, acridone, anthracene and the like are preferred.

Further, it may have a substituent similar to A1, and the substituent is the same as in the case of A1, and the preferred embodiment is also the same. Further, it is preferable that the A2 is a monovalent organic group represented by the above formula (4), and the details, specific examples, and preferred aspects of the organic group are the same. In the above formula (2), R3 represents a (x + y)-valent linking group. The (x + y)-valent linking group represented by the above R3 includes 1 to 60 carbon atoms, one to ten nitrogen atoms, one to 50 oxygen atoms, and one to 100 hydrogen atoms. And a base of 0 to 20 sulfur atoms, which may be unsubstituted or more substituted. The (x + y)-valent linking group represented by the above R3 is synonymous with the (m + n)-valent linking group in the above R1, and the preferred aspects thereof are also the same. Further, specific examples are, for example, the same structural units as described above or a combination of the structural units. Among these, the linking group which R does not have an organic linking group is preferable, and a preferred specific example of the organic linking group is as follows. However, the present invention is not limited by these. -64- 200811249 (r-1) o ft —ch2 — ch2—c- o- ch2, H3C-CH2 i!. -ch2—oc - ch2 , ch2- (r-2) i? •c-ch2 a ch2 - II 2 2oo Π CH2 — C-〇-CH2, /CH2-〇C-GH2 Cvv H3C-CH2 CH2 - Oj^CH2_o (r-3)

0 ^ 0 II II -CH2_CH2 - NH-C-〇-CH2, /CH2 - o-c-nh-ch2-ch2- η3οοηΓ, CH2-0-C-MH-CH2-ch2,

II o (r-4) 0 0

II II-CH2-CHf 〇- O-CH2, 〆CH2-〇-ό· O-QH2—GHa—H3C-CHf, CH2-〇C-〇- ch2-ch2-

II o (r-5) (r a 6)

Ch2-ch2-

Ch2-ch2〆丫, ch2-ch2-o (r-7) if i? CH2 - CH2—N- C-0- CHf CH2_Vr H 〇—CH2-CH2-〇-〇-N-CH2-CH2^ Y &lt ;ch2-ch2-nco-ch2-ch2'

H o

H (r - 8) (r a 9)

-65 200811249 (r-10) if Ο —ch2-ch2 — co-ch2 — —CH2-CH2-C-〇-CH^UsvCH2-〇-C-CH2-CH2- ο ,ch2-oc-ch2-ch2 • G-IIo (卜11) oo II II .CH2 — C-〇CH2, n/CH2_〇-C-CH2- ^CHo-CO-CHs 2 II 2o 'CH2-〇1 - ch2-o (M2) sf CH2-CHfMH-C-0-CH2, /CH2-O-ONH-CHfClV, Ck"CHp-〇-l

_ CH2- CH2 — NH- 〇 CH2 O o-c-nh-ch2-ch2·o (M3) • ch2 - ch2-o- g 〇 ^ch2-ch2-o

C-o-ch2-ch2^ Mine o-ch2-ch2·o (Bu 14) -ch2-ch2-o-c. •ch2-ch2-o-c

C-〇-CH2-CH2 ore 0,2-CH2- (Bu 15) • ch2- gh2, 〆ch2-ch2_ N丄1 —CHg-CHa-OC 0 —ch2-ch2 — —ch2-gh2〆1ST M Ν ^Ν^Ί ,ch2-ch2- XH2-CH2" (Bu 16)

II f? • ch2— ch2— c-0 ch2, < ch2_ o-c-ch2-ch2_ , CHr^CH2- 〇-R-CH2-CH2-o -CH2— CH2— OO-CHf 2 2 II 2o

II • CH2—CH2—C〇—CH2, 〆CHg-CH2—〇CH2—CH2 2 II 2 2o (Bu 17), GH2_C-〇-CH2, /CH2- ch2-c, och2, cnr o II , CH2, 〇-〇CH2- "CH2-0-C-CH2- o CH2-poor-0 - CHf 0 , ch2-og-gh2-o 66 - 200811249 Among the above, the availability of raw materials can be easily synthesized From the viewpoints of the solubility of various solvents, the above (r-彳), (r-2), (r-10), (r-11), (r-16), (1-17) The base is good.

In the case where the above R3 has a substituent, the substituent is, for example, a group having a carbon number of 1 to 20 such as a methyl group or an ethyl group, or an aryl group having a carbon number of 6 to 16 such as a phenyl group or a naphthyl group. a hydroxyl group having 1 to 6 carbon atoms such as a hydroxyl group, an amine group, a carboxyl group, a sulfonylamino group, an N-thioguanamine group or an ethoxylated group, and a carbon number of 1 to 6 such as a methoxy group or an ethoxy group. a halogen atom having an alkoxy group, a chlorine atom or a bromine group, an alkoxycarbonyl group having a carbon number of 2 to 7 such as a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group; a cyano group; a third butyl carbonate; Carbonate groups and the like. In the above formula (2), R4 and R5 each independently represent a single bond or a divalent linking group. The "divalent linking group" represented by the above R4 and R5 may, for example, be an unsubstituted or linear, branched or cyclic alkyl group, an aryl group or an aralkyl group. -0-, -3-, -0 (= 0)-, ^ (foot 19)-, -30-, -802-, -C02-, -N(R2Q)S〇2-, or a combination of two or more The divalent group® of these groups is a preferred example (the above R19 and R2G each independently represent a hydrogen atom or a group having 1 to 4 carbon atoms). Among them, organic linking groups are preferred here. The above R4 is a linear or branched alkyl, aralkyl, -〇_, -C(= 〇)_, -N(R19)_, _s〇2_, -C02_, _N (R2〇) Or a combination of 2 or more of these groups, preferably a linear or branched alkyl group, an aralkyl group, -〇-, -C(= 0) -, -N(R19)·, -C02-, or a combination of two or more of these groups is particularly preferred. The above R5 is a single bond, a straight chain or a branched alkyl group, an aralkyl group, ·0-, -C(= 〇)·, -N(R19)-, -S02-, -C〇2 -, -N(R20)S〇2--67- 200811249, or a combination of two or more of these groups of divalent groups is preferably 'linear or branched alkyl, aralkyl, ...0...-C ( = 0 )...-N ( R19) -, -c 0 2 - , or a combination of two or more such base groups is particularly preferred. Further, in the case where the above R4 and R5 have a substituent, the substituent is, for example, an alkyl group having a carbon number of 1 to 20 such as a methyl group or an ethyl group, a phenyl group having a carbon number of 6 to 16 such as a naphthyl group. a hydroxyl group having 1 to 6 carbon atoms such as a hydroxyl group, an amine group, a carboxyl group, a sulfonylamino group, an N-thioguanamine group or an ethoxylated group, or a carbon number of a methoxy group or an ethoxy group; Alkoxy group of 6, a halogen atom such as chlorine or bromine; alkoxycarbonyl group having a carbon number of 2 to 7 such as a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group; a cyano group; A carbonate group or the like such as a carbonate. In the above formula (2), y represents 1 to 8, 1 to 5 is preferred, 1 to 3 is preferred, and 1 to 2 is particularly preferred. Further, X means 2 to 9, 2 to 8 is preferable, 2 to 7 is preferable, and 3 to 6 is particularly preferable. Further, P2 in the formula (2) represents a polymer skeleton, and can be selected from general polymers and the like according to the purpose and the like. The preferred embodiment of the polymer is synonymous with P 1 in the above formula (1), and the preferred aspects thereof are also the same.

In particular, among the polymer compounds represented by the above formula (2), R3 is the above specific examples (r-1), (r-2), (r_10), (r_11), (r_16), or (b 17). , r4 is a single bond, a straight chain or a branched alkyl group, an aralkyl group, -〇-, -C(= 〇卜, -N(R19)-, ·〇02-, or a combination of 2 More than one such divalent organic group, R5 is a single bond, an extended ethyl group, a propyl group, or a linking group represented by the following formula (sa) or (sb), and the p2 is a vinyl group. a polymer of a monomer or a copolymer, an ester polymer, an ether polymer, an urethane polymer, or a modified substance thereof, wherein y is a polymer compound of which X is 3 to 6 is Further, in the following group, R21 represents a hydrogen atom or a methyl group, and I represents 1 or 2. -68 - 200811249 (sa) i? o

Ch2-ch-c-o-ch2-ch-ch2~o-c·R21 OH

CH 2 (sb) 0 ... Π ch2-ch-co-ch2-ch2— R21 The polymer compound has a mass average molecular weight of 1,000 or more, preferably 1,000 to 500,000 in terms of mass average molecular weight, and preferably 3,000 to 100,000. 5,000~80000 is better, and 7000~60000 is especially good. When the mass average molecular weight is within the above range, the effect of introducing a plurality of functional groups to the polymer end is sufficiently exhibited, and exhibits excellent performance in terms of adsorption to a solid surface, cell formation energy, and interface activity. In particular, in the case where a polymer compound of Φ is used as a pigment dispersant, good dispersibility and dispersion stability can be achieved. The polymer compound represented by the above formula (1) (including those represented by the formula (2)) is not particularly limited, and can be synthesized by the following method or the like. Among the following synthesis methods, the synthesis method of the following 2, 3, 4, and 5 is preferable from the ease of synthesis. The following synthesis methods of 3, 4, and 5 are particularly preferable. 1 a polymer obtained by introducing a functional group selected from a carboxyl group, a hydroxyl group, an amine group or the like to a terminal, a fluorenyl halide having a plurality of functional groups (A1 or A2 in the above formula), or a plurality of functional groups A method of polymerizing a base (the A1 or A2 in the above formula)-69-200811249 fluorenyl halide or an isocyanate having a plurality of functional groups (A1 or A2 in the above formula). 2. A method of subjecting a polymer having a carbon-carbon double bond to a terminal to a Michael addition reaction with a thiol having a plurality of functional groups (A1 or A2 in the above formula). 3. A polymer which introduces a carbon-carbon double bond at its end, and a thiol having a plurality of functional groups (A1 or A2 in the above formula), present in a radical generating agent

The method of carrying out the reaction. 4_ A method in which a polymer of a plurality of thiols is introduced at the terminal and a functional group (A1 or A2 in the above formula) into which a carbon-carbon double bond is introduced is reacted in the presence of a radical generator. A method of radically polymerizing a vinyl monomer as a chain shifting agent having a thiol compound having a plurality of functional groups (A1 or A2 in the above formula). In the above, the polymer compound (preferably the polymer compound of the formula (2)) used in the production method of the present invention can be, for example, any of the above 2, 3, 4, and 5 The method of synthesizing is preferably carried out by the method of the above 5 in terms of ease of synthesis in terms of synthesis. More specifically, it is preferred to use a compound represented by the following formula (3) as a chain shifting agent for radical polymerization.

In the above formula (3), R6, R7, a3, g, and h are each synonymous with R3, r4, a2, x, and y in the above formula (2), and the preferred aspect thereof is also a phase. -70- 200811249 The same. The above vinyl single system is not particularly limited, and examples thereof include (meth) acrylates, crotonates, vinyl esters, maleic acid diesters, and fumaric acid diesters. Further, itaconic acid diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, (meth)acrylonitrile, and the like are preferred. These examples are, for example, the following compounds. Examples of the above (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, η-propyl (meth) acrylate, and isopropyl (meth) acrylate acrylate. N-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, η-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, (methyl) ) Tetbutylcyclohexyl acrylate, 2-ethylhexyl (meth)acrylate, t-octyl (meth)acrylate, dodecyl (meth)acrylate, 18 (meth)acrylate Alkyl ester, ethoxylated ethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (methyl) ) 2-ethoxyethyl acrylate, 2-(2·methoxyethoxy)ethyl (meth)acrylate, 3-phenoxy 2-hydroxypropyl (meth)acrylate, (A) Benzyl acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, triethylene glycol (meth) acrylate Ether, triethylene glycol monoethyl ether (meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, polyethylene glycol monoethyl ether (meth)acrylate, (meth)acrylic acid beta -phenoxyethoxyethyl ester, nonylphenoxy polyethylene glycol (meth)acrylate, biscyclopentenyl (meth) acrylate, dicyclopentanyl hydroxyethyl (meth)acrylate, Trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctyl (meth)acrylate, dicyclopentenyl (meth)acrylate, (meth)propionate Bromophenyl ester, tribromophenyl hydroxyethyl (meth)acrylate, and the like. -71- 200811249 Examples of the above-mentioned butenoic acid esters include, for example, butyl crotonate, hexadecyl acrylate, and the like. Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, ethylene benzoate, and the like. Examples of the above maleic acid diesters include, for example, dimethyl maleate, diethyl maleate, and dibutyl maleate.

Examples of the above-mentioned fumaric acid diesters include, for example, dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like. Examples of the above itaconic acid diesters include, for example, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, and the like. Examples of the above (meth) acrylamide are, for example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl. (Meth) acrylamide, N-isopropyl (meth) acrylamide, N-n-butyl propylene decyl (methyl) decylamine, N-tert-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N-(2-methoxyethyl)(methyl)propanolamine, N,N-^ dimethyl(meth) acrylamide, N, N-diethyl(meth)acrylamide, N-phenyl(meth)acrylamide, N-benzyl(meth)acrylamide, (meth)propenyl porphyrin, diacetone propylene Amidoxime and the like. Examples of the above styrenes are, for example, styrene, methyl styrene, dimethyl styrene, trimethyl phenyl ethane, ethyl styrene, cumene, butyl styrene, hydroxybenzene. Ethylene, methoxystyrene, butoxystyrene, ethoxylated styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, to take off with acidic substances Hydroxystyrene, vinyl benzoic acid methyl-72-200811249 ester, and α-methylstyrene, which are protected by a protecting group (for example, Bo c, etc.). Examples of the vinyl ethers include methyl vinyl ether 'butyl vinyl ether, hexyl vinyl ether, and methoxy ethyl vinyl ether. In addition to the above compounds, (meth)acrylonitrile or a vinyl-substituted heterocyclic group (for example, vinylpyridine, vinylpyrrole-11-butanone, vinylcarbazole, etc.) or fluorene-vinylformamidine may be used. Amine, hydrazine-vinylacetamide, hydrazine-vinylimidazole, vinyl caprolactone, and the like. Further, in addition to the above compounds, a vinyl monomer having a functional group such as a urethane group, a ureido group, a sulfonylamino group, a phenoxy group or an imido group may be used. A single system having such a urethane group or a ureido group can be suitably synthesized by, for example, an addition reaction of an isocyanate group with a hydroxyl group or an amine group. Specifically, an addition reaction of a monomer having an isocyanate group with a compound having one hydroxyl group or a compound having a primary or secondary amine group, or a monomer having a hydroxyl group or containing a grade 1 or 2 The addition reaction of a monomer of a primary amino group with an isocyanate can be suitably synthesized. The above-mentioned vinyl single system may be polymerized by one type or may be copolymerized with two or more types. These radical polymers may be polymerized by a general method and according to a usual method. It is obtained as a vinyl monomer. For example, by dissolving such a vinyl monomer and a chain shifting agent in a suitable solvent, a radical polymerization heuristic agent is added thereto, and dissolved in a solution at about 50 ° C to 2 2 0 ° C. Method (solution polymerization method). An example of a suitable solvent to be used in the solution polymerization method is arbitrarily selected, for example, depending on the monomer used and the solubility of the resulting copolymer. For example: methanol, ethanol, propanol, isopropanol, Imethoxy-2-propanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl- 73- 200811249 Ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene. These solvents can be used in combination of two or more. Further, as the radical polymerization initiator, an azo compound such as 2,2,-azobis(isobutyronitrile HAIBN) or 2,2' azobis(2,4'-dimethylvaleronitrile) can be used. For example, a peroxide of benzamidine peroxide, and a persulfate such as potassium persulfate or ammonium persulfate.

The compound represented by the above formula (3) can be synthesized by the following method or the like, and from the viewpoint of ease of synthesis, the following method is preferred. 6. A method of converting a halide compound having a plurality of functional groups (A1 or A2 in the above formula) into a thiol compound (for example, a method of reacting with thiourea to carry out hydrolysis, and a method of directly reacting with NaSH, a method of reacting with CH3COSNa for hydrolysis, etc.) 7. A compound having 3 to 10 thiol groups in one molecule, and having a functional group (A1 or A2 in the above formula) and having a hydrogenthio group The method of performing the addition reaction of the compound of the functional group of the reaction is preferably a thiol halide, an alkyl halide, an isocyanate, a carbon-carbon double bond or the like in the "functional group reactive with a hydrogenthio group" of the above method 7. . The "functional group reactive with a hydrogenthio group" is a carbon-carbon double bond, and the addition reaction is particularly preferably carried out by a radical addition reaction. The carbon-carbon double bond is preferably a 1-substituted or 2-substituted vinyl group from the viewpoint of reactivity with a hydrogenthio group. The above-mentioned "compound having 3 to 10 thiol groups in one molecule" is exemplified by the following compounds. -74- 200811249

Ο Ο Cu-1 ) 11 II } HS-CH2-GH2-ό-Ο-GH2, /CH2-〇-0_CH2—CHa-SH (u- 2 ) Η3ΟΟηΓ ""CHfO-row-CH2-CH2-SH 0 0 0 II Π c,o-ch2,,ch2 ,-oc-CH· ^ U ^ 〇ffHS-CH2-CH2 — NH-C-〇-CH2, /CH2-〇-C-NH-CH2—CHfSH H3C -CHr, CH2-〇-jj-NH-CH2-CH2-SH O 0 0 fy— A 1 II II kU ” HS-CH2-CH2-〇-C-〇-CH2, /CH2-〇-C,〇- CH2-CH2—SH H3C~ CHf, CH2_ QC-〇-CH2-CH2-SHo (u- 5 )

SH

N SH (u- B ) ch2~ch2-sh 〇丫 N 丫. Μ M HS-CH2-CH, 'ch2-ch2_sho (iW ) i? o

Ch2-ch2-n-c-o-ch2^ch2-sh丫. H

HS-CHfCH2-N-O^O-CHfCH2- SH H 〇 H (u- B ) hs,CH2, (u- 9 ) hs"CH^CH2 HNv^ •CH2,ch/0, I “ 0,e

R〇, CHrCH2, SH HS bird CH, N, f

IJo

, CH2/CH2, SH -75- 200811249 (u-10) ίϊ -ch2- J-ch2-ch2-sh (iH1) HS^CH2—CHfC-Q-CH2, 〆, HS_CH2-CHfJJ-0-CHf, CH2 -〇-p-CH2-CH2-SH 0 ooo ii η HS - CH2-C-〇,CH2, c^CH2 - 〇-C-CH2 - SH HS-CH2-C-〇-CHf, CH2-〇-C -CH2-SH oo (u-12) S? ?l

HS-CH2-CH2 - Nhh C-O-一 0-C_ NH-CH2 - CH2 - SH

HS- CH2- CH2- NH- C- O- CHf O

- NH - CH2 - CH2 - SH O (u-13)

Hs-ch2-ch2-o-c (iH4) hs-ch2-ch2-o-c*o

OO-CH2 — CH2 — SH O0-CH2-CHfSH lio (u-15) II II HS-CH2-CH2-〇— CY〇, ^C-〇-CH2-CH2 — SH HS-CH2-CH2-〇-C ^Y^C-〇-CH2~CH2-SH n^n 11 *) HS-CH2- CH2, shirt man ν^ν』Η2 a ch2-sh

HS-CH2_ CH2, n, CH2-CH2-SH π ο -ch2-ch2~o-c ό HS-CH?-CH〇

, CH2-CH2 — SH (ιΗ 6) II HS - CH2 — CH2 - C-〇-CH2, /CH〆

Hs-ch2 - CH2 - O 〇-CH2, c〆CH HS - CH2— CH2- C- OCH【 0 CH2— o- c- CH2 — CH2_ SH 0 0 H —CH2 — o- c- C H2- CH2 - SH, CH2 - oc-GH2 — CH2- SH o (u -17)

It HS-CH2-C- 〇-CH2, c/CH2 oo li II hs-ch2-co-ch2^ ^ch2-oc-ch2-sh /CH〆, CH2-〇-〇CH2-SHo HS-CH2-C -0-CH2 2 Jl 2 〇ch2-oc-ch2-sh o Among the above, from the viewpoint of availability of raw materials, easy synthesis, and solubility of various solvents, (u-1), (U) -2), (u-10), (u-11), (u · 1 6 ), (u -1 7 ) are preferred. -76- 200811249 The compound having a functional group (A1 or A2 in the above formula) and having a carbon-carbon double bond is not particularly limited, and examples thereof are as follows. (k-1) (k-2) (k-3) (k-4) H〇2〇

CC〇2H ho2c

Co2h co2h co2h

(k-11) (k-12) (k-13)

-77- 200811249 (lc-17) Ο h2n person Μ (卜 20) (k-18) (k-19) again

M S / good (k-21)

Person ° R (k-22) (k-23)

An><W^ Jy〇^X

H (ic - 24) (k-25) (k-26> 0 (k-27) (k-28) (k -29) Production <och3 h3c〇-^ X〇ch〇| 〇CH3 〒i_ 0CH3 〇〇ch3 (k-30) (k-31) (k-32) o OCN*^^ Λτ( O (k-33) (k-34) (k-35) a OH 〇OH a

NCO

.OH -78- 200811249

(k a 36) (k-37)

(k a 40) (k a 41)

(k-46)

-79- 200811249

(k-47) (k-48) (k-49) (k-50) (k-51)

(k- 55) (k-56)

(k - 60) (k-59)

-80- 200811249

For example, the above "a compound having 3 to 10 thiol groups in one molecule" and the above "having a group selected from an acidic group, having a basic nitrogen atom, a urea group, a urethane group, and having a compound a radical of a terminal oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxyalkyl group, an epoxy group, an isocyanate group, and at least one functional group of a hydroxyl group, and a compound having a carbon-carbon double bond For the reaction product formation, for example, the above-mentioned "compound having .3 to 10 thiol groups in one molecule" and "having a group selected from an acidic group, having a basic nitrogen atom, a urea group, and an amine can be used. At least one functional group of a formate group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxyalkyl group, an epoxy group, an isocyanate group, and a hydroxyl group, and having a carbon-carbon double bond The compound can be obtained by dissolving in a suitable solvent, adding a radical generating agent thereto, and adding it at about 50 -81 to 200811249 ° C to 100 ° C (thiol reaction method).

Examples of the preferred solvent used in the above method are, for example, "a compound having 3 to 10 thiol groups in one molecule" and "having an acidic group and having a basic nitrogen atom". a group having at least one functional group, a ureido group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxyalkyl group, an epoxy group, an isocyanate group, and a hydroxyl group; Further, the solubility of a compound capable of reacting with a hydrogenthio group (for example, a carbon-carbon double bond) and the solubility of the generated radical addition reaction product are arbitrarily selected. For example: methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl Ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene. These solvents can be used in combination of two or more. Further, as the radical generating agent, an epoxy such as 2,2'-azobis(isobutyronitrile) (AIBN) or 2,2'-azobis-(2,4'-dimethylvaleronitrile) can be used. Nitrogen compounds, peroxides such as benzammonium peroxide, and persulphates such as potassium persulfate, ammonium persulfate, and the like. Specific examples of the compound represented by the formula (1) which are preferably used in the production method of the present invention are shown below. However, the invention is not limited by any of the specific examples. -82- 200811249 (C~!> ho2c (C-3) _r3-_ (n=5,ra=1) co2ch3

Ch2- gh2- c- o- gh2, c〆ch2- o CH2-C-0-CH2 o r3= -ch2 — ch2 — oo-ch2, ch2— 〇-『03⁄4- ch2*·o .gh2 — oc- Ch2 — ch2-, CH2-. -g_CH2-CH2- ch2-ch2-c-o-c a ch2-ch2— ο o ch2, -CH2~CH2~C- o- ch^

H02C*^Y^S· -R3-H02C Jn LI (n=5, ra=1) co2ch2ch2oh C〇2CH2CH2CH2CH3 (C-4) ho2c H02C〇ks· -R3- nc〇2ch3 m (n=5, m= 1) R3=

o II H2S〆ch2-o- c- ch2 a ch2-, CHi ch2-oc-ch2-ch2-o, ch2-oc-ch2-ch2— 0 ^ch2-o ?l CH^—CH2—C·O- CH2, 〆CH2—〇C· CH2—CH2_ i? /CHf °^Η2 - 〇-C-CH2-CH2--CH2-CH2-C-ο-CH2, /CH2-0 m -ch2- ch2~ c- Ο- οηΓ" ^ch2-oc-ch2- ch2- o IIo o -83- 200811249 R3= (G"5) Η〇2〇•一R3 - -s^ n 〇—CH2-CH2—C-〇-CH2 , C/CH2—〇-〇CH2—Cj U /CHf ~CH2-〇-C-CH2-CH2·—CH2—CH2—C—〇-CH2, c/CH2-〇' ^—ch2- ch2- c- O- ch^ ^ch2-oc- ch2- ch2—, oo h2-\ (n=5, itf1) co2ch2ch2oh co2ch2ch2ch2ch3 (C-6) factory·' ho2c ) ho2c

—CH2-CH2-C-〇-CH2v U /CHf CH2-CH2-C-〇-CH2, /CH2-0 ch2-ch2-co-ch^ ^ch2-oc-ch2-ch2· oo <ch2-qc -ch2-ch2-, CH2-〇-g-CH2 - eH2·o (rt=5r (tp1> (C-7)n 〇HO-PO^ OH I(n=5, m=1) 〇u υ r3 = li ii 一CH2~ CH2~ C-〇- CH2^^CH2~0~ C*· CH2~ CH2~ Π ^CH2-〇-C-CH2-CH2- -ch2- ch2- c- o- CH2\ ^ Ch2-o '1 -ch2-ch2-co-ch^ ^ch2-oc*-ch2-ch2- ooo co2ch3 R^= (G-8) ho3s

Co2ch3. -ch2-ch2—co-ch2, -CH2~ CH2~ C-ο- CHf CH2"~ CH2~ c~ o~ ch2^ /CH2〆ch2-o - ch2- 〇-c-ch2 — gh2- CHfO C_CH2—CH2_o ch2-oc - ch2 — ch2-o -84- 200811249 R3= (C-9) -ch2-ch2 — co-ch2, 〆^ 〇II /CHg -CH2 — CH2-C-0-CH2\〆 CH2 — o {? .CH2"-〇-C-CH2-CH2-, ch2-oc-ch2 - ch2- _0Π2 0Π2 v-* vi un2\ ^on2 —ch2-ch2-co- ch^ ^ch2-o- C-ch2-ch2- o II o co2ch3· (n=5t m=t) ¢-10) "〇"^Y^S--R3—

RT= II II —CH2 — CH2-C-〇-CH2, /CH2-〇-C-CHj-CH2- 拳ί? ^ CH?^ ^ ch2— 〇- c~ ch2—ch2- •CH2-CH2-C -〇-CH2, /CH2-. g -CH2— CH2H - CHf s ch2- o- - CH2— CH2— oo (n=5, m=t) co2ch2ch2oh co2ch2ch2ch2ch3 m R3= π . 〇—CH2-CH2-C-〇-CH2^c^CH2- 〇-O-CH2-CH2- Π /CH broad, gh2-oc-ch2-ch2--CH2-CH2 — C-OCH2, /CH2-〇^-gh2-ch2-co-· ch^ ^οη2- oc- Ch2- ch2— oo co2ch3_ (n=5f m=1) (C-12) -R3· (n=5, ra=1)

—ch2-ch2-c- o-ch2, CH2-C(VC-〇-CH2, /CH2-〇CH2—CH2-C”〇-CHf, CH2-0-C-CH2-oo, ch2- 0 c, Ch2 — ch2-"ch2-oc-ch2-ch2-0 C〇2CH2CH2CH2CM3 co2ch2ch2oh m -85- II200811249 (C-13)

S—R3· (n=5, tn=1) r3= u —ch2-ch2_c-o_ch: i? /CH; -ch2- ch2 — c- o- ch2, 〆ch2- o -CH2-CH2-C- 〇~CH5o ch2-oc-ch2-ch2-o .ch2—o-c_ch2-ch2' , ch2- o - c-ch2 - ch2-o co2ch3- (C-14)

Ch2_ch2—c-o,ch2,CH2-CH2-trans-O-CHf o co2ch2ch2oh :CH2CH2CH2CH3 (n=5,m=1) o II •ch2-ch2—c-o-ch2, .ch2-o /CH2

〇C oh2~oc-ch2-ch2-o ch2-oc - ch2 — ch2- ch2—oc-ch2—ch2-o (C-15) i? I! HOzC'^Y^S ho2c (n=3t m= 1) (C-16) co2ch3-CH2-CH2-C-〇-*CH2^ ^ch2-oc-ch2-ch2*- -CH2-CH2-C-〇**CHf, CH2-〇-C-CH2— CH2o o

Ch2- ch2— c- o- CH2, c〆 ch2- o* CH2-CH2-C~〇-CHi o

II II •ch2-ch2-c - o-ch2 CHi CH2—OC-CH2—ch2· CH2-OC-CH2-CH2-o ch2—o_c-ch2-0 H02C*^Y^S- A R3— η〇2 〇. n • CO2CH3 (η=5, ηΐ=1) (x:y=9:t) -86- 200811249 CC-17)

—ch2- ch2 - C-0-CH2. 〆CH2*~0- CH2 — CH2—CO-CHf o C02CH3J mi? oo II fl -CH2- CH2-C- o- CH2 V. cx-CH2- 〇c- ch2- ch2-^CH2-〇-C- CH2-CH2-k o ch2—o- c-ch2—CH2-o CC-19)

(0-2Q)

-R3--

II - CH2 - CH2 - c- o- CH2 v n CH2-CH2- C-〇-CH2, /CH2_0 CH2—CH2-C-〇*-CHf" ^CH2-〇-C-CH2~CH2·o o

C02CH2CH20H C(D2CH2CH2GH2CH3 co2ch3_ {?CH2~〇-C-CH2~CH2-ch2*-oc-ch2-ch2-o m II -CH2— oh2~ C~ 0*~CH2' /CHi II ch2-oc - ch2 — Ch2- , ' s ch2- o- c- ch2~ ch2- , ch2-ch2-co-ch2, /CH2-(T o "^CH2-〇*-C-CH2-CH2-o CH2-CH2- -O-CHf m -87- 200811249 (C-21)

;-一R3——; (n=5, m=1)

Co2ch2ch2ch2ch3 R°= n ti a CH wide ch2-CO-CH2, c〆ch2- o- c- ch2- ch2- /CHf, CH2-〇-C-CH2-CH2-CH2-CH2-C-〇-CH2 /CH2-〇» CH2- CH2-好-O-, CH2- o-anti-ch2-ch2— oo

C02CH2CH20H (C-22)

R3= :o2ch3· (n=5, m=1) (C-23) RIsxors (n=5,m=1) mf? —qh2-ch2-c-〇-CH2\ ^ch2-oc~oh2-ch2 i? /CHf,CH2-〇-C-CH2-CH2-CHz-CHz-CO-CHa^CHs-O & ch2-ch2 - o o-(3)广°^η2 - 〇- c-ch2-ch2- oom -ch2-ch2-c-〇-ch2^c^ch2-oc-ch2-ch2· , ΟΗί c h2- ch2- c- 〇ch2, 〆ch2- O' / o 斤-ch2-ch2· o GH2-〇 -C-CH2-CH2- -CH2-CH2-〇-〇-CHi o co2ch2ch2oh co2ch2ch2ch2ch3 mo (C-24) cia. fork (n=5, m=1)

Ch2- ch2- c- o- ch2, r

• R3--S • CH2 — CH2-C-0-CH2, /CH2-0-C-GH2-GH2-(3), OH2-0---CH2-CH2_CH2—CH2-C- 〇- CH2 C"&quot ;ch2- o- c- ch2- ch2— ° oo oo2ohz i? m -88- 200811249 (C-25)

Ch2-ch2-co-ch2 CH2-CH2-C-〇-CH2 o {n=5rm=1) o If CM2— C 0-〇-CH2, /CHr .ch2~o ch2—〇- c- ch2~ ch2 ~oo IJ .ch2-oc-ch2-ch2- , CH2-〇CH2-o (C-26) ?l ch2- ch2 — co- ch2, /CH: <

C02CH2CH20H C02CH2CH2CH2CH3 (π=5, ιπρ1) • ch2- ch2- c- o-ch2, 〆ch2- ύ όη2-οη2-ο-ο-οη^ ^ ch2-o_c-ch2-ch2-CH2-〇-C-CH2 -CH2' ch2_o-Khan-ch2—ch2-o (C-27)

CH2-CH2- c- o- CH2\c^.CH2-〇- CH2*-*CH2-C-〇-CHf o ?l ch2-ch2~ c- 〇-CH2\〇^CH2*-〇- g- Ch2- ch2- /CHf ch2—o-good-ch2-ch2-o "ch2-oc~ch2-ch2o (C-28) oo H II —ch2-ch2-co-ch2^ ^ch2-oc-ch2- Ch2 /CHf",CH2-〇_C-CH2-CH2 CH2 - CH2 — C- 0-CH2, 〇/〇{*1_ o -ch2- ch2 - c- 0-CH wide, ch2- o-c_ Ch2 - οη2·

S--R3· (n=5, itfI)

IIo IIo co2ch2ch2oh co2ch2gh2ch2ch3 -89- 200811249 Μ (G-29)

- R3__ (n=5, vcri) (C-30) vN^so (n=5t m=1) (C-31) a ch2—ch2 - c-〇面ch2, Η - CH2-CH2 - C- 〇-CH2v^CH2-〇-CHfCHfOOCHf 'CIV-. -OCH2-CH2, 0 0 O It ch2-o-c-ch2-ch2-ch2 — o-c-ch2 — ch2-o co2ch3. m -R3_

Co2ch2ch2oh co2ch2ch2ch2ch3 k°= II Jl —CH2-CH Guang OOCH2, /CH2-〇-C-CH2-ch2- n ^ch2-oo-ch2*-ch2 CHz-CHg-CO-CHa^^CHa-O ^ CH2~ CH2-C-〇-〇H^^CH2-〇-C-CH2-*CH2-- oo sWr o 〇U II CH2-CH2-C-〇-CH2, /CHf oc-ch2-ch2-Π /CHf, Ch2-oc-ch2-ch2- " o VH, -〇-ds- -R3- _ n . co2ch3· m (n=5,m=1) ch2-ch2 — oo-ch2, ch2—or a ch2 - ch2-only -o-cur", CH2-o-anti-ch2-ch2-of? i? _ ch2 - ch2- C· o- CH2, c〆ch2- o- c- ch2- ch2 CH; (0 -32)

(n=5, m=l) /^ri2 CH2 — 〇-C-CH2 —CH2- ch2 - ch2 - c-och2,<ch2- 0 » CH2-CH2- C-〇-CHr^CH2-〇C -CH2 - CH2— co2ch2ch2oh C〇2CH2CH2CH2CH3 m -90- 200811249 (C-33)

-R3· (n=4. 5, m=1 5) (C-34)

—ch2-ch2-co-ch2, /CH2-oc-ch2 — α f? /CHr,CH2-〇C-CH2-CH2·CH2-CH2-C-〇-CH2,/CH2-0 ^-ch2-ch2 -co-ch^ ^ch2-oc-ch2-ch2— h2—\ s^r co2ch3_

CH2—CH2-C-O-CH2 o i? o

II f? CH2-CH2—C-〇-CH2, /CH2-〇-C-CH2 — ch2-/CHf vch2~oc~ch2-ch2· ch2-ch2-co~oh2^ ^ch2-o" ** » Less, ch2-oc-ch2-ch2—S-R3—co2ch2ch2oh (n=4.5, iif1.5) CO2CH2CH2CH2CH3 (C-35)

Co^ch5 (n=3,m=1) m R3=

II CH2-CH2-C-〇-CH2, 乂ch2- o‘c-ch2-ch2, ch2—ch2-c- 〇** gh2 o ch2-o-c-ch2~ch2- o

II.ch2-oc-ch2-ch2-, ch2-o-iso-ch2-ch2-o-91 - 200811249, the polymer compound is preferably a polymer compound having an acidic group and having a carboxyl group The compound is preferably a copolymerized compound which contains (A) at least one repeating unit derived from a compound having a carboxyl group and (B) at least one repeating unit derived from a compound having a carboxylate group. The above repeating unit derived from the compound having a carboxyl group (A) is preferably a repeating unit represented by the following formula (I), and a repeating unit derived from acrylic acid or methacrylic acid is preferred, and the above (B) is preferred. The repeating unit derived from the compound having a carboxylate group is preferably a repeating unit represented by the following formula (II), and a repeating unit represented by the following formula (IV) is preferred, from benzyl acrylate, The repeating unit derived from benzyl methacrylate, phenylethyl acrylate, phenylethyl methacrylate, 3-phenylpropyl acrylate or 3-phenylpropyl methacrylate is a special unit.

General formula (11) ch2 - C- General formula (I) c = tx3 (R2 represents a hydrogen atom or a hospital group having 1 to 5 carbon atoms. R3 represents a general formula (丨丨)丨) The base shown) -92- 200811249

General formula (1) 丨) γ r5 AR (R4 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, a hydroxyalkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms. And the heart system respectively represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. i represents a number of 1 to 5)

I R8 (R7 is a group having no hydrogen atom or a carbon number of 1 to 5; 1^8 is a group represented by the following formula (V))

(R9 represents an alkyl group having 2 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms. R1〇 and Rn represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. j represents a number of 1 to 5) Further, the polymerization ratio of (A) from the repeating unit derived from the compound having a carboxyl group to the repeating unit derived from the above (B) from the compound having a carboxylate group, with respect to the repeating unit (A) The total number of repeating units is preferably 3 to 40, and preferably 5 to 35. In the production method of the present invention, the molecular weight of the polymer is not particularly limited as defined in the above-mentioned -93-200811249, and is referred to as mass average molecular weight. The method for measuring the molecular weight of the polymer is, for example, a chromatography method, a viscosity method, a light scattering method, a sedimentation rate method, or the like. In the present invention, the mass average molecular weight measured by a chromatographic method which is not particularly limited is used. The polymer compound may be either water-soluble or oil-soluble, or may be water-soluble and oil-soluble. The method of adding the polymer compound may be a solution dissolved in an aqueous solvent or an organic solvent, or a solid state, or a combination thereof. The method of adding a high-molecular compound to a solution dissolved in a solvent is, for example, a method of adding the same in a state in which the solvent dissolved in the organic nanoparticle liquid is dissolved in the same solvent as the solvent of the aggregated organic nanoparticle liquid. A method of adding in a state of being compatible with a solvent of the agglomerated organic nanoparticle liquid and dissolving in a different solvent. In the case of adding the solution in a solvent, the concentration of the polymer compound is not particularly limited, and is preferably 1 to 70% by mass, preferably 2 to 65% by mass, more preferably 3 to 60% by mass. . The polymer compound may be added when the organic nanometer particles are formed by the re-precipitation method (or before or after), during extraction or concentration (or before or after), and after concentration, the organic nanoparticles are dispersed and dispersed (or Add before or after the end of the steps, or a combination of these. In the production method of the present invention, the polymer compound having a mass average molecular weight of 1,000 or more can be contained in the composition as a binder to be described later, for example, after the organic nanoparticle is concentrated and re-sinked, the organic dispersion is agglomerated in a finely dispersed manner. When the rice particles are added, the amount of the polymer compound added is preferably 1 part by mass of the organic nano particles contained in the aggregated organic natrile particles. - 200811249 is preferred, 5 ~ 500 parts by mass is preferred, and 1 〇 to 300 parts by mass is particularly good. The polymer compound having a molecular weight of 1,000 or more is, for example, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, polypropylene decylamine, ethylene. Alcohol-vinyl acetate copolymer, polyvinyl alcohol-partial methylal sulphate & polyvinyl alcohol-partial butyral acetal, vinyl pyrrolidone-vinyl acetate copolymer, polyethylene oxide/ring

Oxypropane block copolymer, polyamine, cellulose derivative, starch derivative, and the like. Further, natural macromolecular compounds such as alginate, gelatin, albumin, casein, gum arabic, toluene gum, and lignosulfonate can also be used. The polymer compound having an acidic group is, for example, polyethylenylsulfate or condensed naphthalenesulfonic acid. The polymer compound having a carboxyl group is, for example, polyacrylic acid, polymethacrylic acid, or a cellulose derivative having a carboxyl group in a side chain. The copolymerized Φ compound comprising at least one repeating unit derived from a compound having a carboxyl group and at least one repeating unit derived from a compound having a carboxylate group, for example, Japanese Patent Publication No. 59-4461, Japanese Patent Publication No. Sho 54-34327, Japanese Patent Publication No. SHO-5-8-251, and Japanese Patent Publication No. Sho 59-53. A methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a butyl succinic acid copolymer, a maleic acid copolymer, a partially esterified cis-butyl succinate, as described in JP-A-59-71 048 Acid copolymers, etc. Further, a particularly preferred example is an acrylic acid-acrylic acid ester copolymer, a methylpropionic acid-acrylic acid ester copolymer, and a propionic acid-methyl ketone acid ester copolymer described in the specification of U.S. Patent No. 4,139,391. , a methacrylic acid-methacrylate copolymer, or a polyacrylic acid or methacrylic acid-95-200811249, a multi-copolymer with a propylene acrylate or methacrylate, and other vinyl compounds. Examples of the ethoxylated compound are, for example, styrene or substituted styrene (e.g., ethyl benzene, vinyl ethyl benzene), vinyl naphthalene or substituted ethyl phthalene, acrylamide, methacryl Acetone, acrylonitrile, methacrylonitrile, etc. are preferably styrene.

These polymer compounds may be used alone or in combination of two or more, and may be used in combination with a compound having a molecular weight of less than 1 〇 。. In the method for producing an organic nanoparticle of the present invention, the dispersion of the organic nanoparticle is preferably 60% by mass or more of an organic solvent, and is preferably 65 mass%. /. The above is preferred. The organic solvent is not particularly limited and can be suitably selected from the general ones. For example, an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, an aliphatic compound solvent, or a ketone compound solvent is preferred, an ester compound solvent, and a ketone compound solvent are particularly preferred. These may be used alone or in combination of two or more. The ester compound solvent is, for example, 2-(1-methoxy)propyl acetate, ethyl acetate or ethyl lactate. The alcohol compound solvent is, for example, n-butanol or isobutanol. Examples of the aromatic compound solvent include benzene, toluene, xylene, and the like. The aliphatic compound solvent is, for example, η-hexane or cyclohexane. The ketone compound solvent is, for example, methyl ethyl ketone, acetone, cyclohexanone or the like. [Organic Nanoparticle Dispersion Composition] Next, a method for producing the organic nanoparticle of the present invention and the organic nanoparticle obtained thereby, for example, when used in a color filter, an inkjet ink or the like, form a composition. The situation. Further, the ink jet ink can be used as an ink jet ink for color filters, and can also be used as a general ink jet ink such as ink jet ink for printing - 96-200811249. The organic nanoparticle of the present invention can be used in a state of being dispersed in, for example, a vehicle. It is preferable that the color developing agent-based coating material is a medium portion in which a pigment is dispersed in a liquid state, and is a liquid-like portion containing a portion (adhesive) which bonds the reinforcing coating film with the above pigment, and a component (organic solvent) which dissolves and dilutes the pigment. . In addition, the binder used in the formation of the nanoparticles in the present invention may be the same as or different from the binder used for the redispersion, and may be separately classified into a nanoparticle to form a binder and a redispersion bond. Agent.

The organic nanoparticle concentration of the dispersed composition of the organic nanoparticle after re-dispersion is appropriately determined depending on the purpose, and is preferably 2 to 30% by mass based on the total amount of the organic nanoparticle dispersed in the composition. ～20 mass% is preferred, and 5-15 mass% is particularly preferred. In the case where the toner is dispersed by the above-described color developing agent, the amount of the binder and the dissolved and diluted component is appropriately determined depending on the type of the organic pigment, etc., and the binder is 1~ with respect to the total amount of the dispersed composition. 30% by mass is preferred, 3 to 20% by mass is preferred, and 5 to 15% by mass is particularly preferred. The dissolved diluent component is preferably from 5 to 80% by mass, preferably from 10 to 70% by mass. In the above-mentioned concentrated and extracted nanoparticle liquid, as described above, since rapid filter filtration is possible, the organic nanoparticle is preferably concentrated by concentration, and concentrated by centrifugation or drying. It is better to make it agglutinate. The method of finely dispersing such aggregated nanoparticles can be carried out, for example, by a method of dispersing ultrasonic waves or a method of applying physical energy. The ultrasonic irradiation device to be used has a function of applying a supersonic wave of 10 kHz or more, and examples thereof include an ultrasonic homogenizer and an ultrasonic cleaner. When the liquid temperature rises during ultrasonic irradiation, in order to cause thermal agglomeration of the nanoparticles (-97-200811249, refer to "Latest Pigment Dispersion Technology" - Technical Information Association, 995, p. 1 66), the liquid temperature is set to 1 to 1 00 ° C is preferred, and 5 to 60 ° C is preferred. The temperature control method is carried out according to the control of the temperature of the dispersion liquid, the temperature control of the temperature control layer of the temperature control dispersion liquid, and the like.

In addition to the physical energy, the dispersing machine used for dispersing the concentrated organic nanoparticles is not particularly limited, and examples thereof include a kneader, a roll mill, a vertical ball mill, a super honing machine, and a high-speed disperser. A homogenizer, a sander, or the like. Further, a high-pressure dispersion method or a dispersion method using fine particle beads is also suitable. <1> A preferred method for producing an organic nanoparticle-dispersed composition of a dispersion type, wherein the colorant is kneaded at 25 ° C at a viscosity of 1 10,000 mPa s or more, preferably 100,000 after kneading and dispersing with a resin component. The kPa.s or higher is a relatively high viscosity of the crucible to carry out the kneading and dispersing treatment, and then the viscosity after the microdispersion treatment is generally 1,000 mPa»s or less, preferably 100 mPa·s or less. The method of performing microdispersion treatment is preferred. The mechanical system used in the mixing and dispersing treatment is a two-roll honing machine, a three-roll honing machine, a ball mill, a drum honing machine, a dispersing machine, a kneading machine, a kneading extruder, a homogenizer, a blending machine, The uniaxial and biaxial extruders are dispersed while imparting a strong shearing force. Next, a solvent is added, and a sand mill, a pin mill, a slit honing machine, an ultrasonic disperser, a high-pressure disperser, etc., which are mainly vertical or horizontal, are used, and the glass is oxidized by a particle size of 0.1 to 1 mm. The beads produced by chromium or the like are subjected to precise dispersion treatment. Further, fine particle beads of 0.1 m m or less may be used for precise dispersion treatment. In addition, -98 - 200811249 can also omit the mixing and dispersing process. In this case, the pigment, the dispersing agent or the surface treating agent is dispersed in the acrylic copolymer and the solvent of the present invention. _ After dispersing the main pigment and the supplementary pigment separately, the dispersion of the two is mixed and further dispersed, or the main pigment and the supplementary pigment may be dispersed together. In addition, a detailed description of mixing and dispersion is at T.C. Patton, "Paint Flow and Pigment Dispersion" (John Wiley, 1964)

And So ns (the journal) and others have also been recorded, and this method can also be used. <2 > Example of Dispersant The organic nanoparticle-dispersed composition is intended to add a general pigment dispersant or a surfactant in order to improve the dispersibility of the organic nanoparticles. These dispersants use a wide variety of compounds, for example, phthalocyanine derivatives (commercial product EFKA-6745 (manufactured by EFCA)), Sorospas 500 (manufactured by ZENECA Co., Ltd.); Oxytomane polymer KP 34 1 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer Po丨yflow Φ . No.75 ^ No. 9 0 ^ Νο·95 (Common Society Cationic surfactants such as oleochemicals (manufactured by Oil & Fats Chemicals Co., Ltd.), W 00 1 (manufactured by Yusho Co., Ltd.); polyoxyethylene lauryl ether, polyoxyethylene stearyl sulfonyl ether, polyoxyethylene oleyl ether Non-ionic systems such as polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester Surfactant; anionic surfactant such as W004, W005, W017 (manufactured by Yusho Co., Ltd.); EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA Polymer 450 (manufactured by Morishita Industries Co., Ltd.), DISPERSAID 6, -99- 200811249 DISPERSAID 8, DISPERS Polymer dispersant such as AID 15, DISPERSAID 9100 (manufactured by Sanyo Chemical Co., Ltd.); various Sorospas dispersants of Soros Pass 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc. (ZENECA Co., Ltd.); ADEKAPLRONIC L31, F38, L42, L44 ' L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F1 08, L121, P-1 23 ( Asahi Denchu Co., Ltd. and ISONET S_20 (Sanyo Chemical Co., Ltd.). Further, the pigment component described in JP-A-2000-239554, or the compound (C) described in JP-A-H05-72943, or the compound of Synthesis Example 1 described in JP-A-200-31885 Also suitable for use. The compound represented by the dispersing agent [dispersion phase] used in the formation of the organic nanoparticles during redispersion may be used again. In the organic nanoparticle dispersion composition, the redispersed organic nanoparticles (primary particles) can be formed into finely dispersed particles, and the particle diameter can be preferably 2 0 〇 nm, 2 to 1 0 0 Nm is preferred, and 5 to 50 nm is particularly preferred. Further, the Mv/Mn of the particles after φ redispersion is preferably 1·0 to 2·0, preferably 1·0...1 _8, and 1.0 to 1.5. According to the production method of the present invention, for example, the pigment particles contained in the organic nanoparticle dispersion composition or the colored photosensitive resin composition described later are so-called nanometer sizes (for example, 10 to 1 〇〇 nm). It has a small particle size, but it can still be concentrated and redispersed. For this reason, when used in a color filter, the optical density is high and the uniformity of the surface of the filter is excellent. 'The contrast is high, and the noise of the image can be reduced. Further, since the organic nanoparticle contained in the organic nanoparticle-dispersed composition and the colored photosensitive composition-100 - 200811249 is highly and uniformly dispersed finely, it is possible to exhibit high coloring with a thin film thickness. The concentration can be, for example, a thin layer of a color filter or the like. Further, the organic nanoparticle-dispersed composition and the colored photosensitive resin composition are formed by using a pigment which exhibits a vivid color tone and a high coloring power, for example, a col or proof or a color filter. The forming material is excellent.

In addition, in the alkaline developing solution used for exposure and development at the time of formation of a colored image, the organic nanoparticle dispersion composition and the colored photosensitive resin composition are those which are soluble in an alkaline aqueous solution as a binder. (Binder) and can also respond to environmental requirements. Further, an organic solvent having a moderate drying property can be used as a solvent (dispersion medium for pigment) for the organic nanoparticle dispersion composition and the colored photosensitive resin composition, even from the point of drying after coating. Can meet their requirements. [Coloring photosensitive resin composition] The colored photosensitive resin composition of the present invention contains at least: (a) organic nanoparticles, (b) a binder, (c) a monomer or a low polymer, and (d) Photopolymerization heuristics or photopolymerization heuristics. Hereinafter, each component of the colored photosensitive resin composition of the present invention will be described. (a) Organic Nanoparticles The method for producing organic nanoparticles has been described in detail. The content of the organic nanoparticles is based on the total solid content of the colored photosensitive resin composition (in the present invention, the total solid content is a total of the composition containing no organic solvent), preferably 3 to 90% by mass, 20~ 80% by mass is preferred, 25~60 -101-200811249 quality. /. For better. When the amount is too large, the viscosity of the dispersion rises and there is a problem in that the manufacturing suitability is formed. When too little, the coloring power is insufficient. The organic nanoparticle (pigment fine particles) functioning as a coloring agent is preferably a particle diameter of 〇·1 # m or less, and particularly preferably a particle diameter of 0.08 or less. Further, it can also be used in combination with a general pigment for coloring. For the pigment system, those described above can be used. (b) Adhesive

The binder in the colored photosensitive resin composition is preferably a polymer compound having a mass average molecular weight of 1,000 or more as described above. The content of the binder is generally from 15 to 50% by mass, preferably from 20 to 45% by mass, based on the total solid content of the colored photosensitive resin composition. When the amount is too large, the viscosity of the composition is too high and there is a problem in manufacturing suitability. When there is too little, there is a problem in the formation of a coating film. (c) Monomer or Low Polymer The monomer or oligomeric polymer contained in the coloring photosensitive resin composition of the present invention has two or more ethylenically unsaturated double bonds, and can be subjected to addition polymerization by light irradiation. Monomer or low polymer is preferred. Such a monomer and a low polymer may, for example, be a compound having at least one addition-polymerizable ethylenically unsaturated group in a molecule and having a boiling point of at most 100 ° C under normal pressure. In this example, for example, dipentaerythritol hexa(meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxy (meth) acrylate Functional propionate or monofunctional methacrylate; polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolethane triacrylate, trimethylolpropane Tris(meth)acrylate, trimethylolpropane diacrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol -102- 200811249

Alcohol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di(meth) acrylate, trimethylolpropane tris(propylene oxypropyl) ether, tris(propylene hydrazine) Oxyethyl)trimeric isocyanate, tris(propylene methoxyethyl) cyanurate, glycerol tri(meth)acrylate; polyfunctional alcohol addition ring in trimethylolpropane or glycerol After the oxyethane or propylene oxide, a polyfunctional acrylate or a polyfunctional methacrylate such as a (meth) acrylated one is used. Further, (meth)acrylic acid may be mentioned after the addition of ethylene oxide or propylene oxide to a polyfunctional alcohol as described in the general formulae (1) and (2) of JP-A-10-62986. The esterified compound is suitable. Further, the urethane acrylates described in JP-A-48-41, 708, JP-A-59-036, and JP-A-51-37193; Polyester acrylates described in JP-A-43-431, JP-A-49-431, and JP-A-52-30490; epoxy acrylates of epoxy resin and (meth)acrylic acid And other multifunctional acrylates, methacrylates. Among these, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylic acid Esters are preferred. In addition, the "polymerizable compound B" described in JP-A-11-133600, for example, may be mentioned. These monomers or low polymers (monomer or low polymer are preferably used in a molecular weight of 200 to 1 000), and may be used singly or in combination of two or more kinds, with respect to the all solid of the colored photosensitive resin composition. The content of the component is generally 5 to 50 mass%, preferably 10 to 40% by mass. When the amount is too large, the viscosity of the composition is too high to cause a problem of manufacturing suitability. When the amount is too small, the hardening force at the time of exposure is -103. - 200811249 Not enough. (d) Photopolymerization heuristic or photopolymerization heuristic system

A photopolymerization initiator or a photopolymerization initiator which is contained in the colored photosensitive resin composition of the present invention (in the present invention, a photopolymerization heuristic system is a mixture in which a photopolymerization initiation function is found by a combination of a plurality of compounds) For example, the vicinal polyketide-based compound disclosed in the specification of U.S. Patent No. 2,236,660, the acylate ether compound described in the specification of U.S. Patent No. 2,448,828, and the α-described in the specification of U.S. Patent No. 2,725,251 Aromatic auxin compound substituted by a hydrocarbon, a polynuclear ruthenium compound described in the specification of U.S. Patent No. 3,046, 127, and the specification of No. 2,591,758, and a triaryl imidazole dimer described in the specification of U.S. Patent No. 3,454,7, The combination of the aminoketones, the benzothiazole compound described in Japanese Patent Publication No. Sho 51-4851, and the trihalomethyl-s-three-till compound, and the trihalomethyl group described in the specification of U.S. Patent No. 4,239,850 The tri-trap compound, the trihalomethyloxadiazole compound described in the specification of U.S. Patent No. 4,221,976, and the like. In particular, a trihalomethyl-s-tripper, a trihalogen, a methyloxadiazole and a triarylimidazole dimer are preferred. Further, for example, "polymeric heuristic agent C" described in JP-A No. 1 -1 33600, or 1-phenyl-1,2-propanedione-2-(o-ethoxy) as a lanthanoid system Carbonyl) hydrazine, hydrazine-benzylidene-4'-(phenylhydrothio)benzimidyl-hexyl ketone oxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphine oxide, Hexafluorophosphoryl-trialkylphenyl scale salts are also suitable. These photopolymerization initiators or photopolymerization heuristics may be used singly or in combination of two or more kinds, and it is preferred to use two or more kinds thereof. When at least two kinds of photopolymerization heuristic agents are used, the display characteristics, particularly the unevenness of display, can be made small. The content of the photopolymerization initiator or the photopolymerization heuristic agent is generally 0.5 to 20% by mass and preferably 1 to 15% by mass based on the total solid content of the colored photosensitive resin composition. When the amount is too large, the sensitivity becomes too high and it is difficult to control. When the amount is too small, the exposure sensitivity is too low. (Other additives) [Solvent] In the colored photosensitive resin composition of the present invention, an organic solvent may be further used in addition to the above components. Examples of the organic solvent are not particularly limited, and examples thereof include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, and butyl acrylate. Ester, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl glycolate, ethyl hydroxyacetate, butyl glycolate, methoxyacetic acid 3_ of methyl ester, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, etc. Alkyl hydroxypropionates; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate Φ, 2 - methyl hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropanoate, ethyl 2-methoxypropionate, 2-methoxypropane Acid propyl ester, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2-methylpropanoate Ester, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, pyruvic acid Ethyl ester, propyl pyruvate, methyl acetate methyl acetate, ethyl acetate ethyl acetate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate, etc.; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran , ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, propylene glycol methyl ether - 105 -

200811249 Acetate, etc.; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; aromatic hydrocarbons, xylene, and the like. Among these solvents, ethyl 3-ethoxypropoxypropionate, ethyl cellosolve acetate, ethyl lactate, methyl 3-methoxypropionate, 2-heptanone, Cyclohexanone, acetate, butyl carbitol acetate, propylene glycol methyl ether acetate The solvent of the present invention is preferred. These solvents can be used singly or in combination of two or more. Further, a high boiling point solvent having a boiling point of from 180 ° C to 250 ° C may be used as exemplified below. Diethylene glycol monobutyl ethyl ether acetate, diethylene glycol monoethyl ether, 3,5,5-triene-1-one, butyl lactate, dipropylene glycol monomethyl ether acetate Methyl ether acetate, propylene glycol diacetate, propylene glycol-n-ester, diethylene glycol diethyl ether, 2-ethylhexyl acetate, 3-butylbutyl acetate, Y-butyl The lactone, tripropylene glycol methyl ethyl propylene glycol-n-butyl acetate, propylene glycol phenyl ether acetate, and the solvent content are preferably 1% based on the total amount of the resin composition. [Surfactant] In the color filter which can be used in the past, there is a problem that the color of each pixel is increased for the sake of realism, and the unevenness of the thickness of the pixel is uneven. For this reason, when the film thickness of the pixel is formed (coating), the film thickness is required to be changed. The color filter of the present invention or the photosensitive dentin of the present invention, cyclohexene such as toluene, Methyl ester, 3-ester, butyl carbitol ethyl acetate, etc., or as a combination of 2 solvents. These ethers, diethylene glycol methyl-2-cyclohexyl ester, propylene glycol propyl ether acetate methoxy-3-methyl acetate, di 1, 3-butanediol ~ 95% by mass is the current high color purity From the viewpoint of controlling the uniform film thickness and effectively preventing coating unevenness (color unevenness due to film thickness variation), it is possible to control the uniform film thickness in the photosensitive resin transfer material-106-200811249. It is preferred that the colored photosensitive resin composition contains a suitable surfactant. The content of the interface-active homogeneous surfactant disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. The following is better. [thermal polymerization inhibitor]

The colored photosensitive resin composition of the present invention preferably contains a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor are, for example, hydroquinone, hydroquinone monomethyl ether 'ρ·methoxyphenoxy, di-tert-butyl-p-cresol, gallic phenol, tert-butyl phthalic acid Diphenol, benzoquinone, 4,4'-thiobis(3-methyl-6-t-butylphenoxy), 2,2'-methylenebis(4-methyl-6-third Butylphenoxy), 2-hydrothiobenzimidazole, phenothiazine, and the like. The content of the thermal polymerization inhibitor is preferably 1% by mass or less based on the total amount of the resin composition. ‘Dye and pigment for auxiliary use>> In the colored photosensitive resin composition of the present invention, a coloring agent (dye, pigment) may be added in addition to the above-mentioned coloring agent (pigment). In the case where a pigment is used in the coloring agent, it is desirable to uniformly disperse it in the colored light-emitting resin composition, and the particle diameter is preferably 0. 1 μm or less, particularly preferably 0.08 μΓΠ or less. Specifically, the dyes and the pigments can be suitably used in the color materials described in JP-A No. 2,005-17, pp. [0038] to [0040], or in JP-A-2005-361447 [0068] to [0072]. The pigment is used as the pigment described in JP-A No. 2 0 0 5 · 1 7 5 2 1 [0 0 8 0 ] to [0 0 8 8 ]. The content of the dye or the auxiliary material to be used in an auxiliary manner is preferably 5% by mass or less based on the total amount of the composition of the resin -107-200811249. [Ultraviolet absorber] The coloring photosensitive resin composition of the present invention may optionally contain an ultraviolet absorber. The ultraviolet absorber is, for example, a salicylate-based, a benzophenone-based, a benzotriazole-based, a cyanoacrylate-based, or a nickel chelating agent, in addition to the compound described in JP-A-H05-72 72, Hindered amines and the like. Specifically, for example, phenyl salicylate, 4-tert-butylphenyl salicylate, 2,4-di-t-butylphenyl-3', 5'-di-hydroxybenzoic acid Acid ester #, 4-t-butylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n- Octyloxybenzophenone, 2-(2'-hydroxy-5, methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methyl Phenyl)-5-chlorobenzotriazole, ethyl-2-cyano-3,3-diphenyl acrylate, 2,2'-hydroxy-4-methoxybenzophenone, nickel two Butyl dithiocarbamate, bis(2,2,6,6-tetramethyl-4-pyridine)-sebacate, 4-t-butylphenyl salicylate, phenyl salicylate Ester, 4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinic-bis(2,2,6,6-tetramethyl-4-piperidinyl)-ester, 2- [2-hydroxyl-3,5·bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 7-{[4-chloro-6-(diethylamino) )-5-Triso-2-yl]amino}-3-phenylcoumarin. The content of the ultraviolet ray absorbing agent is preferably 5% by mass or less based on the total amount of the resin composition. In addition, the coloring photosensitive resin composition of the present invention may contain, in addition to the above-mentioned additives, a "adhesive auxiliary" described in JP-A No. 1 1 -13,300, or other additives. [Coating film of the coloring photosensitive resin composition] The component contained in the coating film of the coloring photosensitive resin composition of the present invention -108-200811249 is the same as the above-mentioned [coloring photosensitive resin composition]. the same. Further, the thickness of the coating film used for the coloring photosensitive resin composition of the present invention can be appropriately determined depending on the use thereof, and preferably 〇5~5_〇um is preferably 1.0 to 3.0 μm. The coating film using the colored photosensitive resin composition of the present invention is a polymeric film obtained by polymerizing (c) a monomer or a low polymer contained therein to form a colored photosensitive resin composition, and then producing a color filter containing the same The sheet (the production of the color filter is as described later). The polymerization of the polymerizable monomer or the polymerizable oligomer can be carried out by light irradiation to cause (d) a photopolymerization initiator or a photopolymerization initiator. (Slit-shaped nozzle) The coating film can be formed by applying and drying the colored photosensitive resin composition by a general coating method. However, in the present invention, the portion of the discharge liquid has a slit-like cavity. It is preferable to apply the slit nozzle. Specifically, it is preferable to use the publications of JP-A No. 20 04-89851, JP-A-2004-1 7043, JP-A-2003-170098, JP-A-2003-164787, and JP-A-2003-10767. The slit nozzle and the slit coater described in JP-A-2002-31 01, and the like. The method of applying a colored photosensitive resin composition to a substrate is excellent in spin coating from the viewpoint of uniformly and accurately applying a film of 1 to 3 μm, and is widely used in the production of a color filter. of. However, in recent years, with the increase in size and mass production of the liquid crystal display device, the manufacturing efficiency and the manufacturing cost are further improved, and slit coating which is more suitable for coating of a wide-area and large-area substrate than spin coating is employed. The production of color filters. Further, even from the viewpoint of the so-called liquid-saving property, the slit coating-109-200811249 is excellent in spin coating, and a uniform coating film can be obtained with a smaller amount of coating liquid. The slit coating is a slit (gap) having a width of several tens of micrometers at the front end, and the coating head having a width corresponding to the width of the rectangular substrate is generally kept at a gap of 10 to 1 in the gap with the substrate. 00 μm, a coating method in which a coating liquid supplied from a slit is applied to a substrate at a predetermined discharge speed while maintaining a relative speed between the substrate and the coating head. The slit coating system has: (1) less loss of liquid than the spin coating, (2) reduction of the cleaning treatment due to the absence of scattering of the coating liquid, and (3) scattering of the liquid component without being mixed into the coating film, (4) Since the start time is not started by the rotation, the flow time (tact time) can be shortened, and (5) the application to the large substrate is easy, and the like. According to these advantages, the slit coating is suitable for the production of a color filter for a large-screen liquid crystal display device, and an advantageous coating method is also desired for the reduction of the amount of the coating liquid. In the slit coating system, since a large-area coating film can be applied from a long distance by spin coating, when the coating liquid is discharged from a wide slit outlet, it is necessary to maintain a certain degree between the coating machine and the object to be coated. Relative speed. For this reason, it is required that the coating liquid used in the slit coating method has good fluidity. Further, in the slit coating, the conditions of the coating liquid supplied from the slit of the coating head to the substrate are particularly required to cover the entire coating width and remain constant. When the liquid properties such as the fluidity or the viscoelastic property of the coating liquid are insufficient, coating unevenness is likely to occur, and it is difficult to maintain a coating thickness in the coating width direction, and finally there is a problem that it is difficult to obtain a uniform coating film. As described above, in order to obtain a coating film which is not uneven and uniform, most of the attempts have been made to improve the fluidity and viscoelastic properties of the coating liquid. However, although -110-200811249 has proposed a polymer having a molecular weight lowering as described above, or selecting a polymer having excellent solubility in a solvent, or a solvent selected for controlling the evaporation rate, or a surfactant, or the like. Means, but none of the above problems have been sufficiently improved. .

[Photosensitive Resin Transfer Material] Next, the photosensitive resin transfer material of the present invention will be described.

The photosensitive resin transfer material of the present invention is preferably formed by using a photosensitive resin transfer material described in Japanese Laid-Open Patent Publication No. Hei. The configuration of the integrated film may be, for example, a structure in which a temporary support/thermoplastic resin layer/intermediate layer/photosensitive resin layer/protective film is laminated, and the color transfer material of the present invention can be used by using the aforementioned invention. A photosensitive resin composition is colored, and a photosensitive resin is provided. (Temporary Support) In the photosensitive resin transfer material of the present invention, the temporary support system has flexibility, and does not cause significant deformation, shrinkage or elongation under pressure, pressure or heat. necessary. Examples of such temporary support systems include, for example, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, a polycarbonate film, etc., among which a 2-axis extended polyterephthalic acid Ethylene diester film is particularly preferred. (The thermoplastic resin layer) The component to be used in the thermoplastic resin layer is preferably an organic polymer material described in JP-A-5-7 2724, which is preferably selected from the Vicat Vi cat method (specifically, according to the United States). It is particularly preferable that the organic polymer material having a softening point of about 80 ° C or less in the material test method ASTM D 1 235 (softening point of polymer softening). Specifically, for example, polyolefin such as polyethylene or polypropylene, -111- 200811249

An ethylene copolymer of ethylene and vinyl acetate or an allylate thereof, a copolymer of ethylene and acrylate or a saponified product thereof, a polyvinyl chloride, a vinyl chloride copolymer of ethylene chloride and vinyl acetate, and a saponified product thereof, Polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer of styrene and (meth) acrylate or its saponified product, polyvinyl toluene, vinyl toluene and (methyl a vinyl toluene copolymer such as acrylate or a saponified product thereof, a (meth) acrylate copolymer of methacrylate acrylate (meth)acrylate, and a (meth) acrylate copolymer such as vinyl acetate, and copolymerization of vinyl acetate. An organic polymer such as nylon, copolymerized nylon, N-alkoxymethylated nylon, or polyamine resin such as N-dimethylaminolated nylon. (Intermediate layer) In the photosensitive resin transfer material of the present invention, it is preferable to provide an intermediate layer in order to prevent mixing of components during coating of a plurality of coating layers and storage after coating. The intermediate layer is preferably an oxygen barrier film which is described as a "separation layer" and an aerobic blocking function in the Japanese Patent Publication No. Hei 5-72724. In this case, the sensitivity during exposure can be improved, and the time load of the exposure machine can be reduced. Further, it is preferable that the oxygen barrier film system exhibits low oxygen permeability, dispersion or dissolution in water or an alkaline aqueous solution, and can be appropriately selected from a conventional one. Among the above, the best ones are the combination of polyethyl alcohol and polyethyl sulphate. (Protective film) It is preferable to provide a thin protective film on the photosensitive resin layer in order to protect it from contamination or damage at the time of storage. The protective film may be composed of the same or similar material as the temporary support, but must be easily separated from the photosensitive resin layer. The protective film material is suitably made of, for example, crepe paper, polyolefin or -112-200811249 polytetrafluoroethylene sheet. (Manufacturing Method of Photosensitive Resin Transfer Material) The photosensitive resin transfer material of the present invention is produced on a temporary support by applying a coating liquid (coating liquid for a thermoplastic resin layer) in which a thermoplastic resin layer additive is dissolved and dried. Providing a layer of a thermoplastic resin, followed by coating and drying an intermediate layer material solution composed of a solvent of the undissolved thermoplastic resin layer on the thermoplastic resin layer, and then the composition for the photosensitive resin layer can be used to dissolve the intermediate layer The solvent is applied, dried, and set, and is produced. Further, a sheet in which a thermoplastic resin layer and an intermediate layer are provided on the temporary support, and a sheet in which a photosensitive resin layer is provided on the protective film may be prepared, and the intermediate layer and the photosensitive resin layer may be brought into contact with each other. Further, a sheet in which a thermoplastic resin layer is provided on the temporary support, and a sheet in which a photosensitive resin layer and an intermediate layer are provided on the protective film may be prepared so that the thermoplastic resin layer and the intermediate layer are in phase. The methods of connecting are made to fit each other.

In the photosensitive resin transfer material of the present invention, the film thickness of the photosensitive resin layer is preferably 1 · 〇 to 5 · 0 μ m, preferably 1 · 0 to 40 μm, and 1 · 0 to 3 _ 0 μ m is especially good. Further, it is not particularly limited, but the preferred film thickness of the other layers is generally: temporary support 15 to 100 Mm, thermoplastic resin layer 2 to 30 μm, intermediate layer 0 to 5 to 3.0 μm, protective film 4 to 4 0 μ m. In addition, the coating in the above-described production method can be carried out by a general coating device or the like, and the coating device using the slit-shaped nozzle described in the above [Coating film for coloring photosensitive resin composition] is used in the present invention. It is preferable to carry out (slit coater). A preferred embodiment of the slit coater is the same as the above-mentioned -113-200811249. [Color Filter] The color filter of the present invention is characterized by excellent contrast. The comparison of the present invention shows the ratio of the amount of transmitted light when the two polarizing plates are parallel to the polarizing axis and perpendicular thereto (refer to "the 7th color optical conference in 1990, the 512 color display 1 0.4" size TFT- LCD color filter, Ueki, Xiaoguan, Fuyong, Shanzhong, etc.).

Color filter The so-called high contrast i system combines with liquid crystal to produce a bright and dark degree of discrimination. It is a very important performance for liquid crystal display instead of CRT. The color filter of the present invention is used as a TV, from F1. The monochromatic chromaticity of each of the 0 light source, the red (R), the green (G), and the blue (B) is the same as that described in the following table (hereinafter, referred to as "target chromaticity" in the present invention). The difference (Δ E ) is preferably within a range of 5, more preferably within 3, or within 2 within a particularly good system. X y YR 0.656 0.336 21.4 G 0.293 0.634 52.1 B 0,14 6 0.088 6.90 The chromaticity in the present invention is determined by a micro spectrophotometer (manufactured by Olympic Optical Co., Ltd.; 〇 SP1 〇〇 or 200), and the field of view of the F10 source The result of 2 degrees is calculated and expressed by xyY値 of the xyz color system. Further, the difference from the target chromaticity -114 - 200811249 is expressed by the color difference of the La + b + color system. [Manufacturing Method of Color Filter] The color filter of the present invention is formed on a partition wall having a light-shielding property on a substrate, and a plurality of concave portions partitioned by the partition walls are provided, and R (red) is printed by an ink jet method. Ink, G (green) ink, and B (blue) ink are sprayed onto the concave portion and stacked, and colored resin layers of respective colors are formed in each concave portion to make the R ink, the G ink, and the B ink. At least one of them contains precipitated fine particles. Then, at this time, the precipitated pigment fine particles are mixed with a pigment solution in which a pigment is dissolved in a good solvent, and a solvent which is compatible with the above-mentioned good solvent and which is a poor solvent for the pigment, and is a nanometer-sized fine particle as the pigment. The generator is better. In addition, when a partition having a light-shielding property is formed on a substrate, a photosensitive resin transfer material having a light-shielding resin layer on a temporary support is prepared, and a light-shielding resin is used from the photosensitive resin transfer material. It is preferred that the layer be transferred onto the substrate. (colored resin layer)

In the method of producing a color filter of the present invention, the inkjet ink for color filter is sprayed and deposited on the concave portion provided on the substrate to form a colored resin layer. For the spray coating of the ink filter ink for the color filter, a general spray device can be used. As described in the above section [Painting of the ink jet ink for color filter], it is preferable to use a general ink jet device. In the case of spraying or stacking to form a colored resin layer, it is preferable that the layer thickness is sprayed to be 1·〇~3·Ομηι, and it is preferably formed as 1·0~2·5μηι, and is formed as ι·5~2. -5μηι is particularly good (transfer of the light-shielding resin layer) -115- 200811249 The photosensitive resin transfer material is used to form a film-like resin layer having a light-shielding property on a substrate to be described later, and is heated and 7 The pressure roller or the flat plate is pressed or heated to perform transfer bonding. Specifically, the laminating machine and the laminating method described in JP-A-2002-148794, JP-A-2002-148794, JP-A-2002-148794, and JP-A-2002-148794, From the viewpoint of low foreign matter, it is preferred to use the method described in JP-A-7-10-1575. Further, the resin layer having a light-shielding property is formed by the above-mentioned photosensitive resin transfer material, and is preferably a film of a preferred film thickness and a film of the [photosensitive resin transfer material]. The same thickness. (The concave portion provided in the resin layer having a light-shielding property and the partition wall having a light-shielding property) In the case where the colored pixel is produced by the ink-jet method, the height of the partition wall having the light-shielding property is 1 in the case of the coloring pixel. Preferably, 〇μ m or more is preferably 1·5 μm or more and 1 Ομπι or less, and more preferably ·8·ηι or more and 7·0 μΓΠ or less, and particularly preferably 2.0 μm or more and 5·0 μmη or less. For example, by setting it to 1·5 μηι or more and 10 μπι Φ or less, it is possible to effectively prevent inkjet ink from overflowing and crossing (mixing color) to adjacent pixels. When the height is less than 1.5 μm, color mixing is likely to occur, and when it exceeds 10 μm, it is difficult to form a partition wall having light shielding properties. Further, the light-shielding partition wall preferably has an optical density of 555 nm of 2.5 or more, preferably 2.5 to 10.0, more preferably 2·5 to 6.0, and more preferably 3·0 to 5.0. Preferably, a relatively high color filter can be obtained within the above optical density range. (Substrate) In the present invention, the substrate on which the color filter is formed is, for example, a transparent-116-200811249 substrate, a soda lime glass plate having a ruthenium oxide film on the surface, a low-expansion glass, an alkali-free glass, a quartz glass plate, or the like. A known glass plate or a plastic film is used, and the substrate can be adhered to the color filter inkjet ink or the photosensitive resin transfer material by applying a pre-coupling treatment. . The coupling treatment is preferably carried out by the method described in JP-A-2000-39-33. Further, it is not particularly limited that the film thickness of the substrate is generally 700 to 1200 μm and 500 to 1,100 μm.

In the color filter of the present invention, in the case where the light-shielding partition wall is formed, the oxygen barrier film is further provided on the resin layer having the light-shielding property, whereby the exposure sensitivity can be improved. The oxygen barrier film is, for example, the same as those described in the section (middle layer) of the above [photosensitive resin transfer material]. Further, it is not particularly limited, but the film thickness of the oxygen barrier film is generally from 55 to 3.0 pm. As a manufacturing step of the partition having the light-shielding property of the present invention, there are steps of exposure, development, post-exposure, heat treatment, and the like, and the step number of the opening paragraph Φ 20 05-3861 can be used [0067] to [0074] The steps described in the ] are suitable. (Water-repellent treatment) In the case of forming a colored pixel by the ink-jet method of the present invention, a water-repellent treatment is applied to a partition having a light-shielding property so that at least a portion of the upper surface of the light-shielding partition wall is formed. It is better to have a water-repellent state. The reason is that when droplets of the inkjet ink are applied to the partition wall having the light-shielding property after the partition having the light-shielding property is formed, no ink crosses the partition wall having the light-shielding property, and color mixture is formed with the adjacent color. Not suitable. -117- 200811249 The water repellent treatment system is, for example, a method of applying a water-repellent material to a part of a partition having a light-shielding property (for example, refer to Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. For example, a method of imparting water repellency by plasma treatment (for example, see JP-A-2020-62420), and a method of incorporating a water-repellent substance into a partition wall having a light-shielding property, for example, refer to JP-A No. 5-241011) (For example, refer to Japanese Laid-Open Patent Publication No. 2005-361 60). (Protective coating) After the production of the light-shielding partition wall and the color filter sheet having the colored pixels, there is a case where a protective coating for comprehensively improving the resistance is provided. The protective coating protects the cured layers of the inks R, G, and B while making the surface flat, but may not be provided from the viewpoint of increasing the number of steps. The resin (OC agent) which forms the protective coating layer is, for example, an acrylic resin composition, an epoxy resin composition, a polyimine resin composition or the like. In particular, the resin component is excellent in transparency in the visible light region, and the resin component in the photocurable photocurable composition is preferably an acrylic resin as a main component and an adhesiveness is excellent, and an acrylic resin is used. The composition is expected to be expected. Examples of the protective coating are described in, for example, the paragraph number 〇〇1 8 to 0028 of JP-A-2003-28761, or the commercial product as a protective coating agent, "0ptmer SS6699G" manufactured by JSR Corporation). <Liquid Crystal Display Device> The liquid crystal display device of the present invention uses the color filter of the present invention excellent in contrast, and the degree of sharpness such as blackness is excellent. A liquid crystal display device that is a large screen such as a display for a personal computer or a television screen can be suitably used. The liquid crystal display device is described in, for example, "Second Generation Liquid Crystal Display -118-200811249 Technology (Endowed by Natsuda Ryuo, Industrial (Stock) Survey Association, issued in 1994). The liquid crystal display device to which the inkjet ink, the color filter, and the method for producing the color filter of the present invention are applicable is not particularly limited, and can be applied, for example, to the various types described in the above/next generation liquid crystal display technology. Various types of liquid crystal display devices. Among them, it is effective especially for a liquid crystal display device of a color TFT type. A liquid crystal display device of a color T FT type is described, for example, in "Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., issued in 1996)". In addition, it is also applicable to a liquid crystal display device that expands the viewing angle, such as a lateral electric field driving method such as IPS or a pixel division @ method such as MVA. Regarding such methods, for example, "EL, PDP, LCD Display - Latest Trends in Technology and Markets - (Dongli Research Center Survey Research Division, 2001 issue)" is recorded on page 43. The liquid crystal display device may be composed of a wide variety of members such as an electrode substrate, a polarizing film, a phase difference film, a backlight, a spacer, and a viewing angle securing film, in addition to the color filter. The black matrix of the present invention is suitable for use in a liquid crystal display device comprising such general components. Such a component # is for example, "The market of Ί4 liquid crystal display peripheral materials and chemistry (issued by Kanda Shimaro Co., Ltd. in CMC 1994)", "The current status and future prospects of the 2〇〇3 LCD related market (volume)" There are records in Liangji (share) Fuji Chimera, issued in 2003). [CCD device] The c C D device of the present invention comprises a color filter produced by using the pigment nanoparticle obtained by the production method of the present invention. Hereinafter, the CCD device of the present invention will be described in detail. Alkali soluble resin -119- 200811249

The alkali-soluble resin used in the CCD device is preferably a linear organic polymer, an organic solvent, and a weak alkaline solution. These linear organic polymer polymers are side-locked with a polymer of a carboxylic acid, for example, JP-A-59-4461, JP-A-54-34327, JP-A-58-1 2577, and JP-A 54-25957 A methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a butenoic acid copolymer, a maleic acid copolymer described in the specification of JP-A-59-53836, JP-A-59-71 0 48 A partially esterified maleic acid copolymer or the like is similarly locked to an acid cellulose derivative having a carboxylic acid. Further, it is also useful as a polymer addition anhydride having a hydroxyl group. In particular, among them, a (meth) acrylate/(meth)acrylic copolymer, a benzyl (meth)acrylate/(meth)acrylic acid/and a multicomponent copolymer with other monomers are suitable. Further, 2-hydroxyethyl methacrylate, polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol or the like is also useful as a water-soluble polymer. Further, for example, 2-hydroxypropyl (meth) acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer described in JP-A-7-140654, 2-hydroxyl acrylate -3-phenoxypropyl ester / polymethyl methacrylate macromer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methyl acrylate / polystyrene macromolecule / A Methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methyl acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, and the like. The amount of the alkali-soluble resin added to the curable composition is preferably from 5 to 90% by mass, more preferably from 10 to 60% by mass based on the total mass of the composition. /〇. The polymerizable monomer polymerizable single system is preferably a compound having at least one addition-polymerizable ethyl group having an ethylenically unsaturated group having a boiling point of from 1 〇〇 ° C above atmospheric pressure of from -120 to 200811249. . The compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of at most 100 ° C under normal pressure may, for example, be polyethylene glycol mono(meth)acrylate or polypropylene glycol ( Methyl) acrylate, phenoxy (meth) acrylate, monofunctional acrylate or methacrylate; polyethylene glycol di(meth) acrylate, trimethylolethane tris (A) Acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, Glycol (meth) acrylate, trimethylolpropane tris(propylene methoxypropyl) ether, tris(propylene methoxyethyl) trimeric isocyanate, glycerin or trimethylolethane Addition of functional alcohols to ethylene oxide or propylene oxide, followed by (meth) acrylated, special public, No. 48-41, 708, special public, No. 50-6034, such as JP-A-51-371, No. 3 The urethane acrylates described in the publication, JP-A-48-641 δ 3, and the special public 49- A polyfunctional acrylate or the like such as an epoxy acrylate such as a polyester acrylate or a reaction product of an epoxy resin and (meth) Φ acrylic acid described in each of the publications of the Japanese Patent Publication No. 431-91 Acrylate. Further, it is also possible to use the Japanese Society of Associations Vo I. 20, No. 7, and pages 300 to 308 as photocurable monomers and low polymers. Further, a compound represented by the following formula (B-1) or (B-2) can also be used. -121- 200811249 General formula (B-1) : }... 〇"(Β)π-Χ ^ Η2-Η^(Β)η-Χ X-{B)n—OCH2_?m2· ch2-o - oc (B)

X ch2-〇· tearing formula (B»2> o-

In CH2-〇-(B〇rT-X {prints-1) and (B-2), the B series independently represent any of _(Ch2CH2〇)_ and -(CH2CH(CH3)〇)· X each independently represents any one of a acrylic acid group, a methacryl fluorenyl group, and a hydrogen atom, and in the formula (B-1), the total of the acryl fluorenyl group and the methacryl fluorenyl group is 5 or 6 In the formula (B_2), they are 3 or 4; the n series each independently represent an integer of 0 to 6, and the total of each n is 3 to 24; the m series each independently represent an integer of 0 to 6. In addition, the total amount of each of (7) is 2 to 1 6 . The polymerizable monomer can be used in any ratio as long as it can form a coating film having an adhesive property by irradiation with radiation. The amount used is usually from 5 to 90% by mass based on the total solid content of the group Φ. /. Preferably, it is 10 to 50% by mass. Colorant The colorant may be used alone or in combination of two or more kinds of dyes, inorganic pigments or organic pigments which have been conventionally known. The dye system is not particularly limited, and a well-known dye used as a conventional color filter can be used. For example, JP-A-64-9 0403, JP-A-64-91 01, JP-A-1-94301, JP-A-6-116, JP-A No. 2,592,207, US Pat. -122-200811249, U.S. Patent No. 5,567,920, U.S. Patent No. 5, 560, 950, U.S. Patent No. 5, 595, 950, U.S. Patent No. 5,567, 920, U.S. Patent No. 5,333, 207, Japanese Patent Application Laid-Open No. Hei No. Hei.

The pigment disclosed in Japanese Laid-Open Patent Publication No. 6-1 948, No. 2, and the like. As the chemical structure, a pyrazole azo system, an anilino azo system, a triphenylmethane system, an anthracene system, a benzene system, an oxaphthalocyanine system, a pyrazolone, a triazole azo system or a pyridone group can be used. A dye such as a nitrogen system, a cyanine system, a phenothiazine system, or a pyrazolopyrazole-based imine system. In particular, since the curable composition can be hardened at a relatively low temperature, it is possible to reduce the dye which is inferior to the heat resistance of the pigment or to further improve the durability of the cured film at a high temperature. Decomposition and other issues. The inorganic pigment is a metal compound represented by a gold ruthenium oxide or a metal salt, and specifically, a metal such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc or ruthenium. An oxide and a composite oxide of the above metals. The organic pigments may, for example, be CI Pigment Yellow 11, 24, 31, 53, 83, 85, 99, 1 08, 1 09, 1 1 0, 1 3 8, 1 39, 150, 1 51, 154, 167, 185, C. I. · Pigment Orange 36, 38, 43, 71, C· l_ Pigment Red 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 224, 242, 254, CI Pigment Violet 19, 23, 32 39, C. I· Pigment Blue 1, 2,15,16, 22,60, 66, 15:3, 15:6 > CI Pigment Green 7, 36,37 ^0. I. Pigment Brown 25, 28 , CI Pigment Black 1, 7, carbon black and so on. These organic pigments can be used singly or in various combinations which enhance color purity. The specific examples are as follows. Red pigments can be used alone -123- 200811249 Mixtures of lanthanide pigments, phenanthrene pigments, or at least one of them with a diazo yellow pigment or an isophthalocyanine yellow pigment. For example, an anthraquinone pigment is, for example, CI Pigment Red]77, and an anthracene pigment is, for example, c·丨Pigment Red 55, from the point of color reproducibility, with C·丨.Pigment Yellow 83 or C· The mixing of bismuth pigment yellow 139 is good. The mass ratio of red pigment to yellow pigment is 1〇 〇 : 5~ 100:50 is good. Within this range, it is preferable to suppress the light transmittance of 4 〜 to 5 ’ and to improve the color purity. φ Green pigment is used alone as a halogenated phthalocyanine pigment, or in combination with a diazo yellow pigment, a quinoline yellow dye or an isoporphyrin yellow pigment, for example, CI·Pigment Green 7, 36, 37 It is preferred to mix with C"·Pigment Yellow 83, 138, and 139. The mass ratio of the green pigment to the yellow pigment is preferably from 100:5 to 100:100. Within this range, light transmittance of 4 〇〇 nm to 45 〇 nm _ can be suppressed, and good color purity can be obtained. The blue pigment may be used alone or in combination with a dioxin violet pigment, for example, C.L Pigment Blue 15:6 and C_l_Pigment Violet 23 φ are preferred. The mass ratio of the blue pigment to the violet pigment is preferably from 100:0 to 100:50. Within this range, the light transmittance of 4 0 0 n 4 to 4 2 0 n m can be suppressed, and the color purity can be improved. Further, the above pigments can be produced by using a powdery processed pigment which is finely dispersed such as an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate copolymer, or an ethyl cellulose resin. A pigment-containing photosensitive resin having good dispersibility and dispersion stability is obtained. Further, the pigment for the black matrix is preferably carbon, titanium oxide or iron oxide alone or in combination with carbon and titanium oxide. The mass ratio is preferably 1 〇 〇: 5 -124- 200811249 ~1 00: 40 is better. The long-wavelength light transmittance in this range is small and the dispersion stability is also good. Solvent

Solvents are, for example, esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyric acid. Ethyl ester, butyl butyrate, alkyl ester, methyl lactate, ethyl lactate, methyl glycolate, ethyl hydroxyacetate, butyl glycolate, methyl methoxyacetate, ethyl methoxyacetate, 3-hydroxypropionic acid alkyl esters such as butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate; Methyl oxypropionate, ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate , propyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2 -ethyl ethoxypropionate, methyl 2-oxy-2-methylpropanoate, ethyl 2-oxy-2-methylpropionate, 2-methoxy-2-methylpropionic acid Ester, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate Ethyl acetate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate, etc.: ethers, such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene Alcohol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol Ethyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; aromatic Hydrocarbons such as toluene, xylene, and the like. -125- 200811249 Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl Ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate It is better. The amount of the solvent to be added is usually 60 to 90% by mass in the composition, and preferably 70 to 90% by mass.

These solvents may be used singly or in combination of two or more. * Can use sensitizers more. Specific examples thereof include, for example, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-fluorenone, 2-bromo-9-fluorene ketone, 2-B. 9-fluorenone, 9,10-fluorene, 2-ethyl-9,10-fluorene, 2-tert-butyl-9,10-fluorene, 2,6-dichloro-9, 10-蒽醌, benzophenone, dibenzylideneacetone, p-(dimethylamino)phenylstyryl ketone, P-(dimethylamino)phenyl-p-methylstyrylone A benzothiazole-based compound described in Japanese Patent Publication No. Sho 51-45815. The above-mentioned main components and other additives which are required to be used can be prepared by mixing and dispersing them by using various mixers and dispersers. A general manufacturing method for manufacturing a color filter for a CCD device will be described later. The step of applying and drying the composition (color resist liquid) of the present invention onto the substrate, the step of patterning the obtained dried coating film by an i-line stepper or the like, and performing the exposure after exposure are sequentially performed. The step of alkali development, followed by the heat treatment, is repeated by repeating the above steps for each color (three colors or four colors) to form a hardened film to obtain a color filter. More specifically, the above-mentioned curable composition is applied onto a suitable substrate by a rotator, and the film thickness at the time of drying is generally 〇_1 to 5 μΓΠ, preferably -126 - 200811249 is applied as 〇.2 to 2μηι. At 85. Place in the oven for 2 minutes to obtain a smooth coating. The substrate system is not particularly limited, and examples thereof include a substrate of an electronic component such as a glass plate, a plastic plate, an alumina plate, and a wafer for an image sensor, and a transparent resin plate, a resin film, a brown tube display surface, and a light-receiving image. Wafer formed by solid-state imaging elements such as CCD, BBD, CID, and BASIS

A compact image sensor using a thin film semiconductor, a liquid crystal display surface, a photoreceptor for color electrophotography, a substrate of an electrochromic (EC) display device, or the like. Further, in order to improve the adhesion between the substrate and the color filter layer, it is preferable to apply a high-density treatment. Specifically, a pattern of a curable composition may be formed by thinly coating a substrate with a decane coupling agent or the like, or a decane coupling agent may be contained in advance in the hardening composition. Further, in the case where there is a step on the substrate, the curable composition of the present invention can be applied by coating a flattening film for smoothing the coating surface on the substrate. For example, an image sensor such as a CCD is composed of a photoelectron conversion unit (photodiode) that generates electrons based on the amount of received light on the germanium substrate β, and a read gate portion for outputting electrons generated therefrom. When the read gate portion is irradiated, the cause of the noise is that the correct information is not output. Therefore, the upper portion of the read gate portion is formed with a light shielding film layer, and the photodiode portion having and without the light shielding film layer is formed. A situation in which a step is generated. When the color resist is applied to the step difference and the color filter is directly formed, the image is darkened due to the length of the optical path, and the light collection property is also deteriorated. In order to improve them, the purpose is to compensate for the step, and it is preferable to form a transparent planarizing film between the CCD and the color filter. The material of the planarizing film is -107 - 200811249. The photocurable photoresist liquid of the present invention, a thermosetting resin such as an acrylic or epoxy resin, and the like are exemplified.

After the photocurable composition is applied, in order to obtain a dried coating film in which the solvent evaporates, prebaking is usually performed. The prebaking method is dry under reduced pressure, indirect heat drying using high-temperature air, or the like, and direct heating drying (about 80 to 140 ° C, 50 to 200 seconds) by a hot plate or the like. Further, post-baking is performed in order to sufficiently harden the pattern obtained after development and form a permanent film having improved mechanical strength. For example, when a three-color color filter is manufactured, the initially formed pattern is subsequently coated with a photoresist of another color, and then subjected to exposure and development twice. At this time, post-baking was performed so as not to mix with the applied photoresist liquid and without pattern defects due to exposure or development. This post-baking is carried out in the same manner as in the prebaking, and is carried out at a high temperature for a long period of time according to the conditions of the prebaking. For example, in the case of indirect heating by an oven, about 180 to 250 ° C for about 0.5 to 2 hours, by direct heating of the hot plate, about 180 to 250 ° C for about 2 to 10 minutes. The light source for exposure is not particularly limited, and may be, for example, an i-line of a light source mercury lamp which is associated with pattern formability and which has a remarkable effect. The feature of the present invention is particularly remarkable in the manufacture of color filters for image sensors using one of the line spectra of mercury lamps from the appropriate side of the step, not to mention the use of LCDs. be usable. The image liquid system used for the development of the curable composition is not particularly limited, and a conventionally known developer liquid can be used. Among them, an organic alkali-based developing liquid of a quaternary ammonium salt such as tetramethylammonium hydroxide (T oxime) can be preferably used for the purpose of the present invention. -128- 200811249 Polymeric Heuristics Polymeric heuristics can use general photopolymerization heuristics. Specifically, the conjugated polyketal aldehyde-based compound described in the specification of U.S. Patent No. 2,367,660, the α-carbonyl compound described in the specification of U.S. Patent Nos. 2,367,661 and 2,367,670, and the U.S. Patent No. Aromatic aldehydes substituted by α-hydrocarbons described in the specification of No. 2,448,828, and in the specification of U.S. Patent No. 2,722,51

The polynuclear oxime compound described in the specification of U.S. Patent Nos. 3,046,1, and 2,951,758, and the triallyl imidazole dimer/ρ-amino group described in the specification of U.S. Patent No. 3,549,36. A combination of a phenyl ketone, a benzothiazole-based compound, a trihalomethyl-s-trin-based compound, and the like described in Japanese Patent Publication No. 51-48516. The content of the photopolymerization-inducing agent (including the above-mentioned general photopolymerization initiator) in the negative-type curable composition containing the dye is 0.01 to 50% by mass based on the solid content (mass) of the radical polymerizable monomer. Preferably, 1 to 30% by mass is preferred, and 1 to 20% by mass is particularly preferred. When the content is in the above range, sufficient polymerization hardening is not performed, and polymerization is difficult to proceed, the polymerization rate is increased, the molecular weight is lowered, and the film strength is also weakened. Further, specific examples of the sensitizer and the photosensitizer which can be used in the above photopolymerization initiator include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone. 2·methyl·9-fluorenone, 9-fluorenone '2-bromo-9·fluorenone, 2-ethyl-9-fluorenone, 9,10-fluorene, 2·ethyl-9, 10-蒽醌, 2-t-butyl-9,10-fluorene, 2,6-dichloro-9,10-onion, xanthone, 2-methylindole-129- 200811249 ton ketone, 2-methoxyxanthone, 2-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 1 〇-butyl-2-chloroacridone , benzophenone, dibenzylideneacetone, P·(dimethylamino)phenylstyryl ketone, P_(dimethylamino)phenyl-P-methylstyrylone' benzophenone , P-(dimethylamino)benzophenone (or mischrone), p-(diethylamino)benzophenone, benzoxanthone, etc., or special public Zhao 5 1 - 4 8 The benzothiazole-based compound described in the publication No. 5-16, Tirruvin 1 1 30, the same 400, and the like.

Next, the present invention will be described in further detail based on examples. However, the invention is not limited thereto. Hereinafter, the term "parts" means mass parts, and the "%" means mass% unless otherwise specified. (Example 1) [Modulation of concentrated pigment liquid]

Prepared in 2000 ml of dimethyl sulfoxide, adding sodium methoxide 28% methanol solution 6 0.0 ml > Pigment CI·Pigment Red 254: trade name Irgaphor Red BT-CF φ Ciba Specialty Chemicals Co., Ltd.) 1〇〇g, A pigment solution A of polyvinyl ketone ketone 180.0 g. Further, 1 800 m of water containing 20 ml of 1 mol/l hydrochloric acid was prepared as a poor solvent. Here, the temperature was controlled at 18 ° C, and Np_KX-made by Nippon Precision Chemical Co., Ltd. was used in 1800 ml of water of a poor solvent stirred at 500 rpm by a GK-0222-10 type Lamodo mixer manufactured by Fujisawa Pharmaceutical Co., Ltd. A 5 〇〇 type large-capacity pulseless flow pump was used to inject 500 m I of pigment solution a at a flow rate of 80 m I/m in to form organic pigment particles and prepare a pigment dispersion. The pigment dispersion liquid was measured using a Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd., and the particle size and monodisperse -130 to 200811249 degrees were measured as a number average particle diameter of 48 nm and Mv/Mn of 1.44. The pigment nanoparticle dispersion adjusted by the above method was prepared by using the KU-1 22 centrifugal filter manufactured by KOKUSAN Co., Ltd. and the P89C filter cloth manufactured by Kasuga CANVAS Co., Ltd., and concentrated at 2900 rpm for 90 minutes.丨/m In was added with 50 00 m of washing water, and then concentrated under the same conditions for 90 minutes, and the obtained pigment nanoparticle concentrated paste was recovered.

The pigment content of the paste was determined to be .11.0% by weight when measured by an Agilent 8453 spectrophotometer. Adding ethyl lactate 6 0 _ 0 cc to the above pigment nanoparticle adjusting paste 2 0 _ 〇g, stirring with a dissolver at 1 500 rpm _ 60 minutes, by using Sumitomo Electric F ine Ρ ο I ymer A FP-0-11 filter made by the company was filtered to obtain a paste-like concentrated pigment liquid A (nano pigment concentration: 34% by mass). The total concentration of the residual alkali metal and the alkaline earth metal in the concentrated pigment liquid A is 9 5 ppm 〇 [Preparation of the pigment dispersion composition] The pigment dispersion composition A having the following composition is prepared by using the above-mentioned paste-like concentrated pigment liquid A . The paste-like concentrated pigment liquid A 1 8.8 g The polymer compound C-16 of the general formula (1) 4.4 g 4-methoxy-2-propyl acetate 47.3 g [Production of photosensitive resin transfer material] The slit nozzle was coated with a coating liquid for a thermoplastic resin layer composed of the following formula i 'i, and dried on a polyethylene terephthalate film temporary support having a thickness of 75 μm. Then, the coating liquid for an intermediate layer composed of the following formula P1 -131 - 200811249 is applied and dried. Further, a resin composition K1 having a light-shielding property, which is composed of the composition described in the following Table 1, is applied and dried, and a thermoplastic resin layer having a dry film thickness and a dry film thickness are provided on the temporary support. An intermediate layer of 1 6 μm and a light-shielding resin layer having a dry film thickness of 2.4 μm were rolled to protect the film (thickness 12-layer polypropylene film).

In this manner, a photosensitive resin transfer material in which a temporary support, a thermoplastic resin layer, an intermediate layer (oxygen barrier film), and a light-blocking resin layer are integrated is prepared, and the sample name is a photosensitive resin transfer. Material Κ1. * Coating solution for thermoplastic resin layer: Formulation Η 1 • Methanol 1 1 · 1 part • Propylene glycol monomethyl ether acetate 6.4 parts • Methyl ethyl ketone 52.4 parts • Methyl methacrylate / 2-ethyl acrylate Hexyl ester / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (mole ratio) = 55/1 1.7/4.5/28.8, molecular weight = 1 million, Tg and 70 ° C) 5.83 parts • benzene B. Burning / acrylic acid copolymer (copolymerization composition ratio (mole ratio) = 63/37, molecular weight = 10,000, Tg = 100 〇 C) 3.6 parts • 2, 2 _ [4-(methacrylofluorene) Poly(ethoxy)phenyl]propane (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 9.1 parts • Surfactant 1 0.54 parts > Surfactant 1 (Megafac F-780-F (Daily Ink Chemical Industry Co., Ltd.) The composition of the system)): -132- 200811249 • C6Fi3CH2CH2OCOCH = CH2: 40 parts, H(OCH(CH3)CH2)7OCOCH = CH2: 55 parts, H(OCH2CH2)7OCOCH = CH2: 5 parts copolymer, (Molecular weight 30,000) 30 parts • Methyl ethyl ketone 70 parts * Intermediate lip (oxygen barrier layer) coating solution Formula: P1 • Polyvinyl alcohol................. ..............32_2 copies

(PVA20 5 (saponification rate = 88%); manufactured by Kuraray Co., Ltd.) • Polyvinylpyrrolidone........................ .14·9 copies (PVP, K-30; ISP·Sakamoto Co., Ltd.) • Methanol.............. · · ........... ......... 4 2 9 copies • ^ fI 7jc · · ............................... 5 2 4f^ [Table 1] Composition K Content (parts by mass) Part 1 ---- (Carbon Black) 25 Methyl Ether ' 8.0 Methyl Ethyl Ketone 53 ^ Constituent - 1 9.1 Methyl Ether ~ 0.002 DPHA solution 4.2 ^4_^(dichloromethyl)·6-[4,-(Ν,Ν_bisethoxycarbonylmethyl)amino group•3, bromophenyl]-s-di-dope 0.16 interfacial activity Agent 1 0.044 Here, the preparation of the light-shielding resin composition κ 1 described in Table 1 above is described. For the preparation of the light-shielding resin composition κ 1, first, the amount of the K pigment dispersion 1 and the propylene glycol monomethyl ether acetate described in Table 1 were weighed at a temperature of -133 - 200811249 24 ° C (± 2 °). C) Mixing and stirring at 150 rpm for 1 minute, and then extracting the amounts of methyl ethyl ketone, binder 1, hydroquinone monomethyl ether, DPHA liquid, 2,4-double (described in Table 1) Trichloromethyl)-6-[4,-(Ν,Ν-bisethoxycarbonylmethyl)amino-3'-bromophenyl]-s-tripper trap surfactant 1, in sequence It was added at a temperature of 25 ° C (± 2 ° C) and was obtained by stirring at 150 rpm for 30 minutes at a temperature of 40 ° C (± 2 ° C). In addition, among the compositions described in Table 1,

* The composition of K Pigment Dispersion 1 contains: • Carbon black (manufactured by Degussa Corporation, trade name Special Black 4250) 13.1 parts • The above pigment dispersant Α 〇 · 65 parts • Polymer (benzyl methacrylate / A) Acrylic acid = 72/28 molar ratio random copolymer, molecular weight 37,000) 6.72 parts • Propylene glycol monomethyl ether acetate 79.53^ > The composition of the binder 1 comprises: • Polymer ( Benzyl methacrylate / methyl propyl acid = 7 8 / 2 2 random copolymer of molar ratio, molecular weight 40,000) • Propylene glycol monomethyl ether acetate ★ DPHA liquid composition includes: • Dipentaerythritol Hexaacrylate 50 0ppm, made by Nippon Kayaku Co., Ltd., 27 parts of 73 parts (containing polymerization inhibitor Μ EHQ trade name: KAYARAD DPHA) 76 parts 24 parts • propylene glycol monomethyl ether acetate In addition, surfactant The first embodiment is the same as the surfactant 1 used in the above-mentioned coating liquid for thermoplastic resin layer-134-200811249 Η1. [Formation of a partition wall having a light-shielding property]

Spray the alkali-free glass substrate with a glass detergent solution adjusted to 25 ° C, and then wash it with a rotating brush with nylon hair while blowing for 20 seconds, and wash it with pure water spray. By spraying a decane coupling solution (Ν-β(aminoethyl) Υ-aminopropyltrimethoxydecane 〇. 3 mass% aqueous solution, trade name ΙΚΒΜ603, Shin-Etsu Chemical Co., Ltd.) and blowing for 20 seconds Clock and wash with pure ice spray. The substrate was heated by a substrate preheating apparatus at 1 ° C for 2 minutes. After peeling off the protective film of the photosensitive resin transfer material K1, the temperature of the rubber roll was performed on the substrate heated by the above-mentioned 100 ° 2 for 2 minutes by a laminator (manufactured by Hitachi Industrial Co., Ltd. (Lamicll type)). 130 ° C, line pressure 100 N / cm, conveying speed 2.2 m / part force D to laminate. After the temporary support is peeled off, a Proximity exposure machine (manufactured by Hitachi High-Tech Electronics Co., Ltd.) having an ultrahigh pressure mercury lamp is used, and the substrate and the mask (a quartz exposure mask having an image pattern) are vertically erected. In the state, the distance between the exposure mask surface and the thermoplastic resin layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 100 mJ/cm 2 . The mask shape is a lattice shape, and in a portion corresponding to a boundary line between the pixel and the light-shielding partition wall, the radius of curvature of the lobe on the partition wall side having the light-shielding property is 0.6 μm, and then the triethanolamine-based developing liquid (containing 2.5% triethanolamine, containing nonionic surfactant, containing polypropylene-based defoamer, trade name: T-PD1, Fuji Photo Film Co., Ltd.) in 3 ° C for 50 seconds, with flat - 135 - 200811249 Spray development was performed at a nozzle pressure of 0.04 M Pa to remove the thermoplastic resin layer and the intermediate layer (oxygen barrier layer).

After that, continue to use sodium carbonate imaging solution (containing 〇.〇6 mol / liter of sodium bicarbonate, the same concentration of sodium carbonate, 1% of sodium dibutylnaphthalene sulfonate, anionic surfactant, defoaming Agent, stabilizer, trade name: T-CD1, Fuji Photo Film Co., Ltd.), spray development at 29 ° C for 30 seconds, with a cone nozzle pressure of 0_15M Pa, to develop a resin layer with a light-shielding property. In order to obtain a patterned pattern partition wall (having a light-blocking partition pattern). After that, the detergent (containing a phosphate, a citrate, a nonionic surfactant, an antifoaming agent, a stabilizer, and a product name "T-SD1 (manufactured by Fuji Photo Film Co., Ltd.))) When spraying at a cone nozzle pressure of 0·02 M Pa at 33 ° C for 20 seconds, the residue was removed by a rotating brush having nylon wool to obtain a partition wall having a light-shielding property. Subsequently, the substrate was further exposed to light from a side of the resin layer by an ultrahigh pressure mercury lamp at 500 m J/cm 2 and then heat treated at 240 ° C for 50 minutes. [Milling water repellency treatment] Subsequently, plasma water repellency treatment was carried out according to the following method. The above-mentioned substrate on which the light-shielding partition wall was formed was subjected to plasma water repellency treatment using a cathode coupling type parallel plate type plasma processing apparatus under the following conditions. Gas used: CF4 gas flow rate: 8 〇 sccm Pressure: 40 Pa RF power: 50 W Processing time: 30 sec - 136 - 200811249 [Preparation of inkjet ink for color filter] Example of JP-A-2002-201 387 1. Use the following formula to modulate the ink. Using the pigment dispersion composition A prepared as described above, the R ink 1 was prepared in the composition shown in Table 2. Further, the same table shows the compositions of the R inks 2 to 7 and the g inks i and B inks used in Examples 2 to 6 and Comparative Examples 1 and 2 which will be described later.

-137 - 200811249 [Table 2] Composition content (parts by mass) R ink 1 R ink 2 R ink 3 R ink 4 R ink 5 R ink 6 R ink 7 G ink 1 B ink 1 Concentrated Pigment Liquid A (CIPR 254 > 15 Concentrated Pigment Liquid B (C.LP.R. 254) 15 Concentrated Pigment Liquid C (CURR· 254) 15 Concentrated Pigment Liquid D (CIPR· 254) 15 Concentrated Pigment Liquid E (C .LP.R· 254) 15 \ Concentrated Pigment Liquid F (C_IP.R.254) 15 Concentrated Pigment Liquid G (C.LRR. 254) 15 G Pigment (CIRG. 36) 5.0 B Pigment (CIPB 15:6) 5.0 Polymer Dispersant (Soros Pass 24000 made by AVECIA) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 2.0 2.0 Adhesive (benzyl methacrylate methacrylate copolymer) 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Dipentaerythritol Acrylate 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Tripropylene glycol diacrylate 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 2-Methyl-1-[4-(methylthio)phenyl]-2-flavor -1. 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Diethylene glycol monobutyl ether acetate, 29.9 dyn/cm 70 70 70 70 70 70 70 81 81

With respect to the mixing of the components in the above Table 2, the pigment and the polymer dispersing agent are first introduced into a part of the solvent, mixed, and stirred by a three-roller and a bead mill to obtain a pigment dispersion liquid. On the other hand, the other compounding component is supplied to the residual portion of the solvent, and stirred to be dissolved and dispersed to obtain a binder solution. Then, the pigment dispersion liquid was added to the binder solution in a small amount, and the mixture was sufficiently stirred by a dissolver to prepare an ink jet ink for color filter. [Pixel formation] The R ink 1, G ink 1, and B ink 1 obtained as described above are the nozzles of the piezoelectric method -138-200811249, and the ink is printed on the concave portion surrounding the light-shielding partition wall as described below. . Then, it is carried out as follows to obtain the color filter of the present invention. The nozzle has 318 nozzles per 25.4 mm and 150 nozzle densities, which are fixed by 1 /2 in the direction of the two nozzle rows with the nozzle spacing offset, and arranged in the nozzle arrangement direction on the substrate. Drip 300 drops per 25.4mm.

The nozzle and the ink are controlled by circulating warm water in the nozzle to control the vicinity of the discharge portion to be 50 ± 0.5 °C. The ink discharged from the head is controlled by the piezoelectric driving signal applied to the head, so that each drop can be discharged 6 to 42 pi. In this embodiment, the glass substrate is conveyed while being placed at a position 1 mm below the head. Drip. The transport speed can be set in the range of 50 to 200 mm/s. Moreover, the piezoelectric driving frequency can be up to 4.6 KHz, and the amount of dripping can be controlled by such a setting. In this embodiment, the coating amounts of the respective pigments of R, G, and B are controlled to be 1.1, 1.8, 0.75 g/m2, the conveying speed, and the driving frequency, so that the inks of R, G, and B are dripped to correspond to the The recesses of R, G, and B are expected. The dripped ink is transferred to the exposure portion, and exposure is performed by an ultraviolet light emitting diode (UV-LED). In the present embodiment, the UV-LED system uses NCCU0 33 manufactured by Nichia Chemical Co., Ltd. This LED emits ultraviolet light having a wavelength of 365 nm from one wafer, and emits light of about 1 〇〇mW from the wafer by energizing a current of about 500 mA. A plurality of them are arranged at intervals of 7 mm, and a power of 〇3 W/cm 2 is obtained on the surface. The time from the drip to the exposure and the exposure time may be changed depending on the transport speed of the medium and the distance between the head and the LED transport direction. Ben-139-200811249 The embodiment is made to be dried at 1 ο 1 after drying for 1 ,, then exposure 0. Depending on the distance and the setting of the conveying speed, the exposure energy on the medium can be adjusted to 0.01~15J. Between /cm2. In this embodiment, the exposure energy is adjusted in accordance with the transport speed. The measurement of the exposure power and the exposure energy is performed by using the tidal current mechanism radiation spectrometer URS-40D, which uses a wavelength between 22 〇 nm and 400 nm.

The point of the points. The light-shielding partition walls and the respective pixels were completely cured together by baking the dripped glass substrate in an oven at 230 ° C for 30 minutes. (Formation of ITO electrode) The glass substrate formed by the color filter was placed in a sputtering apparatus, and ITO (Indium Tin Oxide) having a thickness of 1 300 A was vacuum-deposited at 1 ° C and then annealed at 240 ° C. The ITO was crystallized for 90 minutes to form an ITO transparent electrode. (Formation of a spacer) A spacer is formed on the ITO transparent electrode produced as described above by the same method as the spacer formation method described in [Example 1] of JP-A-2004-240335. (Formation of liquid crystal alignment control projections) The liquid crystal alignment control projections were formed on the ITO transparent electrode formed of the spacers by using the coating liquid for a positive photosensitive resin layer described below. However, the exposure, development, and baking steps utilize the following methods. A proximity exposure machine (manufactured by Hitachi High-Tech Electronics Co., Ltd. -140-200811249) is disposed at a distance of 1 Ο Ο μ m from the surface of the photosensitive resin layer, and the reticle is passed through the HV The mercury lamp was exposed to the vicinity by using an irradiation energy of 150 mJ/cm 2 .

Thereafter, the 2.38% aqueous solution of tetramethylammonium hydroxide was continuously sprayed on the substrate at 33 ° C for 30 seconds while developing the image by a shower type developing device. In this case, by removing the unnecessary portion (exposure portion) of the photosensitive resin layer, it is possible to obtain a liquid crystal alignment control for forming a photosensitive resin layer having a desired shape on the color filter side substrate. A substrate for a liquid crystal display device in which protrusions are formed. Then, the substrate for a liquid crystal display device formed by the projection of the liquid crystal alignment device was baked at 230 ° C for 30 minutes to form a liquid crystal alignment control projection which was cured on the substrate for a liquid crystal display device. <Formulation liquid coating solution for positive photosensitive resin layer> • Positive photoresist liquid (FH-241 3F manufactured by Fujifilm Electronic Materials Co., Ltd.): 53·3 parts • Methyl ethyl ketone: 46·7 ·Megafac F-780F (manufactured by Otsuka Ink Chemicals Co., Ltd.): 0.04 parts (manufacture of liquid crystal display device) The substrate for liquid crystal display device obtained above is further provided with polyimine. Into the alignment film. Then, at the position corresponding to the outer frame of the light-shielding partition provided around the color filter group, the epoxy resin sealant is dripped, and the liquid crystal for the VA form and the counter substrate are dropped. After bonding, the bonded substrate is heat treated to harden the sealant. On both sides of the thus obtained -141 - 200811249 liquid crystal cell, a polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached. Next, a backlight of a three-wavelength cold cathode tube light source (FWL18EX-N manufactured by Toshiba LITEC Co., Ltd.) was formed, and the polarizing plate was placed on the side of the back surface of the liquid crystal cell to form a liquid crystal display device. (Example 2) The addition of 10 g of the pigment dispersant A (exemplified compound (7) of the compound represented by the formula (D1)) to the pigment solution A of Example 1 was carried out in the same manner.

A paste-like concentrated pigment liquid B (nano pigment concentration: 35 mass%) was produced. The number average particle diameter of the pigment fine particles measured in the same manner as in Example 1 was 3 8 n m, and ϊ .. Μ ν / Μ η was 1.38. The total concentration of residual alkali metal and alkaline earth metal in the concentrated pigment liquid B is 1 1 〇 P p m. In the preparation of the pigment dispersion composition A of Example 1, the pigment dispersion composition B was prepared in the same manner as in Example 1 except that the concentrated pigment liquid B was used instead of the concentrated pigment liquid A. Then, a liquid crystal display device was produced in the same manner as in Example 1 except that the component pigment liquid enthalpy of the R ink was changed to a concentrated pigment liquid Β and the R ink φ 2 shown in Table 2 was used. (Example 3) A paste was prepared in the same manner except that the polyvinylpyrrolidone was replaced with the polymer compound C-1 represented by the formula (1) in the preparation of the concentrated pigment liquid A of Example 1. Concentrated pigment liquid C (nano pigment concentration: 29% by mass). The number average particle diameter of the pigment fine particles measured in the same manner as in Example 1 was 38 nm, and the total Mv/Mn ratio was 1.38 〇, and the total concentration of the residual alkali metal and the alkaline earth metal was 1 ο 〇 P p m. Next, in the preparation of the pigment dispersion composition A of Example 1, the concentrated pigment dispersion liquid C was replaced with -142-200811249 to concentrate the pigment dispersion liquid A to prepare a pigment dispersion composition C. Then, a liquid crystal display device was produced in the same manner as in Example 1 except that the constituent concentrated pigment liquid A of the R ink 1 was changed to the concentrated pigment liquid C and the R ink 3 shown in Table 2 was used. (Example 4)

In the same manner as in Example 1 except that the addition of the washing water was not carried out in the centrifugal filtration apparatus using the centrifugal filtration apparatus, the concentrated pigment liquid D (nummy) was prepared in the form of a paste. The pigment concentration was 32% by mass). The number average particle diameter of the pigment fine particles and the Mv/Mn system were 46 nm and 1.48 as in the case of Example 1. The total concentration of residual alkali metal and alkaline earth metal was 390 ppm. Further, in the preparation of the pigment dispersion composition A of Example 1, the pigment dispersion composition D was prepared in the same manner as in Example 1 except that the concentrated pigment liquid D was used instead of the concentrated pigment liquid A. Next, a liquid crystal display device was produced in the same manner as in Example 1 except that the pigment liquid A was used to concentrate the pigment liquid A and the φ was the R ink 4 of the concentrated pigment liquid D. (Example 5) In the same manner as in Example 1, except that the pigment PR1 77 (Cromophtai Red A2B manufactured by Ciba Specialty Chemicals Co., Ltd.) was used in the same amount to replace the pigment CL Pigment Red 254, the pigment dispersion liquid E was produced in the same manner as in Example 1. Paste concentrated pigment liquid E (nano pigment concentration: 35 mass%). The number average particle diameter of the pigment fine particles measured in the same manner as in Example 1 was 44, and the Mv/Mn was 1.49. Residual alkali metal and alkali of concentrated pigment liquid E -143- 200811249 The total concentration of soil metals is 140 ppm. Further, in the preparation of the pigment dispersion composition of Example 1, the pigment dispersion composition E was prepared in the same manner as in Example 1 except that the concentrated pigment liquid was used instead of the concentrated pigment liquid A. Next, a liquid crystal display device was produced in the same manner as in Example 1 except that the R-ink 5 in which the constituent pigment concentrate liquid A of the R ink 1 was changed to the concentrated pigment liquid E was used. (Comparative Example 1)

The pigment dispersion composition liquid F of the following composition was prepared by using a bead disperser as follows. The number of the fine particles of the pigment measured in the same manner as in Example 1 was 10 nm, and the Mv/Mn was 1.50. This was concentrated under reduced pressure in the inkjet ink production to a concentration of the nano pigment of 35 % to obtain a concentrated pigment dispersion F. The total concentration of residual alkali metal and alkaline earth metal was 700 ppm. Next, a liquid crystal display device was produced in the same manner as in Example 1 except that the R-ink 6 in which the constituent pigment concentrate liquid A of the R ink 1 was changed to the concentrated pigment liquid F was used. Pigment (Pigment Red 254) 6.4 g Polyvinylpyrrolidone 1 1.5 g (manufactured by Wako Pure Chemical Industries, Ltd., K30, molecular weight 40, 〇〇〇) Polymer compound C-1 of the formula (1) 4.4 g 47.3 g of 1-methoxy-2-propyl acetate was added to the powder of the stirring pigment (Pigment Red 254) in 1-methoxy-2-propyl acetate, and the formula was obtained. The polymer compound C-1 ' of (1) is used to obtain a mixed solution. Then, this mixture was dispersed by a honing machine -144 - 200811249 M-50 (manufactured by Eiger Japan Co., Ltd.) using zirconium oxide particles having a diameter of 65.65 mm at a peripheral speed of 9 m/s for 7 hours. (Comparative Example 2) A pigment dispersion composition G having the following composition was produced as follows. Pigment (Pigment Red 254) 6.4g 6 4.0 g Sodium chloride Polymer compound c-1 of formula (1) 4.4g

1-methoxy-2-propanacetate 47_3g In 8 g of 1-methoxy-2-propyl acetate, powder of sodium chloride and pigment (pigment red 254) was fed by a two-arm type kneader. The polymer compound C-1 methacrylic acid/benzyl methacrylate copolymer of the formula (1) was kneaded at 80 ° C for 10 hours. After kneading, 500 parts by weight of a 1% hydrochloric acid aqueous solution at 80 ° C was taken out, stirred for 1 hour, and then filtered, washed, dried, and pulverized, and then mixed with 1-methoxy-2-propyl acetate was added to the pulverized product. The above pigment composition was dispersed by a honing machine M-50 (manufactured by Eiger Japan Co., Ltd.) using zirconia particles having a diameter of 65.65 mm at a peripheral speed of 9 m/s for one hour. The pigment dispersion composition G was obtained. In the same manner as in Comparative Example 1, the inkjet ink was produced under reduced pressure to a concentration of 35% of the pigment of the ink to obtain a concentrated pigment liquid G. The number average particle diameter of the pigment fine particles measured in the same manner as in Example 1 was 49 nm, and the Mv/Mn was 1.58 °. The alkali and alkaline earth metal concentrations were 9000 p p m. Next, a liquid crystal display device was produced in the same manner as in Example 1 except that the R-ink 7 in which the constituent pigment concentrate liquid A of the R ink 1 was changed to the concentrated pigment liquid G was used. -145- 200811249 Further, in the above examples and comparative examples, the following reagents were used. Pharmacy Manufacturing Source Pigment Red 254 • Pigment Green 36

Pigment Blue 1 5 : 6 Pigment Yellow 1 38 Product Name: lrgaphor Red BT-CF, Ciba Special Chemicals Co., Ltd. Trade Name: R i 〇η ο IG ree η 6 YK, Toyo Ink Manufacturing Co., Ltd. Name: Ri〇nol Blue ES, manufactured by Toyo Ink Co., Ltd., trade name: Ero 3A1 01 OFine, Sumitomo Color Co., Ltd. Pigment Yellow 1 50 Product Name: Bayplast Yellow 5GN 01, manufactured by Wako Pure Chemical Co., Ltd. Wako Pure Chemical Co., Ltd. and Wako Pure Chemical Co., Ltd. and Kogaku Pure Chemical Co., Ltd. and Wako Pure Chemical Co., Ltd. and Wako Pure Chemical Co., Ltd. Bayer (share) company 1 _ methyl-2-pyrrolidone

2-(1-methoxy)propyl acetate 1 πιο |/|hydrochloric acid aqueous solution methanol to sodium 2 8 % methanol solution 8 m ο | /1 aqueous cesium hydroxide solution [performance as inkjet ink] (measurement of comparison) The R inks 1 to R ink 7 obtained in the above examples and comparative examples were applied to a glass substrate to have a thickness of 2 pm to prepare a sample. -146-200811249 A diffuser is provided in a three-wavelength cold cathode tube light source (FWL1 8EX-N made by Toshiba LITEC Co., Ltd.) as a backlight unit, and two polarizing plates (Sanritsu Co., Ltd.) Set the test between the polarizer HLC2-2518)

For example, measure the amount of transmitted light when it is parallel to the polarization axis and perpendicular to it. Compare it with the ratio (refer to "7th Color Optics Conference in 1990, 51 2 Color Display 1CK4" size TFT-LCD color filter , Zhimu, Xiaoguan, Fuyong, Shanzhong, etc.). For the measurement of the chromaticity, a color luminance meter (B Μ-5 manufactured by TOP CON Co., Ltd.) was used. Two polarizing plates, a sample, and a color luminance meter are disposed at a position of 13 mm from the backlight, and a cylinder having a diameter of 11 mm and a length of 20 mm is disposed at a position of 40 mm to 60 mm, and the light system is transmitted through the light system. The measurement sample at the position of 65 mm was passed through a polarizing plate set at a position of 100 mm and measured by a color luminance meter set at a position of 40 mm. The measurement angle of the color luminance meter is set to 2°. The amount of light in the backlight was set to be 1 280 cd/m2 when two polarizing plates were placed in parallel Nicols in a state where no sample was set. The results of the comparative measurement of each sample are shown in Table 3. (Measurement of color spots (measurement of chromatic aberration)) The chromaticity of the end portion and the center portion of the substrate was measured using a microscopic spectrophotometer (Olympic Optical Co., Ltd.; OSP 00) at a needle aperture of 5 μΓΠ, and F1 0 was measured. The result of the light source field of view of 2 degrees is calculated and expressed by xyY値 of the xyz color system, and the difference in chromaticity (the color difference of the La#b# color system) is calculated. The smaller the color difference, the better. The degree of coloration is estimated from the difference in chromaticity at the two positions. The results are shown in Table 3 below. -147- 200811249 [Table 3] Contrast color difference (ΔΕ) Remarks R ink 1 5900 0.1 R ink 2 6000 of the invention 0.1 R ink 3 4500 of the invention 0.2 R ink 4 4800 of the invention 0.2 R ink 5 of the invention 4200 0.1 R ink 6 3200 0.4 of the invention Comparative Example R ink 7 4300 0.9 Comparative example

From the results of the above Table 3, it is shown that the R inks 7 and 6 of the comparative example are low in contrast, and the color difference (spot) of either or both is large, but the R inks 1 to 5 of the present invention show a high contrast. , the color difference (stain) is also small and excellent. [Performance Test of Color Filter] The color spots and long-term display characteristics of the color filter prepared in the production of the liquid crystal display devices produced in Examples 1 to 5 and Comparative Examples 1 and 2 were as follows. Test it. The results are shown in Table 4. (Test for uneven display): The display at the time of red display by visual observation and magnifying glass was used to evaluate the level of unevenness according to the following criteria. A: No unevenness is observed at all (very good) B: There is a slight unevenness in the edge portion of the glass substrate, but there is no problem in the display portion (good) C: There is a slight unevenness in the display portion but a practical level (Normal) D: There is unevenness in the display section (slightly bad) E : There is a strong unevenness in the display section (very bad) -148- 200811249 (Long-term display test of liquid crystal display device) 1 000 consecutive hours The liquid crystal display device produced was displayed, and the illuminance of the red light (the illuminance at the time of red display) was set to 2 in the dark room at a position of 400 mm on the screen of the liquid crystal display device. The illuminance meter was measured by UV-M1 0-S (manufactured by Oak Co., Ltd.), and the relative enthalpy before and after the test (illuminance after the test/illuminance before the test) is shown in Table 4. [Table 4] Display uneven time display characteristics Remarks Example 1 A 0.1 Inventive Example 2 A 0, 1 Inventive Example 3 A 0.2 Inventive Example 4 B 0.2 Inventive Example 5 B 0.1 Comparison of the Invention Example 1 C 0.4 Comparative Example Comparative Example 2 E 0.9 Comparative Example

As is apparent from the results of Table 4, in the case where the pigment forms the nanoparticles, the liquid crystal display devices of Comparative Examples 1 and 2 have poor performance and display unevenness, and display characteristics are deteriorated for a long period of time. On the other hand, the liquid crystal display devices of the first to fifth embodiments of the present invention are excellent in display unevenness and long-term display characteristics, and are consistent with the above-described high contrast. It is known to provide a high performance liquid crystal display device. (Example 6) The MVA liquid crystal display device of the above-described Examples 1 to 5 and Comparative Examples 1 and 2 was produced, and the liquid crystal display device was produced in the following manner using the same color filter. -149-200811249 [Production of liquid crystal display device for PVA mode] On the R pixel, G pixel, and B pixel and black matrix of the color filter substrate obtained above, ITO is formed by sputtering (Indium Tin Transparent electrode of Oxide, indium tin oxide. Next, according to Example 1 of JP-A-2006-64921, a spacer is formed on the ITO film formed as described above with respect to the upper portion of the black matrix.

Further, a glass substrate as a counter substrate is prepared, and a pattern for PVA mode is applied to the transparent electrode of the color filter substrate and the counter substrate, and an alignment film made of polyimine is further provided thereon. . Subsequently, a sealant for the ultraviolet curable resin is applied to the periphery of the pixel group surrounding the color filter, corresponding to the position of the black matrix outer frame, and the liquid crystal for PVA mode is dropped to make it and the opposite direction After the substrates are bonded together, the bonded substrates are subjected to UV irradiation, and then heat-treated to cure the sealant. A polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached to both sides of the liquid crystal cell thus obtained. Next, FR111 2H (a wafer-type LED manufactured by Stella) and a DG1112H (a wafer-type LED manufactured by Starley) as a green (G) LED are used as blue The DB1112H (wafer type LED manufactured by Stella) of the color (B) LED constitutes a backlight of the side light type, and the polarizing plate is disposed on the back side of the liquid crystal cell to be provided as a liquid crystal display device. When the evaluations of Examples 1 to 5 and Comparative Examples 1 and 2 were carried out using the display device, the same effects as those of the present invention were found. [Production of liquid crystal display device for IPS mode]

A transparent electrode of ITO (Indium Tin Oxide) is formed by sputtering on the R pixel, the G pixel, and the B-150-200811249 pixel and the black matrix of the color filter substrate obtained above. Next, according to Example 1 of JP-A-2006-64921, a spacer is formed on the ITO film formed as described above with respect to the upper portion of the black matrix. On the color filter substrate to which the spacer was attached, the polyimide was coated and rubbed to form an alignment film.

Further, a liquid crystal display element is produced by combining a driving side substrate and a liquid crystal material with respect to the color filter substrate obtained as described above. In other words, a surface of the IPS TFT substrate in which the TFT and the comb-shaped pixel electrode (conductive layer) are arranged as a driving side substrate, a surface on which the pixel electrode of the TFT substrate or the like is provided, and the color obtained as described above are obtained. The surface on the side on which the colored pixel layer of the filter substrate is formed is disposed to face each other, and has a gap due to the spacer formed as described above and is fixed. A liquid crystal material is sealed in the gap, and a liquid crystal layer having an artifact display is provided. On both sides of the liquid crystal cell thus obtained, a polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached. Next, the backlight of the cold cathode tube is placed, and the polarizing plate is placed on the back side of the liquid crystal cell to be provided as a liquid crystal display device. When the evaluations in the same manner as in the first to fifth embodiments and the comparative examples 1 and 2 were carried out using the display device, the effects of the present invention were similarly found in comparison with the comparative examples. (Comparative Example 3) [Production of CCD Device] (Production of Pigment Dispersion Liquid for CCD) A pigment dispersion liquid was prepared by using the pigment dispersion group of 151-200811249 obtained in Comparative Example 1 according to the following formulation. (1)· · · Green G, (2) · •• Blue B, (3) · · · Red R. Pigment Dispersion (1 ) · CIPG36 90 parts by mass • CIPG7 2 5 parts by mass • CIPY1 39 4 0 parts by mass • PLAAD ED1 51 20 parts by mass (made by Nanben Chemical Co., Ltd.) • Benzyl methacrylate/A 25 parts by mass of the acrylic copolymer (copolymerized molar ratio 70:30, weight average molecular weight 30,000) propylene glycol monomethyl ether acetate 625 parts by mass (2) · CIPB 1 5:6 • CIPV2 3 • PLAAD ED1 51 125 parts by mass 25 parts by mass 40 parts by mass

(Kanben Chemical Co., Ltd.) • 5% benzyl methacrylate/methacrylic acid copolymer (copolymerized molar ratio 70:30, weight average molecular weight 30,000) • Propylene glycol monomethyl ether acetate 785 Parts by mass (3)·Pigment dispersion composition F 650 parts•Dispersant C-1 6 of the present invention 40 parts • Benzyl methacrylate/methacrylic acid copolymer 25 parts by mass (copolymerized molar ratio 70:30, Weight average molecular weight 30,000) • Propylene glycol monomethyl ether acetate 3 3 5 parts by mass - 152 - 200811249 (Preparation of colored resin composition) Each of the pigment dispersion liquids obtained above is used in each of the 00 parts by mass, respectively, in a blender The composition is uniformly mixed with the following composition to adjust the colored resin composition for color filters for each color. <Composition> • 35 parts by mass of benzyl acrylate/methacrylic acid copolymer (copolymerized molar ratio = 70/30, weight average molecular weight: 30,000) 38 parts by mass, 120 parts by mass, 40 parts by mass, 4 parts by mass, of dipentaerythritol Pentaacrylate Propylene Glycol Monomethyl Ether Acetate Propionate Ethyl-3-Ethoxyacetate Halogenated Methyl Triad System Heuristics (Photopolymerization Initiator Product Name TAZ 107 Green Chemicals Co., Ltd.) (Color Filter Production of light sheet and CCD device) The following composition was mixed with a stirrer to adjust the photoresist for flattening film [composition] • 650 parts by mass of benzyl acrylate/methacrylic acid copolymer (copolymerized molar ratio = 70/30) , weight average molecular weight 30,000) • dipentaerythritol pentaacrylate 65 parts by mass • propylene glycol monomethyl ether acetate 138 parts by mass • ethyl propionate 3-ethoxylate 12 3 parts by mass • halogenated methyl three 3 parts by mass of the cultivating heuristic agent (photopolymerization inspiring product name ΤΑΖ1 07 Green Chemical Co., Ltd.) -153- 200811249 The resulting planarization photoresist liquid is uniformly applied to the photodiode 6 inches by spin coating. On the wafer. Further, spin coating was carried out under the conditions of a surface temperature of the coated film after coating at 100 ° C for 120 seconds, and the number of coating rotations was adjusted so as to have a film thickness of about 1.5 μ m while being heated by a heating plate. Subsequently, the coating film was cured by placing it in an oven at 220 ° C for 1 hour so that the surface of the formed photodiode was similarly coated on the silicon wafer.

The film is flattened. Then, in the order of the respective colors G, R, and B, the photoresist composition for the flattening film is adjusted, and 100 parts by mass of the coloring resin composition for the color filter is applied onto the planarizing film. Drying (prebaking), pattern exposure, alkali development, rinsing, hardening and drying (post-baking) to form a colored resin film, and a color filter is formed on a wafer with a photodiode. Further, the pattern exposure was performed by a 2 // m mask pattern, using an i-line stepper (trade name: FPA-3000i5+, manufactured by Canon), at 500 mJ/cm2. In addition, the alkali image development system uses a 40% by mass aqueous solution of an organic alkaline developing solution (trade name: CD-2000, Fujifilm Electronic Materials Co., Ltd.), and the mixture is incubated at room temperature for 60 seconds. The spray was spun for 20 seconds and rinsed with pure water, followed by water washing with pure water. Subsequently, the water droplets were blown off with high-temperature air, and the substrate was naturally dried to obtain a pattern, and then post-baking treatment was applied to the hot plate at a surface temperature of 200 ° C for 5 minutes. The CCD device obtained as described above is mounted on a digital camera, and the image of the KODAK standard color card-154-200811249 (color chart) with the gray scale is observed on the screen under the same light source. To the undulations of the portrait, or the red spots. When the pigment dispersion composition F is changed to G, the undulation or unevenness is further deteriorated. (Example 7)

A CCD apparatus manufactured in the same manner as in Comparative Example 3 was mounted on a digital camera, except that the pigment dispersion composition A was used instead of the pigment dispersion composition F or G used in Comparative Example 3, and when the same evaluation was performed, the undulation was less. A uniform, delicate image. Further, when the pigment dispersion compositions B to E were replaced, it was confirmed that the same undulations were obtained. As described above, by using the organic material dispersion of the present invention and the ink jet ink formed therefrom, the display characteristics of the liquid crystal display device can be improved while the color filter is highly contrasted, in particular The display unevenness is improved, and similarly, in the production of the solid-state image sensor, the organic pigment dispersion of the present invention can realize a good reproduction image with less undulation. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1-1 is a cross-sectional view schematically showing a preferred embodiment of a manufacturing apparatus used in the manufacturing method of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Figures 1-2 are schematic cross-sectional views showing another preferred embodiment of a manufacturing apparatus used in the manufacturing method of the present invention. Fig. 1-3 is a partially enlarged cross-sectional view showing a mixing chamber as an embodiment of the manufacturing apparatus of Figs. 1-2 by a partial cross section. Figures 1-4 are schematic cross-sectional views showing, by partial cross-section, enlarged portions of a mixing chamber as another embodiment of the apparatus of Figures 1-2. Fig. 2 is a cross-sectional view showing another preferred embodiment of the manufacturing apparatus for use in the manufacturing method of the present invention, 155-200811249. Figure 3 is a schematic cross-sectional view showing still another preferred embodiment of the manufacturing method of the present invention. Fig. 4-1 is a front view schematically showing an example of a dissolver agitating blade used in the production method of the present invention. Fig. 4-2 is a diagram showing a substitute of the dissolver stirring blade of Fig. 4-1.

Fig. 5 is a schematic view showing an example of a stirring portion composed of a turbine portion of the manufacturing method of the present invention and a baffle portion having a slight gap around it. Sectional view. The sixth embodiment is an explanatory view showing a configuration example of the ultrafiltration device used in the production method of the present invention. [Main component symbol description] 11 Container 11a Liquid tank (solvent) 11b Liquid level 12 Stirring blade 13 Mixing chamber 14 Supply pipe 14a Supply pipe opening 15 Rotating shaft 16 Motor 17 Housing (mixing chamber wall) 18 Hole (round hole ) -156- 200811249

1 9 a, 1 9 b agitating blade 2 1 container (outer wall of agitating tank) 21 a agitating tank 22 agitating blade 23 discharging pipe 24a, 24b supply pipe 25 rotating shaft 50 stirring device 32, 33 supply port 36 discharge port 40 sealing plate 41 , 42 agitating blade 46 external magnet 48, 49 motor 61 disk portion 62 blade 63 rotating shaft 74 f 能够 rotatable turbine portion 75 fixed baffle portion 81 container for storing the dispersion 82 circulation pump 83 ultrafiltration mode Group 84 Supplementary pure water metering flow meter 85 Water metering flow meter 86 Reverse direction cleaning pump-157-

Claims (1)

200811249 X. Patent application scope: 1. An organic pigment nanoparticle dispersion characterized by the content of alkali or alkaline earth metal in the organic pigment dispersion of the organic pigment-containing nanoparticle. Controlled from 0.001 ppm to 500 ppm. 2. The organic pigment nanoparticle dispersion according to claim 1, wherein the alkali or alkaline earth metal is contained in an amount of from 0.01 ppm to 350 ppm. 3. The organic pigment nanoparticle dispersion according to claim 1 or 2, wherein the nanoparticle dispersion of the organic pigment contains a polymer compound having a mass average molecular weight of 1,000 or more. [4] The organic pigment nanoparticle dispersion according to claim 3, wherein the polymer compound is represented by the following formula (1), and the soup is exposed to a formula (1). Wherein R1 represents a (m + n)-valent linking group, R2 represents a single bond or a divalent linking group, and A1 represents a group selected from an acidic group, a group having a basic nitrogen atom, a urea group, a monovalent organic group of a group of a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxyalkyl group, an epoxy group, an isocyanate group, and a hydroxyl group; or a monovalent organic group containing an organic dye structure which may have a substituent or a heterocyclic ring; wherein, η Α 1 series may be identical to each other ' or different, m represents a number from 1 to 8, and η represents a number from 2 to 9, The m + n system satisfies 3 to 10, and Ρ1 represents a polymer compound residue]. A method for producing an organic pigment nanoparticle dispersion according to claim 1 or 2, which comprises: a solution of an organic pigment-158 - 200811249 dissolved in a good solvent, and a good solvent as described above A step of mixing the organic pigment as a solvent of a poor solvent and precipitating the organic pigment into fine particles having a nanometer size. 6. The method for producing an organic pigment nanoparticle dispersion according to claim 5, wherein the method for producing the nanoparticle dispersion comprises the step of precipitating the nanoparticle-sized fine particles and then concentrating the dispersion. 7. The organic pigment nanoparticle dispersion according to claim 1 or 2, wherein the pigment in the pigment dispersion is a pyrrolopyrrole pigment. 8 - a colored photosensitive resin composition containing at least an organic pigment nanoparticle dispersion, a binder, a monomer or a low polymer, a photopolymerization initiator or a photopolymerization as in the scope of claim 1 Heuristic system. 9. The organic pigment nanoparticle dispersion according to claim 1 or 2, wherein the organic pigment nanoparticle dispersion is an inkjet ink. A photosensitive resin transfer material characterized in that at least a photosensitive resin layer containing the colored photosensitive resin composition of the eighth aspect of the patent application is provided on the temporary support. ^ 1 1 _ A color filter which is produced by using the colored photosensitive resin composition of claim 8 and/or the photosensitive resin transfer material of the above-mentioned patent application. 1 2 _ - A liquid crystal display device characterized by having a color filter as claimed in the patent application. 1 3 · A liquid crystal display device according to claim 2, wherein the display device is a VA mode. 1 4 _ A C C D device characterized by having a color filter as in the scope of the patent application. -159-