KR101486322B1 - Dispersing aid, aqueous dispersion of organic pigment nanoparticle using the same, agglomerates, nonaqueous dispersion, colored photosensitive resin composition obtained by the same, color filter using the same and liquid crystal display device - Google Patents

Abstract

The present invention provides a basic dispersion aid capable of improving the display characteristics of a color filter used in a liquid crystal display device and the like, and a dispersion of the organic pigment nanoparticles obtained thereby.

The present invention also provides an acidic dispersion auxiliary used in a pigment dispersion capable of improving display characteristics of a color filter such as a liquid crystal display device. Particularly, the present invention relates to an acidic dispersion aid capable of realizing high contrast of a color filter, its production efficiency and realizing good display characteristics in a liquid crystal display, an aqueous dispersion of organic pigment nanoparticles using the same, Water, a colored photosensitive resin composition obtained therefrom, a color filter, and a liquid crystal display device.

(Solution) A dispersion aid characterized by the following formula (1-1) or (1-2).

(In the formula (1-1), A represents a heterocyclic group bonded by a linking group and a nitrogen atom. X represents a divalent linking group having at least 2 to 20 carbon atoms. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. R ₁ and R ₂ may be connected to each other or may form a heterocycle further containing an oxygen atom, a nitrogen atom, and / or a sulfur atom. and m represents a natural number of 1 or 2.

(In the formula (1-2), A ¹¹ represents a heterocyclic group connected to a carbonyl group by a nitrogen atom. X ¹¹ represents a divalent alkylene, ether or polyether group having 2 to 10 carbon atoms which may have a substituent.

Dispersion preparation

Description

DISPERSING AID, AQUEOUS DISPERSION OF ORGANIC PIGMENT NANOPARTICLE USING THE SAME, AND COLOR FILTER AND LIQUID CRYSTAL DISPLAY USING THE SAME TECHNICAL FIELD The present invention relates to a dispersion aid, an aqueous dispersion, an aggregate, a non-aqueous dispersion of organic pigment nano- , AGGLOMERATES, NONAQUEOUS DISPERSION, COLORED PHOTOSENSITIVE RESIN COMPOSITION OBTAINED BY THE SAME, COLOR FILTER USING THE SAME AND LIQUID CRYSTAL DISPLAY DEVICE}

The present invention relates to a dispersion aid, particularly a basic dispersion aid and an acidic dispersion aid, an aqueous dispersion, an aggregate, a non-aqueous dispersion of organic pigment nanoparticles using the same, a colored photosensitive resin composition obtained thereby, ≪ / RTI >

As nanotechnologies, for example, researches for energizing various kinds of particles by reducing the particle size to a range of 10 to 100 nm have been energetically advanced. By the nanometer size, it is intended to bring out new characteristics that could not be expected in the past due to the action effect that is first manifested. On the other hand, in the field of organic pigments, for example, research and development have been conducted in paints, printing inks, electrophotographic toners, inkjet inks, color filters and the like. Particularly, for color filters and inkjet inks, efforts are being made for high performance using fine chemical technology, and the results are expected.

As for the color filter, thin layer is required. As a result, it is possible to realize high performance including high-definition of image-related devices such as a liquid crystal display device, a digital camera, and a CCD sensor. In recent years, organic pigments have been used instead of dyes in consideration of weatherability and heat resistance as color materials of color filters. The thickness of the color filter using the pigment depends largely on the particle diameter of the pigment. That is, the development of good pigment microparticles holds the key to improving the performance of image-related devices. Specifically, it is a nanometer size level, and stable pigment particles are required by monodisperse.

Here, as for the method of refining the organic particles, conventionally, it has been common practice to use a dispersing machine such as a roll mill, a ball mill, and an attritor. Recently, a vapor-phase method, a liquid phase method, a laser ablation method, and the like have been studied. Among them, the liquid phase method is attracting attention as a process for producing organic particles excellent in simplicity and productivity. Specifically, a method of precipitating nanoparticles by mixing a pigment solution and a poor solvent (see Japanese Patent Application Laid-Open No. 2004-91560), and a method of adding a predetermined polymer compound at this time (Japanese Patent Application Laid- 43776, International Publication No. WO 2006/121016 pamphlet, and Japanese Patent Application Laid-Open No. 2007-119586).

The object of the present invention is to provide a dispersion aid (for example, a basic dispersion aid and an acidic dispersion aid) used in a pigment dispersion which can improve the display characteristics of a color filter such as a liquid crystal display. Particularly, it is an object of the present invention to provide a dispersion aid capable of realizing high contrast of a color filter, its production efficiency and realizing good display characteristics in a liquid crystal display device, an aqueous dispersion, an aggregate and a nonaqueous dispersion of organic pigment nanoparticles , A colored photosensitive resin composition obtained therefrom, a color filter using the same, and a liquid crystal display device.

According to the present invention, the following means are provided:

(1) A dispersion aid characterized by the following formula (1-1) or (1-2).

(In the formula (1-1), A represents a heterocyclic group bonded by a linking group and a nitrogen atom. X represents a divalent linking group having at least 2 to 20 carbon atoms. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. R ₁ and R ₂ may be connected to each other or may form a heterocycle further containing an oxygen atom, a nitrogen atom, and / or a sulfur atom. and m represents a natural number of 1 or 2.

(In the formula (1-2), A ¹¹ represents a heterocyclic group connected to a carbonyl group by a nitrogen atom. X ¹¹ represents a divalent alkylene, ether or polyether group having 2 to 10 carbon atoms which may have a substituent.

(2) The dispersion auxiliary according to (1), which is a basic dispersion auxiliary represented by the general formula (1-1).

(3) The dispersion auxiliary according to (2), wherein the basic dispersion auxiliary is represented by the following general formula (2-1).

Y represents an oxygen atom or a sulfur atom, l represents an integer of 0 or 1, n represents a natural number of 1 to 19. R represents an oxygen atom or a sulfur atom, R represents a heterocyclic group bonded by a linking group and a nitrogen atom, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, R ₁ and R ₂ may be connected to each other, or may be a heterocyclic ring containing an oxygen atom, a nitrogen atom and / M represents a natural number of 1 or 2.)

(4) The dispersion aid according to (2) or (3), characterized in that in the non-aqueous dispersion obtained by switching the medium from the aqueous dispersion, dispersibility is imparted to the organic pigment nanoparticles together with the non-aqueous dispersing agent.

(5) An aqueous dispersion containing organic pigment nanoparticles, water, and a basic dispersion aid as described in any one of (2) to (4), wherein the organic pigment nanoparticles are obtained by dissolving an organic pigment Wherein the organic pigment is precipitated as fine particles of nanometer size in the presence of the basic dispersion aid in the mixed solution by mixing a solution of the organic pigment with the poor solvent for the organic pigment by mixing with the good solvent, Aqueous dispersion.

(6) The aqueous dispersion of the organic pigment nanoparticles according to (5), wherein the average particle size of the primary particles of the organic pigment nanoparticles is 10 to 500 nm.

(7) An agglomerate of organic pigment nanoparticles in which the pH of the aqueous dispersion described in (5) or (6) is changed so that the organic pigment nanoparticles can be redispersed.

(8) A non-aqueous dispersion of organic pigment nanoparticles obtained by releasing aggregation of aggregates described in (7) and redispersed in a non-aqueous medium.

(9) A non-aqueous dispersion of the organic pigment nanoparticles according to (8), which contains at least one polymer compound having an acidic group and a number average molecular weight of 1000 or more.

(10) A colored photosensitive resin composition comprising at least the non-aqueous dispersion according to (8) or (9), a binder, a monomer or oligomer, and a photopolymerization initiator or a photopolymerization initiator system.

(11) A color filter produced by using the colored photosensitive resin composition according to (10).

(12) A liquid crystal display device comprising a color filter according to (11).

(13) The dispersion auxiliary according to (1), which is an acidic dispersion auxiliary represented by the general formula (1-2).

(14) The dispersion aid according to (13), wherein the dispersibility is imparted to the organic pigment nanoparticles together with the non-aqueous dispersing agent in the non-aqueous dispersion obtained by switching the medium from the aqueous dispersion.

(15) An aqueous dispersion containing organic pigment nanoparticles, water and an acidic dispersion aid as described in (13), wherein the organic pigment nanoparticles are prepared by dissolving an organic pigment in a good solvent and an organic pigment solution Wherein the organic pigment is precipitated as fine particles having a size of nanometer size in the presence of the acid dispersion auxiliary agent in the mixed solution by mixing the poor solvent for the organic pigment.

(16) The aqueous dispersion of the organic pigment nanoparticles according to (15), wherein the primary particles of the organic pigment nanoparticles have an average particle diameter of 10 to 500 nm.

(17) An aggregate of organic pigment nanoparticles in which the pH of the aqueous dispersion described in (15) or (16) is changed so that the organic pigment nanoparticles can be redispersed.

(18) A non-aqueous dispersion of organic pigment nanoparticles obtained by releasing aggregation of aggregates described in (17) and redispersed in a non-aqueous medium.

(19) A non-aqueous dispersion of the organic pigment particle according to (18), which contains at least one polymer compound having a number average molecular weight of 1,000 or more.

(20) A colored photosensitive resin composition characterized by containing at least a non-aqueous dispersion according to (18) or (19), a binder, a monomer or oligomer, and a photopolymerization initiator or photopolymerization initiator system.

(21) A color filter produced by using the colored photosensitive resin composition according to (20).

(22) A liquid crystal display device comprising a color filter according to (21).

The aqueous dispersion described in the above items (5) to (6), the aggregate described in the above (7), and the aqueous dispersion described in the above items (8) to (9) The colored photosensitive resin composition described in the above item (10), the color filter described in the above (11), and the liquid crystal display device described in the above (12) are also referred to as the first embodiment of the present invention.

The aqueous dispersion described in the above items (1), (13) to (14), the aqueous dispersion described in the above (15) to (16), the aggregate described in the above (17) (20), the color filter described in (21), and the liquid crystal display device described in (22) above, as well as the non-aqueous dispersion according to the present invention 2 embodiment.

Unless specifically stated otherwise, the present invention includes both the first and second embodiments.

(Effects of the Invention)

The dispersion auxiliary (for example, the basic dispersion auxiliary and the acidic dispersion auxiliary) of the present invention can provide a high-contrast color filter produced by using the dispersion prepared by using the dispersion and improve the production efficiency thereof, And excellent display characteristics can be realized. Further, the dispersion aid of the present invention enables efficient production of a non-aqueous dispersion having stable dispersibility by maintaining a good dispersion state of the organic pigment microparticles even when the medium is switched from an aqueous dispersion to a non-aqueous dispersion. Further, the color filter produced using this excellent dispersion exhibits the above-mentioned high performance, and exhibits an excellent effect of exhibiting high image display performance because of its excellent sharpness of black when mounted on a liquid crystal display and displaying images.

Hereinafter, the present invention will be described in detail.

In the present invention, the organic pigment is not limited in color but may be, for example, perylene, perynone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimadazolone, disazo condensation, Azo dyes, azo dyes, azo dyes, azo dyes, azo dyes, azo dyes, azo dyes, azo dyes, azodicarboxylic acids, azodicarboxylic acids, And mixtures thereof.

More specifically, for example, C.I. Pigment Red 190 (C.I. No. 71140), C.I. A pigment such as CI Pigment Orange 43 (CI No. 71105) or CI Pigment Red 194 (CI No. 71100) such as Pigment Red 224 (CI No. 71127), CI Pigment Violet 29 (CI No. 71129) (CI No. 73900), CI Pigment Violet 42, CI Pigment Red 122 (CI No. 73915), CI Pigment Red 192, CI Pigment Red 202 (CI No. 73907) CI Pigment Red 206 (CI No. 73900/73920), CI Pigment Orange 48 (CI No. 73900, 73906), or CI Pigment Red 209 (CI No. 73905) No. 73900/73920) or quinacridone quinone compound pigments such as CI Pigment Orange 49 (CI No. 73900/73920), anthraquinone compound pigments such as CI Pigment Yellow 147 (CI No. 60645), CI Pigment Red 168 CI No. 59300) and the like CI Pigment Yellow 181 (CI No. 11777), CI Pigment Orange (CI Pigment Yellow 30), CI Pigment Yellow 30 CI Pigment Yellow 93 (CI No. 20710), CI Pigment Yellow 94 (CI No. 20038), CI Pigment (CI No. 11735) or CI Pigment Red 185 CI Pigment Orange 13 (CI No. 21110), CI Pigment Yellow 163 (CI No. 20035), CI Pigment Orange 34 (CI No. 21115), CI Pigment Orange 13 ), CI Pigment Orange 31 (CI No. 20050), CI Pigment Red 144 (CI No. 20735), CI Pigment Red 166 (CI No. 20730), CI Pigment Red 220 (CI No. 20055), CI Pigment Red 221 (CI No. 20065), CI Pigment Red 242 (CI No. 20067), CI Pig Disazo condensed compound pigments such as CI Pigment Yellow 13 (CI No. 21100), CI Pigment Yellow 83 (CI No. 21108) or CI Pigment Yellow 23 CI Pigment Yellow 188 (CI No. 21094), CI Pigment Red 187 (CI No. 12486), CI Pigment Red 170 (CI No. 12475), CI Pigment Yellow 74 (CI No. 11714) CI Pigment Yellow 55 (CI No. 48545), CI Pigment Red 48 (CI No. 15865), CI Pigment Red 53 (CI No. 15585), CI Pigment Orange 64 (CI No. 12760), or CI Pigment Red 247 (CI No.15915), indanthrone compound pigments such as CI Pigment Blue 60 (CI No. 69800), CI Pigment Green 7 (CI No. 74260), CI Pigment Green 36 (CI No. 74265) Pigment Green 37 (CI No. 74255), Pigment Blue 16 (CI CI Pigment Blue 56 (CI No. 42800) or CI Pigment Blue 61 (CI No. 42765: CI Pigment Blue 65) (CI No. 74160: 2) or 15 (CI No. 74160) (CI No. 51319) or CI Pigment Violet 37 (CI No. 51345), CI Pigment Red 177 (CI No. 65300), and the like can be used as the pigment of the triarylcarbonium compound such as CI Pigment Violet 23 CI Pigment Red 264, CI Pigment Red 272 (CI No. 561150), CI Pigment Orange (CI Pigment Red 254), CI Pigment Red 255 71 or CI Pigment Orange 73, a thioindigo compound pigment such as CI Pigment Red 88 (CI No. 73312), CI Pigment Yellow 139 (CI No. 56298), CI Pigment Orange 66 CI No. 48210) , Isoindolinone compound pigments such as CI Pigment Yellow 109 (CI No. 56284) or CI Pigment Orange 61 (CI No. 11295), CI Pigment Orange 40 (CI No. 59700) or CI Pigment Orange (CI No. 59710) or an isobiorantron compound pigment such as CI Pigment Violet 31 (60010). Among them, quinacridone compound pigments, diketopyrrolopyrrole compound pigments, dioxazine compound pigments, phthalocyanine compound pigments and azo compound pigments are preferable, and diketopyrrolopyrrole compound pigments, phthalocyanine compound pigments and dioxazine compound pigments are more preferable Do.

In the present invention, two or more organic pigments or solid solutions of organic pigments may be used in combination. Further, it may be combined with an organic coloring matter, a polymer organic material or the like.

The dispersion aid of the present invention is prepared by mixing an organic pigment solution obtained by dissolving an organic pigment in a good solvent (first solvent) and a solvent having compatibility with the good solvent and a poor solvent (second solvent) with respect to the organic pigment It can be used when precipitating nanoparticles of organic pigments. The combination of the good solvent and the poor solvent preferably has a sufficient difference in the solubility of the organic pigment, and it is necessary to select a suitable one in accordance with the organic pigment, but any combination may be selected as long as the combination makes it possible.

Both solvents can dissolve the organic pigment to be used and are not particularly limited as long as they are compatible with or can be uniformly mixed with the poor solvent. The solubility of the organic pigment in a good solvent is preferably 0.2 mass% or more, and more preferably 0.5 mass% or more. Although there is no particular upper limit on the solubility of the organic pigment in a good solvent, it is practically 50% by mass or less in consideration of the conventionally used organic pigment. The solubility may be the solubility in the presence of an acid or an alkali. The compatibility or homogeneous mixing of the good solvent with the poor solvent is preferably 30% by mass or more, more preferably 50% by mass or more, of the good solvent in the poor solvent. There is no particular upper limit on the amount of dissolution of the good solvent in the poor solvent, but it is practically practically mixed with each other at an arbitrary ratio.

Examples of the positive solvent include aqueous solvents (e.g., water or hydrochloric acid, sodium hydroxide aqueous solution), alcohol compound solvents, amide compound solvents, ketone compound solvents, ether compound solvents, aromatic compound solvents, disulfide carbon solvents, , A nitrile compound solvent, a sulfoxide compound solvent, a halogen compound solvent, an ester compound solvent, an ionic liquid, and a mixed solvent thereof. Examples of the solvent include an aqueous solvent, an alcohol compound solvent, a ketone compound solvent, The solvent is preferably an aqueous solvent, an alcohol compound solvent, an ester compound solvent, a sulfoxide compound solvent or an amide compound solvent, and an aqueous solvent, a sulfoxide compound solvent or an amide compound A solvent is more preferable, and a sulfoxide compound Particularly preferred are water solvents or amide compound solvents.

Examples of the sulfoxide compound solvent include dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, sulfolane, and the like. Examples of the amide compound solvent include N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, , ε-caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide and hexamethylphosphoric triamide.

The concentration of the organic pigment solution obtained by dissolving the organic pigment in the good solvent is preferably in the range of about 1/100 of the saturated concentration of the organic pigment with respect to the good solvent in the dissolution condition.

The conditions for preparing the organic pigment solution are not particularly limited, and the range of the sub-critical and supercritical conditions can be selected from the atmospheric pressure. The temperature at normal pressure is preferably -10 to 150 占 폚, more preferably -5 to 130 占 폚, particularly preferably 0 to 100 占 폚.

It is not necessary to combine the same as a good solvent and a poor solvent, and the solubility in both solvents may be sufficiently higher than the solubility in a poor solvent, depending on the relationship with each organic pigment employed. For example, the solubility difference is preferably 0.2 mass% or more, and more preferably 0.5 mass% or more. There is no particular upper limit on the difference in solubility in the good solvent and the poor solvent, but it is practically 50% by mass or less in consideration of the commonly used organic pigment.

When the organic pigment is uniformly dissolved in a good solvent, it may be dissolved in an acidic or alkaline solution. Generally, in the case of a pigment having a group capable of dissociating into alkaline in the molecule, acidity is used when there is no alkaline dissociative group and the nitrogen atom which is likely to be added with protons is contained in the molecule. For example, quinacridone, diketopyrrolopyrrole, and disazo condensed compound pigments are alkaline and phthalocyanine compound pigments are acidic.

In the case of dissolving in an alkaline state, it is preferable to use inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide or organic bases such as trialkylamine, diazabicyclo-undecene (DBU) and metal alkoxide , And it is more preferable to use an inorganic base among them.

The amount of the base to be used is not particularly limited, but in the case of an inorganic base, it is preferably 1.0 to 30 molar equivalents, more preferably 1.0 to 25 molar equivalents, and particularly preferably 1.0 to 20 molar equivalents with respect to the organic pigment. In the case of an organic base, the amount is preferably 1.0 to 100 molar equivalents, more preferably 5.0 to 100 molar equivalents, and particularly preferably 20 to 100 molar equivalents with respect to the organic pigment.

In the case of dissolving in an acidic state, it is preferable to use an inorganic acid such as sulfuric acid, hydrochloric acid or phosphoric acid, or an organic acid such as acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid or trifluoromethanesulfonic acid, , And sulfuric acid is more preferably used.

The amount of the acid to be used is not particularly limited, but it is often used in an excess amount as compared with the base. The amount is preferably 3 to 500 molar equivalents, more preferably 10 to 500 molar equivalents, and particularly preferably 30 to 200 molar equivalents with respect to the organic pigment, regardless of the case of the inorganic acid and the organic acid.

When an alkali or an acid is mixed with an organic solvent and used as a good solvent for an organic pigment, a solvent having a high solubility in an alkali or an acid such as water or a lower alcohol may be added to the organic solvent in order to completely dissolve the alkali or acid have. The amount of water or lower alcohol is preferably 50 mass% or less, more preferably 30 mass% or less, based on the total amount of the organic pigment solution. Specifically, water, methanol, ethanol, n-propanol, isopropanol, butyl alcohol and the like can be used.

The viscosity of the organic pigment solution is preferably 0.5 to 80.0 mPa · s, more preferably 1.0 to 50.0 mPa · s.

The poor solvent is not particularly limited, but the solubility of the organic pigment is preferably 0.02 mass% or less, and more preferably 0.01 mass% or less. There is no particular limitation on the solubility of the organic pigment in a poor solvent, but 0.000001 mass% or more is practically considered in view of the organic pigments usually used. The solubility may be the solubility in the presence of an acid or an alkali. The preferred range of compatibility or homogeneous mixing of the poor solvent and the good solvent is as described above.

Examples of the poor solvent include aqueous solvents (e.g., water or hydrochloric acid, aqueous sodium hydroxide solution), alcohol compound solvents, ketone compound solvents, ether compound solvents, aromatic compound solvents, carbon disulfide solvents, aliphatic compound solvents, An alcohol compound solvent, a ketone compound solvent, an ether compound solvent, an ester compound solvent, or a mixture thereof are preferable, and the solvent is preferably an alcohol solvent, An aqueous solvent, an alcohol compound solvent or an ester compound solvent is more preferable.

Examples of the alcohol compound solvent include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-methoxy-2-propanol and the like. Examples of the ketone compound solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the ether compound solvent include dimethyl ether, diethyl ether, tetrahydrofuran and the like. Examples of the aromatic compound solvent include benzene, toluene, and the like. Examples of the aliphatic compound solvent include hexane and the like. Examples of the nitrile compound solvent include acetonitrile and the like. Examples of the halogen compound solvent include dichloromethane, trichlorethylene, and the like. Examples of the ester compound solvent include ethyl acetate, ethyl lactate, and 2- (1-methoxy) propyl acetate. Examples of the ionic liquid include salts of 1-butyl-3-methylimidazolium and PF ₆ ^- .

Whether one of the solvents is a good solvent or a poor solvent depends on the type of the organic pigment to be used. In the present invention, the positive and negative solvents do not become the same compound for any organic pigment.

There is no particular limitation on the condition of the poor solvent at the time of precipitation of the organic particles, and the range from normal pressure to subcritical and supercritical conditions can be selected. The temperature at normal pressure is preferably -30 to 100 占 폚, more preferably -10 to 60 占 폚, and particularly preferably 0 to 30 占 폚.

When the organic pigment solution and the poor solvent are mixed, any of them may be added and mixed. However, it is preferable to mix the organic pigment solution into a poor solvent (jet flow), and it is preferable that the poor solvent is in a stirred state . The stirring speed is preferably 100 to 10000 rpm, more preferably 150 to 8000 rpm, and particularly preferably 200 to 6000 rpm. A pump or the like may be used for the addition. In this case, the solution may be added in the liquid or out of the liquid, but is more preferably added in the liquid. In addition, it is preferable to continuously supply the liquid in the liquid by the pump through the supply pipe. The inner diameter of the supply pipe is preferably 0.1 to 200 mm, and more preferably 0.2 to 100 mm. The rate of supplying the liquid from the supply pipe is preferably 1 to 10,000 ml / min, more preferably 5 to 5000 ml / min.

The particle diameter of the organic nanoparticles to be precipitated can be controlled by controlling the Reynolds number in the mixing of the organic pigment solution and the poor solvent. Here, the Reynolds number is a dimensionless number representing the state of the fluid flow and is expressed by the following equation.

Re = ρUL / μ ... Equation (1)

In the formula (1), Re represents the Reynolds number, ρ represents the density of the organic pigment solution [kg / m 3], U represents the relative velocity [m / s] of the organic pigment solution and the poor solvent, L represents the equivalent diameter [m] of the flow path or feed port at the portion where the organic pigment solution and the poor solvent meet, and μ represents the viscosity coefficient [Pa · s] of the organic pigment solution.

The equivalent diameter L refers to the diameter of the equivalent circular tube when an equivalent circular tube is assumed for the diameter of the opening or the flow path of the pipe of arbitrary sectional shape. The equivalent diameter L is expressed by the following equation (2), where A is the end surface area of the pipe, and W is the wet circumference length (circumferential length) of the pipe or p is the circumference of the flow path.

L = 4A / p ... Equation (2)

It is preferable to form particles by injecting the organic pigment solution into the poor solvent through the pipe, and when the pipe is used as the pipe, the equivalent diameter agrees with the diameter of the pipe. For example, the equivalent diameter can be adjusted by varying the opening diameter of the liquid supply port. The value of the equivalent diameter L is not particularly limited, but is, for example, the same as the preferable inner diameter of the above-described supply port.

The relative velocity U when the solvent solution of the organic pigment meets the poor solvent is defined as the relative velocity in the vertical direction with respect to the plane where the two meet. That is, for example, when the positive solvent solution of the organic pigment is injected into the stationary poor solvent and mixed, the rate of injection from the supply port becomes equal to the relative velocity U. The value of the relative speed U is not particularly limited, but is preferably 0.5 to 100 m / s, more preferably 1.0 to 50 m / s, for example.

The density rho of the organic pigment solution is a value determined according to the kind of the selected material, but it is practically 0.8 to 2.0 kg / m < 3 > in the range of the material preferably used in the manufacturing method of the present invention. The viscosity coefficient μ of the organic pigment solution is a value determined by the material to be used, the environmental temperature, and the like, but the preferable range is a preferable viscosity and agreement with the above-mentioned organic pigment solution.

The smaller the Reynolds number (Re) is, the more easily the laminar flow is formed, and the larger the Reynolds number (Re) is, the more easily the turbulent flow is formed. For example, the Reynolds number can be controlled by adjusting the particle diameter of the organic nanoparticles to 60 or more, preferably 100 or more, and more preferably 150 or more. There is no particular upper limit on the number of Reynolds numbers, but it is preferable that the Reynolds number can be obtained by controlling good organic nanoparticles by controlling them in the range of, for example, 100000 or less. Or the Reynolds number may be increased so that the average particle diameter of the obtained nanoparticles becomes 60 nm or less. At this time, within the above range, it is possible to obtain organic nanoparticles having smaller particle diameters by controlling the Reynolds number.

The volume ratio of the organic pigment solution to the poor solvent (the ratio of the good solvent to the poor solvent in the precipitated liquid of the organic fine particles) is preferably 1/50 to 2/3, more preferably 1/40 to 1/2, ~ 3/8 is particularly preferred.

When the organic fine particles are precipitated, the concentration of the nanoparticles in the dispersion is not particularly limited. However, the organic particles are preferably in the range of 10 to 40,000 mg, more preferably 20 to 30,000 mg, Is in the range of 50 to 25000 mg.

The preparation scale at the time of producing the pigment nanoparticles is not particularly limited, but it is preferable that the blending amount of the poor solvent is 10-2000 L, more preferably 50-1000 L.

As for the particle size of the organic particles, there is a method of expressing the average size of the group by numerical measurement by the measurement method. However, there is a method which is well used. The mode diameter representing the maximum value of the distribution, the median diameter corresponding to the median value of the integral distribution curve, (Number average, length average, area average, mass average, volume average and the like). In the present invention, unless otherwise stated, the average particle diameter refers to the number average diameter. The average particle diameter of the pigment nanoparticles (primary particles) is preferably 10 to 500 nm, more preferably 10 to 200 nm, further preferably 10 to 100 nm, particularly preferably 20 to 80 nm . The particles formed by the production method of the present invention may be either crystalline particles or amorphous particles or a mixture thereof.

Unless otherwise specified in the present invention, the ratio (Mv / Mn) of the volume average particle diameter (Mv) to the number average particle diameter (Mn) is used as an index showing the monodispersibility of the particles. The monodispersibility (Mv / Mn) of the organic pigment nanoparticles (primary particles) is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, and particularly preferably 1.0 to 1.5.

Examples of the method for measuring the particle size of the organic particles include a microscopic method, a mass method, a light scattering method, a light shielding method, an electric resistance method, an acoustic method and a dynamic light scattering method. Microscopic method and dynamic light scattering method are particularly preferable. Examples of the microscope used in the microscopic method include a scanning electron microscope and a transmission electron microscope. As a particle measuring apparatus by the dynamic light scattering method, for example, a nano-track UPA-EX 150 manufactured by Nikkiso Co., Ltd., and a dynamic light scattering photometer DLS-7000 series manufactured by Otsuka Denki Co., Ltd. (all trade names).

In the present invention, in preparing the dispersion by precipitating the organic pigment nanoparticles, a dispersant may be contained in at least one of the pigment solution and the poor solvent. At this time, it is preferable that at least the dispersing agent (in the present invention, the dispersing agent to be added to the aqueous dispersion is specifically referred to as an aqueous dispersing agent and sometimes referred to as a non-aqueous dispersing agent to be described later) is preferably contained in at least the pigment solution.

The polymer dispersant used as the aqueous dispersant preferably has a mass average molecular weight of 1,000 to 500,000, more preferably 10,000 to 500,000, and particularly preferably 10,000 to 100,000.

Specific examples include polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, polyvinyl alcohol-partial formaldehyde, polyvinyl alcohol- Poly (vinylpyridine) salts, polyamides, polyallylamine salts, polyvinyl pyrrolidone-vinyl acetate copolymers, polyethylene oxide / propylene oxide block copolymers, polyacrylic acid salts, Condensed naphthalenesulfonic acid salts, cellulose derivatives, starch derivatives and the like. In addition, natural polymers such as alginate, gelatin, albumin, casein, gum arabic, tragacanth gum, and lignin sulfonate may be used. Among them, polyvinyl pyrrolidone is preferable. These polymer compounds may be used singly or in combination of two or more, and a low molecular weight dispersant may be used in combination. The dispersing agent used for dispersing the pigment is described in detail in "Pigment dispersion stabilization and surface treatment technology and evaluation" (issued by the Chemical Information Society, December 2001), pages 29 to 46 in detail.

Examples of the anionic dispersant (anionic surfactant) include N-acyl-N-alkyltaurine salts, fatty acid salts, alkylsulfuric acid ester salts, alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, dialkylsulfosuccinic acid salts, alkylphosphoric acid ester salts, Sulfonic acid formalin condensate, and polyoxyethylene alkyl sulfate ester salt. Of these, N-acyl-N-alkyltaurine salts are preferred. As the N-acyl-N-alkyltaurine salt, it is preferable to be described in the specification of Japanese Patent Application Laid-Open No. 3-273067. These anionic dispersants may be used alone or in combination of two or more.

Cationic dispersants (cationic surfactants) include quaternary ammonium salts, alkoxylated polyamines, aliphatic amine polyglycol ethers, aliphatic amines, diamines and polyamines derived from aliphatic amines and aliphatic alcohols, imidazolines derived from fatty acids and their cations Salt of the sex material. These cationic dispersants may be used alone or in combination of two or more.

The cationic dispersant is a dispersant having in its molecule both an anionic group portion in the molecule of the anionic dispersant and a cationic group portion in the molecule of the cationic dispersant.

Examples of nonionic dispersants (nonionic surfactants) include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamine, glycerin fatty acid Esters and the like. Of these, polyoxyethylene alkyl aryl ethers are preferred. These nonionic dispersants may be used alone or in combination of two or more.

The content of the dispersant is preferably in the range of 0.1 to 1000 parts by mass, more preferably in the range of 1 to 500 parts by mass, more preferably in the range of 1 to 500 parts by mass with respect to 100 parts by mass of the pigment in order to further improve the uniform dispersibility and storage stability of the pigment nanoparticles And preferably from 10 to 300 parts by mass. If the amount is less than 0.1 part by mass, the dispersion stability of the pigment nanoparticles may not be improved, and if it is more than 1000 parts by mass, the viscosity may increase. The dispersant may be used alone or in combination of a plurality of dispersants.

&Quot; Dispersion aid " means both of a basic dispersion aid and an acidic dispersion aid, unless otherwise specified in the present invention. The dispersion aid of the present invention is preferably a basic dispersion aid or an acidic dispersion aid, and the basic dispersion aid is more preferably a basic dispersion aid represented by the general formula (1-1) or (2-1) It is more preferable that the auxiliary agent is an acidic dispersion auxiliary agent represented by the general formula (1-2).

Hereinafter, the basic dispersion auxiliary of the first embodiment of the present invention will be described in detail. The basic dispersion aid of the first embodiment of the present invention is used for the purpose of controlling the particle diameter at the nanoscale level of pigment particles, imparting pH responsiveness and basic treatment (improving redispersibility) in preparing a dispersion by precipitating organic pigment nanoparticles It is preferable that at least one of the pigment solution and the poor solvent contains the following basic dispersion auxiliary, and it is more preferable to contain the pigment in the pigment solution. It is also preferable to use them in combination with the above-mentioned dispersant.

The basic dispersion auxiliary of the first embodiment of the present invention is represented by the following general formula (1-1).

In the formula, A represents a heterocyclic group bonded by a linking group and a nitrogen atom. X represents a divalent linking group having at least 2 to 20 carbon atoms. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. R ₁ and R ₂ may be connected to each other or may form a heterocycle further containing an oxygen atom, a nitrogen atom and / or a sulfur atom. and m represents a natural number of 1 or 2.

Examples of A include, for example, pyrazole, imidazole, indole, carbazole, 5-aminobenzimidazole, 3-aminoanthraquinone, acridone, 5-aminobenzimidazolone, 5-aminouracil, And preferably 5-aminobenzimidazole, 3-aminoanthraquinone, acridone, 5-aminobenzimidazolone and 5-aminouracil, and more preferably 5-aminobenzimidazole , 3-aminoanthraquinone, 5-aminobenzimidazolone, and 5-aminouracil.

X may be, for example, a linking group containing alkylene, polyethylene oxide or polypropylene oxide, preferably alkylene.

Examples of the alkyl group in R ₁ or R ₂ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, Methyl group, ethyl group, propyl group, isopropyl group and n-butyl group are preferable, and methyl group, ethyl group and propyl group are more preferable.

As the aralkyl group, a benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-butoxybenzyl group, 4-methoxybenzylmethoxyphenyl group and 4-hydroxybenzyl group are preferable. Particularly preferred are benzyl, 4-chlorobenzyl, 4-methylbenzyl and 4-butoxybenzyl.

The aryl group is preferably a phenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, a 4-butoxyphenyl group, a 4-methoxyphenyl group or a 4-hydroxyphenyl group. Particularly preferred are phenyl, 4-chlorophenyl, 4-methylphenyl and 4-butoxyphenyl.

Examples of the heterocyclic group in which R ₁ and R ₂ are connected to each other include imidazole and morpholine.

m represents a natural number of 1 or 2, preferably 1 in the aspect of particle shape control, and 2 in view of pH control and dispersibility improvement.

The basic dispersion auxiliary is preferably represented by the following general formula (2-1).

In the formula, A represents a heterocyclic group bonded by a linking group and a nitrogen atom. Y represents an oxygen atom or a sulfur atom. and l represents an integer of 0 or 1. n represents a natural number of 1 to 19. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. R ₁ and R ₂ may be connected to each other or may form a heterocycle further containing an oxygen atom, a nitrogen atom, and / or a sulfur atom. and m represents a natural number of 1 or 2.

In the formula, preferred ranges of A and m are the same as in the general formula (1).

The group formed by Y is preferably a carbonyl group or a thiocarbonyl group, and more preferably a carbonyl group.

l represents an integer of 0 or 1, but is appropriately selected depending on the structure of the heterocyclic group of A for synthetic reasons.

n is preferably 4 to 19, more preferably 6 to 17, and particularly preferably 8 to 15.

Hereinafter, specific compounds represented by the general formula (1-1) or (2-1) are shown, but the present invention is not limited thereto.

The amount of the basic dispersion aid to be added to the aqueous dispersion is preferably 0.1 parts by mass to 1000 parts by mass, more preferably 5 parts by mass to 500 parts by mass, and particularly preferably 10 parts by mass to 300 parts by mass, relative to 100 parts by mass of the pigment . If the addition amount is too small, flocculation for isolation to be described later may be insufficient, and if it is too much, excessive flocculation may occur and redispersibility, which will be described later, may become difficult.

In the first embodiment of the present invention, the organic pigment nanoparticles can be aggregated to facilitate isolation by neutralizing the aqueous dispersion of the organic pigment nanoparticles described above.

When the two solvents are acidic, the aqueous dispersion of the organic pigment nanoparticles is acidic, and when the two solvents are basic, the aqueous dispersion is also basic. The basic dispersion aid in the first embodiment of the present invention is most effective when the aqueous dispersion is acidic.

At this time, although the basic dispersion auxiliary covers the periphery of the organic pigment nanoparticles in the state of being protonated, as the base to be added, it is necessary to neutralize the proton to generate a basic dispersion auxiliary around the organic pigment nanoparticles. Therefore, it is necessary to appropriately select the basicity and amount of addition, which neutralizes the protonated state of the basic dispersion aid.

The base to be added is an inorganic base such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide or barium hydroxide or an organic base such as trialkylamine, diazabicyclo-undecene (DBU) or metal alkoxide, Is preferably an inorganic base. In the case of neutralization by these, it is preferable to neutralize the system to a pH of 7 or more, more preferably to a pH of 9 or more.

In the first embodiment of the present invention, the basic dispersion auxiliary having a basic group as described above under acidic conditions is protonated and positively charged, whereby the particles repel each other and tend to disperse. The positive charge disappears and the repulsive force between the particles disappears, resulting in agglomeration.

Further, in the basic dispersion auxiliary in the first embodiment of the present invention, since it has a basic group, it strongly interacts with a non-aqueous dispersing agent having an acidic group described later, and it is possible to improve dispersibility and improve contrast. The basic dispersion aid covers the periphery of the pigment particle so that the surface of the pigment particle can be treated with a basic treatment. This makes it possible to strongly bond the pigment particle and the non-aqueous dispersing agent having an acidic group by an acid-base interaction, and to improve the dispersibility of the pigment particle by the non-aqueous dispersing agent having the acidic group.

Since nanoparticles having a tendency to disperse are originally small in size, if they are to be isolated by filter filtration or centrifugal filtration as they are, the nanoparticles will escape or become clogged and take a long time to isolate. However, isolation is greatly improved by forming a large aggregate by the pH control as described above. In the first embodiment of the present invention, the width of the pH change is not particularly limited, but the width of the pH change is preferably 7 to 12, more preferably 9 to 12. Although the direction of the pH change is not particularly limited, it is preferable that the pH is changed from the (low) pH side to the (high) pH side, that is, the pH direction is changed to the alkaline direction.

As the agglomerate, the average particle diameter is preferably 10000 nm or more, and the larger the agglomerate, the more preferable. There is no particular upper limit to the average particle diameter, but it is practically 10000000 nm or less. If the average particle diameter of the agglomerate is too small, it may take a long time to isolate the agglomerate, or it may pass through the filter paper or filter or be clogged even if it is to be filtered. If the average particle diameter of the agglomerate is too large, there is a case that the re-dispersion requires a long time.

Next, the acidic dispersion auxiliary according to the second embodiment of the present invention will be described in detail.

The acidic dispersion aid of the second embodiment of the present invention is intended for the purpose of particle size control at the nanoscale level of pigment particles, imparting pH responsiveness and acid treatment (improving redispersibility) in preparing a dispersion by precipitating organic pigment nanoparticles It is preferable that at least one of the pigment solution and the poor solvent contains the following acidic compound, and it is more preferable to contain the pigment in the pigment solution. It is also preferable to use them in combination with the above-mentioned dispersant.

The acidic dispersion auxiliary of the second embodiment of the present invention is represented by the following general formula (1-2).

In the formulas, A ¹¹ represents a heterocyclic group connected to a carbonyl group by a nitrogen atom. X ¹¹ represents a divalent alkylene, ether or polyether group having 2 to 10 carbon atoms which may have a substituent T.

As A ¹¹ , there can be mentioned, for example, pyrazole, imidazole, indole, carbazole, 5-aminobenzimidazole, 3-aminoanthraquinone, acridone, 5-aminobenzimidazolone, Aminobenzimidazole, 3-aminoanthraquinone, acridone, 5-aminobenzimidazolone, and 5-aminouracil, and more preferably, 5-aminobenzimidazole, 3-aminoanthraquinone, 5-aminobenzimidazolone, and 5-aminouracil.

X ^{11 is,} for example, a linking group containing alkylene, polyethylene oxide or polypropylene oxide, and is preferably alkylene.

Hereinafter, specific structures are shown, but the present invention is not limited thereto.

The amount of the acidic dispersion aid to be added to the aqueous dispersion is preferably 0.1 part by mass to 1000 parts by mass, more preferably 5 parts by mass to 500 parts by mass, and particularly preferably 10 parts by mass to 300 parts by mass, relative to 100 parts by mass of the pigment . If the addition amount is too small, flocculation for isolation to be described later may be insufficient, and if it is too much, excessive flocculation may occur and redispersibility, which will be described later, may become difficult.

In the second embodiment of the present invention, the organic pigment nanoparticles can be aggregated to facilitate isolation by neutralizing the aqueous dispersion of the organic pigment nanoparticles described above.

When the two solvents are acidic, the aqueous dispersion of the organic pigment nanoparticles is acidic, and when the two solvents are basic, the aqueous dispersion is also basic. The acidic dispersion aid in the second embodiment of the present invention is most effective when the aqueous dispersion is basic.

If the aqueous dispersion is basic, it can be agglomerated by neutralization from neutral to slightly acidic by acid addition. At this time, although the acidic dispersion aid covers the organic pigment nanoparticles in the anionized state, it is necessary as an acid to neutralize the anion to form a neutral acidic dispersion auxiliary around the organic pigment nanoparticles. Therefore, it is necessary to appropriately select the acidity and the addition amount to neutralize the anionization state of the acidic dispersion aid.

Examples of the acid to be added include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid, and organic acids such as acetic acid, propionic acid, butyric acid, valeric acid and hexanoic acid. In the case of neutralization by these, it is preferable to neutralize the pH of the whole system to 7 or less, more preferably 3 or less.

Further, in the acidic dispersion auxiliary in the second embodiment of the present invention, since it has an acidic group, it strongly interacts with the non-aqueous dispersant described later, and it is possible to improve the dispersibility and the contrast. The acidic dispersion aid covers the periphery of the pigment particle so that the surface of the pigment particle can be treated with an acid. As a result, the pigment particles and the non-aqueous dispersant are strongly bonded by the acid-base interaction, and it becomes possible to improve the dispersibility of the pigment particles by the non-aqueous dispersant. At this time, when the non-aqueous dispersing agent has an acidic group, it interacts with the acidic dispersing assistant by hydrogen bonding, and when the non-aqueous dispersing agent has a basic group, the acidic dispersing agent interacts with the acidic dispersing agent by an acid- A more preferred group having a non-aqueous dispersing agent is a non-aqueous dispersing agent having a basic group which can expect stronger interaction with the acidic dispersing aid.

In the second embodiment of the present invention, under the basic condition, the above-mentioned acidic dispersion auxiliary is anionized and negatively charged, so that the particles repel each other and tend to disperse. The negative charge disappears and the repulsive force between the particles disappears, resulting in agglomeration.

Since nanoparticles having a tendency to disperse are originally small in size, if they are to be isolated by filter filtration or centrifugal filtration as they are, the nanoparticles will escape or become clogged and take a long time to isolate. However, isolation is greatly improved by forming a large aggregate by the pH control as described above. In the second embodiment of the present invention, the width of the pH change is not particularly limited, but the width of the pH change is preferably 1 to 7, more preferably 1 to 3. Although the direction of the pH change is not particularly limited, it is preferable to change the pH from the (high) pH side to the (low) pH side, that is, to change it in the acidic direction.

The aggregate of the present invention preferably has an average particle diameter of 10000 nm or more, more preferably larger. There is no particular upper limit to the average particle diameter, but it is practically 10000000 nm or less. If the average particle diameter of the agglomerate is too small, it may take a long time to isolate the agglomerate, or it may pass through the filter paper or filter or be clogged even if it is to be filtered. If the average particle diameter of the agglomerate is too large, there is a case that the re-dispersion requires a long time.

Hereinafter, configuration requirements and other conditions common to the first and second embodiments of the present invention will be described.

In the present invention, the pH of the aqueous dispersion of the organic pigment nanoparticles described above may be changed to cause aggregation (soft aggregation) to such an extent that the organic pigment nanoparticles can be redispersed so as to be easily isolated. Here, soft aggregation is weak aggregation to such an extent that it can be re-dispersed if necessary, and the soft agglomerates are sometimes referred to as flocs in particular. By doing so, for example, the organic pigment fine particles precipitated in the water-based dispersion composition can be quickly separated by filtration or the like. Then, the separated soft agglomerates are re-dispersed in an organic solvent suitable for the production of color filters, so that an organic solvent-based dispersion composition can be efficiently obtained. That is, when a mixed solvent of a good solvent and a poor solvent is used for a water-based solvent, it can be efficiently replaced with a third solvent composed of an organic solvent to switch the dispersion medium (continuous phase). The average particle size of the agglomerate is not particularly limited, but is preferably 10 to 5000 占 퐉, more preferably 100 to 5000 占 퐉 in consideration of the above-mentioned filtration property.

In order to re-disperse the particles in the soft agglomerated state, the ordinary dispersing method may be insufficient. The formation of such a flocculated body (flocs) and the redispersion can be effected by the above-mentioned dispersion aid, so that the redispersion can be promptly performed even once the flocculation is carried out, and a good dispersion state can be realized. Therefore, it is preferable to use a medium in which the medium is dispersed in a mixed solvent of a good solvent and a poor solvent and a dispersion stability (property of realizing a uniform and minute particle diameter) and a dispersion stability (uniform and fine particle diameter are maintained for a long time) It can be held even after redispersing by switching to the final solvent, thereby realizing high performance in the color filter. In addition, the dispersion aid can realize high performance in a color filter and a liquid crystal display device without interfering with the optical characteristics and the like of the color filter.

Hereinafter, a method of isolating aggregated organic pigment nanoparticles will be described.

First, the solution agglomerated before isolation may be allowed to stand for 0.5 to 2 hours. Since the aggregate quickly precipitates, it can be removed by decanting or absorbing the supernatant, making it easier to isolate the aggregate. In addition, centrifugal separation is performed instead of centrifugal separation, so that sedimentation of agglomerates can be performed more quickly, and time can be shortened.

As the isolation method, various filtration methods are available, such as limiting filtration, centrifugation, filtration by filtration or filtration.

In the case of ultrafiltration, for example, a method used for desalting / concentration of a silver halide oil agent can be applied. Research Disclosure. 10208 (1972), No. 13 122 (1975), and No. 16 351 (1977). An important pressure difference or flow rate as an operating condition can be selected with reference to the characteristic curve described in "Membrane Handling Technology Handbook" published by Saiwa Shobo Publishing Co. (1978), p275 by Haruhiko Oya. However, in processing the desired organic nanoparticle dispersion, It is necessary to find out the optimum condition for suppressing the defects. In addition, in the method of replenishing the solvent lost from permeation through the membrane, there is a batch system in which the solvent is added in an intermittent manner to a fixed-dose system in which a solvent is continuously added, but a fixed-dose system having a relatively short desalination time is preferable. The pure water obtained by ion exchange or distillation is used as the solvent to be supplemented in this way, but a poor solvent of the dispersant and the dispersant may be mixed in pure water or may be added directly to the organic nanoparticle dispersion.

Filter filtration may employ, for example, a device such as pressure filtration. Preferable filters include filter paper, nanofilters, ultrafilters, and the like.

The centrifugal separator used for concentrating the organic nanoparticles by centrifugation may be any device as long as it can precipitate the organic nanoparticles in the organic nanoparticle dispersion (or concentrated organic nanoparticle extract). Examples of the centrifugal separator include, in addition to a general-purpose apparatus, a skimming function (a function of sucking a supernatant layer during rotation and discharging it out of the system) or a continuous centrifugal separator continuously discharging solids.

The centrifugal separation conditions are preferably centrifugal force (value indicating whether centrifugal acceleration of several tens of times of gravity acceleration is applied), preferably 50 to 10000, more preferably 100 to 8000, and particularly preferably 150 to 6000. The temperature at the time of centrifugation is preferably from -10 to 80 캜, more preferably from -5 to 70 캜, particularly preferably from 0 to 60 캜, though it depends on the solvent type of the dispersion.

The isolated aggregates may be washed for the purpose of desalting, dewatering, and removal of the excess dispersant. The cleaning operation may be performed by limiting filtration, centrifugation, filtration or filtration by filtration, followed by washing with the cleaning liquid. Alternatively, the filtrate may be subjected to limiting filtration, centrifugation, filtration or filtration Or they may be washed in combination.

The cleaning may be performed not only after isolation as described above but also before isolation. The aggregated nanopigment particle dispersion is allowed to stand, the supernatant is removed, and the cleaning liquid is added to the nanoparticle dispersion. After the reslurry, the solution may be allowed to stand and be filtered by removing the supernatant, but it may be filtrated as it is. If the cleaning is carried out before isolation, the aggregation is always wet, so that the cleaning efficiency is improved and the re-dispersion described later becomes easier.

The cleaning liquid is not particularly limited as long as it is capable of achieving desalting, dehydration, removal of excess dispersing agent, and coagulant. An aqueous solvent (for example, water or hydrochloric acid, sodium hydroxide aqueous solution), an alcohol compound solvent, , Ketone compound solvents, ether compound solvents, aromatic compound solvents, carbon disulfide solvents, aliphatic compound solvents, nitrile compound solvents, sulfoxide compound solvents, halogen compound solvents, ester compound solvents, ionic liquids and mixed solvents thereof And is preferably an aqueous solvent, an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, a nitrile compound solvent, a sulfoxide compound solvent, an ester compound solvent, an amide compound solvent or a mixture thereof, Compound solvent, nitrile compound Solvent Wind It is right.

The washed agglomerates may be redispersed as described later or redispersed by a redispersion solvent (described later), or may be redispersed after being dried and drawn as a powder of the organic nanoparticle dispersion.

In the present invention, the organic pigment nanoparticles isolated as described above may be re-dispersed in a non-aqueous medium to obtain a non-aqueous dispersion. In this case, the organic pigment nanoparticles may have a boiling point of 150 캜 or higher (preferably 180 캜 or higher and lower than 300 캜) It is preferable to disperse them in a solvent. In the present invention, " boiling point " means the boiling point at 1 atm, unless otherwise specified. Hereinafter, this organic solvent may also be referred to as " high boiling point organic solvent ". At this time, the organic pigment nanoparticles are usually dispersed in the mixed solvent of the good solvent and the poor solvent in the precipitated state, and it is preferable that the mixed solvent and the high boiling point organic solvent are substituted. Here, the total amount of the solvent may be substituted, but it is usually difficult to replace the entire amount, and in the present invention, the main solvent may be substituted when it is referred to as the substitution of the solvent.

The content of the pigment in the non-aqueous dispersion of the present invention is not particularly limited, but is preferably from 10 to 20% by mass, and more preferably from 5 to 15% by mass. The content of the dispersing aid contained in the non-aqueous dispersion of the present invention is not particularly limited, but is practically contained in an amount of 0.05 to 5% by mass.

The substitution of the solvent may be carried out in any order. For example, it can be carried out as follows. First, the solvent content of the dispersion liquid containing the precipitated fine particles is reduced or removed (hereinafter sometimes referred to as "concentration and removal"). Accordingly, the organic pigment nanoparticles are once concentrated into a paste or paste, or the organic pigment nanoparticles are powdered. Adding a predetermined high boiling point organic solvent thereto, and dispersing the pigment nanoparticles in the organic solvent. Further, in the present invention, when a high boiling point organic solvent is dispersed in the high boiling point organic solvent, it is indicated that the high boiling point organic solvent accounts for more than 50% by mass in the solvent fraction from which the solid content in the dispersion is removed, The solvent is preferably 70% by mass or more.

In the present invention, the particles may be directly substituted with the high boiling point organic solvent after the precipitation, but before the solvent substitution by the high boiling point organic solvent is performed, the third solvent is substituted once, and then a third solvent It is also preferable to reduce or remove the solvent by the high boiling point solvent. (First replacement) from a mixed solvent of a good solvent (first solvent) and a poor solvent (second solvent), and then substituting the third solvent with a predetermined high boiling point organic solvent Second substitution), it is preferable to carry out the solvent substitution in two stages. In the present invention, the term " dispersion " means a composition in which predetermined fine particles are dispersed, and its form is not particularly limited, and may be used in the meaning of a liquid composition (dispersion), a paste composition and a solid composition do.

The organic solvent having a boiling point of 150 ° C or higher can be selected from the following solvents: glycol ether compounds such as diethylene glycol monomethyl ether, glycol ester compounds such as diethylene glycol monomethyl ether acetate or propylene glycol diacetate, Aliphatic carboxylic acid compounds such as lactic acid or its acid anhydrides, aliphatic or aromatic ester compounds such as butyl butyrate, propyl benzoate, dicarboxylic acid diester compounds such as diethyl malonate, alkoxycarboxylic acids such as methyl 3-methoxypropionate Ketocarboxylic acid ester compounds such as ethyl acetoacetate; Halogenated carboxylic acid compounds such as chloroacetic acid and dichloroacetic acid; Alcohol compounds such as lauryl alcohol, phenol or phenol compounds; Ether compounds such as anisole; Alkoxy alcohol compounds such as 3-methoxybutanol; Glycol oligomer compounds such as diethylene glycol, tripropylene glycol; Amino alcohol compounds such as triethanolamine; Alkoxy alcohol ester compounds such as 3-methoxybutyl acetate; Ketone compounds such as dibutyl ketone; Morpholine compounds such as N-phenyl morpholine; Aliphatic or aromatic amine compounds such as 1-octylamine, dicyclohexylamine, and aniline.

Among them, it is preferable to use a glycol ether compound, a glycol ester compound or a carboxylic acid ester compound in the present invention.

Specific examples of the organic solvent having a boiling point of 150 캜 or more include ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 1,3-butylene glycol diacetate, diethylene glycol dibutyl ether, di Diethylene glycol monobutyl ether, ethylene glycol monoethyl ether, tripropylene glycol n-butyl ether, diethyl adipate, dibutyl oxalate, dimethyl malonate, diethyl malonate, dimethyl succinate and diethyl succinate.

The organic solvent having a boiling point of 150 占 폚 or more may be used alone or in combination with a solvent used for preparing a conventional pigment dispersion such as 3-methoxybutyl acetate or propylene glycol monomethyl ether acetate (PGMEA).

The organic solvent having a boiling point of 150 캜 or more may be used alone or in a plurality of kinds.

The amount of the organic solvent having a boiling point of 150 占 폚 or more is not particularly limited, but is preferably 50 to 300,000 parts by mass, more preferably 500 to 1000 parts by mass with respect to 100 parts by mass of the pigment nanoparticles.

The form of concentration and removal when replacing the solvent is not particularly limited. For example, a method of concentrating and extracting the pigment nanoparticles into an extraction solvent by adding and mixing an extraction solvent to the pigment nano-particle dispersion, A method of concentrating the pigment nanoparticles by centrifugation, a method of concentrating the pigment nanoparticles by centrifugation, a method of concentrating desalting by ultrafiltration, a method using spray drying, a method of sublimating and concentrating the solvent by vacuum freeze drying , A form in which the solvent is dried and concentrated by heating or decompression, a form in which the solvent is dried and concentrated, and a form in which the solvent is condensed by centrifugal separation, spray drying and the like, Concentration is preferred.

The extraction solvent used for the concentration and extraction is not particularly limited, but is not substantially mixed with a dispersion solvent (for example, an aqueous solvent) of the pigment nanoparticle dispersion (in the present invention, It is preferable that the dissolution amount is not more than 50% by mass, more preferably not more than 30% by mass. However, it is practically 1% by mass or more in consideration of the solubility of a conventional solvent. And it is preferably a solvent that forms an interface. Further, the extraction solvent is preferably a solvent which generates weak aggregation (floc which can be re-dispersed without applying a high shearing force such as milling or high-speed stirring) in which the pigment nanoparticles can be redispersed in an extraction solvent. In such a state, it is preferable that the desired pigment nanoparticles are wetted by the extraction solvent without causing strong aggregation to change the particle size, and that the dispersion solvent such as water can be easily removed by filtration with a filter or the like. The extraction solvent is preferably an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent or an aliphatic compound solvent, more preferably an ester compound solvent, an aromatic compound solvent or an aliphatic compound solvent, and particularly preferably an ester compound solvent.

Examples of the ester compound solvent include 2- (1-methoxy) propyl acetate, ethyl acetate, ethyl lactate and the like. Examples of the alcohol compound solvent include n-butanol and isobutanol. Examples of the aromatic compound solvent include benzene, toluene, and xylene. Examples of the aliphatic compound solvent include n-hexane, cyclohexane, and the like. The extraction solvent may be a pure solvent by the above-mentioned preferable solvent or a mixed solvent by a plurality of solvents.

The amount of the extraction solvent is not particularly limited as far as the pigment nanoparticles can be extracted, but it is preferable that the extraction solvent is smaller than the pigment nanoparticle dispersion in consideration of concentration and extraction. When this is expressed as a volume ratio, the extraction solvent to be added is preferably in the range of 1 to 100, more preferably in the range of 10 to 90, and particularly preferably in the range of 20 to 80 when the pigment nanoparticle dispersion is 100. If it is too large, it takes a great deal of time to concentrate, and if it is too small, the extraction is insufficient and nanoparticles remain in the dispersion solvent.

After the extraction solvent is added, it is preferable to stir and mix sufficiently to contact the dispersion. For stirring mixing, a usual method can be used. The temperature at which the extraction solvent is mixed is not particularly limited, but is preferably 1 to 100 ° C, more preferably 5 to 60 ° C. Addition or mixing of the extraction solvent may be carried out by any apparatus as long as the respective steps can be preferably carried out. For example, it may be carried out using a separating lot apparatus.

For the ultrafiltration, filter filtration and centrifugation, the above-described methods can be used.

The lyophilization is not particularly limited, and any method may be employed as long as it is a usual method. For example, a refrigerant direct expansion method, an indirect heating freezing method, and more preferably an indirect heating freezing method may be used, although a refrigerant direct expansion method, a redundant freezing method, a heat transfer method, a triple heat exchange method, It is better to use the method. In either method, it is preferable to perform freeze-drying after preliminary freezing. The conditions of the preliminary freezing are not particularly limited, but it is necessary that the sample to be freeze-dried is frozen uniformly.

Examples of the indirect freezing and freezing method include a small freeze dryer, an FTS freeze dryer, a LYOVAC freeze dryer, a laboratory freeze dryer, a research freeze dryer, a triple heat exchange vacuum freeze dryer, a mono cooling type freeze dryer and a HULL freeze dryer. A small lyophilizer, a laboratory lyophilizer, a research lyophilizer, a mono cooling lyophilizer, more preferably a small lyophilizer or a mono cooling lyophilizer.

The temperature for freeze-drying is not particularly limited, but is, for example, -190 to -4 캜, preferably -120 to -20 캜, more preferably about -80 to -60 캜. The pressure for freeze-drying is not particularly limited and may be appropriately selected by a person skilled in the art. For example, it is preferably 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 6 to 36 hours, more preferably 16 to 26 hours. Naturally, these conditions can be appropriately selected by those skilled in the art. The freeze-drying method is described, for example, in "Preparation Machinery Technology Handbook: Preparation of Mechanical Engineering Technology", Chijinshokan, p.120-129 (September 2000); Vacuum Handbook: Nippon Shinko Gijutsu Co., Ltd., Omusa, p. 328-331 (1992); Freezing and Drying Research Meeting: KOJI Ito et al., No.15, p.82 (1965).

The reduced-pressure drying is not particularly limited as long as the solvent can be evaporated. For example, a general vacuum dryer and a rotary pump, a device capable of heating and drying under reduced pressure while stirring the liquid, and an apparatus capable of continuously drying the liquid by passing the liquid through a tube subjected to heat and pressure reduction.

The drying temperature under reduced pressure is preferably 30 to 230 ° C, more preferably 35 to 200 ° C, and particularly preferably 40 to 180 ° C. The pressure at the time of decompression is preferably 100 to 100000 Pa, more preferably 300 to 90000 Pa, and particularly preferably 500 to 80000 Pa.

Further, it may be dried in the following manner. Examples of the dryer using hot air include a lathe dryer, a band dryer, a stirring dryer, a fluidized bed dryer, a spray dryer and an air dryer, and drum dryers, multiple tube dryers, cylindrical dryers and the like are preferably used as driers using heat conduction . Depending on the solvent composition, a freeze dryer or an infrared dryer may also be used.

Among these means, a spray dryer (for example, COC-12 manufactured by Okawa Rakako Co., Ltd.), a fluidized bed dryer (for example, MSD-100} is particularly preferably used. A plurality of drying means may be used in combination for producing a pigment powder having a small residual solvent amount. For example, a process of completely drying a pigment dispersion preliminarily concentrated by a cylindrical dryer with a drum dryer to obtain a powder Can be used.

The drying conditions are not particularly limited as long as the solvent can be evaporated and the materials such as the pigment and the dispersant can not be denatured. For the purpose of increasing the drying speed, means such as reduced pressure, stirring mixing, and multi-shading may be combined depending on the type of dryer.

The amount of reducing or removing the solvent is not particularly limited, but in the form of reducing the solvent content, it is preferable to remove 50 mass% or more of the total solvent amount, more preferably 75 mass% or more. In the form of removing the solvent component, it is preferable to remove 80 mass% or more of the entire solvent component, more preferably 90 mass% or more.

When the solvent content is reduced by the concentration and removal process, the water content in the remaining dispersion is not particularly limited, but is preferably 0.01 to 3% by mass, more preferably 0.01 to 1% by mass. At this time, it is preferable to remove the solvent component by, for example, the above-mentioned drying method to form the powder of the pigment nanoparticles. For example, the solid content is preferably 50 to 100 mass%, more preferably 70 to 100 mass% % Is more preferable. Further, the concentration and removal step may be performed a plurality of times.

In the present invention, it is preferable to redisperse the organic particles in a coagulated state by the concentration and removal step. The organic particles contained in the organic particle liquid sometimes undergo aggregation due to isolation and solvent replacement. It is possible to perform rapid filter filtration. However, even in such a case, it is preferable to make the flocculated flock agglomerate to such an extent that it can be redispersed again in order to obtain a good dispersion state.

Further, in order to disperse the particles in the aggregated state, the ordinary dispersion method may be insufficient. Even in the case of the organic particles in such a coagulated state, in the present invention, the organic particles can be preferably redispersed by incorporating a predetermined dispersant in the non-aqueous dispersion together with the above-described dispersion aid. In this case, the dispersant to be added in order to prepare a non-aqueous dispersion is sometimes referred to as a non-aqueous dispersant.

As the non-aqueous dispersing agent, a polymer compound having a mass average molecular weight of 1,000 or more is preferably used, and a polymer compound represented by the following general formula (1) is more preferably used.

In the general formula (1), A ¹ represents an acidic group, a basic group having a nitrogen atom, a urea group, a urethane group, a group having a saturated oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, A monovalent organic group having a group selected from a hydroxyl group or a monovalent organic group containing an organic pigment structure or a heterocyclic ring which may have a substituent. n A ¹ may be the same or different.

Specifically, A ¹ is not particularly limited, and examples of the "monovalent organic group having an acidic group" include a carboxylic acid group, a sulfonic acid group, a monosulfuric acid ester group, a phosphoric acid group, a monophosphoric acid ester group, , And the like. Examples of the "monovalent organic group having a basic group having a nitrogen atom" include a monovalent organic group having an amino group (-NH ₂ ), a substituted imino group (-NHR ⁸ , -NR ⁹ R ¹⁰ ) (Wherein R ⁸ , R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms) A monovalent organic group having a guanidyl group represented by the following general formula (a1): wherein, in the general formula (a1), R ^a1 and R ^a2 each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms Or an aralkyl group having a carbon number of 7 or more and 30 or less; a monovalent organic group having an amidinyl group represented by the following general formula (a2): wherein R ^a3 and R ^a4 each independently represent a An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, And an aralkyl group having a number of 7 or more and 30 or less].

Examples of the monovalent organic group having a urea group include -NHCONHR ¹⁵ wherein R ¹⁵ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl group having 7 to 30 carbon atoms , And the like).

Examples of the "monovalent organic group having a urethane group" include -NHCOOR ¹⁶ , -OCONHR ¹⁷ (wherein R ¹⁶ and R ¹⁷ each independently represent an alkyl group having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms Or an aralkyl group having 7 to 30 carbon atoms), and the like.

Examples of the "monovalent organic group having a group having a double oxygen atom" include groups having an acetylacetonato group and groups having a crown ether.

Examples of the "monovalent organic group having a hydrocarbon group having 4 or more carbon atoms" include an alkyl group having 4 or more carbon atoms (eg, octyl group, dodecyl group, etc.), an aryl group having 6 or more carbon atoms (eg, phenyl group, naphthyl group, (For example, a benzyl group), and the like. At this time, although there is no upper limit to the carbon number, it is preferably 30 or less.

Examples of the "monovalent organic group having an alkoxysilyl group" include groups having a trimethoxysilyl group, a triethoxysilyl group, and the like.

Examples of the "monovalent organic group having an epoxy group" include groups having a glycidyl group and the like.

Examples of the "monovalent organic group having an isocyanate group" include a 3-isocyanatopropyl group and the like.

Examples of the "monovalent organic group having a hydroxyl group" include a 3-hydroxypropyl group and the like.

The A ¹ is preferably a monovalent organic group having an acidic group, a basic group having a nitrogen atom, a urea group or a hydrocarbon group having 4 or more carbon atoms.

The organic dye structure or heterocycle is not particularly limited, but more specifically, examples of the organic dye structure include phthalocyanine compounds, insoluble azo compounds, azo lake compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds, A diketopyrrolopyrrole compound, an anthra pyridine compound, an anthrone compound, an indanthrone compound, a pravantron compound, a perinone compound, a perylene compound, and a thioindigo compound. Examples of the heterocycle include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole The present invention relates to a process for the preparation of benzimidazolone derivatives of the general formula (I) or a pharmaceutically acceptable salt thereof, which comprises administering an effective amount of at least one compound selected from the group consisting of a prodrug, a triazole, a thiazole, a thiadiazole, a pyran, a pyridine, a piperidine, a dioxane, a morpholine, a pyridazine, , Succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, and anthraquinone.

Examples of the substituent T include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, and the like. An alkoxy group having 1 to 6 carbon atoms such as methoxy group or ethoxy group, a halogen atom such as chlorine or bromine, a methoxycarbonyl group, an ethoxycarbonyl group, a cyclohexyl An alkoxycarbonyl group having 2 to 7 carbon atoms such as an oxycarbonyl group, a carbonic ester group such as cyano group and t-butyl carbonate, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group and an N-sulfonylamide group.

The above-mentioned A ¹ can be represented by the following general formula (4).

In the general formula (4), B ¹ represents an acidic group, a basic group having a nitrogen atom, a urea group, a urethane group, a group having a saturated oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, An organic pigment structure or heterocyclic ring which may have a substituent or a group selected from a hydroxyl group, and R ¹⁸ represents a single bond or an aliphatic organic or inorganic linking group. a1 represents 1 to 5, and a1 B ¹ may be the same or different. The preferred form of the group represented by the general formula (4) is the same as the above-mentioned A ¹ .

R ¹⁸ represents a single bond or a linking group of a 1 + 1 valency, and a 1 represents 1 to 5. The linking group R ¹⁸ contains 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms and 0 to 20 sulfur atom-forming groups, You can have it. R ¹⁸ is preferably an organic linking group.

Specific examples of R < ¹⁸ > include groups in which the following structural units or structural units thereof are combined. The linking group R ¹⁸ may have the substituent T.

In the general formula (1), R ¹ represents an (m + n) linking group. and m + n satisfies 3 to 10.

The (m + n) linking group represented by R ¹ is preferably a group having 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms and 0 to 20 sulfur atoms And may be substituted or unsubstituted. R ¹ is preferably an organic linking group.

As a specific example of R ¹ , there may be mentioned groups (t-1) to (t-34) or groups formed by combining these groups (may form a ring structure). When the linking group R ¹ has a substituent, examples of the substituent include the substituent T.

R ² represents a single bond or a divalent linking group. R ² contains 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atom-forming groups, There may be. Specific examples of R ² include groups represented by the above-mentioned groups t-3 to 5, 7 to 18, 22 to 26, 32, and 34, or a combination thereof. It is preferable that R ² has a sulfur atom at a connecting position with R ¹ . When R ² has a substituent, examples of the substituent include the substituent T described above.

In the general formula (1), m represents 1 to 8. m is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 to 2.

In addition, n represents 2 to 9. n is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.

In the general formula (1), P ¹ represents a polymer compound residue (polymer skeleton), and can be appropriately selected from a chain polymer or the like.

In order to form a polymer skeleton among polymers, a polymer or copolymer of a vinyl monomer, an ester compound polymer, an ether compound polymer, a urethane compound polymer, an amide compound polymer, an epoxy compound polymer, a silicone compound polymer and their modified products or copolymers (Including random copolymers, block copolymers and graft copolymers) of a polyether / polyurethane copolymer, a copolymer of a polymer of a polyether / vinyl monomer, and the like] And more preferably at least one member selected from the group consisting of a polymer or copolymer of a vinyl monomer, an ester compound polymer, an ether compound polymer, a urethane compound polymer and a modified product or copolymer thereof, and more preferably a vinyl monomer Polymer or Polymer is particularly preferred.

The polymer is preferably soluble in an organic solvent. If the affinity with an organic solvent is low, for example, when it is used as a pigment dispersant, the affinity with the dispersion medium becomes weak, so that it may become impossible to secure a sufficient adsorption layer for dispersion stabilization.

In addition, it is preferable that P ¹ has a sulfur atom at a connecting position with R ¹ .

Among the macromolecular compounds represented by the general formula (1), macromolecular compounds represented by the following general formula (2) are more preferable.

In the general formula (2), A ² is synonymous with A ¹ in the general formula (1), and its specific preferred form is also the same. Further, A ² may have a substituent, and the above substituent T can be exemplified.

In the general formula (2), R ³ represents a linking group of (x + y). R ³ is synonymous with R ¹ and the preferred range is also the same. In this case, R ³ is a linking group of x + y, but the value of x and its preferable range are the same as n in formula (1), the value of y and its preferable range are equal to m, and the value of x + y And its preferable range is equal to m + n.

The linking group represented by R ³ is preferably an organic linking group, and specific examples of the organic linking group are shown below. However, the present invention is not limited thereto.

(R-1), (r-2), (r-10), (r-11), (r-16), (r-17) is preferable.

When R ³ has a substituent, the substituent T is the substituent.

In the general formula (2), R ⁴ and R ⁵ each independently represent a single bond or a divalent linking group.

Wherein R ^4, R As the "divalent linking group" represented by ⁵ may have a substituent a straight-chain, branched or cyclic alkylene group, arylene group or aralkyl group, -O-, -S-, -C (= O) ^{-, -N (R 19) -} , -SO-, -SO 2 -, -CO 2 - or -N (R ²⁰⁾ SO ₂ - or a group thereof is preferably a divalent group combining two or more (the R ¹⁹ And R < ²⁰ > each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Among them, an organic linking group is preferable.

Examples of the R ⁴ a straight-chain or branched alkylene group or an aralkyl group, -O-, -C (= O) -, -N (R ¹⁹⁾ -, ₂ -SO -, -CO ₂ - or -N (R ²⁰ ) SO ₂ -, or a divalent group formed by combining two or more of these groups, and more preferably a linear or branched alkylene group or an aralkylene group, -O-, -C (= O) -, -N (R ¹⁹ ) -CO ₂ - or a divalent group obtained by combining two or more of these groups is particularly preferable.

R ^{5 is a} single bond, a straight chain or branched alkylene group, an aralkylene group, -O-, -C (= O) -, -N (R ¹⁹ ) -, -SO ₂ -, -CO ₂ - (R ²⁰⁾ SO ₂ - or a divalent group of these groups than in combination two or more preferably, linear or branched alkylene group, an aralkyl group, -O-, and -C (= O) -, -N (R 19 ) - or -CO ₂ - or a divalent group obtained by combining two or more of these groups is particularly preferable.

When R ⁴ and R ⁵ have a substituent, examples of the substituent include the substituent T described above.

Further, P ² in the general formula (2) represents a polymer skeleton and can be appropriately selected from ordinary polymers and the like. The preferable form of the polymer agrees with P ¹ in the above general formula (1), and the preferred form thereof is also the same.

Among the polymer compounds represented by the above general formula (2), particularly preferred are those in which R ³ is at least one of the above-mentioned specific examples (r-1), (r-2), (r- or (r-17), and, r ⁴ is a single bond, a linear or branched alkylene group or an aralkyl group, -O-, -C (= O) -, -N (r 19) - or -CO ₂ - or And R ⁵ is a single bond, an ethylene group, a propylene group, or a linking group represented by the following formula (sa) or (sb), and P ² is a polymer or a copolymer of vinyl monomers An ester compound polymer, an ether compound polymer, a urethane-based polymer or a modified product thereof, and particularly preferably a polymer compound in which y is 1 to 2 and x is 3 to 6. In the following groups, R ²¹ represents a hydrogen atom or a methyl group, and 1 represents 1 or 2.

The mass average molecular weight of the polymer compound is preferably 1,000 or more, more preferably from 3,000 to 100,000, still more preferably from 5,000 to 80,000, and particularly preferably from 7,000 to 60,000 as a mass average molecular weight. When the mass average molecular weight is within the above range, the effects of a plurality of functional groups introduced at the ends of the polymer are sufficiently exerted to exhibit excellent adsorption on the solid surface, micelle formation ability, and excellent surface activity, can do.

Specific examples of the compound represented by the general formula (1) are shown below. However, the present invention is not limited to these specific examples.

The polymer compound represented by the general formula (1) or (2) can be synthesized, for example, by the following methods.

1. A polymer having a functional group selected from a carboxyl group, a hydroxyl group, an amino group and the like, and an acid halide having a plurality of functional groups (A ¹ or A ² in the above formula) or a plurality of functional groups ¹ or A ² ) or an isocyanate having a plurality of functional groups (A ¹ or A ² in the general formula).

2. A method in which a polymer having a carbon-carbon double bond introduced at its terminal and a mercaptan having a plurality of functional groups (A ¹ or A ² in the above formula) are subjected to Michael addition reaction.

3. A method of reacting a polymer having a carbon-carbon double bond introduced at its terminal and a mercaptan having a plurality of functional groups (A ¹ or A ² in the above formula) in the presence of a radical generator.

4. A method of reacting a polymer having a plurality of mercaptans introduced at its terminal and a functional group having a carbon-carbon double bond introduced therein (A ¹ or A ² in the above formula) in the presence of a radical generator.

5. A method for radical polymerization of a vinyl monomer using a mercaptan compound having a plurality of functional groups (A ¹ or A ² in the above formula) as a chain transfer agent.

Among them, 2, 3, 4 and 5 are preferable, 3, 4 and 5 are more preferable, and 5 is particularly preferable in view of easiness of synthesis. For the synthesis methods, refer to paragraphs 0184 to 0216 of Japanese Patent Application No. 2006-129714.

As a polymer compound having a molecular weight of 1,000 or more, the following polymeric compound having an acidic group (hereinafter, this compound may also be referred to as an " acidic group-containing polymeric compound ") may be used, and a polymer compound having a carboxyl group (A) at least one kind of repeating unit introduced from a compound having a carboxyl group and (B) a repeating unit introduced from a compound having a carboxylic acid ester group are more preferable.

The repeating unit introduced from the compound having a carboxyl group (A) is preferably a repeating unit represented by the following formula (I), more preferably a repeating unit introduced from acrylic acid or methacrylic acid, The repeating unit introduced from the compound having a carboxylic acid ester group is preferably a repeating unit represented by the following formula (II), more preferably a repeating unit represented by the following formula (IV), and benzyl acrylate , Benzyl methacrylate, phenethyl acrylate, phenethyl methacrylate, 3-phenylpropyl acrylate or 3-phenylpropyl methacrylate.

In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ₂ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ₃ represents a group represented by the following general formula (III). R ₄ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxy group, a hydroxyalkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R ₅ and R ₆ each represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. i represents a number of 1 to 5; R ₇ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ₈ represents a group represented by the following formula (V). R ₉ represents an alkyl group having 2 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms. R ₁₀ and R _{11 each} represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. j represents a number of 1 to 5;

The polymerization ratio of the repeating unit introduced from the compound having a carboxyl group (A) and the repeating unit introduced from the compound having a carboxylate group (B) is not particularly limited as long as the ratio of the number of repeating units (A) % Is preferably 3 to 40, more preferably 5 to 35.

In the production method of the present invention, the molecular weight refers to the mass average molecular weight unless otherwise specified. Examples of the method for measuring the molecular weight include a chromatography method, a viscosity method, a light scattering method and a sedimentation rate method. However, unless specifically mentioned in the present invention, the polystyrene The mass average molecular weight in terms of conversion is used.

The polymer compound has good water solubility and good usability, and may be water-soluble and useful.

The method of adding the polymer compound may be a solution in an aqueous solvent or an organic solvent, a solid state, or a combination thereof. Examples of the method of adding a solution dissolved in a solvent include a method of adding the solution to the coagulated organic particle solution in the same solvent as that of the coagulated organic particle solution, a method of dissolving the coagulated organic particle solution in another solvent In a state of being added. The concentration of the polymer compound when added as a solution dissolved in a solvent is not particularly limited, but is preferably 1 to 70% by mass, more preferably 2 to 65% by mass, and particularly preferably 3 to 60% by mass.

The addition of the polymer compound may be added at any time during or after the precipitation of the pigment nanoparticles, before or after the condensation, before or after the condensation, before or after the condensation of the condensed organic particles, Multiple circuits may be added. Among them, in the present invention, it is preferable to add a polymer compound having a mass average molecular weight of 1000 or more at the same time as a third solvent to be described later. The polymer compound is mixed with a third solvent, and the mixture is added to the concentrated pigment nanoparticle solution . The addition amount of the polymer compound is preferably 0.1 to 1000 parts by mass, more preferably 5 to 500 parts by mass, and particularly preferably 10 to 300 parts by mass with respect to 100 parts by mass of the pigment.

As the polymer compound having a molecular weight of 1,000 or more, for example, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol- , Polyvinyl alcohol-partial formaldehyde, polyvinyl alcohol-partial butyralate, vinylpyrrolidone-vinyl acetate copolymer, polyethylene oxide / propylene oxide block copolymer, polyamide, cellulose derivative, . In addition, natural polymer compounds such as alginate, gelatin, albumin, casein, gum arabic, tragacanth gum, and lignin sulfonate may be used. Examples of the polymer compound having an acidic group include polyvinyl sulfuric acid and condensed naphthalenesulfonic acid.

Examples of the polymer compound having a carboxyl group include polyacrylic acid, polymethacrylic acid, and a cellulose derivative having a carboxyl group in the side chain. As the copolymerizable compound containing at least one repeating unit introduced from a compound having a carboxyl group (A) and at least one repeating unit introduced from a compound having a carboxylic acid ester group (B), JP-A 59-44615 Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Laid-Open Publication No. 59-53836 and Japanese Patent Laid-Open No. 59-71048 A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, and the like as described in the publication. Particularly preferred examples thereof include acrylic acid-acrylic acid ester copolymers, methacrylic acid-acrylic acid ester copolymers, acrylic acid-methacrylic acid ester copolymers, methacrylic acid-methacrylic acid ester copolymers and methacrylic acid-methacrylic acid ester copolymers described in United States Patent No. 4,139,391 Acrylic acid or methacrylic acid, acrylic acid ester or methacrylic acid ester, and other vinyl compounds.

Examples of the vinyl compound include styrene or substituted styrene (e.g., vinyltoluene, vinyl ethylbenzene), vinylnaphthalene or substituted vinylnaphthalene, acrylamide, methacrylamide, acrylonitrile and methacrylonitrile , And styrene are preferable.

The polymer compound having a molecular weight of 1,000 or more may be used alone or in combination of two or more, or in combination with a compound having a molecular weight of less than 1,000.

In the method for producing the pigment nanoparticles of the present invention, it is preferable that the third solvent is contained after the precipitation of the pigment nanoparticles. The kind of the third solvent is not particularly limited, but an organic solvent is preferable. For example, an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, an aliphatic compound solvent and a ketone compound solvent are preferable, and an ester compound solvent, Solvents are particularly preferred.

In the present invention, both of the first solvent and the second solvent which are ultimately the desired dispersion medium (continuous phase) in the meaning of containing the third solvent and the fourth solvent to be described later are collectively referred to as " third solvent "

Examples of the ester compound solvent include 2- (1-methoxy) propyl acetate, ethyl acetate, ethyl lactate and the like. Examples of the alcohol compound solvent include methanol, ethanol, n-butanol and isobutanol. Examples of the aromatic compound solvent include benzene, toluene, and xylene. Examples of the aliphatic compound solvent include n-hexane, cyclohexane, and the like. Examples of the ketone compound solvent include methyl ethyl ketone, acetone, and cyclohexanone.

Among them, ethyl lactate, ethyl acetate, acetone and ethanol are preferable, and ethyl lactate is more preferable. These may be used singly or in combination of two or more. Further, the positive solvent (the first solvent), the poor solvent (the second solvent), the third solvent, and the high boiling point organic solvent are not necessarily the same.

The addition timing of the third solvent is not particularly limited as long as it is after the precipitation of the pigment nanoparticles, but it is preferable that the pigment nanoparticles are precipitated and then concentrated and removed to add thereto. As described above, after the first concentration and removal step, it is preferable to add a third solvent and reduce or remove the solvent content again by the second concentration and removal step. Then, it is preferable to add a predetermined high boiling point organic solvent thereafter.

The amount of the third solvent to be added is not particularly limited, but is preferably 100 to 300000 parts by mass, more preferably 500 to 1000 parts by mass with respect to 100 parts by mass of the pigment nanoparticles.

The organic pigment nanoparticles which are in a coagulated state can be finely dispersed as required (in the present invention, finely dispersing means that aggregation of particles in the dispersion is released to increase dispersion).

It is preferable to obtain the flocculated flocculated flocculated organic pigment nanoparticles as described above so as to enable rapid filter filtration and again obtain a good dispersion state.

Therefore, there is a need for a method which is insufficient for fine particle formation and has a high refining efficiency to the extent that it is dispersed by using the ordinary dispersion method.

As a method of finely dispersing such agglomerates of nanoparticles, for example, a method of dispersing by ultrasonic waves or a method of applying physical energy can be used.

The ultrasonic wave irradiation apparatus to be used preferably has a function of applying an ultrasonic wave of 10 kHz or more, and examples thereof include an ultrasonic homogenizer and an ultrasonic wave cleaner. Since the nanoparticles undergo thermal agglomeration when the liquid temperature rises during the ultrasonic irradiation, the liquid temperature is preferably 1 to 100 ° C, more preferably 5 to 60 ° C. The temperature can be controlled by controlling the temperature of the dispersion liquid, or by controlling the temperature of the temperature control layer for controlling the temperature of the dispersion liquid.

The dispersing machine used for dispersing the concentrated organic nanoparticles by adding physical energy is not particularly limited and examples thereof include dispersing machines such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, . A dispersion method by using a high-pressure dispersion method or a method using fine particle beads is also preferable.

As a preferable production method of the organic nanoparticle dispersion, a kneading dispersion treatment is carried out so that the viscosity at 25 캜 after the colorant is kneaded and dispersed with a resin component becomes a relatively high viscosity of 10,000 mPa 이상 or more, preferably 100,000 mPa 쨌 s or more, Then, it is preferable to add a solvent and finely disperse the solution so that the viscosity after the micro-dispersion treatment becomes a relatively low viscosity of 1,000 mPa · s or less, preferably 100 mPa · s or less.

The machine used in the re-dispersion treatment is a two roll, three roll, a ball mill, a throm mill, a disperser, a kneader, a coneerator, a homogenizer, a blender, a single shaft and a biaxial extruder and is dispersed while giving a strong shearing force . Subsequently, a solvent is added and finely dispersed by beads made of glass or zirconia having a particle diameter of 0.1 to 1 mm mainly by using a vertical or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, a high pressure disperser or the like. It is also possible to perform fine dispersion treatment using fine particle beads of 0.1 mm or less.

It is also possible to disperse the main pigment and the auxiliary pigment, respectively, and then to mix the dispersions of the two to further disperse the mixture, or to disperse the main pigment and the auxiliary pigment together.

Further, details of dispersion are described in T.C. Patton, " Paint Flow and Pigment Dispersion " (John Wiley and Sons, 1964), and the like may also be used.

The pigment nanoparticles can be used, for example, in a dispersed state in a vehicle. The vehicle refers to a portion of the medium in which the pigment is dispersed when it is in a liquid state, that is, in a liquid state, a portion (binder) which is in a liquid state and is combined with the pigment to solidify the coating, Lt; / RTI >

The concentration of the pigment nanoparticles in the dispersion composition of the pigment nanoparticles after re-dispersion is appropriately determined according to the purpose, but it is preferable that the pigment nanoparticles are contained in an amount of 2 to 30 mass%, preferably 4 to 20 mass% , And particularly preferably from 5 to 15% by mass. In the case of dispersing in the above-mentioned vehicle, the amount of the binder and the diluting component is appropriately determined according to the type of the organic pigment and the like, but the amount of the binder is preferably 1 to 30 mass%, more preferably 3 to 20 mass% , And particularly preferably from 5 to 15 mass%. The content of the dissolved and diluted component is preferably 5 to 80% by mass, more preferably 10 to 70% by mass.

In the organic nanoparticle-dispersed composition, the organic nanoparticles (primary particles) after redispersion can be finely dispersed particles, and the particle diameter can be preferably 10 to 1000 nm, more preferably 10 to 500 nm , And particularly preferably from 10 to 50 nm. The Mv / Mn of the particles after re-dispersion is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, particularly preferably 1.0 to 1.5.

According to the production method of the present invention, for example, even when the pigment particles contained in the organic pigment nano-particle dispersion composition or the colored photosensitive resin composition described below have a minute particle size of nanometer size (for example, 10 to 100 nm) , The concentrated material can be dispersed. Therefore, when used for a color filter, the optical density is high, the uniformity of the filter surface is excellent, the contrast is high, and the noise of the image can be reduced.

In addition, since the organic pigment nanoparticle dispersion composition and the organic pigment nanoparticles contained in the colored photosensitive composition can be finely and uniformly dispersed at a high level, the organic pigment nanoparticles can be thinly formed and exhibit a high coloring density. For example, And the like.

In addition, the organic pigment nano-particle dispersion composition and the colored photosensitive resin composition are excellent as an image forming material for producing, for example, a color proof, a color filter and the like by containing a bright color tone and a pigment exhibiting high coloring power.

Further, with respect to an alkaline developing solution used for exposure and development at the time of color image formation, an organic nano-particle dispersion composition and a binder soluble in an alkaline aqueous solution as a binder (binder) can be used in the colored photosensitive resin composition, .

In addition, an organic solvent having a proper drying property can be used as a solvent (a dispersion medium of the pigment) used in the organic pigment nano-particle dispersion composition and the colored photosensitive resin composition, and the requirement can be satisfied also in terms of drying after coating.

The colored photosensitive resin composition of the present invention contains a dispersion of the organic pigment nanoparticles, a binder, a monomer or an oligomer, and a photopolymerization initiator or a photopolymerization initiator system. Hereinafter, each component of the colored photosensitive resin composition will be described.

The procedure for producing the organic pigment nanoparticles and the dispersion thereof has already been described in detail. The content of the pigment nanoparticles is preferably from 3 to 90% by mass, more preferably from 20 to 80% by mass, based on the total solid content in the colored photosensitive resin composition (the total solid content in the present invention means the total amount of the composition excluding the organic solvent) , And still more preferably from 25 to 60 mass%. If this amount is too large, the viscosity of the dispersion liquid may increase, which may cause problems in manufacturing suitability. If it is too small, the coloring power is not sufficient. The pigment nano-particles (pigment particles) functioning as a coloring agent preferably have a particle size of 0.1 탆 or less, particularly 0.08 탆 or less. It may be used in combination with an ordinary pigment for coloring. The pigment described above can be used.

The monomer or oligomer is preferably a multifunctional monomer having two or more ethylenically unsaturated double bonds and subjected to addition polymerization by light irradiation. Examples of such monomers and oligomers include compounds having at least one ethylenically unsaturated group capable of addition polymerization in the molecule and having a boiling point of 100 DEG C or higher at normal pressure. Examples thereof include monofunctional acrylates such as dipentaerythritol hexa (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate, Rate; (Meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylol ethane triacrylate, trimethylol propane tri (meth) acrylate, trimethylol propane diacrylate, neopentyl glycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (metha) acrylate, dipentaerythritol penta Acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; Polyfunctional acrylate or polyfunctional methacrylate such as ethylene oxide or propylene oxide added to a polyfunctional alcohol such as trimethylol propane or glycerin and (meth) acrylate. Also, as described in general formulas (1) and (2) in Japanese Patent Application Laid-Open No. 10-62986, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then forming a (meth) .

The urethane acrylates described in JP-A-48-41708, JP-A-50-6034 and JP-A-51-37193; Polyester acrylates described in JP-B-48-64183, JP-A-49-43191 and JP-B-52-30490; Polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid.

Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (metha) acrylate and dipentaerythritol penta (meth) acrylate are preferable.

In addition, "polymerizable compound B" described in Japanese Patent Application Laid-Open No. 11-133600 is also preferable.

The monomer or oligomer may be used alone or in admixture of two or more. The content of the colored photosensitive resin composition relative to the total solid content is generally from 5 to 50 mass%, and preferably from 10 to 40 mass%. If the amount is too large, control of developability becomes difficult, which is a problem in manufacturing suitability. If it is too small, the curing force at the time of exposure is insufficient.

The binder is preferably a binder having an acidic group and may be added at the time of preparing the inkjet ink for a color filter or the colored photosensitive resin composition, but it is also preferable to add the pigment at the time of preparing the pigment nanoparticle dispersion composition or at the time of forming the pigment nanoparticle . An organic pigment solution and an organic pigment solution may be added to add a binder to either or both of the poor solvent for producing the pigment nanoparticles. It is also preferable to add the binder solution to the other system at the time of forming the pigment nanoparticles.

As the binder, an alkali-soluble polymer having a polar group such as a carboxylic acid group or a carboxylic acid group on the side chain is preferable. For example, Japanese Patent Application Laid-open No. 59-44615, Japanese Laid-Open Patent Publication No. 54-34327, Japanese Laid-Open Patent Publication No. 58-12577, Japanese Laid-Open Patent Publication No. 54-25957, Japanese Laid-Open Patent Publication No. 59-53836 Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like as described in Japanese Patent Application Laid-open No. 59-71048 . A cellulose derivative having a carboxylic acid group, a carboxylate, or the like in the side chain may also be used, and a cyclic acid anhydride may be further added to a polymer having a hydroxyl group. Particularly preferred examples thereof include copolymers of benzyl (meth) acrylate and (meth) acrylic acid, benzyl (meth) acrylate and poly (meth) acrylic acid and other monomers described in U.S. Patent No. 4,139,391 have.

The binder may be used alone or in the form of a composition for use with a conventional film-forming polymer. The amount of the binder to be added to 100 parts by mass of the pigment nanoparticles is generally from 10 to 200 parts by mass, preferably from 25 to 100 parts by mass Do.

In addition, in order to improve crosslinking efficiency, a polymerizable group may be present in the side chain, and UV curable resins, thermosetting resins and the like are also useful. Further, as the binder resin, an organic polymer polymer having a water-soluble atomic group in a part of the side chain can be used.

As a photopolymerization initiator or a photopolymerization initiator system (a photopolymerization initiator in the present invention refers to a mixture for expressing a photopolymerization initiating function by a combination of an egg, a plurality of compounds), there can be mentioned bisphenol polyketal dopyl Compounds described in U.S. Patent No. 2448828, aromatic acyloin compounds substituted with [alpha] -hydrocarbon described in U.S. Patent No. 2722512, U.S. Patent Nos. 3046127 and 2951758 A combination of a triarylimidazole dimer and a p-amino ketone described in the specification of U.S. Patent No. 3549367, a combination of a benzothiazole compound described in JP-B-51-48516 and a trihalomethyl compound described in JP- -s-triazine compounds, trihalomethyl-triazine compounds described in U.S. Patent No. 4239850, Trihaloalkyl described in Patent No. 4,212,976 specification and methyl oxadiazole compound. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole and triarylimidazole dimer are preferable.

In addition, as the polymerization initiator C described in JP 11-133600 A, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O- Hexafluorophosphorothio-trialkylphenylphosphonium salts, and the like can also be preferably used. Examples of the compound represented by the general formula (1) include, but are not limited to, 4'- (benzmercapto) benzoylhexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyloxide, have.

The photopolymerization initiator or the photopolymerization initiator system may be used singly or in combination of two or more types, but it is particularly preferable to use two or more types. When at least two kinds of photopolymerization initiators are used, the display characteristics, particularly, display irregularities can be reduced.

The content of the photopolymerization initiator or the photopolymerization initiator system based on the total solid content of the colored photosensitive resin composition is generally from 0.5 to 20% by mass, and preferably from 1 to 15% by mass. If the amount is too large, the sensitivity becomes too high and control becomes difficult. If it is too small, the exposure sensitivity becomes too low.

In the colored photosensitive resin composition, an organic solvent for preparing a resin composition (fourth solvent) may be further used in addition to the above components. Examples of the organic solvent include, but are not limited to, esters, ethers, and ketones. Among these solvents, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethylcarbitol acetate , Butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferably used as a solvent. These solvents may be used alone or in combination of two or more kinds. The high boiling point organic solvent may be used as the fourth solvent. For example, a solvent having a boiling point of 180 ° C to 250 ° C may be used as needed. The content of the fourth solvent is preferably 10 to 95% by mass relative to the total amount of the resin composition.

In addition, it is preferable that a suitable surfactant is contained in the colored photosensitive resin composition. As the surfactant, surfactants disclosed in JP-A-2003-337424 and JP-A-11-133600 are preferable. The content of the surfactant is preferably 5% by mass or less based on the total amount of the resin composition.

The colored photosensitive resin composition preferably contains a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl catechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole and phenothiazine. The content of the thermal polymerization inhibitor is preferably 1% by mass or less based on the total amount of the resin composition.

A colorant (dye, pigment) may be added to the colored photosensitive resin composition in addition to the colorant (pigment) as necessary. When a pigment is used in the colorant, it is preferably dispersed uniformly in the colored photosensitive resin composition, and therefore, it is preferable that the particle size is 0.1 탆 or less, particularly 0.08 탆 or less.

Specific examples of the dyes and pigments include pigments described in JP-A-2005-17716, JP-A-2005-361447, JP-A-2005-361447 and JP-A- The colorants described in JP-A-2005-17521 [0080] to [0088] can be preferably used. The content of the dye or pigment to be used as an auxiliary is preferably 5% by mass or less based on the total amount of the resin composition.

The colored photosensitive resin composition may contain an ultraviolet absorber if necessary. Examples of the ultraviolet absorber include salicylate, benzophenone, benzotriazole, cyanoacrylate, nickel chelate, hindered amine and the like in addition to the compounds described in JP-A-5-72724.

The content of the ultraviolet absorber is preferably 5% by mass or less based on the total amount of the resin composition.

In addition, in the colored photosensitive resin composition, in addition to the above-described additives, " adhesion aid " and other additives described in JP-A-11-133600 can be incorporated.

The color filter of the present invention is excellent in contrast. The contrast in the present invention indicates the ratio of the amount of transmitted light when the polarizing axis is parallel and perpendicular to the polarizing axis between two polarizing plates ("Seventh Color Optics Conference, 1990, 10.4" size TFT- LCD color filter, Ueki, Ozeki, Fukunaga, Yamanaka ").

The high contrast of the color filter means that it is possible to increase the discrimination of light and dark in combination with the liquid crystal, and it is a very important performance for the liquid crystal display to be replaced with the CRT.

When the color filter of the present invention is used for a television, the chromaticity of all monochromatic colors of red (R), green (G) and blue (B) by the F10 light source is the value described in the following table Target chromaticity "), and is preferably within a range of 5, more preferably within 3, particularly preferably within 2.

In the present invention, the chromaticity is measured by a microscopic spectrophotometer (OSP100 or 200, manufactured by Olympus Kogaku Co., Ltd.) and expressed as the xyy value of the xyz color system as a result of F10 light source field 2 degree. The difference from the target chromaticity is represented by the color difference of the La * b * color system.

The liquid crystal display device provided with the color filter of the present invention has a high contrast and a good depiction power such as a sharpness of black, and particularly preferably a VA mode. And can be preferably used as a liquid crystal display device of a large screen such as a notebook display or a television monitor. Further, the color filter of the present invention can be used in a CCD device, and exhibits excellent performance.

(Example)

Hereinafter, the present invention will be described in more detail based on embodiments, but the present invention is not limited to this.

(Synthesis Example-1) Synthesis of basic dispersion auxiliary agent

Thionyl chloride (20.0 parts by mass) was added to bromomodecanoic acid (10.0 parts by mass), and after refluxing for 1 hour, excess thionyl chloride was distilled off under reduced pressure. This was added dropwise to a solution of NMP (Wako Pure Chemical Industries, Ltd.) (100 parts by mass) in which 5-aminobenzimarazolone (7.0 parts by mass) and triethylamine (3.8 parts by mass) were dissolved and heated at 100 占 폚 for 1 hour. Water (200 parts by mass) was added, and the precipitated solid was collected by filtration and washed with water and methanol to obtain a BA-1 precursor (12.6 parts by mass) in a yield of 83%. A BA-1 precursor (5 parts by mass) was dissolved in NMP (40 parts by mass), and a 50% dimethylamine aqueous solution (20 parts by mass) was added and heated at 100 占 폚 for 3 hours. Methanol (100 parts by mass) was added, and the precipitated solid was collected by filtration and washed with methanol to obtain Example Compound BA-1 (3.5 parts by mass) at a yield of 78% (m.p.

^{1 H NMR (300MHz, DMSO-} d 6) δ1.2 (s, 12H), 1.2-1.4 (m, 2H), 1.5-1.6 (m, 2H), 2.0 (s, 6H), 2.1 (t, 2H ), 2.2 (t, 2H), 6.8 (d, IH), 7.0 (d, IH), 7.4 (s, IH), 9.6 (s, .

(3 parts by mass) synthesized in the same manner as in the synthesis of the above Exemplary Compound BA-1 was dissolved in NMP (24 parts by mass), and morpholine (6.5 parts by mass) was added thereto. And heated. Methanol (100 parts by mass) was added, and the precipitated solid was collected by filtration and washed with methanol to obtain an exemplified compound BA-2 (2.6 parts by mass) in a yield of 86% (m.p.

^{1 H NMR (300MHz, DMSO-} d 6) δ1.2 (s, 12H), 1.3-1.4 (m, 2H), 1.5-1.6 (m, 2H), 2.2-2.3 (m, 8H), 3.5 (t 1H), 6.8 (d, 1H), 7.0 (d, 1H), 7.4 (s, 1H), 9.6 (s, 1H), 10.4 (s, 1H), 10.5

(3 parts by mass) synthesized in the same manner as in the synthesis of the above Exemplary Compound BA-1 was dissolved in NMP (24 parts by mass), imidazole (5.1 parts by mass) was added thereto, Time heating. Acetonitrile (200 parts by mass) was added and the precipitated solid was collected by filtration and washed with acetonitrile to obtain Example Compound BA-3 (2.3 parts by mass) in a yield of 80% (mp 276-278 캜).

^{1 H NMR (300MHz, DMSO-} d 6) δ1.2 (s, 12H), 1.5-1.6 (m, 2H), 1.6-1.7 (m, 2H), 3.9 (t, 2H), 6.8 (d, 1H ), 6.9-7.0 (s, 1H), 10.4 (s, 1H), 7.2 (s, 1H).

Thionyl chloride (20.0 parts by mass) was added to bromohexanoic acid (7.4 parts by mass), and after refluxing for 1 hour, excess thionyl chloride was distilled off under reduced pressure. This was added dropwise to a solution of NMP (100 parts by mass) in which 5-aminobenzimarazanol (7.0 parts by mass) and triethylamine (3.8 parts by mass) were dissolved and heated at 100 占 폚 for 1 hour. Water (200 parts by mass) was added and the precipitated solid was collected by filtration and washed with water to obtain a BA-4 precursor (12.0 parts by mass) in a yield of 88%. A BA-4 precursor (5 parts by mass) was dissolved in NMP (46 parts by mass), 50% dimethylamine aqueous solution (22 mass parts) was added and the mixture was heated at 100 占 폚 for 3 hours. Acetonitrile (100 parts by mass) was added, and the precipitated solid was collected by filtration and washed with acetonitrile to obtain Example Compound BA-4 (3.4 parts by mass) in a yield of 85% (m.p.

^{1 H NMR (300MHz, DMSO-} d 6) δ1.2-1.3 (m, 2H), 1.3-1.4 (m, 2H), 1.5-1.6 (m, 2H), 2.0 (s, 6H), 2.1 (t (S, 2H), 2.2 (t, 2H), 6.8 (d, IH), 7.0 (d, IH), 7.4 1H).

Thionyl chloride (20.0 parts by mass) was added to bromomodecanoic acid (10.0 parts by mass), and after refluxing for 1 hour, excess thionyl chloride was distilled off under reduced pressure. This was added dropwise to a solution of NMP (100 parts by mass) in which 2-aminobenzimidazole (5.0 parts by mass) and triethylamine (3.8 parts by mass) were dissolved and heated at 100 占 폚 for 3 hours. Water (200 parts by mass) was added, and the precipitated solid was collected by filtration and washed with water to obtain a BA-5 precursor (11.5 parts by mass) at a yield of 80%. A BA-5 precursor (5 parts by mass) was dissolved in NMP (43 parts by mass), 50% dimethylamine aqueous solution (21 parts by mass) was added thereto, and the mixture was heated at 100 占 폚 for 3.5 hours. Water (100 parts by mass) was added, and the precipitated solid was collected by filtration and washed with water to obtain Example Compound BA-5 (4.0 parts by mass) in a yield of 88% (mp 137-139 ° C).

^{1 H NMR (300MHz, DMSO-} d 6) δ1.2-1.4 (m, 14H), 1.5-1.6 (m, 2H), 2.0 (s, 6H), 2.1 (t, 2H), 2.4 (t, 2H ), 6.8 (d, 1H), 7.0-7.1 (m, 2H), 7.4-7.5 (m, 2H).

Thionyl chloride (20.0 parts by mass) was added to bromomodecanoic acid (10.0 parts by mass), and after refluxing for 1 hour, excess thionyl chloride was distilled off under reduced pressure. This was added dropwise to a solution of NMP (100 parts by mass) in which 3-aminoanthraquinone (8.4 parts by mass) and triethylamine (3.8 parts by mass) were dissolved and heated at 100 占 폚 for 3 hours. Water (200 parts by mass) was added, and the precipitated solid was collected by filtration and washed with water to obtain a BA-6 precursor (15.0 parts by mass) in a yield of 85%. A BA-6 precursor (5 parts by mass) was dissolved in NMP (35 parts by mass), and a 50% dimethylamine aqueous solution (17 parts by mass) was added and heated at 100 占 폚 for 6.5 hours. The precipitated solid was collected by filtration with a 1: 1 acetonitrile-water (100 parts by mass) solution and washed with a 1: 1 acetonitrile-water solution to obtain Example Compound BA-6 (3.8 parts by mass) (Mp 176-178 < 0 > C).

^{1 H NMR (300MHz, DMSO-} d 6) δ1.2-1.3 (m, 14H), 1.6-1.7 (m, 2H), 2.0 (s, 6H), 2.1 (t, 2H), 2.4 (t, 2H ), 7.8-7.9 (m, 2H), 8.0-8.2 (m, 4H), 8.4 (s, 1H), 10.5 (s, 1H).

Thionyl chloride (20.0 parts by mass) was added to bromomodecanoic acid (10.0 parts by mass), and after refluxing for 1 hour, excess thionyl chloride was distilled off under reduced pressure. This was added dropwise to a solution of NMP (100 parts by mass) in which 5-aminouracil (4.8 parts by mass) and triethylamine (3.8 parts by mass) were dissolved and heated at 100 占 폚 for 3 hours. Water (200 parts by mass) was added, and the precipitated solid was collected by filtration and washed with water to obtain a BA-7 precursor (11.8 parts by mass) in a yield of 84%. A BA-7 precursor (5 parts by mass) was dissolved in NMP (44 parts by mass), and a 50% dimethylamine aqueous solution (21 parts by mass) was added and heated at 100 占 폚 for 4 hours. Acetonitrile (100 parts by mass) was added and the precipitated solid was collected by filtration and washed with acetonitrile to obtain Example Compound BA-7 (3.0 parts by mass) in a yield of 66% (bp. 183-185 캜).

^{1 H NMR (300MHz, DMSO-} d 6) δ1.2 (s, 12H), 1.3-1.4 (m, 2H), 1.4-1.5 (m, 2H), 2.0 (s, 6H), 2.1 (t, 2H ), 2.3 (t, 2H), 8.0 (s, IH), 9.0 (s, IH).

≪ Example 1-1-1 >

45 parts by mass of Pigment CI Pigment Violet 23 (Hostaperm Violet RL-NF manufactured by Kurarianto Co., Ltd.) and 1,000 parts by mass of the above-mentioned Exemplified Compound BA-1 (manufactured by Tokyo Kasei Kogyo Co., Ltd., 4.5 parts by mass) was added thereto to prepare a pigment solution A-1.

Separately, 4000 parts by mass of water was prepared as a poor solvent.

Here, the pigment solution A-1, which was controlled at 25 占 폚 and cooled to 80 占 폚 in a poor solvent stirred at 500 rpm by Gamma-type GK-0222-10 Lamondstar (trade name, manufactured by Fujisawa Yakuhin Co., -500 type large capacity non-pulsating pump (trade name, manufactured by Nippon Seimitsu Kabushiki Kaisha). Organic pigment particles were formed by injecting 220 ml at a flow rate of 200 ml / min into the poor solvent with the channel diameter of the transfer liquid pipe of the pigment solution A-1 and the diameter of the supply port being 2.2 mm to prepare a pigment dispersion A-1 . The particle size of the pigment dispersion was measured using NIKKISO NANOTRACE UPA-EX150 (trade name).

The pH of the pigment dispersion was measured by a pH test paper (manufactured by ADVANTEC CO., LTD.). The result was 1, and 48% sodium hydroxide aqueous solution was added until the pH was 9 to neutralize. The resulting aggregates were observed by an optical microscope.

The above-mentioned aggregates were filtered by a filter paper (manufactured by ADVANTEC, No. 2), and the time required for filtration at this time was measured. The filtered organic nano-pigment was washed with water (300 parts by mass).

A solution prepared by adding 80 parts by mass of the non-aqueous dispersing agent C-1 (the above-mentioned polymeric compound C-1) to 300 parts by mass of ethyl lactate was added to the pigment nanoparticle concentrated paste and stirred with a dissolver at 1500 rpm for 60 minutes And 25 parts by mass of ethyl acetate were added and stirred with a dissolver at 500 rpm for 10 minutes to obtain a pigment nanoparticle-derived ethyl acetate dispersion A-1. The organic pigment powder A-1 of the present invention was obtained by removing the solvent of the pigment nano-particle ethyl ester dispersion A-1 by an evaporator.

Using the organic pigment powder A-1, a pigment dispersion composition A-1 having the following composition was prepared.

1 part by mass of the above-mentioned organic pigment powder A-1

1,3-butylene glycol diacetate 4 parts by mass

The pigment-dispersed composition A-1 having the above composition was dispersed for 1 hour at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm by Motor Mill M-50 (manufactured by Eiger Japan Co.).

The obtained pigment dispersion composition was evaluated in the following manner. The results are shown in Table 1.

(1) Average particle size of aqueous dispersion of organic nanoparticles

The number average particle size was measured using UPA-EX150 manufactured by NIKKISO Corporation.

(2) Diameter of agglomerate

The agglomerate was observed by an optical microscope, and the diameter of agglomerate was measured with reference to the separately observed standard. With respect to the diameter of the aggregate referred to herein, the length of the end of the agglomerate was measured, and the longest part of the aggregate was defined as the diameter. The agglomerates referred to here are nano particles, which are primary particles that can not be seen by the naked eye, are gathered together and grown to become secondary particles.

(3) Filtration time

The filtration time per 1 g of the pigment was measured by filtration under reduced pressure using an aspirator using a nutsche having a diameter of 9 cm and a filter paper (manufactured by Adovan Tech, No. 2 (trade name)).

(4) Contrast evaluation

Each of the obtained Pigment Dispersion Compositions A-1 to F-1 was coated on a glass substrate to a thickness of 2 占 퐉 to prepare samples. (FWL18EX-N manufactured by Toshiba Latec Co., Ltd.) was used as a backlight unit, and a polarizing plate (polarizer HLC2-2518 manufactured by Sanritz Co., Ltd.) A sample was placed, and the amount of transmitted light when the polarization axis was parallel and vertical was measured, and the ratio was used as a contrast ("7th Color Optics Conference in 1990, color filter for 512 color display 10.4" size TFT- Ueki, Ozeki, Fukunaga, and Yamanaka "). Two polarizing plates, a sample, and a chromaticity luminance meter were installed at a position of 13 mm from the backlight, a polarizer was placed at a position of 40 mm to 60 mm, a cylinder of 11 mm in diameter and 20 mm in length, And the transmitted light was measured by a color luminance meter provided at a position of 400 mm through a polarizing plate provided at a position of 100 mm. The measurement angle of the color luminance meter was set to 2 degrees. The light amount of the backlight was set so that the luminance when the two polarizing plates were placed on the parallel Nicole with no sample installed was 1280 cd / m 2.

≪ Example 1-1-2 &

The same procedure as in Example 1-1-1 was carried out except that the Exemplary Compound BA-1 of Example 1-1-1 was changed to Exemplary Compound BA-6. The obtained non-aqueous dispersion of organic nanoparticles is also referred to as pigment-dispersed composition B-1. The evaluation results of the pigment dispersion composition B-1 were evaluated in the same manner as in Example 1-1-1.

<Example 1-1-3>

The same procedure as in Example 1-1-1 was carried out except that the Exemplary Compound BA-1 of Example 1-1-1 was changed to Exemplary Compound BA-7. The obtained non-aqueous dispersion of organic nanoparticles is also referred to as a pigment dispersion composition C-1. The pigment dispersion composition C-1 was subjected to the same evaluation test as in Example 1-1-1, and the results are shown in Table 1.

<Example 1-1-4>

Polyvinyl pyrrolidone (K-25, trade name, manufactured by Wako Pure Chemical Industries, Ltd., 90 parts by mass) was added together with the above Exemplary Compound BA-1 of Example 1-1-1, An operation was performed. The obtained non-aqueous dispersion of organic nanoparticles is also referred to as a pigment dispersion composition D-1. The evaluation results of the pigment dispersion composition D-1 were evaluated in the same manner as in Example 1-1-1.

&Lt; Comparative Example 1-1-1 &

Except that polyvinyl pyrrolidone (K-25, trade name, manufactured by Wako Pure Chemical Industries, Ltd., 90 parts by mass) was used instead of the polymer compound BA-1 in Example 1-1-1, The same operation as in Example 1-1-1 was carried out except that a methacrylic acid / methacrylic acid benzyl copolymer was used. The obtained non-aqueous dispersion of organic nanoparticles is also referred to as pigment-dispersed composition E-1. The pigment dispersion composition E-1 was subjected to the same evaluation test as in Example 1-1-1, and the results are shown in Table 1.

<Reference Example 1-1-1>

The aqueous pigment dispersion was adjusted by the same procedure as in Example 1-1-1 and isolated without pH manipulation to obtain a dispersion composition F-1. The filtration time at this time was evaluated. The results are shown in Table 1.

As shown in Table 1, according to the basic dispersion aid of the present invention, it is possible to realize a high contrast in a non-aqueous dispersion obtained by coagulating fine particles once in an aqueous dispersion and switching the medium with an organic solvent to redisperse the dispersion, It is possible to remarkably reduce the isolation time and significantly improve the characteristics and productivity of the desired dispersion and color filter.

&Lt; Example 1-2 >

Hereinafter, a method of producing a colored photosensitive resin composition and a color filter will be described.

[Formation of black (K) image]

The alkali-free glass substrate was cleaned by an UV cleaning device, then cleaned with a detergent using a detergent, and further ultrasonically washed with ultrapure water. The substrate was heat treated at 120 ° C for 3 minutes to stabilize the surface state.

The substrate was cooled and the temperature was adjusted to 23 캜. Thereafter, a colored photosensitive resin composition K1 having the composition shown in the following Table 2 was applied by means of a coater for a glass substrate having a slit-shaped nozzle (product name: MH-1600, manufactured by F. did. Then, a VCD (vacuum drying apparatus; A part of the solvent was dried for 30 seconds by removing the fluidity of the coating layer and then prebaked at 120 캜 for 3 minutes to obtain a photosensitive resin layer K1 having a thickness of 2.4 占 퐉.

A distance between the exposure mask surface and the photosensitive resin layer in a state in which the substrate and the mask (quartz exposure mask having an image pattern) are vertically set by a proximity type exposure device having an ultra-high pressure mercury lamp (manufactured by Hitachi High-Tech Denki Engineering Co., Ltd.) Was set to 200 mu m and pattern exposure was performed at an exposure amount of 300 mJ / cm &lt; 2 &gt;.

Then, pure water was sprayed by a shower nozzle to uniformly wet the surface of the photosensitive resin layer K1, and then the surface of the photosensitive resin layer K1 was uniformly wetted with a KOH-based developer (KOH, containing a nonionic surfactant, trade name: CDK-1, manufactured by Fuji Film Electronics Materials Co., Ltd.) At 23 캜 for 80 seconds, and at a flat nozzle pressure of 0.04 MPa to obtain a patterned image. Subsequently, ultra pure water was jetted at a pressure of 9.8 MPa by means of an ultra high pressure cleaning nozzle to remove residues to obtain an image K of black (K). Then, it was heat-treated at 220 DEG C for 30 minutes.

[Formation of red (R) pixel]

On the substrate on which the image K was formed, a colored photosensitive resin composition R1 having the composition shown in the following Table 3 was used, and the heat-treated pixel R was formed in the same process as the formation of the black (K) image. The film thickness of the photosensitive resin layer R1 and the application amounts of the pigments (C. I. P. R. 254 and C. I. P. R. 177) are shown below.

Photosensitive resin film thickness (占 퐉) 1.60

Pigment application amount (g / m &lt; 2 &gt;) 1.00

C. I. P. R. 254 Application amount (g / m 2) 0.70

C. I. P. R. 177 Application amount (g / m 2) 0.30

[Formation of green (G) pixel]

A pixel G which was heat-treated in the same process as the formation of the black (K) image was formed on the substrate on which the image K and the pixel R were formed using the colored photosensitive resin composition G1 having the composition shown in Table 4 below. The film thickness of the photosensitive resin layer G1 and the application amounts of the pigments (C. I. P. G. 36 and C. I. P. Y. 150) are shown below.

Photosensitive resin film thickness (占 퐉) 1.60

Pigment application amount (g / m &lt; 2 &gt;) 1.92

C. I. P. G. 36 Application amount (g / m 2) 1.34

C. I. P. Y. 150 Application amount (g / m 2) 0.58

[Formation of Blue (B) Pixel]

A color photosensitive resin composition B1 having the composition shown in the following Table 5 was used for the substrate on which the image K, the pixel R and the pixel G were formed, and the heat-treated pixel B was formed by the same process as the formation of the black (K) A desired color filter A was obtained.

The film thickness of the photosensitive resin layer B1 and the application amounts of the pigments (C. I. P. B. 15: 6 and C. I. P. V. 23) are shown below.

Photosensitive resin film thickness (占 퐉) 1.60

Pigment application amount (g / m 2) 0.75

C. I. B. B. 15: 6 Application amount (g / m 2) 0.45

C. I. P. V. 23 Application amount (g / m 2) 0.30

Here, the preparation of the colored photosensitive resin compositions K1, R1, G1 and B1 described in Tables 2 to 5 will be described in more detail.

The colored photosensitive resin composition K1 was obtained by weighing K pigment dispersion 1 and propylene glycol monomethyl ether acetate in an amount as shown in Table 2, mixing at a temperature of 24 占 폚 (占 2 占 폚), stirring at 150 rpm for 10 minutes, 2, a hydroquinone monomethyl ether, a DPHA solution, a polymerization initiator A (2,4-bis (trichloromethyl) -6- [4'-N, N-bisethoxycar 3-bromophenyl] -s-triazine) and Surfactant 1 were weighed and added in this order at a temperature of 25 DEG C (+/- 2 DEG C) And stirring at 150 rpm for 30 minutes.

The compositions shown below in Table 2 are shown below for the following components.

&Lt; K Pigment Dispersion 1 >

Carbon black (trade name: Nipex 35, manufactured by Degussa Japan Co., Ltd.) 13.1 parts by mass

Pigment Dispersion A 0.65 parts by mass (Compound C-1 synthesized in accordance with Japanese Unexamined Patent Application Publication No. 2000-239554)

(Refer to Japanese Patent Application Laid-Open No. 2000-239554).

Polymer (random copolymer of benzyl methacrylate / methacrylic acid = 72/28 mole ratio, molecular weight: 3.7 million) 6.72 parts by mass

Propylene glycol monomethyl ether acetate 79.53 parts by mass

<Surfactant 1>

[Megapac F-780-F (manufactured by Dainippon Ink and Chemicals, Incorporated)]

40 parts by mass of C ₆ F ₁₃ CH ₂ CH ₂ OCOCH = CH ₂

H (OCH (CH ₃ ) CH ₂ ) ₇ OCOCH = CH ₂ : 55 parts by mass

H (OCH ₂ CH ₂ ) ₇ OCOCH═CH ₂ : 5 parts by mass (molecular weight: 30,000) 30 parts by mass

<Binder 2>

Polymer (benzyl methacrylate / methacrylic acid = 78/22 mole ratio

         , A molecular weight of 3.8 million) 27 parts by mass

Propylene glycol monomethyl ether acetate 73 parts by mass

<DPHA liquid>

Dipentaerythritol hexaacrylate (containing 500ppm of polymerization inhibitor MEHQ, trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) 76 parts by mass

Propylene glycol monomethyl ether acetate 24 parts by mass

The colored photosensitive resin composition R1 was obtained by weighing the R pigment dispersion 1, the R pigment dispersion 2 and the propylene glycol monomethyl ether acetate in an amount as shown in Table 3 at a temperature of 24 ° C (± 2 ° C) And then the mixture was stirred at the same temperature for 1 hour, and then methyl ethyl ketone, binder 1, DPHA solution and polymerization initiator B (2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole Sol), a polymerization initiator A (2,4-bis (trichloromethyl) -6- [4 '- (N, N-bisethoxycarbonylmethyl) amino-3'-bromophenyl] ) And phenothiazine were weighed and added in this order at a temperature of 24 ° C (± 2 ° C), and the mixture was stirred at 150 rpm for 30 minutes. Then, the surfactant 1 in the amount shown in Table 3 was weighed, 2 占 폚), stirred at 30 rpm for 5 minutes, and filtered through a nylon mesh # 200.

Of the compositions shown in Table 3, R pigment dispersions 1 and 2 were each prepared so as to have a composition in the following mass amounts by using the method described in Example 1 of International Publication WO 2006/121016 pamphlet.

&Lt; R pigment dispersion 1 >

10 parts by mass of C. I. P. R. 254 {trade name: Irgaphor Red BT-CF manufactured by Ciba Specialty Chemicals)

Pigment dispersant A 1 part by mass

Polymer (benzyl methacrylate / methacrylic acid = 72/28 mole ratio

                  , Molecular weight: 30,000) 10 parts by mass

Propylene glycol monomethyl ether acetate (79 parts by weight)

Polymer (benzyl methacrylate / methacrylic acid = 72/28 mole ratio

                  , Molecular weight: 30,000) 15 parts by mass

Propylene glycol monomethyl ether acetate 62.5 parts by mass

<Binder 1>

Polymers (benzyl methacrylate / methacrylic acid / methyl methacrylate

= 38/25/37 molar ratio, molecular weight: 40,000) 27 parts by mass

Propylene glycol monomethyl ether acetate 73 parts by mass

&Lt; R pigment dispersion 2 >

C. I. P. R. 177 {trade name: Cromophtal Red A2B, manufactured by Ciba Specialty Chemicals)} 22.5 parts by mass

Polymer (benzyl methacrylate / methacrylic acid = 72/28 mole ratio

                 , Molecular weight: 30,000) 15 parts by mass

Propylene glycol monomethyl ether acetate 62.5 parts by mass

The colored photosensitive resin composition G1 was obtained by weighing the G pigment dispersion 1, the Y pigment dispersion 1 and the propylene glycol monomethyl ether acetate in an amount as shown in Table 4 at a temperature of 24 占 폚 (占 2 占 폚) And then the mixture was stirred. Then, a solution of methyl ethyl ketone, cyclohexanone, binder 2, DPHA solution and polymerization initiator B (2-trichloromethyl-5- (p-styrylstyryl) Oxadiazole), polymerization initiator A (2,4-bis (trichloromethyl) -6- [4 '- (N, N-bisethoxycarbonylmethyl) amino-3'- (2 占 폚) were added in this order and stirred at 150 rpm for 30 minutes. Further, the surfactant 1 in an amount as shown in Table 4 was weighed, and the temperature Added at 24 占 폚 (占 2 占 폚), stirred at 30 rpm for 5 minutes, and filtered through a nylon mesh # 200.

Among the compositions shown in Table 4, "G-Pigment Dispersion 1", "Trade name: GT-2" manufactured by FUJIFILM ELECTRONICS MATERIALS CO., LTD. Was used. Y pigment dispersion 1 was "trade name: CF Yellow EX3393" manufactured by Mikuni Shikiso Co., Ltd.

The colored photosensitive resin composition B1 was prepared by first weighing the amounts of B pigment dispersion 1, V pigment dispersion composition 1 and propylene glycol monomethyl ether acetate as shown in Table 5 at a temperature of 24 캜 (占 2 占 폚) Followed by stirring. Then, a solution of methyl ethyl ketone, binder 3, DPHA solution and polymerization initiator B (2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole And the mixture was stirred at 150 rpm for 30 minutes at a temperature of 40 占 폚 (占 2 占 폚), and further stirred at an interface of the amount shown in Table 5 Active agent 1 was weighed, added at a temperature of 24 占 폚 (占 2 占 폚), stirred at 30 rpm for 5 minutes, and filtered through a nylon mesh # 200.

Of the compositions shown in Table 5, the B pigment dispersion 1 was "trade name: CF Blue EX3357" manufactured by Mikuni Shikiso Co., Ltd. V pigment dispersion composition 1, the pigment dispersion composition A-1 was used.

The composition of the binder 3 is as follows.

<Binder 3>

27 parts by mass of a polymer (random copolymer of benzyl methacrylate / methacrylic acid / methyl methacrylate = 36/22/42 molar ratio, molecular weight: 3.7 million)

Propylene glycol monomethyl ether acetate 73 parts by mass

The color filter A-1 was produced as described above. 1 to E-2 were prepared in the same manner as the color filter A-1 except that the pigment dispersion composition A-1 used as the V pigment dispersion composition 1 in the color filter A-1 was replaced with B-1 to E-1, -1.

Table 6 shows the results of measuring the contrast for each color filter in the same manner as the measurement of the contrast.

From the above results, all of the color filters of the present invention have high contrast and are good color filters.

&Lt; Example 1-3 >

A liquid crystal display was manufactured using the color filters A-1 to E-1, and the display characteristics were evaluated.

(Formation of ITO electrode)

The glass substrate on which the color filter was formed was placed in a sputtering apparatus, and ITO (indium tin oxide) having a thickness of 1300 Å was vacuum deposited on the entire surface at 100 ° C. and then annealed at 240 ° C. for 90 minutes to crystallize the ITO transparent electrode.

(Formation of spacer)

A spacer was formed on the ITO transparent electrode prepared in the same manner as the spacer forming method described in [Example 1] of Japanese Patent Application Laid-Open No. 2004-240335.

(Formation of Liquid Crystal Alignment Control Projections)

A liquid crystal alignment control projection was formed on the ITO transparent electrode on which the spacer was formed by using the following coating liquid for a positive-type photosensitive resin layer.

However, the following methods were used for the exposure, developing and baking steps.

A proximity photolithography machine (manufactured by Hitachi High-Tech Engineering Co., Ltd.) was arranged so that a predetermined photomask was located at a distance of 100 mu m from the surface of the photosensitive resin layer, and the photomask was irradiated with ultraviolet light at an irradiation energy of 150 mJ / Proximity was exposed.

Subsequently, a 2.38% aqueous solution of tetramethylammonium hydroxide was developed by spraying the substrate with a shower type developing device at 33 占 폚 for 30 seconds. Thus, the unnecessary portion (exposed portion) of the photosensitive resin layer was developed and removed to obtain a substrate for a liquid crystal display having a liquid crystal alignment control protrusion formed of a photosensitive resin layer patterned in a desired shape on a color filter side substrate.

Subsequently, the liquid crystal display device substrate having the projection for controlling liquid crystal alignment control was baked at 230 캜 for 30 minutes to form a cured liquid crystal alignment control projection on the substrate for a liquid crystal display.

&Lt; Prescription of Coating Liquid for Positive Photosensitive Resin Layer >

Positive type resist liquid (FH-2413F manufactured by Fuji Film Electronics Materials Co., Ltd.): 53.3 parts by mass

Methyl ethyl ketone: 46.7 parts by mass

Megapac F-780F (manufactured by Dainippon Ink and Chemicals, Incorporated): 0.04 parts by mass

An alignment film made of polyimide was further formed on the substrate for a liquid crystal display obtained above.

Thereafter, an epoxy resin sealant is printed at a position corresponding to the black matrix outer frame formed around the pixel groups of the color filter, and the liquid crystal for the MVA mode is dropped and adhered to the counter substrate, The substrate was heat treated to cure the sealant. On both sides of the liquid crystal cell thus obtained, a polarizing plate HLC2-2518 manufactured by SANRITZ Co., Ltd. was attached. Subsequently, a backlight of a three-wavelength cold cathode tube light source (FWL18EX-N manufactured by Toshiba Latech Co., Ltd.) was constituted, and was disposed on the back surface side of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display device.

It was confirmed that the liquid crystal display device using the color filter of the present invention exhibited excellent black clarity and blue color rendering power and good display characteristics for the liquid crystal display device using the color filter of the comparative example.

(Synthesis Example 2) Synthesis of acidic compound

5-Aminobenzuimadazolone (30.0 parts by mass) was dissolved in NMP (manufactured by Wako Pure Chemical Industries, Ltd.) (160 parts by mass), and glutaric anhydride (18.6 parts by mass) was added thereto. The mixture was stirred at room temperature for 1.5 hours. Water (100 parts by mass) was added, and the precipitated solid was collected by filtration and washed with water and methanol to obtain Example Compound A-1 (39 parts by mass) in a yield of 80% (m.p.

^{1 H NMR (300MHz, DMSO-} d 6) δ1.7-1.9 (m, 2H), 2.2-2.4 (m, 4H), 6.8 (d, 1H), 7.0 (d, 1H), 7.4 (s, 1H ), 9.7 (s, 1H), 10.4 (s, 1H), 10.5 (s, 1H).

5-Aminobenzimarazolone (10.0 parts by mass) was dissolved in NMP (55 parts by mass), diglycolic acid anhydride (6.3 parts by mass) was added thereto, and the mixture was stirred at room temperature for 1 hour. Water (100 parts by mass) was added and the precipitated solid was collected by filtration and washed with water and methanol to obtain Exemplary Compound A-2 (9.8 parts by mass) in a yield of 60% (mp 290-291 ° C (dec)) .

^{1 H NMR (300MHz, DMSO-} d 6) δ4.1 (s, 2H), 4.2 (s, 2H), 6.8 (d, 1H), 7.1 (d, 1H), 7.5 (s, 1H), 9.7 ( s, 1 H), 10.4 (s, 1 H), 10.5 (s, 1 H).

5-Aminobenzimidazole (10.0 parts by mass) was dissolved in NMP (75 parts by mass), glutaric anhydride (8.6 parts by mass) was added thereto, and the mixture was heated at 60 占 폚 for 6 hours. Water (100 parts by mass) was added, and the precipitated solid was collected by filtration and washed with water and methanol to obtain Example Compound A-4 (9.8 parts by mass) in a yield of 60% (m.p.

^{1 H NMR (300MHz, DMSO-} d 6) δ1.8-1.9 (m, 2H), 2.2-2.3 (m, 2H), 2.4-2.5 (m, 2H), 7.0-7.1 (m, 2H), 7.4 -7.5 &lt; / RTI &gt; (m, 2H).

5-Aminouracil (10.0 parts by mass) was dissolved in NMP (80 parts by mass), glutaric anhydride (9.0 parts by mass) was added thereto, and the mixture was heated at 60 占 폚 for 6 hours. Water (100 parts by mass) was added, and the precipitated solid was collected by filtration and washed with water to obtain Exemplary Compound A-5 (12.5 parts by mass) in a yield of 66% (m.p. 265-267 ° C).

^{1 H NMR (300MHz, DMSO-} d 6) δ1.7-1.8 (m, 2H), 2.2-2.3 (m, 2H), 2.3-2.4 (m, 2H), 8.0 (d, 1H), 9.0 (s , 1H), 10.8 (brs, 1H), 11.4 (s, 1H), 12.0 (brs, 1H).

&Lt; Example 2-1-1 >

C.I. Pigment Red 254 (45 parts by mass) and Example Compound A-1 (4.5 parts by mass) were added to dimethylsulfoxide (DMSO) (953 parts by mass) and stirred. A 28 mass% sodium methoxide methanol solution (30 parts by volume) was added to this solution to prepare a pigment solution A-2. On the other hand, water (4000 parts by mass) was prepared as a pigment-insoluble solvent B.

The above pigment-insoluble solvent B was added to the pigment-insoluble solvent B while stirring at 500 rpm by Gamma-type (trade name) GK-0222-10 manufactured by Seiyakuko G. Fujisawa at 30 ° C, and the pigment solution A- And injected at a flow rate of 100 mL / min by a NP-KX-500 high-capacity non-pulsating pump (trade name) manufactured by a company to crystallize the organic pigment nanoparticles to obtain a water-soluble organic nanometer aqueous dispersion. The particle size of the pigment dispersion was measured using a nano-track UPA-EX150 manufactured by Nikkiso Corporation.

The pH of this pigment dispersion was measured by a pH test paper (manufactured by ADVANTEC CO., LTD.) And found to be 12, which was neutralized by adding concentrated hydrochloric acid until the pH reached 3. The resulting aggregates were observed by an optical microscope.

The aggregates were collected by filtration using a filter paper (manufactured by ADVANTEC, No. 2), and the time required for filtration at this time was measured. The filtered organic nano-pigment was washed with water (300 parts by mass).

A solution prepared by adding 80 parts by mass of the non-aqueous dispersing agent C-1 (the above-mentioned polymeric compound C-1) to 300 parts by mass of ethyl lactate was added to the pigment nanoparticle concentrated paste and stirred with a dissolver at 1500 rpm for 60 minutes And 25 parts by mass of ethyl acetate were added and stirred again with a dissolver at 500 rpm for 10 minutes to obtain a pigment nanoparticle-derived ethyl acetate dispersion A-2. The organic pigment powder A-2 of the present invention was obtained by removing the solvent of the above pigment nanoparticle ethylacetate dispersion A-2 by an evaporator.

Using the organic pigment powder A-2, a pigment dispersion composition A-2 having the following composition was prepared.

1 part by mass of the above-mentioned organic pigment powder A-2

4 parts by mass of 1-methoxy-2-propyl acetate

The pigment-dispersed composition A having the above composition was dispersed for 1 hour at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm by Motor Mill M-50 (manufactured by Eiger Japan Co.) to obtain a pigment-dispersed composition A- .

The obtained pigment dispersion composition was evaluated in the same manner as in Example 1-1-1. The results are shown in Table 7.

&Lt; Example 2-1-2 &

The same operation as in Example 2-1-1 was carried out using the following non-aqueous dispersant C-9 (the above-mentioned polymeric compound C-9) instead of the non-aqueous dispersant C-1 in Example 2-1-1. The obtained non-aqueous dispersion of organic nanoparticles is also referred to as a pigment dispersion composition B-2. Table 7 shows the results of the evaluation tests conducted in the same manner as in Example 2-1-1 for the pigment dispersion composition B-2.

&Lt; Example 2-1-3 >

Polyvinyl pyrrolidone (K-25, trade name, manufactured by Wako Pure Chemical Industries, Ltd., 90 parts by mass) was also added during the addition of the above Exemplary Compound A-1 of Example 2-1-2, Was carried out. The non-aqueous dispersion of the obtained organic nanoparticles is also referred to as a pigment dispersion composition C-2. Table 7 shows the results of the evaluation tests of the pigment dispersion composition C-2 which are the same as those in Example 2-1-1.

&Lt; Example 2-1-4 >

The same operation as in Example 2-1-1 was carried out using A-4 instead of the above-mentioned Exemplary Compound A-1 in Example 2-1-1. The obtained non-aqueous dispersion of organic nanoparticles is also referred to as pigment-dispersed composition D-2. Table 7 shows the results of the evaluation tests of the pigment dispersion composition D-2 which are the same as those in Example 2-1-1.

&Lt; Comparative Example 2-1-1 >

(K-25, trade name, product of Wako Pure Chemical Industries, Ltd., 90 parts by mass) was used instead of the above-mentioned Exemplary Compound A-1 in Example 2-1-1, The same operation as in Example 2-1-1 was carried out except that methacrylic acid / benzyl methacrylate copolymer was used. However, the isolation was done by a filter (H010A 047A, trade name, manufactured by ADOBAN TECH CO., LTD.) Because the pigment was leaked from the filter paper (filter paper No. 2 (trade name) manufactured by Adobantech Co., Ltd.).

The obtained non-aqueous dispersion of organic nanoparticles is also referred to as pigment-dispersed composition E-2. The pigment dispersion composition E-2 was subjected to the same evaluation test as in Example 2-1-1, and the results are shown in Table 7.

&Lt; Comparative Example 2-1-2 &

An aqueous pigment dispersion was prepared by the same procedure as in Example 2-1-1, and isolated without pH manipulation, and the filtration time was evaluated. The results are shown in Table 7. The filtrate was filtered with a filter paper (filter paper No. 2 (trade name) manufactured by Adoban Tech Co., Ltd.) as a result of which the pigment had leaked. Instead, the filtrate was filtered through a filter (H010A047A, trade name, It was prepared.

As shown in Table 7, according to the acidic dispersion aid of the present invention, it is possible to realize a high contrast in a non-aqueous dispersion in which fine particles are once aggregated in an aqueous dispersion, and the medium is switched by switching the medium with an organic solvent, It is found that the isolation time is greatly reduced and the characteristics and the productivity of the desired dispersion and the color filter are remarkably improved.

&Lt; Example 2-2 >

A colored photosensitive resin composition and a color filter were produced in the same manner as in Example 1-2 except for the following points.

The following pigment dispersions were used.

&Lt; R pigment dispersion 1 >

· Pigment dispersion composition A-2

Polymer (benzyl methacrylate / methacrylic acid = 72/28 mole ratio

                     , Molecular weight: 30,000) 15 parts by mass

Propylene glycol monomethyl ether acetate 62.5 parts by mass

Further, CF blue EX3383 manufactured by Mikuni Shikiso Co., Ltd. was used as the V pigment dispersion in the composition shown in Table 5.

The color filter A-2 was produced as described above. The color filters B-2 to B-2 were prepared in the same manner as the color filter A-2 except that the pigment dispersion composition A-2 used as the R pigment dispersion 1 was replaced with B-2 to E-2 by the color filter A- E-2 was produced.

Table 8 shows the results of measuring the contrast for each color filter in the same manner as the measurement of the contrast.

From the above results, all of the color filters of the present invention have high contrast and are good color filters.

&Lt; Example 2-3 >

A liquid crystal display device was manufactured in the same manner as in Example 1-3 except that the color filters A-2 to E-2 were used to evaluate the display characteristics.

It was confirmed that the liquid crystal display device using the color filter of the present invention exhibited excellent sharpness of black color and red coloring ability and good display characteristics for the liquid crystal display device using the color filter of the comparative example.

Claims (22)

A dispersion aid characterized by being represented by the following general formula (1-1) or (1-2).

(In the formula (1-1), A represents a heterocyclic group bonded by a linking group and a nitrogen atom. X represents a divalent linking group having at least 2 to 20 carbon atoms. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. R ₁ and R ₂ may be connected to each other or may form a heterocyclic ring further containing at least one of an oxygen atom and a nitrogen atom. and m represents a natural number of 1 or 2.

(In the formula (1-2), A ¹¹ represents a heterocyclic group connected to a carbonyl group by a nitrogen atom. X ¹¹ represents a divalent alkylene, ether or polyether group having 2 to 10 carbon atoms which may have a substituent. The dispersion auxiliary according to claim 1, which is a basic dispersion auxiliary represented by the general formula (1-1). 3. The dispersion aid according to claim 2, wherein the basic dispersion auxiliary is represented by the following general formula (2-1).

Y represents an oxygen atom or a sulfur atom, l represents an integer of 0 or 1, n represents a natural number of 1 to 19. R represents an oxygen atom or a sulfur atom, R represents a heterocyclic group bonded by a linking group and a nitrogen atom, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and R ₁ and R ₂ may be connected to each other or may form a heterocyclic ring containing at least one of an oxygen atom and a nitrogen atom M represents a natural number of 1 or 2.) 4. The dispersion aid according to claim 2 or 3, wherein the dispersing agent is imparted to the organic pigment nanoparticles together with the non-aqueous dispersing agent in the non-aqueous dispersion obtained by switching the medium from the aqueous dispersion. An aqueous dispersion containing organic pigment nanoparticles, water, and a basic dispersion aid as described in claim 2 or 3: wherein the organic pigment nanoparticles are prepared by dissolving an organic pigment solution in a good solvent in an organic solvent, Wherein the organic pigment is precipitated as fine particles having a size of nanometer size in the presence of the basic dispersion aid in the mixture of the poor solvent for the organic pigment. The aqueous dispersion of organic pigment nanoparticles according to claim 5, wherein the average particle size of the primary particles of the organic pigment nanoparticles is 10 to 500 nm. An agglomerate of organic pigment nanoparticles characterized in that the pH of the aqueous dispersion according to claim 5 is changed so that the organic pigment nanoparticles can be redispersed. A non-aqueous dispersion of organic pigment nanoparticles characterized by releasing aggregation of the agglomerate according to claim 7 and redispersing the dispersion in a non-aqueous medium. 9. The non-aqueous dispersion of organic pigment nanoparticles according to claim 8, wherein the non-aqueous dispersion of organic pigment nanoparticles comprises an acidic group and at least one polymer compound having a number average molecular weight of 1,000 or more. A colored photosensitive resin composition characterized by comprising at least the non-aqueous dispersion according to claim 8, a binder, a monomer or oligomer, and a photopolymerization initiator or a photopolymerization initiator system. A color filter produced by using the colored photosensitive resin composition according to claim 10. A liquid crystal display device comprising the color filter according to claim 11. The dispersion aid according to claim 1, which is an acidic dispersion auxiliary represented by the general formula (1-2). 14. The dispersion aid according to claim 13, wherein a dispersing agent is imparted to the organic pigment nanoparticles together with the non-aqueous dispersing agent in the non-aqueous dispersion obtained by switching the medium from the aqueous dispersion. Wherein the organic pigment nanoparticle comprises an organic pigment solution in which an organic pigment is dissolved in a good solvent and an organic pigment solution in which the organic Wherein the organic pigment is precipitated as fine particles having a size of nanometer size in the presence of the acid dispersion auxiliary agent in the mixed solution. 16. The aqueous dispersion of organic pigment nanoparticles according to claim 15, wherein the average particle size of the primary particles of the organic pigment nanoparticles is 10 to 500 nm. An aggregate of organic pigment nanoparticles characterized in that the pH of the aqueous dispersion according to claim 15 or 16 is changed so that the organic pigment nanoparticles can be redispersed. A non-aqueous dispersion of organic pigment nanoparticles characterized in that aggregation of the aggregate according to claim 17 is released and redispersed in a non-aqueous medium. The non-aqueous dispersion of organic pigment nanoparticles according to claim 18, which comprises at least one polymer compound having a number average molecular weight of 1,000 or more. A colored photosensitive resin composition characterized by containing at least the non-aqueous dispersion according to claim 18, a binder, a monomer or oligomer, a photopolymerization initiator or a photopolymerization initiator system. A color filter produced by using the colored photosensitive resin composition according to claim 20. A liquid crystal display device comprising the color filter according to claim 21.