KR20080099208A - Method of producing organic pigment nanoparticle agglomerate and organic pigment nanoparticle nonaqueous dispersion, colored photosensitive resin composition containing the dispersion, and color filter using the same - Google Patents

Abstract

A method of producing organic pigment nanoparticle agglomerate and organic pigment nanoparticle nonaqueous dispersion is provided to manufacture a color filter coating solution, an organic pigment nanoparticle dispersion suitable for the inkjet ink, and the dispersion. The organic pigment nanoparticle nonaqueous dispersion has excellent disperibility and high contrast. An organic pigment nanoparticle agglomerate is prepared by reacting at least one organic low molecular compound having the molecular weight of 1000 or less and at least one organic high molecular compound having the molecular weight of 1000 or more to the organic pigment nanoparticle dispersed in the aqueous medium; and after cohering, isolating it. The organic pigment nanoparticle dispersed in the aqueous medium can be cohered by dissolving the organic low molecular compound and the organic high molecular compound with a solvent mixed in the aqueous medium and adding it in the aqueous medium.

Description

Manufacturing method of organic nano pigment particle aggregate and organic nano pigment particle non-aqueous dispersion, coloring photosensitive resin composition containing this dispersion, and color filter using the same RESIN COMPOSITION CONTAINING THE DISPERSION, AND COLOR FILTER USING THE SAME}

The present invention relates to a method for preparing an organic nano pigment particle non-aqueous dispersion obtained by phase-inverting an organic nano pigment particle aqueous dispersion to a non-aqueous medium. More specifically, the present invention is an organic nano pigment pigment which is a filterable aggregate of organic nano pigment particles in an organic nano pigment particle aqueous dispersion, which has been difficult to filter in the past, and is isolated by filtration and obtained by redispersing in a non-aqueous medium. It relates to a particle non-aqueous dispersion.

In recent years, research is being conducted to reduce the size of particles. In particular, studies are being conducted to reduce the size to a nanometer size (for example, in the range of 10 to 100 nm) that is difficult to manufacture by a grinding method, a precipitation method, or the like. In addition, it has been attempted to reduce the size to nanometer size and to make the particles highly monodisperse (in the present invention, monodisperse refers to an even particle diameter).

It is pointed out that the size of such nanometer-sized fine particles is located in the middle of larger bulk particles, smaller molecules or atoms, and is a size region which does not exist in the past, and can bring out unexpected new properties. In addition, as long as the monodispersity can be increased, it is also possible to stabilize the properties, and the possibility of such nanoparticles is expected in various fields, and it is widely used in biochemistry, new materials, electronic devices, light emitting display devices, printing, and medical. Research continues to be active in the field.

In particular, organic nanoparticles made of organic compounds have a high potential as functional materials because the organic compounds themselves have a variety. For example, polyimide has been used in many fields because of its chemical and mechanically stable materials, such as heat resistance, solvent resistance, and mechanical properties, and excellent electrical insulation. And polyimide is made into microparticles | fine-particles, the characteristic and shape which have polyimide are combined, and it is used in the wider field | area. For example, what is used as an additive of the powder toner for image formation etc. is proposed (patent document 1).

Among organic nanoparticles, organic pigments include, for example, paints, printing inks, electrophotographic toners, inkjet inks and color filters. These are important compounds that are indispensable in life. Among them, high performance is required, and pigments for ink jet inks and pigments for color filters are particularly important in practical use.

Dye has been used conventionally for the colorant of inkjet ink, but there exists a problem in water resistance and light resistance, and the pigment is used to improve this. The image obtained by the pigment ink has the advantage of being excellent in light resistance and water resistance as compared with the image by dye ink. However, it is difficult to make monodispersity high in the nanometer size which can be penetrated into the gap of the paper surface, and adhesiveness to paper is inferior.

In addition, with the high pixel of a digital camera, the thin film of the color filter used for optical elements, such as a CCD sensor, and a display element is calculated | required. Organic pigments are used for color filters, but since the thickness of the filter depends largely on the particle diameter of organic pigments, production of fine particles stable at a nanometer size level and monodisperse is required.

As to the method for producing organic particles, a gas phase method (sublimation of a sample in an inert gas atmosphere to recover the particles onto a substrate), a liquid phase method (for example, a sample dissolved in a good solvent is injected into a poor solvent controlled by stirring conditions or temperature). The reprecipitation method which obtains microparticles | fine-particles, the laser cutting method (the method which refine | miniaturizes a particle by irradiating and cutting a laser to the sample disperse | distributed in solution), etc. are researched. In addition, by these methods, production examples have been reported in which monodispersion is attempted at a desired size. Especially, the liquid phase method attracts attention as a manufacturing method of organic particle | grains excellent in simplicity and productivity (refer patent document 2, 3 etc.). The organic particles prepared by this liquid phase method can adjust the crystalline form and the particle surface properties by adjusting the precipitation conditions to the solvent type, the injection speed and the temperature, etc., and Patent Document 3 describes the crystalline form of quinacridone pigment as a poor solvent type. The example adjusted accordingly is described.

On the other hand, in terms of improving the dispersibility of particles, dispersion of organic pigments has been conventionally performed industrially using various dispersers (roll mills, ball mills, attritors, etc.), but the viscosity may increase by miniaturizing the particles. have. If the viscosity rises, it becomes difficult to take it out of the disperser, it becomes impossible to transport by pipeline, or it becomes gelatinized during storage and cannot be used. In order to solve these, although the addition of the dispersing agent which helps dispersion | distribution and the polymer which stabilizes dispersion | distribution is performed, sufficient effect cannot be acquired (refer nonpatent literature 1 etc.).

In addition, in the organic pigment dispersion for color filters, in order to increase the dispersibility, polymers or pigment dispersants which can impart the alkali developability and dispersion stability necessary for the production of color filters are added (for example, a patent). See Document 4. However, in these methods, dispersion takes a long time and the viscosity does not rise to meet the demand.

Moreover, the example which improved the dispersibility using the pigment particle prepared by the said liquid phase method is reported. In patent document 5, the example which prepared the pigment particle water dispersion by the liquid phase method is described. However, this method is a method of finally providing it as an aqueous component, and there is no mention of the method of providing it as an organic solvent dispersion.

In patent document 6, the example provided as an organic solvent dispersion using the pigment particle prepared by the liquid phase method is described. In Patent Literature 6, a method is disclosed in which a pigment is dissolved in a basic compound and / or a basic solution, and then the pigment is precipitated by adding a liquid neutral compound and / or acid compound, and also a neutral liquid and / or acid liquid. It is. However, the organic pigment particle obtained by this method became large in primary particle diameter, and did not fully satisfy the requirement of micronization.

In the preparation of the nanoparticles in the liquid phase method, in order to prevent aggregation of the nanoparticles, a low molecular weight surfactant and a neutral water-soluble nonionic polymer compound are used. Therefore, even if it is possible to disperse nanoparticles at a high concentration, there is a drawback that a large amount of the dispersing aid to be used is required, and in the case where the viscosity is low and the content of the polymer compound is extremely low, such as inkjet, applying these techniques as it is is It is difficult. In addition, in order to prepare the aqueous nanoparticles and phase-change to a solvent system, an aqueous slurry or an aqueous paste containing a high concentration of a pigment is prepared, a resin or a resin solution is added, mixed and stirred, and the water around the pigment is mixed with a resin or The flushing method to substitute with the resin solution is known. However, in this method, since the aqueous particles undergo a strongly aggregated form, the coating efficiency in the resin is deteriorated, and redispersion is difficult (see Patent Documents 7 to 8, etc.). In addition, such a method also includes a method of filtering the aqueous nano pigment particles as they are or in the form of agglomerated particles in order to produce an aqueous paste. However, there is a problem that the filtration takes a long time and is very inefficient and complicated industrially. In addition, although a low molecular anionic or cationic surfactant can be used as a dispersant, there is a problem in that the dispersion stability due to being a low molecule is insufficient. There has also been attempted a method of phase-converting to an ionic liquid without undergoing a step of filtering the aqueous particles with a cationic polymer compound (see Non-Patent Document 2, for example). However, in the method described in Non Patent Literature 2, it is limited to low concentration inorganic particles, and Non Patent Literature 2 does not mention organic pigments, and the final dispersion medium is also referred to as a nonvolatile ionic liquid. The method is not suitable for industrial use.

[Patent Document 1] Japanese Patent Laid-Open No. 11-237760

[Patent Document 2] Japanese Patent Application Laid-Open No. 6-79168

[Patent Document 3] Japanese Patent Laid-Open No. 2004-91560

[Patent Document 4] Japanese Patent Laid-Open No. 2000-239554

[Patent Document 5] Japanese Patent Laid-Open No. 2004-43776

[Patent Document 6] Japanese Patent Laid-Open No. 2004-123853

[Patent Document 7] Japanese Patent Application Laid-Open No. 5-301037

[Patent Document 8] Japanese Patent Laid-Open No. 6-161154

[Non-Patent Document 1] Pigment Dispersion Technology-Surface Treatment and Dispersant Usage and Dispersibility Evaluation-

Alcohol Information Association 1999

[Non-Patent Document 2] 「small」, 2006, Vol. 2, No. 7, p.879-883

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and its object is to produce an aqueous paste once represented by flushing, namely a filter, when an organic nano pigment particle aqueous dispersion is converted to an organic nano pigment particle non-aqueous dispersion. For complicated processes that require enormous time, such as filtration, the nano pigment particles in the organic nanoparticle pigment aqueous dispersion are easily filterable aggregates, which are isolated and redispersed in a non-aqueous medium to obtain good efficiency. It is to provide a method for producing an organic nano pigment particle non-aqueous dispersion. Moreover, it aims at providing the coloring photosensitive resin composition using the said organic nano pigment particle dispersion, and the color filter created by it.

As a result of intensive studies, the present inventors aggregated the organic nano-pigment particles dispersed in the aqueous medium into a solution which is easy to filter by adding a solution in which an organic low molecular weight compound and an organic high molecular compound were dissolved, and isolated the aggregate. It was found that a highly efficient organic nano pigment particle non-aqueous dispersion can be obtained by redispersing in a non-aqueous medium. The present invention has been completed based on this.

The said subject was achieved by the following means.

[1] The organic nanopigment particles dispersed in the aqueous medium are isolated after being aggregated by reacting at least one organic low molecular weight compound having a molecular weight of less than 1000 and at least one organic polymer compound having a weight average molecular weight of at least 1000. The manufacturing method of the organic nano pigment particle | grain aggregate which is used.

[2] the above-mentioned [1],

The organic low-molecular-weight compound and the organic high-molecular compound are dissolved in a solvent mixed with the aqueous medium and added to the aqueous medium to agglomerate organic nano-pigment particles dispersed in the aqueous medium. Manufacturing method.

[3] The method of [1] or [2], wherein

The said isolation | separation is performed by filtration, The manufacturing method of the organic nano pigment particle aggregate.

[4] The method according to any one of [1] to [3],

A process for producing an organic nano-pigmented particle aggregate comprising the step of removing at least the excess organic low molecular weight compound.

[5] The method according to any one of [1] to [4],

A solution of an organic pigment in which the organic nano-pigment particles dispersed in the aqueous medium is dissolved in a good solvent and a medium compatible with the good solvent and a poor solvent for the organic pigment are mixed to produce fine particles of nano size. A method for producing an organic nano pigment particle aggregate, which can be obtained.

[6] The method according to any one of [1] to [5],

Method for producing an organic nano-pigment particle aggregate, characterized in that the average primary particle diameter of the organic nano-pigment particles is 100nm or less.

[7] The method according to any one of [1] to [6],

The average particle diameter of the aggregate is 10000nm or more method for producing an organic nano pigment particle aggregate.

[8] A method for producing an organic nano pigment particle non-aqueous dispersion, wherein the isolated organic nano pigment particle aggregate according to any one of [1] to [7] is obtained by redispersing in a non-aqueous medium.

[9] The method according to any one of [1] to [8],

A method for producing an organic nano pigment particle non-aqueous dispersion, wherein the organic polymer compound is represented by the following General Formula (11) or (14).

(In formula (11), A ¹ represents an acid group, a group containing a basic nitrogen atom, a urea group, a urethane group, a group containing a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate). A monovalent organic group containing a group selected from a group and a hydroxyl group, or a monovalent organic group containing an organic dye structure or a heterocyclic ring which may contain a substituent, n A ¹ may be the same or different R ¹ is (m m + n represents 3-10, m represents the integer of 1-8, n represents the integer of 2-9, R <^2> represents a single bond or a bivalent coupling group. P ¹ is It shows a polymer residue.)

(G- In the above general formula (14) _{^{-COO -, -SO 3 -, -OSO}} 3 -, -P (O) (OH) O -, or -OP (O) (OH) O ^- represents a. J represents a divalent linking group or a single bond Q represents a (m + 1) valent linking group R represents a polymer compound residue Z ⁺ represents an organic or inorganic cation m + 1 represents 3-6 .)

[10] The method of [9],

A method for producing an organic nano pigment particle non-aqueous dispersion, wherein the organic polymer compound is used as a dispersant in a non-aqueous medium as it is.

[11] The organic nano pigment particle non-aqueous dispersion as described in the above [9] or [10] (an organic nano pigment particle non-aqueous dispersion (or aggregate) prepared by the method as described in the above [9] or [10].) ), A binder, a monomer or an oligomer, and a photopolymerization initiator or photopolymerization initiator system.

[12] A color filter comprising the colored photosensitive resin composition according to the above [11].

According to the production method of the present invention, an organic nano pigment particle aggregate can be efficiently produced from an organic nano pigment particle aqueous dispersion. In addition, by using the aggregate of the organic nano pigment particles, it is possible to easily phase-reverse and solve (redisperse) the non-aqueous medium so that the organic nano pigment particle non-aqueous dispersion can be efficiently produced on an industrial scale. Can be. According to the production method of the present invention, an organic nano pigment particle dispersion suitable for a color filter coating liquid or an inkjet ink and a dispersion thereof can be produced on an industrial scale. In addition, the organic nano pigment particle non-aqueous dispersion of the present invention has excellent dispersion and high contrast, and the color filter using the same has the desired color purity and high contrast.

Hereinafter, the manufacturing method of the organic nano pigment particle of this invention is demonstrated.

[Organic Pigments]

The organic pigments that can be used in the method for producing organic nano pigment particles of the present invention are not particularly limited as long as they can form particles by a liquid phase method, and may be used alone or in combination of a plurality thereof.

Organic pigments are not limited in color, for example, perylene, perinone, quinacridone, quinacridonequinone, andhraquinone, anthrone, benzimidazolone, disazo condensation, disazo, azo, Indanthrone, phthalocyanine, triarylcarbonium, dioxazine, aminoandroquinone, diketopyrrolopyrrole, thioindigo, isoindolin, isoindolinone, pyrantrone or isobioanthrone compound pigments, or mixtures thereof do.

In more detail, for example, C.I. Pigment Red 190 (C.I. No. 71140), C.I. Pigment Red 224 (C.I. No. 71127), C.I. Pigments of perylene compounds such as pigment violet 29 (C.I. No. 71129), C.I. Pigment Orange 43 (C.I. No. 71105), or C.I. Pigments of perinone compounds such as Pigment Red 194 (C.I. No. 71100), C.I. Pigment Violet 19 (C.I. No. 73900), C.I. Pigment Violet 42, C.I. Pigment Red 122 (C.I. No. 73715), C.I. Pigment Red 192, C.I. Pigment Red 202 (C.I. No. 73907), C.I. Pigment Red 207 (C.I. Nos. 73900, 73906), or C.I. Pignalidone pigment pigment of Pigment Red 209 (C.I. No. 73905), C.I. Pigment Red 206 (C.I. No. 73900/73920), C.I. Pigment Orange 48 (C.I. No. 73900/73920), or C.I. Pigments such as pigment orange 49 (C.I. No. 73900/73920), C.I. Pigments of andhraquinone compounds such as Pigment Red Yellow 147 (C.I. No. 60645), C.I. Pigments such as pigment red 168 (C.I. No. 59300), C.I. Pigment Brown 25 (C.I. No. 12210), C.I. Pigment Violet 32 (C.I. No. 12517), C.I. Pigment Yellow 180 (C.I. No. 21290), C.I. Pigment Yellow 181 (C.I. No. 11777), C.I. Pigment Orange 62 (C.I. No. 111775), or C.I. Pigments of benzimidazolone compounds such as Pigment Red 185 (C.I. No. 12516), C.I. Pigment Yellow 93 (C.I. No. 20710), C.I. Pigment Yellow 94 (C.I. No. 20038), C.I. Pigment Yellow 95 (C.I. No. 20034), C.I. Pigment Yellow 128 (C.I. No. 20037), C.I. Pigment Yellow 166 (C.I. No. 20035), C.I. Pigment Orange 34 (C.I. No. 21115), C.I. Pigment Orange 13 (C.I. No. 21110), C.I. Pigment Orange 31 (C.I. No. 20050), C.I. Pigment Red 144 (C.I. No. 20735), C.I. Pigment Red 166 (C.I. No. 20730), C.I. Pigment Red 220 (C.I. No. 20055), C.I. Pigment Red 221 (C.I. No. 20065), C.I. Pigment Red 242 (C.I. No. 20067), C.I. Pigment Red 248, C.I. Pigment Red 262, or C.I. Disazo condensed compound pigments such as Pigment Brown 23 (C.I. No. 20060), C.I. Pigment Yellow 13 (C.I. No. 21100), C.I. Pigment Yellow 83 (C.I. No. 21108), or C.I. Disazo compound pigments such as Pigment Yellow 188 (C.I. No. 21094), C.I. Pigment Red 187 (C.I. No. 12486), C.I. Pigment Red 170 (C.I. No. 12475), C.I. Pigment Yellow 74 (C.I. No. 1714), C.I. Pigment Yellow 150 (C.I. No. 48545), C.I. Pigment Red 48 (C.I. No. 15865), C.I. Pigment Red 53 (C.I. No. 15585), C.I. Pigment Orange 64 (C.I. No. 12760), or C.I. Azo compound pigments such as Pigment Red 247 (C.I. No. 15915), C.I. Pigments such as pigment blue 60 (C.I. No. 69800), C.I. Pigment Green 7 (CI No. 36 (CI No. 74265), CI Pigment Green 37 (CI No.74255), CI Pigment Blue 16 (CI No. 74100), CI Pigment Blue 75 (CI No. 74160: 2), or Phthalonyanine compound pigments, such as 15 (CI number 74160), CI pigment blue 56 (CI number 42800), or triaryl carbonium compound pigments, such as CI pigment blue 61 (CI number 42765: 1), CI pig Dioxazine compound pigments such as Cement Violet 23 (CI No. 51319) or CI Pigment Violet 37 (CI No. 51345), amino anddraquinone compound pigments such as CI Pigment Red 177 (CI No. 65300), CI Pigment Red 254 Diketopyrrolo such as (CI No. 56110), CI Pigment Red 255 (CI 561050), CI Pigment Red 264, CI Pigment Red 272 (CI No. 561150), CI Pigment Orange 71, or CI Pigment Orange 73 Thio indie such as pyrrole compound pigment and CI pigment red 88 (CI number 73312) Isoindolin compound pigments such as compound pigments, CI pigment yellow 139 (CI number 56298), CI pigment orange 66 (CI number 448210), CI pigment yellow 109 (CI number 56284), or CI pigment orange 61 ( Isoindolinone pigments such as CI No. 11295, Pi Pigron Compound Pigments such as CI Pigment Orange 40 (CI No. 59700), or CI Pigment Red 216 (CI No. 59710), or CI Pigment Violet 31 (60010) Isobioanthrone compound pigments, etc. Among them, quinacridone compound pigments, diketopyrrolopyrrole compound pigments, dioxazine compound pigments, phthalocyanine compound pigments, or azo compound pigments are preferable, and diketopy is preferred. More preferred are rolopyrrole compound pigments or dioxazine compound pigments.

C.I.P.R. Pyrrolopyrrole compound pigments represented by 254, 255, 264 have an absorption area suitable for increasing the color purity of the red pixels constituting the color filter, and because it can widen the color reproduction area, it is attempted to use it in the color filter. have. However, conventional pigments cannot satisfy the requirements such as color purity and contrast. For example, a good color filter cannot be obtained from the inkjet ink described in Japanese Patent Laid-Open No. 2003-336001, obtained by a method by bead dispersion, salt milling, or the like.

According to the production method of the present invention, nano-sized pyrrolopyrrole compound pigment fine particles can be obtained in a state where the particle diameter distribution is sharp. In addition, when the pigment fine particles are used in a color filter, the desired color purity and high contrast can be made compatible, and also excellent in light resistance, and the generation of precipitates can be suppressed.

In the present invention, two or more organic pigments or solid solutions of organic pigments may be used in combination.

[Preparation of Aqueous Dispersion of Organic Nano Pigment Particles]

Next, preparation of the organic nano pigment particle aqueous dispersion liquid is demonstrated.

In the present invention, the organic nano-pigment particles are compatible with the organic pigment solution in which the organic pigment is dissolved in the good solvent and the good solvent, and the solvent which becomes a poor solvent for the organic pigment (hereinafter referred to as "organic pigment"). It is also produced by mixing "poor solvent", or simply "poor solvent" (hereinafter, this method is also referred to as "reprecipitation"), and the dispersion containing organic nanoparticles obtained at this time is "organic nano Pigment particle reprecipitation liquid).

The organic pigment poor solvent is not particularly limited as long as it is compatible with a good solvent in which the organic pigment is dissolved or uniformly mixed. It is preferable that the solubility of an organic pigment is 0.02 mass% or less, and, as a poor solvent of an organic pigment, it is more preferable that it is 0.01 mass% or less. There is no particular lower limit to the solubility in organic pigment poor solvents, but considering the organic pigments that are usually used, 0.000001 mass% or more is practical. This solubility may be solubility when melt | dissolved in presence of an acid or an alkali. In addition, the compatibility or homogeneity of the good solvent and the poor solvent is preferably 30 mass% or more, more preferably 50 mass% or more in the poor solvent. Although there is no upper limit in particular in the amount of melt | dissolution with respect to the poor solvent of a good solvent, it is practical to mix with each other in arbitrary ratios.

The poor solvent is not particularly limited as long as it is an aqueous medium. For example, an aqueous solvent (for example, water or hydrochloric acid, an aqueous sodium hydroxide solution), an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, an aromatic compound solvent, and carbon disulfide Solvents, aliphatic solvents, nitrile solvents, halogenated solvents, ester compound solvents, ionic liquids, mixed solvents thereof, and the like, including aqueous solvents, alcohol compound solvents, ketone compound solvents, ether compound solvents, ester compound solvents, Or a mixture thereof is preferable, and 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. As a ketone compound solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are mentioned, for example. As an ether compound solvent, dimethyl ether, diethyl ether, tetrahydrofuran, etc. are mentioned, for example. As an aromatic compound solvent, benzene, toluene, etc. are mentioned, for example. As an aliphatic compound solvent, hexane etc. are mentioned, for example. As a nitrile compound solvent, acetonitrile etc. are mentioned, for example. As a halogen compound solvent, dichloromethane, trichloroethylene, etc. are mentioned, for example. As an ester compound solvent, ethyl acetate, ethyl lactate, 2- (1-methoxy) propyl acetate, etc. are mentioned, for example. Examples of the ionic liquids include salts of 1-butyl-3-methylimidazolium and PF ₆ ⁻ and the like.

Next, the good solvent which melt | dissolves an organic pigment is demonstrated.

The good solvent is not particularly limited as long as it can dissolve the organic pigment to be used and is compatible with the poor solvent or mixed uniformly. It is preferable that the solubility of an organic material is 0.2 mass% or more, and, as for the solubility to the good solvent of an organic pigment, it is more preferable that it is 0.5 mass% or more. There is no particular upper limit to the solubility of the organic pigment in the good solvent, but it is practical that it is 50% by mass or less in consideration of the organic pigment that is usually used. This solubility may be solubility when melt | dissolved in presence of an acid or an alkali. The preferable range of compatibility or homogeneous mixing of the poor solvent and the good solvent is as described above.

As a good solvent, For example, an aqueous solvent (for example, water or hydrochloric acid, a sodium hydroxide aqueous solution), an alcohol compound solvent, an amide compound solvent, a ketone compound solvent, an ether compound solvent, an aromatic compound solvent, a carbon disulfide solvent, Aliphatic compound solvents, nitrile compound solvents, sulfoxide compounds, halogen compound solvents, ester compound solvents, ionic liquids, carboxylic acid compounds, sulfonic acid compounds, sulfuric acid, mixed solvents thereof, and the like. A solvent, an ether compound solvent, a sulfoxide compound solvent, an ester compound solvent, an amide compound solvent, a carboxylic acid compound, a sulfonic acid compound, sulfuric acid, or a mixture thereof is preferable, and an aqueous solvent, an alcohol compound solvent, an ester compound solvent, a sulfoxide compound solvent , Amide compound solvent, carboxylic acid compound, sulfonic acid compound and sulfuric acid are more preferable. Compound solvent, an amide compound solvent, a carboxylic acid compound, sulfonic acid compound, sulfuric acid is particularly preferred.

Examples of the sulfoxide compound solvent include dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, sulfolane and the like. As the amide compound solvent, for example, N, N-dimethylformamide. 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, formamide, N-methylformamide, aceto Amide, N-methylacetoamide, N, N-dimethylacetoamide, N-methylpropanamide, hexamethylphosphoric triamide and the like. Whether one solvent present becomes a good solvent or a poor solvent depends on the type of organic pigment to be targeted. A good solvent and a poor solvent do not become the same compound with respect to one organic pigment which exists in this invention.

The concentration of the organic pigment solution in which the organic pigment is dissolved in the good solvent is preferably in the range of saturated concentration to about 1/100 of that of the good solvent of the organic pigment under the conditions of dissolution.

There are no particular restrictions on the preparation conditions of the organic pigment solution, and a range of atmospheric pressure to subcritical and supercritical conditions can be selected. -10-150 degreeC is preferable, as for the temperature in normal pressure, -5-130 degreeC is more preferable, and 0-100 degreeC is especially preferable.

In the present invention, the organic pigment must be dissolved uniformly in a good solvent, but is preferably dissolved in an acidic or alkaline state. In general, in the case of a pigment having an alkaline-dissociable group in a molecule, acidity is used in the case of alkalinity, there is no alkaline-dissociable group, and when a molecule has a large number of nitrogen atoms to which protons are easily added. For example, quinacridone, diketonepyrrolopyrrole and disazo condensation compounds are alkaline and phthalocyanine compound pigments are soluble in acid.

Bases that can be used when dissolved in alkaline are inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide or barium hydroxide, or organic such as trialkylamine, diazabicycloundecene (DBU), metal alkoxide, etc. Base, but inorganic base is preferred.

The amount of the base to be used is an amount which can dissolve the pigment uniformly and is not particularly limited. In the case of inorganic bases, the amount of the base is preferably 1.0 to 30 molar equivalents, more preferably 1.0 to 25 molar equivalents, more preferably 1.0 to 1 relative to the organic material. It is more preferable that it is 20 molar equivalent. In the case of an organic base, it is preferable that it is 1.0-100 molar equivalent with respect to an organic material, It is more preferable that it is 5.0-100 molar equivalent, It is more preferable that it is 20-100 molar equivalent.

The acid that can be used when dissolved in acid is 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, but an inorganic acid is preferable. Sulfuric acid is particularly preferred.

The amount of acid to be used is an amount which can dissolve the organic pigment uniformly, and is not particularly limited, but an excess amount of the acid can be used in many cases. Regardless of the case of the inorganic acid and the organic acid, 3-500 molar equivalents are preferable with respect to an organic material, 10-500 molar equivalents are more preferable, and 30-200 molar equivalents are more preferable.

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

There is no restriction | limiting in particular in the conditions of the poor solvent at the time of preparation of an organic particle, ie, precipitating and forming organic particle | grains, The range of normal pressure to subcritical and supercritical conditions can be selected. -30-100 degreeC is preferable, as for the temperature in normal pressure, -10-60 degreeC is more preferable, and 0-30 degreeC is especially preferable.

When mixing an organic pigment solution and a poor solvent, you may add and mix both, but it is preferable to add and mix an organic pigment solution to a poor solvent, and it is preferable that the poor solvent is stirred at that time. As for stirring speed, 100-10000rpm is preferable, 150-8000rpm is more preferable, 200-6000rpm is especially preferable. A pump etc. can also be used for addition and it is not necessary to use it. In addition, although addition in a liquid may be sufficient as addition in liquid, addition in a liquid is more preferable. The mixing ratio of the organic pigment solution and the poor solvent (good solvent / poor solvent ratio in the organic nano pigment particle reprecipitation solution) is preferably 1/50 to 2/3 by volume ratio, more preferably 1/40 to 1/2, It is especially preferable that it is 1 / 20-3 / 8. In the present invention, the organic nano pigment particles are first dispersed in an aqueous medium, and in this case, the aqueous medium contains 60% by mass or more of the aqueous solvent, and preferably 80% by mass or more.

The concentration of the organic nano-pigment particle reprecipitation liquid is not particularly limited as long as it can produce organic nano-pigment particles, but it is preferable that the organic pigment particles are in the range of 10 to 40000 mg, more preferably in the range of 20 to 30000 mg, for 1000 ml of an aqueous medium. It is preferable and it is especially preferable that it is the range of 50-25000 mg.

Moreover, although the preparation scale at the time of producing an organic nano pigment particle is not specifically limited, It is preferable that it is a preparation scale of 1-1000L, and, as for the mixing amount of a poor solvent, it is more preferable that it is a preparation scale of 1-100L.

As regards the particle diameter of the organic nano-pigment particles, there is a method of quantifying by means of the measurement method and showing the average size of the population. However, the particle diameter of the organic nano-pigment particles is often used. There are various average diameters (number average, length average, area average, mass average, volume average, etc.), and in the present invention, unless otherwise specified, the average particle diameter refers to the number average diameter. The average particle diameter of the organic pigment nanoparticle (primary particle) is nanometer size, it is preferable that average particle diameter is 1 nm-1 micrometer, It is more preferable that it is 1-200 nm, It is further more preferable that it is 2-100 nm, 5 It is especially preferable that it is -80 nm. The particles formed in the present invention may be crystalline particles, amorphous particles, or a mixture thereof.

In addition, unless otherwise indicated in this invention, the ratio (Mv / Mn) of volume average particle diameter (Mv) and number average particle diameter (Mn) is used as an index which shows monodispersibility of particle | grains. It is preferable that monodispersity, ie Mv / Mn, of the particle | grains (primary particle) contained in the organic nano pigment particle dispersion liquid used for the concentration method of organic nano pigment particle is 1.0-2.0, It is more preferable that it is 1.0-1.8, 1.0 It is especially preferable that it is -1.5.

Examples of the method for measuring the particle diameter of the organic nano-pigment particles include microscopy, gravimetric method, light scattering method, light blocking method, electric resistance method, acoustic method, and dynamic light scattering method, and microscopic method and dynamic light scattering method are particularly preferable. As a microscope used for a microscopic method, a scanning electron microscope, a transmission electron microscope, etc. are mentioned, for example. As a particle measuring device by the dynamic light scattering method, for example, Nikkiso Co., Ltd. Product Nano Truck UPA-EX150, otsuka electronics Co., Ltd. Dynamic Light Scattering Photometer DLS-7000 Series, Horiba, Ltd. Product LB-400 etc. are listed (all are brand names).

It is suitable to prepare an organic nano pigment particle aqueous dispersion liquid, and to contain a dispersing agent (henceforth a dispersing agent of an aqueous dispersion liquid). Although the process of containing a dispersing agent is not specifically limited, It is preferable to add a dispersing agent to both or one side of an organic pigment solution and a poor solvent, and to contain it. It is also preferable to add the dispersant solution when forming the organic nano pigment particles in a system different from the above two liquids. It is also preferable to use the pigment particle which surface-treated with the dispersing agent previously, and the surface treatment which may promote the adsorption of a dispersing agent may be given to the pigment particle. The dispersant has the effect of (1) quickly adsorbing onto the precipitated pigment surface to form fine nanoparticles, and (2) preventing these particles from agglomerating again.

As a dispersant which can be used, for example, an anionic, cationic, zwitterionic, nonionic or pigment derivative low molecular weight or polymer dispersant may be used. On the other hand, it is preferable that the addition amount of a low molecular weight or a polymeric dispersing agent is 10 mass% or more and 1000 mass% or less with respect to the dissolved pigment. Moreover, 50 mass% or more and 200 mass% or less are more preferable. When the addition amount is too small, the effect of suppressing the growth and aggregation of the pigment particles is less. When the amount is too large, problems such as an increase in viscosity and poor dissolution occur.

Hereinafter, the polymer dispersant will be described.

As for the molecular weight of a polymer dispersing agent, 1,000 or more and 200,000 or less are preferable as a number average molecular weight. Moreover, 3,000 or more and 40,000 or less are more preferable. When the molecular weight is too small, the effect of inhibiting the growth and aggregation of the pigment particles is less. When the molecular weight is too large, problems such as an increase in viscosity and poor dissolution occur. In addition, the polymer in this invention shows a 1,000 or more thing by a number average molecular weight.

The polymer dispersant is nonionic, and specifically, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethyl glycol, polypropylene glycol, poly acrylamide, vinyl alcohol vinyl acetate copolymer, polyvinyl alcohol part Formalate, polyvinyl alcohol partial butyrate, vinylpyrrolidone vinyl acetate copolymer, polyethylene oxide / propylene oxide proxy copolymer, etc. are mentioned, Among these, polyvinylpyrrolidone is preferable.

Examples of the anionic include polyacrylate salts, polyvinyl sulfates, poly (4-vinylpyridine) salts, polyamides, polyarylamine salts, polybenzenesulfonates, condensed naphthalenesulfonates, cellulose derivatives, starch derivatives and the like. . Especially, polybenzene sulfonate and condensation naphthalene sulfonate are more preferable.

Although these anionic can be obtained by copolymerizing an anionic monomer, what was copolymerized with not only anionic monomer itself but a nonionic monomer may be sufficient as it. Specific examples of the nonionic monomers include vinylpyrrolidone, styrene, naphthalene, styrylmethyl chloride, vinylimidazole, vinylpyridine, acrylamide, and vinylamide.

As the cationic one, a polymer compound having a quaternary ammonium moiety is particularly preferable, and a poly (methacryloxyalkylammonium salt), poly (methacryloxyarylammonium salt), poly (acryloxyalkylammonium salt), and poly (acryloxyarylammonium salt) ), Poly (diarylammonium salts) and the like are listed, but the polymer compound having a quaternary ammonium moiety is preferably a polymer compound containing a cationic repeating unit represented by the following general formula (1).

(Wherein, R ₁ to R ₃ each independently represent an alkyl group, an aralkyl group, or an aryl group. Any _{two of} R ₁ , R ₂ , and R ₃ may be connected to each other, and an oxygen atom, a nitrogen atom, and // Or a heterocyclic ring containing a sulfur atom, X represents a halogen atom, or an organic or inorganic anion, n represents a natural number of 1 to 5. A represents a hydrogen atom or an alkyl group, L represents a single bond or A divalent linking group, or of R ₁ , R ₂ , R ₃ A tetravalent linking group combined with any two.)

In general formula (1), the alkyl group which R <_1> -R <_3> represents is a substituted or unsubstituted linear, branched, or cyclic alkyl group, a C1-C12 alkyl group is preferable, and a C1-C4 alkyl group is more preferable. . The aralkyl group represented by R ₁ to R ₃ is a substituted or unsubstituted aralkyl group, and an aralkyl group having 7 to 10 carbon atoms is preferable. The aryl group which R <_1> -R <_3> represents is a substituted or unsubstituted aryl group, and a C6-C10 aryl group is preferable. The aralkyl group or the aryl group may be monocyclic or condensed, respectively.

Specific examples of the alkyl group include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group and octa Preferred are a methyl group, tert-octyl group, 2-ethylhexyl group, decyl group, and dodecyl group. Especially preferably, they are a methyl group, an ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, and tert- butyl group.

As an aralkyl group, a benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-butoxybenzyl group, 4-methoxybenzyl methoxyphenyl group, and 4-hydroxybenzyl group are preferable specifically ,. Especially preferably, they are a benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, and 4-butoxybenzyl group.

As an aryl group, a phenyl group, 4-chlorophenyl group, 4-methylphenyl group, 4-butoxyphenyl group, 4-methoxyphenyl group, and 4-hydroxyphenyl group are preferable specifically ,. Especially preferably, they are a phenyl group, 4-chlorophenyl group, 4-methylphenyl group, and 4-butoxyphenyl group.

When any _{two of} R ₁ , R ₂ and R ₃ are connected to each other to form a nitrogen-containing hetero ring having a quaternary ammonium moiety, the hetero ring is preferably a 4-6 membered ring. The heterocycle may further contain an oxygen atom, a nitrogen atom and / or a sulfur atom. Examples of the hetero ring include imidazolium, pyridinium, oxazolium, thiazolium, imidazolinium, oxazolium, thiazolium and the like. More preferred are imidazolium, pyridinium, oxazolium, thiazolium.

X in general formula (1) may be monovalent or polyvalent, and the halogen atom which X represents is a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Specific examples of the organic anion represented by X include carboxylate anion, sulfonate anion, alkoxide, benzene sulfonate anion, naphthalene sulfonate anion, naphthalene disulfonate anion, anthracene disulfonic anion and the like. Specific examples of the inorganic anion represented by X include bromide tetrafluoride anion, phosphorus hexafluoride anion, hydroxide and the like. Especially preferably, it is organic or inorganic anion which satisfy | fills the conditions which n is a natural number of 1-2.

In general formula (1), as an alkyl group which A represents, a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, and tert- butyl group are specifically, preferable. Especially preferably, they are a methyl group and an ethyl group.

In general formula (1), L represents a single bond or a bivalent coupling group, or the tetravalent coupling group couple | bonded with any two of R <_1> , R <_2> , R <_3> . The divalent linking group represented by L is a linking group containing an aryl group and an aralkyl group. The aryl group and aralkyl group contained in the divalent linking group represented by L may be monocyclic or may be condensed. The tetravalent linking group also bonded to any _{two of} R ₁ , R ₂ and R ₃ represented by L forms a heterocyclic group with the ammonium salt moiety in the general formula (1).

Specific examples of the divalent linking group represented by L include phenylene, naphthylene and the like as aryl groups, and phenylmethylene and naphthylmethylene and the like as aralkyl groups. Examples of the heterocyclic ring in which a tetravalent linking group bonded to any _{two of} R ₁ , R ₂ and R ₃ represented by L form a heterocyclic group with the ammonium salt moiety in the general formula (1) include imidazolium, pyridinium, oxazolium, Thiazolium, imidazolinium, oxazolinium, thiazolinium and the like. More preferably, imidazolium, pyridinium, oxazolium, thiazolium are listed.

Any _{two of} R ₁ , R ₂ , and R ₃ are connected to each other, and also include specific examples of heterocycles containing oxygen atoms, nitrogen atoms, and sulfur atoms formed therefrom, and are represented by the following general formula (1) The example of the high molecular compound containing the cationic repeating unit shown is shown. For example, polyvinylimidazolinium salts, polyvinylbenzimidazolinium salts, polyvinylpyridinium salts, polystyrylmethylene imidazolium salts, polystyrylmethylene imidazolinium salts, polystyrylmethylene pyridinium salts , Polystyryl methylene oxazolinium salts, polystyryl methylene oxazolinium salts, polystyryl methylene thiazolium salts, polystyryl methylene ammonium salts, polynaphthyl methylene imidazolium salts, polynaphthyl methylene imidazolinium salts, polynaphthyl Till methylene pyridinium salts, polynaphthyl methylene oxazolinium salts, polynaphthyl methylene oxazolinium salts, polynaphthyl methylene thiazolium salts, and poly naphthyl methylene ammonium salts are mentioned.

Among these, as a particularly preferable example, polystyrylmethylene imidazolium salts, polystyrylmethylene imidazolinium salts, polystyrylmethylene pyridinium salts, polystyrylmethylene oxazolinium salts, polystyrylmethylene oxazolinium salts, polystyrylmethylene thiatia Zolium salts and polystyrylmethylene ammonium salts are mentioned.

The polymer compound having a quaternary ammonium moiety used in the present invention is more preferably a polymer compound containing a cationic repeat unit represented by the following general formula (2).

The formula (2) means of, R ₁ ~ R _3, X and n are the same as R ₁ ~ R _3, X and n in the general formula (1) Also, the preferable range is the same.

The polymer compound having a quaternary ammonium moiety used in the present invention may be a random copolymer composed of a cationic repeating unit represented by the general formula (1) and other repeating units. It is preferable to copolymerize 0.1-0.7 mass% repeating unit with respect to the high molecular compound which has a former quaternary ammonium site | part, and, as for polymerization ratio, 0.1-0.5 mass% is more preferable.

As a copolymerization component, vinylimidazolinium salt, vinylbenzimidazolinium salt, vinylpyridinium salt, styrylmethylene imidazolium salt, styryl methylene imidazolinium salt, styryl methylene pyridinium salt, for example. , Styryl methylene oxazolinium salts, styryl methylene oxazolinium salts, styryl methylene thiazolium salts, styryl methylene ammonium salts, naphthyl methylene imidazolium salts, naphthyl methylene imidazolinium salts, naphthyl methylene pyridine Dinium salts, naphthyl methylene oxazolinium salts, naphthyl methylene oxazolinium salts, naphthyl methylene thiazolium salts, naphthyl methylene ammonium salts, vinylpyrrolidone, styrene, naphthalene, styryl methyl chloride, vinylimida Sol, vinylpyridine, acrylamide, vinylamide and the like. Especially preferably, styryl methylene imidazolium salt, styryl methylene imidazolinium salt, styryl methylene pyridinium salt, styryl methylene ammonium salt, vinylpyrrolidone, styrene, naphthalene, styryl methyl chloride, vinyl Imidazole, vinylpyridine, acrylamide, vinylamide and the like.

Although the specific example of the high molecular compound which has a quaternary ammonium site which can be used by this invention is shown below, this invention is not limited to these. In the following embodiments, the polymer compound used in the present invention is a polymerized repeating unit.

The polymer compound having the quaternary ammonium moiety can be prepared by referring to “small”, 2006, Vol. 2, No. 7, p879-883.

In addition, natural polymers such as alginate, gelatin, albumin, casein, gum arabic, tragant rubber and lignin sulfonate can also be used.

These polymers can be used individually by 1 type or in combination of 2 or more type. These dispersants can be used individually or in combination. Dispersants used for dispersing pigments are described in detail on pages 29 to 46 of "Pigment Dispersion Stabilization and Surface Treatment Technology and Evaluation" (Chemical Information Association, issued January 2, 2001).

Hereinafter, the low molecular weight dispersant will be described.

Low molecular dispersants are anionic and are N-acyl-N-alkyltaurine salts, fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkyl sulfosuccinate salts, alkyl phosphate ester salts, naphthalene sulfonic acid formalin condensates , Polyoxyethylene alkyl sulfate ester salts, and the like. Especially, N-acyl-N-alkyl taurine salt is preferable. As the N-acyl-N-alkyltaurine salt, those described in JP-A-3-273067 are preferable. These anionic dispersants can be used individually or in combination of 2 or more types.

Cationic, including quaternary ammonium salts, alkoxylated polyamines, aliphatic amine polyglycol ethers, diamines and polyamines derived from aliphatic amines, aliphatic amines and aliphatic alcohols, imidazolines derived from fatty acids and salts of their cationic materials It is. These cationic dispersants can be used individually or in combination of 2 or more types.

As anionic, it is a dispersing agent which has the anionic group part which the said anionic dispersing agent has in a molecule | numerator, and the cationic group part which a cationic dispersing agent has in a molecule | numerator simultaneously in a molecule | numerator.

Examples of the nonionics include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, and the like. can do. Especially, polyoxyethylene alkyl aryl ether is preferable. These nonionic dispersants can be used individually or in combination of 2 or more types.

As a pigment derivative type, it is defined as a pigment derivative type dispersant derived from an organic pigment as a parent material and prepared by chemically modifying a friend, or a pigment derivative type dispersant obtained by a pigmentation reaction of a chemically modified pigment precursor. do. For example, sugar-containing pigment-derived dispersants, piperidyl-containing pigment-derived dispersants, naphthalene or perylene-derived pigment-derived dispersants, pigment-derived dispersants having functional groups linked to the pigment friend via methylene groups, chemically modified with polymers Pigment derivatives, pigment derivative dispersants having sulfonic acid groups, pigment derivative dispersants having sulfonamide groups, pigment derivative dispersants having ether groups, or pigment derivative dispersants having carboxylic acid groups, carboxylic acid ester groups or carboxyamides.

In this invention, when preparing the organic pigment solution melt | dissolved in the good solvent, it is preferable to make the pigment dispersant containing an amino group coexist. Here, as an amino group, a primary amino group, a secondary amino group, and a tertiary amino group are mentioned, and the number of amino groups may be one or plural. The pigment derivative compound which introduce | transduced the substituent which has an amino group in a pigment skeleton may be sufficient, or the polymer compound which makes the monomer which has an amino group the polymerization component may be sufficient. As examples of these, for example, Japanese Patent Laid-Open Nos. 2000-239554, 2003-96329, 2001-31885, Japanese Patent Laid-Open No. 10-339949, and Japanese Patent Laid-Open No. 5-72943 Listed compounds and the like are listed, but are not limited thereto.

Organic Low Molecular Compounds and Organic High Molecular Compounds

In the present invention, with respect to the organic nano-pigment particles dispersed in an aqueous medium, at least one organic low molecular weight compound having a molecular weight of less than 1000 (hereinafter referred to as a low molecular compound), and at least one organic polymer compound having a weight average molecular weight of 1000 or more (hereinafter And agglomerated by a high molecular compound), and then the organic nanoparticle aggregate is isolated. In the present invention, the low molecular weight compound condenses organic nano pigment particles. Agglomerates formed by condensation aggregate the polymer compound to form large aggregates that are easy to filter. In the present invention, the low molecular weight compound and the high molecular weight compound are used in combination, and the low molecular weight compound alone does not form organic aggregates but becomes a large aggregate. It takes time. Moreover, with only the high molecular compound, the aggregate itself hardly occurs, and filtration becomes impossible. In the polymer compound of the present invention, since the aqueous solvent in which the organic nano-pigment particles are dispersed is a poor solvent, by adsorbing to the above-mentioned agglomerates, the polarity of the agglomerates is not dissolved in the aqueous solvent, and the agglomerates are large. Grow in aggregates.

As an aggregate, it is preferable that an average particle diameter is 10000 nm or more, and it is more preferable that it is large. Although there is no upper limit in particular in this average particle diameter, 10 million nm or less is practical. If the average particle diameter of the aggregate is too small, a large amount of time may be required for isolation of the aggregate, or the filter paper or the filter may be pulled out or clogged even if the aggregate is to be filtered. When the average particle diameter of an aggregate is too big | large, the problem which may require a lot of time for redispersion may arise.

In addition, since the low molecular weight compound and the high molecular weight compound in the present invention are adsorbed on the aggregated organic nano pigment particles, they are filtered and washed in the non-aqueous medium as it is after the washing and the redispersion (peptize) described later. Since it can use as a dispersing agent (henceforth a dispersing agent of a non-aqueous dispersion), it is not necessary to add a dispersing agent newly. Although a dispersing agent may be added later for adjustment of dispersibility, it is preferable not to add in view of a manufacturing price.

In addition, in the present invention, since the organic nano-pigment particles constituting the aggregates are aggregated in a state in which they are coated on a low molecular weight and a high molecular compound, when the low molecular weight and high molecular weight compounds are aggregated, for example, when aggregated with hydrochloric acid or the like. Compared with that, subsequent redispersion is easy, organic nano pigment particles are easily released into primary particles, and contrast is increased.

Although the said low molecular weight compound and a high molecular compound may be added as it is, it is preferable from a viewpoint of obtaining the favorable filterability to melt | dissolve and add the said low molecular weight compound and a high molecular compound in a solvent.

The solvent is not particularly limited as long as it can be mixed with an aqueous organic nano-pigment particle aqueous dispersion and at the same time can dissolve the low molecular weight compound and the high molecular compound, and the low molecular weight compound and the high molecular compound do not precipitate themselves after addition.

In addition, the solvent does not agglomerate even when the organic nano pigment particles are added to the aqueous dispersion of the organic pigment pigment itself, or does not add a weak agglomeration (high shearing force such as milling or high speed agitation) that can be redispersed even when agglomerated. It is preferable that it is a solvent which flocks to enable redispersion.

As the solvent, for example, an aqueous solvent (for example, water or hydrochloric acid, sodium hydroxide aqueous solution), alcohol compound solvent, amide compound solvent, ketone compound solvent, ether compound solvent, aromatic compound solvent, carbon disulfide solvent, aliphatic Compound solvents, nitrile compound solvents, sulfoxide compound solvents, halogenated compound solvents, ester compound solvents, ionic liquids, mixed solvents thereof, and the like, include aqueous solvents, alcohol compound solvents, ketone compound solvents, ether compound solvents, and sulfoxides. Compound solvents, ester compound solvents, amide compound solvents, nitrile compound solvents, or mixtures thereof are preferable, and ketone compound solvents, ether compound solvents, nitrile compound solvents, or mixtures thereof are more preferable.

Examples of the alcohol compound solvent include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-methoxy-2-propanol and the like. As a ketone compound solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are mentioned, for example. As an ether compound solvent, dimethyl ether, diethyl ether, tetrahydrofuran, etc. are mentioned, for example. As an aromatic compound solvent, benzene, toluene, etc. are mentioned, for example. As an aliphatic compound solvent, hexane etc. are mentioned, for example. As a nitrile compound solvent, acetonitrile etc. are mentioned, for example. As a halogen compound solvent, dichloromethane, trichloroethylene, etc. are mentioned, for example. As an ester compound solvent, ethyl acetate, ethyl lactate, 2- (1-methoxy) propyl acetate, etc. are mentioned, for example. Examples of the ionic liquids include 1-butyl-3-methylimidazolium, salts with PF ₆ ⁻ , and the like.

The amount of the solvent used is not particularly limited as long as it can dissolve a low molecular weight compound and a high molecular compound and form an aggregate that is easy to filter, but it is possible to take into consideration the complexity of manufacturing and further reducing raw material cost. It is preferable that it is a small amount. When this is represented by mass ratio, when the organic nano pigment particle aqueous dispersion liquid is 100, it is preferable that the solvent added is the range of 1-100, It is more preferable that it is the range of 10-70, Especially it is the range of 20-70 desirable. When too large, it may require many hours for the settling time of an aggregate, and when too small, formation of an aggregate may become inadequate and it may become difficult to settle an aggregate.

After adding the solvent, it is preferable to stir to sufficiently mix with the organic nano pigment particle aqueous dispersion. Stirring mixing can use a conventional method. Although there is no restriction | limiting in particular in the temperature at the time of adding and mixing the said solvent, It is preferable that it is 1-100 degreeC, and it is more preferable that it is 5-60 degreeC. Any solvent may be used as long as the solvent can be added and mixed preferably, but for example, a stirring blade, a Raymond stirrer, or the like may be used.

In addition, as mentioned above, in this invention, it corresponds to the aggregation of the organic nano pigment particle in the organic nano pigment particle aqueous dispersion liquid, and can contain the low molecular weight compound and the high molecular compound in this invention separately. Although the process of containing a low molecular weight compound and a high molecular compound in this invention is not specifically limited, The method of adding the said low molecular weight compound and a high molecular compound in this invention together after adding the said solvent to an organic nano pigment particle aqueous dispersion liquid may be sufficient, Or after dissolving these in the said solvent, the method of adding to an organic nano pigment particle aqueous dispersion liquid may be sufficient, A more preferable method is the method of adding to an organic nano pigment particle aqueous dispersion liquid after melt | dissolving in the said solvent. In this case, a low molecular weight compound and a high molecular compound may be added separately, and after dissolving the high molecular compound in the solvent, the organic nano pigment particle is added to the aqueous dispersion, and then the low molecular weight compound is added as it is. The method of adding the solution which melt | dissolved a high molecular compound after adding a low molecular weight compound to an aqueous pigment particle dispersion liquid is also good.

On the other hand, as for the addition amount of a low molecular weight and a high molecular compound, 10 mass% or more and 1000 mass% or less are preferable with respect to a pigment. Moreover, 50 mass% or more and 200 mass% or less are more preferable. If the amount is too small, the aggregation effect of the nanoparticles may be less. If the amount is too large, problems such as viscosity increase during redispersion, which will be described later, may easily occur. Although it does not specifically limit as an addition ratio of a low molecular weight compound and a high molecular compound, It is preferable that it is 1-50, and, as for a low molecular weight compound with respect to 1 as a high molecular compound by mass ratio, it is more preferable that it is 10-30.

Hereinafter, the low molecular weight compound will be described in more detail.

As an organic low molecular weight compound, anionic, cationic, or nonionic low molecular weight compound is mentioned, for example. As a low molecular weight compound to be used, it can select according to the dispersing agent of the water-based acid used in preparation of the said organic nano pigment particle aqueous dispersion liquid. For example, if the dispersant of the aqueous acid solution is nonionic (especially basic), the low molecular weight compound is preferably nonionic (especially acidic). If the dispersant of the aqueous acid solution is anionic, the low molecular weight compound is preferably cationic. If the dispersant of is cationic, it is preferable that the low molecular weight compound is anionic. Especially, it is more preferable that the dispersing agent of an aqueous acid solution is nonionic (especially basic), and that it is nonionic (especially acidic) as a low molecular weight compound, It is more preferable that the dispersing agent of an aqueous acid solution is cationic, and that it is anionic as a low molecular weight compound.

The nonionic low molecular weight compound is particularly preferably an acidic organic low molecular weight compound, and is not particularly limited as long as it has a molecular weight of less than 1000. Among them, monovalent or higher carboxylic acid, sulfonic acid, and phosphoric acid compound are preferred, and monovalent to carboxylic acid, sulfonic acid, and phosphoric acid compound. This is more preferable.

Specifically as carboxylic acid, formic acid, acetic acid, propionic acid, butyl acetic acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, isobutyric acid, 2- Ethylbutyric acid, trimethylacetic acid, t-butylacetic acid, 2-propylpentanoic acid, 2-ethylhexanoic acid, malonic acid, butylmalonic acid, dimethylmalonic acid, diethylmalonic acid, succinic acid, glutaric acid, tricarvalic acid, 1,2,3,4-butanetetracarboxylic acid, cis-5,8,11,14,17-eicosapentanoic acid, cis-4,7,10,13,16,19-docosahexaenoic acid, benzoic acid , Phenylacetic acid, 11-phenoxy undecanoic acid, phenylmalonic acid and the like.

Specific examples of the sulfonic acid include methanesulfonic acid, N-cyclohexyl-2-aminoethanesulfonic acid, N-cyclohexyl-3-aminopropanesulfonic acid, benzene sulfonic acid, and the like.

Specific examples of the phosphoric acid include dimethyl phosphonic acid and methylenediphosphonic acid.

The anionic low molecular weight compound is not particularly limited as long as it is less than 1000, but the anionic compound is preferably an anionic compound represented by the following general formula (3).

(Wherein, D is _{^{-COO -, -SO 3 -, -OSO}} 3 -, -P (O) (OH) O -, or OP (O) (OH) O -. E is a small number of 10 to 100 shows a bullet An alkyl group, an aralkyl group, an aryl group, or an alkoxy group which may have a phosphorus substituent. Y represents an organic or inorganic cation.)

In the general formula (3), D is _{^{-COO -, -SO 3 -, -OSO}} 3 -, -P (O) (OH) O -, or OP (O) (OH) O - represents the, more preferably is -SO ₃ ^- is a ^{-, -P (O) (OH} ) O.

In general formula (3), E is an alkyl group, an aralkyl group, an aryl group, or an alkoxy group which may have a substituent of 10-10 total carbons, More preferably, an alkyl group which may have a substituent of 20-20 total carbons, Aralkyl group, an aryl group, or an alkoxy group. The alkyl group or the alkoxy group or the substituent may be linear or branched, respectively, and the aralkyl group or the aryl group may be monocyclic or condensed, respectively.

Specific examples of the alkyl group include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group and octyl group , tert-octyl group, 2-ethylhexyl group, decyl group, dodecyl group, octadecyl group and the like are listed, and preferably methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, tert -A butyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, and a heptyl group are mentioned.

Specifically as an arylalkyl group, a benzyl group and a naphthyl methylene group are mentioned, Especially a benzyl group is preferable. Specifically as an aryl group, a phenyl group and a naphthyl group are mentioned, A phenyl group is especially preferable.

Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a normal propyloxy group, an isopropyloxy group, a normal butyloxy group, an isobutyloxy group, a tert-butyloxy group, a pentyloxy group, a cyclopentyloxy group and a hexyl jade. Period, a cyclohexyloxy group, heptyloxy group, octyloxy group, tert-octyloxy group. 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group are mentioned, Preferably a methoxy group, an ethoxy group, normal propyloxy group, isopropyloxy group, normal butyloxy group, isobutyloxy Groups are listed.

Examples of the organic cation represented by Y in the general formula (3) include imidazolium salts, pyridinium salts, thiazolium salts, oxazolinium salts, imidazolinium salts, thiazolinium salts and oxazolinium salts. From the ease of desalination described later, inorganic cations are preferably listed, and examples of the inorganic cations include lithium ions, sodium salts and potassium ions.

Hereinafter, although the specific example of the anionic compound represented by the said General formula (3) is shown, it is not limited to these.

As molecular weight of these low molecular weight compounds, any may be sufficient as it is less than 1000. If it is 1000 or more, the properties of the polymer compound will appear, making it difficult to agglomerate the nanoparticles. Although there is no restriction | limiting in particular in the lower limit of this molecular weight, Usually, it is 40 or more.

Hereinafter, the polymer compound will be described in more detail.

In a preferred embodiment, the dispersant of the organic nano-pigment particle aqueous dispersion is nonionic, particularly basic, such as a low molecular weight compound. The polymer compound is nonionic, particularly acidic, and the dispersant of an aqueous acid solution is a cation. desirable. In this invention, it is preferable that the weight average molecular weight of a high molecular compound is 1,000 or more. Although there is no upper limit in particular, It is more preferable that it is 3000000 or less, It is further more preferable that it is 300000 or less. As a specific example of the well-known high molecular compound used for this invention, "Disperbyk-110 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer) manufactured by BYK Chemie Copolymer) "," BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) "," EFKA4047, 4050, 4010, 4165 (polyurethane type), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified by EFKA company) Polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), AJINOMOTO FINE TECHNO CO., INC., "AJISUPER-PB821, PB822", KYOEISHA CHEMICAL CO., LTD products `` FLOWLEN TG-710 '' (urethane oligomer), `` Polypro No. 50E, No. 300 (acrylic copolymer), DISPARLON KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, manufactured by KUSUMOTO CHEMICALS, Ltd. DA-725, `` DEMOL RN, N (naphthalene sulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) '' from Kao Chemicals, `` HOMOGENOL-18 (polymer polycarboxylic acid) '', `` EMULGEN '' 920, 930, 935, 985 (polyoxetylene nonylphenylethyl) "," acetamine 86 (stearylamine acetate) ", Solsparse 55000 (graft type polymer), 13240 (polyesteramine) from Lubrizol Corporation, 3000, 17000, 27000 (Polymer having functional part at the end), 24000, 28000, 32000, 385000 (graft type polymer), Nikko Chemicals `` NIKKOL T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (poly Oxetylene monostearate) ", and the like. As the polymer compound in the present invention, a known polymer compound may be used alone, or two or more kinds thereof may be used. In addition, a well-known high molecular compound may be used together with 1 or more types of high molecular compounds mentioned later, and the high molecular compound mentioned later may be used independently.

Hereinafter, a nonionic high molecular compound is demonstrated in detail.

It is preferable that a nonionic high molecular compound is represented by following General formula (11).

In Formula (11), A ¹ represents an acid group, a group containing a basic nitrogen atom, a urea group, a urethane group, a group containing a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, and an isocyanate group. And a monovalent organic group containing a group selected from hydroxyl groups, or a monovalent organic group containing an organic pigment structure or a heterocyclic ring which may contain a substituent. n pieces A ¹ may be the same or different.

Specifically, A ¹ is in particular, but not limited, wherein as the "monovalent organic group containing an acidic group", for example, carboxylate, sulfonate, mono-sulfate ester group, a phosphate group, monophosphate ester group, boric acid group The monovalent organic group which has etc. is mentioned. Further, as the "monovalent organic group containing a group having a basic nitrogen atom" mentioned above, for example, an amino group (-NH ₂₎ a monovalent organic group, a substituted imino group ^{(-NHR 8, -NR 9 R 10} ) having a Monovalent organic groups having 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, an aralkyl group having 7 to 30 carbon atoms), and a guanidyl group represented by the following general formula (a1): Valent organic group [R ^{a1 in} general formula (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, an aralkyl group having 7 to 30 carbon atoms, and 1 having an amidinyl group represented by the following general formula (a2). Valent organic groups [in the general formula (a2), R ^a3 And R ^a4 each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, and the like.

As said "monovalent organic group which has a urea group", for example, -NHCONHR ¹⁵ (wherein R ¹⁵ is Hydrogen atom or a C1-C20 alkyl group, a C6-C20 aryl group, a C7-C30 aralkyl group, etc. are mentioned.

As said "monovalent organic group which has a urethane group", for example, -NHCOOR ¹⁶ , -OCONHR ¹⁷ (here, R ¹⁶ And R ¹⁷ is Each one independently And an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, and the like.

As said "group containing a group which has a coordinating oxygen atom", the group containing an acetylacetonate group, the group which has a crown ether, etc. are mentioned, for example.

As said "group which has a C4 or more hydrocarbon group", For example, an C4 or more alkyl group (for example, an octyl group, a dodecyl group, etc.), a C6 or more aryl group (for example, a phenyl group, a naphthyl group, etc.), And aralkyl groups having 7 or more carbon atoms (eg, benzyl groups). Although there is no upper limit in carbon number at this time, it is preferable that it is 30 or less. As said "group which has an alkoxy silyl group", the group which has a trimethoxy silyl group, a triethoxy silyl group, etc. is mentioned, for example.

As said "group which has an epoxy group", the group which has glycidyl group etc. is mentioned, for example.

As said "group which has an isocyanate group", 3-isocyanate propyl group etc. are mentioned, for example.

As said "group which has a hydroxyl group", 3-hydroxypropyl group etc. are mentioned, for example.

Among the above, as the A ^1, it is preferable that the acidic group, a group having a basic nitrogen atom, a urea group and a monovalent organic group having a group selected from a hydrocarbon group having 4 or more carbon atoms.

The organic pigment structure or hetero ring is not particularly limited. More specifically, the organic pigment structure may include, for example, a phthalocyanine compound, an insoluble azo compound, an azolake compound, an anthraquinone compound, a quinacridone compound, Dioxazine compounds, diketopyrrolopyrrole compounds, anthrapyridine compounds, andanthrone compounds, indanthrone compounds, flavantron compounds, perinone compounds, perylene compounds, thioindigo compounds, and the like. Moreover, as a hetero ring, For example, thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, Oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindolin, isoindolinone, benz Imidazolone, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridon, anthraquinone and the like.

Moreover, the said organic pigment | dye structure or heterocyclic ring may have a substituent, As said substituent, C1-C16 alkyl groups, such as a C1-C20 alkyl group, such as a methyl group and an ethyl group, a phenyl group, a naphthyl group, and a hydroxyl group, for example. Alkoxy groups having 1 to 6 carbon atoms such as acyloxy groups, such as amide groups, carboxyl groups, sulfonamide groups, N-sulfonylamide groups and acetoxy groups, methoxy groups and ethoxy groups, chlorine and bromine Carbonate ester groups, such as a C2-C7 alkoxycarbonyl group, a cyano group, t-butyl carbonate, etc., such as a halogen atom, a methoxycarbonyl group, an ethoxycarbonyl group, and a cyclohexyloxycarbonyl group, are mentioned.

In addition, as the A ^1, preferably to a monovalent organic group represented by the general formula (4).

In the general formula (4), B ¹ is an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group And an organic pigment structure or a heterocyclic ring which may have a group selected from a hydroxyl group or a substituent, and R ¹⁸ represents a single bond or a monovalent organic or inorganic linking group. a1 represents a 1 ~ 5, a1 of B ¹ may be the same or different.

B ¹ is the same meaning as the A ¹ in the formula (4), but also preferred embodiments, as the organic dye structure or a heterocyclic ring, for example, a phthalocyanine compound, an insoluble azo compound, an azo lake compounds, anthraquinone Organic pigment structures such as compounds, quinacridone compounds, dioxazine compounds, diketopyrrolopyrrole compounds, anthrapyridine compounds, andanthrone compounds, indrone compounds, flavantron compounds, perinone compounds, perylene compounds, and thioindigo compounds For example, thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, tria Sol, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindolin, isoindolinone, benzimidazolone, succinate Imide, phthalimi Heterocyclic rings, such as de, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridon, anthraquinone, are mentioned.

Moreover, the said organic pigment | dye structure or heterocyclic ring may have a substituent, As said substituent, C1-C16 aryl groups, such as a C1-C20 alkyl group, such as a methyl group and an ethyl group, a phenyl group, a naphthyl group, C1-C6 alkoxy groups such as hydroxyl, amino, carboxyl, sulfonamide, N-sulfonylamide and acetoxy groups, alkoxy groups such as chlorine, bromine, and the like. Carbonate ester groups, such as a C2-C7 alkoxycarbonyl group, a cyano group, t-butyl carbonate, etc., such as a halogen atom, a methoxycarbonyl group, an ethoxycarbonyl group, and a cyclohexyloxycarbonyl group, are mentioned.

R <^18> represents a single bond or a1 + monovalent coupling group, and a1 represents 1-5. The linking group R ^{18 includes a} group consisting of 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. You may have it. R ¹⁸ is preferably an organic linking group.

As a specific example of R <^18> , the following structural unit or the group comprised by the said structural unit can be enumerated.

If you have a substituent R ¹⁸ in the above, examples of the substituent group, e.g., methyl, ethyl, etc. having 1 to 20 carbon alkyl group, a phenyl group, a naphthyl group having 6 to 16 aryl group, a hydroxyl group, an amino group, a carboxyl group of the a, sulfone C1-C6 alkoxy groups, such as an acyloxy group, such as an amide group, N-sulfonylamide group, and an acetoxy group, a methoxy group, an ethoxy group, halogen atoms, such as chlorine and a bromine, and methoxycarbonyl group Carbonate ester groups, such as a C2-C7 alkoxycarbonyl group, a cyano group, and t-butyl carbonate, such as an ethoxy carbonyl group and a cyclohexyloxycarbonyl group, etc. are mentioned.

In said general formula (11), R <^1> represents a (m + n) valent coupling group. m + n satisfies 3-10.

Examples of the (m + n) valence group represented by R ¹ include 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. The group to be included is included and you may further have a substituent which is unsubstituted. R ¹ is preferably an organic linking group.

As a specific example of R <^1> , the structural unit of said (t-1)-(t-34) or the group (you may form ring structure) comprised by combining these can be mentioned.

When said linking group has a substituent, as said substituent, a C6-C16 aryl group, such as a C1-C20 alkyl group, such as a methyl group and an ethyl group, a phenyl group, a naphthyl group, a hydroxyl group, an amino group, a carboxyl group, a sulfone, for example C1-C6 alkoxy groups, such as an acyloxy group, such as an amide group, N-sulfonylamide group, and an acetoxy group, a methoxy group, an ethoxy group, halogen atoms, such as chlorine and a bromine, and methoxycarbonyl group Carbonate ester groups, such as a C2-C7 alkoxycarbonyl group, a cyano group, and t-butyl carbonate, such as an ethoxy carbonyl group and a cyclohexyloxycarbonyl group, etc. are mentioned.

R ² represents a single bond or a divalent linking group. As R ² , The group consisting of 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 is included, and may be unsubstituted or further have a substituent. R ² is preferably an organic linking group.

Of R ² As a specific example, the structural unit of t-3, 4, 7-18, 22-26, 32, 34, or the group comprised by the said structural unit can be enumerated.

Among the above, R ² is When having a substituent, as said substituent, a C6-C16 aryl group, a hydroxyl group, an amino group, a carboxy group, a sulfonamide group, N-, such as a methyl group, a C1-C20 alkyl group of a ethyl group, a phenyl group, a naphthyl group, is mentioned, for example. C1-C6 alkoxy groups, such as a C1-C6 acyloxy group, a methoxy group, an ethoxy group, such as a sulfonylamide group and an acetoxy group, halogen atoms, such as chlorine and a bromine, a methoxycarbonyl group, an ethoxycarbonyl group, Carbonate ester groups, such as a C2-C7 alkoxycarbonyl group, a cyano group, t-butyl carbonate, such as a cyclohexyloxycarbonyl group, etc. are mentioned.

In said general formula (11), m shows the integer of 1-8. As m, 1-5 are preferable, 1-3 are more preferable, and 1-2 are especially preferable.

In addition, n represents the integer of 2-9. As n, it is preferable that it is 2-8, It is more preferable that it is 2-7, 3-6 are especially preferable.

P <^1> in the said General formula (11) represents a polymer residue, It can select from a normal polymer etc. according to the objective.

Among polymers, polymers or copolymers of vinyl monomers, ester-based polymers, ether-based polymers, urethane-based polymers, amide-based polymers, epoxy-based polymers, silicone-based polymers and modified products thereof, or copolymers may be used to form a polymer skeleton. And a copolymer of a polyether / polyurethane copolymer, a polyether / vinyl monomer polymer, or the like (any of random copolymers, block copolymers, and graft copolymers) may be included. 1 or more types are preferable, It is more preferable that they are 1 or more types chosen from the group which consists of a polymer or copolymer of a vinyl monomer, an ester type polymer, an ether type polymer, a urethane type polymer, and these modified | denatured products or a copolymer, and of a vinyl monomer Particular preference is given to polymers or copolymers.

In addition, the polymer is preferably soluble in an organic solvent. If the affinity with an organic solvent is low, for example, when used as a pigment dispersant, the affinity with a dispersion medium may become weak and it may become impossible to ensure the adsorption layer sufficient for dispersion stabilization.

Among the polymer compounds represented by the general formula (11), the polymer compounds represented by the following general formula (12) are more preferable.

In the formula (12), A ² is remind In general formula (11), A ¹ and Although the same meaning and the specific preferable aspect are the same, as a specific example of an organic pigment | dye structure, a phthalocyanine compound, an azo lake compound, an anthraquinone compound, a dioxazine compound, a diketone pyrrolopyrrole compound, etc. are more preferable, and imidazole as a hetero ring , Triazole, pyridine, piperidine, morpholine, triazine, isoindolin, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, More preferred are indole, quinoline, carbazole, acridine, acridon, anthraquinone and the like.

Moreover, you may have a substituent like A <^1>, and in the said substituent, it is the same as the case in A <^1> , and a preferable aspect is also the same.

Moreover, as A <^2> , the monovalent organic group represented by the said General formula (4) is preferable, A detailed description, a specific example, and a preferable aspect of the said organic group are the same.

In the said General formula (12), R <^3> represents a (x + y) valent coupling group. The (x + y) valence group represented by R ³ includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 20 sulfur atoms It may contain a group, may be unsubstituted, and may have a substituent further.

As a (x + y) valent coupling group represented by said R <^3> , it is the same as the (m + n) valent coupling group in said R <^1> , The preferable aspect is also the same. Moreover, as a specific example, the group comprised by the same structural unit or the said structural unit combined is enumerated.

It is preferable that the coupling group represented by R <^3> among these is an organic coupling group, and the preferable specific example [specific example (r-1)-(r-17)] of this organic coupling group is shown below. However, in this invention, it is not limited to these.

From the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents in the above, (r-1), (r-2), (r-10), (r-11), and (r-16) and (r-17) are preferable.

In addition, when said R <^3> has a substituent, as said substituent, a C1-C20 alkyl group, such as a C1-C20 alkyl group, such as a methyl group and an ethyl group, a phenyl group, a naphthyl group, an aryl group, a hydroxyl group, an amino group, C1-C6 alkoxy groups, such as carboxyl group, sulfonamide group, N-sulfonylamide group, and acetoxy group, C1-C6 alkoxy group, such as alkoxy group, halogen atom, such as chlorine and bromine, Carbonate ester groups, such as a C2-C7 alkoxycarbonyl group, a cyano group, t-butyl carbonate, etc., such as a methoxycarbonyl group, an ethoxycarbonyl group, and a cyclohexyloxycarbonyl group, are mentioned.

In the formula (12), R ⁴ And R ⁵ is Each independently represents a single bond or a divalent linking group.

As a "bivalent coupling group" represented by said R <^4> , R <^5> , it may be unsubstituted or may have a substituent, and may be a linear, branched, or cyclic alkylene group, arylene group, aralkylene group, and -O-, -S-, -C (= O)-, -N (R ¹⁹ )-, -SO-, -SO _2- , -CO _2- , -N (R ²⁰ ) SO _2- , or two groups thereof It can be exemplified divalent or more that combination as a preferable example. (wherein R ¹⁹ And R ²⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Especially, it is preferable that it is an organic coupling group.

The R ⁴ as straight chain, alkyl group, aralkyl group and -O-, -C (= O) on the branch ^{-, -N (R 19) -} , -SO 2 -, -CO 2 -, -N (R ²⁰⁾ SO ₂ - (wherein R ¹⁹ And R ²⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), or a divalent group obtained by combining two or more of these groups is more preferable, and a linear, branched alkylene group, aralkylene group, and -O group. -, -C (= O)-, -N (R ¹⁹ )-(wherein R ¹⁹ is Particularly preferable is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), -CO _2- , or a combination of two or more of these groups.

R ^{5 may be a} single bond or a linear, branched alkylene group, aralkylene group, and —O—, —C (═O) —, —N (R ¹⁹ ) —, —SO ₂ —, —CO ₂ —, N (R ²⁰ ) SO _2- (R ¹⁹ above) And R ²⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), or a divalent group obtained by combining two or more of these groups is more preferable, and a linear, branched alkylene group, aralkylene group, and -O- , -C (= 0)-, -N (R ¹⁹ )-(wherein R ¹⁹ is Particularly preferable is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), -CO _2- , or a combination of two or more of these groups.

In addition, R ⁴ , R ⁵ is When it has a substituent, As said substituent, For example, C1-C20 aryl groups, such as a C1-C20 alkyl group, such as a methyl group and an ethyl group, a phenyl group, a naphthyl group, a hydroxy group, an amino group, a carboxy group, a sulfonamide group, N C1-C6 alkoxy groups such as acyloxy groups such as sulfonylamide groups and acetoxy groups, methoxy groups and ethoxy groups, halogen atoms such as chlorine and bromine, methoxycarbonyl groups and ethoxycarbonyl groups Carbonate ester groups, such as a C2-C7 alkoxycarbonyl group, a cyano group, t-butyl carbonate, such as a cyclohexyloxycarbonyl group, etc. are mentioned.

In said general formula (12), y represents 1-8, 1-5 are preferable, 1-3 are more preferable, and 1-2 are especially preferable. Moreover, x represents 2-9, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

In addition, P <^2> in General formula (12) is A polymer residue is shown and can be selected from a normal polymer etc. according to the objective. About a preferable aspect of a polymer, it is the same as P <^1> in the said General formula (11), and its preferable aspect is also the same.

Among the polymer compounds represented by the general formula (12), in particular, R ³ represents the specific examples (r-1), (r-2), (r-10), (r-11), and (r-16). , Or (r-17), R ⁴ is a single bond, a straight chain, a branched alkylene group, an aralkylene group, -O-, -C (= O)-, -N (R ¹⁹ )-(the above R ¹⁹ Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), -CO _2- , or a divalent organic group in which two or more of these groups are combined, and R ⁵ is a single bond, an ethylene group, a propylene group, or the following general formula a linking group represented by (sa) or (sb), P ² is a polymer or copolymer of a vinyl monomer, an ester polymer, an ether polymer, a urethane polymer, or a modified product thereof, and y is 1 to 2, x Particularly preferred are polymer compounds having 3 to 6 carbon atoms. On the other hand, in the following group, R ²¹ represents a hydrogen atom or a methyl group, and l represents 1 or 2.

Although the weight average molecular weight of the high molecular compound which can be used for the manufacturing method of this invention is 1000 or more, 3000-100000 are preferable at a weight average molecular weight, 5000-80000 are more preferable, 7000-60000 are especially preferable. If the weight average molecular weight is in the above range, the effect of the plurality of functional groups introduced into the terminal portion of the polymer is sufficiently exhibited, and the excellent performance in adsorption to the solid surface, micelle formation ability, and surfactant activity. In particular, when the polymer compound according to the present invention is used as the pigment dispersant, good dispersibility and dispersion stability can be achieved.

The polymer compound represented by the general formula (11) (including one represented by the general formula (12)) is not particularly limited, but may be synthesized by the following method or the like. Among the following synthesis methods, from the ease of synthesis, synthesis methods such as 2, 3, 4, and 5 are more preferable, and synthesis methods such as 3, 4 and 5 are particularly preferable.

1. An acid halide having a polymer having a functional group selected from a carboxyl group, a hydroxyl group, an amino group, and the like at the terminal, and a plurality of functional groups (A ¹ or A ² in the general formula), or a plurality of functional groups (A ¹ in the general formula) or an alkyl halide, or a plurality of functional groups (such as isocyanate method when the key is in polymers having a ¹ or a ²⁾ in the formula having the a ^2).

2. at the terminal carbon-carbon double bond functional group and the introduction of polymer, a plurality of methods of a mercaptan having a (A ¹ or A ² in the formula), the Michael addition reaction.

3. 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 general formula) are reacted under a radical generator.

4. A method in which a polymer having a plurality of mercaptans introduced at its terminal and a functional group (A ¹ or A ² in the general formula) having introduced a carbon-carbon double bond are reacted under a radical generator.

5. A plurality of functional groups (A ¹ or A method of radically polymerizing a vinyl monomer using a mercaptan compound having A ² ) as a chain transfer agent.

Among the above, the high molecular compound (preferably the high molecular compound represented by General formula (12)) which can be used for the manufacturing method of this invention can be synthesize | combined also by any of the methods of said 2, 3, 4, 5. Although it is possible, it is more preferable to synthesize | combine by the method of said 5 from the ease of synthesis.

More specifically, it is preferable to radical-polymerize using the compound represented by following General formula (13) as a chain transfer agent.

In the formula (13), R ^{6 ,} R ⁷ , A ³ , g and h are the same as R ³ , R ⁴ , A ² , x and y in the formula (12), respectively, The preferred embodiment is also the same.

Although it does not restrict | limit especially as said vinyl monomer, For example, (meth) acrylic acid ester, crotonic acid ester, vinyl ester, maleic acid diester, fumaric acid diester, itaconic acid ester, (meth) acrylamide Drew, vinyl ether, ester of vinyl alcohol, styrene, (meth) acrylonitrile, etc. are preferable. Such compounds include the following compounds.

As an example of the said (meth) acrylic acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl ( Meth) acrylate, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxy Ethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2 -Hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol Nomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (Meth) acrylate, polyethyleneglycol monoethyl ether (meth) acrylate, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylic Rate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) Acrylate, tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, etc. are mentioned.

Examples of the crotonic acid esters include butyl crotonate, hexyl crotonate, and the like.

Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, vinyl benzoate and the like.

Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, dibutyl maleate and the like.

Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.

Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, dibutyl itaconate and the like. As an example of the said (meth) acrylamide, (meth) acrylamide, N-propyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) Acrylamide, Nn-butylacryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N- Dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloyl morpholine, diacetone acrylamide And the like.

Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene and bromine Examples thereof include styrene styrene, methylvinylbenzoate and α-methyl styrene, which are protected by a group such as mostyrene, chloromethyl styrene, and deprotectable groups (eg, t-Boc) by an acidic substance.

Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, and the like.

In addition to the above compounds, (meth) acrylonitrile, a heterocyclic group substituted with a vinyl group (for example, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinyl caprolactone, etc. can also be used.

In addition to the above compounds, vinyl monomers having functional groups such as urethane groups, urea groups, sulfonamide groups, phenol groups and imide groups can also be used. As a monomer which has such a urethane group or a urea group, it is possible to synthesize | combine suitably using the addition reaction of an isocyanate group, a hydroxyl group, or an amino group, for example. Specifically, addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxy group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or a primary or secondary amino group-containing monomer and a monoisocyanate It can synthesize | combine suitably by addition reaction with etc.

Said vinyl monomer may be superposed | polymerized only by 1 type, and may be copolymerized in combination of 2 or more types, and such radical polymers can respectively superpose | polymerize a corresponding vinyl monomer by a conventional method according to a conventional method.

For example, these vinyl monomers and chain transfer agents can be obtained by dissolving them in a suitable solvent, adding a radical polymerization initiator thereto, and polymerizing them in a solution at about 50 ° C to 220 ° C (solution polymerization method). .

As an example of the suitable solvent which can be used by solution polymerization method, it can select arbitrarily according to the solubility of the monomer to be used and the copolymer to produce | generate. For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate , Ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene. You may use these solvent in mixture of 2 or more type.

Moreover, as a radical polymerization initiator, Azo compounds, such as 2,2'- azobis (isobutyronitrile) (AIBN), 2,2'- azobis- (2,4'- dimethylvaleronitrile), and benzoyl perox Peroxides such as seeds and persulfates such as potassium persulfate and ammonium persulfate may be used.

Although the compound represented by the said General formula (13) can be synthesize | combined by the following method etc., the method of following 7 is more preferable from the ease of synthesis.

6. A method of converting a halide compound having a plurality of functional groups (A ¹ or A ² in the general formula) to a mercaptan compound (reaction with thiourea, hydrolysis, direct reaction with NaSH, CH ₃ COSNa and The method of reacting and hydrolyzing is mentioned).

7.1 a compound having 3 to 10 mercapto groups in a molecule and a functional group having a method of (A ¹ or A ² in the formula), and the addition reaction of a compound having a mercapto group and a reactive functional group.

In the said method 7, as a "functional group which can react with a mercapto group," an acid halide, an alkyl halide, an isocyanate, a carbon-carbon double bond, etc. can be mentioned as a preferable example.

It is especially preferable that "the functional group which can react with a mercapto group" is a carbon-carbon double bond, and the addition reaction synthesize | combines by radical addition reaction. As a carbon-carbon double bond, a mono- or bi-substituted vinyl group is more preferable from a reactive viewpoint with a mercapto group.

The following compounds can be mentioned as a specific example [specific example (18)-(34)] of the said "compound which has 3-10 mercapto groups in 1 molecule."

Among them, from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents, (u-18), (u-19), (u-27), (u-28), and (u-33) and (u-34) are preferred.

It has a functional group (A ¹ or A ² in the formula), and carbon-be, but are not especially limited Examples of the compound having a carbon-carbon double bond, such as listed below that.

For example, "the compound which has 3-10 mercapto groups in 1 molecule" and the said "acid group, group which has basic nitrogen atom, urea group, urethane group, coordination oxygen atom group, carbon number 4 or more The radical addition reaction product with the "compound which contains 1 or more types of functional groups chosen from a hydrocarbon group, an alkoxy silyl group, an epoxy group, an isocyanate group, and a hydroxyl group, and also has a carbon-carbon double bond", for example, said "1 Compounds having 3 to 10 mercapto groups in the molecule &quot; and &quot; acid group, group having basic nitrogen atom, urea group, urethane group, group containing coordinating oxygen atom, hydrocarbon group having 4 or more carbon atoms, alkoxysilyl group, Compound having one or more functional groups selected from an epoxy group, an isocyanate group and a hydroxyl group and having a carbon-carbon double bond ”is dissolved in a suitable solvent, and A radical generator can be added and the method (thiolene reaction method) of adding at about 50 degreeC-100 degreeC can be used.

As an example of the preferable solvent which can be used by the said method, "The compound which has 3-10 mercapto groups in 1 molecule" used, "The group which has an acidic group, a basic nitrogen atom, a urea group, a urethane group, a coordination oxygen atom A functional group having at least one functional group selected from a group having 4, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group, and capable of reacting with a mercapto group (for example, a carbon-carbon double bond). Compound having a) &quot; and the solubility of the resulting radical addition reaction product. For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate , Ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene. You may use these solvent in mixture of 2 or more type.

Moreover, as a radical generator, azo compounds, such as 2,2'- azobis (isobutyronitrile) (AIBN), 2,2'- azobis- (2,4'- dimethylvaleronitrile), and benzoyl peroxide Peroxides such as and persulfates such as potassium persulfate and ammonium persulfate may be used.

The specific example of the compound represented by General formula (11) which can be used suitably for the manufacturing method of this invention is shown below. However, this invention is not limited to these specific examples at all.

In addition, the polymer compound is preferably a polymer compound having an acidic group, and more preferably a polymer compound having a carboxyl group. Particular preference is given to copolymers containing at least one of the repeating units derived from a compound having (A) a carboxyl group and at least one of the repeating units derived from a compound having a (B) a carboxylic acid ester group.

As a repeating unit derived from the compound which has the said (A) carboxyl group, it is preferable that it is a repeating unit represented with the following general formula (I), It is more preferable that it is a repeating unit derived from acrylic acid or methacrylic acid, (B) As a repeating unit derived from the compound which has a carboxylic acid ester group, it is preferable that it is a repeating unit represented with the following general formula (II), It is more preferable that it is a repeating unit represented with the following general formula (IV), Benzyl acrylate, Benzyl It is preferably a repeating unit derived from methacrylate, phenethyl acrylate, phenethyl methacrylate, 3-phenylpropyl acrylate, or 3-phenylpropyl methacrylate.

(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 6 to 20 carbon atoms in the aryl group. R ₅ And R ₆ each represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. X1 represents the number of 1-5.)

(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 general formula (V).)

(R ₉ is An alkyl group having 2 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms is represented. R ₁₀ And R ₁₁ is Hydrogen atom or a C1-C5 alkyl group is represented. Y1 represents the number of 1-5.)

In addition, in terms of the polymerization ratio between the repeating unit derived from the compound having a carboxyl group (A) and the repeating unit derived from the compound having a carboxylic acid ester group (B), the yield ratio% of all repeating units of the repeating unit (A) It is preferable that it is 3-40, and it is more preferable that it is 5-35.

Moreover, in the manufacturing method of the organic nanoparticle of this invention, it is also preferable to use the high molecular compound containing the graft copolymer which has an amino group and an ether group, and contains the other component suitably selected as needed.

The said graft copolymer may contain a little amino group and an ether group, and may contain other monomers etc. as a copolymer unit.

As a median average molecular weight (Mw) of the said graft copolymer, it is preferable that it is 3000-100000, and it is more preferable that it is 5000-50000. When the weight average molecular weight (Mw) is too small, aggregation of organic nanoparticles cannot be prevented, the viscosity increases, and when too large, the solubility in an organic solvent is insufficient and the viscosity increases. In addition, the said weight average molecular weight is the polystyrene conversion weight average molecular weight measured by gel permeation chromatography (carrier: tetrahydrofuran).

The graft copolymer comprises (i) a polymerizable oligomer having an ethylenically unsaturated double bond at its terminal, (ii) a monomer having an amino group and an ethylenically unsaturated double bond, and (iii) a polymerizable monomer having an ether group as a copolymer unit. It is preferable to contain even a small amount and to contain (iv) other monomer as a copolymerization unit as needed.

As content in the said graft copolymer of these copolymer units, it is preferable that (i) the said polymeric oligomer is 15-98 mass%, It is more preferable that it is 25-90 mass%, (ii) Amino group It is preferable that containing monomer is 1-40 mass%, It is more preferable that it is 5-30 mass%, (iii) It is preferable that the polymerizable monomer which has the said ether group is 1-70 mass%, It is 5-60 mass It is more preferable that it is%.

When the content of the polymerizable oligomer is too small, the steric repulsion effect as a dispersant may not be obtained, and aggregation of the organic nanoparticles may not be prevented. When the content is too high, the proportion of the nitrogen-containing monomer decreases to the organic particles. The adsorption capacity with respect to this may fall, and dispersibility may not be enough. When the content of the nitrogen-containing monomer is too small, the adsorption capacity to organic particles may be lowered, and the dispersibility may not be sufficient. If the content is too high, the proportion of the polymerizable oligomer is reduced, so that the steric repulsion effect as a dispersant is exerted. It may not be obtained, and aggregation of organic particles may not be prevented sufficiently. When there is too little content of the polymerizable monomer which has the said ether group, developability at the time of manufacture of color filters etc. may not be enough, and when too large, the ability as a dispersing agent may fall.

(i) polymerizable oligomers

The said polymerizable oligomer (henceforth a "macromonomer") is an oligomer which has a terminal which has an ethylenically unsaturated double bond at the terminal. In this invention, it is preferable to contain the group which has the said ethylenically unsaturated double bond only in one side in the terminal part of the said oligomer among the said polymerizable oligomers.

 As said oligomer, generally, homopolymer or air formed from one or more monomers selected from alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, styrene, acrylonitrile, vinyl acetate and butadiene, for example. The copolymer etc. are enumerated, Among these, the homopolymer or copolymer of alkyl (meth) acrylate, polystyrene, etc. are preferable. In the present invention, these oligomers may be substituted with substituents, and are not particularly limited as the substituents. Examples thereof include halogen atoms and the like.

As group containing the said ethylenically unsaturated double bond, a (meth) acryloyl group, a vinyl group, etc. are mentioned preferably, for example, Among these, a (meth) acrylo group is especially preferable.

In this invention, among the said polymerizable oligomers, the oligomer represented by the following general formula (E6) is preferable.

In General Formula (E6), R ⁶¹ and R ⁶³ represent a hydrogen atom or a methyl group. R ⁶² is The alkylene group which may be substituted by the C1-C8 alcoholic hydroxyl group is shown, and the C2-C4 alkylene group is preferable. Y ⁶ is a phenyl group, a phenyl group having an alkyl group having 1 to 4 carbon atoms, or -COOR ⁶⁴ (wherein R ⁶⁴ is an alcoholic hydroxy group having 1 to 6 carbon atoms, an alkyl group which may be substituted with halogen, a phenyl group, or an arylalkyl group having 7 to 10 carbon atoms). Phenyl group or -COOR ⁶⁴ (where R ⁶⁴ represents an alkyl group which may be substituted with an alcoholic hydroxy group having 1 to 4 carbon atoms). q represents 20-200.

As a specific example of the said polymeric oligomer, poly-2hydroxyethyl (meth) acrylate, polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, poly-i-butyl (meth) acryl In the rate and these copolymers, the polymer which the (meth) acryloyl group couple | bonded with one of the molecular terminal is preferable.

The polymerizable oligomer may be commercially available or may be appropriately synthesized. Examples of commercially available oligomers include single-terminal methacryloylated polystyrene oligomers (Mn = 6000, trade name: AS-6, TOAGOSEI CO., LTD.). ), Single-ended methacryloylated polymethylmethacrylate oligomer (Mn = 6000, trade name: AA-6, manufactured by TOAGOSEI CO., LTD), single-ended methacryloylated poly-n-butylacrylate oligomer (Mn = 6000, trade name: AB-6, manufactured by TOAGOSEI CO., LTD), single-terminal methacryloylated polymethylmethacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7000, trade name: AA-714, TOAGOSEI CO) , LTD), single-ended methacryloylated polybutyl methacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7000, trade name: 707S, manufactured by TOAGOSEI CO., LTD), single-ended methacryloylated Poly 2-ethylhexyl methacrylate / 2-hydroxyethyl methacrylate oligomer ( Mn = 7000, trade name: AY-707S, AY-714S, manufactured by TOAGOSEI CO., LTD.

Preferable specific examples of the polymerizable oligomers in the present invention include at least one oligomer selected from alkyl (meth) acrylate polymers and copolymers of alkyl (meth) acrylates and polystyrenes, and have a number average molecular weight of 1000 to 20000. The thing which has a (meth) acryloyl group in is mentioned.

(ii) amino group-containing monomers

As said amino group containing monomer, 1 or more types chosen from the compound represented, for example by the following general formula (E2) is mentioned preferably.

In the general formula (E2), R ²¹ is Hydrogen atom or a methyl group is represented. R <^22> represents a C1-C8 alkylene group, Among these, a C1-C6 alkylene group is preferable and a C2-C3 alkylene group is especially preferable. X ² represents —N (R ²³ ) (R ²⁴ ), —R ²⁵ N (R ²⁶ ) (R ²⁷ ). Where R ²³ And R <^24> represents a hydrogen atom, a C1-C6 alkyl group, or a phenyl group. R ²⁵ represents an alkylene group having 1 to 6 carbon atoms, and R ²⁶ And R ²⁷ is Hydrogen atom, a C1-C6 alkyl group, or a phenyl group is represented.

In the -N (R ²³⁾ R ²³ a (R ²⁴⁾ And R ²⁴ is an alkyl group or a phenyl group of a hydrogen atom or a group having from 1 to 4 carbon atoms ^{preferably, -R 25 -N (R 26)} (R 27) R 25 is preferably an alkylene group having 2 to 6 carbon atoms, and the R ²⁶ And R ²⁷ is preferably an alkyl group having 1 to 4 carbon atoms. m2 and n2 represent 1 or 0, and m2 = 1 and n2 = 1 or m2 = 1 and n2 = 0 are preferable (that is, correspond to the monomer represented by following General formula (E3) and (E4)).

In this invention, it is preferable that it is 1 or more types chosen from the monomer represented by any of the following general formula (E3) and (E4) also in the monomer represented by the said general formula (E2).

In the general formula (E3), R ³¹ is It is the same as R ²¹ in General Formula (E2). R ³² is the same as R ²² in General Formula (E2). X ³ is and X ² in the formula (E2) same.

In General Formula (E4), R ⁴¹ is the same as R ²¹ in General Formula (E2). X ⁴ is the same as X ² in formula (E2), and —N (R ⁴³ ) (R ⁴⁴ ), wherein R ⁴³ and R ⁴⁴ are the same as R ²³ and R ²⁴ in formula (E2). ), Or -R ⁴⁵ -N (R ⁴⁶ ) (R ⁴⁷ ), wherein R ⁴⁵ , R ⁴⁶ and R ⁴⁷ are the same as R ²⁵ , R ²⁶ and R ²⁷ in formula (E2), respectively. desirable.

As a specific example of the monomer represented by the said general formula (E2), dimethyl (meth) acrylamide, diethyl (meth) acrylamide, diisopropyl (meth) acrylamide, di-n-butyl (meth) acrylamide, di- i-butyl (meth) acrylamide, morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide and N, N-methyl phenyl (meth ) Acrylamide (above, (meth) acrylamide); 2- (N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, N-diethylamino) ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth) Acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylamide, 6- (N, N- Diethylamino) hexyl (meth) acrylamide (above, aminoalkyl (meth) acrylamides) etc. are mentioned as preferable.

(iii) a polymerizable monomer containing an ether group

As a polymerizable monomer containing the said ether group, 1 or more types chosen from the monomer represented by following General formula (E1) is mentioned preferably, for example.

In General Formula (E1), R ¹¹ represents a hydrogen atom or a methyl group. R <^12> represents a C1-C8 alkylene group, Especially, a C1-C6 alkylene group is preferable and a C2-C3 alkylene group is more preferable. X ¹ represents -OR ¹³ or -OCOR ¹⁴ . Here, R <^13> represents a hydrogen atom, a C1-C18 alkyl group, a phenyl group, or the phenyl group substituted by the C1-C18 alkyl group. R <^14> represents a C1-C18 alkyl group. Moreover, m3 represents 2-200, 5-100 are preferable and 10-100 are especially preferable.

The polymerizable monomer containing an ether group is not particularly limited as long as it has an ether group and is polymerizable, and can be appropriately selected from conventional ones. For example, polyethylene glycol mono (meth) acrylate and polypropylene glycol mono ( Meta) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, polytetramethylene glycol monomethacrylate, and the like, and the like may be commercially available products, or may be appropriately synthesized. As said commercial item, methoxy polyethyleneglycol methacrylate (brand name: NK ester M-40G, M-90G, M-230G (above, TOAGOSEI CO., LTD product); brand name: BLEMMER PME-100, PME-200, PME -400, PME-1000, PME-2000, PME-4000 (above, NOF CORPORATION), polyethylene glycol monomethacrylate (trade name: BLEMMER PE-90, PE-200, PE-350, NOF CORPORATION), poly Propylene glycol monomethacrylate (brand name: BLEMMER PP-500, PP-800, PP-1000, NOF CORPORATION products), polyethylene glycol polypropylene glycol monomethacrylate (brand name: BLEMMER 70PEP-370B, NOF CORPORATION products), polyethylene Glycol polytetramethylene glycol monomethacrylate (trade name: BLEMMER 55PET-800, manufactured by NOF CORPORATION), polypropylene glycol polytetramethylene glycol monomethacrylate (trade name: BLEMMER NHK-5050, NOF CORPORATION).

(iv) other monomers

The graft copolymer may further contain the other monomer as a copolymer unit, and is not particularly limited as the other monomer, and may be appropriately selected according to the purpose. For example, an aromatic vinyl compound (eg, styrene , α-methylstyrene and vinyltoluene), alkyl (meth) acrylates (e.g., methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate and i-butyl (meth) acrylate ), (Meth) acrylic acid alkylaryl esters (e.g. benzyl (meth) acrylate), glycidyl (meth) acrylates, carboxylic acid vinyl esters (e.g. vinyl acetate and vinyl propionate), vinyl cyanide (e.g. ( Meta) acrylonitrile and α-chloroacrylonitrile) and aliphatic conjugated dienes (eg, 1,3-butadiene and isoprene), (meth) acrylates, and the like. Among these, unsaturated carboxylic acid, (meth) acrylic-acid alkylester, (meth) acrylic-acid alkylaryl ester, and carboxylic acid vinyl ester are preferable.

As content of the said other monomer in the said graft copolymer, it is preferable that it is 5-70 mass%, for example. When the content is too small, the coating film physical properties may not be controlled, and when too large, the capacity may not be sufficiently exhibited as a dispersant.

As a preferable specific example of the said graft copolymer

(11) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,

(12) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminal methacryloylated polystyrene copolymer,

(13) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / methyl (meth) acrylate terminal methacryloylated polystyrene copolymer,

(14) of the copolymer of 3- (N, N-dimethylamino) propylacrylamide / polyethyleneglycol mono (meth) acrylate / terminal methacryloylated methyl (meth) acrylate and 2-hydroxyethylmethacrylate Copolymer,

(15) Copolymer of 3- (N, N-dimethylamino) propylacrylamide / polyethyleneglycol mono (meth) acrylate / terminated methacryloylated methyl methacrylate and 2-hydroxyethyl methacrylate ,

(16) Copolymer of 3- (N, N-dimethylamino) propylacrylamide / polyethyleneglycol mono (meth) acrylate / terminated methacryloylated methyl methacrylate and 2-hydroxyethyl methacrylate ,

(17) 3- (N, N-dimethylamino) propylacrylamide / polypropylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,

(18) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol polypropylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,

(19) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol polytetramethylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,

(20) 3- (N, N-dimethylamino) propylacrylamide / polypropylene glycol polytetramethylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer and the like.

Especially, (11), (14) and (18) are preferable and the compound represented by a following formula (D4) is more preferable. In formula (D4), Me represents a methyl group.

The said graft copolymer can be obtained by radically polymerizing the component used as each said copolymer unit, for example in a solvent. At the time of the said radical polymerization, a radical polymerization initiator can be used and a chain transfer agent (for example, 2-mercaptoethanol and dodecyl mercaptan) can also be used. As for the pigment dispersant containing the graft copolymer, reference may be made to the description of Japanese Patent Laid-Open No. 2001-31885.

In order to further improve the homogeneous dispersibility and storage stability of the organic particles, the content of the graft copolymer is preferably in the range of 0.1 to 1,000 parts by mass with respect to 100 parts by mass of the pigment, and more preferably in the range of 1 to 500 parts by mass. It is preferable and it is more preferable that it is the range of 5-20 mass parts. When there is too little content, the improvement of the dispersion stability of organic nanoparticles may not appear. In addition, you may use a graft copolymer individually or in combination of several.

As a molecular weight of a polymer in the manufacturing method of this invention, a weight average molecular weight is mentioned unless there is particular notice. As a measuring method of the molecular weight of a polymer, a chromatography method, a viscosity method, a light scattering method, a sedimentation rate method, etc. are mentioned. In the present invention, unless otherwise specified, the weight average molecular weight measured by chromatography is used.

Hereinafter, the anionic polymer compound will be described.

The agglomeration may add a high molecular compound having at least one anionic group. It is preferable that the said high molecular compound has a weight average molecular weight 1000 or more, and is a high molecular compound represented by following General formula (14).

(In the formula, G is _{^{-COO -, -SO 3 -, -OSO}} 3 -, -P (O) (OH) O -, or -OP (O) (OH) O -. J represents a divalent connecting group is Or a single bond, Q represents a (m + 1) valent linking group, R represents a polymer compound moiety, Z represents an organic or inorganic cation, and m + 1 represents 3-6.)

In the general formula (14), G is _{^{-COO -, -SO 3 -, -OSO}} 3 -, -P (O) (OH) O -, or -OP (O) (OH) O - represents the, -SO _{^{3 -, -OSO 3 -, -P}} (O) (OH) O - is more preferable that the. When there are a plurality of G's, G may be the same anionic group or may be different.

Formula (14) wherein J represents a divalent connecting group as a straight chain alkyl group on the branch, aralkyl group and -O-, -C (= O) - , -SO 2 -, -CO 2 -, or their The divalent group which combined two or more groups is preferable, and it is more preferable that the site | part connected with Q in General formula (14) is a sulfur atom.

Moreover, when it has a substituent, as said substituent, a C6-C16 aryl group, such as a C1-C20 alkyl group, such as a methyl group and an ethyl group, a phenyl group, a naphthyl group, a hydroxy group, an amino group, a carboxy group, a sulfonamide group, C1-C6 alkoxy groups, such as N-sulfonylamide group and acetoxy group, C1-C6 alkoxy groups, such as a methoxy group and an ethoxy group, Halogen atoms, such as chlorine and a bromine, methoxycarbonyl group, and ethoxy Carbonate ester groups, such as a C2-C7 alkoxycarbonyl group, a cyano group, t-butyl carbonate, such as a carbonyl group and a cyclohexyloxycarbonyl group, etc. are mentioned.

Examples of the organic cation represented by Z in General Formula (14) include imidazolium salts, pyridinium salts, thiazolium salts, oxazolium salts, imidazolinium salts, thiazolinium salts and oxazolinium salts. Examples of the inorganic cations include lithium ions, sodium ions and potassium ions. Z is preferably an inorganic cation.

In said general formula (14), Q represents a (m + 1) valent coupling group. m + 1 represents 3-6.

Examples of the (m + 1) -valent linking group represented by Q include a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200 hydrogen atoms. You may have a substituent further. It is preferable that Q is an organic coupling group, and the preferable specific example [example compound (r-1)-(r-17)] of this organic coupling group is shown below. However, in this invention, it is not limited to these.

In said general formula (14), m shows the integer of 1-5. As m, it is preferable that it is 2-5, and 3-5 are more preferable. In addition, 1 represents the integer of 1-5. As 1, it is preferable that it is 1-4, It is more preferable that it is 1-3, It is especially preferable that it is 1-2.

In said general formula (14), R represents a high molecular compound residue (polymer skeleton), and can be selected from a normal polymer etc. according to the objective. In this case, the polymer skeleton refers to a polymer structure having a number average molecular weight of 1000 or more. Among the polymers, in order to form a polymer skeleton, polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, amide polymers, epoxy polymers, silicone polymers and modified products thereof or copolymers [for example, For example, a copolymer of a polyether / polyurethane copolymer, a polymer of a polyether / vinyl monomer, or the like (any of random copolymers, block copolymers, and graft copolymers) may be selected. It is preferable that it is at least 1 sort (s), The at least 1 sort (s) chosen from the group which consists of a polymer or a copolymer of a vinyl monomer, an ester type polymer, an ether type polymer, a urethane type polymer, and these modified | denatured products or a copolymer is more preferable, and a vinyl monomer Particular preference is given to polymers or copolymers of.

In addition, the polymer is preferably soluble in an organic solvent. If the affinity with an organic solvent is low, for example, when used as a pigment dispersant, the affinity with a dispersion medium will become weak and it will become impossible to ensure the adsorption layer sufficient for dispersion stabilization.

Although the weight average molecular weight of the high molecular compound which has an anionic group used for this invention is 1000 or more, it is preferable that it is 3000-100000 in a weight average molecular weight, It is more preferable that it is 5000-80000, It is especially preferable that it is 7000-60000. When the weight average molecular weight is within the above range, the effects of the plurality of functional groups introduced at the ends of the polymer are sufficiently exhibited, and the excellent performance in adsorption to the solid surface, micelle formation ability, and surfactant activity is exhibited. In particular, when the polymer compound having the anionic group is used as a pigment dispersant when redispersing the organic nano pigment particle aggregate, good dispersibility and dispersion stability can be achieved.

Although the polymer compound represented by the said General formula (14) is not specifically limited, It can synthesize | combine by the following method etc .. A mercaptan compound having a plurality of functional groups (G in the general formula) is a method of radical polymerization of a vinyl monomer as a chain transfer agent.

More specifically, it is preferable to radical-polymerize using the compound represented by following General formula (15) as a chain transfer agent.

In General formula (15), G, J, Q, Z, and m + 1 are the same as G, J, Q, Z, and m + 1 in the said General formula (14), and its preferable range is also the same.

Although it does not restrict | limit especially as said vinyl monomer, For example, (meth) acrylic acid ester, crotonic acid ester, vinyl ester, maleic acid diester, fumaric acid diester, itaconic acid diester, (meth) acrylamide Drew, vinyl ether, ester of vinyl alcohol, styrene, (meth) acrylonitrile, etc. are preferable. Such compounds include the following compounds.

As an example of the said (meth) acrylic acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl ( Meth) acrylate, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxy Ethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethyleneglycol Monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (Meth) acrylate, polyethyleneglycol monoethyl ether (meth) acrylate, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate , Dicyclopentenyloxyethyl (meth) acrylate, trichloroethyl (meth) acrylate, octachloropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate , Tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, etc. are mentioned.

Examples of the crotonic acid esters include butyl crotonate, hexyl crotonate, and the like. Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, vinyl benzoate and the like. Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, dibutyl maleate and the like. Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like. Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, dibutyl itaconate and the like. Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, and N-isopropyl (meth) acryl Amide, Nn-butylacryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (Meth) acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloyl morpholine, diacetone acrylamide, etc. This is listed.

Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene and bromo Styrene, chloromethylstyrene, hydroxystyrene, methylvinylbenzoate, α-methylstyrene, etc. which are protected by a group which can be deprotected by an acidic substance (for example, t-Boc). Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, and the like.

The said vinyl monomer may be superposed | polymerized only by 1 type, and may be copolymerized in combination of 2 or more types, and such radical polymers can respectively be obtained by polymerizing corresponding vinyl monomers according to the method commonly used by a conventional method.

For example, these vinyl monomers and chain transfer agents can be obtained by dissolving them in a suitable solvent, adding a radical polymerization initiator thereto, and polymerizing them into a solution at about 50 ° C to 220 ° C (solution polymerization method). As an example of the suitable solvent which can be used for a solution polymerization method, it can select arbitrarily according to the solubility of the monomer to be used and the copolymer to be produced. For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate , Ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene, dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), dimethylacetamide (DMAc), N-methyl-2- Pyrrolidone (NMP) is listed. You may use these solvent in mixture of 2 or more type.

Moreover, as a radical polymerization initiator, azo compounds, such as 2,2'- azobis (isobutyronitrile) (AIBN), 2,2'- azobis- (2,4'- dimethylvaleronitrile), and benzoyl peroxide And persulfates such as potassium persulfate, ammonium persulfate, and the like.

Hereinafter, although the specific example of the high molecular compound represented by the said General formula (14) is shown, it is not limited to these.

[Isolation]

Hereinafter, the isolation method of the aggregated organic nanoparticles is demonstrated.

First, it is preferable to leave the aggregated liquid as it is for 0.5 to 2 hours before isolation. Since the aggregates settle, the supernatant can be removed by separating or absorbing, and the isolation of the aggregates becomes easier. In addition, by centrifugation instead of leaving it as is, faster settling of aggregates is possible and time can be shortened.

As an isolation method, various filtration methods are possible, and filtration by limit filtration, centrifugation, a filter paper, and a filter is mentioned.

In case of ultrafiltration, for example, a method which can be used for desalting / concentrating silver halide emulsions may be applied. Research Disclosure No. 10208 (1972), No. 13122 (1975), and No. 16351 (1977) are known. Pressure differentials and flow rates that are important as operating conditions can be selected with reference to the characteristic curves described in Oyaharuhiko's "Technology Handbook for Membrane" published by SAIWAI SHOBO (1978), p275. Optimal conditions need to be found to prevent aggregation. In addition, in the method of replenishing the solvent lost by membrane permeation, there are a continuous type in which the solvent is continuously added and a batch type in which the solvent is added intermittently, but a continuous type having a relatively short desalting time is preferable. Pure water obtained by ion exchange or distillation is used as the solvent to be supplemented in this way. However, the poor solvent of the dispersant and the dispersant may be mixed in the pure water, or may be added directly to the organic nanoparticle dispersion.

Filter filtration can use, for example, a device such as pressure filtration. Preferred filters include filter papers, nanofilters, ultrafilters and the like.

The centrifuge which can be used for the concentration of the organic nanoparticles by centrifugation may use any apparatus as long as the organic nanoparticles in the organic nanoparticle dispersion liquid (or the organic nanoparticle concentrate extract liquid) can be precipitated. As the centrifuge, for example, in addition to the general-purpose apparatus, a skimming function (a function of sucking the supernatant liquid during rotation and discharging to the outside of the system) is attached, and a continuous centrifuge for continuously discharging solid matters is exemplified.

The centrifugal conditions are preferably 50-10000, more preferably 100-8000, particularly preferably 150-6000 in terms of centrifugal force (a value indicating how many times centrifugal acceleration is applied). Although the temperature at the time of centrifugation depends on the kind of solvent of a dispersion liquid, -10-80 degreeC is preferable, -5-70 degreeC is more preferable, and 0-60 degreeC is especially preferable.

Isolated aggregates may be washed for the purpose of desalination, dehydration and removal of excess dispersant. The washing operation may be washed after adding the washing liquid as it is after the filtration by centrifugation, centrifugal separation, filter paper or filter, and once the aggregates are removed and reslurried in the washing liquid, and then separated by limit filtration, centrifugation, filtration by filter paper or filter. You may perform the washing | cleaning which combined them.

In addition, washing may be performed not only after isolation as described above but also before isolation. This is accomplished by leaving the aggregated nano pigment particle dispersion intact and removing the supernatant and adding a washing solution to reslurry. After leaving the slurry, the supernatant may be removed and filtered, but may be filtered as it is. If washing prior to isolation, the agglomerates are always wet, which not only increases the cleaning effect but also facilitates the redispersion described later.

The cleaning liquid is not particularly limited as long as it can achieve desalination, dehydration, and removal of excess dispersant and flocculant. Specifically, the cleaning liquid is an aqueous solvent (for example, water or an aqueous solution of hydrochloric acid, sodium hydroxide), an alcohol compound solvent, Amide compound solvent, ketone compound solvent, ether compound solvent, aromatic compound solvent, carbon disulfide solvent, aliphatic compound solvent, nitrile compound solvent, sulfoxide compound solvent, halogen compound solvent, ester compound solvent, ionic liquid, mixed solvent thereof, etc. Examples thereof include 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, and particularly, an aqueous solvent and an alcohol. Compound solvents, ester compound solvents and nitrile compound solvents are preferable.

The washed agglomerates may be redispersed as described later, may be wetted with a redispersion solvent (described later), redispersed, or dried and taken out as a powder of an organic nanoparticle dispersion, followed by redispersion.

The freeze-drying method is not particularly limited, and any method may be employed as long as it can be used by those skilled in the art. For example, the refrigerant direct expansion method, the redundant freezing method, the fruit circulation method, the triple heat exchange method, the indirect heating freezing method are listed, but the refrigerant direct expansion method, the indirect heating freezing method is preferable, and the indirect heating freezing method is used. It is more preferable. In either method, it is preferable to perform freeze drying after prefreezing. The conditions for preliminary freezing are not particularly limited, but it is necessary to freeze all samples subjected to lyophilization.

Indirect heating freeze dryers include small freeze dryers, FTS freeze dryers, LYOVAC freeze dryers, laboratory freeze dryers, research freeze dryers, triple heat exchange vacuum freeze dryers, monocooling freeze dryers, and HULL freeze dryers. A freeze dryer, a research freeze dryer, and a monocooled freeze dryer are preferable, and more preferably, a small freeze dryer and a monocooled freeze dryer are used.

The temperature of the lyophilization is not particularly limited, but is, for example, -190 to -4 ° C, preferably -120 to -20 ° C, more preferably about -80 to -60 ° C. The pressure of the lyophilization is not particularly limited and can be appropriately selected by those skilled in the art. For example, the pressure is preferably 0.1 to 35 Pa, preferably 1 to 15 Pa, and more preferably about 5 to 10 Pa. The freeze drying time is, for example, 2 to 48 hours, preferably 6 to 36 hours, more preferably about 16 to 26 hours. However, these conditions can be suitably selected by those skilled in the art. For the lyophilization method, for example, Formulation Machine Technology Handbook: Formulation Machine Technology Research Group, CHIJIN SHOKAN CO., LTD, p. 120-129 (September 2000); Vacuum Handbook: Japanese Vacuum Technology, Inc., Ohmsha, Ltd., p. 328-331 (1992); Journal of Freezing and Drying Research Society: Itokoji et al., No. 15, p. 82 (1965), and the like.

The apparatus which can be used for the concentration of the organic nanoparticles by vacuum drying is not particularly limited as long as the solvent of the organic nanoparticle dispersion liquid (or organic nanoparticle concentrated extract liquid) can be evaporated. For example, a general-purpose vacuum dryer and a rotary pump, the apparatus which can heat-dry under reduced pressure, stirring a liquid, the apparatus which can continuously dry by passing a liquid through the tube which heated and reduced pressure etc. are mentioned.

30-230 degreeC is preferable, 35-200 degreeC is more preferable, and 40-180 degreeC of heating under reduced pressure drying temperature is especially preferable. 100-100000 Pa is preferable, as for the pressure at the time of reduced pressure, 300-90000 Pa is more preferable, 500-80000 Pa is especially preferable.

Redistribution

According to the production method of the present invention, it is possible to finely disperse the organic nanoparticles in the aggregated state as necessary (in the present invention, microdispersion means to loosen particles in the dispersion to increase the degree of dispersion).

In order to be able to filter-filter agglomerated organic nano pigment particle mentioned above promptly, and to obtain a favorable dispersion state again, it is preferable to obtain it as the floc which was aggregated to the extent which can be redispersed.

Therefore, the degree of dispersion using a conventional dispersion method is insufficient for fine particle formation, and a method with higher micronization efficiency is required.

As a method of finely dispersing aggregates of such nanoparticles, for example, a dispersion method by ultrasonic waves and a method of adding physical energy can be used.

It is preferable that the ultrasonic irradiation apparatus which can be used has a function which can apply the ultrasonic wave 10kHz or more, For example, an ultrasonic homogenizer, an ultrasonic cleaner, etc. are mentioned. When liquid temperature rises during ultrasonic irradiation, since thermal aggregation of nanoparticles generate | occur | produces (refer nonpatent literature 1), it is preferable to make liquid temperature 1-100 degreeC, and 5-60 degreeC is more preferable. The temperature control method can be performed by controlling the dispersion temperature, controlling the temperature of the temperature adjusting layer controlling the dispersion temperature, and the like.

There is no restriction | limiting in particular as a disperser used when disperse | distributing concentrated organic nanoparticles by adding physical energy, For example, dispersers, such as a kneader, a roll mill, an attorney, a super mill, a dissolver, a homomixer, and a sand mill, are mentioned. . Moreover, the high pressure dispersion method and the dispersion method by use of microparticle beads are also listed as preferable.

As a preferred method for producing the organic nanoparticle dispersion, the colorant is kneaded and dispersed in a resin component at 25 ° C. after kneading and dispersing so as to have a relatively high viscosity of 10,000 mPa · s or more, preferably 100,000 mPa · s or more, and then a solvent is added. And the method after microdispersion is preferable so that the viscosity after a microdispersion process may be comparatively low viscosity of 1,000 mPa * s or less, Preferably it is 100 mPa * s or less.

Machines used in the redispersion process are two rolls, three rolls, ball mills, trommills, dispersers, kneaders, corniders, homogenizers, blenders, single screw and twin screw extruders, and disperse with strong shear. Next, a solvent is added, and fine dispersion is performed with beads made of glass, zirconia, or the like having a particle diameter of 0.1 to 1 mm, using a longitudinal or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, a high pressure disperser, or the like. In addition, fine dispersion beads may be used for fine dispersion beads of 0.1 mm or less.

Furthermore, after disperse | distributing a main pigment and an auxiliary pigment, respectively, it is also possible to add a dispersion process by mixing both dispersion liquids, or to disperse | distribute a main pigment and an auxiliary pigment together.

On the other hand, the details of dispersion are described in T.C. Patton's "Paint Flow and pigment Dispersion" (published by John Wiley and Sons, 1964), and the like, may be used.

A conventional pigment dispersant or a surfactant can be added to the organic nano pigment particle dispersion in order to improve the dispersibility of the organic nano pigment particle. Although many kinds of compounds can be used as these dispersing agents, For example, Phthalocyanine derivative | guide_body (commercially available EFKA-6745 (made by EFKA)), Solspas 5000 (made by zeneca Co., Ltd.); Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based (co) polymer polyflow No. 75, No. 90, No. 95 (manufactured by KYOEISHA CHEMICAL Co., LTD.), Cationic surfactants such as W001 (manufactured by Yusu Co., Ltd.); Polyoxyethylene lauryl ether, polyoxyethylene stearyl aryl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid Nonionic surfactants such as esters; Anionic surfactants such as W004, W005, and W017 (manufactured by Yusu Co., Ltd.); EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (above, manufactured by Morishita & Co., Ltd), Dispasade 6, Dispasade 8, Dispasade Polymer dispersants such as 15 and dispasade 9100 (manufactured by SANNNOPCO LIMITED); Various types of Sol-Spas dispersants (products of zeneca) such as Sol-Spas 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000; Adeka Pluronic L31, F38, L42, L44, L61, L64, L68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (product of ADEKA CORPORATION) and Isonet S-20 (Manufactured by SANYOKASEI Co., Ltd.). In addition, the pigment dispersant described in JP-A-2000-239554, the compound (C) described in JP-A-5-72943, the compound of Synthesis Example 1 described in JP-A-2001-31885, and the like are also preferably used. Can be.

In the organic nanoparticle dispersion composition, the particles obtained by finely dispersing the organic nanoparticles (primary particles) after redispersion, preferably have a particle diameter of 1 to 200 nm, more preferably 2 to 100 nm, It is especially preferable that it is 5-50 nm. Moreover, it is preferable that Mv / Mn of the particle | grains after redispersion is 1.0-2.0, It is more preferable that it is 1.0-1.8, It is especially preferable that it is 1.0-1.5.

According to the production method of the present invention, for example, the pigment particles contained in the organic nano-pigment particle dispersion composition or the colored photosensitive resin composition to be described later have a small particle diameter of nanometer size (for example, 10 to 100 nm). Nevertheless, it can be concentrated redispersed. For this reason, when used for a color filter, optical density is high, it is excellent in the uniformity of a filter surface, a contrast is high, and an image noise can be reduced.

In addition, since the organic nano-pigment particles dispersed composition and the organic nano-pigment particles contained in the colored photosensitive composition can be highly and uniformly microdispersed, a high color density can be exerted at a thin film thickness, such as a color filter. It is also possible to enable thinning.

In addition, in the organic nano pigment particle dispersion composition and the colored photosensitive resin composition, by containing a pigment showing vivid color tone and high coloring power, for example, it becomes excellent as an image forming material for producing a color proof, a color filter, or the like. .

In addition, about the alkaline developing solution which can be used for exposure and development at the time of coloring image formation, what was soluble in alkaline aqueous solution as a binder (binder) to organic nanoparticle dispersion composition and coloring photosensitive resin composition can be used, and it responds to environmental requirements. Can be.

Moreover, as a solvent (dispersion medium of a pigment) which can be used for an organic nano pigment particle dispersion composition and a coloring photosensitive resin composition, the organic solvent which has suitable dryness can be used, and the request | requirement can be satisfied also at the drying point after application | coating.

[Coloring Photosensitive Resin Composition]

The coloring photosensitive resin composition of this invention contains at least (a) organic nano pigment particle, (b) binder, (c) monomer or oligomer, and (d) photoinitiator or photoinitiator system. Hereinafter, each component of the coloring photosensitive resin composition of this invention is demonstrated.

(a) Organic Nano Pigment Particles

The method for producing the organic nano pigment particle has already been described in detail. As for content of organic nano pigment particle, 3-90 mass% is preferable with respect to the total solid in a coloring photosensitive resin composition (in this invention, total solid means the composition total except an organic solvent), 20-80 mass% Is more preferable, and 25-60 mass% is more preferable. If this amount is too large, the viscosity of the dispersion increases, which is a problem in production aptitude. When too small, the coloring power may not be enough. As organic nanoparticles which function as a coloring agent, it is preferable that it is 0.1 micrometer or less of particle diameters, and especially 0.08 micrometer or less of particle diameters. Although there is no restriction | limiting in particular in the minimum of particle diameter, It is the same as the minimum of the particle diameter of the said organic pigment nanoparticle (primary particle). Moreover, you may combine with a normal pigment for color tone. The pigment can use what was described above. In this invention, it is preferable that organic nanoparticles can be used as said organic nano pigment non-aqueous dispersion.

(b) binder

As a binder in a coloring photosensitive resin composition, the high molecular compound which is the weight average molecular weight 1000 or more mentioned above can be used preferably. As for content of a binder, 15-50 mass% is common with respect to the total solid of colored photosensitive resin composition, and 20-45 mass% is preferable. When this amount is too large, the viscosity of the composition becomes too high, which may cause a problem in manufacturing aptitude. When too small, it will become a problem in formation of a coating film.

(c) monomers or oligomers

As a monomer or oligomer contained in the coloring photosensitive resin composition of this invention, it is preferable that it is a monomer or oligomer which has two or more ethylenically unsaturated double bonds and adds polymerization by light irradiation. As such a monomer and an oligomer, the compound which has one or more ethylenically unsaturated groups which can be superpolymerized in a molecule | numerator, and whose boiling point is 100 degreeC or more at normal pressure is mentioned. Examples thereof include monofunctional acrylates and monofunctional methacrylates such as dipentaerythritol hexa (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate. Acrylates; Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylol ethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropanediacrylate, neopentyl glycol di (meth) Acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) Acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; Polyfunctional acrylates and polyfunctional methacrylates, such as those obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as trimethylolpropane and glycerin and then (meth) acrylated, can be enumerated. In addition, as described in General Formulas (1) and (2) of Japanese Patent Application Laid-Open No. Hei 10-62986, a compound obtained by adding (meth) acrylated after adding ethylene oxide or propylene oxide to a polyfunctional alcohol is also listed as preferred. .

Urethane acrylates described in Japanese Patent Application Laid-Open No. 48-41708, Japanese Patent Application Laid-open No. 50-6034 and Japanese Patent Application Laid-open No. 51-37193; Polyester acrylates described in Japanese Patent Laid-Open No. 48-64183, Japanese Patent Laid-Open No. 49-43191 and Japanese Patent Laid-Open No. 52-30490; And polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resins and (meth) acrylates.

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

In addition, "polymerizable compound B" of Unexamined-Japanese-Patent No. 11-133600 can also be enumerated as a preferable thing.

These monomers or oligomers (preferably as monomers or oligomers have a molecular weight of 200 to 1000) may be used alone or in combination of two or more thereof, and the content is 5 to 50% by mass based on the total solids of the colored photosensitive resin composition. Generally, 10-40 mass% is preferable. If the amount is too large, control of developability may become difficult or a problem may arise in manufacturing aptitude. When too small, the hardening force at the time of exposure may be insufficient.

(d) photoinitiator or photoinitiator system

As a photoinitiator or a photoinitiator type | system | group contained in the coloring photosensitive resin composition of this invention (in this invention, a photoinitiator type | system | group refers to the mixture which expresses the function at the time of photoinitiation by combining several compound), US Patent No. 2367660 specification. Bisinal polyketaldonyl compound disclosed in the, Acyloin ether compound described in US Patent 2448828, Aromatic acyl phosphorus compound substituted with α-hydrocarbon described in US Patent 2722512, US Patent The combination of the polynuclear quinone compound described in US Pat. No. 3046127 and US Pat. No. 2951758, the triarylimidazole dimer described in US Pat. No. 3549367, and p-aminoketone, and the benzo in Japanese Patent Publication No. 51-48516. Thiazole compounds and trihalomethyl-s-triazine compounds, trihalomethyl as described in US Pat. No. 4,39,850. Triazine compounds, can be exemplified, such as U.S. Patent No. 4,212,976 specification, methyl-oxadiazole compound as described in trihalomethyl. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole and triarylimidazole dimers are preferred.

In addition, "Polymerization initiator C" described in Japanese Patent Application Laid-Open No. 11-133600 or 1-phenyl-1,2-propanedione-2- (ο-ethoxycarbonyl) oxime, O-benzyl-4 as an oxime system '-(Benzmercapto) benzoyl-hexyl-ketooxime, 2,4,6-trimethylphenylcarbonyldiphenylphosphonyl oxide, hexafluorophosphorotrialkylphenylphosphonium salt and the like can also be listed as preferred.

Although these photoinitiator or photoinitiator system may be used individually or in mixture of 2 or more types, it is preferable to use two or more types especially. When two or more photopolymerization initiators are used, display characteristics, in particular, display stains can be reduced.

As for content of a photoinitiator or a photoinitiator system, 0.5-20 mass% is common with respect to the total solid of colored photosensitive resin composition, and 1-15 mass% is preferable. When this amount is too large, sensitivity may become high too much and control may become difficult. When too small, exposure sensitivity may become low too much. Especially as a radiation which can be used at the time of exposure, ultraviolet rays, such as g line | wire and i line | wire, are used preferably. 5-1500mJ / cm <2> is preferable, 10-1000mJ / cm <2> of irradiation amount is more preferable, and 10-500mJ / cm <2> is the most preferable.

(Other additives)

[menstruum]

In the coloring photosensitive resin composition of this invention, in addition to the said component, you may use an organic solvent further. Examples of the organic solvent include, but are not particularly limited to, esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amylformate, isoamyl acetate, isobutyl acetate, butylpropionate, isopropylbutyrate, ethyl Butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyloxy acetate, ethyl oxy acetate, butyl oxy acetate, methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl 3-oxypropionate alkyl esters such as ethoxy acetate, methyl-3-oxypropionate and ethyl-3-oxypropionate; Methyl-3-methoxypropionate, ethyl-3-methoxypropionate, methyl-3-ethoxypropionate, ethyl-3-ethoxypropionate, methyl-2-oxypropionate, ethyl -2-oxypropionate, propyl-2-oxypropionate, methyl-2-methoxypropionate, ethyl-2-methoxypropionate, propyl-2-methoxypropionate, methyl-2 Ethoxypropionate, ethyl-2-ethoxypropionate, methyl-2-oxy-2-methylpropionate, ethyl-2-oxy-2-methylpropionate, methyl-2-methoxy- 2-methylpropionate, ethyl-2-ethoxy-2-methylpropionate, methylpyruvate, ethylpyruvate, propylpyruvate, methylacetoacetate, ethylacetoacetate, methyl-2-oxobutyrate, ethyl- 2-oxobutyrate and the like; Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, propylene glycol methyl Ether acetates and the like; Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclohexanol, 2-heptanone, 3-heptanone and the like; Aromatic hydrocarbons such as toluene, xylene and the like. In these solvents, methyl-3-ethoxypropionate, ethyl-3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, methyl-3-methoxypropionate, 2-heptanone , Cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like can be preferably used as the solvent in the present invention. You may use these solvent individually or in combination of 2 or more types.

Moreover, the solvent whose boiling point is 180 degreeC-250 degreeC can be used as needed. As these high boiling solvents, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, 3,5,5-trimethyl-2-cyclohexen-1-one, butyl lactate, di Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol diacetate, propylene glycol-n-propyl ether acetate, diethylene glycol diethyl ether, 2-ethylhexyl acetate, 3-methoxy-3-methylbutyl Acetate, γ butyl lactone, tripropylene glycol methyl ethyl acetate, dipropylene glycol-n-butyl acetate, propylene glycol phenyl ether acetate, 1,3-butanediol diacetate are exemplified.

As for content of a solvent, 10-95 mass% is preferable with respect to resin composition whole quantity.

[Surfactants]

In the color filter which can be used conventionally, in order to implement | achieve high color purity, there existed a problem that the color of each pixel became dark and the unevenness of the film thickness of a pixel was recognized as a color spot as it is. Therefore, the film thickness of the pixel is directly affected, and the improvement of the film thickness variation at the time of formation (application) of the photosensitive resin layer has been demanded.

In the transfer material using the color filter of the present invention or the colored photosensitive resin composition of the present invention, the coloring photosensitive property can be controlled at a uniform film thickness and is effective in preventing coating spots (color spots caused by film thickness variation). It is preferable to contain an appropriate surfactant in the resin composition.

As said surfactant, surfactant disclosed by Unexamined-Japanese-Patent No. 2003-337424 and Unexamined-Japanese-Patent No. 11-133600 is mentioned as a preferable thing. It is preferable that content of surfactant is 5 mass% or less with respect to resin composition whole quantity.

[Heat polymerization inhibitor]

It is preferable that the coloring photosensitive resin composition of this invention contains a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogarol, t-butylcatechol, benzoquinone, 4,4'- Thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like are listed. . As for content of a thermal polymerization inhibitor, 1 mass% or less is preferable with respect to resin composition whole quantity.

[Dyestuffs and Pigments for Secondary Use]

A coloring agent (dye, pigment) can be added to the coloring photosensitive resin composition of this invention as needed in addition to the said coloring agent (pigment). When using a pigment in a coloring agent, it is preferable to disperse | distribute uniformly in a coloring photosensitive resin composition, for that reason, it is preferable that particle diameter is 0.1 micrometer or less, especially 0.08 micrometer or less.

As a dye or a pigment, Specifically, as the said pigment, the color material of Unexamined-Japanese-Patent No. 2005-17716 [0038]-[0040], the pigment of Unexamined-Japanese-Patent No. 2005-361447 [0068]-[0072], The coloring agent of Unexamined-Japanese-Patent No. 2005-17521 [0080]-[0088] can be used preferably. As for content of the dye or pigment used auxiliary, 5 mass% or less is preferable with respect to the resin composition whole quantity.

[UV absorber]

The coloring photosensitive resin composition of this invention can contain a ultraviolet absorber as needed. Examples of the ultraviolet absorber include salicylates, benzophenones, benzotriazoles, cyanoacrylates, nickel chelates, hindered amines, and the like, in addition to the compounds described in JP-A-5-72724.

Specifically, phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ', 5'-di-t-4'-hydroxybenzoate, 4-t -Butylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2'-hydroxy Hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3, 3-diphenylacrylate, 2,2'-hydroxy-4-methoxybenzophenone, nickel dibutyldithiocarbamate, bis (2,2,6,6-tetramethyl-4-pyridine) -sebacate , 4-t-butylphenylsalicylate, phenylsalicylate, 4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinic acid-bis (2,2,6,6-tetra Methyl-4-piperidenyl) -ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6 -(Diethylamino) -5-triin-2-yl] amino} -3-phenylcoumarin It is listed. As for content of a ultraviolet absorber, 5 mass% or less is preferable with respect to resin composition whole quantity.

In addition, in the coloring photosensitive resin composition of this invention, in addition to the said additive, the "adhesion adjuvant" of Unexamined-Japanese-Patent No. 11-133600, other additives, etc. can be contained.

[Coating Film of Colored Photosensitive Resin Composition]

About the containing component in the coating film using the coloring photosensitive resin composition of this invention, it is the same as that of what was already described in the term of [coloring photosensitive resin composition]. Moreover, although the thickness of the coating film using the coloring photosensitive resin composition of this invention can be suitably determined according to the use, it is preferable that it is 0.5-5.0 micrometers, and it is more preferable that it is 1.0-3.0 micrometers. In the coating film using the coloring photosensitive resin composition of this invention, the (c) monomer or oligomer contained therein can be superposed | polymerized and it can produce the color filter which has it as a polymerization film of a coloring photosensitive resin composition (production of a color filter). Will be described later). The polymerization of the polymerizable monomer or the polymerizable oligomer can be performed by actuating the photopolymerization initiator or photopolymerization initiator system (d) by light irradiation.

<Color filter and manufacturing method thereof>

Next, the color filter of this invention and its manufacturing method are demonstrated.

The color filter of this invention has a coloring pattern formed using the photocurable composition (colored photosensitive resin composition) of this invention on a support body.

Hereinafter, the color filter of this invention is demonstrated through the manufacturing method (manufacturing method of the color filter of this invention).

The method for producing a color filter of the present invention is a step of forming a photosensitive film by supplying the photocurable composition of the present invention directly or on a substrate with another layer therebetween (hereinafter, appropriately referred to as a "photosensitive film forming step") and the formed photosensitive Process of exposing film | membrane (exposure through a mask) (hereinafter abbreviate-wise abbreviating "exposure process") and process of developing the photosensitive film after exposure, and forming a coloring pattern (hereafter abbreviated "development process suitably"). ), Characterized by containing.

Hereinafter, each process in the manufacturing method of the color filter of this invention is demonstrated.

(Photosensitive film forming process)

In the photosensitive film formation process, the photocurable composition of this invention is apply | coated (granted) directly or on the board | substrate which has another layer to form a photosensitive film.

As the substrate used in this step, for example, soda glass, pyrex (registered trademark) glass, quartz glass, which can be used for a liquid crystal display device, etc., and a transparent conductive film attached thereto, or photoelectric conversion that can be used for an imaging device, etc. Device substrates such as silicon substrates, complementary metal oxide semiconductors (CMOS), and the like. These board | substrates may be provided with the black stripe which isolate | separates each pixel.

Moreover, on these board | substrates, an undercoat layer (other layer) may be provided as needed for the improvement of close_contact | adherence with the upper layer, the prevention of the diffusion of a substance, or the planarization of a board | substrate surface.

As a method of apply | coating the photocurable composition of this invention on a board | substrate, various coating methods, such as a slit application | coating, an inkjet method, a rotary application | coating, cast | coating application | coating, roll coating, and screen printing, can be applied.

As coating film thickness of a photocurable composition, 0.1-10 micrometers is preferable, 0.2-5 micrometers is more preferable, It is still more preferable that it is 0.2-3 micrometers.

Drying (PRE-BAKE) of the photosensitive film | membrane apply | coated on the board | substrate can be 10-300 second by the temperature of 50 degreeC-140 degreeC in a hotplate, oven, etc.

(Exposure process)

In an exposure process, the photosensitive film formed in the said photosensitive film formation process is exposed through the mask which has a predetermined mask pattern. That is, pattern exposure is performed.

In this process, only the part of the coating film irradiated with light can be hardened by exposing the photosensitive film which is a coating film through the predetermined mask pattern.

As a radiation which can be used at the time of exposure, especially ultraviolet rays, such as g line | wire and i line | wire, can be used preferably. 5-1500mJ / cm <2> is preferable, 10-1000mJ / cm <2> of an irradiation amount is more preferable, and 10-500mJ / cm <2> is the most preferable.

When the color filter of this invention is for liquid crystal display elements, 5-200mJ / cm <2> is preferable in the said range, 10-150mJ / cm <2> is more preferable, 10-100mJ / cm <2> is the most preferable. In addition, when the color filter of this invention is for a solid-state image sensor, it is preferable that it is 30-1500mJ / cm <2> in the said range, It is more preferable that it is 50-1000mJ / cm <2>, It is most preferable that it is 80-500mJ / cm <2>.

(Developing process)

Next, by developing, the unexposed part in the exposure process elutes with the developing solution, and only the photocured part remains. As the developing solution, any film can be used as long as it dissolves the film of the photocurable composition in the uncured portion and does not dissolve the cured portion. Specifically, combinations of various organic solvents and alkaline aqueous solutions can be used.

As image development temperature, it is 20 degreeC-30 degreeC normally, and developing time is 20 to 90 second.

As said organic solvent, the solvent described as what can be used when manufacturing the pigment dispersion composition or photocurable composition of this invention is mentioned.

As said alkaline aqueous solution, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl 0.001-10 mass% of alkaline compounds, such as ammonium hydroxide, choline, a pyrrole, a piperidine, and 1,8- diazabicyclo- [5,4,0] -7-undecene, Preferably it is 0.01- An alkaline aqueous solution diluted with pure water so as to have a concentration of 1% by mass is preferably used as a developer.

On the other hand, in the case of using a developer made of such an alkaline aqueous solution, it is generally washed (rinsed) with pure water after development.

After the developing step, excess developer is washed and removed, dried and then subjected to heat treatment (POST-BAKE).

Post-baking process is the heat processing after image development in order to complete hardening, and usually heat-processes 100 degreeC-240 degreeC. When a board | substrate is a glass substrate or a silicon substrate, 200 degreeC-240 degreeC is preferable among the said temperature ranges.

This post-baking process can be performed continuously or batch type using heating means, such as a hotplate, a convection oven (hot air circulation type dryer), and a high frequency heater, so that the coating film after image development may be said conditions.

By repeating the photosensitive film formation process, exposure process, and image development process (in addition, heat processing as needed) by the desired number of colors, the color filter which becomes a desired color is produced.

When supplying the photocurable composition of this invention on a board | substrate, and forming a film, as a dry thickness of a film, it is generally 0.3-5.0 micrometers, Preferably it is 0.5-3.5 micrometers, Most preferably, it is 1.0-2.5 micrometers.

Examples of the substrate include alkali-free glass, soda glass, pyrex (registered trademark) glass, quartz glass, and a transparent conductive film attached thereto, or photoelectric conversions used in solid state imaging devices. Device substrates such as silicon substrates, and plastic substrates. On these board | substrates, the black stripe which isolate | separates each pixel is normally formed.

The plastic substrate preferably has a gas barrier layer and / or solvent resistant layer on its surface.

Although the use of the photocurable composition of the present invention has been mainly described as the use of the color filter to pixels, it goes without saying that the present invention can also be applied to a black matrix provided between pixels of the color filter. The black matrix is subjected to pattern exposure and alkali development in the same manner as the pixel manufacturing method except that a black colorant such as carbon black or titanium black is added to the photocurable composition of the present invention. -BAKE) to accelerate the curing of the film.

<Example 1>

[Production of Aqueous Dispersion of Organic Nano Pigment Particles]

CI pigment red 254 (45 parts by mass) and polyvinylpyrrolidone (K-25, manufactured by WAKO Pure Chemical Industries, LTD., 90 parts by mass) were added to dimethyl sulfoxide (DMSO) (953 parts by mass) and stirred. . 28 mass% sodium methoxide methanol solution (30 volume parts) was added to this solution, and pigment solution A was prepared. On the other hand, water (4000 parts by mass) was prepared as a pigment insoluble solvent B.

The pigment insoluble solvent B was added to Nippon Seimitsu Kagaku Co., Ltd. while the pigment insoluble solvent B was stirred at 30 ° C. at 500 rpm using a GK-0222-10 Raymond Agitator (trade name) manufactured by Fujisawa Pharmaceutical Co., Ltd. Ltd. The product NP-K-500 large-capacity no-flow pump (trade name) was injected at a flow rate of 100 mL / min for 4 minutes 4 seconds to crystallize the organic pigment nanoparticles to obtain an aqueous organic nano-aqueous dispersion.

It evaluated by the dynamic light scattering method using LB-400 (brand name) which is a product of HORIBA Co., Ltd., The median diameter was made into the index of dispersibility as an average particle diameter. In the dynamic light scattering method, secondary aggregated particles are also observed. Therefore, evaluation as primary particles was also made as a transmission electron microscope.

[Aggregation]

Acetic acid (45 parts by mass) as a nonionic low molecular compound and C-1 (3 parts by mass) as a nonionic high molecular compound are dissolved in acetone (200 parts by mass) and added to the above-mentioned organic nanoparticle aqueous acid solution (300 parts by mass). And stirred for 0.5 hour. After leaving for 0.5 hours, the resulting aggregates were observed under an optical microscope, and then the aggregates were allowed to settle and the supernatant was separated and removed.

[Isolation, washing, drying}

The agglomerates mentioned above were obtained by filter paper (ADVANTEC, N0.2), and the time required for filtration was measured at this time. About the solid obtained by filtration, it wash | cleaned with water (300 mass parts) and methanol (200 volume parts). The obtained solid was reslurried in acetonitrile (100 parts by volume) for 0.5 hours, and left for 0.5 hours to separate and remove the supernatant. The solid obtained was vacuum dried overnight at room temperature.

Redistribution

The following non-aqueous solvent 1-methoxy-2-propyl acetate (4 parts by mass) is added to this organic pigment solid (1 part by mass), and Nippon Seimitsu Co. Ultrasonic irradiation was carried out using ultrasonic homogenizer-US series (trade name) manufactured by Ltd. for 3 hours to obtain an organic nanoparticle non-aqueous dispersion (hereinafter referred to as pigment dispersion composition A) using a non-aqueous solvent as a dispersant.

Evaluation test

The following evaluation was performed about the obtained dispersion composition. The results are shown in Table 1.

(1) Average Particle Diameter of Organic Nanoparticle Aqueous Dispersion

It evaluated by dynamic light scattering method using LB-500 (brand name) which is a product of HORIBA Co., Ltd, and measured the average particle diameter of the organic nanoparticle aqueous component liquid by making the median particle diameter into the average particle diameter.

(2) diameter of aggregates

The aggregate was observed with an optical microscope, and the diameter of the aggregate was measured with reference to the criteria observed separately. About the diameter of the aggregate here, the length of the edge was measured from the edge of the aggregate, and the longest part was defined as the diameter. The aggregates referred to here are nanoparticles that are primary particles that are not visible to the naked eye, but have become secondary particles that are more aggregated and grow larger.

(3) filtration time

The filtration time per 1 g of pigment was measured by filtration under reduced pressure with an aspirator using a suction filter having a diameter of 9 cm and a filter paper (ADVANTEC Co., LTd. Filter paper No. 2 (trade name)).

(4) viscosity measurement

Use, E-type viscometer, of the resulting dispersion composition after the pigment viscosity η ¹ and dispersion of the dispersion composition immediately after dispersion (at room temperature) 1 week elapsed after the viscosity of the pigment dispersion composition measuring η ^2, and the increase point Evaluated the degree. The low viscosity here shows that dispersibility and dispersion stability are good.

(5) contrast evaluation

The obtained pigment dispersion composition A was apply | coated so that a thickness might be set to 2 micrometers on the glass substrate, respectively, and the sample was produced. This sample was used between two polarizers (polarizers HLC 2-2518 manufactured by SANRITSU Corp.) using a diffuser plate installed at a three-wavelength cold cathode tourism facility (FWL18EX-N manufactured by TOSHIBA LIGHTING & TECHNOLOGY CORPORATION) as the backlight unit. The amount of transmitted light when the polarization axes were parallel and perpendicular was measured, and the comparison was made as a comparison ("7th Color Optical Conference of 1990, 512 Color Display 10.4" Size TFT-LCD Color Filter, Ueki "). The color chromaticity meter (TOPCON CORPORATION BM-5) was used for the measurement of chromaticity.The installation positions of the two polarizing plates, the sample, and the color luminance meter were 13 mm from the backlight. A polarizing plate was installed at a position of 40 mm to 60 mm, and a cylinder having a diameter of 11 m and a length of 20 mm was installed, and the light transmitted through this was irradiated to a measurement sample provided at a position of 65 mm, and the transmitted light was installed at a position of 100 mm. At a position of 400 mm through The measurement angle of the color luminance meter was set to 2 ° The luminance of the backlight was 1280 cd when two polarizers were installed in Parallel Nicol without a sample installed. / M <2> was set.

<Example 2>

The nonionic low molecular weight compound of Example 1 was changed to nonionic 2-propylpentanoic acid, and operation similar to Example 1 was performed. The obtained organic nanoparticle non-aqueous acid solution is also called pigment dispersion composition B. About the pigment dispersion composition B, the result of having carried out the same evaluation test as Example 1 is shown in Table 1.

<Example 3>

The nonionic high molecular compound of Example 1 was changed to nonionic C-10, and operation similar to Example 1 was performed. The obtained organic nanoparticle non-aqueous acid solution is also called pigment dispersion composition C. Table 1 shows the results of the same evaluation test as in Example 1 for the pigment dispersion composition C.

<Example 4>

The polyvinylpyrrolidone of Example 1 was changed to cationic polymer dispersant C-5, the nonionic low molecular compound to anionic low molecular compound E-3, and the anionic polymer compound to anionic polymer compound F-2, The same operation as in Example 1 was performed. The obtained organic nanoparticle non-aqueous acid solution is also called pigment dispersion composition D. Table 1 shows the results of the same evaluation tests as in Example 1 for the pigment dispersion composition D.

Example 5

In Example 1, operation similar to Example 1 was performed except having changed the nonionic high molecular compound into the nonionic methacrylate / benzyl methacrylate copolymer about the organic nanoparticle aqueous acid solution. The obtained organic nanoparticle non-aqueous acid solution is also called pigment dispersion composition E. Table 1 shows the results of the same evaluation test as in Example 1 for the pigment dispersion composition E.

<Example 6>

In Example 1, except that acetic acid was added as a nonionic low molecular weight compound to the aqueous organic nanoparticle dispersion, and then C-1 was dissolved in acetone as a nonionic polymer compound and added to the aqueous organic nanoparticles dispersion. The same operation was performed. The obtained organic nanoparticle non-aqueous acid solution is also called pigment dispersion composition F. Table 1 shows the results of the same evaluation test as in Example 1 for the pigment dispersion composition F.

<Example 7>

In Example 1, C-1 was dissolved in acetone as a nonionic low molecular weight compound to the organic nanoparticle aqueous dispersion, and then acetic acid was added as a nonionic low molecular weight compound. The same operation was performed. The obtained organic nanoparticle non-aqueous acid solution is also called pigment dispersion composition G. Table 1 shows the results of the same evaluation tests as in Example 1 for the pigment dispersion composition G.

<Example 8>

In Example 1, the obtained aggregates were allowed to settle and the supernatant was separated and removed, followed by adding water (200 parts by mass) and performing a slurry for 0.5 hours. The dispersion was allowed to settle for 0.5 hour and the supernatant was separated and removed. In addition, methanol (100 parts by mass) was added thereto, and the mixture was reslurried for 0.5 hour. The dispersion was allowed to settle for 0.5 hour and the supernatant was separated and removed. In addition, acetonitrile (100 parts by mass) was added and reslurried for 0.5 hour. Leave for 0.5 hour and the dispersion was allowed to settle and remove the supernatant. Thereafter, the same operation as in Example 1 was performed. The obtained organic nano pigment particle non-aqueous acid solution is also called pigment dispersion composition H. Table 1 shows the results of the same evaluation tests as in Example 1 for the pigment dispersion composition H.

Comparative Example 1

Hydrochloric acid (64 parts by mass) was added to the organic nanoparticle aqueous component solution prepared in the same manner as in Example 1, the nanoparticles were agglomerated to filter by using a filter (ADVANTEC Co., LTd. H010A047A, trade name). The time to make it was measured. About the solid obtained by filtration, the methacrylate / benzyl methacrylate copolymer (1 mass part) and 1-methoxy- 2-propyl acetate (8 mass) with respect to the washing and dry solid (1 mass part) similar to Example 1 Part), and Nippon Seimitsu Co. Ultrasonic irradiation was carried out using ultrasonic homogenizer-US series (trade name) manufactured by Ltd. for 3 hours to obtain an organic nanoparticle non-aqueous dispersion containing the following non-aqueous solvent as a dispersant. The obtained organic nanoparticle non-aqueous acid solution is also called pigment dispersion composition I. Evaluation performed the same evaluation as Example 1. Table 1 shows the results of the same evaluation tests as in Example 1 for Pigment Dispersion Composition I.

<Test Example 1>

Acetone (200 parts by mass) in which acetic acid (45 parts by mass) was dissolved was added to an organic nanoparticle aqueous acid solution (300 parts by mass) prepared in the same manner as in Examples 1 to 8 and Comparative Example 1, and the aggregates were determined by an optical microscope. After observing, the filter was filtered using a filter (ADVANTEC Co., H010A047A, brand name), and the time required was measured.

The evaluation results are shown below.

Reference Example 1

After adding acetone (200 parts by mass) in which acetic acid (45 parts by mass) was dissolved in an organic nanoparticle aqueous acid solution (300 parts by mass) prepared in the same manner as in Example 1, the aggregate was observed with an optical microscope, and then a filter The filter was filtered using (ADVANTEC Co., LTd. Product H010A047A, brand name), and the time required was measured.

The evaluation results are shown below.

As described above, the process of preparing the aqueous paste, which is represented by flushing when the organic nanoparticle aqueous dispersion is phase-inverted into the organic nanoparticle non-aqueous dispersion, requires a huge time such as filter filtration and the like. Organic nanoparticles non-aqueous dispersion and a method for producing the same, wherein the nanoparticles in the organic nanoparticles aqueous dispersion can be easily aggregated for the process, which can be isolated and redispersed in a non-aqueous solvent to obtain high efficiency. Can be provided. In addition, it is possible to provide an organic nanoparticle non-aqueous dispersion having excellent dispersibility and high contrast, and a method of manufacturing the same.

[Production of Colored Photosensitive Resin Composition]

The pigment | dye of the following composition was further added to the pigment dispersion compositions A-I obtained by Examples 1-8 and Comparative Example 1, and it stirred and mixed, and manufactured the coloring photosensitive resin composition (color resist liquid) of this invention.

[Furtherance]

· Dipentaerythritol hexaacrylate... 80 parts by mass

4- [o-bromo-p-N, N-di (ethoxycarbonyl) aminophenyl] -2,6

-Di (trichloromethyl) -S-triazine (photoinitiator). 30 parts by mass

Propylene glycol monomethyl ether acetate solution (40% solids) of benzyl methacrylate / methacrylate (= 70/30 [molar ratio] copolymer (weight average molecular weight: 10,000)) 200 parts by mass

1-methoxy-2-propyl acetate... 490 parts by mass

The obtained photocurable composition (color resist liquid) was applied onto a 100 mm x 100 mm glass substrate (1737, manufactured by Corning) so that the x value of the color concentration index was 0.650, and dried in an oven at 90 ° C. for 60 seconds (free). Bake). Then, it exposed to 200mJ / cm <2> (roughness 20mW / cm <2>) on the whole surface of a coating film, The coating film after exposure was covered with 1% aqueous solution of alkaline developing solution CDK-1 (made by FUJIFILM Electronic Materials Co. Ltd), and it stopped for 60 second. After stopping, pure water was sprayed in the shower state to wash off the developer. The coating film subjected to the exposure and development as described above was heat-treated in an oven at 220 ° C. for 1 hour (post bake), and a colored resin film for color filters was formed on the glass substrate to produce a colored filter substrate (color filter). did.

The result of having measured the contrast of R component of each obtained film like Example 1 is shown in the following table.

As mentioned above, the color filter created from the coloring photosensitive resin composition using the organic nanoparticle non-aqueous dispersion organic particle | grains obtained by this invention showed the extremely outstanding contrast compared with the comparative example.

Claims (12)

The organic nano-pigment, characterized in that the organic nano-pigment particles dispersed in an aqueous medium are agglomerated by reacting at least one organic low molecular weight compound having a molecular weight of less than 1000 and at least one organic polymer compound having a weight average molecular weight of at least 1000, followed by isolation. Method for producing particle aggregates. The method of claim 1, The organic low molecular weight compound and the organic high molecular compound are dissolved in a solvent mixed with the aqueous medium, and added to the aqueous medium to agglomerate the organic nano pigment particles aggregate characterized in that the organic nano pigment particles dispersed in the aqueous medium to agglomerate. . The method according to claim 1 or 2, The said isolation | separation is performed by filtration, The manufacturing method of the organic nano pigment particle aggregate. The method according to any one of claims 1 to 3, A process for producing an organic nano-pigmented particle aggregate comprising the step of removing at least the excess organic low molecular weight compound. The method according to any one of claims 1 to 4, The organic nano pigment particles dispersed in the aqueous medium are mixed with a solution of an organic pigment dissolved in a good solvent, and a medium compatible with the good solvent and a poor solvent for the organic pigment, thereby producing nanoparticles. It is obtained by making a process for producing an organic nano pigment particle aggregate. The method according to any one of claims 1 to 5, Method for producing an organic nano-pigment particle aggregate, characterized in that the average primary particle diameter of the organic nano-pigment particles is 100nm or less. The method according to any one of claims 1 to 6, The average particle diameter of the aggregate is 10000nm or more method for producing an organic nano pigment particle aggregate. A method for producing an organic nano pigment particle non-aqueous dispersion, wherein the isolated organic nano pigment particle aggregate according to any one of claims 1 to 7 is obtained by redispersing in a non-aqueous medium. The method according to any one of claims 1 to 8, A method for producing an organic nano pigment particle non-aqueous dispersion, wherein the organic polymer compound is represented by the following General Formula (11) or (14).

(In formula (11), A ¹ represents an acid group, a group containing a basic nitrogen atom, a urea group, a urethane group, a group containing a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate). A monovalent organic group containing a group selected from a group and a hydroxyl group, or a monovalent organic group containing an organic dye structure or a heterocyclic ring which may contain a substituent, n A ¹ may be the same or different R ¹ is (m m + n represents 3-10, m represents the integer of 1-8, n represents the integer of 2-9, R <^2> represents a single bond or a bivalent coupling group. P ¹ is It shows a polymer residue.)

(G- In the above general formula (14) _{^{-COO -, -SO 3 -, -OSO}} 3 -, -P (O) (OH) O -, or -OP (O) (OH) O ^- represents a. J represents a divalent linking group or a single bond Q represents a (m + 1) valent linking group R represents a polymer compound residue Z ⁺ represents an organic or inorganic cation m + 1 represents 3-6 .) The method of claim 9, A method for producing an organic nano pigment particle non-aqueous dispersion, wherein the organic polymer compound is used as a dispersant in a non-aqueous medium as it is. A coloring photosensitive resin composition comprising at least the organic nano pigment particle non-aqueous dispersion according to claim 9 or 10, a binder, a monomer or an oligomer, a photoinitiator or a photoinitiator system. The color filter formed using the coloring photosensitive resin composition of Claim 11.