JP2008280391A - Method for producing organic nano pigment particle aggregate and non-aqueous dispersion of organic nano pigment particle, colored photosensitive resin composition containing the dispersion, and color filter using the same - Google Patents

Abstract

[PROBLEMS] To create an aqueous paste as represented by flushing, that is, enormous steps such as filter filtration, when phase-transforming an organic nanopigment particle aqueous dispersion into an organic nanopigment particle non-aqueous dispersion. Provided is a method for producing an aggregate capable of easily filtering nanopigment particles in an organic nanoparticle pigment aqueous dispersion for a complicated process requiring time.
SOLUTION: At least one kind of organic low molecular weight compound having a molecular weight of less than 1000 and at least one kind of organic polymer compound having a weight average molecular weight of 1000 or more act on organic nanopigment particles dispersed in an aqueous medium. A method for producing an organic nanopigment particle aggregate that is aggregated and then isolated.
[Selection figure] None

Description

  The present invention relates to a method for producing an organic nano pigment particle non-aqueous dispersion obtained by phase-transforming an organic nano pigment particle aqueous dispersion into a non-aqueous medium. More specifically, the present invention has hitherto been difficult to filter. Organic nano pigment particles in aqueous dispersion of organic nano pigment particles made into easily filterable aggregates, which are isolated by filtration operation and redispersed in non-aqueous medium Non-aqueous dispersion of organic nano pigment particles Related to things.

  In recent years, efforts have been made to reduce the size of particles. In particular, research is being conducted to reduce the size to nanometer size (for example, in the range of 10 to 100 nm), which is difficult to produce by a pulverization method, a precipitation method, or the like. Furthermore, attempts have been made to reduce the size to nanometer size and to obtain particles having high monodispersity (in the present invention, monodispersity means the degree of uniform particle size).

  The size of such nanometer-sized fine particles is located in the middle of larger bulk particles, smaller molecules and atoms, and is an unprecedented size region, which can bring out new characteristics that could not be anticipated. It has been pointed out. Moreover, if this monodispersity can be increased, it is possible to stabilize the characteristics, and the potential of such nanoparticles is expected in various fields. Biochemistry, new materials, electronic devices, light-emitting displays Research is growing in a wide range of fields such as devices, printing, and medicine.

  In particular, organic nanoparticles made of an organic compound have a high potential as a functional material because the organic compound itself has diversity. For example, polyimide is used in many fields because it is a chemically and mechanically stable material such as heat resistance, solvent resistance, and mechanical properties, and has excellent electrical insulation. Then, the polyimide is finely divided and combined with the characteristics and shape possessed by the polyimide, and has been used in a wider range of fields. For example, it has been proposed to use finely divided polyimide as an additive for powder toner for image formation (Patent Document 1).

  Further, regarding organic pigments among organic nanoparticles, for example, paints, printing inks, electrophotographic toners, inkjet inks, color filters, and the like can be cited as applications. These are now important compounds that are indispensable in daily life. Among them, high performance is required, and pigments for inkjet ink and pigments for color filters are particularly important in practical use.

  Conventionally, dyes have been used for coloring materials for ink jet inks, but there are problems in terms of water resistance and light resistance, and pigments have been used to improve them. An image obtained with the pigment ink has an advantage of being excellent in light resistance and water resistance as compared with an image obtained with a dye-based ink. However, it is difficult to increase the monodispersity at a nanometer size that can penetrate into the voids on the paper surface, and the adhesion to paper is poor.

  In addition, with the increase in the number of pixels in a digital camera, it is desired to reduce the thickness of color filters used for optical elements such as CCD sensors and display elements. An organic pigment is used for the color filter. However, since the thickness of the filter greatly depends on the particle diameter of the organic pigment, it is desired to produce fine particles having a nanometer size level and being monodispersed and stable.

  Regarding the method for producing organic particles, a gas phase method (a method in which a sample is sublimated in an inert gas atmosphere and the particles are collected on a substrate), a liquid phase method (for example, a sample dissolved in a good solvent under stirring conditions and temperature). Research into reprecipitation method to obtain fine particles by injecting into a controlled poor solvent), laser ablation method (method of refining particles by ablating by irradiating laser to sample dispersed in solution) Has been. In addition, production examples in which monodispersion with a desired size is attempted by these methods have been reported. Among these, the liquid phase method has attracted attention as a method for producing organic particles having excellent simplicity and productivity (see Patent Documents 2 and 3). The organic particles produced by this liquid phase method can adjust the crystal form and particle surface properties by adjusting the precipitation conditions with the solvent species, injection speed, temperature, etc. Patent Document 3 describes the crystal form of the quinacridone pigment. Examples adjusted by the poor solvent species are described.

  On the other hand, regarding the improvement of the dispersibility of particles, the dispersion of organic pigments is conventionally carried out industrially using various dispersers (roll mill, ball mill, attritor, etc.), but by making the particles finer The viscosity may increase. If the viscosity increases, it becomes difficult to take out from the disperser, it cannot be transported by pipeline, or it becomes gelled during storage and becomes unusable. In order to solve these problems, a dispersing agent that aids dispersion and a polymer that stabilizes dispersion are added, but a sufficient effect is not obtained (see Non-Patent Document 1, etc.).

  In addition, in order to improve the dispersibility of organic pigment dispersions for color filters, polymers and pigment dispersants that can provide both the properties of alkali developability and dispersion stability necessary for the production of color filters are added. (For example, refer to Patent Document 4). However, these methods do not satisfy the requirements because dispersion takes time and the viscosity increases.

  In addition, an example in which dispersibility is improved using pigment particles prepared by the liquid phase method has been reported. Patent Document 5 describes an example in which a pigment particle aqueous dispersion is prepared by a liquid phase method. However, this method is finally a method of providing as an aqueous dispersion, and no mention is made of a method of providing as an organic solvent dispersion.

  Patent Document 6 describes an example in which pigment particles prepared by a liquid phase method are used and provided as an organic solvent dispersion. In Patent Document 6, a pigment is precipitated by dissolving the pigment in a basic compound and / or a basic solution, and then adding a liquid neutral compound and / or an acidic compound, or a neutral liquid and / or an acidic liquid. Is described. However, the organic pigment particles obtained by this method have a large primary particle size, and have not been fully satisfied with the demand for fine particles.

In the preparation of nanoparticles in the liquid phase method, a low molecular surfactant or a neutral water-soluble nonionic polymer compound is used in order to prevent aggregation of the nanoparticles. Therefore, even if the nanoparticles can be dispersed at a high concentration, there is a disadvantage that a large amount of the dispersion aid to be used is necessary. When the viscosity is low and the content of the polymer compound is extremely low as in the ink jet, those It is difficult to apply the technology as it is. In addition, for the requirement of phase conversion to a solvent system after preparing aqueous nanoparticles, an aqueous slurry or aqueous paste containing a high concentration of pigment is prepared, a resin or resin solution is added, mixed and stirred, and the pigment There is known a flushing method in which water around the resin is replaced with a resin or a resin solution. However, in this method, the aqueous particles once go through a strongly aggregated form, so that there is a problem that the efficiency of coating with the resin is deteriorated and redispersion becomes difficult (for example, see Patent Documents 7 to 8). Furthermore, in such a method, there is a method of filtering the aqueous nanopigment particles once in the form of primary particles or agglomerated in order to make an aqueous paste, but it takes an enormous amount of time for filtration and is industrially difficult. There is a problem that it becomes inefficient and complicated. A low molecular weight anionic or cationic surfactant can also be used as a dispersant, but there is a problem of insufficient dispersion stability due to the low molecular weight. Therefore, a method has also been attempted in which aqueous particles are phase-converted into an ionic liquid without passing through the filtration step with a cationic polymer compound (see, for example, Non-Patent Document 2). It is limited to low-concentration inorganic particles, and there is no mention of organic pigments in Non-Patent Document 2, and the final dispersion medium may be a non-volatile ionic liquid, and the method described in Non-Patent Document 2 is industrial. It is not suitable for use.
JP-A-11-237760 JP-A-6-79168 JP 2004-91560 A JP 2000-239554 A JP 2004-43776 A JP 2004-123853 A JP-A-5-301037 JP-A-6-161154 Pigment Dispersion Technology-Surface Treatment and Use of Dispersing Agents and Dispersibility Evaluation-Technical Information Association 1999 “Small”, 2006, Vol.2, No.7, p.879-883

  The present invention has been made in view of the above-mentioned problems, and the purpose thereof is to temporarily represent, for example, flushing when phase-converting an organic nanopigment particle aqueous dispersion into an organic nanopigment particle non-aqueous dispersion. For the process of creating an aqueous paste, that is, a complicated process that requires enormous time such as filter filtration, the nano pigment particles in the aqueous dispersion of organic nano particles are made into aggregates that can be easily filtered. Is isolated and redispersed in a non-aqueous medium to provide a method for producing a non-aqueous dispersion of organic nanopigment particles efficiently obtained. Furthermore, it aims at provision of the color photosensitive resin composition using the said organic nano pigment particle dispersion, and the color filter produced by it.

  As a result of intensive studies, the present inventor has added organic nanopigment particles dispersed in an aqueous medium to a solution in which an organic low-molecular compound and an organic polymer compound are dissolved, thereby allowing easy filtration. It was found that an organic nanopigment particle non-aqueous dispersion can be efficiently obtained by aggregating into an aggregate, isolating the aggregate and redispersing it in a non-aqueous medium. The present invention has been made based on such findings.

The above object has been achieved by the following means.
[1] At least one kind of organic low molecular compound having a molecular weight of less than 1000 and at least one kind of organic polymer compound having a weight average molecular weight of 1000 or more are allowed to act on the organic nanopigment particles dispersed in an aqueous medium. A method for producing an aggregate of organic nanopigment particles, characterized in that the organic nanopigment particle aggregate is isolated after aggregation.
[2] The organic low molecular weight compound and the organic polymer compound are dissolved in a solvent miscible with the aqueous medium, and added to the aqueous medium, whereby organic nanopigment particles dispersed in the aqueous medium are obtained. The method for producing an organic nanopigment particle aggregate according to [1], wherein the aggregation is performed.
[3] The method for producing an organic nanopigment particle dispersion according to [1] or [2], wherein the isolation is performed by filtration.
[4] The method for producing an organic nanopigment particle aggregate according to any one of [1] to [3], including a step of removing at least the excess organic low-molecular compound.
[5] Organic nanopigment particles dispersed in the aqueous medium, a solution of an organic pigment dissolved in a good solvent, a medium compatible with the good solvent and a poor solvent for the organic pigment; The method for producing an organic nano pigment particle aggregate according to any one of [1] to [4], wherein the organic nano pigment particle aggregate is obtained by mixing and producing nano-sized fine particles.
[6] The method for producing an organic nanopigment particle aggregate according to any one of [1] to [7], wherein an average primary particle size of the organic nanopigment particles is 100 nm or less.
[7] The method for producing an organic nanopigment particle dispersion according to any one of [1] to [6], wherein the aggregate has an average particle size of 10,000 nm or more.
[8] Organic nanopigment particle non-characteristic obtained by re-dispersing the isolated organic nanopigment particle aggregate according to any one of [1] to [7] in a non-aqueous medium A method for producing an aqueous dispersion.
[9] The organic nanopigment particle non-containing material according to any one of [1] to [8], wherein the organic polymer compound is represented by the following general formula (11) or general formula (14): A method for producing an aqueous dispersion.

(In the general formula (11), A ¹ represents an acidic 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, or alkoxysilyl. A monovalent organic group having a group selected from a group, an epoxy group, an isocyanate group, and a hydroxyl group, or a monovalent organic group containing an organic dye structure or a heterocyclic ring which may have a substituent. A ¹ may be the same or different, R ¹ represents a (m + n) -valent linking group, m + n represents 3 to 10, m represents an integer of 1 to 8, and n Represents an integer of 2 to 9. R ² represents a single bond or a divalent linking group, and P ¹ represents a polymer residue.)

(In the general formula (14), G represents —COO ⁻ , —SO ₃ ⁻ , —OSO ₃ ⁻ , —P (O) (OH) O ⁻ , or —OP (O) (OH) O ^— . J represents a divalent linking group or a single bond, Q represents an (m + 1) -valent linking group, R represents a polymer compound residue, Z represents an organic or inorganic cation, and m + 1 represents 3 to 6. To express.)
[10] The method for producing a non-aqueous dispersion of organic nanopigment particles according to [9], wherein the organic polymer compound is used as it is as a dispersant in a non-aqueous medium.
[11] A colored photosensitive resin composition comprising at least a non-aqueous dispersion of organic nanopigment particles according to [9] or [10], a binder, a monomer or an oligomer, and a photopolymerization initiator or a photopolymerization initiator system. .
[12] A color filter comprising the colored photosensitive resin composition according to [11].

  According to the production method of the present invention, an organic nanopigment particle aggregate can be efficiently produced from an organic nanopigment particle aqueous dispersion. In addition, by using this organic nano pigment particle aggregate, it is possible to easily phase change and unwind (redispersion) into a non-aqueous medium, and the organic nano pigment particle non-aqueous dispersion is efficient on an industrial scale. Can be manufactured well. According to the production method of the present invention, it is possible to produce an organic nano pigment particle dispersion suitable for color filter coating liquid and ink jet ink and a dispersion thereof on an industrial scale. Moreover, the organic nano pigment particle non-aqueous dispersion of the present invention has excellent dispersibility and high contrast, and a color filter using the same has target color purity and high contrast.

Hereinafter, the manufacturing method of the organic nano pigment particle of this invention is demonstrated.
[Organic pigments]
The organic pigment used in the method for producing organic nanopigment particles of the present invention is not particularly limited as long as it can form particles by a liquid phase method, and may be used alone or in combination. It may be.

  The organic pigment is not limited in hue, for example, perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, triarylcarbonium , Dioxazine, aminoanthraquinone, diketopyrrolopyrrole, thioindigo, isoindoline, isoindolinone, pyranthrone or isoviolanthrone compound pigment, or a mixture thereof.

  More specifically, for example, C.I. I. Pigment red 190 (C.I. No. 71140), C.I. I. Pigment red 224 (C.I. No. 71127), C.I. I. Perylene compound pigments such as C.I. Pigment Violet 29 (C.I. No. 71129); I. Pigment orange 43 (C.I. No. 71105), or C.I. I. Perinone compound pigments such as C.I. Pigment Red 194 (C.I. No. 71100); I. Pigment violet 19 (C.I. No. 73900), C.I. I. Pigment violet 42, C.I. I. Pigment red 122 (C.I. No. 73915), C.I. I. Pigment red 192, C.I. I. Pigment red 202 (C.I. No. 73907), C.I. I. Pigment Red 207 (C.I. No. 73900, 73906) or C.I. I. Pigment Red 209 (C.I. No. 73905), a quinacridone compound pigment; I. Pigment red 206 (C.I. No. 73900/73920), C.I. I. Pigment orange 48 (C.I. No. 73900/73920), or C.I. I. Quinacridonequinone compound pigments such as CI Pigment Orange 49 (C.I. No. 73900/73920); I. Anthraquinone compound pigments such as C.I. Pigment Yellow 147 (C.I. No. 60645); I. Anthanthrone compound pigments such as CI Pigment Red 168 (C.I. No. 59300); I. Pigment brown 25 (C.I. No. 12510), C.I. I. Pigment violet 32 (C.I. No. 12517), C.I. I. Pigment yellow 180 (C.I. No. 21290), C.I. I. Pigment yellow 181 (C.I. No. 11777), C.I. I. Pigment orange 62 (C.I. No. 11775), or C.I. I. Benzimidazolone compound pigments such as CI Pigment Red 185 (C.I. No. 12516); I. Pigment yellow 93 (C.I. No. 20710), C.I. I. Pigment yellow 94 (C.I. No. 20038), C.I. I. Pigment yellow 95 (C.I. No. 20034), C.I. I. Pigment yellow 128 (C.I. No. 20037), C.I. I. Pigment yellow 166 (C.I. No. 20035), C.I. I. Pigment orange 34 (C.I. No. 21115), C.I. I. Pigment orange 13 (C.I. No. 21110), C.I. I. Pigment orange 31 (C.I. No. 20050), C.I. I. Pigment red 144 (C.I. No. 20735), C.I. I. Pigment red 166 (C.I. No. 20730), C.I. I. Pigment red 220 (C.I. No. 20055), C.I. I. Pigment red 221 (C.I. No. 20065), C.I. I. Pigment red 242 (C.I. No. 20067), C.I. I. Pigment red 248, C.I. I. Pigment red 262, or C.I. I. Disazo condensed compound pigments such as CI Pigment Brown 23 (C.I. No. 20060); I. Pigment yellow 13 (C.I. No. 21100), C.I. I. Pigment yellow 83 (C.I. No. 21108), or C.I. I. Disazo compound pigments such as CI Pigment Yellow 188 (C.I. No. 21094); I. Pigment red 187 (C.I. No. 12486), C.I. I. Pigment red 170 (C.I. No. 12475), C.I. I. Pigment yellow 74 (C.I. No. 11714), C.I. I. Pigment yellow 150 (C.I. No. 48545), C.I. I. Pigment red 48 (C.I. No. 15865), C.I. I. Pigment red 53 (C.I. No. 15585), C.I. I. Pigment orange 64 (C.I. No. 12760), or C.I. I. Azo compound pigments such as CI Pigment Red 247 (C.I. No. 15915), C.I. I. Indanthrone compound pigments such as C.I. Pigment Blue 60 (C.I. No. 69800); I. Pigment green 7 (C.I. No. 74260), C.I. I. Pigment Green 36 (C.I. No. 74265), Pigment Green 37 (C.I. No. 74255), Pigment Blue 16 (C.I. No. 74100), C.I. I. Phthalocyanine compound pigments such as CI Pigment Blue 75 (C.I. No. 74160: 2) or 15 (C.I. No. 74160); I. Pigment blue 56 (C.I. No. 42800), or C.I. I. Pigment Blue 61 (C.I. No. 42765: 1) and the like triarylcarbonium compound pigments, C.I. I. Pigment violet 23 (C.I. No. 51319) or C.I. I. Pigment Violet 37 (C.I. No. 51345) and other dioxazine compound pigments, C.I. I. Aminoanthraquinone compound pigments such as C.I. Pigment Red 177 (C.I. No. 65300); I. Pigment red 254 (C.I. No. 56110), C.I. I. Pigment Red 255 (C.I. No. 561050), C.I. I. Pigment red 264, C.I. I. Pigment red 272 (C.I. No. 561150), C.I. I. Pigment orange 71, or C.I. I. Diketopyrrolopyrrole compound pigments such as C.I. Pigment Orange 73; I. Thioindigo compound pigments such as C.I. Pigment Red 88 (C.I. No. 7313); I. Pigment yellow 139 (C.I. No. 56298), C.I. I. Pigment Orange 66 (C.I. No. 48210), an isoindoline compound pigment such as C.I. I. Pigment yellow 109 (C.I. No. 56284), or C.I. I. Pigment Orange 61 (C.I. No. 11295) and the like, an inindolinone compound pigment such as C.I. I. Pigment Orange 40 (C.I. No. 59700), or C.I. I. Pigment red 216 (C.I. No. 59710) and the like, or C.I. I. And isoviolanthrone compound pigments such as CI Pigment Violet 31 (60010). Among these, a quinacridone compound pigment, a diketopyrrolopyrrole compound pigment, a dioxazine compound pigment, a phthalocyanine compound pigment, or an azo compound pigment is preferable, and a diketopyrrolopyrrole compound pigment or a dioxazine compound pigment is more preferable.

  C. I. P. R. Since pyrrolopyrrole compound pigments represented by 254, 255, and 264 have an absorption range suitable for increasing the color purity of the red pixel constituting the color filter and the color reproduction range can be expanded, An attempt is being made to use it. However, conventional pigments do not meet demands such as color purity and contrast. For example, an ink-jet ink described in JP-A-2003-336001, an ink obtained by a method using bead dispersion or salt milling, or the like cannot provide a good color filter.

According to the production method of the present invention, nano-sized pyrrolopyrrole compound pigment fine particles can be obtained with a sharp particle size distribution. In addition, when the pigment fine particles are used in a color filter, desired color purity and high contrast can be achieved at the same time, and the light resistance is excellent, and the occurrence of protrusions can be suppressed.
In the present invention, two or more kinds of organic pigments or solid solutions of organic pigments can be used in combination.

[Preparation of organic nano pigment particle aqueous dispersion]
Next, preparation of the organic nano pigment particle aqueous dispersion will be described.
In the present invention, the organic nanopigment particles are an organic pigment solution in which an organic pigment is dissolved in a good solvent, a solvent that is compatible with the good solvent and is a poor solvent for the organic pigment (hereinafter referred to as the following). This solvent is also referred to as [poor solvent of organic pigment] or simply [poor solvent].) (Hereinafter, this method is sometimes referred to as “reprecipitation method”. The dispersion containing the organic nanoparticles sometimes obtained is sometimes referred to as “organic nanopigment particle reprecipitation liquid”.

  The poor solvent for the organic pigment is not particularly limited as long as it is compatible with or uniformly mixed with a good solvent for dissolving the organic pigment. As a poor solvent for the organic pigment, the solubility of the organic pigment is preferably 0.02% by mass or less, and more preferably 0.01% by mass or less. Although there is no particular lower limit to the solubility of the organic pigment in the poor solvent, 0.000001% by mass or more is practical in consideration of a commonly used organic pigment. This solubility may be the solubility when dissolved in the presence of an acid or alkali. In addition, the compatibility or uniform mixing property of the good solvent and the poor solvent is preferably 30% by mass or more, more preferably 50% by mass or more, with respect to the poor solvent. There is no particular upper limit to the amount of good solvent dissolved in the poor solvent, but it is practical to mix them in an arbitrary ratio.

  The poor solvent is not particularly limited as long as it is an aqueous medium. For example, an aqueous solvent (for example, water, hydrochloric acid, sodium hydroxide aqueous solution), alcohol compound solvent, ketone compound solvent, ether compound solvent, aromatic compound solvent , Carbon disulfide solvent, aliphatic compound solvent, nitrile compound solvent, halogen compound solvent, ester compound solvent, ionic liquid, mixed solvent thereof, and the like, aqueous solvent, alcohol compound solvent, ketone compound solvent, ether compound solvent , Ester compound solvents, or mixtures thereof are preferred, and aqueous solvents, alcohol compound solvents, or ester compound solvents are more preferred.

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

Next, a good solvent for dissolving the organic pigment will be described.
The good solvent is not particularly limited as long as it can dissolve the organic pigment to be used and is compatible with or uniformly mixed with the poor solvent. The solubility of the organic pigment in a good solvent is such that the solubility of the organic material is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. Although there is no particular upper limit to the solubility of the organic pigment in the good solvent, it is practical that it is 50% by mass or less in consideration of a commonly used organic pigment. This solubility may be the solubility when dissolved in the presence of an acid or alkali. The preferred range of the compatibility or uniform mixing property between the poor solvent and the good solvent is as described above.

  Examples of the good solvent include an aqueous solvent (for example, water or hydrochloric acid, an aqueous sodium hydroxide 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, and a fat. Group compound solvents, nitrile compound solvents, sulfoxide compound solvents, halogen compound solvents, ester compound solvents, ionic liquids, carboxylic acid compounds, sulfonic acid compounds, sulfuric acid, mixed solvents thereof, aqueous solvents, alcohol compound solvents, Ketone compound solvents, ether compound solvents, sulfoxide compound solvents, ester compound solvents, amide compound solvents, carboxylic acid compounds, sulfonic acid compounds, sulfuric acid, or mixtures thereof are preferred, aqueous solvents, alcohol compound solvents, ester compound solvents, sulfoxide compounds. solvent Amide compound solvent, a carboxylic acid compound, sulfonic acid compound, more preferably sulfuric acid, the sulfoxide compound solvent, the amide compound solvent, a carboxylic acid compound, sulfonic acid compound, is particularly preferred sulfate.

  Examples of the sulfoxide compound solvent include dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, sulfolane and the like. Examples of the amide compound solvent include N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, formamide, N -Methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like.

  In addition, the concentration of the organic pigment solution in which the organic pigment is dissolved in the good solvent is preferably a saturated concentration of the organic pigment with respect to the good solvent under the dissolution conditions or a range of about 1/100 of this.

  There are no particular limitations on the conditions for preparing the organic pigment solution, and a range from normal pressure to subcritical and supercritical conditions can be selected. The temperature at normal pressure is preferably −10 to 150 ° C., more preferably −5 to 130 ° C., and particularly preferably 0 to 100 ° C.

  In the present invention, the organic pigment must be uniformly dissolved in a good solvent, but it is also preferable to dissolve it in an acidic or alkaline manner. In general, in the case of a pigment having an alkaline and dissociable group in the molecule, the alkalinity is used, and when there is no alkaline and dissociable group and there are many nitrogen atoms to which protons can easily be added, acidity is used. For example, quinacridone, diketopyrrolopyrrole, disazo condensation compound pigments are alkaline, and phthalocyanine compound pigments are acidic.

  Bases used for alkaline dissolution are inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, or barium hydroxide, or trialkylamine, diazabicycloundecene (DBU), An organic base such as a metal alkoxide is preferable, but an inorganic base is preferable.

  The amount of the base used is an amount capable of uniformly dissolving the pigment, and is not particularly limited. However, in the case of an inorganic base, it is preferably 1.0 to 30 molar equivalents relative to the organic material, more preferably 1 0.0 to 25 molar equivalents, more preferably 1.0 to 20 molar equivalents. In the case of an organic base, it is preferably 1.0 to 100 molar equivalents, more preferably 5.0 to 100 molar equivalents, still more preferably 20 to 100 molar equivalents relative to the organic material.

  The acid used for the acidic dissolution is preferably 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. It is an inorganic acid. Particularly preferred is sulfuric acid.

  The amount of the acid used is an amount capable of uniformly dissolving the organic pigment, and is not particularly limited, but is often used in an excessive amount as compared with the base. Regardless of inorganic acid or organic acid, it is preferably 3 to 500 molar equivalents, more preferably 10 to 500 molar equivalents, still more preferably 30 to 200 molar equivalents relative to the organic material.

  When mixing alkali or acid with an organic solvent and using it as a good solvent for organic pigments, a solvent having high solubility in some alkali or acid such as water or lower alcohol in order to completely dissolve the alkali or acid Can be added to the organic solvent. 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, or the like can be used.

  There is no particular limitation on the conditions of the poor solvent when the organic particles are produced, that is, when the organic particles are deposited and formed, and a range from normal pressure to subcritical and supercritical conditions can be selected. The temperature at normal pressure is preferably −30 to 100 ° C., more preferably −10 to 60 ° C., and particularly preferably 0 to 30 ° C.

  When mixing the organic pigment solution and the poor solvent, either of them may be added and mixed. However, the organic pigment solution is preferably added to the poor solvent and mixed, and the poor solvent is stirred at that time. It is preferable that the The stirring speed is preferably 100 to 10,000 rpm, more preferably 150 to 8000 rpm, and particularly preferably 200 to 6000 rpm. A pump or the like may be used for the addition, or it may not be used. Moreover, although addition in a liquid or addition outside a liquid may be sufficient, addition in a liquid is more preferable. The mixing ratio of the organic pigment solution and the poor solvent (ratio of good solvent / poor solvent in the organic nanopigment particle reprecipitation liquid) is preferably 1/50 to 2/3, more preferably 1/40 to 1/2 in volume ratio. 1/20 to 3/8 is particularly preferable. In the present invention, the organic nano pigment particles are first dispersed in an aqueous medium. In this case, the aqueous medium contains at least 60% by mass of the above aqueous solvent, preferably 80 mass% or more is contained.

  The concentration of the organic nanopigment particle reprecipitation liquid is not particularly limited as long as the organic nanopigment particle can be produced, but the organic pigment particle is preferably in the range of 10 to 40,000 mg, more preferably 20 to 1000 ml of the aqueous medium. It is the range of -30000 mg, Most preferably, it is the range of 50-25000 mg.

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

  Regarding the particle size of the organic nano pigment particles, there is a method of expressing the average size of the population by quantifying by a measurement method, but as a common use, the mode diameter indicating the maximum value of the distribution, the integral distribution curve There are median diameter corresponding to the median, various average diameters (number average, length average, area average, mass average, volume average, etc.). In the present invention, unless otherwise specified, the average particle diameter is Number average diameter. The average particle diameter of the organic pigment nanoparticles (primary particles) is a nanometer size, the average particle diameter is preferably 1 nm to 1 μm, more preferably 1 to 200 nm, and further preferably 2 to 100 nm. Preferably, it is 5-80 nm, and it is especially preferable. The particles formed in the present invention may be crystalline particles, amorphous particles, or a mixture thereof.

  In the present invention, the ratio (Mv / Mn) of the volume average particle diameter (Mv) and the number average particle diameter (Mn) is used as an index representing the monodispersity of the particles unless otherwise specified. The monodispersity, that is, Mv / Mn, of particles (primary particles) contained in the organic nanopigment particle dispersion used in the organic nanopigment particle concentration method is preferably 1.0 to 2.0. It is more preferably 0 to 1.8, and particularly preferably 1.0 to 1.5.

  Examples of methods for measuring the particle size of organic nano pigment particles include microscopy, weight method, light scattering method, light blocking method, electrical resistance method, acoustic method, and dynamic light scattering method. The method is particularly preferred. Examples of the microscope used for the microscopy include a scanning electron microscope and a transmission electron microscope. Examples of the particle measuring apparatus based on the dynamic light scattering method include Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd., Dynamic Light Scattering Photometer DLS-7000 series manufactured by Otsuka Electronics Co., Ltd., and LB-400 manufactured by Horiba, Ltd. Product name).

  In preparing the organic nano pigment particle aqueous dispersion, it is preferable to contain a dispersant (hereinafter also referred to as a dispersant for the aqueous dispersion). The step of incorporating the dispersant is not particularly limited, but it is preferable to add the dispersant to the organic pigment solution and / or the poor solvent. Moreover, it is also preferable to add a dispersing agent solution at the time of formation of organic nano pigment particles in a system different from the above two solutions. It is also preferable to use pigment particles that have been surface-treated with a dispersant in advance, and the pigment particles may be subjected to a surface treatment that can promote adsorption of the dispersant. The dispersant (1) has a function of quickly adsorbing on the surface of the deposited pigment to form fine nanoparticles and (2) preventing these particles from aggregating again.

  As a dispersant that can be used, for example, a low molecular or high molecular dispersant of anionic, cationic, amphoteric, nonionic or pigment derivative can be used. In addition, the addition amount of the low molecular weight or polymer dispersing agent is preferably 10% by mass or more and 1000% by mass or less with respect to the dissolved pigment. Furthermore, 50 mass% or more and 200 mass% or less are more preferable. If it is less than 10% by mass, the effect of suppressing the growth and aggregation of the pigment particles is reduced, and if it exceeds 1000% by mass, problems such as an increase in viscosity and poor dissolution tend to occur.

Hereinafter, the polymer dispersant will be described.
The molecular weight of the polymer dispersant is preferably 1,000 to 200,000 in terms of number average molecular weight. Furthermore, 3,000 or more and 40,000 or less are more preferable. If it is less than 1,000, the effect of suppressing the growth and aggregation of pigment particles is reduced, and if it exceeds 200,000, problems such as increased viscosity and poor dissolution tend to occur. The polymer in the present invention refers to a polymer having a number average molecular weight of 1000 or more.

  The polymer dispersant is nonionic, specifically, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, polyvinyl alcohol-part. Formalized products, polyvinyl alcohol-partially butyralized products, vinyl pyrrolidone-vinyl acetate copolymers, polyethylene oxide / propylene oxide block copolymers, and the like are mentioned, among which polyvinyl pyrrolidone is preferred.

  Examples of anionic substances include polyacrylates, polyvinyl sulfates, poly (4-vinylpyridine) salts, polyamides, polyallylamine salts, polybenzenesulfonates, condensed naphthalenesulfonates, cellulose derivatives, and starch derivatives. Can be mentioned. Among these, polybenzene sulfonate and condensed naphthalene sulfonate are more preferable.

  These anionic ones can be obtained by copolymerizing an anionic monomer, but they may be copolymerized with not only the anionic monomer itself but also a nonionic monomer. Specific examples of the nonionic monomer include vinyl pyrrolidone, styrene, naphthalene, styryl methyl chloride, vinyl imidazole, vinyl pyridine, acrylamide, and vinyl amide.

  As the cationic compound, a polymer compound having a quaternary ammonium moiety is particularly preferable. Poly (methacryloxyalkylammonium salt), poly (methacryloxyarylammonium salt), poly (acryloxyalkylammonium salt), poly (acrylic) Oxyarylammonium salt), poly (diallylammonium salt), and the like. The polymer compound having a quaternary ammonium moiety is a polymer compound having a cationic repeating unit represented by the following general formula (1). Preferably there is.

(In the formula, R _{1 to} R ₃ each independently represents an alkyl group, an aralkyl group, or an aryl group. Any _{two of} R ₁ , R ₂ , and R ₃ may be linked to each other, and oxygen A heterocycle containing an atom, a nitrogen atom, and / or a sulfur atom may be formed, 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 L represents a single bond or a divalent linking group, or a tetravalent linking group further bonded to any _{two of} R ₁ , R ₂ and R _3. )
The alkyl group represented by R _{1 to} R ₃ in the general formula (1) is a substituted or unsubstituted linear, branched or cyclic alkyl group, preferably an alkyl group having 1 to 12 carbon atoms, more preferably Is an alkyl group having 1 to 4 carbon atoms. The aralkyl group represented by R _{1 to} R ₃ is a substituted or unsubstituted aralkyl group, and preferably an aralkyl group having 7 to 10 carbon atoms. The aryl group represented by R _{1 to} R ₃ is a substituted or unsubstituted aryl group, preferably an aryl group having 6 to 10 carbon atoms. Each aralkyl group or aryl group may be monocyclic or condensed.

  Specific examples of the alkyl group include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, tertiary butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, Octyl, tertiary octyl, 2-ethylhexyl, decyl, and dodecyl groups are preferred. Particularly preferred are a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, and a tertiary butyl group.

  Specifically, the aralkyl group is preferably a benzyl group, a 4-chlorobenzyl group, a 4-methylbenzyl group, a 4-butoxybenzyl group, a 4-methoxybenzylmethoxyphenyl group, or a 4-hydroxybenzyl group. Particularly preferred are a benzyl group, a 4-chlorobenzyl group, a 4-methylbenzyl group, and a 4-butoxybenzyl group.

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

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

  In general formula (1), X may be monovalent or polyvalent, and the halogen atom represented by X is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Specific examples of the organic anion represented by X include a carboxylate anion, a sulfonate anion, an alkoxide, a benzenesulfonate anion, a naphthalenesulfonate anion, a naphthalene disulfonate anion, and an anthracene disulfonate anion. Specific examples of the inorganic anion represented by X include a bromine tetrafluoride anion, a phosphorous hexafluoride anion, and a hydroxide. Particularly preferred is an organic or inorganic anion that satisfies the condition that n is a natural number of 1 to 2.

  In general formula (1), the alkyl group represented by A is specifically preferably a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, or a tertiary butyl group. Particularly preferred are a methyl group and an ethyl group.

In the general formula (1), L represents a single bond or a divalent linking group, or a tetravalent linking group further bonded to any _{two of} R ₁ , R ₂ and 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 condensed. The tetravalent linking group 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 general formula (1).

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

The following formula (1) includes those in which any _{two of} R ₁ , R ₂ , and R ₃ are connected to each other, and specific examples of the heterocyclic ring containing oxygen, nitrogen, and sulfur atoms. The example of the high molecular compound which has a cationic repeating unit represented by this is shown. For example, polyvinyl imidazolinium salts, polyvinyl benzimidazolinium salts, polyvinyl pyridinium salts, polystyryl methylene imidazolium salts, polystyryl methylene imidazolinium salts, polystyryl methylene pyridinium salts, polystyryl methylene oxazolium salts, polystyryl Methylene oxazolinium salts, polystyryl methylene thiazolium salts, polystyryl methylene thiazolium salts, polystyryl methylene ammonium salts, polynaphthyl methylene imidazolium salts, polynaphthyl methylene imidazolinium salts, polynaphthyl methylene pyridinium salts, poly Naphthylmethyleneoxazolium salts, polynaphthylmethyleneoxazolinium salts, polynaphthylmethylenethiazolium salts, poly Borderless Le methylene thiazolium salts, poly-naphthyl methylene ammonium salts.

  Among these, particularly preferred examples include polystyryl methylene imidazolium salts, polystyryl methylene imidazolinium salts, polystyryl methylene pyridinium salts, polystyryl methylene oxazolium salts, polystyryl methylene oxazolinium salts, polystyryl. Examples include methylene thiazolium salts, polystyryl methylene thiazolium salts, and polystyryl methylene ammonium salts.

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

In the general formula (2), R ₁ to R _3, X and n have the same meanings as R ₁ to R _3, X and n in the general formula (1), and preferred ranges are also the same.

  The polymer compound having a quaternary ammonium moiety used in the present invention may be a random copolymer composed of the cationic repeating unit represented by the general formula (1) and other repeating units. The polymerization ratio is preferably 0.1 to 0.7% by mass, more preferably 0.1 to 0.5% by mass, based on the former polymer compound having a quaternary ammonium moiety. .

  Examples of copolymerization components include vinyl imidazolinium salts, vinyl benzimidazolinium salts, vinyl pyridinium salts, styryl methylene imidazolium salts, styryl methylene imidazolinium salts, styryl methylene pyridinium salts, styryl methylene oxazolium salts, styryl. Methylene oxazolinium salts, styryl methylene thiazolium salts, styryl methylene thiazolium salts, styryl methylene ammonium salts, naphthyl methylene imidazolium salts, naphthyl methylene imidazolinium salts, naphthyl methylene pyridinium salts, naphthyl methylene oxazolium salts, Naphthyl methylene oxazolinium salts, naphthyl methylene thiazolium salts, naphthyl methylene thiazolium salts, naphthyl methylene an Iodonium salts, vinylpyrrolidone, styrene, naphthalene, styryl methyl chloride, vinyl imidazole, vinyl pyridine, acrylamide, and the like vinylamides. Particularly preferred are styryl methylene imidazolium salts, styryl methylene imidazolinium salts, styryl methylene pyridinium salts, styryl methylene ammonium salts, vinyl pyrrolidone, styrene, naphthalene, styryl methyl chloride, vinyl imidazole, vinyl pyridine, acrylamide, vinyl amide, and the like. .

  Specific examples of the polymer compound having a quaternary ammonium moiety used in the present invention are shown below, but the present invention is not limited thereto. In the following specific examples, the polymer compound used in the present invention is obtained by polymerizing the exemplified repeating units.

  The polymer compound having a quaternary ammonium moiety can be produced with reference to “small”, 2006, Vol. 2, No. 7, p. 879-883.

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

  These polymers can be used alone or in combination of two or more. These dispersants can be used alone or in combination. The dispersant used for dispersing the pigment is described in detail on pages 29 to 46 of “Pigment dispersion stabilization and surface treatment technology / evaluation” (Chemical Information Association, issued in December 2001).

Hereinafter, the low molecular dispersant will be described.
As low molecular weight dispersants, anionic ones include N-acyl-N-alkyl taurine salts, fatty acid salts, alkyl sulfate salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphates. Examples include ester salts, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl sulfate esters, and the like. Of these, N-acyl-N-alkyltaurine salts are preferred. As the N-acyl-N-alkyltaurine salt, those described in JP-A-3-273067 are preferable. These anionic dispersants can be used alone or in combination of two or more.

  As cationic ones, quaternary ammonium salts, alkoxylated polyamines, aliphatic amine polyglycol ethers, aliphatic amines, diamines and polyamines derived from aliphatic amines and fatty alcohols, imidazolines derived from fatty acids and their Salts of cationic substances are included. These cationic dispersants can be used alone or in combination of two or more.

  The amphoteric one is a dispersant having both an anionic group part in the molecule of the anionic dispersant and a cationic group part in the molecule of the cationic dispersant.

  Nonionic ones 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, etc. Can do. Among these, polyoxyethylene alkyl aryl ether is preferable. These nonionic dispersants can be used alone or in combination of two or more.

  The pigment derivative type is derived from an organic pigment as a parent substance and is obtained by a pigmentation reaction of a pigment derivative type dispersant produced by chemically modifying the parent structure or a chemically modified pigment precursor. Defined as a pigment derivative type dispersant. For example, a sugar-containing pigment derivative-type dispersant, a piperidyl-containing pigment derivative-type dispersant, a naphthalene or perylene-derived pigment derivative-type dispersant, a pigment derivative-type dispersant having a functional group linked to a pigment parent structure via a methylene group, Pigment parent structure chemically modified with polymer, pigment derivative type dispersant having sulfonic acid group, pigment derivative type dispersant having sulfonamide group, pigment derivative type dispersant having ether group, carboxylic acid group, carboxylic acid ester And pigment derivative type dispersants having a group or a carboxamide group.

  In the present invention, when preparing an organic pigment solution dissolved in a good solvent, it is preferable to coexist a pigment dispersant containing an amino group. Here, the amino group includes a primary amino group, a secondary amino group, and a tertiary amino group, and the number of amino groups may be one or more. A pigment derivative compound in which a substituent having an amino group is introduced into the pigment skeleton, or a polymer compound having a monomer having an amino group as a polymerization component may be used. Examples thereof include, for example, compounds described in JP-A Nos. 2000-239554, 2003-96329, 2001-31885, JP-A-10-339949, and JP-B-5-72943. However, it is not limited to these.

[Low molecular organic compounds and organic high molecular compounds]
In the present invention, at least one organic low molecular weight compound having a molecular weight of less than 1000 (hereinafter also referred to as low molecular weight compound) and at least one weight average molecular weight with respect to organic nanopigment particles dispersed in an aqueous medium. After agglomerating by acting 1000 or more organic polymer compounds (hereinafter also referred to as polymer compounds), the organic nanoparticle aggregates are isolated. In the present invention, the low molecular weight compound aggregates the organic nano pigment particles. The polymer compound aggregates the aggregate produced by the aggregation, and forms a large aggregate that can be easily filtered. In the present invention, the low molecular weight compound and the high molecular weight compound are used in combination. Although the organic nanoparticles are condensed only with the low molecular weight compound, the filter paper does not form a large aggregate and is filtered through the filter paper. Even if it slips through or is filtered with a filtration filter, it takes an enormous amount of time for filtration. In addition, with the polymer compound alone, the aggregate itself hardly occurs, and filtration is impossible. For the polymer compound in the present invention, since the aqueous solvent in which the organic nano pigment particles are dispersed is a poor solvent, the polarity of the aggregate becomes insoluble in the aqueous solvent due to adsorption to the aggregate, and the aggregation Grows the body into large aggregates.

  As an aggregate, it is preferable that an average particle diameter is 10,000 nm or more, and a larger one is more preferable. When the thickness is less than 10,000 nm, it takes a long time to isolate the aggregate, and even if it is attempted to be filtered, it passes through the filter paper or filter, or is clogged.

  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 not removed even after filtration, washing described below, and redispersion (melting) described below. Since it can be used as a dispersant in an aqueous medium (hereinafter also referred to as a dispersant for a non-aqueous dispersion), it is not necessary to add a new dispersant. In order to adjust the dispersibility, a dispersant may be newly added later, but it is preferable not to add it from the viewpoint of production cost.

  Furthermore, since the organic nano pigment particles constituting the aggregate in the present invention are aggregated in a state where they are coated with a low molecular weight and high molecular compound, when they aggregate without these low molecular weight and high molecular compounds, for example, hydrochloric acid or the like Compared with the case of agglomerating with, the subsequent re-dispersion is easy, the organic nano pigment particles are easily loosened to the primary particles, and the contrast becomes high.

  The low molecular compound and the high molecular compound may be added as they are, but it is preferable to add the low molecular compound and the high molecular compound after dissolving them in a solvent from the viewpoint of obtaining good filterability.

  The solvent is miscible with the organic nanopigment particle aqueous dispersion and can dissolve the low-molecular compound and the high-molecular compound. Further, the low-molecular compound and the high-molecular compound precipitate themselves even after the addition. If not, there is no particular limitation.

  In addition, even if the solvent itself is added to the organic nanopigment particle aqueous dispersion, the organic nanopigment particles do not agglomerate, or weak agglomeration that can be redispersed even when agglomerated (high shear such as milling or high-speed stirring) A solvent that generates a floc that can be redispersed without applying force is preferred.

  Examples of the solvent include aqueous solvents (for example, water or hydrochloric acid, aqueous sodium hydroxide), alcohol compound solvents, amide compound solvents, ketone compound solvents, ether compound solvents, aromatic compound solvents, carbon disulfide solvents, fats. Group compound solvents, nitrile compound solvents, sulfoxide compound solvents, halogen compound solvents, ester compound solvents, ionic liquids, mixed solvents thereof, and the like, aqueous solvents, alcohol compound solvents, ketone compound solvents, ether compound solvents, sulfoxide compounds A solvent, an ester compound solvent, an amide compound solvent, a nitrile compound solvent, or a mixture thereof is preferable, and a ketone compound solvent, an ether compound solvent, a nitrile compound solvent, or a mixture thereof is more preferable.

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

  The amount of the solvent used is not particularly limited as long as it is an amount that can dissolve a low molecular compound and a high molecular compound and can form an aggregate that can be easily filtered, but can further reduce the complexity of production and the raw material cost. In view of the above, it is preferable that the amount be as small as possible. When this is shown by mass ratio, when the organic nano pigment particle aqueous dispersion is 100, the added solvent is preferably in the range of 1 to 100, more preferably in the range of 10 to 70, and 20 to 20 A range of 70 is particularly preferred. If the amount is too large, it takes a long time to settle the aggregate. If the amount is too small, the formation of the aggregate becomes insufficient, and the aggregate becomes difficult to settle.

  After adding the solvent, it is preferable to stir so that the organic nano pigment particle aqueous dispersion is sufficiently mixed. A normal method can be used for stirring and mixing. Although there is no restriction | limiting in particular in the temperature when adding and mixing this solvent, It is preferable that it is 1-100 degreeC, and it is more preferable that it is 5-60 degreeC. The addition and mixing of the solvent may be carried out by any apparatus as long as each step can be preferably carried out. For example, the apparatus can be carried out using an apparatus such as a stirring blade or a Lamond stirrer.

  Further, as described above, in the present invention, when the organic nanopigment particles in the aqueous dispersion of organic nanopigment particles are aggregated, the low molecular compound and the high molecular compound in the present invention can be separately contained. The step of containing the low molecular compound and the high molecular compound in the present invention is not particularly limited, but the low molecular compound and the high molecular compound in the present invention are added together after the solvent is added to the organic nano pigment particle aqueous dispersion. Even if it is a method, it may be a method of dissolving them in the solvent and then adding them to the aqueous dispersion of organic nanopigment particles, but more preferably, after dissolving in the solvent, the aqueous organic nanopigment particles It is a method of adding to the dispersion. In this case, the low molecular weight compound and the high molecular weight compound may be added separately. After the high molecular weight compound is dissolved in the solvent, it is added to the organic nano pigment particle aqueous dispersion, and then the low molecular weight compound is added. A method of adding it as it is, or a method of adding a solution in which a polymer compound is dissolved after adding a low molecular weight compound to an aqueous dispersion of organic nanopigment particles may be used.

  In addition, the addition amount of the low molecular weight and high molecular compound is preferably 10% by mass or more and 1000% by mass or less with respect to the pigment. Furthermore, 50 mass% or more and 200 mass% or less are more preferable. If the amount is less than 10% by mass, the aggregation effect of the nanoparticles is reduced, and if it exceeds 1000% by mass, problems such as an increase in viscosity during redispersion described later tend to occur. The addition amount ratio of the low molecular compound and the high molecular compound is not particularly limited, but when the high molecular compound is 1 in terms of mass ratio, the low molecular compound is preferably 1 to 50, and more preferably 10 to 30.

Hereinafter, the low molecular weight compound will be described in more detail.
Examples of the low molecular compound include anionic, cationic, and nonionic low molecular compounds. The low molecular compound to be used can be selected according to the aqueous dispersion dispersant used in the preparation of the above-mentioned organic nanopigment particle aqueous dispersion. For example, if the dispersant of the aqueous dispersion is nonionic, particularly basic, the low molecular weight compound is nonionic, particularly acidic, and if the dispersant of the aqueous dispersion is anionic, the low molecular compound As a low molecular weight compound, it is preferable that it is cationic and the low molecular weight compound is anionic if the dispersant of the aqueous dispersion is cationic. As a particularly preferred form, the dispersant in the aqueous dispersion is nonionic, particularly basic, and the low molecular weight compound is nonionic, particularly acidic. The dispersant in the aqueous dispersion is cationic, and the low molecular weight The compound is preferably anionic.

  In the nonionic low molecular weight compound, particularly acidic compounds are not particularly limited as long as the molecular weight is less than 1000, but monovalent or higher carboxylic acid, sulfonic acid, and phosphoric acid compounds are preferable, and 1 to 5 valences are particularly preferable. Of these, carboxylic acids, sulfonic acids, and phosphoric acid compounds are preferred. Specific examples of the carboxylic acid include acetic acid, propionic acid, butyric acetic acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, isobutyric acid, 2- Ethyl butyric acid, trimethyllacetic acid, t-butylacetic acid, 2-propylpentanoic acid, 2-ethylhexanoic acid, malonic acid, butylmalonic acid, dimethylmalonic acid, diethylmalonic acid, succinic acid, Glutaric acid, tricarbacrylic acid, 1,2,3,4-butanetetracarboxylic acid, cis-5,8,11,14,17-eicosapentaenoic acid, cis-4,7,10,13, 16,19-docosahexaenoic acid, benzoic acid, pheny Acetate, 11-phenoxy undecanoate dichroic acid, and phenyl malonate.

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

  Specific examples of phosphoric acid include dimethyl phosphonic acid and methylene diphosphonic acid.

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

(In the formula, D represents —COO ⁻ , —SO ₃ ⁻ , —OSO ₃ ⁻ , —P (O) (OH) O ⁻ , or —OP (O) (OH) O ⁻ ). An alkyl group, an aralkyl group, an aryl group, or an alkoxy group which may have a substituent having 10 to 100 carbon atoms, and Y represents an organic or inorganic cation.

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

  In General Formula (3), E is an alkyl group, an aralkyl group, an aryl group, or an alkoxy group that may have a substituent having a total carbon number of 10 to 100, more preferably a total carbon number of 20 to 50. An alkyl group, an aralkyl group, an aryl group, or an alkoxy group which may have a substituent. The alkyl group, alkoxy group or substituent may be linear or branched, and the aralkyl group or aryl group may be monocyclic or condensed.

  As the alkyl group, specifically, methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, tertiary butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, Examples include octyl group, tertiary octyl group, 2-ethylhexyl group, decyl group, dodecyl group, octadecyl group and the like, preferably methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, tertiary. Examples thereof include a butyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, and a heptyl group.

  Specific examples of the aralkyl group include a benzyl group and a naphthylmethylene group, and a benzyl group is particularly preferable.

  Specific examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is particularly preferable.

  Specific examples of the alkoxy group include methoxy group, ethoxy group, normal propyloxy group, isopropyloxy group, normal butyloxy group, isobutyloxy group, tertiary butyloxy group, pentyloxy group, cyclopentyloxy group, and hexyloxy. Group, cyclohexyloxy group, heptyloxy group, octyloxy group, tertiary octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, preferably methoxy group, ethoxy group, normal propyl Examples thereof include an oxy group, an isopropyloxy group, a normal butyloxy group, and an isobutyloxy group.

  In the general formula (3), examples of the organic cation represented by Y include imidazolium salts, pyridinium salts, thiazolium salts, oxazolium salts, imidazolium salts, thiazolinium salts, oxazolinium salts, and the like. In view of the ease of desalting described later, an inorganic cation is preferable, and examples of the inorganic cation include lithium ions, sodium ions, potassium ions, and the like.

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

  The molecular weight of these low molecular compounds may be any as long as it is less than 1000. If it is 1000 or more, the properties of the polymer compound will appear and it will be difficult to condense the nanoparticles.

Hereinafter, the polymer compound will be described in more detail.
As a preferred form, as in the case of the low molecular weight compound, the dispersant of the organic nano pigment particle aqueous dispersion is nonionic, particularly basic, and the polymer compound is nonionic, particularly acidic, dispersion of the aqueous dispersion The agent is cationic and the polymer compound is preferably anionic. In the present invention, the weight average molecular weight of the polymer compound is preferably 1000 or more. There is no particular upper limit, but it is more preferably 3000000 or less, and more preferably 300000 or less. Specific examples of known polymer compounds that can be used in the present invention include “Disperbyk-110 (a copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, manufactured by BYK Chemie. , 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, 4010, 4165 (polyurethane type), EFKA 4330, 4340 (block copolymer) manufactured by EFKA Combined), 4400, 4402 (modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester) ”,“ Ajisper PB821, PB822 ”manufactured by Ajinomoto Fan Techno Co., Kyoeisha Chemical Co., Ltd. “Floren TG-710 (Ure Tan oligomer) "," Polyflow No. 50E, No. 300 (acrylic copolymer) "," Disparon KS-860, 873SN, 874, # 2150 (aliphatic polyvalent carboxylic acid) ", # 7004 manufactured by Enomoto Kasei Co., Ltd. (Polyetherester), DA-703-50, DA-705, DA-725 "," Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfone) manufactured by Kao Corporation Acid formalin polycondensate) ”,“ homogenol L-18 (polymeric polycarboxylic acid) ”,“ emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ” "Solsperse 55000 (graft type polymer), 13240 (poly Sterolamine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ", Nikko Chemical's" Nikkor T106 (polyoxyethylene sorbitan monooleate) " , MYS-IEX (polyoxyethylene monostearate) ”and the like. As a high molecular compound in this invention, a well-known high molecular compound may be used independently and 2 or more types may be used. Moreover, a well-known high molecular compound may be used together with 1 or more types of high molecular compounds mentioned later, and also the high molecular compound mentioned later may be used independently.

Hereinafter, the nonionic polymer compound will be described in more detail.
The nonionic polymer compound is preferably represented by the following general formula (11).

In the general formula (11), A ¹ is an acidic 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, or an alkoxysilyl group. , A monovalent organic group having a group selected from an epoxy group, an isocyanate group and a hydroxyl group, or a monovalent organic group containing an organic dye structure or a heterocyclic ring which may have a substituent. The n A ^{1 s} may be the same or different.

Specifically, A ¹ is not particularly limited, and examples of the “monovalent organic group having an acidic group” include a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, Examples thereof include monovalent organic groups having a monophosphate ester group, a boric acid group, and the like. Examples of the “monovalent organic group having a group having a basic nitrogen atom” include, for example, a monovalent organic group having an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R). ¹⁰ ) having a monovalent organic group (wherein R ⁸ , R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, 7 carbon atoms) Represents an aralkyl group of 30 or less.), A monovalent organic group having a guanidyl group represented by the following general formula (a1) [in the general formula (a1), R ^a1 and R ^a2 are each independently a carbon number. An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms. A monovalent organic group having an amidinyl group represented by the following general formula (a2) [in the general formula (a2), R ^a3 and R ^a4 are each independently an alkyl group having 1 to 20 carbon atoms, carbon An aryl group having 6 to 20 carbon atoms and an aralkyl group having 7 to 30 carbon atoms are represented. And the like.

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

As the “monovalent organic group having a urethane group”, for example, —NHCOOR ¹⁶ , —OCONHR ¹⁷ (wherein R ¹⁶ and R ¹⁷ are each independently an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms, And an aryl group having 20 or less and an aralkyl group having 7 to 30 carbon atoms).

  Examples of the “group having a group having a coordinating oxygen atom” include a group having an acetylacetonato group and a group having a crown ether.

  Examples of the “group having a hydrocarbon group having 4 or more carbon atoms” include an alkyl group having 4 or more carbon atoms (for example, octyl group, dodecyl group, etc.) and an aryl group having 6 or more carbon atoms (for example, phenyl group, naphthyl group). And an aralkyl group having 7 or more carbon atoms (for example, a benzyl group). At this time, there is no upper limit to the number of carbon atoms, but it is preferably 30 or less. Examples of the “group having an alkoxysilyl group” include groups having a trimethoxysilyl group, a triethoxysilyl group, and the like.

  Examples of the “group having an epoxy group” include a group having a glycidyl group.

  Examples of the “group having an isocyanate group” include a 3-isocyanatopropyl group.

  Examples of the “group having a hydroxyl group” include a 3-hydroxypropyl group.

Among the above, A ¹ is preferably a monovalent organic group having a group selected from an acidic group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms. .

  The organic dye structure or heterocyclic ring is not particularly limited. More specifically, examples of the organic dye structure include phthalocyanine compounds, insoluble azo compounds, azo lake compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds, Examples include diketopyrrolopyrrole compounds, anthrapyridine compounds, ansanthrone compounds, indanthrone compounds, flavanthrone compounds, perinone compounds, perylene compounds, and thioindigo compounds. Examples of the heterocyclic ring include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, Examples include morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, and anthraquinone.

  In addition, the organic dye structure or the heterocyclic ring may have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. C1-C16 acyloxy groups such as aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc., methoxy groups, ethoxy groups, etc. Alkoxy groups having 1 to 6 carbon atoms such as halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, cyano group, t- And carbonic acid ester groups such as butyl carbonate.

Further, as the A ^1, it is preferably a monovalent organic group represented by the following general formula (4).

In the general formula (4), B ¹ is an acidic 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, or an alkoxysilyl group. Represents an organic dye structure or a heterocyclic ring optionally having a substituent selected from an epoxy group, an isocyanate group, and a hydroxyl group, and R ¹⁸ represents a single bond or an a1-valent organic or inorganic linking group. . a1 represents 1 to 5, a1 amino B ¹ represents may be the same or different.

B ¹ has the same meaning as A ¹ in formula (4), and the preferred embodiment is also the same. Examples of the organic dye structure or heterocyclic ring include phthalocyanine compounds, insoluble azo compounds, azo lake compounds, anthraquinone compounds, Organic pigment structures such as quinacridone compounds, dioxazine compounds, diketopyrrolopyrrole compounds, anthrapyridine compounds, ansanthrone compounds, indanthrone compounds, flavanthrone compounds, perinone compounds, perylene compounds, thioindigo compounds, such as thiophene, furan, xanthene, Pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, Heterocycles such as dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, anthraquinone Can be mentioned.

  In addition, the organic dye structure or the heterocyclic ring may have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. C1-C16 acyloxy groups such as aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc., methoxy groups, ethoxy groups, etc. Alkoxy groups having 1 to 6 carbon atoms such as halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, cyano group, t- And carbonic acid ester groups such as butyl carbonate.

R ¹⁸ represents a single bond or an a1 + 1 valent linking group, and a1 represents 1 to 5. The linking group R ¹⁸ includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to Groups comprising up to 20 sulfur atoms are included and may be unsubstituted or further substituted. R ¹⁸ is preferably an organic linking group.

Specific examples of R ¹⁸ include the following structural units or groups formed by combining the structural units.

Among the above, when having a substituent R ¹⁸ , examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group. Aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group and the like, such as acyloxy group having 1 to 6 carbon atoms, methoxy group, ethoxy group and the like having 1 to 6 carbon atoms Alkoxy groups, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, carbonate groups such as cyano group and t-butyl carbonate, etc. Is mentioned.

In the general formula (11), R ¹ represents a (m + n) -valent linking group. m + n satisfies 3-10.

Examples of the (m + n) -valent linking group represented by R ¹ include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200. Groups comprising up to 0 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or further substituted. R ¹ is preferably an organic linking group.

Specific examples of R ¹ include the structural units (t-1) to (t-34) or a group formed by combining the structural units (which may form a ring structure). be able to.

  When the linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group. Alkyl groups having 1 to 6 carbon atoms such as aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfonylamide groups, and acetoxy groups, alkoxy groups having 1 to 6 carbon atoms such as methoxy groups and ethoxy groups. Groups, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, carbonate groups such as cyano group and t-butyl carbonate, etc. Can be mentioned.

R ² represents a single bond or a divalent linking group. R ² includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 atoms. Group consisting of up to sulfur atoms is included, and may be unsubstituted or may further have a substituent. R ² is preferably an organic linking group.

Specific examples of R ² include the structural units of t-3, 4, 7-18, 22-26, 32, and 34, or groups configured by combining the structural units.

Among the above, when R ² has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, 6 to 16 carbon atoms such as a phenyl group and a naphthyl group. Up to 1 to 6 carbon atoms such as an acyloxy group, 1 to 6 carbon atoms such as an aryl group, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group and an acetoxy group, a methoxy group and an ethoxy group Alkoxy groups, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, carbonate groups such as cyano group and t-butyl carbonate, Etc.

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

  N represents an integer of 2 to 9. As n, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

In the general formula (11), P ¹ represents a polymer residue and can be selected from ordinary polymers according to the purpose and the like.

  Among polymers, in order to constitute a polymer skeleton, a vinyl monomer polymer or copolymer, ester polymer, ether polymer, urethane polymer, amide polymer, epoxy polymer, silicone polymer, and these Modified product or copolymer [for example, polyether / polyurethane copolymer, copolymer of polyether / vinyl monomer, etc. (any of random copolymer, block copolymer, graft copolymer) May be included). Is preferably selected from the group consisting of vinyl monomer polymers or copolymers, ester polymers, ether polymers, urethane polymers, and modified products or copolymers thereof. At least one kind is more preferred, and a polymer or copolymer of vinyl monomers is particularly preferred.

  Furthermore, the polymer is preferably soluble in an organic solvent. If the affinity with the organic solvent is low, for example, when used as a pigment dispersant, the affinity with the dispersion medium is weakened, and it may not be possible to secure a sufficient adsorption layer for stabilizing the dispersion.

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

In the general formula (12), A ² has the same meaning as A ¹ in the general formula (11), and the specific preferred embodiment thereof is also the same. As specific examples of the organic dye structure, a phthalocyanine compound, An azo lake compound, an anthraquinone compound, a dioxazine compound, a diketopyrrolopyrrole compound and the like are more preferable. More preferred are succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, anthraquinone and the like.

Further, may have the same substitution group and A ^1, for the substituents are the same as in A ^1, preferred embodiment is also the same.

Further, as A ² , a monovalent organic group represented by the general formula (4) is preferable, and the details, specific examples, and preferred embodiments of the organic group are the same.

In the general formula (12), R ³ represents a (x + y) -valent linking group. Examples of the (x + y) -valent linking group represented by R ³ include 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 100. Groups comprising up to 0 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or may further have a substituent.

The (x + y) -valent linking group represented by R ³ has the same meaning as the (m + n) -valent linking group in R ¹ , and the preferred embodiments thereof are also the same. Further, specific examples include the same structural unit as described above or a group formed by combining the structural units.

Of these, the linking group represented by R ³ is preferably an organic linking group, and preferred specific examples [specific examples (r-1) to (r-17)] of the organic linking group are as follows. Show. However, the present invention is not limited to these.

  Among these, (r1), (r2), (r-10), (r-11), (r-16) from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents. , (R-17) is preferred.

When R ³ has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a carbon group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group. Up to 1 to 6 carbon atoms such as an acyloxy group, 1 to 6 carbon atoms such as an aryl group, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group and an acetoxy group, a methoxy group and an ethoxy group Alkoxy groups, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, carbonate groups such as cyano group and t-butyl carbonate, Etc.

In the general formula (12), R ⁴ and R ⁵ each independently represents a single bond or a divalent linking group.

The “divalent linking group” represented by R ⁴ and R ⁵ may be unsubstituted or substituted, and may be a linear, branched, or cyclic alkylene group, an arylene group, an aralkylene group, and, -O -, - S -, - C (= O) -, - N (R 19) -, - SO -, - SO 2 -, - CO 2 -, - N (R 20) SO 2 -, or it can be given a divalent group formed by combining two or more of these groups as preferred examples (wherein R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ). Of these, an organic linking group is preferred.

Examples of R ⁴ include linear and branched alkylene groups, aralkylene groups, and —O—, —C (═O) —, —N (R ¹⁹ ) —, —SO ₂ —, —CO ₂ —, — N (R ²⁰ ) SO ₂ — (wherein R ¹⁹ and R ²⁰ each independently represents 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 Are more preferable, a linear or branched alkylene group, an aralkylene group, and —O—, —C (═O) —, —N (R ¹⁹ ) — (wherein R ¹⁹ represents a hydrogen atom or a carbon number of 1 to 4). Represents an alkyl group), —CO ₂ — or a divalent group in which two or more of these groups are combined is particularly preferred.

R ⁵ includes a single bond or a linear or branched alkylene group, an aralkylene group, —O—, —C (═O) —, —N (R ¹⁹ ) —, —SO ₂ —, —CO _2. —, —N (R ²⁰ ) SO ₂ — (wherein R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), or a combination of two or more of these groups And a linear or branched alkylene group, an aralkylene group, and —O—, —C (═O) —, —N (R ¹⁹ ) — (wherein R ¹⁹ represents a hydrogen atom or a carbon number). Represents 1 to 4 alkyl groups), —CO ₂ — or a divalent group in which two or more of these groups are combined is particularly preferable.

Moreover, when said R < ⁴ >, R < ⁵ > has a substituent, as this substituent, it is C6-C20, such as a C1-C20 alkyl group, such as a methyl group and an ethyl group, a phenyl group, a naphthyl group, for example. 1 to 16 carbon atoms such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group, etc. Carbon atoms such as alkoxy groups up to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups up to 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, cyano groups and t-butyl carbonate Group, and the like.

  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.

Further, P ² in the general formula (12) represents a polymer residue, can be selected according to the purpose or the like from such conventional polymers. The preferred embodiment of the polymer, has the same meaning as P ¹ in the general formula (11), the same applies to its preferred embodiment.

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), (r -16) or (r-17), wherein R ⁴ is a single bond, a linear or branched alkylene group, an aralkylene group, —O—, —C (═O) —, —N (R ¹⁹ ). - (wherein R ¹⁹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.), - CO ₂ -, or a divalent organic group formed by combining two or more of these groups, R ⁵ Is a single bond, an ethylene group, a propylene group, or a linking group represented by the following general formula (s-a) or (s-b), and P ² is a polymer or copolymer of a vinyl monomer, an ester type A polymer, an ether-based polymer, a urethane-based polymer, or a modified product thereof, wherein y is 1 to 2 and x is 3 to 6 That the polymer compound is particularly preferable. In the following groups, R ²¹ represents a hydrogen atom or a methyl group, and l represents 1 or 2.

Although the weight average molecular weight of the polymer compound used in the production method of the present invention is 1000 or more, the weight average molecular weight is preferably 3000 to 100,000, more preferably 5000 to 80000, and particularly preferably 7000 to 60000. When the weight average molecular weight is within the above range, the effects of the multiple functional groups introduced at the polymer ends are fully exhibited, and the performance of adsorbing to the solid surface, micelle forming ability, and surface activity is excellent. To do. In particular, when the polymer compound according to the present invention is used as a pigment dispersant, good dispersibility and dispersion stability can be achieved.
The polymer compound represented by the general formula (11) (including the polymer compound represented by the general formula (12)) is not particularly limited, but can be synthesized by the following method. Of the following synthesis methods, the following synthesis methods such as 2, 3, 4, 5 and the like are more preferable, and the following synthesis methods such as 3, 4, 5, and the like are particularly preferable because of ease of synthesis.

1. A polymer in which a functional group selected from a carboxyl group, a hydroxyl group, an amino group, or the like is introduced at the terminal; an acid halide having a plurality of functional groups (A ¹ or A ² in the general formula); or a plurality of functional groups ( A method of polymerizing an alkyl halide having A ¹ or A ² ) in the general formula or an isocyanate having a plurality of functional groups (A ¹ or A ² in the general formula).

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

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

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

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

  Among the above, the polymer compound (preferably the polymer compound represented by the general formula (12)) used in the production method of the present invention is synthesized, for example, by any one of the above methods 2, 3, 4, and 5. However, from the viewpoint of ease of synthesis, it is more preferable to synthesize by the above method 5.

  More specifically, radical polymerization is preferably performed using a compound represented by the following general formula (13) as a chain transfer agent.

In the general 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 general 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 esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides , Vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable. Examples of such include the following compounds.

  Examples of the (meth) acrylate esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate. Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2 -Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (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, diethylene glycol monomethyl ether (meth) acrylate, (meth) Acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether , Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, disi (meth) acrylate Clopentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromo (meth) acrylate Examples thereof include phenyl and tribromophenyloxyethyl (meth) acrylate.

  Examples of the crotonic acid esters include butyl crotonic acid and hexyl crotonic acid.

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

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

  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, and dibutyl itaconate. Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- n-butylacryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Examples thereof include N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, 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, chlorostyrene, dichlorostyrene, bromostyrene, chloro Examples thereof include methylstyrene, hydroxystyrene protected with a group deprotectable by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

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

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

  In addition to the above compounds, vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used. Such a monomer having a urethane group or a urea group can be appropriately synthesized using, for example, an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Specifically, an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or primary or secondary amino group containing It can be appropriately synthesized by an addition reaction between a monomer and monoisocyanate.

  The above vinyl monomers may be polymerized alone or in combination of two or more, and such radical polymers are prepared according to ordinary methods in the usual manner for the corresponding vinyl monomers. It is obtained by polymerizing.

  For example, a method (solution polymerization method) in which these vinyl monomers and a chain transfer agent are dissolved in a suitable solvent, a radical polymerization initiator is added thereto and polymerized in a solution at about 50 ° C. to 220 ° C. It is obtained by using.

  Examples of suitable solvents used in the solution polymerization method can be arbitrarily selected depending on the monomers used and the solubility of the resulting copolymer. 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, dimethyl Examples include formamide, chloroform, and toluene. These solvents may be used as a mixture of two or more.

  Examples of radical polymerization initiators include azo compounds such as 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile), benzoyl par Peroxides such as oxides, and persulfates such as potassium persulfate and ammonium persulfate can be used.

  The compound represented by the general formula (13) can be synthesized by the following method or the like, but the following method 7 is more preferable because of ease of synthesis.

6). A method of converting a halide compound having a plurality of functional groups (A ¹ or A ² in the above general formula) into a mercaptan compound (a method of reacting with thiourea and hydrolyzing, a method of reacting directly with NaSH, CH ₃ COSNa and (For example, a method of reacting and hydrolyzing)
7). Addition of a compound having 3 to 10 mercapto groups in one molecule and a compound having a functional group (A ¹ or A ² in the above general formula) and a functional group capable of reacting with a mercapto group Method of reacting As the “functional group capable of reacting with a mercapto group” in the method 7, an acid halide, an alkyl halide, an isocyanate, a carbon-carbon double bond, and the like are preferably exemplified.

  It is particularly preferable that the “functional group capable of reacting with a mercapto group” is a carbon-carbon double bond, and the addition reaction is synthesized by a radical addition reaction. The carbon-carbon double bond is more preferably a mono- or di-substituted vinyl group in terms of reactivity with the mercapto group.

  Specific examples of the "compound having 3 to 10 mercapto groups in one molecule" [specific examples (18) to (34)] include the following compounds.

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

A functional group (A ¹ or A ² in the formula), and carbon - The compound having a carbon double bond is not particularly limited, include the following.

  For example, “the compound having 3 to 10 mercapto groups in one molecule” and the above “the acid group, the group having a basic nitrogen atom, the urea group, the urethane group, the group having a coordinating oxygen atom, carbon Radical addition with a compound having at least one functional group selected from a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group having a carbon number of 4 or more and having a carbon-carbon double bond Examples of the reaction product include the above-mentioned “compound having 3 to 10 mercapto groups in one molecule” and “acid group, group having basic nitrogen atom, urea group, urethane group, and coordinating oxygen atom. A group having at least one functional group selected from a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group, and a carbon-carbon double Obtained using the - (ene reaction method thiol) compound having a slip "was dissolved in a suitable solvent, here by adding a radical generator, at about 50 ° C. to 100 ° C., a method of adding.

  Examples of preferable solvents used in the above method include “compound having 3 to 10 mercapto groups in one molecule”, “acid group, group having basic nitrogen atom, urea group, urethane group, and coordination. A functional group having at least one functional group selected from a group having a reactive oxygen atom, 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 It can be arbitrarily selected according to the solubility of the compound having a group (for example, a carbon-carbon double bond) and 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, dimethyl Examples include formamide, chloroform, and toluene. These solvents may be used as a mixture of two or more.

  As the radical generator, azo compounds such as 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile), benzoyl peroxide And persulfates such as potassium persulfate and ammonium persulfate can be used.

  Specific examples of the compound represented by the general formula (11) preferably used in the production method of the present invention are shown below. However, the present invention is not limited to these specific examples.

  Further, this polymer compound is preferably a polymer compound having an acidic group, more preferably a polymer compound having a carboxyl group, and (A) at least a repeating unit derived from the compound having a carboxyl group. A copolymer compound containing at least one repeating unit derived from one type and a compound having (B) a carboxylic acid ester group is particularly preferred.

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

(R ₁ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

(R ₂ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ₃ represents a group represented by the following general formula (III).)

(R ₄ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxy group, a hydroxyalkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R ₅ and R ₆ are And each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, X1 represents a number of 1 to 5)

(R ₇ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ₈ represents a group represented by the following general formula (V).)

(R ₉ represents an alkyl group having 2 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms. R ₁₀ and R ₁₁ represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Y1 represents 1 Represents a number of ~ 5.)
Further, in terms of the polymerization ratio of the repeating unit derived from the compound having (A) carboxyl group and the repeating unit derived from the compound having (B) carboxylate group, all of the repeating units (A) The quantity ratio% to the number of repeating units is preferably 3 to 40, more preferably 5 to 35.

  Further, in the method for producing organic nanoparticles of the present invention, it is also preferable to use a polymer compound containing a graft copolymer having an amino group and an ether group and containing other components appropriately selected as necessary. .

  The graft copolymer has at least an amino group and an ether group, and may contain other monomers as copolymer units.

  As a weight average molecular weight (Mw) of the said graft copolymer, 3000-100000 are preferable and 5000-50000 are more preferable. When the weight average molecular weight (Mw) is less than 3000, aggregation of the organic nanoparticles cannot be prevented and the viscosity may increase. When the weight average molecular weight (Mw) exceeds 100,000, the solubility in an organic solvent is insufficient. , The viscosity may increase. The weight average molecular weight is a polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (carrier: tetrahydrofuran).

  The graft copolymer includes (i) a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal, (ii) a monomer having an amino group and an ethylenically unsaturated double bond, and (iii) an ether group. It is preferable that it contains at least a polymerizable monomer having a copolymer unit and, if necessary, (iv) another monomer as a copolymer unit.

  The content of these copolymer units in the graft copolymer is preferably (i) 15 to 98% by mass of the polymerizable oligomer, more preferably 25 to 90% by mass, (Ii) The amino group-containing monomer is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, and (iii) the polymerizable monomer having an ether group is 1 to 70% by mass. It is preferably 5 to 60% by mass.

  If the content of the polymerizable oligomer is less than 15% by mass, a steric repulsion effect as a dispersant may not be obtained, and aggregation of organic nanoparticles may not be prevented. In some cases, the proportion of the monomer is reduced, the adsorption ability to organic particles is lowered, and the dispersibility is not sufficient. When the content of the nitrogen-containing monomer is less than 1% by mass, the adsorption ability with respect to the organic particles is lowered and the dispersibility may not be sufficient. When the content exceeds 40% by mass, the ratio of the polymerizable oligomer is decreased. For this reason, the steric repulsion effect as a dispersant cannot be obtained, and aggregation of organic particles may not be sufficiently prevented. When the content of the polymerizable monomer having an ether group is less than 1% by mass, the development suitability in the production of a color filter or the like may not be sufficient, and when it exceeds 70% by mass, the ability as a dispersant. May decrease.

(I) Polymerizable oligomer The polymerizable oligomer (hereinafter sometimes referred to as “macromonomer”) is an oligomer having a terminal group having an ethylenically unsaturated double bond at the terminal. In the present invention, among the polymerizable oligomers, it is preferable to have a group having the ethylenically unsaturated double bond only at one of both ends of the oligomer.

  The oligomer is generally a homopolymer formed from at least one monomer selected from, for example, alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, styrene, acrylonitrile, vinyl acetate, and butadiene. Examples of the copolymer include alkyl (meth) acrylate homopolymers or copolymers, polystyrene, and the like. In the present invention, these oligomers may be substituted with a substituent, and the substituent is not particularly limited, and examples thereof include a halogen atom.

  Preferred examples of the group having an ethylenically unsaturated double bond include a (meth) acryloyl group and a vinyl group. Among these, a (meth) acryloyl group is particularly preferred.

  In the present invention, among the polymerizable oligomers, oligomers represented by the following general formula (E6) are preferable.

In the general formula (E6), R ⁶¹ and R ⁶³ represent a hydrogen atom or a methyl group. R ⁶² represents an alkylene group which may be substituted by an alcoholic hydroxyl group having 1 to 8 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms. 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 hydroxyl group having 1 to 6 carbon atoms, alkyl optionally substituted with halogen). Represents a group, a phenyl group, or an arylalkyl group having 7 to 10 carbon atoms.), A phenyl group or —COOR ⁶⁴ (wherein R ⁶⁴ may be substituted with an alcoholic hydroxyl group having 1 to 4 carbon atoms). Represents a good alkyl group). q represents 20-200.

  Specific examples of the polymerizable oligomer include poly-2hydroxyethyl (meth) acrylate, polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, poly-i-butyl (meth) acrylate, and those A copolymer which is a copolymer and has a (meth) acryloyl group bonded to one molecular end is preferable.

  The polymerizable oligomer may be a commercially available product or an appropriately synthesized product. Examples of the commercially available product include a one-end methacryloylated polystyrene oligomer (Mn = 6000, trade name: AS-6). , Manufactured by Toa Gosei Chemical Co., Ltd.), one-end methacryloylated polymethyl methacrylate oligomer (Mn = 6000, trade name: AA-6, manufactured by Toa Gosei Chemical Co., Ltd.), one-end methacryloylated poly-n -Butyl acrylate oligomer (Mn = 6000, trade name: AB-6, manufactured by Toa Gosei Chemical Co., Ltd.), one-end methacryloylated polymethyl methacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7000, trade name: AA) -714, manufactured by Toa Gosei Chemical Co., Ltd.), one-end methacryloylated polybutylmethacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7000, trade name: 707S, manufactured by Toa Gosei Chemical Co., Ltd.), one-end methacryloylated poly-2-ethylhexyl methacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7000) And trade names: AY-707S, AY-714S, manufactured by Toagosei Chemical Co., Ltd.), and the like.

  Preferred specific examples of the polymerizable oligomer in the present invention include at least one oligomer selected from a polymer of alkyl (meth) acrylate and a copolymer of alkyl (meth) acrylate and polystyrene, A number average molecular weight is 1000-20000, and what has a (meth) acryloyl group at the terminal is mentioned.

(Ii) Amino group-containing monomer As the amino group-containing monomer, for example, at least one selected from compounds represented by the following general formula (E2) is preferably exemplified.

In the general formula (E2), R ²¹ represents a hydrogen atom or a methyl group. R ²² represents an alkylene group having 1 to 8 carbon atoms, and among these, an alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 2 to 3 carbon atoms is particularly preferable. X ² represents —N (R ²³ ) (R ²⁴ ), —R ²⁵ N (R ²⁶ ) (R ²⁷ ). Here, R ²³ and R ²⁴ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. R ²⁵ represents an alkylene group having 1 to 6 carbon atoms, and R ²⁶ and R ²⁷ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

Among the above, R ²³ and R ²⁴ in —N (R ²³ ) (R ²⁴ ) are preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and —R ²⁵ —N (R ²⁶ ) (R R ²⁵ of ²⁷⁾ is preferably an alkylene group having 2 to 6 carbon atoms, R ²⁶ and R ^27, 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, corresponding to monomers represented by the following general formulas (E3) and (E4)) To do).

  In the present invention, among the monomers represented by the general formula (E2), at least one selected from monomers represented by any of the following general formulas (E3) and (E4) is preferable.

In the general formula (E3), R ³¹ has the same meaning as R ²¹ in the general formula (E2). R ³² has the same meaning as R ²² in formula (E2). X ³ has the same meaning as X ² in formula (E2).

In the general formula (E4), R ⁴¹ has the same meaning as R ²¹ in the general formula (E2). X ⁴ has the same meaning as X ² in formula (E2), and —N (R ⁴³ ) (R ⁴⁴ ) (where 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 ) (where R ⁴⁵ , R ⁴⁶ and R ⁴⁷ are R ²⁵ , R ²⁶ and R ²⁷ in the general formula (E2), respectively). Are preferred).

  Specific examples of the monomer represented by the general formula (E2) include dimethyl (meth) acrylamide, diethyl (meth) acrylamide, diisopropyl (meth) acrylamide, di-n-butyl (meth) acrylamide, and di-i-butyl. (Meth) acrylamide, morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide and N, N-methylphenyl (meth) acrylamide (above (meth) acrylamides); (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) acrylic 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylamide, 6- (N, N-diethylamino) hexyl (meth) acrylamide (aminoalkyl (meth) acrylamides) and the like. It is mentioned as preferable.

(Iii) Polymerizable monomer having an ether group Preferred examples of the polymerizable monomer having an ether group include at least one selected from monomers represented by the following general formula (E1).

In the general formula (E1), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² represents an alkylene group having 1 to 8 carbon atoms, among which an alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 2 to 3 carbon atoms is more preferable. X ¹ represents —OR ¹³ or —OCOR ¹⁴ . Here, R ¹³ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a phenyl group substituted with an alkyl group having 1 to 18 carbon atoms. R ¹⁴ represents an alkyl group having 1 to 18 carbon atoms. Moreover, m3 represents 2-200, 5-100 are preferable and 10-100 are especially preferable.

  The polymerizable monomer having an ether group is not particularly limited as long as it has an ether group and is polymerizable, and can be appropriately selected from ordinary ones. For example, polyethylene glycol mono (meth) Examples include acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, polytetramethylene glycol monomethacrylate, etc., and these may be commercially available products or may be appropriately synthesized. Good. Examples of the commercially available products include methoxypolyethylene glycol methacrylate (trade names: NK esters M-40G, M-90G, M-230G (manufactured by Toa Gosei Chemical Co., Ltd.); trade names: BLEMMER PME-100, PME. -200, PME-400, PME-1000, PME-2000, PME-4000 (manufactured by Nippon Oil & Fats Co., Ltd.)), polyethylene glycol monomethacrylate (trade names: BLEMMER PE-90, PE-200, PE- 350, manufactured by NOF Corporation), polypropylene glycol monomethacrylate (trade names: BLEMMER PP-500, PP-800, PP-1000, manufactured by NOF Corporation), polyethylene glycol polypropylene glycol monomethacrylate (trade name) : Bremmer 70PEP-370B, Japan Manufactured by Yushi Co., Ltd.), polyethylene glycol polytetramethylene glycol monomethacrylate (trade name: Blemmer 55PET-800, manufactured by Nippon Oil & Fats Co., Ltd.), polypropylene glycol polytetramethylene glycol monomethacrylate (trade name: Blemmer NHK-5050) , Manufactured by Nippon Oil & Fats Co., Ltd.).

(Iv) Other monomer The graft copolymer may further contain the other monomer as a copolymer unit, and the other monomer is not particularly limited and is appropriately selected depending on the purpose. For example, aromatic vinyl compounds (eg, styrene, α-methylstyrene and vinyltoluene), (meth) acrylic acid alkyl esters (eg, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl) (Meth) acrylate and i-butyl (meth) acrylate), (meth) acrylic acid alkylaryl ester (eg, benzyl (meth) acrylate), glycidyl (meth) acrylate, carboxylic acid vinyl ester (eg, vinyl acetate and propionic acid) Vinyl), vinyl cyanide (eg, (meth) acrylonitrile and And α-chloroacrylonitrile), aliphatic conjugated dienes (eg, 1,3-butadiene and isoprene), (meth) acrylic acid, and the like. Among these, unsaturated carboxylic acid, (meth) acrylic acid alkyl ester, (meth) acrylic acid alkyl aryl ester, and carboxylic acid vinyl ester are preferable.

  As content of this other monomer in the said graft copolymer, 5-70 mass% is preferable, for example. When the content is less than 5% by mass, the physical properties of the coating film may not be controlled. When the content exceeds 70% by mass, the ability as a dispersant may not be sufficiently exhibited.

As a preferred specific example of the 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-terminated methacryloylated polystyrene copolymer,
(14) a copolymer of a copolymer of 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminal methacryloylated methyl (meth) acrylate and 2-hydroxyethyl methacrylate,
(15) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminated methacryloylated methyl methacrylate and 2-hydroxyethyl methacrylate copolymer,
(16) a copolymer of a copolymer of 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminal 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.

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

  The graft copolymer can be obtained, for example, by radical polymerization of the components to be the copolymer units in a solvent. In the radical polymerization, a radical polymerization initiator can be used, and a chain transfer agent (eg, 2-mercaptoethanol and dodecyl mercaptan) can be further used. JP-A-2001-31885 can be referred to for the pigment dispersant containing the graft copolymer.

  In order to further improve the uniform dispersibility and storage stability of the organic particles, the content of the graft copolymer is preferably in the range of 0.1 to 1000 parts by mass with respect to 100 parts by mass of the pigment. Preferably it is the range of 1-500 mass parts, More preferably, it is the range of 5-20 mass parts. If the amount is less than 0.1 parts by mass, the dispersion stability of the organic nanoparticles may not be improved. Moreover, a graft copolymer may be used independently or may be used in combination of multiple things.

  In the production method of the present invention, the molecular weight of the polymer means a weight average molecular weight unless otherwise specified. Examples of the method for measuring the molecular weight of the polymer include a chromatography method, a viscosity method, a light scattering method, and a sedimentation rate method. In the present invention, a weight average molecular weight measured by a chromatography method is used unless otherwise specified.

Hereinafter, the anionic polymer compound will be described.
A polymer compound having at least one anionic group can be added to the aggregation. The polymer compound has a weight average molecular weight of 1000 or more, and is preferably a polymer compound represented by the following general formula (14).

(In the formula, G represents —COO ⁻ , —SO ₃ ⁻ , —OSO ₃ ⁻ , —P (O) (OH) O ⁻ , or —OP (O) (OH) O ⁻ ). Represents a linking group or a single bond, Q represents an (m + 1) -valent linking group, R represents a polymer compound residue, Z represents an organic or inorganic cation, and m + 1 represents 3 to 6.
In General Formula (14), G represents —COO ⁻ , —SO ₃ ⁻ , —OSO ₃ ⁻ , —P (O) (OH) O ⁻ , —OP (O) (OH) O ⁻ , and more preferably. Are —SO ₃ ⁻ , —OSO ₃ ⁻ , and —P (O) (OH) O ⁻ . When there are a plurality of G, G may be the same anionic group or different.

In the general formula (14), examples of the divalent linking group represented by J include linear and branched alkylene groups, aralkylene groups, and —O—, —C (═O) —, —SO ₂ —, and —CO. _2- or a divalent group in which two or more of these groups are combined is preferable, and the site connected to Q in the general formula (14) is more preferably a sulfur atom.

  In the case of having a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, a hydroxyl group, and an amino group. Group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group and other C1-C6 acyloxy groups, methoxy group, ethoxy group and other C1-C6 alkoxy groups, halogen such as chlorine and bromine Examples thereof include C2-C7 alkoxycarbonyl groups such as atoms, methoxycarbonyl groups, ethoxycarbonyl groups, and cyclohexyloxycarbonyl groups, cyano groups, and carbonate ester groups such as t-butyl carbonate.

  In the general formula (14), examples of the organic cation represented by Z include imidazolium salts, pyridinium salts, thiazolium salts, oxazolium salts, imidazolinium salts, thiazolinium salts, oxazolinium salts, and the like. Inorganic cations include lithium ions, sodium ions, potassium ions, and the like. Z is preferably an inorganic cation.

  In the general formula (14), Q represents an (m + 1) -valent linking group. m + 1 represents 3-6.

  The (m + 1) -valent linking group represented by Q is composed of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200 hydrogen atoms. A group is included and may be unsubstituted or may further have a substituent. Q is preferably an organic linking group, and preferred specific examples of the organic linking group [Exemplary compounds (r-1) to (r-17)] are shown below. However, the present invention is not limited to these.

  In the general formula (14), m represents an integer of 1 to 5. As m, 2-5 are preferable and 3-5 are more preferable. L represents an integer of 1 to 5. As l, 1-4 are preferable, 1-3 are more preferable, and 1-2 are especially preferable.

  In the general formula (14), R represents a polymer compound residue (polymer skeleton) and can be selected from ordinary polymers according to the purpose and the like. In this case, the polymer skeleton refers to a polymer structure having a number average molecular weight of 1000 or more. Among polymers, in order to constitute a polymer skeleton, a vinyl monomer polymer or copolymer, ester polymer, ether polymer, urethane polymer, amide polymer, epoxy polymer, silicone polymer, and these Modified product or copolymer [for example, polyether / polyurethane copolymer, copolymer of polyether / vinyl monomer, etc. (any of random copolymer, block copolymer, graft copolymer) May be included). Is preferably selected from the group consisting of vinyl monomer polymers or copolymers, ester polymers, ether polymers, urethane polymers, and modified products or copolymers thereof. At least one kind is more preferred, and a polymer or copolymer of vinyl monomers is particularly preferred.

  Furthermore, the polymer is preferably soluble in an organic solvent. If the affinity with the organic solvent is low, for example, when used as a pigment dispersant, the affinity with the dispersion medium is weakened, and it may not be possible to secure a sufficient adsorption layer for stabilizing the dispersion.

  Although the weight average molecular weight of the polymer compound having an anionic group used in the present invention is 1000 or more, the weight average molecular weight is preferably 3000 to 100,000, more preferably 5000 to 80000, and particularly preferably 7000 to 60000. When the weight average molecular weight is within the above range, the effects of the multiple functional groups introduced at the polymer ends are fully exhibited, and the performance of adsorbing to the solid surface, micelle forming ability, and surface activity is excellent. To do. In particular, when the polymer compound having an anionic group is used as a pigment dispersant for redispersing the organic nanopigment particle aggregate, good dispersibility and dispersion stability can be achieved.

  The polymer compound represented by the general formula (14) is not particularly limited, but can be synthesized by the following method. In this method, a vinyl monomer is radically polymerized using a mercaptan compound having a plurality of functional groups (G in the above general formula) as a chain transfer agent.

  More specifically, radical polymerization is preferably performed using a compound represented by the following general formula (15) as a chain transfer agent.

  In the general formula (15), G, J, Q, Z, and m + 1 are synonymous with G, J, Q, Z, and m + 1 in the general formula (14), and preferred ranges are also the same.

  Although it does not restrict | limit especially as said vinyl monomer, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides , Vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable. Examples of such include the following compounds.

  Examples of the (meth) acrylate esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate. Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2 -Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (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, diethylene glycol monomethyl ether (meth) acrylate, (meth) Acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether , Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, disi (meth) acrylate Clopentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromo (meth) acrylate Examples thereof include phenyl and tribromophenyloxyethyl (meth) acrylate.

  Examples of the crotonic acid esters include butyl crotonic acid and hexyl crotonic acid. Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate and the like. Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate. 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, and dibutyl itaconate. Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- n-butylacryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Examples thereof include N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, 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, chlorostyrene, dichlorostyrene, bromostyrene, chloro Examples thereof include methylstyrene, hydroxystyrene protected with a group deprotectable by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene. Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  The above vinyl monomers may be polymerized alone or in combination of two or more, and such radical polymers are prepared according to ordinary methods in the usual manner for the corresponding vinyl monomers. It is obtained by polymerizing.

  For example, a method (solution polymerization method) in which these vinyl monomers and a chain transfer agent are dissolved in a suitable solvent, a radical polymerization initiator is added thereto and polymerized in a solution at about 50 ° C. to 220 ° C. It is obtained by using. Examples of suitable solvents used in the solution polymerization method can be arbitrarily selected depending on the monomers used and the solubility of the resulting copolymer. 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, dimethyl Examples include formamide, chloroform, toluene, dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), dimethylacetamide (DMAc), and N-methyl-2-pyrrolidone (NMP). These solvents may be used as a mixture of two or more.

  Examples of radical polymerization initiators include azo compounds such as 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile), benzoyl par Peroxides such as oxides, and persulfates such as potassium persulfate and ammonium persulfate can be used.

  Specific examples of the polymer compound represented by the general formula (14) are shown below, but are not limited thereto.

[Isolation]
Hereinafter, a method for isolating the aggregated organic nanoparticles will be described.

  First, it is preferable that the aggregated liquid is allowed to stand for 0.5 to 2 hours before isolation. Since the aggregate is settled, the supernatant can be removed by decanting or sucking, and the isolation of the aggregate is further facilitated. Further, by performing centrifugation instead of standing, faster aggregate sedimentation is possible, and the time can be shortened.

  As an isolation method, various types of filtration methods are possible, and examples thereof include ultrafiltration, centrifugal separation, and filtration with a filter paper or a filter.

  In the case of ultrafiltration, for example, a method used for desalting / concentration of a silver halide emulsion can be applied. Research Disclosure No. 10208 (1972), no. 13 122 (1975) and no. 16 351 (1977) is known. The pressure difference and flow rate that are important as operating conditions can be selected by referring to the characteristic curve described in Haruhiko Oya's “Membrane Utilization Technology Handbook”, Koshobo Publishing (1978), p275. In order to process the particles, it is necessary to find an optimum condition in order to suppress the aggregation of particles. There are two methods for replenishing the solvent that is lost due to membrane permeation: a constant volume method in which the solvent is continuously added and a batch method in which the solvent is intermittently added, but the desalting time is relatively short. The formula is preferred. As the solvent to be replenished, pure water obtained by ion exchange or distillation is used. However, a dispersant, a poor solvent for the dispersant may be mixed in pure water, or directly into the organic nanoparticle dispersion. It may be added.

  For the filter filtration, for example, an apparatus such as pressure filtration can be used. Examples of preferable filters include filter paper, nanofilters, and ultrafilters.

  The centrifuge used for concentration of the organic nanoparticles by centrifugation may be any device as long as it can precipitate the organic nanoparticles in the organic nanoparticle dispersion (or the organic nanoparticle concentrated extract). As a centrifuge, for example, in addition to a general-purpose device, a device with a skimming function (a function of sucking the supernatant layer during rotation and discharging it out of the system) or continuous centrifugation for continuously discharging solid matter Machine.

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

  The isolated aggregate can be washed for the purposes of desalting, dehydration, and removal of excess dispersant. The washing operation may be subjected to ultrafiltration, centrifugation, filtration through a filter paper or filter, and then the washing solution may be added as it is to wash it. Once the aggregate is taken out and reslurried in the washing solution, ultrafiltration, centrifugation, You may isolate by filtration with a filter paper or a filter, and you may perform washing | cleaning which combined them.

  In addition, the washing can be performed not only after the isolation as described above but also before the isolation. This is achieved by allowing the agglomerated nanopigment particle dispersion to stand, removing the supernatant, adding a washing solution, and reslurry. After reslurry, the slurry is allowed to stand and the supernatant liquid is removed and filtered, or may be filtered as it is. When washing is performed before isolation, the aggregates are always wet, so that not only the washing efficiency is increased, but also redispersion described later becomes easier.

  The washing liquid is not particularly limited as long as it can achieve desalting, dehydration, removal of excess dispersant / flocculant, and specifically an aqueous solvent (for example, water, hydrochloric acid, aqueous sodium hydroxide), 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 , And mixed solvents thereof are preferable, and aqueous solvents, alcohol compound solvents, ketone compound solvents, ether compound solvents, nitrile compound solvents, sulfoxide compound solvents, ester compound solvents, amide compound solvents, or a mixture thereof are preferable, and particularly aqueous. Solvent, alcohol compound solvent, ester compound solution , Nitrile compound solvent.

  The washed agglomerates can be re-dispersed as described below, or can be re-dispersed after being wetted with a re-dispersing solvent (described later), or dried and taken out as a powder of organic nanoparticle dispersion. Dispersion may be performed.

  The lyophilization method is not particularly limited, and any method that can be used by those skilled in the art may be adopted. For example, a refrigerant direct expansion method, an overlap refrigeration method, a heat medium circulation method, a triple heat exchange method, and an indirect heating freezing method can be mentioned, preferably a refrigerant direct expansion method, an indirect heating freezing method, more preferably an indirect heating freezing method. It is good to use. In any method, it is preferable to perform freeze-drying after preliminary freezing. The pre-freezing conditions are not particularly limited, but it is necessary that the sample to be freeze-dried is completely frozen.

  Indirect heating freezing equipment includes small freeze dryer, FTS freeze dryer, LYOVAC freeze dryer, experimental freeze dryer, research freeze dryer, triple heat exchange vacuum freeze dryer, mono-cooling freeze dryer , HULL freeze dryers, preferably small freeze dryers, laboratory freeze dryers, research freeze dryers, monocooling freeze dryers, more preferably small freeze dryers, monocooling freeze dryers Should be used.

  Although the temperature of freeze-drying is not specifically limited, For example, it is -190--4 degreeC, Preferably it is -120--20 degreeC, More preferably, it is about -80--60 degreeC. The pressure of lyophilization is not particularly limited, and can be appropriately selected by those skilled in the art. For example, the pressure may be 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, and more preferably about 16 to 26 hours. However, these conditions can be appropriately selected by those skilled in the art. Regarding the freeze-drying method, for example, Formulation Machine Technology Handbook: Formulation Machine Technology Study Group, Jinshokan, p. 120-129 (September 2000); Vacuum Handbook: Japan Vacuum Technology Co., Ltd., Ohm, p. 328-331 (1992); Journal of the Research Group on Freezing and Drying: Koji Ito et al. 15, p. 82 (1965) or the like.

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

  The heating and drying temperature is preferably 30 to 230 ° C, more preferably 35 to 200 ° C, and particularly preferably 40 to 180 ° C. The pressure during decompression is preferably 100 to 100,000 Pa, more preferably 300 to 90,000 Pa, and particularly preferably 500 to 80,000 Pa.

[Redistribution]
According to the production method of the present invention, it is possible to finely disperse the organic nanopigment particles in an agglomerated state as necessary (in the present invention, fine dispersal is the deaggregation of particles in a dispersion liquid). To increase the degree of dispersion).

  In order to enable rapid filter filtration and obtain a good dispersion state again, the agglomerated organic nanopigment particles described above are preferably obtained as flocs aggregated to such an extent that they can be redispersed.

  For this reason, the degree of dispersion using an ordinary dispersion method is insufficient for the formation of fine particles, and a method with higher micronization efficiency is required.

  As a method for finely dispersing such an aggregate of nanoparticles, for example, a dispersion method using ultrasonic waves or a method of applying physical energy can be used.

  The ultrasonic irradiation device used preferably has a function capable of applying an ultrasonic wave of 10 kHz or higher, and examples thereof include an ultrasonic homogenizer and an ultrasonic cleaner. When the liquid temperature rises during ultrasonic irradiation, thermal aggregation of the nanoparticles occurs (see Non-Patent Document 1). Therefore, the liquid temperature is preferably 1 to 100 ° C, more preferably 5 to 60 ° C. The temperature control method can be performed by controlling the dispersion temperature, controlling the temperature of the temperature adjusting layer that controls the temperature of the dispersion, or the like.

  There are no particular restrictions on the dispersing machine used to disperse the concentrated organic nanoparticles by applying physical energy. For example, kneader, roll mill, atrider, super mill, dissolver, homomixer, sand mill, etc. Machine. Further, a high-pressure dispersion method and a dispersion method using fine particle beads are also preferable.

  As a preferred method for producing the organic nanoparticle dispersion, the viscosity at 25 ° C. after kneading and dispersing the colorant with the resin component is 10,000 mPa · s or higher, desirably 100,000 mPa · s or higher. The method of kneading and dispersing as described above, and then adding a solvent and finely dispersing so that the viscosity after the fine dispersion treatment is 1,000 mPa · s or less, desirably 100 mPa · s or less, is relatively low. .

  The machines used in the redispersion process are two rolls, three rolls, ball mills, tron mills, dispersers, kneaders, kneaders, homogenizers, blenders, single- and twin-screw extruders, etc., which disperse while giving a strong shearing force. . Next, a solvent was added, and a vertical or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, a high pressure disperser, etc. were used, and it was made of glass having a particle diameter of 0.1 to 1 mm, zirconia, or the like. Fine dispersion with beads. Furthermore, it is possible to perform a fine dispersion treatment using fine particle beads of 0.1 mm or less.

  It is also possible to disperse the main pigment and the complementary pigment separately, and then mix the dispersions of the two to add further dispersion treatment, or to disperse the main pigment and the complementary pigment together.

  For details on dispersion, see T.W. C. It is also described in “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964), and this method may be used.

  For the purpose of improving the dispersibility of the organic nanopigment particles, a normal pigment dispersant or surfactant can be added to the organic nanopigment particle dispersion. As these dispersants, many kinds of compounds are used. For example, a phthalocyanine derivative (commercially available product EFKA-6745 (manufactured by Efka)), Solsperse 5000 (manufactured by Geneca), organosiloxane polymer KP341 ( Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl Nonionic surfactants such as ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; anionic surfactants such as W004, W005, W017 (manufactured by Yusho); EFKA- 46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), Disperse Aid 6, Polymer dispersants such as ISPER SIDE 8, DISPER SIDE 15, DISPER SIDE 9100 (manufactured by San Nopco); various sparses such as Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 Dispersant (manufactured by Zeneca); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka Co., Ltd.) and Isonet S-20 (Sanyo Kasei Co., Ltd.). Further, the pigment dispersant described in JP 2000-239554 A, the compound (C) described in JP-B-5-72943, the compound of Synthesis Example 1 described in JP 2001-31885 A, and the like are also preferably used. Can be used.

  In the organic nanoparticle-dispersed composition, the re-dispersed organic nanoparticles (primary particles) can be finely dispersed particles, and the particle size can be preferably 1 to 200 nm, and 2 to 100 nm. More preferred is 5 to 50 nm. Further, the Mv / Mn of the particles after redispersion is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, and 1.0 to 1.5. Is particularly preferred.

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

  Furthermore, since the organic nano pigment particles contained in the organic nano pigment particle dispersion composition and the colored photosensitive composition can be finely dispersed highly and uniformly, a high color density can be achieved with a thin film thickness. For example, it is possible to reduce the thickness of a color filter or the like.

  In addition, in the organic nano pigment particle dispersion composition and the colored photosensitive resin composition, by including a pigment showing a clear color tone and high coloring power, for example, as an image forming material for producing a color proof or a color filter Are better.

  Furthermore, with respect to an alkaline developer used for exposure / development in the formation of a colored image, an organic nanoparticle dispersion composition, a colored photosensitive resin composition, a binder (binder) soluble in an alkaline aqueous solution It can be used and can meet environmental requirements.

  In addition, an organic solvent having an appropriate drying property can be used as a solvent (pigment dispersion medium) used in the organic nano pigment particle dispersion composition and the colored photosensitive resin composition. Can be satisfied.

[Colored photosensitive resin composition]
The colored photosensitive resin composition of the present invention contains at least (a) organic nanopigment particles, (b) a binder, (c) a monomer or oligomer, and (d) a photopolymerization initiator or photopolymerization initiator system. Hereinafter, each component of the colored photosensitive resin composition of the present invention will be described.
a) Organic Nano Pigment Particles The method for producing organic nano pigment particles has already been described in detail. The content of the organic nano pigment particles is 3 to 90% by mass with respect to the total solid content in the colored photosensitive resin composition (in the present invention, the total solid content refers to the total composition excluding the organic solvent). Is preferable, 20-80 mass% is more preferable, and 25-60 mass% is further more preferable. If this amount is too large, the viscosity of the dispersion increases, which may cause problems in production suitability. If the amount is too small, the coloring power is not sufficient. The organic nano pigment particles functioning as a colorant preferably have a particle size of 0.1 μm or less, particularly 0.08 μm or less. Moreover, you may use it in combination with a normal pigment for toning. As the pigment, those described above can be used. In the present invention, the organic nanoparticles are preferably used as the organic nanopigment non-aqueous dispersion.
(B) Binder As the binder in the colored photosensitive resin composition, the above-described polymer compound having a weight average molecular weight of 1000 or more can be preferably used. As for content of a binder, 15-50 mass% is common with respect to the total solid of a colored photosensitive resin composition, and 20-45 mass% is preferable. If the amount is too large, the viscosity of the composition becomes too high, causing a problem in production suitability. If the amount is too small, there is a problem in forming a coating film.

(C) Monomer or oligomer The monomer or oligomer contained in the colored photosensitive resin composition of the present invention is a monomer or oligomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. It is preferable. Examples of such monomers and oligomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Examples 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; polyethylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentylglycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, Pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipenta Rithritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate And polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as trimethylolpropane or glycerin and then (meth) acrylated. In addition, as described in JP-A-10-62986, general formulas (1) and (2), a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated is also suitable. As mentioned.

  Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in Japanese Patent Publication No. 52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid.

  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” described in JP-A-11-133600 can also be mentioned as a preferable example.

  These monomers or oligomers (monomers or oligomers having a molecular weight of 200 to 1000 are preferred) may be used alone or in admixture of two or more, and may be used for the total solid content of the colored photosensitive resin composition. The content is generally 5 to 50% by mass, and preferably 10 to 40% by mass. If this amount is too large, it becomes difficult to control the developability, which causes a problem in production suitability. If the amount is too small, the curing power at the time of exposure is insufficient.

(D) Photopolymerization initiator or photopolymerization initiator system The photopolymerization initiator or photopolymerization initiator system contained in the colored photosensitive resin composition of the present invention (in the present invention, the photopolymerization initiator system is a plurality of compounds) And a vicinal polyketaldonyl compound disclosed in US Pat. No. 2,367,660, which is described in US Pat. No. 2,448,828. An acyloin ether compound, an aromatic acyloin compound substituted with an α-hydrocarbon described in US Pat. No. 2,722,512, a polynuclear quinone compound described in US Pat. Nos. 3,046,127 and 2,951,758, A combination of a triarylimidazole dimer and a p-aminoketone described in US Pat. No. 3,549,367, JP-B 51-4 Benzothiazole compounds and trihalomethyl-s-triazine compounds described in US Pat. No. 516, trihalomethyl-triazine compounds described in US Pat. No. 4,239,850, trihalomethyl described in US Pat. No. 4,221,976 An oxadiazole compound etc. can be mentioned. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable.

  In addition, “polymerization initiator C” described in JP-A-11-133600, oxime-based compounds such as 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O— Benzoyl-4 '-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenyl phosphonyl oxide, hexafluorophospho-trialkylphenyl phosphonium salt and the like may be mentioned as suitable ones. it can.

  These photopolymerization initiators or photopolymerization initiator systems may be used singly or as a mixture of two or more, but it is particularly preferable to use two or more. When at least two kinds of photopolymerization initiators are used, display characteristics, particularly display unevenness, can be reduced.

The content of the photopolymerization initiator or photopolymerization initiator system with respect to the total solid content of the colored photosensitive resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass. If this amount is too large, the sensitivity becomes too high and control becomes difficult. If the amount is too small, the exposure sensitivity becomes too low. As radiation that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferably used. Irradiation dose is more preferably preferably ^{10~1000mJ / cm 2 5~1500mJ / cm 2} , and most preferably 10 to 500 mJ / cm ^2.

(Other additives)
〔solvent〕
In the colored photosensitive resin composition of the present invention, an organic solvent may be further used in addition to the above components. Examples of organic solvents include, but are not limited to, esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, Alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, -3-oxypropionic acid alkyl esters such as ethyl oxypropionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2-oxypropionic acid Chill, 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, methyl pyruvate, pyrubin Ethyl acetate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ether Ren glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, propylene glycol methyl ether acetate, etc .; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclohexanol, 2-heptanone, 3-heptanone, etc .; Aromatic hydrocarbons such as toluene, xyles and the like can be mentioned. Among 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 are preferably used as the solvent in the present invention. These solvents may be used alone or in combination of two or more.

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

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

[Surfactant]
Conventionally used color filters have a problem that the color of each pixel becomes dark in order to achieve high color purity, and the film thickness unevenness of the pixel is recognized as color unevenness as it is. For this reason, it has been demanded to improve the film thickness variation during the formation (application) of the photosensitive resin layer, which directly affects the pixel film thickness.

  In the transfer material using the color filter of the present invention or the colored photosensitive resin composition of the present invention, the film thickness can be controlled to be uniform, and coating unevenness (color unevenness due to film thickness variation) can be effectively prevented. It is preferable that an appropriate surfactant is contained in the colored photosensitive resin composition.

  Preferred examples of the surfactant include surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600. The content of the surfactant is preferably 5% by mass or less with respect to the total amount of the resin composition.

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

[Additive dyes and pigments]
In addition to the said colorant (pigment), a colorant (dye, pigment) can be added to the colored photosensitive resin composition of this invention as needed. In the case of using a pigment among the colorants, it is desirable that the pigment is uniformly dispersed in the colored photosensitive resin composition. Therefore, the particle diameter is preferably 0.1 μm or less, particularly 0.08 μm or less.

  Specific examples of the dye or pigment include the colorant described in JP-A-2005-17716 [0038] to [0040] and JP-A-2005-361447 [0068] to [0072]. And the colorants described in JP-A-2005-17521 [0080] to [0088] can be suitably used. The content of the auxiliary dye or pigment is preferably 5% by mass or less based on the total amount of the resin composition.

[Ultraviolet absorber]
The colored photosensitive resin composition of the present invention may contain an ultraviolet absorber as necessary. Examples of the UV absorber include salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, nickel chelate-based, hindered amine-based compounds, etc., 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-5′-methylphenyl) benzotriazole, 2- (2 '-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3-diphenyl acrylate, 2,2'-hydroxy-4-methoxybenzophenone, nickel Dibutyldithiocarbamate, bis (2,2,6,6-tetramethyl-4-pyridine Sebacate, 4-tert-butylphenyl salicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinic acid-bis (2,2,6,6-tetramethyl-4 -Piperenyl) -ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- (diethylamino) -5 And triazin-2-yl] amino} -3-phenylcoumarin. As for content of a ultraviolet absorber, 5 mass% or less is preferable with respect to the resin composition whole quantity.

  In addition, the colored photosensitive resin composition of the present invention may contain “adhesion aid” described in JP-A No. 11-133600, other additives and the like in addition to the above additives.

[Coating film of colored photosensitive resin composition]
The components contained in the coating film using the colored photosensitive resin composition of the present invention are the same as those already described in the section of [Colored photosensitive resin composition]. Moreover, although the thickness of the coating film using the colored photosensitive resin composition of this invention can be suitably determined with the use, it is preferable that it is 0.5-5.0 micrometers, and 1.0-3. More preferably, it is 0 μm. In the coating film using the colored photosensitive resin composition of the present invention, (c) the monomer or oligomer contained therein is polymerized to form a colored photosensitive resin composition polymer film, and a color filter having the same is prepared. (The production of the color filter will be described later). Polymerization of the polymerizable monomer or polymerizable oligomer can be carried out by allowing (d) a photopolymerization initiator or a photopolymerization initiator system to act upon irradiation with light.

<Color filter and manufacturing method thereof>
Next, the color filter of the present invention and the manufacturing method thereof will be described.

  The color filter of the present invention is characterized in that it has a colored pattern formed on the support using the photocurable composition (colored photosensitive resin composition) of the present invention.

  Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

  The method for producing a color filter of the present invention comprises a step of forming a photosensitive film by applying the photocurable composition of the present invention directly or through another layer (hereinafter referred to as “photosensitive film formation” as appropriate). Abbreviated as “step”), a step of pattern exposure (exposure through a mask) of the formed photosensitive film (hereinafter abbreviated as “exposure step” as appropriate), and a photosensitive film after exposure. And a step of developing a colored pattern (hereinafter, abbreviated as “development step” as appropriate).

Hereinafter, each process in the manufacturing method of the color filter of this invention is demonstrated.
(Photosensitive film forming process)
In the photosensitive film forming step, the photocurable composition of the present invention is applied (applied) directly or on a substrate having another layer to form a photosensitive film.

  Examples of the substrate that can be used in this step include soda glass, Pyrex (registered trademark) glass, quartz glass, and those in which a transparent conductive film is attached to these substrates, photoelectric sensors used in image sensors, and the like. Examples include a conversion element substrate such as a silicon substrate and a complementary metal oxide semiconductor (CMOS). These substrates may have black stripes that separate pixels.

  Further, if necessary, an undercoat layer (other layers) may be provided on these substrates for improving adhesion to the upper layer, preventing diffusion of substances, or flattening the substrate surface.

  As a coating method of the photocurable composition of the present invention on the substrate, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied.

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

The photosensitive film coated on the substrate can be dried (prebaked) at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds using a hot plate, an oven, or the like.
(Exposure process)
In the exposure step, the photosensitive film formed in the photosensitive film forming step is exposed through a mask having a predetermined mask pattern, that is, pattern exposure is performed.

  In this step, only the coating film portion irradiated with light can be cured by exposing the photosensitive film as the coating film through a predetermined mask pattern.

As radiation that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferably used. Irradiation dose is more preferably preferably ^{10~1000mJ / cm 2 5~1500mJ / cm 2} , and most preferably 10 to 500 mJ / cm ^2.

If the color filter of the present invention is a liquid crystal display device, it is more preferably preferably 10~150mJ / cm ² 5~200mJ / cm ² within the above range, and most preferably 10 to 100 mJ / cm ^2. Further, when the color filter of the present invention is for a solid-state imaging device, more preferably 30~1500mJ / cm ² is preferably 50~1000mJ / cm ² within the above range, and most preferably 80~500mJ / cm ^2.

(Development process)
Next, by performing development processing, the unexposed portion in the exposure step is eluted in the developer, and only the photocured portion remains. Any developer can be used as long as it dissolves the film of the photocurable composition in the uncured part while not dissolving the cured part. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

  The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

  Examples of the organic solvent include the solvents described above that can be used in preparing the pigment dispersion composition or the photocurable composition of the present invention.

  Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Concentration of an alkaline compound such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, in a concentration of 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution diluted with pure water so as to be 1% by mass is preferably used as the developer.

  In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

  After the development step, excess developer is washed away and dried, followed by heat treatment (post-bake).

  The post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 100 ° C. to 240 ° C. is performed. When the substrate is a glass substrate or a silicon substrate, 200 ° C. to 240 ° C. is preferable in the above temperature range.

  This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.

  By repeating the photosensitive film formation step, the exposure step, and the development step (and heat treatment as necessary) described above for the desired number of hues, a color filter having a desired hue is manufactured.

  When the film is formed by applying the photocurable composition of the present invention on a substrate, the dry thickness of the film is generally 0.3 to 5.0 μm, preferably 0.5 to 3.5 μm, Most desirably, the thickness is 1.0 to 2.5 μm.

  As the substrate, for example, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film to these, solid-state imaging elements, etc. Examples of the photoelectric conversion element substrate include a silicon substrate and a plastic substrate. On these substrates, usually, black stripes for isolating each pixel are formed.

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

  As the application of the photocurable composition of the present invention, the application mainly to the pixel of the color filter has been mainly described, but it goes without saying that it can also be applied to a black matrix provided between the pixels of the color filter. The black matrix is the same as the above-described pixel manufacturing method except that a black colorant such as carbon black or titanium black is added as a colorant to the photocurable composition of the present invention. The film can be developed and then post-baked to accelerate the curing of the film.

<Example 1>
[Preparation of organic nano pigment particle aqueous dispersion]
C. I. Pigment Red 254 (45 parts by mass) and polyvinylpyrrolidone (K-25, Wako Pure Chemical Industries, 90 parts by mass) were added to dimethyl sulfoxide (DMSO) (953 parts by mass) and stirred. A 28% by mass sodium methoxide methanol solution (30 parts by volume) was added to this solution to prepare a pigment solution A. On the other hand, water (4000 parts by mass) was prepared as the pigment-insoluble solvent B.

  While the pigment insoluble solvent B was stirred at 500 rpm with a GK-0222-10 type Lamond Stirrer (trade name) manufactured by Fujisawa Pharmaceutical Co., Ltd. at 30 ° C., the pigment solution A was added to the pigment insoluble solvent B by Nippon Seimitsu Kagaku The organic pigment nanoparticles were crystallized by injecting with an NP-KX-500 type large-capacity non-pulsating flow pump (trade name) at a flow rate of 100 mL / min for 4 minutes and 4 seconds to obtain an aqueous organic nanoaqueous dispersion.

  Evaluation was performed by a dynamic light scattering method using LB-400 (trade name) manufactured by HORIBA, Ltd., and the median diameter was defined as an average particle diameter as an index of dispersibility. In addition, since the secondary agglomerated particles are also observed in the dynamic light scattering method, evaluation as primary particles was also performed with a transmission electron microscope.

[Agglomeration]
Acetic acid (45 parts by mass) as a nonionic low molecular compound and C-1 (3 parts by mass) as a nonionic polymer compound are dissolved in acetone (200 parts by mass), and the above organic nanoparticle aqueous dispersion (300 parts by mass) is dissolved. And stirred for 0.5 hour. After standing for 0.5 hour and observing the resulting aggregate with an optical microscope, the aggregate was settled, and the supernatant was removed by decantation.

[Isolation / Washing / Drying]
The above-mentioned aggregate was filtered off with a filter paper (manufactured by ADVANTEC, No. 2), and the time required for filtration at this time was measured. The solid collected by filtration was washed with water (300 parts by mass) and methanol (200 parts by volume). The obtained solid was reslurried in acetonitrile (100 parts by volume) for 0.5 hour, allowed to stand for 0.5 hour, and the supernatant was removed by decantation. The obtained solid was vacuum-dried overnight at room temperature.

[Redistribution]
The following non-aqueous solvent 1-methoxy-2-propylacetate (4 parts by mass) is added to this organic pigment solid (1 part by mass), and ultrasonic is applied using an ultrasonic homogenizer US series (trade name) manufactured by Nippon Seimitsu Seisakusho. By performing irradiation for 3 hours, an organic nanoparticle non-aqueous dispersion (hereinafter, also referred to as “pigment dispersion composition A”) using the following non-aqueous solvent as a dispersant was obtained.

(Evaluation test)
The following evaluation was performed about the obtained dispersion composition. The results are shown in Table 1.
(1) Average particle size of organic nanoparticle aqueous dispersion The organic nanoparticle is evaluated by the dynamic light scattering method using LB-500 (trade name) manufactured by HORIBA, Ltd., and the median diameter is set to the average particle size. The average particle size of the aqueous particle dispersion was measured.
(2) Diameter of aggregates The aggregates were observed with an optical microscope, and the diameters of the aggregates were measured with reference to a separately observed monosashi. As for the diameter of the aggregate here, the length from end to end of the aggregate was measured, and the longest length was defined as the diameter. The aggregates referred to here are those in which nanoparticles, which are primary particles that cannot be seen with the naked eye, are gathered and grown to become secondary particles.
(3) Filtration time Filtration time per 1 g of pigment was measured by filtering under reduced pressure with an aspirator using Nutsche and filter paper (Advantech filter paper No. 2 (trade name)) having a diameter of 9 cm.
(4) Viscosity measurement About the obtained dispersion composition, using an E-type viscometer, the viscosity η ¹ of the pigment dispersion composition immediately after dispersion and the pigment dispersion composition after 1 week after dispersion (at room temperature) The viscosity η ² of the product was measured to evaluate the degree of thickening. Here, a low viscosity indicates that the dispersibility and dispersion stability are good.
(5) Contrast evaluation The obtained pigment dispersion composition A was applied on a glass substrate so as to have a thickness of 2 μm, and a sample was prepared. As the backlight unit, a three-wavelength cold cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) with a diffusion plate installed was used, and two polarizing plates (polarizing plates HLC2-2518 manufactured by Sanritsu Co., Ltd.) were used. ), The amount of transmitted light when the polarization axis is parallel and vertical is measured, and the ratio is defined as the contrast (“1990 Seventh Color Optical Conference, 512-color display 10. 4 ”size TFT-LCD color filter, planting, Koseki, Fukunaga, Yamanaka etc.). A color luminance meter (BM-5 manufactured by Topcon Corporation) was used for the measurement of chromaticity. Two polarizing plates, a sample, and a color luminance meter are installed at a position where the polarizing plate is 13 mm from the backlight, and a cylinder having a diameter of 11 mm and a length of 20 mm is installed at a position of 40 mm to 60 mm. Was measured on a color luminance meter installed at a position of 400 mm through a polarizing plate installed at a position of 100 mm. The measurement angle of the color luminance meter was set to 2 °. The light amount of the backlight was set so that the luminance when the two polarizing plates were installed in parallel Nicol was 1280 cd / m ² without the sample being installed.

<Example 2>
The same operation as in Example 1 was performed except that the nonionic low molecular weight compound of Example 1 was changed to nonionic 2-propylpentanoic acid. The obtained organic nanoparticle non-aqueous dispersion is also referred to as pigment dispersion composition B. Table 1 shows the results of the same evaluation test as in Example 1 for the pigment dispersion composition B.

<Example 3>
The same operation as in Example 1 was performed except that the nonionic polymer compound of Example 1 was changed to nonionic C-10. The obtained organic nanoparticle non-aqueous dispersion is also referred to as 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 polyvinyl pyrrolidone of Example 1 is changed to the cationic polymer dispersant C-5, the nonionic low molecular compound is changed to the anionic low molecular compound E-3, and the anionic high molecular compound is changed to the anionic high molecular compound F-2. Then, the same operation as in Example 1 was performed. The obtained organic nanoparticle non-aqueous dispersion is also referred to as pigment dispersion composition D. Table 1 shows the results of the same evaluation test as in Example 1 for the pigment dispersion composition D.

<Example 5>
In Example 1, the same operation as in Example 1 was performed on the organic nanoparticle aqueous dispersion, except that the nonionic polymer compound was changed to a nonionic methacrylic acid / benzyl methacrylate copolymer. . The obtained organic nanoparticle non-aqueous dispersion is also referred to as 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, after adding acetic acid as a nonionic low molecular weight compound to an organic nanoparticle aqueous dispersion, C-1 is dissolved in acetone as a nonionic high molecular compound and added to the organic nanoparticle aqueous dispersion. Except that, the same operation as in Example 1 was performed. The obtained organic nanoparticle non-aqueous dispersion is also referred to as 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 the nonionic polymer compound in the organic nanoparticle aqueous dispersion and added to the organic nanoparticle aqueous dispersion, and then acetic acid was added as the nonionic low molecular compound. Except that, the same operation as in Example 1 was performed. The obtained organic nanoparticle non-aqueous dispersion is also referred to as pigment dispersion composition G. Table 1 shows the results of the same evaluation test as in Example 1 for the pigment dispersion composition G.
<Example 8>
The aggregate obtained in Example 1 was allowed to settle, and the supernatant was removed by decantation. Then, water (200 parts by mass) was added and reslurried for 0.5 hours. The mixture was allowed to stand for 0.5 hour, the dispersion was allowed to settle, and the supernatant was removed by decantation. Moreover, methanol (100 mass parts) was added to this, and it reslurried for 0.5 hour. The mixture was allowed to stand for 0.5 hour, the dispersion was allowed to settle, and the supernatant was removed by decantation. Further, 100 parts by mass of acetonitrile) was added and reslurried for 0.5 hours. The mixture was allowed to stand for 0.5 hour, the dispersion was allowed to settle, and the supernatant was removed by decantation. Thereafter, the same operation as in Example 1 was performed. The obtained organic nano pigment particle non-aqueous dispersion is also referred to as a pigment dispersion composition H. Table 1 shows the results of the same evaluation test as in Example 1 for the pigment dispersion composition H.

<Comparative Example 1>
Hydrochloric acid (64 parts by mass) is added to the organic nanoparticle aqueous dispersion prepared in the same manner as in Example 1, the nanoparticles are aggregated, filtered using a filter (H010A047A, trade name, manufactured by Advantech), and required. Time was measured. The solid collected by filtration was washed and dried in the same manner as in Example 1 (1 part by mass), the methacrylic acid / benzyl methacrylate copolymer (1 part by mass), 1-methoxy-2- Propyl acetate (8 parts by mass) was added, and ultrasonic irradiation was performed for 3 hours using an ultrasonic homogenizer US series (trade name) manufactured by Nippon Seimitsu Seisakusho. An aqueous dispersion was obtained. The obtained organic nanoparticle non-aqueous dispersion is also referred to as pigment dispersion composition I. Evaluation was performed in the same manner as in Example 1. Table 1 shows the results of the same evaluation test as in Example 1 for the 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 the organic nanoparticle aqueous dispersion (300 parts by mass) prepared in the same manner as in Examples 1 to 8 and Comparative Example 1. After observing the aggregate with an optical microscope, the aggregate was filtered using a filter (H010A047A, trade name, manufactured by Advantech), and the time required was measured.
The evaluation results are shown below.

<Reference Example 1>
Acetone (200 parts by mass) in which acetic acid (45 parts by mass) is dissolved is added to the organic nanoparticle aqueous dispersion (300 parts by mass) prepared in the same manner as in Example 1, and the aggregates are observed with an optical microscope. After observation, the filter was filtered using a filter (H010A047A, trade name, manufactured by Advantech), and the time required was measured.
The evaluation results are shown below.

  As described above, according to the present invention, when the aqueous organic nanoparticle dispersion is phase-converted into the non-aqueous organic nanoparticle dispersion, a process of once creating an aqueous paste as represented by flushing, that is, enormous such as filter filtration For complex processes that require a long time, the nanoparticles in the aqueous dispersion of organic nanoparticles can be easily filtered to form aggregates that are isolated and redispersed in a non-aqueous solvent for efficient production. The organic nanoparticle non-aqueous dispersion obtained, and the manufacturing method thereof can be provided. Furthermore, it is possible to provide an organic nanoparticle non-aqueous dispersion having excellent dispersibility and high contrast, and a method for producing the same.

[Preparation of colored tourism resin composition]
The components of the following composition were further added to the pigment dispersion compositions A to I obtained in Examples 1 to 8 and Comparative Example 1, and the mixture was stirred and mixed to obtain the colored photosensitive resin composition (color resist solution) of the present invention. Prepared.

〔composition〕
-Dipentaerythritol hexaacrylate-80 parts by mass-4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine (light (Polymerization initiator) 30 parts by mass-Benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 10,000) propylene glycol monomethyl ether acetate solution (solid content 40) %) ... 200 parts by mass, 1-methoxy-2-propyl acetate ... 490 parts by mass

The obtained photocurable composition (color resist solution) was applied on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) so that the x value serving as an index of color density was 0.650. It was dried in an oven at 90 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film was 1% aqueous solution of alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). And rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film subjected to exposure and development as described above is heat-treated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored resin film for a color filter on a glass substrate. Color filter) was produced.
The results of measuring the contrast of the R component of each film obtained in the same manner as in Example 1 are shown in the following table.

  As described above, the color filter prepared from the colored photosensitive resin composition using the organic nanoparticles non-aqueous dispersion organic particles obtained by the present invention showed extremely excellent contrast as compared with the comparative example.

Claims (12)

  Aggregation by causing 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 1000 or more to act on the organic nanopigment particles dispersed in an aqueous medium. And then, isolating the organic nano pigment particle aggregate.   The organic low molecular weight compound and the organic high molecular weight compound are dissolved in a solvent miscible with the aqueous medium, and added to the aqueous medium, thereby aggregating the organic nano pigment particles dispersed in the aqueous medium. The method for producing an organic nano pigment particle aggregate according to claim 1.   The said isolation is performed by filtration, The manufacturing method of the organic nano pigment particle aggregate of Claim 1 or 2 characterized by the above-mentioned.   The method for producing an organic nanopigment particle aggregate according to any one of claims 1 to 3, further comprising a step of removing at least the excess organic low-molecular compound.   An organic nanopigment particle dispersed in the aqueous medium is mixed with a solution of an organic pigment dissolved in a good solvent and a medium that is compatible with the good solvent and that is a poor solvent for the organic pigment. The method for producing an organic nanopigment particle aggregate according to any one of claims 1 to 4, wherein the organic nanopigment particle aggregate is produced as nanosized fine particles.   The average primary particle diameter of the organic nano pigment particles is 100 nm or less, The method for producing an organic nano pigment particle aggregate according to any one of claims 1 to 5.   The method for producing an organic nanopigment particle aggregate according to any one of claims 1 to 8, wherein the average particle size of the aggregate is 10,000 nm or more.   Production of an organic nanopigment particle non-aqueous dispersion obtained by redispersing the isolated organic nanopigment particle aggregate according to any one of claims 1 to 7 in a non-aqueous medium. Method. The organic polymer compound is represented by the following general formula (11) or general formula (14), wherein the organic nanopigment particle non-aqueous dispersion according to any one of claims 1 to 8 is produced. Method.

(In the general formula (11), A ¹ represents an acidic 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, or alkoxysilyl. A monovalent organic group having a group selected from a group, an epoxy group, an isocyanate group, and a hydroxyl group, or a monovalent organic group containing an organic dye structure or a heterocyclic ring which may have a substituent. A ¹ may be the same or different, R ¹ represents a (m + n) -valent linking group, m + n represents 3 to 10, m represents an integer of 1 to 8, and n Represents an integer of 2 to 9. R ² represents a single bond or a divalent linking group, and P ¹ represents a polymer residue.)

(In the general formula (14), G represents —COO ⁻ , —SO ₃ ⁻ , —OSO ₃ ⁻ , —P (O) (OH) O ⁻ , or —OP (O) (OH) O ^— . J represents a divalent linking group or a single bond, Q represents an (m + 1) -valent linking group, R represents a polymer compound residue, Z represents an organic or inorganic cation, and m + 1 represents 3 to 6. To express.)   The method for producing a non-aqueous dispersion of organic nanopigment particles according to claim 9, wherein the organic polymer compound is used as a dispersant in a non-aqueous medium as it is.   A colored photosensitive resin composition comprising at least the organic nanopigment particle non-aqueous dispersion according to claim 9 or 10, a binder, a monomer or an oligomer, and a photopolymerization initiator or a photopolymerization initiator system.   A color filter comprising the colored photosensitive resin composition according to claim 11.