JP2007321106A - Method for producing pigment nano particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing pigment nano particles, by which the pigment nano particles having high and excellent dispersion stability, nano sizes, a sharp particle size distribution peak, and characteristics suitable for color filters and ink jet inks can efficiently be produced. <P>SOLUTION: This method for producing pigment nano particles is characterized by mixing a pigment solution obtained by dissolving an organic pigment in an organic acid or a solvent containing an organic acid with an organic solvent for deposition to deposit the organic pigment nano particles. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing pigment nanoparticles. Furthermore, it is related with the manufacturing method of the pigment nanoparticle suitable for a color filter or an inkjet ink material.

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 becoming active 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 used. 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 that are monodisperse and stable at the nanometer size level.

  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.

Regarding the improvement of particle dispersibility, organic pigments are conventionally dispersed industrially using various dispersing machines (roll mill, ball mill, attritor, etc.). It may rise. If the viscosity increases, it becomes difficult to take out from the disperser, it cannot be transported by a 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 order to enhance the dispersibility of organic pigment dispersions for color filters, polymers and pigment dispersants that can impart both properties of alkali developability and dispersion stability necessary for the production of color filters are added ( For example, see Patent Document 4). However, these methods do not satisfy the requirements because dispersion takes time and the viscosity increases.
Patent Document 5 discloses a method for producing pigment particles by mixing a solution obtained by dissolving a pigment in an organic acid with water which is a poor solvent. However, it is unclear whether it is suitable as a color filter or inkjet material.

JP-A-11-237760 JP-A-6-79168 JP 2004-91560 A JP 2000-239554 A JP 2003-336001 A Pigment Dispersion Technology-Surface Treatment and Use of Dispersing Agents and Dispersibility Evaluation-Technical Information Association 1999

An object of this invention is to provide the manufacturing method of a pigment nanoparticle. It is another object of the present invention to provide a method for efficiently producing pigment nanoparticles having high dispersion stability.
Furthermore, the present invention aims to provide a method for producing pigment nanoparticles having a nano-size and a sharp particle size distribution peak, which is excellent in dispersion stability and has properties suitable for color filters and inkjet inks. The purpose is to provide a manufacturing method.

The above problems have been achieved by the following means.
(1) A method for producing pigment nanoparticles, wherein organic pigment nanoparticles are precipitated by mixing a pigment solution obtained by dissolving an organic pigment in an organic acid or a solvent containing an organic acid, and an organic solvent for precipitation. .
(2) The method for producing pigment nanoparticles according to (1), wherein the organic solvent for precipitation contains a polymer compound having a weight average molecular weight of 1,000 to 500,000.

  According to the production method of the present invention, it is possible to efficiently obtain pigment nanoparticles that have been refined to a nanometer size, and furthermore, it is possible to obtain pigment nanoparticles that are nano-sized and highly monodispersed. Further, according to the production method of the present invention, pigment nanoparticles having high dispersion stability and having spectral absorption characteristics and X-ray diffraction patterns suitable for color filters and inkjet inks can be obtained. Therefore, according to the production method of the present invention, it is possible to efficiently produce pigment nanoparticles suitable for color filter coating liquids and ink jet inks on an industrial scale.

Hereafter, the manufacturing method of the pigment nanoparticle of this invention is demonstrated.
[Organic pigments]
The organic pigment used in the production method of the present invention is not particularly limited as long as it can form particles by a reprecipitation method, and may be used alone, in plural, or in combination thereof. .

  The organic pigment is not limited in terms of hue. , 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.
Hereinafter, the diketopyrrolopyrrole compound pigment or the dioxazine compound pigment will be described in more detail.
C. I. P. R. Since pyrrolopyrrole compound pigments typified 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 No. 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. And the liquid crystal display device provided with the color filter is excellent in blackness and red descriptive power, and display unevenness is suppressed.

  Among the above diketopyrrolopyrrole compound pigments, C.I. I. P. R. 254 (compound represented by the following formula (Z)), 255 (compound represented by the following formula (W)), and 264 (compound represented by the following formula (V)) are preferable. I. P. R. 254 is more preferable from the viewpoint of the absorption spectrum. Note that C.I. I. P. R. As 254, any commercially available product such as Irgaphor Red B-CF, Chromophthal DPP Red BO, Irgadin DPP Red BO, and Microlen DPP RED BP can be used. C. I. P. R. As 255, Croftal Coral Red C, Irgadin DPP Red 5G, or the like can be used. C. I. P. R. As H.264, Hostepperum Rubin D3B LP2615, Irgadin DPP Rubin TR, or the like can be used.

Next, the dioxazine compound pigment will be described. In recent years, C.I. I. P. B. 15: 6 has been frequently used, and the color purity of the color filter has increased. However, a light source such as a cold-cathode tube, which is a light source frequently used in liquid crystal display devices, emits a little light on the long wave side of the blue light emission peak, which makes the chromaticity inferior to NTSC.
The problem is that C.I. I. P. V. It can be improved by adding a dioxazine compound pigment represented by Nos. 23 and 37 (for example, about 5%). Although it is conceivable to improve contrast and further improve display characteristics with this color filter having high color purity, satisfactory results cannot be obtained by the conventional bead dispersion method or salt milling method.
On the other hand, according to the production method of the present invention, the dioxazine compound pigment can be obtained as a nano-sized pigment having a uniform particle size distribution. The dispersion containing the dioxazine compound pigment fine particles can be excellent in stability over time. Therefore, the color filter used therefor can achieve both high color purity and high contrast, and is excellent in light resistance. In addition, the liquid crystal display device provided with the color filter is excellent in depiction and reproducibility of black spots and blue, and display unevenness can be suppressed. Note that C.I. I. P. V. As 23, all commercially available ones such as Cromofine Violet RE, Fastgen Super Violet BBL, Helio Fast Violet EB, Microlith Violet RL-WA, and Sanyo Fast Violet BLD can be used. C. I. P. V. As 37, it is possible to use any commercially available product such as Chromophthal Violet B and Microlith Violet B-A.

In the production method of the present invention, among others, a pigment having a dioxazine structure, a pigment having a phthalocyanine structure, a pigment having an aminoanthraquinone structure, a pigment having a diketopyrrolopyrrole structure, a pigment having an aromatic condensed ring structure, or a metal It is preferable to use a pigment having a complex structure. In the production method of the present invention, two or more kinds of organic pigments or solid solutions of organic pigments can be used in combination. Moreover, you may combine with an organic pigment | dye, a polymeric organic material, etc.
Examples of organic dyes include azo dyes, cyanine dyes, merocyanine dyes, and coumarin dyes. Examples of the polymer organic material include polydiacetylene and polyimide.

[Generation of organic pigment nanoparticles]
The method for producing organic pigment nanoparticles will be described below.
In the present invention, pigment nanoparticles (hereinafter sometimes referred to as “organic nanoparticles”) are organic pigments or organic acids or solvents containing organic acids (hereinafter referred to as [organic acid solvent] or It is compatible with the organic pigment solution dissolved in [good solvent]) and the organic acid or the solvent containing the organic acid, and is a poor solvent for the organic pigment. It is produced by mixing with an organic solvent (hereinafter also referred to as “poor solvent”) (hereinafter, this method is sometimes referred to as “reprecipitation method”), and a dispersion containing organic nanoparticles obtained at this time is prepared. Sometimes called “organic particle reprecipitation solution”.)

First, the organic solvent for precipitation is demonstrated.
The organic solvent for precipitation is not particularly limited as long as it is compatible or uniformly mixed with the organic acid solvent that dissolves the organic pigment. As the organic solvent for precipitation, the solubility of the organic pigment is preferably 0.02% by mass or less, and more preferably 0.01% by mass or less. There is no particular lower limit on the solubility of the organic pigment in the organic solvent for precipitation, but considering the commonly used organic pigment, 0.0001% by mass or more is practical. 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 organic acid solvent and the organic solvent for precipitation is preferably such that the amount of the organic acid solvent dissolved in the organic solvent for precipitation is 30% by mass or more, and is 50% by mass or more. More preferred. There is no particular upper limit on the amount of the organic acid solvent dissolved in the organic solvent for precipitation, but it is practical to mix the organic acid solvent in an arbitrary ratio.
Examples of the organic solvent for precipitation include alcohol compound solvents, ketone compound solvents, ether compound solvents, aromatic compound solvents, carbon disulfide solvents, aliphatic compound solvents, nitrile compound solvents, sulfoxide compound solvents, halogen compound solvents, and ester compounds. Examples thereof include a solvent, an ionic liquid, an amide compound solvent, and a mixed solvent thereof. A ketone compound solvent, an alcohol compound solvent, a sulfoxide compound solvent, an ester compound solvent, an amide compound solvent, and a nitrile compound solvent are preferable. As an organic solvent for precipitation, except for inevitable ones, the water content is preferably 20% or less, and when excluding the influence of the contained water, it is preferable not to contain water. More preferred are organic solvents containing nitrogen such as dimethyl sulfoxide and N-methylpyrrolidone, or a mixed solvent thereof.

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 sulfoxide compound solvent include dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, sulfolane and the like.
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, the organic acid that dissolves the organic pigment or the solvent containing the organic acid will be described.
The organic acid or the solvent containing the organic acid 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 organic solvent for precipitation. The solubility of the organic pigment in the organic acid solvent is such that the solubility of the organic pigment 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 organic acid solvent, it is practical that it is 50% by mass or less in consideration of a commonly used organic pigment. The preferable range of the compatibility or uniform mixing property between the organic solvent for precipitation and the organic acid solvent is as described above.
Examples of the organic acid include alkyl sulfonic acid, alkyl carboxylic acid, halogenated alkyl sulfonic acid, halogenated alkyl carboxylic acid, aromatic sulfonic acid, aromatic carboxylic acid, or a mixed solvent of two or more of these. Sulfonic acid or aromatic sulfonic acid is preferred, and methanesulfonic acid is more preferred.

In the solvent containing an organic acid, the solvent combined with the organic acid includes, for example, an alcohol compound solvent, an amide compound solvent, a ketone compound solvent, an ether compound solvent, an aromatic compound solvent, a carbon disulfide solvent, an aliphatic compound solvent, and a nitrile. Examples include compound solvents, sulfoxide compound solvents, halogen compound solvents, ester compound solvents, ionic liquids, mixed solvents thereof, alcohol compound solvents, amide compound solvents, ketone compound solvents, aromatic compound solvents, ester compound solvents, and the like. preferable. The organic acid solvent preferably does not contain water except for inevitable ones.
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 organic acid solvent is preferably a saturated concentration of the organic pigment with respect to the organic acid solvent in the dissolution condition 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.

There are no particular restrictions on the conditions of the organic solvent for precipitation 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 organic solvent for precipitation, either of them may be added and mixed. However, it is preferable to add and mix the organic pigment solution into the organic solvent for precipitation. It is preferable that the organic solvent is stirred. 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 organic solvent for precipitation (the ratio of organic acid solvent in the organic particle reprecipitation liquid / the organic solvent for precipitation) is preferably 1/50 to 2/3 by volume, and preferably 1/40 to 1 /. 2 is more preferable, and 1/20 to 3/8 is particularly preferable. At this time, it is preferable that unnecessary water is not mixed with the mixed solution of the organic pigment solution and the organic solvent for precipitation except for inevitable ones.
The concentration of the organic particle reprecipitation liquid is not particularly limited as long as the organic particles can be generated, but the organic particles are preferably in the range of 10 to 40000 mg, more preferably in the range of 20 to 30000 mg with respect to 1000 ml of the dispersion solvent. Yes, particularly preferably in the range of 50 to 25000 mg.
Moreover, the preparation scale at the time of producing | generating an organic nanoparticle is although it does not specifically limit, It is preferable that the mixing amount of the organic solvent for precipitation is 10-2000L preparation scale, and it is more preferable that it is a 50-1000L preparation scale. preferable.

Regarding the particle size of organic particles, there is a method of expressing the average size of the population by quantifying by a measurement method, but the mode diameter indicating the maximum value of the distribution and the median value of the integral distribution curve are often used Median diameter, various average diameters (number average, length average, area average, weight average, volume average, etc.), etc. in the present invention, unless otherwise specified, the average particle diameter is the number average. The diameter. The average particle size of the organic particles (primary particles) is nanometer size, the average particle size is preferably 1 nm to 1 μm, more preferably 1 to 200 nm, further preferably 2 to 100 nm, A thickness of 5 to 80 nm is particularly preferable. The particles formed by the production method of 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 of particles (primary particles) contained in the organic particle dispersion used in the organic particle concentration method, that is, Mv / Mn, is preferably 1.0 to 2.0, and 1.0 to 1. 8 is more preferable, and 1.0 to 1.5 is particularly preferable.
Examples of the method for measuring the particle size of organic particles include microscopy, gravimetric method, light scattering method, light blocking method, electrical resistance method, acoustic method, and dynamic light scattering method. 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 by the dynamic light scattering method include Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd. and Dynamic Light Scattering Photometer DLS-7000 series manufactured by Otsuka Electronics Co., Ltd.

[Dispersant]
In the method for producing organic nanoparticles of the present invention, it is preferable to contain a dispersant when preparing the organic nanoparticle dispersion. The step of containing the dispersant is not particularly limited, but it is preferable to add the dispersant to and / or one of the organic pigment solution and the organic solvent for precipitation. Moreover, it is also preferable to add a dispersing agent solution at the time of formation of organic nanoparticles 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. The molecular weight of the polymer dispersant can be used without limitation as long as it can be uniformly dissolved in a solution, but preferably has a molecular weight of 1,000 to 2,000,000, and 5,000 to 1,000,000. 000 is more preferable, 10,000 to 500,000 is more preferable, and 10,000 to 100,000 is particularly preferable. Specific examples of the polymer dispersant include polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, polyvinyl alcohol-partial formalized product, polyvinyl alcohol- Partial butyral, vinyl pyrrolidone-vinyl acetate copolymer, polyethylene oxide / propylene oxide block copolymer, polyacrylate, polyvinyl sulfate, poly (4-vinylpyridine) salt, polyamide, polyallylamine salt, condensed naphthalene sulfone Acid salts, cellulose derivatives, starch derivatives and the like can be mentioned. In addition, natural polymers such as alginate, gelatin, albumin, casein, gum arabic, tonganto gum and lignin sulfonate can also be used. Of these, polyvinylpyrrolidone is preferable. These polymers can be used singly or in combination of two or more.
The 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).

  Examples of anionic dispersants (anionic surfactants) include N-acyl-N-alkyl taurine salts, fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphorus Examples include acid ester salts, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl sulfate ester salts, 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.

  Cationic dispersants (cationic surfactants) include quaternary ammonium salts, alkoxylated polyamines, aliphatic amine polyglycol ethers, aliphatic amines, diamines and polyamines derived from aliphatic amines and fatty alcohols, fatty acids And imidazolines derived from these and salts of these cationic substances. These cationic dispersants can be used alone or in combination of two or more.

The amphoteric dispersant is a dispersant having both an anion group part in the molecule of the anionic dispersant and a cationic group part in the molecule of the cationic dispersant.
Nonionic dispersants (nonionic surfactants) include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, Examples thereof include glycerin fatty acid esters. Of these, polyoxyethylene alkylaryl ether is preferable. These nonionic dispersants can be used alone or in combination of two or more.

  A pigment derivative type dispersant 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 production method of the present invention, it is also preferable to use a pigment dispersant containing an amino group as the dispersant. 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.

The dispersant having an amino group used in the production method of the present invention is not limited thereto, but is selected from the compounds represented by the following general formulas (D1), (D3), and (D4). Can be used.
<1. Compound represented by general formula (D1)>

  In general formula (D1), A represents a component capable of forming an azo dye together with XY. A can be arbitrarily selected as long as it is a compound capable of forming an azo dye by coupling with a diazonium compound. Specific examples of A will be shown below, but the present invention is not limited thereto.

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

  In General Formula (D1), Y represents a group represented by the following General Formula (D2).

In general formula (D2), Z represents a lower alkylene group. Z is represented as — (CH ₂ ) _b —, wherein b represents an integer of 1 to 5, preferably 2 or 3. In General Formula (D2), —NR ₂₁ represents a lower alkylamino group or a 5- to 6-membered saturated heterocyclic group containing a nitrogen atom. When —NR ₂₁ represents a lower alkylamino group, it is represented as —N (C _r H _{2r + 1} ) ₂ , r represents an integer of 1 to 4, preferably 1 or 2. When —NR ₂₁ represents a 5- to 6-membered saturated heterocyclic group containing a nitrogen atom, any heterocyclic group represented by the following structural formula is preferable.

In the general formula (D2), Z and —NR ₂₁ may each have a lower alkyl group or an alkoxy group as a substituent. In the general formula (D2), a represents 1 or 2, preferably 2.

  Specific examples of the compound represented by the general formula (D1) are shown below, but the present invention is not limited to these specific examples.

  The compound represented by the general formula (D1) can be synthesized by, for example, a method described in JP-A No. 2000-239554.

<2. Compound represented by general formula (D3)>

In general formula (D3),
Q is an anthraquinone compound dye, azo compound dye, phthalocyanine compound dye, quinacridone compound dye, dioxazine compound dye, anthrapyrimidine compound dye, ansanthrone compound dye, indanthrone compound dye, flavanthrone compound dye, pyranthrone compound dye, perinone compound It represents an organic dye residue selected from a dye, a perylene compound dye, and a thioindigo compound dye. Among them, an azo compound dye or a dioxazine compound dye is preferable, and an azo compound dye is more preferable.
X ₁ represents —CO—, —CONH—Y ₂ —, —SO ₂ NH—Y ₂ —, or —CH ₂ NHCOCH ₂ NH—Y ₂ —, and is —CO— or —CONH—Y ₂ —. It is preferable.
Y ₂ represents an alkylene group or an arylene group that may have a substituent, and among them, phenylene, toluylene, or hexylene is preferable, and phenylene is more preferable.
R ₁₁ and R ₁₂ may each independently form a substituted or unsubstituted alkyl group or a heterocyclic group containing at least a nitrogen atom with R ₁₁ and R ₁₂ . Of these, a methyl group, an ethyl group, a propyl group, or a pyrrolidinyl group including a nitrogen atom is preferable, and an ethyl group is more preferable.
Y ₁ represents —NH— or —O—.
Z ₁ represents a hydroxyl group or a group represented by the general formula (D3a), or when n 1 is 1, —NH—X ₁ -Q may be used. m1 represents the integer of 1-6, and 2-3 are preferable. n1 represents the integer of 1-4, and 1-2 are preferable.

In General Formula (D3a), Y ₃ represents —NH— or —O—, and m1, R ₁₁ , and R ₁₂ have the same meaning as those in General Formula (D3).

  More specifically, the compound represented by the general formula (D3) is represented by the following general formula, for example.

In general formulas (D3-1) to (D3-6), Q, m1, n1, R ₁₁ , and R ₁₂ have the same meanings as those in general formula (D3). Specific examples of the compound represented by formula (D3) are shown below, but the present invention is not limited thereto. In the formula, Cu-Pc represents copper phthalocyanine.

Compound represented by the general formula (D3), for example R ₁₁ and alcohol compounds having amine compound with R ₁₁ and R ₁₂ having the R ₁₂ and reacted with a halogenated triazine compound, a dye compound resulting intermediate Can be obtained by reacting. The description in Japanese Patent Publication No. 5-72943 can also be referred to.

<3. Pigment Dispersant Containing Graft Copolymer>
In the production method of the present invention, it is also preferable to use a dispersant 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 pigment 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 pigment nanoparticles may not be prevented. In some cases, the proportion of the contained monomer is reduced, the adsorption ability to the pigment 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 the aggregation of pigment 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 represents a phenyl group, a phenyl group having an alkyl group having 1 to 4 carbon atoms, or —COOR ⁶⁴ (where R ⁶⁴ is an alcoholic hydroxyl group having 1 to 6 carbon atoms, or an alkyl which may be substituted with a halogen atom). 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 ). ^{Wherein, R 23} and ^{R 24} represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 6 carbon atoms. 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 . R ³² has the same meaning as R ²² . X ³ has the same meaning as X ² .

In the general formula (E4), R ⁴¹ has the same meaning as R ²¹ . X ⁴ is synonymous with X ² , and —N (R ⁴³ ) (R ⁴⁴ ) (where R ⁴³ and R ⁴⁴ are synonymous with R ²³ and R ²⁴ ), or —R ⁴⁵ —. N (R ⁴⁶ ) (R ⁴⁷ ) (where R ⁴⁵ , R ⁴⁶ and R ⁴⁷ have the same meanings as R ²⁵ , R ²⁶ and R ²⁷ , respectively) is preferable.

  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 Suitable 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 them, 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 alkyl aryl 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 weight% is preferable, for example. When the content is less than 5% by weight, the physical properties of the coating film may not be controlled, and when it exceeds 70% by weight, 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 pigment particles, the content of the dispersant is preferably in the range of 0.1 to 1000 parts by weight, more preferably 100 parts by weight of the pigment. 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 dispersing agent may be used independently or may be used in combination of multiple things.

[Manufacturing equipment]
In the production method of the present invention, a preferred embodiment of the production apparatus used for forming the organic nanoparticles will be described, but the present invention is not construed as being limited thereto.

(Manufacturing device example 1)
FIG. 1-1 is a schematic view of a production apparatus used as an embodiment in the production method of the present invention. In FIG. 1, the organic pigment solution is continuously supplied into the container 11 through the supply pipe 14. Here, the container 11 contains a precipitation solvent 11a, and the bulk precipitation solvent is always convected by the action of stirring.
FIG. 1-2 is a schematic view of a production apparatus used as another more preferable embodiment of the present invention. In the production apparatus of FIG. 1-1, a mixing chamber (stirring region) 13 is provided in a container 11. The mixing chamber 13 is provided below the surface of the precipitation solvent, and the inside thereof is filled with the precipitation solvent. Further, the bulk precipitation solvent in the reaction vessel 11 is constantly convected across the mixing chamber 13 from below to above (in the direction of the arrow in the figure) by the action of stirring in the mixing chamber 13. .

  1-3 is an enlarged partial cross-sectional view schematically showing the mixing chamber 13 in an enlarged manner as an embodiment of the manufacturing apparatus of FIG. 1-2. The organic pigment solution is supplied from the supply pipe 14 into the mixing chamber 13. The mixing chamber 13 is formed by a casing 17 formed of a rectangular cylinder having a constant cross-sectional area, and the upper end of the casing 17 is an open end (open portion), and a circular hole 18 is provided at the lower end. The precipitation solvent is connected to the bulk precipitation solvent outside the stirring region (in the configuration shown in the figure, the region other than the mixing chamber 13 in the precipitation solvent 11a is outside the stirring region and is also referred to as the non-stirring region). It is supposed to be. Here, the organic pigment solution supply pipe 14 is provided in a wall constituting the lower end of the casing 17 and opens toward the circular hole. A stirring blade 12 is provided in the mixer 13. The stirring blade is attached to a shaft 15 and is rotated by a motor 16. By the rotation of the stirring blade 12, the solvent for precipitation constantly circulates through the circular hole 18 from the lower side to the upper side in the mixer 13.

The stirring blade 12 provided in the mixing chamber 13 must produce a desired mixing strength in the mixing chamber. This mixing strength is presumed to be an important operating factor for the size of the droplet when the organic pigment solution is mixed.
In addition, the stirring blade 12 is configured so that organic nanoparticles generated in the mixing space stay in the mixing chamber 13 so as to be combined with other organic nanoparticles to become larger particles or to be supplied to the mixing chamber 13. In order to prevent large particles from being generated by exposure to a solution, the organic nanoparticles that have been generated can be quickly extracted and quickly discharged out of the mixing chamber 13. preferable.
As long as the said objective is achieved as the stirring blade 12, what kind of thing may be sufficient, for example, a turbine type, a fan turbine type, etc. may be used.
Moreover, it is preferable that the casing 17 is comprised by the square cylinder as mentioned above. By doing in this way, the angle of the casing 17 disturbs the flow created by the stirring blade 12, and the mixing effect can be further enhanced without requiring an additional material such as a baffle plate.

  1-4 is an enlarged partial cross-sectional view of a mixer having two stirring blades (mixing stirring blade 19a and discharging stirring blade 19b) in the mixing chamber as another embodiment of the manufacturing apparatus of FIG. 1-2. is there. By providing two stirring blades in this way, the ability to control the mixing strength and the ability to discharge the generated organic pigment particles to the outside of the mixer can be selected independently. It is possible to operate by setting the circulation amount to a desired value independently.

(Manufacturing device example 2)
FIG. 2 is a cross-sectional view schematically showing another embodiment of the production apparatus used in the production method of the present invention. In FIG. 2, the organic pigment solution and the precipitation solvent are continuously supplied into the agitation tank 21a through supply pipes 24a and 24b, respectively. The organic pigment particles generated in the agitation tank 21a stay in the agitation tank 21a, so that the organic pigment particles are combined with other organic pigment particles to become larger particles or exposed to the organic pigment solution supplied from the supply pipes 24a and 24b. The generated organic pigment particle dispersion liquid is quickly drawn out from the discharge pipe 23 so that the large particles are not generated due to the large particles.

FIG. 3 is a sectional view schematically showing still another embodiment of the apparatus used in the production method of the present invention. In the manufacturing apparatus of FIG. 3, the stirring device 50 includes two liquid supply ports 32 and 33 through which the organic pigment solution and the precipitation solvent are respectively introduced, and a liquid discharge port 36 through which the mixed liquid after the stirring process is discharged. A cylindrical stirring tank 38, and a pair of stirring blades 41 and 42 which are stirring means for controlling the stirring state of the liquid in the stirring tank 38 by being driven to rotate in the stirring tank 38. .
The agitation tank 38 includes a cylindrical tank body 39 whose central axis is directed in the vertical direction, and a seal plate 40 serving as a tank wall that closes the upper and lower opening ends of the tank body 39. The agitation tank 38 and the tank body 39 are made of a nonmagnetic material having excellent magnetic permeability. The two liquid supply ports 32 and 33 are provided at positions near the lower end of the tank body 39, and the liquid discharge port 36 is provided at a position near the upper end of the tank body 39.

  Then, the pair of stirring blades 41 and 42 are disposed apart from the upper and lower ends facing each other in the stirring tank 38 and are driven to rotate in opposite directions. Each of the stirring blades 41 and 42 constitutes a magnetic coupling C with an external magnet 46 disposed outside the tank wall (seal plate 40) in which the respective stirring blades 41 and 42 are close to each other. That is, the blades 41 and 42 are coupled to the external magnets 46 by magnetic force, and are rotated in opposite directions by driving the external magnets 46 with independent motors 48 and 49.

A pair of stirring blades 41 and 42 arranged opposite to each other in the tank 38 allows the stirring flows having different directions to flow into the tank 38 as indicated by the wavy arrow (X) and the solid arrow (Y) in FIG. Form. And since the stirring flow which each stirring blade 41 and 42 forms differs in the flow direction, it collides with each other, the high speed turbulent flow which accelerates | stimulates stirring in the tank 38 is produced | generated in the tank 38, Is prevented from becoming steady, and even when the rotation speed of the stirring blades 41 and 42 is increased, the formation of a cavity around the rotation axis of the stirring blades 41 and 42 is prevented, and at the same time, the stirring action is sufficiently achieved. Therefore, it is possible to prevent a disadvantage that a steady flow that flows in the tank 38 along the inner peripheral surface of the stirring tank 38 is formed. Therefore, the processing speed can be easily improved by increasing the speed of rotation of the stirring blades 41 and 42. Further, at this time, the liquid flow in the tank 38 becomes steady, and liquid with insufficient stirring and mixing is obtained. It is possible to prevent discharge and prevent deterioration in processing quality.
In addition, since the stirring blades 41 and 42 in the stirring tank 38 are connected to the motors 48 and 49 disposed outside the stirring tank 38 by the magnetic coupling C, the rotating shaft is attached to the tank wall of the stirring tank 38. Since there is no need for insertion, the stirring tank 38 can be made into a closed container structure without the insertion part of the rotating shaft, so that leakage of the stirred and mixed liquid to the outside of the tank can be prevented and at the same time the lubricating liquid (seal for the rotating shaft) It is possible to prevent deterioration in processing quality due to mixing of the liquid) into the liquid in the tank 38 as an impurity.

In the production method of the present invention, the production apparatus having these configurations can be used to produce organic nanoparticles not only in a batch method but also in a continuous flow method, and can be used for mass production. In addition, since the generated organic nanoparticle dispersion liquid is quickly discharged, the ratio of the organic pigment solution supplied to the stirring tank and the precipitation solvent liquid can be kept constant. For this reason, it becomes possible to make the solubility of the organic pigment of a dispersion liquid constant from the start of manufacture to the end of manufacture, and monodispersed organic nanoparticles can be manufactured stably.
Furthermore, the liquid flow in the tank becomes steady and the organic nanoparticle dispersion liquid with insufficient stirring and mixing is prevented from being discharged, and the lubricating liquid (seal liquid) for the rotating shaft is an impurity in the tank. By preventing mixing in the liquid, monodispersed organic nanoparticles can be produced more stably.

(Manufacturing device example 3)
As a device used in the production method of the present invention, a production method in which stirring is performed using blades having shearing force, which is still another embodiment, will be described.
The shearing force referred to in the present invention is a shearing force exerted on the droplets (droplets) generated by the stirring blade after the organic pigment solution is mixed in the precipitation solvent.
The shape of the stirring section that can be used in the present invention is not particularly limited as long as it can be subjected to a high shearing force, but generally includes paddle blades, turbine blades, screw blades, fowler blades, etc., preferably dissolver blades, An agitating, emulsifying, and dispersing machine of an agitating part composed of a turbine part that can rotate and a fixed stator part that is positioned with a slight gap around it is preferable.
The dissolver blade is a special stirring blade having a function capable of forming a high shearing force. One example of the dissolver blade is schematically shown in a front view in FIG. 4-1, and a drawing substitute photograph is shown in FIG. 4-2.
Further, an apparatus having a stirring unit composed of a rotatable turbine unit as shown in FIG. 5 and a fixed stator unit positioned with a slight gap around the turbine unit is also preferably used. Examples of the disperser include Hiscotron manufactured by Microtech / Nichion Co., Ltd. and T.K. Examples include K homomixer and ULTRA-TURRAX manufactured by IKA.

  The stirring speed varies depending on the viscosity of the solvent for precipitation, the temperature, the type of surfactant and the amount added, but is preferably 100 to 10,000 rpm, more preferably 150 to 8000 rpm, and particularly preferably 200 to 6000 rpm. If the rotational speed is too low, the stirring effect is not sufficiently exhibited. Conversely, if the rotational speed is too high, bubbles are entrained in the solvent for precipitation, which is not preferable.

[concentrated]
In the method for producing organic pigment nanoparticles of the present invention, a mixed liquid (hereinafter referred to as “organic nanoparticle dispersion liquid”) in which an organic pigment solvent and an organic solvent for precipitation are mixed to precipitate organic pigment nanoparticles. ) Can be concentrated on an industrial scale to produce concentrates suitable for color filter coating liquids and ink jet inks.
Below, the concentration method is demonstrated.
The concentration method is not particularly limited as long as the organic nanoparticle liquid can be concentrated. For example, an extraction solvent is added to and mixed with the organic nanoparticle dispersion, and the organic nanoparticles are concentrated and extracted into the extraction solvent phase. The solution is filtered through a filter or the like to make a concentrated nanoparticle solution, the organic nanoparticle is precipitated and concentrated by centrifugation, the salt is concentrated by ultrafiltration, and the solvent is sublimated by vacuum freeze-drying. A method of concentrating, a method of drying and concentrating the solvent by heating or reduced pressure, and the like are preferable. Or a combination thereof is very preferably used.
The concentration of the organic nanoparticles after concentration is preferably 1 to 100% by mass, more preferably 5 to 100% by mass, and particularly preferably 10 to 100% by mass.

Hereinafter, a method of concentration extraction will be described.
The extraction solvent used for the concentration extraction is not particularly limited, but does not substantially mix with the dispersion solvent (for example, an aqueous solvent) of the organic nanoparticle dispersion (in the present invention, substantially does not mix) This means that the solubility is low, preferably 50% by mass or less, and more preferably 30% by mass or less, although there is no particular lower limit to this amount, it is 1% by mass or more considering the solubility of ordinary solvents. It is preferable to use a solvent that forms an interface when allowed to stand after mixing, and this extraction solvent also has weak aggregation (such as milling or high-speed stirring) in which organic nanoparticles can be redispersed in the extraction solvent. It is preferable that the solvent be a floc that can be re-dispersed without applying a high shearing force. The organic nanoparticles are preferably wetted with an extraction solvent, while a dispersion solvent such as water can be easily removed by filter filtration, etc. As the extraction solvent, an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, Aliphatic compound solvents are preferred, ester compound solvents, aromatic compound solvents or aliphatic compound solvents are more preferred, and ester compound solvents are particularly preferred.

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

The amount of the extraction solvent is not particularly limited as long as the organic nanoparticles can be extracted, but is preferably smaller than the organic nanoparticle dispersion in consideration of concentration and extraction. When this is shown by volume ratio, when the organic nanoparticle dispersion liquid is 100, the extraction solvent to be added is preferably in the range of 1 to 100, more preferably in the range of 10 to 90, and 20 to 80. The range of is particularly preferable. If it is too much, it will take a lot of time for concentration, and if it is too little, extraction will be insufficient and nanoparticles will remain in the dispersion solvent.
After adding the extraction solvent, it is preferable to stir and mix so as to be in sufficient contact with the dispersion. 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 an extraction solvent, It is preferable that it is 1-100 degreeC, and it is more preferable that it is 5-60 degreeC. Any device may be used for adding and mixing the extraction solvent as long as each step can be preferably performed. For example, a separation funnel type device can be used.

  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.

  FIG. 6 shows a configuration example of an apparatus for performing ultrafiltration. As shown in FIG. 6, this apparatus comprises a tank 81 containing a fatty acid silver dispersion, a circulation pump 82 for circulating the dispersion in the tank 81, and a dispersion introduced by the circulation pump 82. It has an ultrafiltration module 83 that removes by-product inorganic salts as permeate. The dispersion from which the permeated water has been separated is returned to the tank 81 again, and the same operation is repeated until the predetermined purpose of removing the by-product inorganic salt is achieved. Further, this apparatus is provided with a replenishment pure water measurement flow meter 84 used to replenish a certain amount of solvent lost by permeate as pure water, and is used to determine the replenishment amount of pure water. A permeated water flow meter 85 is installed. Further, a reverse cleaning pump 86 for introducing water for diluting the permeated water is installed.

  Ultrafiltration membranes, such as flat plate type, spiral type, cylindrical type, hollow fiber type and hollow fiber type, which are already incorporated as modules, are available from Asahi Kasei Corporation, Daicel Chemical Co., Ltd., Toray Industries, Inc. ( Although it is commercially available from Nitto Denko Corporation, a spiral type or a hollow fiber type is preferred from the viewpoint of the total membrane area and detergency. In addition, the molecular weight cut off as an index of the threshold value of the component that can permeate the membrane needs to be determined from the molecular weight of the dispersant used, but preferably 5,000 or more and 50,000 or less, More preferred is 5,000 or more and 15,000 or less.

  In order to isolate | separate the dispersion | distribution solvent and concentrated extract of organic nanoparticle dispersion liquid, it is preferable to filter-filter. As the filter filtration device, for example, a device such as pressure filtration can be used. Preferred filters include nanofilters and ultrafilters. It is preferable to remove the remaining dispersion solvent by filter filtration and further concentrate the organic nanoparticles in the concentrated extract to obtain a concentrated nanoparticle solution.

  The method of lyophilization 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 lyophilized 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, monocooling 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 centrifugation will be described below.
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 drying will be described below.
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.

  According to the concentration method as described above, the organic nanoparticles can be efficiently concentrated from the organic nanoparticle dispersion. Regarding the concentration ratio, for example, when the concentration of the nanoparticles in the organic nanoparticle dispersion as a raw material is 1, the concentration in the concentrated organic nanoparticle paste is preferably about 100 to 3000 times, more preferably about 500 to 2000 times. Can be concentrated.

[Redistribution]
In the production method of the present invention, it is preferable to redisperse the organic particles that are in an aggregated state by the above concentration (in the present invention, redispersion refers to increasing the degree of dispersion by deaggregating particles in the dispersion liquid). Sometimes called fine dispersion).
The organic particles contained in the organic particle liquid concentrated by the extraction solvent, centrifugation, and drying described above are usually aggregated by the concentration. At this time, in order to enable rapid filter filtration and obtain a good dispersion state again, it is preferable to obtain 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. Even in such an aggregated organic particle (in the present invention, an aggregated organic particle is a particle in which organic particles such as an aggregate are gathered by a secondary force. When the primary particle is nanometer size, the aggregated nanoparticle According to the production method of the present invention, the organic particles can be suitably finely dispersed by containing a polymer compound having a weight average molecular weight of 1000 or more in the aggregated organic particle liquid (this book). In the invention, the agglomerated organic particle liquid means a liquid containing the agglomerated organic particles in the liquid, and the agglomerated organic particles may be contained even in a dispersion, a concentrated liquid, a paste, a slurry, or the like.

Next, a polymer compound that can be preferably used in the production method of the present invention (in the present invention, “polymer compound” refers to an organic compound having a weight average molecular weight of 1000 or more, and there is no particular upper limit, but a weight average molecular weight of 500, 000 or less is practical, preferably 100,000 or less, and more preferably 50,000 or less.).
The polymer compound that can be preferably used in the production method of the present invention has a weight average molecular weight of 1000 or more, and is preferably a polymer compound represented by the following general formula (1).

In the general formula (1), 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 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 ) (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, or 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. It represents 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.

As the “monovalent organic group having a urea group”, for example, —NHCONHR ¹⁵ (where 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.
Examples of the “monovalent organic group having a urethane group” include —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. .

  Further, the organic dye structure or the 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 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, piperidi , Dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, anthraquinone Is 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 configured by combining the structural units.

When R ¹⁸ 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 an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group. A hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acetoxy group and the like, an acyloxy group having 1 to 6 carbon atoms, a methoxy group, an alkoxy group having 1 to 6 carbon atoms such as an ethoxy group, Examples include 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, and the like. .

In the general formula (1), R ¹ represents an (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 of the above (t-1) to (t-34) or a group formed by combining the structural units (which may form a ring structure). be able to.

When R ¹ 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 an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group. A hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acetoxy group and the like, an acyloxy group having 1 to 6 carbon atoms, a methoxy group, an alkoxy group having 1 to 6 carbon atoms such as an ethoxy group, Examples include 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, and the like. .

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 the above-mentioned t-3, 4, 7-18, 22-26, 32, 34, or groups configured by combining the structural units.

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, and an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group. A hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acetoxy group and the like, an acyloxy group having 1 to 6 carbon atoms, a methoxy group, an alkoxy group having 1 to 6 carbon atoms such as an ethoxy group, Examples include 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, and the like. .

In said general formula (1), m represents 1-8. As m, 1-5 are preferable, 1-3 are more preferable, and 1-2 are especially preferable.
N represents 2-9. As n, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

In the general formula (1), P ¹ represents a polymer skeleton and can be selected from ordinary polymers according to the purpose and the like.
Among polymers, in order to constitute a polymer skeleton, a polymer or copolymer of vinyl monomers, ester polymers, ether polymers, urethane polymers, amide polymers, epoxy polymers, silicone polymers, and these Modified product or copolymer [eg, 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 or copolymers thereof. At least one kind is more preferable, and a polymer or copolymer of vinyl monomers is particularly preferable.
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 (1), the polymer compound represented by the following general formula (2) is more preferable.

In the general formula (2), A ² has the same meaning as A ¹ in the general formula (1), and the specific preferred embodiment thereof is also the same. As a specific example 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.
Furthermore, as A ^2, 1 monovalent organic group is preferably represented by the general formula (4), details and specific examples of the organic groups are the same for the preferred embodiment.

In the general formula (2), 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. Specific examples include the same structural unit as described above or a group constituted by combining the structural units.

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

  Among the above, from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents, the above (r-1), (r-2), (r-10), (r-11), ( The groups of r-16) and (r-17) are 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, and 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 An alkoxy group of 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a cyclohexyloxycarbonyl group, a cyano group, a carbonate ester group such as t-butyl carbonate, Etc.

In the general formula (2), 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, —O—, —S—, —C (═O) —, —N (R ¹⁹ ) —, —SO—, —SO ₂ —, —CO ₂ —, —N (R ²⁰ ) SO ₂ —, or these As a preferred example, a divalent group in which two or more of the above groups are combined can be cited (R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Of these, an organic linking group is preferred.

R ⁴ includes a linear or branched alkylene group, aralkylene group, —O—, —C (═O) —, —N (R ¹⁹ ) —, —SO ₂ —, —CO ₂ —, —N ( R ²⁰ ) SO ₂ — or a divalent group in which two or more of these groups are combined is more preferable, and a linear or branched alkylene group, aralkylene group, —O—, —C (═O) —, —N (R ¹⁹ ) —, —CO ₂ —, or a divalent group in which two or more of these groups are combined is particularly preferable.

As R ⁵ , a single bond, a linear or branched alkylene group, an aralkylene group, —O—, —C (═O) —, —N (R ¹⁹ ) —, —SO ₂ —, —CO ₂ —, —N (R ²⁰ ) SO ₂ — or a divalent group in which two or more of these groups are combined is more preferable, and a linear or branched alkylene group, aralkylene group, —O—, —C (═O) — , —N (R ¹⁹ ) —, —CO ₂ —, or a divalent group obtained by combining two or more of these groups is particularly preferable.

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 (2), 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.

P ² in the general formula (2) represents a polymer skeleton and can be selected from ordinary polymers according to the purpose and the like. The preferred embodiment of the polymer, has the same meaning as P ¹ in Formula (1), the same applies to its preferred embodiment.

Among the polymer compounds represented by the general formula (2), 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 ). —, —CO ₂ —, or a divalent organic group obtained by combining two or more of these groups, wherein R ⁵ is a single bond, an ethylene group, a propylene group, or the following general formula (sa) or (s a linking group represented by -b), polymer or copolymer of P ² is vinyl monomers, ester polymers, ether-based polymer, a urethane polymer, or their modified products, y is 1 A high molecular compound in which x is 2 and x is 3 to 6 is particularly preferable. In the following groups, R ²¹ represents a hydrogen atom or a methyl group, and l represents 1 or 2.

  The polymer compound has a weight average molecular weight of 1000 or more, preferably 1000 to 500,000, more preferably 3000 to 100,000, still more preferably 5000 to 80000, and particularly preferably 7000 to 60000 in terms of weight average molecular weight. 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 such a polymer compound is used as a pigment dispersant, good dispersibility and dispersion stability can be achieved.

The polymer compound represented by the general formula (1) (including those represented by the general formula (2)) 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 and 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 in which 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) is polymerized.
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 of reacting 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) 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 (2)) 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 (3) as a chain transfer agent.

In the general formula (3), 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 (2), 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 include methylstyrene, hydroxystyrene protected with a group that can be deprotected 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 polymerization is performed 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 (3) 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 directly reacting 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 How to react

Suitable examples of the “functional group capable of reacting with a mercapto group” in Method 7 include acid halides, alkyl halides, isocyanates, and carbon-carbon double bonds.
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” include the following compounds.

  Among these, (u-1), (u-2), (u-10), (u-11), (u) from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents. -16) and (u-17) 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 “compounds having 3 to 10 mercapto groups in one molecule”, “acidic groups, groups having basic nitrogen atoms, urea groups, urethane groups, 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 depending on the solubility of the compound having a group (for example, a carbon-carbon double bond) and the radical addition reaction product to be generated. 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 (1) 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は水素原子又は炭素原子数１〜５のアルキル基を表す。）

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

（Ｒ_２は水素原子又は炭素原子数１〜５のアルキル基を表す。Ｒ_３は下記一般式（ＩＩＩ）で表される基を表す。）

(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は水素原子、炭素原子数１〜５のアルキル基、ヒドロキシ基、炭素原子数１〜５のヒドロキシアルキル基、又は炭素原子数６〜２０のアリール基を表す。Ｒ_５及びＲ_６はそれぞれ水素原子又は炭素原子数１〜５のアルキル基を表す。ｉは１〜５の数を表す。）

(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, i represents a number of 1 to 5)

（Ｒ_７は水素原子又は炭素原子数１〜５のアルキル基を表す。Ｒ_８は下記一般式（Ｖ）で表される基を表す。）

(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は炭素原子数２〜５のアルキル基又は炭素原子数６〜２０のアリール基を表す。Ｒ_１０及びＲ_１１は水素原子又は炭素原子数１〜５のアルキル基を表す。ｊは１〜５の数を表す。）
また、（Ａ）カルボキシル基を有する化合物から導かれた繰り返し単位と、前記（Ｂ）カルボン酸エステル基を有する化合物から導かれた繰り返し単位との重合比率としていえば、繰り返し単位（Ａ）の全繰り返し単位数に対する数量比％が３〜４０であることが好ましく、５〜３５であることがより好ましい。
本発明の製造方法において高分子の分子量とは、特に断らない限り、重量平均分子量をいう。高分子の分子量の測定方法としては、クロマトグラフィー法、粘度法、光散乱法、沈降速度法等が挙げられる。本発明では、特に断らない限りクロマトグラフィー法により測定した重量平均分子量を用いる。

(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. J represents 1 Represents a number of ~ 5.)
Further, in terms of the polymerization ratio of the repeating unit derived from the compound having (A) a carboxyl group and the repeating unit derived from the compound having the (B) carboxylic ester group, all of the repeating units (A) can be obtained. The quantity ratio% to the number of repeating units is preferably 3 to 40, more preferably 5 to 35.
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.

The polymer compound may be water-soluble or oil-soluble, and may be water-soluble and oil-soluble.
The polymer compound may be added in a solution in an aqueous solvent or an organic solvent, in a solid state, or a combination thereof. As a method of adding in a solution dissolved in a solvent, for example, a method of adding to an aggregated organic particle liquid in a state dissolved in the same solvent as the solvent of the aggregated organic particle liquid, compatible with the solvent of the aggregated organic particle liquid, The method of adding in the state melt | dissolved in a different solvent is mentioned. The concentration of the polymer compound when added in a solution dissolved in a solvent is not particularly limited, but is preferably 1 to 70% by mass, more preferably 2 to 65% by mass, and particularly preferably 3 to 60% by mass.

  In the production method of the present invention, the polymer compound is added during the formation of organic nanoparticles by reprecipitation (or before and after), during extraction or concentration (or before and after), and during dispersion of aggregated organic particles after concentration ( Or before and after that), after the completion of those steps, it may be added to any of these, or a combination thereof. Moreover, you may contain a high molecular compound in a composition as a binder mentioned later. In the production method of the present invention, the polymer compound is preferably contained in the organic solvent for precipitation.

The amount of the polymer compound added is preferably 0.1 to 1000 parts by mass, more preferably 5 to 500 parts by mass, and more preferably 10 to 300 parts by mass, when the organic particles contained in the aggregated organic particles are 100 parts by mass. Part is particularly preferred.
Examples of the polymer compound having a molecular weight of 1000 or more include, for example, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, and polyvinyl alcohol-partial formalized product. , Polyvinyl alcohol-partially butyralized product, vinylpyrrolidone-vinyl acetate copolymer, polyethylene oxide / propylene oxide block copolymer, polyamide, cellulose derivative, starch derivative and the like. In addition, natural polymer compounds such as alginate, gelatin, albumin, casein, gum arabic, tonganto gum and lignin sulfonate can also be used.
Examples of the polymer compound having an acidic group include polyvinyl sulfate and condensed naphthalene sulfonic acid.

Examples of the polymer compound having a carboxyl group include polyacrylic acid, polymethacrylic acid, and cellulose derivatives having a carboxyl group in the side chain. A copolymer compound containing (A) at least one repeating unit derived from a compound having a carboxyl group and (B) at least one repeating unit derived from a compound having a carboxylic ester group is disclosed in 59-44615, JP-B 54-34327, JP-B 58-12577, JP-B 54-25957, JP-A 59-53836, and JP-A 59-71048. Examples thereof include methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, and partially esterified maleic acid copolymers. Further, as particularly preferred examples, acrylic acid-acrylic acid ester copolymers, methacrylic acid-acrylic acid ester copolymers, acrylic acid-methacrylic acid ester copolymers, methacrylic acid-described in US Pat. No. 4,139,391 Mention may be made of methacrylic acid ester copolymers, multi-component copolymers of acrylic acid or methacrylic acid, acrylic acid esters or methacrylic acid esters, and other vinyl compounds.
Examples of vinyl compounds include styrene or substituted styrene (eg, vinyl toluene, vinyl ethyl benzene), vinyl naphthalene or substituted vinyl naphthalene, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, and the like, and styrene is preferred.
These polymer compounds may be used alone or in combination of two or more, or may be used in combination with a compound having a molecular weight of less than 1000.

  In the production method of the present invention, the organic nanoparticle dispersion preferably contains 60% by mass or more of an organic solvent, and more preferably 65% by mass or more. There is no restriction | limiting in particular as an organic solvent, It can select suitably from normal things. For example, an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, an aliphatic compound solvent, and a ketone compound solvent are preferable, and an ester compound solvent and a ketone compound solvent are particularly preferable. These may be used alone or in combination of two or more.

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

[Organic nanoparticle dispersion composition]
Next, the aspect which makes a composition when using the organic nanoparticle obtained by the manufacturing method of this invention for a color filter, an inkjet ink, etc. is demonstrated in detail. The organic nanoparticles can be used, for example, in a state dispersed in a vehicle. The vehicle refers to a portion of a medium in which a pigment is dispersed when it is in a liquid state, a portion that is liquid and binds to the pigment to harden a coating film (binder). And a component (organic solvent) to be dissolved and diluted. In the present invention, the binder used at the time of nanoparticle formation and the binder used for redispersion may be the same or different, and may be distinguished as a nanoparticle forming binder and a redispersed binder, respectively. .
The concentration of the organic nanoparticles in the dispersion composition of the organic nanoparticles after redispersion is appropriately determined according to the purpose, but preferably the organic nanoparticles are 2 to 30% by mass with respect to the total amount of the dispersion composition. More preferably, it is 4-20 mass%, and it is especially preferable that it is 5-15 mass%. In the case of being dispersed by the vehicle as described above, the amount of the binder and the dissolved dilution component is appropriately determined depending on the kind of the organic pigment, etc. Preferably, it is 3-20 mass%, More preferably, it is 5-15 mass%. It is preferable that a dissolution dilution component is 5-80 mass%, and it is more preferable that it is 10-70 mass%.

In the concentrated and extracted nanoparticle liquid, as described above, in order to enable rapid filter filtration, the organic nanoparticles are preferably aggregated by concentration, and concentrated by centrifugation or drying. Aggregation is preferred.
As a method for finely dispersing such aggregated 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 disperser 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. In addition, a high-pressure dispersion method and a dispersion method using fine particle beads are also preferable.

<1> Dispersion Method As a preferred method for producing the organic nanoparticle dispersion composition, the viscosity at 25 ° C. after kneading and dispersing the colorant with the resin component is 10,000 mPa · s or more, desirably 100,000 mPa · s or more. So that the viscosity after the fine dispersion treatment is 1,000 mPa · s or less, preferably 100 mPa · s or less. A method of fine dispersion treatment is preferred.
The machines used in the kneading and dispersing 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 omit the kneading and dispersing process. In that case, beads are dispersed with a pigment, a dispersant or a surface treatment agent, and the acrylic copolymer and solvent in the present invention.
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 kneading and dispersing, 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.

<2> Examples of Dispersing Agent A normal pigment dispersant or surfactant can be added to the organic nanoparticle dispersion composition for the purpose of improving the dispersibility of the organic nanoparticles. As these dispersants, many types of compounds are used. For example, phthalocyanine derivatives (commercially available products 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 suitable. Can be used.
It is also preferred to use again the compound shown in the section of [Dispersant] as a dispersant used for forming the organic nanoparticles during redispersion.

  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 nanoparticle dispersion composition or a colored photosensitive resin composition to be described later are reduced to a nanometer size (for example, 10 to 100 nm). Regardless, it can be concentrated and redispersed. For this reason, when used in a color filter, the optical density is high, the uniformity of the filter surface is excellent, the contrast is high, and the noise of the image can be reduced.
Furthermore, the organic nanoparticles contained in the organic nanoparticle dispersion composition and the colored photosensitive composition can be finely dispersed in a highly and uniform manner, so that a high color density can be achieved with a thin film thickness. For example, a color filter or the like can be thinned.
In addition, the organic nanoparticle dispersion composition and the colored photosensitive resin composition are excellent as an image forming material for producing, for example, a color proof or a color filter by including a pigment exhibiting a clear color tone and high coloring power. ing.
Furthermore, for 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) that is soluble in an alkaline aqueous solution It can be used and can meet environmental requirements.
In addition, organic solvents with appropriate drying properties can be used as the solvent (dispersion medium for pigments) used in the organic nanoparticle dispersion composition and the colored photosensitive resin composition, and satisfy the requirements in terms of drying after coating. can do.

[Colored photosensitive resin composition]
The colored photosensitive resin composition using the pigment nanoparticles obtained by the production method of the present invention comprises at least (a) organic nanoparticles, (b) a binder, (c) a polyfunctional monomer, and (d) photopolymerization. Contains an initiator or photoinitiator system. Hereinafter, each component of the colored photosensitive resin composition will be described.

(A) Organic nanoparticles The method for producing organic nanoparticles has already been described in detail. The content of the organic nanoparticles 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). Preferably, 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 nanoparticles (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.

(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) Multifunctional monomer The polyfunctional monomer to be contained in the colored photosensitive resin composition is preferably a polyfunctional monomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. . 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, neopentyl glycol 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 polyfunctional alcohols such as trimethylolpropane and 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 polyfunctional monomers (with a molecular weight of 200 to 1000 are preferred as the polyfunctional monomer) 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 Photopolymerization initiator or photopolymerization initiator system contained in the colored photosensitive resin composition (in the present invention, the photopolymerization initiator system is a combination of a plurality of compounds. And a vicinal polyketaldonyl compound disclosed in US Pat. No. 2,367,660 and an acyloin described in US Pat. No. 2,448,828. Ether compounds, aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, US Pat. No. 3549367, a combination of a triarylimidazole dimer and a p-aminoketone, JP-B 51-48516 Benzothiazole compounds and trihalomethyl-s-triazine compounds described in the publication, trihalomethyl-triazine compounds described in US Pat. No. 4,239,850, trihalomethyl oxadi described in US Pat. No. 4,221,976 An azole 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 it is too small, the exposure sensitivity will be too low.

(Other additives)
〔solvent〕
In the colored photosensitive resin composition, an organic solvent may be 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 -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. 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 that directly affects the film thickness of the pixel.
In the color filter or the photosensitive resin transfer material, it can be controlled to a uniform film thickness, and from the viewpoint of effectively preventing coating unevenness (color unevenness due to film thickness fluctuation), it is suitable for the colored photosensitive resin composition. It is preferable to contain a surfactant.
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 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 colorant (pigment), a colorant (dye or pigment) can be added to the colored photosensitive resin composition as necessary. 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 may contain an ultraviolet absorber as necessary. Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, nickel chelate-based, hindered amine-based compounds and the like in addition to the compounds described in JP-A-5-72724.
Specifically, phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-4′-hydroxybenzoate, 4-t-butylphenyl salicylate 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2′-hydroxy-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) -Sebakei 4-t-butylphenyl salicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinic acid-bis (2,2,6,6-tetramethyl-4-piperidenyl ) -Ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- (diethylamino) -5-triazine- 2-yl] amino} -3-phenylcoumarin and the like. As for content of a ultraviolet absorber, 5 mass% or less is preferable with respect to the resin composition whole quantity.

  Further, in the colored photosensitive resin composition, in addition to the above additives, “adhesion aid” described in JP-A-11-133600, other additives, and the like can be contained.

[Coating film of colored photosensitive resin composition]
The components contained in the coating film using the colored photosensitive resin composition are the same as those already described in the section of [Colored photosensitive resin composition]. Moreover, although the thickness of the coating film using a colored photosensitive resin composition can be suitably determined according to the use, it is preferably 0.5 to 5.0 μm, and 1.0 to 3.0 μm. It is more preferable. In a coating film using this colored photosensitive resin composition, (c) a polyfunctional monomer contained therein is polymerized to form a colored photosensitive resin composition polymerized film, and a color filter having the same can be produced. (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.

(Slit nozzle)
In addition, although the said coating film can be formed by apply | coating and drying a colored photosensitive resin composition with a normal coating method, in this invention, it has a slit-shaped hole in the part which discharges a liquid. It is preferable to apply with a slit-like nozzle. Specifically, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002-79163. Slit nozzles and slit coaters described in Japanese Patent Laid-Open No. 2001-310147 and the like are preferably used.

  As a method for applying the colored photosensitive resin composition to the substrate, spin coating is excellent in that a thin film having a thickness of 1 to 3 μm can be uniformly and highly accurately applied, and can be widely used for manufacturing color filters. . However, in recent years, with the increase in size and mass production of liquid crystal display devices, slit coating suitable for coating a substrate that is wider and larger in area than spin coating has been used in order to increase manufacturing efficiency and manufacturing cost. It has come to be adopted in the production of. From the viewpoint of liquid-saving properties, slit coating is superior to spin coating, and a uniform coating film can be obtained with a smaller amount of coating liquid.

  In slit coating, a coating head having a slit (gap) with a width of several tens of microns at the tip and a length corresponding to the coating width of a rectangular substrate is maintained at a clearance (gap) of several tens to several hundreds of microns with the substrate. On the other hand, this is a coating method in which a coating liquid supplied from a slit is applied to a substrate with a predetermined discharge amount by giving a constant relative speed between the substrate and the coating head. This slit coating is (1) less liquid loss compared to spin coating, (2) cleaning process is reduced because there is no flying of the coating liquid, and (3) the scattered liquid components are applied to the coating film again. There is an advantage that there is no mixing, (4) the tact time can be shortened because there is no start-up stop time of rotation, and (5) application to a large substrate is easy. From these advantages, slit coating is suitable for producing a color filter for a large-screen liquid crystal display device, and is expected as an advantageous coating method for reducing the amount of coating liquid.

  Since slit coating forms a coating film with a much larger area than spin coating, it is necessary to maintain a certain relative speed between the coater and the object to be coated when discharging the coating liquid from the wide slit exit. is there. For this reason, good fluidity is required for the coating liquid used in the slit coating method. In addition, the slit coating is particularly required to keep the conditions of the coating solution supplied to the substrate from the slit of the coating head constant over the entire coating width. Insufficient liquid properties such as fluidity and viscoelastic properties of the coating liquid tend to cause coating unevenness, making it difficult to keep the coating thickness constant in the coating width direction, and obtaining a uniform coating film. The problem of not being able to occur.

  For these reasons, many attempts have been made to improve the fluidity and viscoelastic properties of the coating solution in order to obtain a uniform coating film without unevenness. However, as mentioned above, the molecular weight of the polymer is reduced, a polymer with excellent solubility in the solvent is selected, various solvents are selected to control the evaporation rate, and a surfactant is used. Means have been proposed, but none were sufficient to improve the above problems.

[Photosensitive transfer material]
Next, the photosensitive transfer material will be described.
The photosensitive transfer material is preferably formed using a photosensitive resin transfer material described in JP-A-5-72724, that is, an integral film. An example of the structure of the integral film is a structure in which a temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer / protective film are laminated in this order, and the photosensitive transfer material is colored as described above. A photosensitive resin is provided by using a photosensitive resin composition.

(Temporary support)
In the photosensitive transfer material, it is necessary that the temporary support has flexibility and does not cause significant deformation, contraction or elongation even under pressure, or under pressure and heat. Examples of such a temporary support include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, a polycarbonate film, etc. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.

(Thermoplastic resin layer)
As the component used for the thermoplastic resin layer, organic polymer substances described in JP-A-5-72724 are preferable, and the polymer softening point according to the Viker Vicat method (specifically, the American Material Testing Method ASTM D1 ASTM D1235). It is particularly preferable that the softening point by the measurement method is selected from organic polymer substances having a temperature of about 80 ° C. or less. Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof. Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer Combined nylon, copolymer nylon, N-alkoxyme Le nylon, and organic polymeric polyamide resins such as N- dimethylamino nylon.

(Middle layer)
In the photosensitive transfer material, it is preferable to provide an intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application. As the intermediate layer, it is preferable to use an oxygen-blocking film having an oxygen-blocking function, which is described as “separation layer” in JP-A-5-72724. This reduces the time load and improves productivity.
The oxygen barrier film is preferably one that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution, and can be appropriately selected from ordinary ones. Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.

(Protective film)
It is preferable to provide a thin protective film on the photosensitive resin layer in order to protect it from contamination and damage during storage. The protective film may be made of the same or similar material as the temporary support, but must be easily separated from the photosensitive resin layer. For example, silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable as the protective film material.

(Method for producing photosensitive transfer material)
The photosensitive transfer material is provided with a thermoplastic resin layer by applying a coating solution (thermoplastic resin coating solution) in which a thermoplastic resin layer additive is dissolved on a temporary support, followed by drying. An intermediate layer material solution composed of a solvent that does not dissolve the thermoplastic resin layer is applied and dried on the resin layer, and then the photosensitive resin layer is prepared by applying and drying with a solvent that does not dissolve the intermediate layer. Can do.
Also, a sheet provided with the thermoplastic resin layer and the intermediate layer on the temporary support and a sheet provided with the photosensitive resin layer on the protective film are prepared, and the intermediate layer and the photosensitive resin layer are in contact with each other. In addition, a sheet provided with a thermoplastic resin layer on the temporary support and a sheet provided with a photosensitive resin layer and an intermediate layer on a protective film are prepared, and a thermoplastic resin layer is prepared. Can also be produced by bonding them so that the intermediate layer is in contact with each other.

  In the photosensitive transfer material, the thickness of the photosensitive resin layer is preferably 1.0 to 5.0 μm, more preferably 1.0 to 4.0 μm, and particularly preferably 1.0 to 3.0 μm. Further, although not particularly limited, preferred film thicknesses of other layers are 15 to 100 μm for the temporary support, 2 to 30 μm for the thermoplastic resin layer, 0.5 to 3.0 μm for the intermediate layer, and protection. The film is generally preferably 4 to 40 μm.

  In addition, although application | coating in the said preparation method can be performed with a normal coating apparatus etc., in this invention, the slit-shaped nozzle already demonstrated in the term of the coating film of a coloring photosensitive resin composition was used. It is preferable to use a coating apparatus (slit coater). Preferred specific examples of the slit coater are the same as described above.

[Color filter]
The color filter using the pigment nanoparticles obtained by the production method of the present invention can be used as one having excellent contrast. In the present invention, the contrast represents the ratio of the amount of transmitted light between two polarizing plates when the polarization axis is parallel and when it is vertical (“1990 Seventh Color Optical Conference, 512-color display 10.4. "Refer to" Color TFT for size TFT-LCD, Ueki, Koseki, Fukunaga, Yamanaka "etc.).
The high contrast of the color filter means that the bright and dark discrimination when combined with the liquid crystal can be increased, and this is a very important performance in order to replace the liquid crystal display with a CRT.

  When the color filter using the pigment nanoparticles obtained by the production method of the present invention is used for television, all the single colors of red (R), green (G), and blue (B) by the F10 light source are used. Is preferably in the range of 5 or less, more preferably within 3 or less (ΔE) from the values shown in the table below (hereinafter referred to as “target chromaticity” in the present invention). It is preferably 2 or less and particularly preferably.

x y Y
------------------------
R 0.656 0.336 21.4
G 0.293 0.634 52.1
B 0.146 0.088 6.90
------------------------

In the present invention, the chromaticity is measured with a microspectrophotometer (manufactured by Olympus Optical Co., Ltd .; OSP100 or 200), calculated as a result of the F10 light source field of view of 2 degrees, and expressed as an xyY value in the xyz color system. Further, the difference from the target chromaticity is represented by a color difference of the La ^* b ^* color system.

(Photosensitive resin layer)
The color filter can be manufactured by a method such as a method in which a photosensitive resin layer is formed on a substrate, and exposure and development are repeated for the number of colors. If necessary, the boundary may be divided by a black matrix.
In the above production method, the method for forming the photosensitive resin layer on the substrate includes (a) a method of applying each of the colored photosensitive resin compositions with a normal coating apparatus or the like, and (b) the above-described method. Examples thereof include a method of using a photosensitive transfer material and pasting with a laminator.

(A) Application by coating device When a color filter is produced, a normal coating device can be used for coating the colored photosensitive resin composition. The slit coater described in the section] can be suitably used. Note that preferred specific examples of the slit coater are the same as described above. When the photosensitive resin layer is formed by coating, the film thickness is preferably 1.0 to 3.0 μm, more preferably 1.0 to 2.5 μm, and particularly preferably 1.5 to 2.5 μm.

(B) Affixing with a laminator Using a photosensitive transfer material, a photosensitive resin layer formed in a film shape is subjected to pressure bonding or thermocompression bonding with a roller or flat plate heated and / or pressurized on a substrate to be described later. Can be pasted. Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From this point of view, it is preferable to use the method described in JP-A-7-110575. In addition, the preferable film thickness in the case of forming the photosensitive resin layer with the said photosensitive transfer material is the same as the preferable film thickness described in the item of [Photosensitive resin transfer material].

(substrate)
In the present invention, as the substrate on which the color filter is formed, for example, a transparent substrate is used, and a known glass plate such as a soda glass plate having a silicon oxide film on its surface, a low expansion glass, a non-alkali glass, a quartz glass plate, etc. Or a plastic film etc. can be mentioned.
Moreover, the said board | substrate can make favorable adhesion | attachment with a coloring photosensitive resin composition or a photosensitive transfer material by performing a coupling process previously. As the coupling treatment, a method described in JP 2000-39033 A is preferably used. In addition, although it does not necessarily limit, as a film thickness of a board | substrate, 700-1200 micrometers is generally preferable, and 500-1100 micrometers is especially preferable.

(Oxygen barrier membrane)
In the color filter, when the photosensitive resin layer is formed by application of a colored photosensitive resin composition, an oxygen blocking film can be further provided on the photosensitive resin layer, thereby increasing the exposure sensitivity. Can do. Examples of the oxygen blocking film include those already described in the section of (Interlayer) of [Photosensitive resin transfer material]. Although not particularly limited, the thickness of the oxygen blocking film is generally preferably 0.5 to 3.0 μm.

(Exposure and development)
A predetermined mask is disposed above the photosensitive resin layer formed on the substrate, and then exposed from above the mask through the mask, the thermoplastic resin layer, and the intermediate layer, and then developed with a developer. By repeating this process for the number of colors, a color filter can be obtained.
Here, the light source for the exposure can be appropriately selected and used as long as it can irradiate light in a wavelength region capable of curing the photosensitive resin layer (for example, 365 nm, 405 nm, etc.). Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. As an exposure amount, it is about 5-200 mJ / cm < ² > normally, Preferably it is about 10-100 mJ / cm < ² >.

Moreover, there is no restriction | limiting in particular as said developing solution, Normal developing solutions, such as a thing of Unexamined-Japanese-Patent No. 5-72724, can be used. The developer is preferably one in which the photosensitive resin layer exhibits a dissolution type development behavior. For example, a developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L is preferable. A small amount of a miscible organic solvent may be added.
Examples of organic solvents miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, and benzyl alcohol. , Acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like. The concentration of the organic solvent is preferably 0.1% by mass to 30% by mass.
Further, a normal surfactant can be further added to the developer. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.

As a development method, methods such as paddle development, shower development, shower & spin development, and dip development can be used.
Here, the shower development will be described. The uncured portion can be removed by spraying a developer onto the exposed photosensitive resin layer by shower. In addition, it is preferable to spray an alkaline solution having low solubility of the photosensitive resin layer by a shower or the like before development to remove the thermoplastic resin layer, the intermediate layer, and the like. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like.
The liquid temperature of the developer is preferably 20 ° C. to 40 ° C., and the pH of the developer is preferably 8 to 13.

In addition, when manufacturing a color filter, as described in JP-A Nos. 11-248921 and 3255107, a colored photosensitive resin composition for forming a color filter is overlaid to form a base thereon. From the viewpoint of cost reduction, it is preferable to form a transparent electrode and further form a spacer by overlapping projections for split orientation.
When the colored photosensitive resin composition is sequentially applied and stacked, the film thickness becomes thin each time the coating is performed due to the leveling of the coating solution. For this reason, it is preferable to overlap the four colors of K (black), R, G, and B and further overlap the divisional alignment protrusions. On the other hand, in the case of using a transfer material having a thermoplastic resin layer, it is preferable that three or two colors be overlapped because the thickness is kept constant.
The size of the base is preferably 25 μm or more, and particularly preferably 30 μm or more, from the viewpoint of preventing deformation of the photosensitive resin layer when the transfer material is laminated and laminating and maintaining a certain thickness.

[Liquid crystal display devices]
The liquid crystal display device using the pigment nanoparticles obtained by the production method of the present invention is excellent in contrast exhibited by the color filter, and excellent in descriptive power such as black spots. Especially, it is preferable that the color filter using the pigment nanoparticle obtained by the manufacturing method of this invention is a VA system. It can also be suitably used as a large-screen liquid crystal display device such as a notebook personal computer display or a television monitor. Moreover, the color filter using the pigment nanoparticles obtained by the production method of the present invention can be used in a CCD device and exhibits excellent performance.

(Example)
5 g of an organic nano pigment having a dioxazine structure (CI Pigment Violet 23, manufactured by Dainichi Seika Co., Ltd.) was dissolved in 100 ml of methanesulfonic acid. The pigment solution was then poured into 1 L of vigorously stirred dimethyl sulfoxide. This reprecipitation operation was performed at room temperature. When the obtained pigment nanoparticles were observed with an SEM, the number average particle diameter of about 300 particles was about 25 nm. The pigment dispersion was stable even after standing at room temperature for 1 month or longer. The spectral absorption (FIG. 7) and X-ray diffraction pattern (FIG. 8) of the nanopigments prepared by this method are shown in the breakdown pigment fine particles (CI Pigment Violet 23, Dainichi Seiki) currently used in color filters. It was possible to evaluate that it was the same as the product name “Violet RE” manufactured by Kasei Co. (FIGS. 9 and 10). The breakdown type pigment fine particles were obtained as follows.

(Preparation of breakdown type fine particles)
6.4 g of pigment (CI Pigment Violet 23)
Pigment dispersant A (Exemplary compound (7)) 0.6 g
6 g of polyvinyl pyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd., K30, molecular weight 40,000)
Methacrylic acid / benzyl methacrylate copolymer * 15.8 g
Diethylene glycol monobutyl ether acetate 45.3g
* Mole ratio 28/72, mass average molecular weight: 30,000, 40% 1-methoxy-2-propyl acetate solution In the above composition, pigment dispersant A (the above exemplified compound ( 7)), a pigment (Pigment Red 254) powder, 6 g of polyvinyl pyrrolidone, and a methacrylic acid / benzyl methacrylate copolymer were added and stirred to obtain a mixed solution. Next, this mixed liquid was dispersed with a motor mill M-50 (manufactured by Eiger Japan) for 9 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Comparative example)
5 g of an organic nano pigment having a dioxazine structure (CI Pigment Violet 23, manufactured by Dainichi Seika Co., Ltd.) was dissolved in 100 ml of methanesulfonic acid. The pigment solution was then poured into 1 L of vigorously stirred water. This reprecipitation operation was performed at room temperature. The spectral absorption (FIG. 11) and X-ray diffraction pattern (FIG. 12) of the nanopigments prepared by this method were significantly different from the breakdown type pigment fine particles currently used in color filters.

  From the above results, according to the production method of the present invention, pigment nanoparticles exhibiting spectral absorption and X-ray diffraction patterns suitable for color filters and inkjet materials that cannot be achieved when water is used as a poor solvent can be prepared. I understand.

It is sectional drawing which shows schematically the preferable embodiment of the manufacturing apparatus used for the manufacturing method of this invention. It is sectional drawing which shows schematically another preferable embodiment of the manufacturing apparatus used for the manufacturing method of this invention. It is an expanded partial sectional view which shows a mixing chamber roughly with a partial cross section as one embodiment of the manufacturing apparatus of FIGS. It is an expanded partial sectional view which shows a mixing chamber roughly with a partial cross section as another embodiment of the manufacturing apparatus of FIGS. It is sectional drawing which shows schematically another preferable embodiment of the manufacturing apparatus used for the manufacturing method of this invention. It is sectional drawing which shows schematically another preferable embodiment of the manufacturing apparatus used for the manufacturing method of this invention. It is a front view which shows roughly an example of the dissolver stirring blade used for the manufacturing method of this invention. 4 is a drawing-substituting photograph of the dissolver stirring blade shown in FIG. 4-1. It is sectional drawing which shows roughly an example of the stirring part comprised from the turbine part which can be used for the manufacturing method of this invention, and the fixed stator part located in the circumference | surroundings with a slight gap. . It is explanatory drawing which shows one structural example of the ultrafiltration apparatus used for the manufacturing method of this invention. It is a spectral absorption spectrum of the pigment nanoparticles obtained in the examples. It is an X-ray-diffraction pattern of the pigment nanoparticle obtained in the Example. It is a spectral absorption spectrum of the pigment nanoparticles obtained by the breakdown method. It is an X-ray diffraction pattern of pigment nanoparticles obtained by a breakdown method. It is a spectrum absorption spectrum of the pigment nanoparticle obtained by the comparative example. It is an X-ray-diffraction pattern of the pigment nanoparticle obtained by the comparative example.

Explanation of symbols

11 Container 11a Liquid tank (solvent)
11b Liquid level 12 Stirring blade 13 Mixing chamber 14 Supply pipe 14a Supply pipe opening 15 Shaft 16 Motor 17 Casing (mixing chamber wall)
18 holes (circular holes)
19a, 19b Stirring blade 21 Container (outer wall of stirring tank)
21a stirring tank 22 stirring blade 23 discharge pipe 24a, 24b supply pipe 25 shaft 50 stirring device 32, 33 supply port 36 discharge port 40 seal plate 41, 42 stirring blade 46 external magnet 48, 49 motor 61 disk part 62 blade 63 shaft 74 Rotating turbine section 75 Stabilized stator section 81 Container for storing dispersion 82 Circulating pump 83 Ultrafiltration module 84 Replenishment pure measurement flow meter 85 Permeate measurement flow meter 86 Backwash pump

Claims (2)

  A method for producing pigment nanoparticles, wherein organic pigment nanoparticles are precipitated by mixing a pigment solution obtained by dissolving an organic pigment in an organic acid or a solvent containing an organic acid, and an organic solvent for precipitation. The method for producing pigment nanoparticles according to claim 1, wherein the organic solvent for precipitation contains a polymer compound having a weight average molecular weight of 1,000 to 500,000.

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