JP2011042750A - Pigment dispersion composition and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment dispersion composition that achieves a very high contrast in a color filter and yet exhibits far excellent stability against changes with time compared with a dispersion of a pigment fine particle prepared by a simple reprecipitation method. <P>SOLUTION: The pigment dispersion composition contains, in a concentration of at least 5 mass% and at most 30 mass% in a medium, an organic pigment fine particle that has an average particle size of primary particles of less than 60 nm and has a ratio of primary particles, having a particle size larger than 60 nm, of less than 10%, where the organic pigment fine particle is obtained by mixing an organic pigment solution, obtained by dissolving the organic pigment in a good solvent, with a poor solvent compatible with the good solvent and acting as a poor solvent for the organic pigment thereby causing the organic pigment to deposit as a fine particle and the concentration, in the pigment dispersion composition, of the good solvent used on depositing the organic pigment fine particle is suppressed to at least 10 ppm and at most 1,000 ppm. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a pigment dispersion composition and a method for producing the same.

  In recent years, the quality of image-related precision equipment such as a color image sensor and a color liquid crystal display device has been rapidly improved and its application has been rapidly expanded. Reflecting this, there has been a strong demand for high-quality display performance for color filters. As for the color material of the color filter, organic pigments have been used instead of dyes, and recently, pigment fine particles having a nanometer size level and being monodispersed and stable have been demanded. Then, a novel color filter manufacturing method using an ink jet technique is studied, and thereby, a significant improvement in performance and design freedom and a significant reduction in cost are expected.

  As a method for producing organic pigment particles, a breakdown method such as a bead mill method or a salt milling method is generally used. However, in the milling method, it takes a lot of time and energy to sufficiently refine the organic pigment and disperse it in the composition. The kind of pigment that can be used is limited. In addition, as the pigment is refined, the dispersion composition may exhibit a high viscosity. In some cases, the dispersion composition may gel during storage and become unusable.

  On the other hand, recently, a gas phase method, a liquid phase method, a laser ablation method and the like have been studied. Among these, the liquid phase method has attracted attention as a method for producing organic particles having excellent simplicity and productivity. Specifically, it is disclosed that the use of a pigment dispersion composition obtained by the reprecipitation method as a color material for a color filter is effective in increasing the contrast (see Patent Document 1). Furthermore, Patent Document 2 aims at improvement as a color material of the color filter, and increases the contrast by increasing the water content in the pigment dispersion composition obtained by the reprecipitation method to 0.01% by mass to 5% by mass. Disclosing improving light resistance is disclosed. Patent Document 3 proposes replacing the dispersion medium of the pigment dispersion composition obtained by the reprecipitation method with a third solvent different from that used in the reprecipitation method. As a result, it has been confirmed that the contrast when used as a color filter is increased, the increase in the viscosity of the dispersion used in the production thereof is prevented, and the image quality when incorporated in a liquid crystal display device is improved.

JP 2007-262378 A JP 2008-7775 A JP 2008-321169 A

  However, the pigment fine particles obtained by the reprecipitation method are usually extremely fine particles of nanometer size, and the color filter has a high contrast. On the other hand, the finer the particles, the more regrowth and aggregation of particles occur. Therefore, the stability over time is reduced.

  In view of the peculiar problems in the color material of a color filter using pigment fine particles as described above, the present invention provides a dispersion of pigment fine particles prepared by a reprecipitation method while realizing extremely high contrast in the color filter. An object of the present invention is to provide a pigment dispersion composition having a stability over time which is far greater than that of (specifically, there is no decrease in contrast and increase in viscosity over time).

  When the present inventors conducted extensive research on the above problems, the pigment dispersion prepared by the reprecipitation method was not applied as it is as the color material of the color filter, but was used in the reprecipitation method included therein. It has been found that by suppressing the good solvent component to a specific concentration or less, the stability over time is greatly improved as it has been extremely difficult to realize in the past. The present invention has been made based on such knowledge. That is, the above problem has been solved by the following means.

<1> Organic pigment fine particles having an average primary particle diameter of less than 60 nm and a ratio of particles having a primary particle diameter exceeding 60 nm of less than 10% in the medium are 5% by mass or more and 30% by mass or less. A pigment dispersion composition containing at a concentration of
The organic pigment fine particles are prepared by mixing an organic pigment solution in which an organic pigment is dissolved in a good solvent and a solvent that is compatible with the good solvent and that is a poor solvent for the organic pigment. Deposited as fine particles,
A pigment dispersion composition, wherein the concentration of the good solvent used at the time of precipitation of organic pigment fine particles contained in the pigment dispersion composition is suppressed to 10 ppm or more and 1000 ppm or less.
<2> A pigment dispersion composition, wherein the concentration of the good solvent contained in the pigment dispersion composition is 30 ppm or more and 500 ppm or less.
<3> The pigment dispersion composition according to <1> or <2>, further comprising a polymer compound having a mass average molecular weight of 1,000 to 100,000.
<4> The pigment dispersion composition according to <3>, wherein the polymer compound has an acid group in a range of 50 mgKOH / g to 200 mgKOH / g.
<5> comprising the pigment dispersion composition described in any one of <1> to <4>, a binder, a monomer or an oligomer, and a photopolymerization initiator or a photopolymerization initiator system. A colored photosensitive resin composition.
<6> An inkjet ink for a color filter, comprising the pigment dispersion composition described in any one of <1> to <4>, a binder, and a monomer or an oligomer.
<7> A photosensitive resin transfer material, wherein a photosensitive resin layer containing at least the colored photosensitive resin composition according to <5> is provided on a temporary support.
<8> A colored photosensitive resin composition according to <5>, an inkjet ink for a color filter according to <6>, and / or a photosensitive resin transfer material according to <7>. Color filter.
<9> A liquid crystal display device comprising the color filter according to <8>.
<10> 5% by mass or more and 30% by mass or less of organic pigment fine particles in which the average particle size of the primary particles is less than 60 nm and the ratio of the particles having a primary particle size exceeding 60 nm is less than 10% in the medium. A method for producing a pigment dispersion composition containing at a concentration of
An organic pigment solution in which an organic pigment is dissolved in a good solvent and a solvent that is compatible with the good solvent and that is a poor solvent for the organic pigment are mixed, and the organic pigment fine particles are mixed in the mixture. Depositing the organic pigment fine particles in a powder or paste state and dispersing them in the medium to precipitate the organic pigment fine particles contained in the pigment dispersion composition. The manufacturing method of the pigment dispersion composition characterized by making the density | concentration of the said good solvent used into 10 ppm or more and 1000 ppm or less.

The pigment dispersion composition of the present invention is particularly suitable as a color material for a color filter, while achieving extremely high contrast in the color filter, and moreover, compared to a pigment dispersion prepared simply by a reprecipitation method, It has an excellent effect of exhibiting far greater time stability.
The colored photosensitive resin composition of the present invention using the pigment dispersion composition having the above excellent characteristics, the inkjet ink for color filter, and the photosensitive resin transfer material are particularly suitable for the production of high-performance color filters. The produced color filter exhibits extremely high contrast, and a good image display is realized in a liquid crystal display device incorporating the color filter.
In addition, according to the production method of the present invention, the pigment dispersion composition having the above-described excellent characteristics can be produced efficiently while maintaining good quality, and is also suitable for mass production on an industrial scale. It can correspond to.
It is sectional drawing which shows typically an example of the shape of the flow path of the flow type reactor which can be used for this invention.

It is sectional drawing which shows typically an example of the shape of the flow path of the flow type reactor which can be used for this invention.

  Hereinafter, preferred embodiments of the present invention will be described, but the present invention should not be construed as being limited thereto.

  The pigment dispersion composition of the present invention contains organic pigment fine particles having an average primary particle diameter of less than 60 nm and a ratio of particles having a primary particle diameter exceeding 60 nm of less than 10% in a medium. It is contained at a concentration of not less than 30% by mass and not more than 30% by mass. This concentration is determined in relation to the concentration of the residual good solvent described later, and can be appropriately adjusted depending on the application and function within the above range. The concentration of the pigment fine particles is preferably 7% by mass or more and 30% by mass or less, and more preferably 8% by mass or more and 28% by mass or less.

The pigment dispersion composition of the present invention is characterized in that the concentration of a good solvent (concentration of residual good solvent) used in the reprecipitation method described later is suppressed to 10 ppm or more and 1000 ppm or less, and preferably 30 ppm or more and 500 ppm or less. 50 ppm or more and 200 ppm or less is more preferable. By making the concentration of the residual good solvent not more than the above upper limit value, it is possible to suppress the particle growth due to re-dissolution of the pigment particles in the pigment dispersion composition, thereby providing high stability over time. . On the other hand, in order to make it below the said lower limit, it is necessary to use a lot of washing | cleaning solvents, etc., and it can manufacture at low cost by setting it as more than a lower limit.
Further, if the concentration of the residual good solvent is defined in relation to the content of the pigment fine particles, the content of the residual good solvent is 8 × 10 ⁻³ to 8 × 10 ⁻⁵ mass with respect to 100 parts by mass of the pigment fine particles. Parts, preferably 4 × 10 ⁻³ to 2 × 10 ⁻⁴ parts by mass, more preferably 2 × 10 ⁻³ to 4 × 10 ⁻⁴ parts by mass.
In the present invention, the concentration of the residual good solvent is measured by the method shown in Examples described later unless otherwise specified.

  In the present invention, the medium (dispersion medium) of the pigment dispersion composition is not particularly limited, and may contain various solvents used for the reprecipitation method as components, or may contain a third solvent described later different from these. In consideration of the use as a color material for a color filter, it is preferable that the solvent system used in the reprecipitation method is replaced with a solvent suitable for the above application. At this time, in the present invention, the amount of the residual good solvent is suppressed to the above-mentioned concentration range as described above, but it may be used as it is within the concentration range in the dispersion obtained by the reprecipitation method. Usually, however, the dispersion obtained by the reprecipitation method contains a residual good solvent in a concentration larger than the above concentration range, for example, 0.5 to 10% by mass. Or it is preferable to take out in a powder state and to re-disperse to the concentration range of the residual good solvent. As the concentration or drying method, a filtration method or a drying method, which will be described later, can be used. In the present invention, it is particularly preferable that the amount of the residual good solvent is pulverized by drying.

[Pigment fine particles]
The fine pigment particles used in the present invention have an average primary particle size of less than 60 nm, and the proportion of particles having a primary particle size exceeding 60 nm is less than 10%. Regarding the particle size of fine particles, there is a method of expressing the average size of the population by quantifying by a measurement method, but it is often used that the mode diameter indicating the maximum value of the distribution, the median value of the integral distribution curve There are corresponding median diameters, various average diameters (number average, length average, area average, mass average, volume average, etc.). In the present invention, the average particle diameter refers to the number average diameter unless otherwise specified. In the present invention, the average particle size of the pigment fine particles (primary particles) is preferably 40 to 10 nm, and more preferably 30 to 15 nm. High contrast can be realized by setting the average particle size of the pigment fine particles to the upper limit or less. On the other hand, low viscosity can be realized by setting it to the above lower limit value or more.
Further, the ratio of the particles having a primary particle diameter of the pigment fine particles exceeding 60 nm is less than 10%, but is preferably 5 to 0.1%. By doing this, that is, by reducing the number of coarse particles, a high contrast can be realized.

  In the present invention, the ratio (Mv / Mn) of the volume average particle diameter (Mv) to the number average particle diameter (Mn) is used as an index representing the uniformity (monodispersity) of the particles unless otherwise specified. There is. In the present invention, the monodispersity of the pigment fine particles (primary particles) (in the present invention, the monodispersity means the degree of uniform particle size), that is, Mv / Mn is 1.0 to 2.0. Is more preferable, 1.0 to 1.8 is more preferable, and 1.0 to 1.5 is particularly preferable. By making the monodispersity of the pigment fine particles not more than the above upper limit value, it is possible to increase the contrast with a low viscosity.

  Examples of the method for measuring the particle size of the organic particles include microscopy, mass 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. In the present invention, the particle diameter is measured by the method shown in Examples described later unless otherwise specified.

[Pigment]
Examples of the pigment used in the present invention include perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, triarylcarbonium, dioxazine, aminoanthraquinone, Examples thereof include diketopyrrolopyrrole, indigo, thioindigo, isoindoline, isoindolinone, pyranthrone or isoviolanthrone compound pigment, or a mixture thereof.

[Reprecipitation method]
In the present invention, it is preferable to produce fine particles of a pigment by bringing a solution obtained by dissolving a pigment in a good solvent (first solvent) into contact with a poor solvent (second solvent). At this time, the compatibility between the good solvent and the poor solvent for dissolving the pigment is preferably 30% by mass or more, and more preferably 50% by mass or more, with respect to the poor solvent. There is no particular upper limit to the amount of good solvent dissolved in the poor solvent, but it is practical to mix them in an arbitrary ratio.

The good solvent is not particularly limited, but an organic acid (eg, formic acid, dichloroacetic acid, methanesulfonic acid, etc.), an organic base (eg, diazabicycloundecene (DBU), tetrabutylammonium hydroxide, sodium methoxide, etc.) ), Aqueous solvents (for example, water, hydrochloric acid, aqueous sodium hydroxide), alcoholic solvents (for example, methanol, ethanol, n-propanol, etc.), ketone solvents (for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), Ether solvents (eg, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), sulfoxide solvents (eg, dimethyl sulfoxide, hexamethylene sulfoxide, sulfolane, etc.), Stealth solvents (for example, ethyl acetate, n-butyl acetate, ethyl lactate, etc.), amide solvents (for example, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, etc.), aromatic hydrocarbon solvents ( For example, toluene, xylene, etc.), aliphatic hydrocarbon solvents (for example, octane), nitrile solvents (for example, acetonitrile), halogen solvents (for example, carbon tetrachloride, dichloromethane, etc.), ionic liquids (for example, And 1-ethyl-3-methylimidazolium tetrafluoroborate), a carbon disulfide solvent, or a mixture thereof.

  Among these, an organic acid, an organic base, an aqueous solvent, an alcohol solvent, a ketone solvent, an ether solvent, a sulfoxide solvent, an ester solvent, an amide solvent, or a mixture thereof is more preferable, and an organic acid, an organic base , Sulfoxide solvents, amide solvents, or mixtures thereof are particularly preferred.

  Examples of the organic acid include, but are not limited to, sulfonic acid compounds, carboxylic acid compounds, acid anhydride compounds, and the like.

  Examples of the sulfonic acid compound include alkyl sulfonic acid, halogenated alkyl sulfonic acid, and aromatic sulfonic acid, and the alkyl chain and the aromatic ring may be unsubstituted or substituted.

  Specific examples of the sulfonic acid compound used in the present invention include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nona. Fluorobutanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, chlorobenzenesulfonic acid, aminobenzenesulfonic acid, 1,5-naphthalenedisulfonic acid tetrahydrate, etc. It is done.

  Examples of the carboxylic acid compound include alkyl carboxylic acids, halogenated alkyl carboxylic acids, and aromatic carboxylic acids. The alkyl chain and the aromatic ring may be unsubstituted or substituted with the substituent T. Specific examples of carboxylic acid compounds include formic acid, acetic acid, propionic acid, butyric acid, trifluoroacetic acid, trichloroacetic acid, tribromoacetic acid, difluoroacetic acid, dichloroacetic acid, dibromoacetic acid, fluoroacetic acid, chloroacetic acid, bromoacetic acid, chlorodifluoroacetic acid , Cyanoacetic acid, phenoxyacetic acid, diphenylacetic acid, thioacetic acid, mercaptoacetic acid, mercaptopropionic acid, 2-chloropropionic acid, 2,2-dichloropropionic acid, 3-chloropropionic acid, 2-bromopropionic acid, 3-bromopropion Acid, 2,3-dibromopropionic acid, 2-chlorobutyric acid, 3-chlorobutyric acid, 4-chlorobutyric acid, isobutyric acid, 2-bromoisobutyric acid, cyclohexanecarboxylic acid, nitroacetic acid, phosphonoacetic acid, pyruvic acid, oxalic acid, propargyl Acid, trimethylammonium acetic acid Benzoic acid, tetrafluorobenzoic acid, pentafluorobenzoic acid, 2-chlorobenzoic acid, 2-fluorobenzoic acid, benzoyl formate, benzoylbenzoic acid, 2-dimethylaminobenzoic acid, 2,6-dihydroxybenzoic acid, picolinic acid, Citric acid, cysteine, sulfanilic acid, squaric acid and the like can be mentioned.

  In the present invention, in addition to carboxylic acid and sulfonic acid, an acid anhydride can be used as the acid, and specifically, acetic anhydride, propionic acid anhydride, trifluoromethanesulfonic acid anhydride, trichloro And acid anhydrides such as acetic anhydride. Examples of organic acids other than these include isopropyl phosphate, methyl phosphate, phenylphosphonic acid, ethylenediaminetetraphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, and methylenediphosphonic acid.

  As the organic acid, alkylsulfonic acid, alkylcarboxylic acid, halogenated alkylcarboxylic acid, and aromatic sulfonic acid are preferable, and methanesulfonic acid, trifluoromethanesulfonic acid, ethanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, chloroacetic acid. Formic acid, toluenesulfonic acid, and dodecylbenzenesulfonic acid are more preferable.

  Examples of organic bases include primary amines, secondary amines, tertiary amines, quaternary amines, anilines, piperidines, piperazines, amidines, formamidines, pyridines, Examples include, but are not limited to, guanidines, morpholines, nitrogen-containing heterocycles, metal alkoxides and the like. Among these, tertiary amines, quaternary amines, morpholines, nitrogen-containing heterocycles, metal alkoxides and the like are preferable.

  Specifically, aniline, 2-chloroaniline, 3-fluoroaniline, 2,4-difluoroaniline, 2-nitroaniline, N, N-diethylaniline, 2,6-diethylaniline, 2,4-dimethoxyaniline, p-phenylenediamine, pyridine, 2-aminopyridine, pyrimidine, pyridazine, pyrazine, 2,2-dipyridyl, pyrrolidine, piperidine, imidazole, pyrazole, thiazole, benzothiazole, oxazole, diazabicycloundecene, diazabicyclononene, Diazabicyclooctane, 1-cyanoguanidine, N, N′-diphenylguanidine, cyclohexylamine, butylamine, cyclopropylamine, t-butylamine, benzylamine, diisopropylamine, trimethylamine, triethylamine , Tributylamine, tetrahydroquinoline, phenyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, morpholine, thiomorpholine, N-methylmorpholine, hexamethylphosphoramide, 1-methyl -4-piperidone, N- (2-aminoethyl) piperazine, ethylenediamine, diethylenetriamine, bis- (3-aminopropyl) ether, sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium methoxide, potassium Examples include ethoxide and potassium t-butoxide.

  Among these, aniline, 2,4-difluoroaniline, pyridine, diazabicycloundecene, diazabicyclononene, diazabicyclooctane, triethylamine, tetrahydroquinoline, phenyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, tetramethyl Ammonium hydroxide, tetrabutylammonium hydroxide, N-methylmorpholine, N- (2-aminoethyl) piperazine, sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium methoxide, potassium ethoxide, potassium -T-butoxide is preferred, 2,4-difluoroaniline, diazabicycloundecene, diazabicyclononene, tetrahydroquinoline, phenyltrimethylammonium Hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, N- methylmorpholine, sodium methoxide, potassium -t- butoxide preferred.

  More specific examples of the sulfoxide solvent include dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, sulfolane and the like.

  More specifically, examples of the amide 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.

  There are no particular limitations on the preparation conditions for depositing the pigment fine particles, 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.

  When the pigment is uniformly dissolved in a good solvent, generally, in the case of a pigment having an alkaline dissociable group in the molecule, there is no alkali, but there is no alkaline dissociable group, and a nitrogen atom to which a proton is easily added is present. It is preferred that acidity be used when there are many in the molecule. For example, quinacridone, diketopyrrolopyrrole, and disazo condensation compound pigments are alkaline, and phthalocyanine compound pigments are acidic.

  In addition to the organic base, an inorganic base such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, or barium hydroxide can be used as the base used when dissolving in an alkaline manner. The amount of the base used is not particularly limited, but in the case of an inorganic base, it is preferably 1.0 to 30 molar equivalents, more preferably 1.0 to 25 molar equivalents, and 1.0 Particularly preferred is ˜20 molar equivalents. In the case of an organic base, it is preferably 1.0 to 100 molar equivalents, more preferably 5.0 to 100 molar equivalents, and particularly preferably 20 to 100 molar equivalents with respect to the pigment.

  In addition to the organic acid, an inorganic acid such as sulfuric acid, hydrochloric acid, phosphoric acid or the like can be used as an acid used when the acid is dissolved. The amount of the acid to be used is not particularly limited, but it is often used in excess compared to the base, and is preferably 3 to 500 molar equivalents, more preferably 10 to 500 molar equivalents, It is particularly preferably 30 to 200 molar equivalents.

  When mixing an inorganic base or an inorganic acid with an organic solvent and using it as a good solvent for a pigment, the alkali or acid is completely dissolved, so it has a high solubility in some water or lower alcohol or other alkali or acid. A solvent can be added to the organic solvent. The amount of water or lower alcohol is preferably 50% by mass or less, more preferably 30% by mass or less, based on the total amount of the pigment solution. Specifically, water, methanol, ethanol, n-propanol, isopropanol, butyl alcohol, or the like can be used.

  The viscosity of the pigment solution is preferably 0.5 to 100.0 mPa · s, and more preferably 1.0 to 50.0 mPa · s.

The pigment solution may contain the above pigment and other components as required in a good solvent.
Although it does not specifically limit as another component, An acid (an organic compound etc. which has an acidic group) and a base (an organic compound which has basicity) are mentioned suitably. In particular, in the present invention, it is preferable to dissolve the dichlorodiketopyrrolopyrrole pigment in the presence of a base, and it is more preferable that the base is an organic base.

  In the present invention, as an organic base (an organic compound having a basic group), alkylamine, arylamine, aralkylamine, pyrazole derivative, imidazole derivative, triazole derivative, tetrazole derivative, oxazole derivative, thiazole derivative, pyridine derivative, pyridazine Derivatives, pyrimidine derivatives, pyrazine derivatives, triazine derivatives and the like are preferable, and alkylamine, arylamine and imidazole derivatives are preferable. Above all,

  As carbon number of the organic compound which has the said basic group, 6 or more are preferable, More preferably, it is 8 or more, More preferably, it is 10 or more. In the organic compound having a basic group, examples of the alkylamine include butylamine, amylamine, hexylamine, heptylamine, octylamine, 2-hexylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, and tridecylamine. , Tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, isobutylamine, t-butylamine, 1-methylbutylamine, 1-ethylbutylamine, t-amylamine, 3-aminoheptane, t-octylamine, 1,4 -Diaminobutane, 1,6-hexadiamine, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, dibutylamine, dihexylamine, dioctylamine, bis (2- Tylhexyl) amine, didecylamine, N-methyloctadecylamine, triethylamine, tripropylamine, N, N-dimethylbutylamine, N-methyldibutylamine, tributylamine, tripentylamine, N, N-dimethylhexylamine, N, N- Dimethyloctylamine, N-maledioctylamine, trioctylamine, triisooctylamine, N, N-dimethyldodecylamine, tridodecylamine, N-methyl-N-octadecyl-1-octadecylamine, N, N-dibutylethylenediamine N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, N-methylcyclohexylamine, N, N, N ′, N ′, N '' -Pentamethyldiethyl Rentriamine, cyclohexylamine, cycloheptylamine, cyclohexylamine, cyclododecylamine, 1-adamandanamine and the like are preferable, preferably octylamine, 2-hexylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecamine Decylamine, tetradecylamine, octadecylamine, t-octylamine, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, dioctylamine, bis (2-ethylhexyl) amine, didecylamine, N -Methyloctadecylamine, N, N-dimethyloctylamine, N-mail dioctylamine, trioctylamine, triisooctylamine, N, N-dimethyldodecylamine, tridodecylamine N-methyl-N-octadecyl-1-octadecylamine, N, N-dibutylethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexane Examples include diamine, N-methylcyclohexylamine, N, N, N ′, N ′, N ′ ′-pentamethyldiethylenetriamine, cyclododecylamine, 1-adamandanamine, and more preferably decylamine, undecylamine, Examples include dodecylamine, tridecylamine, tetradecylamine, didecylamine, N-methyloctadecylamine, N, N-dimethyldodecylamine, and tridodecylamine. Also suitable are organic polymer compounds having a basic group such as polyallylamine and polyvinylamine.

  As the arylamine, for example, N, N-dibutylaniline, 4-butylaniline, 4-pentylamine, 4-hexylamine, 4-heptylaniline, 4-octylaniline, 4-decylaniline, 4-dodecylaniline, 4 -Tetradecylaniline, 4-hexadecylaniline, 4-butoxyaniline, 4-pentyloxyaniline, 4-hexyloxyaniline, 4-hexyloxyaniline, and the like, preferably 4-octylaniline, 4-decylaniline 4-dodecylaniline, 4-tetradecylaniline, 4-hexadecylaniline, 4-pentyloxyaniline, 4-hexyloxyaniline, 4-hexyloxyaniline, etc., more preferably 4-decylaniline, 4 -Dodecylaniline, 4 Tetradecyl aniline, 4-hexadecyl aniline, 4-pentyloxy aniline, 4-hexyloxy aniline, 4-hexyloxy aniline.

  Examples of the imidazole derivative include 1- (10-hydroxydecyl) imidazole, 1-butylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and the like.

  The organic compound having a basic group is preferably in the range of 0.01 to 30% by mass, more preferably in the range of 0.05 to 20% by mass, and more preferably 0.05 to 15% with respect to the pigment. It is particularly preferable to be in the range of mass%.

It is also preferable to add an organic compound composed of a basic group and a heterocyclic group.
Examples of such organic compounds include 2-aminopyridine, 3-aminopyridine, 1- (2-aminophenyl) pyrrole, 5-aminopyrazole, 3-amino-5-methylpyrazole, 5-amino-1- Ethylpyrazole, 3-aminotriazole, 2-aminothiazole, 5-aminoindole, 2-aminobenzthiazole, 5-aminobenzimidazole, N, N-dimethyl-5-aminobenzimidazole, phthalimide, 5-aminobenzimidazolone N, N-dimethyl-5-aminobenzimidazolone, 5-aminouracil, 6-aminouracil, uracil, thymine, adenine, guanine, melamine, aminopyrazine, 8-aminoquinoline, 3-aminoquinoline, 9-amino Acridine, ASTRA blue 6GLL (base Phthalocyanine derivative), 2-amino-anthraquinone, 3-amino-anthraquinone, acridone, N- acridone, quinacridone, NILE Red, and the like methylene violet naphthalimide is. Preferably, 2-aminobenzthiazole, 5-aminobenzimidazole, N, N-dimethyl-5-aminobenzimidazole, 5-aminobenzimidazolone, N, N-dimethyl-5-aminobenzimidazolone, 5-amino Uracil, 6-aminouracil, uracil, thymine, adenine, guanine, melamine, 8-aminoquinoline, 3-aminoquinoline, 9-aminoacridine, ASTRA blue 6GLL (basic phthalocyanine derivative), 2-aminoanthraquinone, 3-amino Anthraquinone, acridone, N-acridone, quinacridone, NILE red, methylene violet naphthalimide, and more preferably 9-aminoacridine, ASTRA blue 6GLL (basic phthalocyanine derivative), 2-aminoan Laquinone, 3-aminoanthraquinone, acridone, N-acridone, 5-aminobenzimidazole, N, N-dimethyl-5-aminobenzimidazole, 5-aminobenzimidazolone, N, N-dimethyl-5-aminobenzimidazolone , 5-aminouracil, 6-aminouracil, NILE red, and methylene violet naphthalimide.

  The addition amount of the organic compound composed of the basic group and the heterocyclic group is preferably in the range of 0.01 to 30% by mass, and in the range of 0.05 to 20% by mass with respect to the pigment. It is more preferable that it is in the range of 0.05 to 15% by mass.

  In addition to the above, pigment derivatives described in JP-A No. 2007-9096 and JP-A No. 7-331182 can be exemplified. The pigment derivative referred to here is derived from a pigment derivative compound derived from an organic pigment as a parent substance and manufactured by chemically modifying the parent structure, or by a pigmentation reaction of a chemically modified pigment precursor. Refers to a pigment derivative type compound. Examples of commercially available products include “EFKA 6745 (phthalocyanine derivative)” manufactured by EFKA, “Solsperse 5000 (phthalocyanine derivative)” manufactured by Lubrizol (all are trade names), and the like. When a pigment derivative is used, the amount used is preferably in the range of 0.5 to 30% by mass, more preferably in the range of 3 to 20% by mass, and 5 to 15% by mass with respect to the pigment. It is especially preferable that it is in the range.

  The poor solvent is not particularly limited, but the solubility of the pigment in the poor solvent is preferably 0.02% by mass or less, and more preferably 0.01% by mass or less. There is no particular lower limit to the solubility of the pigment in the poor solvent, but 0.0001% by mass or more is practical considering the commonly used one.

The poor solvent is not particularly limited, but an aqueous solvent (for example, water, hydrochloric acid, sodium hydroxide aqueous solution), an alcohol solvent (for example, methanol, ethanol, n-propanol, etc.), a ketone solvent (for example, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone, etc.), ether solvents (eg, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), sulfoxide solvents (eg, dimethyl sulfoxide, hexamethylene sulfoxide, sulfolane, etc.), ester solvents ( For example, ethyl acetate, n-butyl acetate, ethyl lactate, etc.), amide solvents (eg, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, etc.), aromatic hydrocarbon solvents (examples) Toluene, xylene, etc.), aliphatic hydrocarbon solvents (eg, octane, etc.), nitrile solvents (eg, acetonitrile, etc.), halogen solvents (eg, carbon tetrachloride, dichloromethane, etc.), ionic liquids (eg, 1-ethyl-3
-Methylimidazolium tetrafluoroborate etc.), carbon disulfide solvent, or a mixture thereof is preferably mentioned.
Among these, an aqueous solvent, an alcohol solvent, a ketone solvent, a sulfoxide solvent, an ester solvent, an amide solvent, a nitrile solvent, or a mixture thereof is more preferable, and an aqueous medium, an alcohol solvent, or a mixture thereof. Is particularly preferred.

The aqueous medium refers to water alone or water and water-soluble organic solvent or inorganic salt solution, for example, water, organic compound aqueous solution, hydrochloric acid, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution and the like.
Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-methoxy-2-propanol and the like.

  Some are listed as specific examples of good solvents and those listed as poor solvents, but the same as the good solvent and the poor solvent are not combined, and the solubility in the good solvent is related to the pigment. The solubility should be sufficiently higher than the solubility in the poor solvent. For the pigment, for example, the solubility difference is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. There is no particular upper limit on the difference in solubility between the good solvent and the poor solvent, but it is practical that the difference is 50% by mass or less in consideration of a commonly used pigment.

  The state of the poor solvent is not particularly limited, 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. The viscosity of the pigment solution is preferably 0.5 to 100.0 mPa · s, and more preferably 1.0 to 50.0 mPa · s.

There are no particular restrictions on the use conditions of the poor solvent during the preparation of the organic particles, 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.
The mixing ratio of the pigment solution and the poor solvent (ratio of good solvent / poor solvent in the reprecipitation liquid) is preferably 1/50 to 1/1, more preferably 1/40 to 1/1, and more preferably 1/10 to 10 in volume ratio. 1/1 is particularly preferred. This may be the same or different from the volume flow ratio of the pigment solution and the poor solvent in the flow reactor.
Further, the method of mixing the pigment solution and the poor solvent may be a method of injecting the pigment solution into the poor solvent. A flow channel mixing method (flow reactor) in which a pigment solution and a poor solvent are caused to collide with each other through a plurality of flow channels may be used.

By adjusting the Reynolds number in mixing the pigment solution and the poor solvent, the particle diameter of the pigment nanoparticles that are deposited can be controlled. Here, the Reynolds number is a dimensionless number representing the state of fluid flow and is represented by the following equation.
Re = ρUL / μ Equation (1)
In Equation (1), Re represents the Reynolds number, ρ represents the density of the pigment solution [kg / m ³ ], U represents the relative speed [m / s] when the pigment solution and the poor solvent meet, L represents the equivalent diameter [m] of the flow path or supply port where the pigment solution and the poor solvent meet, and μ represents the viscosity coefficient [Pa · s] of the pigment solution.

The equivalent diameter L refers to the diameter of the equivalent circular pipe when assuming an opening diameter of a pipe having an arbitrary cross-sectional shape or a circular pipe equivalent to the flow path. The equivalent diameter L is expressed by the following formula (2), where A is the cross-sectional area of the pipe, p is the wetted length (circumferential length) of the pipe, or p is the outer periphery of the flow path.
L = 4 A / p Equation (2)
It is preferable to form particles by injecting a pigment solution into a poor solvent through a pipe. When a circular pipe is used for the pipe, the equivalent diameter matches the diameter of the circular pipe. For example, the equivalent diameter can be adjusted by changing the opening diameter of the liquid supply port. Although the value of the equivalent diameter L is not specifically limited, For example, it is synonymous with the preferable internal diameter of the supply port mentioned above.

  The relative speed U when the pigment solution and the poor solvent meet is defined by the relative speed in the direction perpendicular to the surface of the portion where both meet. That is, for example, when the pigment solution is injected and mixed in a stationary poor solvent, the injection speed from the supply port becomes equal to the relative speed U. Although the value of the relative speed U is not specifically limited, For example, it is preferable to set it as 0.5-100 m / s, and it is more preferable to set it as 1.0-50 m / s.

The density ρ of the pigment solution is a value determined by the type of material selected, but is practically 0.8 to 2.0 kg / m ³ , for example. The viscosity coefficient μ of the pigment solution is also a value determined by the material used, the ambient temperature, and the like, but its preferred range is synonymous with the preferred viscosity of the pigment solution described above.

  The smaller the Reynolds number (Re) value, the easier it is to form a laminar flow, and the larger the value, the easier it is to form a turbulent flow. For example, it can be obtained by adjusting the Reynolds number to 60 or more to control the particle diameter of the pigment nanoparticles, preferably 100 or more, and more preferably 150 or more. Although there is no particular upper limit to the number of lay nozzles, for example, favorable pigment nanoparticles can be obtained by controlling and controlling in the range of 100,000 or less, which is preferable. Or it is good also as conditions which raised Reynolds number so that the average particle diameter of the nanoparticle obtained may be 60 nm or less. At this time, within the above range, it is possible to control and obtain pigment nanoparticles having a smaller particle size by increasing the Reynolds number.

[Flow reactor]
In the present invention, a flow reactor (continuous flow reactor) can be used. The continuous flow type refers to an apparatus in which a fluid (liquid or gas), which is a reaction raw material, is continuously flowed into a reactor and a product is continuously flowed out after causing desired changes and reactions inside. In many cases, a reaction or the like is caused by mixing the inflowing fluid in some form, but if there is no change in the flow rate and composition of the inflowing fluid, the reaction field, that is, the composition in the mixing field is usually steady. Therefore, a constant composition product can be obtained from the beginning of the reaction. The present invention has the advantage that the shape, diameter, etc. of the generated particles are likely to be uniform.
The flow reactor used in the present invention includes a plurality of (at least one for each of good and poor solvents) raw material inflow passages, a mixing field where the inflowed raw materials are mixed, and the outflow of the product generated therein. It is preferable to have a flow path. The length of each flow path from the mixing field can be appropriately set in consideration of the run-up distance from the change point of the previous flow path, the pressure loss of the entire system, and the like.
As for the number of channels (raw material inflow channels) for supplying a pigment solution, a poor solvent and the like connected to the mixing field, at least two are necessary, and three or more are preferable. By using three or more, at least one of the pigment solution or the poor solvent can be divided and flown from a plurality of flow paths, so that there is an advantage that the mixing is further promoted, and the number of the solution is five or more. Further preferred. The upper limit of the number of raw material inflow channels is not particularly specified, but if it is too large, a large number of pumps are required or a large number of branches need to be provided from one pump. Is practical.
The number of product outlet channels connected to the mixing field may be at least one, and a necessary number may be provided depending on the case of separating the products into different tanks.

  FIG. 1 is a sectional view schematically showing an example of the shape of the flow reactor of the flow reactor that can be used in the present invention. However, the implementation of the present invention is not limited to the case of using this reactor. The reactor shown in FIG. 1 includes a mixing field 1 and a total of six circular pipes (channels 11 to 16) that are connected to the mixing field 1 at an angle of 60 °. Of the flow paths 11 to 16, the raw material inflow flow path and the product outflow flow path can be appropriately distributed, but as an example of usage, for example, a pigment solution in which a pigment is dissolved in a good solvent from the flow paths 13 and 15 is used. The poor solvent can be introduced from the channels 12, 14, and 16 and mixed in the mixing field to be output from the channel 11 (in this case, the raw material inflow channels are the channels 12 to 16, the product outflow The flow path becomes the flow path 11). The introduced solvents collide with each other in the mixing field 1, and fine particles can be efficiently generated. When a reactor having three or more raw material inflow channels is used as described above, the concentration, composition, and flow rate of the pigment solution, the poor solvent supplied separately from the plurality of channels may be the same or different. good. For example, a method of using a solution in which only a pigment is dissolved in the channel 13 and a solution in which a pigment and a dispersant are dissolved in the channel 15 is also preferable. It is also preferable to use a flow rate of 15 at a different flow rate. Of course, which solution is allowed to flow through each channel can be appropriately selected depending on the system.

[Dispersant]
In the present invention, a dispersant may be added to the pigment dispersion composition. 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. Among them, in the present invention, it is preferable to use a polymer compound described later as a dispersant. The addition amount of the dispersant may be appropriately adjusted according to the kind of the pigment or the dispersant. For example, the content in the dispersion composition is preferably 10% by mass to 1000% by mass, and more preferably 10% by mass to 200% by mass. More preferred. When the amount is too small, the effect of suppressing the growth and aggregation of the pigment particles is reduced. When the amount is too large, problems such as an increase in viscosity and poor dissolution are likely to occur.

The polymer compound having a heterocyclic ring in the side chain of this embodiment that can be suitably used as a dispersant preferably further contains a copolymer unit derived from a monomer having an acid group. When the polymer compound further contains a copolymer unit derived from a monomer having an acid group, when the dispersion composition of the water-insoluble compound is applied to the photosensitive composition, it is excellent in the development removability of the unexposed area. .
Monomers having an acid group include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, anhydrous Unsaturated dicarboxylic acids such as itaconic acid, citraconic acid, citraconic anhydride and mesaconic acid or their anhydrides; trivalent or higher unsaturated polycarboxylic acids or their anhydrides; succinic acid mono (2-acryloyloxyethyl) ), Succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) monovalent polyvalent carboxylic acid mono [ (Meth) acryloyloxyalkyl] esters; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolacto It can be mentioned mono (meth) acrylates such as both terminal carboxy polymers such monomethacrylate. The polymer compound of this embodiment may include only one type of copolymer unit derived from a monomer having an acid group, or may include two or more types.

  In the polymer compound having a heterocyclic ring in the side chain of the present embodiment, the content of the copolymer unit derived from the monomer having an acid group is preferably 50 to 200 mgKOH / g, particularly preferably 80 to 200 mgKOH. / G. A more preferable range is 100 to 180 mgKOH / g. That is, in terms of suppressing the formation of precipitates in the developer, the content of copolymer units derived from the monomer having an acid group is preferably 50 mgKOH / g or more. When the acid value is 200 mgKOH / g or more, aggregation between acid groups becomes strong, aggregation between processed pigments occurs, and dispersibility deteriorates. In order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of water-insoluble compounds, or to effectively weaken the cohesive force of secondary aggregates, a monomer having an acid group is used. The content of the derived copolymer unit is preferably in the above range.

The polymer compound having a heterocyclic ring in the side chain in this embodiment may further contain a copolymer unit derived from a copolymerizable vinyl monomer as long as the effect is not impaired.
Although it does not restrict | limit especially as a vinyl monomer which can be used here, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, ( Preference is given to meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like. Specific examples of such vinyl monomers include the following compounds. In addition, in this specification, when showing either or both of "acryl and methacryl", it may describe as "(meth) acryl".

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , 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, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, etc. are mentioned.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, chloromethyl Examples thereof include styrene, 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.

  The preferred molecular weight of the polymer compound having a heterocyclic ring in the side chain according to this embodiment is in the range of 1,000 to 100,000 in terms of mass average molecular weight (Mw) and in the range of 400 to 50,000 in terms of number average molecular weight (Mn). A range is preferable. More preferably, the mass average molecular weight (Mw) is in the range of 5,000 to 50,000, and the number average molecular weight (Mn) is in the range of 2,000 to 30,000. In particular, the mass average molecular weight (Mw) is most preferably in the range of 8,000 to 30,000, and the number average molecular weight (Mn) is in the range of 4,000 to 12,000.

That is, from the viewpoint of effectively suppressing the formation of secondary aggregates, which are aggregates of primary particles of water-insoluble compounds, or effectively reducing the cohesive force of secondary aggregates, The mass average molecular weight (Mw) of the polymer compound having a heterocyclic ring in the side chain is preferably 1,000 or more. In addition, from the viewpoint of developability when producing a color filter with a composition containing a dispersion composition of a water-insoluble compound, the mass average molecular weight (Mw) of the polymer compound having a heterocyclic ring in the side chain of this embodiment is used. Is preferably 100,000 or less.
In the dispersion composition of the water-insoluble compound of the present embodiment, the content of the polymer compound having a heterocyclic ring is a mass ratio, and the polymer compound having a heterocyclic ring in the water-insoluble compound side chain = 1: 0.01 to 1. : 2 is preferable, more preferably 1: 0.05 to 1: 1, and still more preferably 1: 0.1 to 1: 0.6.

  The polymer compound having a heterocyclic ring is, for example, a monomer represented by the general formula (1), a polymerizable oligomer (macromonomer), and another radical polymerizable compound as a copolymerization component. It can be produced by a radical polymerization method. In general, a suspension polymerization method or a solution polymerization method is used. Solvents used in the synthesis of such polymers include, for example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl. Examples include acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. . These solvents may be used alone or in combination of two or more.

  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.

  The monomer having an organic dye structure or a heterocyclic structure is selected from the group consisting of the monomer represented by the general formula (1) described in the high part of the polymer compound A, maleimide, and a maleimide derivative. Preferably it is a seed. The preferred range is also as defined above.

Examples of the monomer having an acidic group include a vinyl monomer having a carboxyl group and a vinyl monomer having a sulfonic acid group.
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Of these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.

  Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.

  The specific polymer in this embodiment preferably includes a repeating unit derived from a monomer having an acidic group as described above. By including such a repeating unit, when the dispersion of the present invention is applied to a colored photosensitive composition, the development removability of an unexposed portion is excellent.

The specific polymer in this embodiment may include only one type of repeating unit derived from a monomer having an acidic group, or may include two or more types.
In the specific polymer, the content of the repeating unit derived from the monomer having an acidic group is preferably 50 mgKOH / g or more, particularly preferably 50 mgKOH / g to 200 mgKOH / g. That is, in terms of suppressing the formation of precipitates in the developer, the content of the repeating unit derived from the monomer having an acidic group is preferably 50 mgKOH / g or more. In order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of a water-insoluble compound, or to effectively weaken the cohesive force of secondary aggregates, it is derived from a monomer having an acidic group. The content of the repeating unit is preferably 50 mgKOH / g to 200 mgKOH / g.

  As a monomer having a basic nitrogen atom, (meth) acrylic acid ester, (meth) acrylic acid N, N-dimethylaminoethyl, (meth) acrylic acid N, N-dimethylaminopropyl, (meth) acrylic acid 1 -(N, N-dimethylamino) -1,1-dimethylmethyl, (meth) acrylic acid N, N-dimethylaminohexyl, (meth) acrylic acid N, N-diethylaminoethyl, (meth) acrylic acid N, N -Diisopropylaminoethyl, N, N-di-n-butylaminoethyl (meth) acrylate, N, N-di-i-butylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, (meth) Piperidinoethyl acrylate, 1-pyrrolidinoethyl (meth) acrylate, N, N-methyl-2-pyrrolidyl (meth) acrylate And (meth) acrylamides include N- (N ′, N′-dimethylaminoethyl) acrylamide, N- (N ′, N ′), and the like. -Dimethylaminoethyl) methacrylamide, N- (N ', N'-diethylaminoethyl) acrylamide, N- (N', N'-diethylaminoethyl) methacrylamide, N- (N ', N'-dimethylaminopropyl) Acrylamide, N- (N ′, N′-dimethylaminopropyl) methacrylamide, N- (N ′, N′-diethylaminopropyl) acrylamide, N- (N ′, N′-diethylaminopropyl) methacrylamide, 2- ( N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, N-diethylamino) ) Ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth) acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 1- (N, N-dimethylamino) -1 , 1-dimethylmethyl (meth) acrylamide and 6- (N, N-diethylamino) hexyl (meth) acrylamide, morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide and the like Examples of styrenes include N, N-dimethylaminostyrene, N, N-dimethylaminomethylstyrene, and the like.

  Moreover, it is also possible to use a monomer having a urea group, a urethane group, a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, or a hydroxyl group. Specific examples include monomers having the following structure.

  Examples of the monomer having an ionic group include vinyl monomers having an ionic group (anionic vinyl monomers and cationic vinyl monomers). Examples of the anionic vinyl monomer include alkali metal salts of vinyl monomers having an acidic group, salts with organic amines (eg, tertiary amines such as triethylamine and dimethylaminoethanol), and the like. As the vinyl monomer, the nitrogen-containing vinyl monomer is an alkyl halide (alkyl group: C1-18, halogen atom: chlorine atom, bromine atom or iodine atom); benzyl halide such as benzyl chloride or benzyl bromide; Alkylsulfonic acid esters such as acids (alkyl groups: C1-18); arylsulfonic acid alkyl esters such as benzenesulfonic acid and toluenesulfonic acid (alkyl groups: C1-18); dialkyl sulfates (alkyl groups: C1-4), etc. Quaternized with dialkyldiallylane Such as salt, and the like.

  The monomer having a functional group capable of adsorbing to the particles of the water-insoluble compound can be appropriately selected according to the type of the water-insoluble compound to be dispersed. These may be used alone or in combination of two or more. Also good.

  The specific polymer in the present embodiment may further contain a repeating unit derived from a copolymerizable vinyl monomer as described above as long as the effect is not impaired.

The preferred molecular weight of the polymer compound having a heterocyclic ring in the side chain according to this embodiment is in the range of 1,000 to 100,000 in terms of mass average molecular weight (Mw) and in the range of 400 to 50,000 in terms of number average molecular weight (Mn). A range is preferable. More preferably, the mass average molecular weight (Mw) is in the range of 5,000 to 50,000, and the number average molecular weight (Mn) is in the range of 2,000 to 30,000. In particular, the mass average molecular weight (Mw) is most preferably in the range of 8,000 to 30,000, and the number average molecular weight (Mn) is in the range of 4,000 to 12,000.
That is, from the viewpoint of effectively loosening secondary aggregates, which are aggregates of primary particles of water-insoluble compounds, or effectively weakening reaggregation, the mass average molecular weight (Mw) of the specific polymer is It is preferable that it is 1000 or more. Moreover, from the viewpoint of developability when producing a color filter with a colored photosensitive composition containing a dispersion composition, the mass average molecular weight (Mw) of the specific polymer is preferably 30000 or less.

  The specific polymer in this embodiment includes, for example, a monomer represented by the following general formula (i), (ii), or (i) -2, and another radical polymerizable compound (described above) as a copolymerization component. Can be produced by a normal radical polymerization method. In general, a suspension polymerization method or a solution polymerization method is used. Examples of the solvent used for synthesizing such a specific polymer include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxy. Examples include ethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. It is done. These solvents may be used alone or in combination of two or more. 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.

  In the dispersion composition of the water-insoluble compound of the present embodiment, the content of the specific polymer is preferably a mass ratio of water-insoluble compound: specific polymer = 1: 0.1 to 1: 2, more preferably 1 : 0.2 to 1: 1, and more preferably 1: 0.4 to 1: 0.7.

  Moreover, in the range which does not impair the effect of this embodiment, you may use another high molecular compound simultaneously with the above-mentioned specific copolymer as needed. As other polymer compounds, natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like are used. The natural resin is typically rosin, and the modified natural resin includes rosin derivatives, fiber derivatives, rubber derivatives, protein derivatives and oligomers thereof. Examples of the synthetic resin include an epoxy resin, an acrylic resin, a maleic acid resin, a butyral resin, a polyester resin, a melamine resin, a phenol resin, and a polyurethane resin. Examples of synthetic resins modified with natural resins include rosin-modified maleic acid resins and rosin-modified phenolic resins. Synthetic resins include polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, polyurethane, polyester, poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate Is mentioned.

The polymer compound of this embodiment can be synthesized by polymerizing monomers as described above, or can be synthesized by reacting a precursor polymer compound with a low molecular compound having an acid group.
The polymer compound of this embodiment is more preferably at least one selected from a block polymer, a graft polymer, and a terminal-modified polymer.

The polymer compound of this embodiment is considered to act to adsorb on the particle surface of the water-insoluble compound and prevent reaggregation in the dispersion step. Therefore, the polymer compound of the present embodiment may be a linear random copolymer, but a block polymer, graft polymer, and terminal-modified polymer that are more effective can be cited as preferred structures. Specific examples include compounds described in JP2009-96977A.
○ Embedding Dispersant In the present invention, when mixing a solution in which the pigment is dissolved in a good solvent and a poor solvent, (i) the dispersant is mixed on the good solvent side and / or the poor solvent side. Alternatively, or (ii) separately from these, a solution in which the dispersant is dissolved in a good solvent may be prepared and mixed together with the two solutions to form build-up fine particles embedding the generated dispersant. The dispersant is preferably a polymer dispersant having a mass average molecular weight of 1000 or more, and more preferably a polymer dispersant having a specific structural site as described later. In the present invention, the term “molecular weight” means a weight average molecular weight unless otherwise specified, and the weight average molecular weight (Mw) is a polystyrene-reduced weight average molecular weight measured by gel permeation chromatography (carrier: tetrahydrofuran).

  The solubility of the embedding dispersant in the good solvent is preferably 4.0% by mass or more, and more preferably 10.0% by mass or more. Although there is no particular upper limit to the solubility, it is practical that the solubility is 70% by mass or less in consideration of a commonly used polymer compound. The solubility of the embedding dispersant in the poor solvent is preferably 0.02% by mass or less, and more preferably 0.01% by mass or less.

  In the present invention, the dispersing agent partially or wholly incorporated inside the particle is not simply physically adsorbed on the particle surface as in the prior art, but is fixed in the particle and irreversibly incorporated. As long as the microparticles are not destroyed or dissolved, they are usually free or detached in the dispersion medium and / or composition solvent. For this reason, the fine particles embedded with the dispersant have a high dispersion effect that the aggregation of the particles can be suppressed, and the dispersion stability is extremely high even if the amount of the dispersant used is small. The characteristics of the fine particles embedded with such a dispersant can be confirmed, for example, by measuring the amount that the dispersant does not desorb even after repeated washing with a solvent in which the dispersant dissolves.

  The method for efficiently embedding the dispersing agent in the particles is not particularly limited. For example, a specific dispersing agent can be selected and used, or by adjusting process conditions such as a channel mixing method. . Below, the preferable embodiment which embeds a dispersing agent in particle | grains is demonstrated in detail.

In order to embed the dispersant in the particles by the usual reprecipitation method, it is preferable to use a specific dispersant. At this time, if all the dispersant molecules are encapsulated in the particles and all the functional groups necessary for the dispersion are also encapsulated in the particles, it may not be possible to sufficiently play the role of imparting the dispersibility of the dispersant. For this reason, it is preferable that all the functional groups necessary for the dispersion are not included in the particles. In order to appropriately encapsulate the dispersant in the fine particles and impart dispersion stability, it is preferable to use a dispersant that satisfies the following requirements. That is,
(1) The medium in which the dispersant can be dissolved is compatible with the medium in which the pigment used in combination can be dissolved;
(2) The dispersant is a polymer dispersant having a mass average molecular weight of 1000 or more,
(3) The dispersant is precipitated by mixing with a poor solvent, but the deposition rate is slower than the precipitation of the pigment,
(4) The dispersant contains at least one functional group that interacts with the pigment;
By satisfying the above requirement, it is preferable that the dispersant can be efficiently and moderately included in the particles.

The dispersant to be embedded used in the present invention is preferably used by dissolving it in a good solvent for dissolving the pigment, a good solvent prepared separately from this, or a poor solvent. The following method is mentioned as a preferable embodiment of dissolution and mixing of the dispersant.
(1) A method in which a dispersant is co-dissolved in a good solvent together with a pigment, and is contacted with a poor solvent, followed by precipitation. (3) A method of bringing a pigment solution and a poor solvent into contact with each other in which a dispersant is dissolved to cause precipitation, and the like.
The fine particles of the present invention may be prepared by any of these methods, but it is preferable that the dispersant-dissolved solution is compatible with the pigment-dissolved solution. If the dispersant solution and the pigment solution are not compatible, mixing with the poor solvent may prevent the dispersant from being sufficiently incorporated into the particles. Among the above methods, the methods (1) and (2) are particularly preferably used.

  In the present invention, in order to incorporate the dispersant into the particles, the dispersant is preferably a polymer dispersant having a mass average molecular weight of 1000 or more, more preferably 3000 to 300,000, particularly preferably 5000. More than 100,000. If the molecular weight of the dispersant is too low, the proportion of the dispersant incorporated into the particle may decrease, and if it is too large, aggregation of the dispersant may increase and redispersibility may deteriorate. The dispersion of the dispersant is preferably narrow, that is, monodisperse. The degree of dispersion of the dispersant is represented by the ratio of the number average molecular weight to the mass average molecular weight, and a dispersant having a dispersity in the range of 1.0 to 5.0 is preferable, and a range of 1.0 to 4.0 is particularly preferable. Is used.

  A dispersant for embedding in fine particles used in the present invention (hereinafter, sometimes referred to as “embedding dispersant” to be distinguished from a simple dispersant) is dissolved in a good solvent in advance, and this is referred to as a poor solvent. What precipitates by mixing is preferable. At this time, the pigment is also preferably dissolved in a good solvent and has a property of being precipitated and brought into fine particles when brought into contact with a poor solvent. In the precipitation behavior of molecules in the formation of such fine particles, when the deposition rate of the dispersant is significantly higher (faster) than the deposition rate of the pigment, the dispersant is deposited before the dispersant is sufficiently incorporated into the particles. End up. Therefore, it is difficult for the dispersant to be taken into the particles. In order to sufficiently incorporate the dispersant into the particles, it is preferable that the deposition rate of the dispersant is lower than the deposition rate of the pigment. And the state which takes in this dispersing agent in microparticles | fine-particles can be controlled by adjusting the deposition rate of the embedding dispersing agent in this way as needed. In this way, from the viewpoint of precipitation so as to form a eutectic, the deposition rate of the embedding dispersant is preferably slower than that of the pigment, and the preferred rate is the type of pigment, the affinity between the pigment and the dispersant, Depending on the precipitation rate of the pigment, the structure of the dispersant, the solvent affinity between the good solvent and the poor solvent, and the like, it is preferable to determine the precipitation rate ratio between the pigment and the dispersant based on each particle forming condition.

Next, the structure and the action of a preferred dispersant for incorporating the embedding dispersant into the particles and further preventing the embedded dispersant from being released in the dispersion medium or the composition medium will be described.
In order to embed the embedding dispersant appropriately in the particles, the chemical structure of the embedding dispersant should be changed so that the dispersing agent and the pigment are interacted with each other at the stage of precipitation through the mixing process. It is preferable to design. In the present invention, it is preferable to mix the embedding dispersant and the pigment in a state of being dissolved in a solvent. At this time, if the above-described interaction between the dispersant and the pigment is small, the incorporation rate of the dispersing agent into the particles is reduced. May become too small, or the embedded dispersant may be easily released in the dispersion medium or the composition medium, or the dispersion stability may deteriorate. Therefore, it is preferable to use an embedding dispersant having a structural part that attracts and interacts strongly with the pigment, and it is preferable to strengthen this interaction and firmly fix the dispersant to the particles.

  In the fine particles of the present invention, it is preferable that 10% by mass or more of the embedding dispersant introduced into the system when the fine particles are formed is embedded. That is, with respect to the mass (A) of the added embedding dispersant, the percentage of the mass (B) of the dispersant incorporated and embedded in the particles ((B) / (A) × 100) ( Hereinafter, this rate may be referred to as “dispersing agent uptake rate.”) Is preferably 10% by mass or more. If the dispersant uptake rate is too small, initial dispersibility and dispersion stability may not be sufficient. Further, the dispersant uptake rate ((B) / (A)) is more preferably 20% by mass or more, and particularly preferably 30% by mass or more. Although there is no particular upper limit on the dispersant uptake rate, the upper limit in calculation is 100% by mass, and it is practical that it is 98% or less. In the present invention, the dispersant uptake rate is calculated according to the method described in the following examples unless otherwise specified.

  When the amount of the embedding dispersant incorporated is the ratio of the fine particles to the mass of components other than the dispersant, that is, the fine particles are considered to be the continuous phase formed by the embedding dispersant forming the dispersed phase and the pigment, etc. % Of the ratio of the mass (X) of the embedding dispersant forming the above dispersed phase to the mass (Y) of the continuous phase of ((X) / (Y) × 100) (hereinafter, this ratio is referred to as “dispersant When it is referred to as “embedding rate”), it is 5 to 200% by mass, and more preferably 8 to 160% by mass. The measurement and calculation of the “dispersing agent embedding rate” is performed according to the method described in the following examples unless otherwise specified.

  The interaction attracting with the embedding dispersant or a pigment preferable as a structural site thereof means an interaction between molecules or the adsorptive property or affinity between the structural sites, specifically, hydrogen bonding interaction, π There are -π interaction, ion-ion interaction, dipole interaction, London dispersion force (Van der Waals force), and charge transfer interaction. Other examples include hydrophobic interaction based on thermodynamic factors. Any of the above-described interactions may be used as the interaction between the dispersant or the structural portion thereof and the pigment, and is not particularly limited. In particular, the hydrogen bond interaction, the π-π interaction, and the interionic interaction It is effective to be an action. Therefore, it is preferable to introduce a site exhibiting the above-mentioned interaction as a partial structure of the embedding / dispersing agent, whereby the dispersing agent is easily taken into the particles and easily embedded.

  In the following, embodiments of hydrogen bond interaction, π-π interaction, and ion-ion interaction will be described as examples, and the molecular structure of the dispersant and its design for imparting these interactions will be described.

  The hydrogen bond interaction occurs in a molecule in which hydrogen is covalently bonded to an atom having high electronegativity such as fluorine, oxygen, and nitrogen. In this case, a polar molecule is generated. At this time, the hydrogen atom is charged to a positive charge smaller than 1, and as a result, an interaction occurs when an attempt is made to adsorb a negatively charged atom such as oxygen contained in another nearby molecule. This results in a stable bond that connects the two molecules. For example, when a dispersant having a functional group that easily causes the above-described interaction via a hydrogen bond with a pigment is used, the incorporation rate of the dispersant into the fine particles can be increased.

  The π-π interaction is a dispersion force acting between aromatic rings of organic compound molecules, and is also called a stacking interaction. For example, aromatic compounds have a strong planar structure and abundant electrons delocalized by the π-electron system, so that the London dispersion force is particularly strong. Therefore, the force attracting each other increases as the number of π electrons increases. For example, when a dispersant having a functional group that easily interacts with the pigment by π-π can be used, the incorporation rate of the dispersant into the fine particles can be increased.

  The ion-ion interaction is an interaction that occurs between charged ions. For example, because different charges attract each other, if the molecular design is such that the dispersant has a charge different from that of the water-insoluble target substance in the dispersion medium, the interaction between the dispersant and the pigment becomes stronger, and the dispersion within the fine particles of the dispersant The uptake rate can be increased.

  In the present invention, it is preferable to use an embedding dispersant and a pigment that are molecularly designed so as to exhibit the plurality of interactions described above. The preferred molecular structure of the dispersant varies depending on the type of the target pigment. For example, in the case where the pigment is an organic pigment, a polymer compound having a heterocyclic moiety is added to impart a hydrogen bonding interaction. A polymer compound having a nitrogen-containing heterocyclic moiety can be used preferably. Furthermore, a dispersant having an aromatic ring as a partial structure is preferable in order to impart π-π interaction and hydrophobic interaction. Moreover, what has a heterocycle and an aromatic ring simultaneously in the same molecular skeleton is especially preferable.

  Specific examples of the heterocyclic partial structure of a preferable dispersant used in the present invention include the following sites (I-1) to (I-29), phthalocyanine-based, insoluble azo-based, azo lake-based, anthraquinone-based, quinacridone-based. Organic dye structures such as dioxazine, diketopyrrolopyrrole, anthrapyridine, ansanthrone, indanthrone, flavanthrone, perinone, perylene, thioindigo, etc. It is not limited to. The unit having these sites is preferably 1.0 to 99.0 mol%, more preferably 3.0 to 95.0 mol% of the entire unit constituting the polymer compound. It is particularly preferable that it be introduced in the range of 0 to 90.0 mol%.

  In addition, as the dispersant used in the present invention, a dispersant having the following sites (II-1) to (II-4) can also be used for the purpose of interaction between ions, but the present invention is particularly limited to these. It will never be done. The unit having these sites is preferably 1.0 to 99.0 mol%, more preferably 3.0 to 95.0 mol% of the entire unit constituting the polymer compound. It is particularly preferable that it be introduced in the range of 0 to 90.0 mol%.

The embedding / dispersing agent is preferably a polymer compound having the above-mentioned interaction group in a partial structure, but further includes an organic solvent-based medium (for example, an alcohol solvent, a ketone solvent, an ether solvent, a sulfoxide solvent, an ester solvent). Preferable examples include solvents, amide solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, nitrile solvents, and mixtures thereof. Among them, ketone solvents, ether solvents, ester solvents An aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, or a mixture thereof is more preferable.
Examples of the ketone solvent include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and the like. Examples of the ether solvent include propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate. Examples of the ester solvent include 1,3-butylene glycol diacetate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, ethyl Examples thereof include carbitol acetate and butyl carbitol acetate. Examples of the aromatic hydrocarbon solvent include toluene and xylene. Examples of the aliphatic hydrocarbon solvent include cyclohexane and n-octane.
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. The content of the organic solvent is preferably 10 to 95% by mass with respect to the total amount of the composition. ) Or reactive diluents (eg 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, ethoxylated phenyl (meth) acrylate, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxytetraethylene glycol) It is preferable that a dispersion medium such as (meth) acrylate, N-vinyl-2-pyrrolidone, N-acryloylmorpholine) has a partial structure having high affinity. Since the steric repulsion part has an affinity for the dispersion medium, dispersibility can be imparted in the dispersion medium by the part (2o part in FIG. 1) of the embedding dispersant outside the particle.

  The affinity site for the dispersion medium is not particularly limited. For example, the (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid described above are used. Preferred examples include diesters, (meth) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile and the like.

  As described above, the embedding dispersant used in the present invention is a polymer dispersant having a structural portion that exhibits an interaction attracting the pigment composed of an aromatic ring and a nitrogen-containing cyclic hydrocarbon group and / or a quaternary ammonium group. It is preferable that At this time, the aromatic ring and the nitrogen-containing cyclic hydrocarbon group and / or the quaternary ammonium group are preferably in the same structural site, and they may be linked to each other to form a ring.

  In the dispersant used in the present invention, various functional groups can be introduced in addition to the interaction group attracting the above-mentioned pigment. Examples of functional groups include a hydrophobic group, an acid group, a basic group, a cross-linking group, a photopolymerizable group, a heat-polymerizable group, etc., depending on the dispersion medium, the medium type of the composition, or the use of the composition. Can be introduced. The unit having these functional groups is preferably 95 mol% or less, more preferably 90.0 mol% or less, and more preferably 85 mol% or less of the entire unit constituting the polymer compound. It is particularly preferable. The embedding dispersant is preferably a water-insoluble polymer compound. If the polymer compound is water-soluble, it may be difficult to incorporate the dispersant into the fine particles when it is brought into contact with a poor solvent containing water as a main component.

  Examples of the acidic group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, (meth) acrylic acid ω- Carboxy-polycaprolactone can also be used. Examples of the carboxyl group precursor include anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride. Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.

  As basic groups, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, 1- (N, N-dimethylamino) -1, (meth) acrylic acid, 1-dimethylmethyl, N, N-dimethylaminohexyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diisopropylaminoethyl (meth) acrylate, N (meth) acrylic acid, N-di-n-butylaminoethyl, N, N-di-i-butylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, piperidinoethyl (meth) acrylate, 1-pyrrole (meth) acrylate Dinoethyl, N, N-methyl-2-pyrrolidylaminoethyl (meth) acrylate and N, N-methylphenyl (meth) acrylate And (meth) acrylamides include N- (N ′, N′-dimethylaminoethyl) acrylamide, N- (N ′, N′-dimethylaminoethyl) methacrylamide, N- (N ', N'-diethylaminoethyl) acrylamide, N- (N', N'-diethylaminoethyl) methacrylamide, N- (N ', N'-dimethylaminopropyl) acrylamide, N- (N', N'-dimethyl) Aminopropyl) methacrylamide, N- (N ′, N′-diethylaminopropyl) acrylamide, N- (N ′, N′-diethylaminopropyl) methacrylamide, 2- (N, N-dimethylamino) ethyl (meth) acrylamide 2- (N, N-diethylamino) ethyl (meth) acrylamide, 3- (N, N-di Tilamino) propyl (meth) acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylamide and 6- (N , N-diethylamino) hexyl (meth) acrylamide, morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide and the like, and styrenes include N, N-dimethylaminostyrene. N, N-dimethylaminomethylstyrene, and the like.

  Moreover, it is also possible to use a monomer having a urea group, a urethane group, a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, or a hydroxyl group. Specifically, for example, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, (meth ) Acrylic acid cyclohexyl, (meth) acrylic acid t-butylcyclohexyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid octyl, (meth) acrylic acid t-octyl, (meth) acrylic acid isobornyl, (meth) Mention may be made of dodecyl acrylate, octadecyl (meth) acrylate, stearyl (meth) acrylate, oleyl (meth) acrylate, adamantyl (meth) acrylate, and monomers having the following structure.

  The other functional group is more preferably a vinyl monomer polymer or copolymer having a hydrocarbon group having 4 or more carbon atoms, and a hydrocarbon group having 6 to 24 carbon atoms. It is particularly preferable that the monomer has a polymer or copolymer.

  Furthermore, a monomer containing an ionic functional group can be used. Among the ionic vinyl monomers (anionic vinyl monomers, cationic vinyl monomers), as the anionic vinyl monomer, alkali metal salts of vinyl monomers having the acidic group, organic amines (for example, triethylamine, dimethylaminoethanol, etc.) A salt with a tertiary amine), and as the cationic vinyl monomer, the nitrogen-containing vinyl monomer is an alkyl halide (alkyl group: C1-18, halogen atom: chlorine atom, bromine atom or iodine atom): Benzyl halides such as benzyl chloride and benzyl bromide; alkylsulfonic acid esters such as methanesulfonic acid (alkyl groups: C1-18); arylsulfonic acid alkyl esters such as benzenesulfonic acid and toluenesulfonic acid (alkyl groups: C1 18); dialky sulfate (Alkyl group: C1 -4) that is quaternized with such, like dialkyl diallyl ammonium salts.

  The fine particles of the present invention can also be used as a colorant for inkjet recording ink. In this case, the main component of the dispersion medium and / or the composition medium is an aqueous solvent (for example, water and a water / water-soluble organic solvent mixture. Examples of the water-soluble organic solvent include glycerin, 1,2,6-hexanetriol, Trimethylolpropane, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2 Alkanediols such as methyl-2,4-pentanediol, 1,2-octanediol, 1,2-hexanediol, 1,2-pentanediol, 4-methyl-1,2-pentanediol (polyhydric alcohols) ); Glucose, Mannose, Fructose, Ribo Sugars such as xylose, arabinose, galactose, aldonic acid, glucitol, maltose, cellobiose, lactose, sucrose, trehalose, maltotriose; sugar alcohols; hyaluronic acids; so-called solid wetting agents such as ureas; ethanol, methanol, butanol Alkyl alcohols having 1 to 4 carbon atoms such as propanol and isopropanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono- n-propyl ether, ethylene glycol mono-iso-propyl ether , Diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl Ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether , Glycol ethers such as dipropylene glycol mono-iso-propyl ether; 2 -Pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, formamide, acetamide, dimethyl sulfoxide, sorbitol, sorbitan, acetin, diacetin, triacetin, sulfolane and the like, one of these Or 2 or more types can be used.

  For the purpose of drying inhibitors and wetting agents, polyhydric alcohols are useful. For example, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol. 2,3-butanediol, 1,4-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, tetraethylene glycol, 1,6-hexanediol, 2-methyl-2, Examples include 4-pentanediol, polyethylene glycol, 1,2,4-butanetriol, 1,2,6-hexanetriol, and the like. These may be used singly or in combination of two or more), and it is possible to suppress aggregation between fine particles by electrostatic repulsion, and the acidity By introducing a group, basic group, or ionic functional group, dispersion in an aqueous medium becomes possible.

  The form of polymerization of the embedding dispersant having the interaction group, the steric repulsion dispersing group, and various functional groups is not particularly limited, but the unit having the interaction group, the unit having the steric repulsion dispersion group, various types Polymers or copolymers of vinyl monomers in units having functional groups (for example, alkyl methacrylate homopolymers, styrene homopolymers, alkyl methacrylate / styrene copolymers, polyvinyl butyral, etc.) , Ester polymers (eg, polycaprolactone), ether polymers (eg, polytetramethylene oxide), urethane polymers (eg, polyurethane made of tetramethylene glycol and hexamethylene diisocyanate), amide polymers (eg, Polyamide 6, polyamide 66, etc. , Silicone polymers (e.g., polydimethyl siloxane, etc.), carbonate-based polymers (e.g., polycarbonate synthesized from bisphenol A and phosgene), and the like.

  Among these, the polymer compound is preferably a polymer or copolymer of each vinyl monomer, an ester polymer, an ether polymer, or a modified product or copolymer thereof. From the viewpoint of adjusting solubility in a solvent, cost, ease of synthesis, etc., the polymer compound is most preferably a polymer or copolymer of each vinyl monomer.

  For production of a polymer or copolymer of each vinyl monomer, for example, a radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing a vinyl monomer polymer or copolymer by radical polymerization can be easily set by those skilled in the art. The conditions can also be determined experimentally.

  As the polymer dispersant used as the embedding dispersant, any binding form may be used. Specifically, any (co) polymers of random (co) polymers, block (co) polymers, and graft (co) polymers can be used. In particular, block (co) polymers, grafts (Co) polymers are preferred.

It is also preferable to use the following polymer compounds as the embedding dispersant.
The polymer compound is not particularly limited, but a vinyl monomer polymer or copolymer (for example, an alkyl methacrylate homopolymer, a styrene homopolymer, an alkyl methacrylate / styrene copolymer), Polyvinyl butyral, etc.), ester polymers (eg, polycaprolactone), ether polymers (eg, polytetramethylene oxide), urethane polymers (eg, polyurethane made of tetramethylene glycol and hexamethylene diisocyanate), amides Polymer (for example, polyamide 6, polyamide 66, etc.), silicone-based polymer (for example, polydimethylsiloxane), carbonate-based polymer (for example, polycarbonate synthesized from bisphenol A and phosgene) And the like.

  Among these, the polymer compound is preferably a polymer or copolymer of a vinyl monomer, an ester polymer, an ether polymer, or a modified product or copolymer thereof. From the viewpoints of adjusting solubility in a solvent, cost, ease of synthesis, and the like, the polymer compound is particularly preferably a vinyl monomer polymer or copolymer.

  Although it does not restrict | limit especially as said vinyl monomer, For example, the above-mentioned (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) Preferred examples include acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile and the like.

  The polymer compound is more preferably a polymer or copolymer of a vinyl monomer having a hydrocarbon group having 4 or more carbon atoms, and further having a hydrocarbon group having 6 to 24 carbon atoms. A monomer polymer or copolymer is particularly preferred. Examples include n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate T-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, t-octyl (meth) acrylate, isobornyl (meth) acrylate, dodecyl (meth) acrylate, Specific examples include octadecyl (meth) acrylate, stearyl (meth) acrylate, oleyl (meth) acrylate, and adamantyl (meth) acrylate.

  In addition to the above, preferred examples of the vinyl monomer include the vinyl monomers having an acidic group and the vinyl monomers having a basic group.

  The polymer compound is preferably a monomer having an organic dye structure or a heterocyclic structure. Examples of the monomer having an organic dye structure or a heterocyclic structure include, for example, phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, anthanthrone Ron, flavanthrone, perinone, perylene, and thioindigo dye structures such as thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadi Azole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolino , Mention may be made of benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, a monomer having a heterocyclic structure anthraquinone.

  Among these monomers having an organic dye structure or a heterocyclic structure, more specifically, the polymer compound is a monomer polymer or copolymer represented by the general formula (11) Is preferred. In the present invention, when the polymer compound is represented by a repeating unit structural formula, the terminal group may be any atom or any group, and may be simply a hydrogen atom, a polymerization terminator residue, or the like.

(Wherein R ¹ represents a hydrogen atom or a methyl group, J represents —CO—, —COO—, —CONR ⁶ —, —OCO—, a phenylene group, or —C ₆ H ₄ CO— group; ⁶ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, W ¹ represents a single bond, a linear, branched, or cyclic alkylene group, or an aralkylene group, and P represents a heterocyclic group.

In formula (1), J is preferably —CO—, a phenylene group, or a benzoyl group. R ⁶ represents a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an n-hexyl group, an n-octyl group, a 2-hydroxyethyl group), an aryl Represents a group (for example, a phenyl group), preferably a hydrogen atom, a methyl group, or an ethyl group.

The alkylene group represented by W ¹ is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms. For example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an octylene group, a decylene group, and the like can be given. Among them, a methylene group, an ethylene group, or a propylene group is preferable. The aralkylene group represented by W ¹ is preferably an aralkylene group having 7 to 13 carbon atoms, and examples thereof include a benzylidene group and a cinnamylidene group. The arylene group represented by W ¹ is preferably an arylene group having 6 to 12 carbon atoms, and examples thereof include a phenylene group, a cumenylene group, a mesitylene group, a tolylene group, and a xylylene group, and among them, a phenylene group is particularly preferable. .

In the linear, branched or cyclic alkylene group and aralkylene group represented by W ¹ , —NR ³² —, —NR ³² R ³³ —, —COO—, —OCO—, —O—, —SO ₂ NH—, —NHSO ₂ —, —NHCOO—, —OCONH—, or a group derived from a heterocyclic ring may be interposed as a linking group. R ³² and R ³³ each independently represent hydrogen or an alkyl group, and preferred examples include hydrogen, a methyl group, an ethyl group, and a propyl group.

Among the linking groups represented by W ¹ , a single bond or an alkylene group is preferable, and a methylene group, an ethylene group, or a 2-hydroxypropylene group is more preferable.

  In formula (1), P represents a heterocyclic group, and among them, a heterocyclic residue constituting an organic pigment is preferable, and phthalocyanine series, insoluble azo series, azo lake series, anthraquinone series, quinacridone series, dioxazine series, diketopyrrolo Examples thereof include heterocyclic residues that form pyrrole, anthrapyrimidine, ansanthrone, indanthrone, flavanthrone, perinone, perylene, thioindigo, and quinophthalone pigments. The heterocyclic residues include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine , Pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, barbitur, thiobarbitur, carbazole, acridine, acridone Quinacridone, anthraquinone, phthalimide, quinaldine, quinophthalone, thiophene, furan, xanthone Pyrrole, imidazole, isoindoline, isoindolinone, benzimidazolone, indole, quinoline, carbazole, acridine, acridone, quinacridone, anthraquinone, phthalimide, quinaldine, quinophthalone, etc. are preferred, benzimidazolone, indole, quinoline, barbitur Thiobarbitur, carbazole, acridine, acridone, anthraquinone, and phthalimide are particularly preferred. These heterocyclic residues can be appropriately selected in view of the structure or electronic properties of the pigment used.

  As the repeating unit represented by the general formula (11), those represented by the general formulas (12) and (13) are preferable.

R ¹ represents a hydrogen atom or a methyl group. Y represents —NH—, —O—, or —S—. W ² represents a single bond or a divalent linking group, and is preferably a single bond, a linear, branched or cyclic alkylene group, or an aralkylene group. P represents a heterocyclic group. In the above formula, the preferred range of W ² is the same as W ¹ in the general formula (11). In the above formula, P is the same as P in the general formula (1).

  Specific preferred examples of the structures represented by the general formulas (11), (12), and (13) are given below. Note that the present invention is not limited to this.

  Along with those exemplified above, P in the repeating unit represented by the general formulas (11), (12), and (13) is represented by the following general formula (14) or a tautomer structure thereof. Is also preferred.

R ² represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R ³ represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, or an azo group.

  Here, tautomerism will be described. Tautomerism is reversible interconversion between isomers, and is a phenomenon in which hydrogen atoms are rearranged mainly by proton rearrangement. The tautomers are those that can reach an equilibrium state in which both isomers can coexist with each other, and the isomers that can convert each other have a high isomerization rate. As a common example, it occurs by a rearrangement reaction of a hydrogen atom, that is, a proton accompanied by conversion of a single bond and a double bond. The rate of isomerization and the equilibrium ratio vary depending on the temperature, pH, liquid phase or solid phase, and in the case of a solution, the type of solvent. Even when equilibrium is reached for several hours to several days, it is often referred to as tautomerism.

  In the present invention, the chemical structure (part) showing the above tautomerism in the polymer compound is referred to as tautomer structure (part), and tautomerization in the repeating unit represented by the general formula (14) is performed. The chemical structure (tautomer structure) obtained by the reaction is as shown in the following formulas (a) to (h).

Among these, R ² is preferably a hydrogen atom, a methyl group, an ethyl group, a 2-ethylhexyl group, or a phenyl group.
Among them, the substituent represented by R ³ preferably has an azo structure represented by the following general formula (17).

R ²³ represents a substituted or unsubstituted aromatic ring or a hetero atom-containing heterocycle (for example, an oxygen atom, a sulfur atom, a nitrogen atom, etc.). Among these, the aromatic ring and heterocyclic ring structure is preferably a 5-membered to 6-membered monocyclic or bicondensed ring. Among them, benzene ring, pyridine ring, pyrimidine ring, imidazole ring, isoxazole ring, oxazole ring, thiazole ring, pyrazole ring, triazole ring, tetrazole ring, benzimidazole ring, benzthiazole ring, benzoxazole ring, benzisoxazole ring A benzothiazole thiadiazole ring is preferred.

  Specific examples of the repeating unit having the group represented by the general formula (14) as the heterocyclic group P are listed below, but the present invention is not limited thereto. In addition, the structure given in this specific example is one example of possible tautomeric structures, and other tautomeric structures can be taken.

  The polymer compound is preferably a graft copolymer containing a repeating unit obtained by copolymerizing a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal. Such a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal is also called a macromonomer because it is a compound having a predetermined molecular weight. This specific polymerizable oligomer is preferably composed of a polymer chain part and a part of a polymerizable functional group having an ethylenically unsaturated double bond at its terminal. It is preferable from the viewpoint of obtaining a desired graft polymer that such a group having an ethylenically unsaturated double bond is present only at one end of the polymer chain. As the group having an ethylenically unsaturated double bond, a (meth) acryloyl group and a vinyl group are preferable, and a (meth) acryloyl group is particularly preferable.

Moreover, it is preferable that this macromonomer has the number average molecular weight (Mn) of polystyrene conversion in the range of 1000-20000, and the range of 2000-10000 is especially preferable.
The polymer chain part is a homopolymer or copolymer formed from at least one monomer selected from the group consisting of alkyl (meth) acrylate, styrene and derivatives thereof, acrylonitrile, vinyl acetate and butadiene, or polyethylene oxide. Polypropylene oxide and polycaprolactone are generally used.
The polymerizable oligomer is preferably an oligomer represented by the following general formula (15).

However, R < ⁹ > and R < ¹¹ > represents a hydrogen atom or a methyl group each independently, R < ¹⁰ > is a C1-C12 alkylene group (preferably C2-C4 alkylene group, a substituent ( For example, it may have a hydroxyl group and may be further linked via an ester bond, an ether bond, an amide bond, etc.), and Z represents a phenyl group or an alkyl group having 1 to 4 carbon atoms. A phenyl group or —COOR ¹² (wherein R ¹² represents an alkyl group having 1 to 6 carbon atoms, a phenyl group or an arylalkyl group having 7 to 10 carbon atoms), and q is from 20 to 200 is there. Z is preferably a phenyl group or —COOR ¹² (wherein R ¹² is an alkyl group having 1 to 12 carbon atoms).
Preferred examples of the polymerizable oligomer (macromonomer) include polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, poly-i-butyl (meth) acrylate, and one molecular end of polystyrene (meth). A polymer having an acryloyl group bonded thereto can be mentioned. As such a polymerizable oligomer available on the market, 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.) and one-terminal methacryloylated poly-n-butyl methacrylate oligomer (Mn = 6000, trade name: AB-6, Toa Gosei Chemical Co., Ltd.) ) Made).

  The polymerizable oligomer is preferably not only a polymerizable oligomer represented by the general formula (15) but also a polymerizable oligomer represented by the following general formula (16).

In the general formula (16), R ¹³ represents a hydrogen atom or a methyl group, and R ¹⁴ represents an alkylene group having 1 to 8 carbon atoms. Q represents ^{-OR 15} or -OCOR ^16. Here, R ¹⁵ and R ¹⁶ represent a hydrogen atom, an alkyl group, or an aryl group. n represents 2 to 200.
In the general formula (16), R ¹³ represents a hydrogen atom or a methyl group. R ¹⁴ 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. Q represents ^{-OR 15} or -OCOR ^16. Here, R ¹⁵ 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 ¹⁶ represents an alkyl group having 1 to 18 carbon atoms. Moreover, n represents 2-200, 5-100 are preferable and 10-100 are especially preferable.

Examples of the polymerizable oligomer represented by the general formula (16) include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, and polytetramethylene glycol monomethacrylate. These may be commercially available products or may be appropriately synthesized.
The polymerizable monomer represented by the general formula (16) is also available as a commercial product as described above, and as a commercial product, methoxypolyethylene glycol methacrylate (trade names: NK ester M-40G, M-90G, M -230G (manufactured by Shin-Nakamura Chemical Co., Ltd.); trade names: Blemmer PME-100, PME-200, PME-400, PME-1000, PME-2000, PME-4000 (above, NOF Corporation) Manufactured)), 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 Methacrylate (Brandmer 70PEP-350B, manufactured by NOF Corporation), Polyethylene glycol polytetramethylene glycol monomethacrylate (Brandmer 55PET-800, manufactured by NOF Corporation), Polypropylene glycol polytetramethylene glycol mono Methacrylate (trade name: Bremmer NHK-5050, manufactured by NOF Corporation), and the like.
In addition to the polymerizable oligomers represented by the general formulas (15) and (16), polycaprolactone monomers are also preferable. Examples of commercially available products include polycaprolactone monomethacrylate (trade names: Plaxel FM2D, FM3, FM5, FA1DDM, FA2D, Daicel Chemical). Kogyo Co., Ltd.).

  For the production of a polymer or copolymer of vinyl monomers, for example, a radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing a vinyl monomer polymer or copolymer by radical polymerization can be easily set by those skilled in the art. The conditions can also be determined experimentally.

  The polymer or copolymer of the vinyl monomer may be a polymer compound having a functional group at the terminal. The functional group is preferably a functional group excellent in adsorbability to the deposited pigment.

  The polymer compound having a functional group at the terminal can be polymerized using, for example, a method of performing radical polymerization using a chain transfer agent containing a functional group, or a polymerization initiator containing a functional group (eg, radical polymerization, cationic polymerization). , Anionic polymerization, etc.).

  Examples of the chain transfer agent capable of introducing a functional group at the terminal of the polymer compound include mercapto compounds (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mecaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto- 2-propanol, 3-mercapto-2- (Tanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, benzenethiol, toluenethiol, mercaptoacetophenone, naphthalenethiol, naphthalenemethanethiol, etc.) or oxidized products of these mercapto compounds Examples thereof include disulfide compounds and halogen compounds (for example, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.).

  Examples of the polymerization initiator capable of introducing a functional group at the terminal of the polymer compound include 2,2′-azobis (2-cyanopropanol), 2,2′-azobis (2-cyanopentanol), 4, 4'-azobis (4-cyanovaleric acid), 4,4'-azobis (4-cyanovaleric acid chloride), 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane ], 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] 2,2′-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -Propionamide] etc. And derivatives thereof.

  The amount of the embedding dispersant used is not particularly limited, but when the pigment fine particles are precipitated, the amount added to the system is preferably in the range of 10 to 300 parts by mass with respect to 100 parts by mass of the pigment. The range of 10 to 120 parts by mass is more preferable, and the range of 20 to 100 parts by mass is particularly preferable. In the fine particles of the present invention, as described above, it is preferable that 10% by mass or more of the embedding dispersant to be added to the reprecipitation method is embedded. The embedding dispersant may be used alone or in combination of two or more. The content of the embedding dispersant in the dispersion of the present invention is not particularly limited, but the upper limit is an amount added in the system, and the lower limit is practically an amount embedded in fine particles. Specifically, it is preferably 1 to 294% by mass, more preferably 2 to 99% by mass.

Examples of the polymer compound that can be used as the embedding dispersant in the present invention are shown below, but the present invention is not limited thereto.
(1) Polymethyl methacrylate (2) Polypropylene glycol (3) Polyε caprolactone (4) Methyl methacrylate / styrene copolymer (5) Benzyl methacrylate / acrylic acid copolymer (6) Methyl methacrylate / dimethylamino Propylacrylamide copolymer (7) Methyl methacrylate / monomer copolymer giving the above constituent Q-17 (8) Methyl methacrylate / monomer giving the above constituent Q-17 / Terminal methacryloylated polymethyl methacrylate copolymer (9) Monomer / Styrene / Methacrylic Acid Copolymer Providing Component M-1 (10) Monomer / Terminal Methacryloylated Polymethyl Methacrylate / Methacrylic Acid Copolymer Providing Component M-1 (11) Configuration Monomer / terminal methacrylate giving component M-1 Ilylated polymethyl methacrylate / dimethylaminopropyl acrylamide copolymer (12) Monomer providing the above component Q-22 / terminal methacryloylated polystyrene / methacrylic acid copolymer (13) Monomer / terminal providing the above component Q-10 Methacryloylated polybutylmethacrylate / methacrylic acid copolymer (14) Monomer / terminal (meth) acryloylated polyethylene glycol polypropylene glycol / methacrylic acid copolymer (15) giving the constituent component M-1 Monomer to give / terminal (meth) acryloylated polyethylene glycol / methacrylic acid copolymer (16) On monomer / terminal (meth) acryloylated polypropylene glycol / methacrylic acid copolymer (17) to give component Q-1 Monomer / terminal methacryloylated polycaprolactone / methacrylic acid copolymer (18) that gives component M-1 Monomer / terminal methacryloylated polystyrene / methacrylic acid / dimethylaminopropylacrylamide copolymer (18) that gives constituent Q-21 19) Monomer / terminal methacryloylated polymethyl methacrylate copolymer that provides the above component M-1 (20) Monomer / styrene / dimethylaminopropylacrylamide copolymer that provides the above component Q-22 (21) Component M -1 monomer / N, N-dimethyl-4-vinylbenzamide / methacrylic acid copolymer (22) Monomer giving the above constituent Q-23 / 4-tbutylstyrene / methacrylic acid copolymer (23) Monomer that provides component M-3 / Tacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (24) Monomer / terminated methacrylic acid / terminated methacryloylated polycaprolactone copolymer (25) Monomer / terminated to provide component M-2 Methacryloylated polymethyl methacrylate / terminated (meth) acryloylated polyethylene glycol polypropylene glycol copolymer (26) Monomer / methacrylic acid / terminated methacryloylated polymethyl methacrylate / polyethylene glycol mono (meth) acrylate copolymer to give the above component M-7 Polymer (27) Monomer that gives component Q-9 / 4-vinylpyridine / terminal methacryloylated polymethyl methacrylate copolymer (28) Monomer / terminal that gives component M-10 Tacryloylated polybutyl methacrylate / N-vinylimidazole copolymer (29) Monomer / methacrylic acid / terminal methacryloylated poly n-butyl methacrylate / terminal methacryloylated polymethyl methacrylate copolymer (30) to give the above component M-1 Monomer / acrylic acid / terminated methacryloylated polymethylmethacrylate copolymer (31) giving the above constituent component Q-4 Monomer / styrene / methacrylic acid copolymer (32) giving the above constituent component M-13 1 monomer / methacrylic acid / terminated methacryloylated polymethyl methacrylate / dodecyl methacrylate copolymer (33) Monomer / methacrylic acid / terminal methacryloylated polystyrene / stearyl methacrylate copolymer giving the above component Q-1 Copolymer (34) Methacrylic acid / Terminal methacryloylated polymethyl methacrylate / Isobornyl methacrylate copolymer (35) Cyclohexyl cyclohexyl / 4-vinylpyridine copolymer (36) Monomer / butyl methacrylate giving the above component Q-1 Copolymer (37) Monomer giving the above component M-1 / styrene / methacrylic acid / methyl methacrylate copolymer (38) Monomer giving the above component M-2 / styrene / butyl methacrylate copolymer ( 39) Monomer giving the above component Q-21 / methacrylic acid tbutyl ester / methacrylic acid copolymer (40) Monomer giving the above component Q-10 / styrene / butylacrylamide copolymer (41) Methyl methacrylate / Methacrylic acid copolymer Alternatively, a commercially available polymer compound may be used. Examples of commercially available block polymers include “Disperbyk-2000, 2001” manufactured by BYK Chemie, “EFKA 4330, 4340” manufactured by EFKA, and the like. Examples of commercially available graft polymers include “Solsperse 24000, 28000, 32000, 38500, 39000, 55000” manufactured by Lubrizol, “Disperbyk-161, 171, 174” manufactured by BYK Chemie, and the like. Examples of commercially available terminal-modified polymers include “Solsperse 3000, 17000, 27000” manufactured by Lubrizol (all commercially available polymers are trade names).

  In the present invention, the embedding dispersant is preferably used in the range of 0.01 to 0.3 parts by mass, more preferably in the range of 0.01 to 0.1 parts by mass with respect to 1 part by mass of the pigment. .

  The fine particles of the pigment of the present invention are preferably those in which the embedding dispersant having the above specific structure portion is mainly used and embedded in the fine particles, but a non-embedded dispersant may be used in combination. Dispersants used in combination are, for example, viscosity adjustment of the dispersion, imparting reactivity with the embedding dispersant, imparting interaction with the embedding dispersant, imparting affinity with the dispersion medium, and precipitation with a poor solvent. It can be used for the purpose of deaggregating particles, the purpose of adjusting the size of fine particles, the purpose of adjusting the affinity between a good solvent and a poor solvent, and the purpose of imparting affinity to a dispersion medium. Ordinary dispersants such as surfactants, low molecular dispersants and polymer dispersants can be used in combination. The use ratio of the dispersant used in combination is not particularly limited, but it is preferably used in the range of 0.01 to 1 part by mass with respect to 1 part by mass of the embedding dispersant, and 0.05 to 0.5 It is more preferable to use in the range of parts by mass. Examples of the dispersant used in combination include the polymer compounds A to D described above.

[Preparation of color material for color filter and production of color filter]
When the crystallization treatment is performed in a state where the good solvent and the poor solvent are included, the good solvent and the poor solvent can be removed using the third solvent. Although the kind of 3rd solvent is not specifically limited, It is preferable that it is an organic solvent, for example, an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, an aliphatic compound solvent is preferable, an ester compound solvent, an aromatic compound solvent or Aliphatic compound solvents are more preferred, and ester compound solvents are particularly preferred. The third solvent may be a pure solvent based on the above solvent or a mixed solvent composed of a plurality of solvents.
In the present invention, not only the above-mentioned third solvent but also a fourth solvent described later, a solvent different from both the good solvent and the poor solvent, which is a medium of the dispersion composition, is collectively referred to as “first solvent”. 3 solvent ".

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

  Of these, ethyl lactate, ethyl acetate, ethanol, and 2- (1-methoxy) propyl acetate are preferable, and ethyl lactate and 2- (1-methoxy) propyl acetate are more preferable. These may be used alone or in combination of two or more. The third solvent is not the same as the good solvent or the poor solvent.

  The timing of the addition of the third solvent is not particularly limited as long as it is after the precipitation of the pigment fine particles. However, the third solvent may be added to the mixed liquid in which the fine particles are precipitated, or after removing a part of the solvent in the mixed liquid. It may be added, or all may be added after removal (concentration) in advance. That is, the third solvent can be used as a substitution solvent, and the solvent component consisting of the good solvent and the poor solvent in the dispersion liquid in which the fine particles are precipitated can be substituted with the third solvent. Alternatively, the third solvent can be added after the good solvent and the poor solvent are completely removed (concentrated) and taken out as pigment particle powder.

  In addition, when a pigment dispersion composition to be described later is used, after the first solvent removal step (first removal), the third solvent is added to replace the solvent, and the second solvent removal step ( The solvent may be removed and powdered by the second removal). Thereafter, a pigment dispersant and / or a solvent can be added to obtain a desired pigment dispersion composition. Alternatively, the good solvent and the poor solvent are completely removed (concentrated) and taken out as pigment particle powder, and then the third solvent and / or the pigment dispersant can be added to obtain a desired pigment dispersion composition. The amount of the third solvent added is not particularly limited, but is preferably 100 to 300,000 parts by mass, and more preferably 500 to 10,000 parts by mass with respect to 100 parts by mass of the fine particles of the water-insoluble colorant.

The process for removing the solvent component from the mixed solution after the pigment fine particles are deposited is not particularly limited, and examples thereof include a method of filtering with a filter and the like, a method of precipitating the pigment fine particles by centrifugation, and concentrating. As the filter filtration device, for example, a device such as reduced pressure or pressure filtration can be used. Examples of preferable filters include filter paper, nanofilters, and ultrafilters.
Any device may be used as the centrifuge as long as the fine pigment particles can be precipitated. For example, in addition to a general-purpose device, a device having a skimming function (a function of sucking a supernatant layer during rotation and discharging it out of the system), a continuous centrifuge that continuously discharges solid matter, and the like can be given. 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.
In addition, as a solvent removal step, a method of concentrating the solvent by sublimation by vacuum freeze-drying, a method of drying and concentrating the solvent by heating or decompression, a method combining them, or the like can also be used.

  The fine particles of the pigment can be used, for example, in a dispersed state 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.

  The concentration of fine particles in the dispersion composition of fine particles after redispersion is appropriately determined according to the purpose, but preferably the fine particles are preferably 2 to 30% by mass with respect to the total amount of the dispersion composition. It is more preferable that it is 5-15 mass%. When dispersed in the vehicle as described above, the amount of the binder and dissolved dilution component is appropriately determined depending on the type of pigment, etc., but the binder is preferably 1 to 30% by mass based on the total amount of the dispersion composition. 3 to 20% by mass is more preferable, and 5 to 15% by mass is particularly preferable. 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 present invention, when the pigment fine particles are redispersed in the third solvent, the aggregation state of the pigment fine particles is spontaneously solved in the third solvent and dispersed in the medium without adding another dispersant or the like. It is preferable to have this property, and this property is referred to as “self-dispersible” or “self-dispersible”. However, in order to further improve the redispersibility in the present invention, a pigment dispersant or the like may be added during redispersion of the fine particles.

As a method of redispersing the fine particles in such an aggregated state, 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, so 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 limitations on the disperser used when dispersing the pigment nanoparticles by applying physical energy, for example, dispersers such as kneaders, roll mills, atriders, super mills, dissolvers, homomixers, and sand mills. Can be mentioned. Further, a high-pressure dispersion method and a dispersion method using fine particle beads are also preferable.

For the purpose of further improving the dispersibility of the pigment, conventionally known dispersants such as pigment dispersants and surfactants can be added to the pigment dispersion composition as long as the effects of the present invention are not impaired. Examples of pigment dispersants include polymer dispersants (for example, linear polymers, block polymers, graft polymers, terminal-modified polymers, etc.), surfactants (polyoxyethylene alkyl phosphate ester, poly Oxyethylene alkylamine, alkanolamine, etc.), pigment derivatives and the like. The dispersant acts to adsorb on the surface of the pigment and prevent reaggregation. For this reason, a block polymer, a graft polymer, and a terminal-modified polymer having an anchor site to the pigment surface can be cited as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.
Examples of the polymer compound include “Disperbyk-2000, 2001” manufactured by BYK Chemie, “EFKA 4330, 4340” manufactured by EFKA, and the like. Examples of the graft polymer include “Solsperse 24000, 28000, 32000, 38500, 39000, 55000” manufactured by Lubrizol, “Disperbyk-161, 171, 174” manufactured by BYK Chemie, and the like. Examples of the terminal-modified polymer include “Solsperse 3000, 17000, 27000” manufactured by Lubrizol (all are trade names).

  In the present invention, the pigment derivative (hereinafter also referred to as “pigment derivative type dispersant”) is derived from an organic pigment as a parent substance, and is manufactured by chemically modifying the parent structure, or It is defined as a pigment derivative type dispersant obtained by a pigmentation reaction of a chemically modified pigment precursor. Generally, it is also called a synergist type dispersant.

  Although not particularly limited, for example, a functional group such as a pigment derivative having an acidic group, a pigment derivative having a basic group, or a phthalimidomethyl group described in JP-A-2007-9096, JP-A-7-331182, or the like. The introduced pigment derivative is preferably used.

  Examples of commercially available products include "EFKA 6745 (phthalocyanine derivative), 6750 (azo pigment derivative)" manufactured by EFKA, "Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative)" manufactured by Lubrizol (any) Also product name). Examples of the linear polymer include an alkali-soluble resin described later, and it is also preferable to use the linear polymer in combination with the pigment derivative. Only one pigment dispersant may be used, or two or more pigment dispersants may be used in combination.

The colored photosensitive resin composition of the present invention comprises the above-mentioned pigment dispersion composition, a binder, a monomer or an oligomer, and a photopolymerization initiator or a photopolymerization initiator system.
The pigment fine particles and the method for producing the dispersion composition have already been described in detail. The content of the fine particles in the composition is preferably 3 to 90% by mass, and preferably 20 to 80% by mass with respect to the total solid content (in the present invention, the total solid content refers to the total composition excluding the organic solvent). % 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. Moreover, you may use it in combination with a normal pigment for toning. As the pigment, those described above can be used.

  As the monomer or oligomer, a photopolymerizable compound is preferable, and the photopolymerizable compound is preferably a polyfunctional monomer having two or more ethylenically unsaturated double bonds and capable of addition polymerization upon irradiation with light. Examples of such a photopolymerizable compound 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 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, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexane All di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; multifunctional such as trimethylolpropane and glycerin Polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to alcohol and then (meth) acrylated can be mentioned. Further, 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.

  The polymerizable compound may be used alone or in combination of two or more, and the content of the composition with respect to the total solid 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.

  As a polymerization initiator or a polymerization initiator system (in the present invention, a polymerization initiator system refers to a mixture that exhibits a polymerization initiation function by a combination of a plurality of compounds), a photopolymerization initiator or a photopolymerization initiator system. Vicinal polyketaldonyl compounds disclosed in US Pat. No. 2,367,660, acyloin ether compounds described in US Pat. No. 2,448,828, US Pat. No. 2,722,512 An aromatic acyloin compound substituted with an α-hydrocarbon described in US Pat. Nos. 3,046,127 and 2,951,758, and a triarylimidazole described in US Pat. No. 3,549,367 Combination of dimer and p-aminoketone, benzothia described in JP-B-51-48516 Compound, trihalomethyl-s-triazine compound, trihalomethyl-triazine compound described in US Pat. No. 4,239,850, trihalomethyloxadiazole compound described in US Pat. No. 4,221,976, 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.

  The polymerization initiator or the polymerization initiator system may be used singly or in combination 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 polymerization initiator or the polymerization initiator system with respect to the total solid content of the curable composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass. If this amount is too large, the sensitivity becomes too high and control becomes difficult. If the amount is too small, the exposure sensitivity becomes too low.

  The alkali-soluble resin can be added at the time of preparing a colored photosensitive resin composition or an ink-jet ink for a color filter, but it is also preferably added at the time of producing the fine particle dispersion composition or at the time of forming fine particles. The alkali-soluble resin can be added to both or one of the poor solvent for adding the pigment solution and the pigment solution to form pigment fine particles. Alternatively, it is also preferable to add an alkali-soluble resin solution at the time of forming fine pigment particles in a separate system.

  As the alkali-soluble resin, a binder having an acidic group is preferable, and an alkali-soluble polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain is preferable. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-57-36. A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer as described in JP-A-59-71048 Etc. Moreover, the cellulose derivative which has a carboxylic acid group, carboxylate, etc. in a side chain can also be mentioned, In addition to this, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. As particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate and (meth) acrylic acid are used. And multi-component copolymers with other monomers.

  The alkali-soluble resin may be used alone or may be used in the state of a composition used in combination with a normal film-forming polymer. The addition amount of pigment to 100 parts by mass of fine particles is 10 to 200 parts by mass. Generally, 25-100 mass parts is preferable.

  In addition, in order to improve the crosslinking efficiency, the side chain of the alkali-soluble resin may have a polymerizable group, and a UV curable resin, a thermosetting resin, or the like is also useful. Furthermore, as the alkali-soluble resin, a resin having a water-soluble atomic group in a part of the side chain can be used.

In the colored photosensitive resin composition, in addition to the above components, an organic solvent (fourth solvent) for preparing the composition may be used. Examples of the fourth solvent include, but are not limited to, alcohol solvents, ketone solvents, ether solvents, sulfoxide solvents, ester solvents, amide solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbons. Preferable examples include a system solvent, a nitrile solvent, or a mixture thereof. Among them, a ketone solvent, an ether solvent, an ester solvent, an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, or these More preferably, a mixture of
Examples of the ketone solvent include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and the like. Examples of the ether solvent include propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate. Examples of the ester solvent include 1,3-butylene glycol diacetate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, ethyl Examples thereof include carbitol acetate and butyl carbitol acetate. Examples of the aromatic hydrocarbon solvent include toluene and xylene. Examples of the aliphatic hydrocarbon solvent include cyclohexane and n-octane.
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. The content of the organic solvent is preferably 10 to 95% by mass with respect to the total amount of the composition.

  Moreover, it is preferable to contain an appropriate surfactant in the colored photosensitive resin composition. Suitable surfactants include those disclosed in JP-A Nos. 2003-337424 and 11-133600. The content of the surfactant is preferably 5% by mass or less based on the total amount of the composition.

  The colored photosensitive resin composition preferably contains a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-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 composition.

  In addition to the colorant (pigment), a colorant (dye or pigment) can be added to the colored photosensitive resin composition as necessary. When using a pigment among the colorants, it is desirable that the pigment is uniformly dispersed in the composition. 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 auxiliary dye or pigment content is preferably 5% by mass or less based on the total amount of the composition.

  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. As for content of a ultraviolet absorber, 5 mass% or less is preferable with respect to the 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. The colored photosensitive resin composition can be made into an inkjet ink by appropriately adjusting the composition. In addition to the color filter, the inkjet ink may be a normal inkjet ink such as for printing. Among them, the inkjet ink for the color filter is preferable.

The inkjet ink for a color filter of the present invention contains the pigment dispersion composition, a binder, and a monomer or oligomer. Here, as the binder, monomer, or oligomer, those described above for the colored photosensitive resin composition can be used.
At this time, it is preferable to control the ink temperature so that the fluctuation range of the viscosity is within ± 5%. The viscosity at the time of injection is preferably 5 to 25 mPa · s, more preferably 8 to 22 mPa · s, and particularly preferably 10 to 20 mPa · s (in the present invention, unless otherwise specified) It is a value at 25 ° C.). In addition to the setting of the injection temperature, the viscosity can be adjusted by adjusting the type and amount of components contained in the ink. The viscosity can be measured, for example, by a normal apparatus such as a conical plate type rotational viscometer or an E type viscometer.
The surface tension of the ink upon ejection is preferably 15 to 40 mN / m from the viewpoint of improving the flatness of the pixel (in the present invention, the surface tension is a value at 23 ° C. unless otherwise specified). ). More preferably, it is 20-35 mN / m, Most preferably, it is 25-30 mN / m. The surface tension can be adjusted by adding a surfactant or the type of solvent. For example, the surface tension is platinum by using a measuring instrument such as a surface tension measuring device (CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.) or a fully automatic balanced electro surface tension meter ESB-V (manufactured by Kyowa Scientific Co., Ltd.). It can be measured by the plate method.

Ink jet ink for color filters can be sprayed by continuously ejecting charged ink and controlled by an electric field, intermittently ejecting ink using piezoelectric elements, or intermittently using ink by heating and foaming. Various methods such as a method of spraying can be employed.
In addition, regarding the ink jet method used for forming each pixel, a normal method such as a method of thermally curing ink, a method of photocuring, or a method of ejecting droplets after forming a transparent image receiving layer on a substrate in advance. Can be used.

  As the ink jet head (hereinafter also simply referred to as a head), a normal one can be applied, and a continuous type and a dot on demand type can be used. Among the dot-on-demand types, the thermal head is preferably a type having an operation valve as described in JP-A-9-323420 for discharging. As the piezo head, for example, the heads described in European Patent A277,703, European Patent A278,590 and the like can be used. The head preferably has a temperature control function so that the temperature of the ink can be controlled. It is preferable to set the injection temperature so that the viscosity at the time of ejection is 5 to 25 mPa · s, and to control the ink temperature so that the fluctuation range of the viscosity is within ± 5%. Moreover, as a drive frequency, it is preferable to operate | move at 1-500 kHz.

In addition, after each pixel is formed, a heating step of performing heat treatment (so-called baking treatment) can be provided. That is, a substrate having a layer photopolymerized by light irradiation is heated in an electric furnace, a dryer or the like, or an infrared lamp is irradiated. The temperature and time of heating depend on the composition of the photosensitive dark color composition and the thickness of the formed layer, but generally from about 120 ° C. to the point of obtaining sufficient solvent resistance, alkali resistance, and ultraviolet absorbance. Heating at about 250 ° C. for about 10 minutes to about 120 minutes is preferred.
The pattern shape of the color filter thus formed is not particularly limited, and may be a general black matrix shape such as a stripe shape, a lattice shape, or a delta arrangement. May be.

  A preparation method in which a partition wall is prepared in advance and the ink is applied to a portion surrounded by the partition wall before the pixel forming step using the color filter inkjet ink described above is preferable. Any partition may be used, but in the case of manufacturing a color filter, it is preferably a light-blocking partition having a black matrix function (hereinafter also simply referred to as “partition”). The partition wall can be produced by the same material and method as those of a normal color filter black matrix. For example, paragraph numbers [0021] to [0074] of JP 2005-3861 A, black matrices described in paragraph numbers [0012] to [0021] of JP 2004-240039 A, and JP 2006-17980 A. And the inkjet black matrix described in paragraphs [0009] to [0044] of JP-A-2006-10875.

  The components contained in the coating film using the photosensitive resin transfer material are the same as those already described. Moreover, although the thickness of the coating film using a colored photosensitive resin composition can be suitably determined according to the use, it is preferable that it is 0.5-5.0 micrometers, and is 1.0-3.0 micrometers. It is more preferable. In the coating film using this composition, the above-mentioned monomer or oligomer is polymerized to form a polymer film of the colored photosensitive resin composition, and a color filter having the same can be produced (the production of the color filter will be described later). To do.) Polymerization of the photopolymerizable compound can be carried out by allowing a photopolymerization initiator or a photopolymerization initiator system to act upon irradiation with light.

  In addition, although the said coating film can be formed by apply | coating and drying a colored photosensitive resin composition with a normal application method, in this invention, it has a slit-shaped hole in the part which discharges a liquid. It is preferable to apply by a slit 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 photosensitive resin transfer material 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.

  In addition, although application | coating in the said preparation method can be performed with a normal coating apparatus etc., in this invention, it is preferable to perform with the coating apparatus (slit coater) using the slit-shaped nozzle already demonstrated. Preferred specific examples of the slit coater are the same as described above.

  The color filter is preferably excellent in contrast. In the present invention, the term “contrast” means a value measured by a measurement method employed in Examples described later unless otherwise specified. The high contrast of the color filter means that the bright and dark discrimination when combined with the liquid crystal can be increased, which is a very important performance in order to replace the liquid crystal display with a CRT.

  When the color filter is used for a television, the chromaticity of all the single colors of red (R), green (G), and blue (B) by the F10 light source are the values shown in the table below (hereinafter referred to as “this”). In the invention, the difference (ΔE) from the “target chromaticity”) is preferably in the range of 5 or less, more preferably 3 or less, and particularly preferably 2 or less.

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.

  A liquid crystal display device provided with a color filter has a high contrast and is excellent in descriptive power such as black spots, and the VA method is particularly preferable. 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. The color filter can be used for a CCD device and exhibits excellent performance.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, this invention is limited to this and is not interpreted. In the examples, “part” and “%” are based on mass unless otherwise specified.

Example 1
An organic pigment dispersion was produced using the flow reactor shown in FIG. The cross section of the flow path was a circular pipe, and all the flow paths had a uniform inner diameter and a representative diameter of 2.0 [mm].
20 parts of dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.), 2.5 parts of 25% aqueous solution of tetramethylammonium hydroxide (manufactured by Tokyo Chemical Industry Co., Ltd.), C.I. I. Pigment Red 254 (trade name: Irgafore Red BT-CF, manufactured by Ciba Specialty Chemicals Co., Ltd.) (2.0 parts) was added, and the pigment dissolved therein was kept at 20 ° C. to obtain a pigment solution.
[Creation of poor solvent]
A mixture of 200 parts of ion-exchanged water and 20 parts of 1N hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared and cooled to 5 ° C. as a poor solvent.
[Creation of organic pigment particles]
Using five double plunger pumps, the pigment solution is introduced from the channels 13 and 15 shown in FIG. 1, the poor solvent is introduced from the channels 12, 14 and 16, and mixed at the junction 1 to re-precipitate the pigment. It was created. At this time, the flow rates of the pigment solution and the poor solvent were 150 mL / min and 200 mL / min, respectively.
[Crystallization of pigment particles]
The pigment re-precipitation liquid prepared above was collected from the flow path 11, transferred to a stirring tank, and stirred at room temperature with a propeller blade. In this state, 50 parts of PGMEA was added to 100 parts of the reprecipitation liquid, and the pigment was crystallized by stirring and mixing in a stirring tank.
[Polymer compound]
Into a 500 mL three-necked flask, 160.0 g of ε-caprolactone and 18.3 g of 2-ethyl-1-hexanol were introduced and dissolved by stirring while blowing nitrogen. Monobutyltin oxide 0.1g was added and it heated at 100 degreeC. After 8 hours, it was cooled to 80 ° C. after confirming disappearance of the raw material by gas chromatography. After adding 0.1 g of 2,6-di-t-butyl-4-methylphenol, 22.2 g of 2-methacryloyloxyethyl isocyanate was added. After 5 hours, after confirming disappearance of the raw material by H NMR, the mixture was cooled to room temperature to obtain 200 g of a solid monomer (A-5). It was confirmed by H NMR, IR, and mass spectrometry that it was a monomer (A-5).
The obtained monomer (A-5) is mentioned as a preferred specific example of the monomer represented by the general formula (i), (ii), or (i) -2.
Monomer (A-5) 37.5 g, monomer M-11 5.0 g, methacrylic acid 7.5 g, dodecyl mercaptan 1.3 and 1-methoxy-2-propanol 116.7 g were substituted with nitrogen. The mixture was introduced into a three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), heated to 75 ° C. while flowing nitrogen into the flask. To this was added 0.3 g of 2,2-azobis (2,4-dimethylvaleronitrile) (“V-65” manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 75 ° C. for 2 hours. After 2 hours, 0.3 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% solution of polymer compound P-10 was obtained.
[Solvent replacement step]
The obtained organic pigment dispersion was filtered to take out pigment particles to obtain a pigment paste. 10 parts of PGMEA was added to 1 part of the pigment content in the paste, reslurried and filtered again to obtain a paste with a pigment concentration of 25% by mass. The reslurry was repeated three times to obtain a cleaning paste. This cleaning paste was used to prepare a pigment dispersion composition A by dispersing with a bead mill (trade name: Sand Grinder Mill, manufactured by Imex) and 0.05 mm zirconia beads.
<Dispersion formulation for contrast evaluation>
-PGMEA cleaning paste 10 parts-PGMEA 12.5 parts-Polymer P-10 2.5 parts [Contrast evaluation of pigment dispersion]
The obtained pigment dispersion composition was applied on a 75 mm × 75 mm glass substrate using a spin coater (1H-D7 (trade name) manufactured by Mikasa Co., Ltd.) so as to have a thickness of 1.3 μm. A membrane sample was prepared by drying at 2 ° C. for 2 minutes.
About the obtained film | membrane sample, what installed the diffusion plate in the three-wavelength cold-cathode tube light source (Toshiba Lighting & Technology Co., Ltd. product FWL18EX-N (brand name)) was used as a backlight unit, and two polarizing plates (( This sample was placed between polarizing plates HLC2-2518 (trade name) manufactured by Sanritsu Co., Ltd., and the amount of transmitted light when the polarization axis was parallel and when it was vertical was measured, and the ratio was defined as the contrast ( (Refer to "The 7th Color Optical Conference in 1990, 512-color display 10.4" size TFT-LCD color filter, Ueki, Koseki, Fukunaga, Yamanaka "). For the measurement of chromaticity, a color luminance meter (BM-5 (trade name) manufactured by Topcon Corporation) was used.
[Contrast evaluation over time]
One month after the dispersion, the time-dependent contrast evaluation was performed in the same manner as the contrast evaluation.
[Evaluation of average particle diameter of pigment particles]
The pigment dispersion composition was applied on a silicon wafer by a spin coater. A particle image of the obtained sample was taken with a scanning electron microscope (trade name: S-5200, manufactured by Hitachi High-Tech Co., Ltd.), the particle size was obtained from the image with a caliper, and the average particle size was calculated.
[Measurement of good solvent concentration]
The concentration of DMSO remaining in the pigment dispersion was measured by gas chromatography using the obtained dispersion.
The performance of the pigment dispersion composition evaluated by the above method is shown in Table 1.

(Example 2)
In the pigment dispersion of Example 1, Pigment Dispersion Composition B was prepared in the same manner as in Example 1 except that the number of reslurries with PGMEA in the solvent replacement step was set to two.

(Example 3)
In the pigment dispersion composition of Example 1, pigment dispersion C was prepared in the same manner as in Example 1 except that methacrylic acid was removed from the polymer compound P-10.

Example 4
A pigment dispersion composition D was prepared in the same manner as in Example 1 except that methacrylic acid was removed from the polymer compound P-10 in the pigment dispersion liquid of Example 2.

(Example 5)
The pigment dispersion composition of Example 3 was the same as that of Example 3 except that 0.1 g of 2,2-azobis (2,4-dimethylvaleronitrile) was used in the synthesis of the polymer compound P-10. Object E was adjusted.

(Example 6)
The pigment dispersion composition of Example 4 was the same as that of Example 3 except that 0.1 g of 2,2-azobis (2,4-dimethylvaleronitrile) was used in the synthesis of the polymer compound P-10. Object F was adjusted.

(Comparative Example 1)
In the pigment dispersion liquid of Example 1, the pigment reprecipitation liquid was concentrated at 5000 rpm for 90 minutes using an H-112 type centrifugal filter manufactured by Kokusan Co., Ltd. and a P89C type ro cloth manufactured by Shikishima Canvas Co., Ltd. The obtained pigment nanoparticle concentrated paste was recovered.
0.1 g of Pigment Dispersant A (Exemplary Compound (7) of Compound Represented by Formula (D1)) Synthesized in 50.0 cc of ethyl lactate according to JP 2000-239554 A, JP 2007-262378 A A solution obtained by adding 2.6 g of the polymer compound C-1 was added to 14.5 g of the pigment nanoparticle concentrated paste, stirred at 1500 rpm for 60 minutes with a dissolver, 25.0 cc of ethyl acetate was added, and a dissolver was further added. The mixture was stirred at 500 rpm for 10 minutes to obtain a pigment nanoparticle ethyl lactate dispersion.
The pigment nanoparticle ethyl lactate dispersion A was removed with an evaporator to obtain an organic pigment powder A (solid content concentration 93 mass%).
Using the organic pigment powder A, a pigment dispersion composition G having the following composition was prepared.
14.0 g of the organic pigment powder A
1,3 Butylene glycol diacetate 46.3g
The pigment dispersion composition A having the above composition was dispersed with a motor mill M-50 (manufactured by Eiger Japan) for 1 hour at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Comparative Example 2)
In Comparative Example 1, a pigment dispersion composition H was prepared in the same manner as in Comparative Example 1, except that the solid content concentration of the organic pigment powder A was changed to 81% by mass.

(Comparative Example 3)
In Comparative Example 1, the pigment nanoparticle ethyl lactate dispersion was filtered using a FP-010 type filter manufactured by Sumitomo Electric Fine Polymer Co. A pigment dispersion composition I was prepared in the same manner as in Comparative Example 1 except that this was dispersed.

(Comparative Example 4)
In Comparative Example 1, 500 ml of 2- (1-methoxy) propyl acetate was added to the pigment reprecipitation liquid, stirred at 25 ° C. for 10 minutes at 500 rpm, and then allowed to stand for 1 day. ) Extracted into a propyl acetate phase to obtain a concentrated extract.
Paste concentrated pigment liquid [B] (pigment particle concentration 30% by mass) is prepared by filtering the concentrated extract from which pigment particles have been extracted using an FP-010 filter manufactured by Sumitomo Electric Fine Polymer. A pigment dispersion composition J was prepared in the same manner as in Comparative Example 1 except that this was dispersed.

［カラーフィルタの作製（スリット状ノズルを用いた塗布による作製）］
〔ブラック（Ｋ）画像の形成〕
無アルカリガラス基板を、ＵＶ洗浄装置で洗浄後、洗浄剤を用いてブラシ洗浄し、更に超純水で超音波洗浄した。該基板を１２０℃３分熱処理して表面状態を安定化させた。
該基板を冷却し２３℃に温調後、スリット状ノズルを有すガラス基板用コーター（エフ・エー・エス・アジア社製、商品名：ＭＨ−１６００）にて、下記表２に記載の組成よりなる着色感光性樹脂組成物Ｋ２を塗布した。引き続きＶＣＤ（真空乾燥装置；東京応化工業（株）社製）で３０秒間、溶媒の一部を乾燥して塗布層の流動性を無くした後、１２０℃で３分間プリベークして膜厚２．４μｍの感光性樹脂層Ｋ２を得た。なお、着色感光性樹脂組成物Ｋ２の調製手順は、先の樹脂組成物Ｋ１の手順と同様である。

[Preparation of color filter (preparation by application using slit nozzle)]
[Formation of black (K) image]
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., the composition described in Table 2 below is applied on a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. A colored photosensitive resin composition K2 was applied. Subsequently, a part of the solvent was dried by VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to obtain a film thickness of 2. A 4 μm photosensitive resin layer K2 was obtained. In addition, the preparation procedure of colored photosensitive resin composition K2 is the same as that of the previous resin composition K1.

[Table 2]
--------------------------------------
K pigment dispersion 2 25 parts by mass Propylene glycol monomethyl ether acetate 8.0 parts by mass Methyl ethyl ketone 53 parts by mass Binder 3 9.1 parts by mass Hydroquinone monomethyl ether 0.002 parts by mass DPHA solution 4.2 parts by mass Polymerization initiator A 0. 16 mass parts Surfactant 1 0.044 mass parts ----------------------------------- −

In a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask having an image pattern) standing vertically, the exposure mask surface and the mask The distance between the photosensitive resin layers was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² .
Next, after spraying pure water with a shower nozzle to uniformly wet the surface of the photosensitive resin layer K1, a KOH developer (KOH, containing nonionic surfactant, trade name: CDK-1, (Fuji Film Electronics Materials Co., Ltd.) was subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove the residue, and a black (K) image K was obtained. Subsequently, heat treatment was performed at 220 ° C. for 30 minutes.

<K pigment dispersion 2>
・ Carbon black (trade name: Nippon 35, manufactured by Degussa Japan Co., Ltd.)
13.1 parts by mass / dispersant (compound 2J below) 0.65 parts by mass / polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio
Random copolymer of, molecular weight 37,000) 6.72 parts by mass / propylene glycol monomethyl ether acetate 79.53 parts by mass

<Binder 3>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio
Random copolymer of, molecular weight 38,000) 27 parts by mass / propylene glycol monomethyl ether acetate 73 parts by mass

[Formation of red (R) pixels]
A heat-treated pixel R was formed in the same process as the formation of the black (K) image using a colored photosensitive resin composition R1 having a composition shown in Table 3 below on the substrate on which the image K was formed. The film thickness of the photosensitive resin layer R1 and the coating amount of the pigment are shown below. The procedure for preparing the colored photosensitive resin composition is the same as that for the colored photosensitive resin composition K2.
Photosensitive resin film thickness (μm) 1.60
Pigment coating amount (g / m ² ) 1.00
C. I. P. R. 254 coating amount (g / m ² ) 0.80
C. I. P. R. 177 coating amount (g / m ² ) 0.20

[Table 3]
--------------------------------------
R pigment dispersion 01 40 parts by mass R pigment dispersion 2 (CIPR177) 4.5 parts by mass Propylene glycol monomethyl ether acetate 7.6 parts by mass Methyl ethyl ketone 37 parts by mass Binder 2 0.7 parts by mass DPHA solution 3.8 parts by mass 2 -Trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 0.12 parts by mass Polymerization initiator A 0.05 parts by mass Phenothiazine 0.01 parts by mass Surfactant 2 0.06 parts by mass ----------- -------------------------

<R pigment dispersion composition 01>
-11 parts by mass of pigment dispersion composition A (CIPR 254) of Example 1-68.2 parts by mass of propylene glycol monomethyl ether acetate <R pigment dispersion 2>
・ C. I. P. R. 177 (Product name: Chromophthal Red A2B,
Ciba Specialty Chemicals Co., Ltd.) 18 parts by mass Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio)
Random copolymer, molecular weight 30,000) 12 parts by mass / 70 parts by mass of propylene glycol monomethyl ether acetate

[Formation of green (G) pixels]
Using the colored photosensitive resin composition G1 having the composition shown in Table 4 below on the substrate on which the image K and the pixel R are formed, the heat-treated pixel G is formed in the same process as the formation of the black (K) image. Formed. The film thickness of the photosensitive resin layer G1 and the coating amount of the pigment are shown below. The procedure for preparing the colored photosensitive resin composition is the same as that for the colored photosensitive resin composition K2.
Photosensitive resin film thickness (μm) 1.60
Pigment application amount (g / m ² ) 1.92
C. I. P. G. 36 coating amount (g / m ² ) 1.34
C. I. P. Y. 150 coating amount (g / m ² ) 0.58

[Table 4]
--------------------------------------
G pigment dispersion 1 (CIPG36) 28 parts by mass Y pigment dispersion 1 (CIPI150) 15 parts by mass Propylene glycol monomethyl ether acetate 29 parts by mass Methyl ethyl ketone 26 parts by mass Cyclohexanone 1.3 parts by mass Binder 3 2.5 parts by mass DPHA solution 3 .5 mass parts 2-trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 0.12 parts by weight Polymerization initiator A 0.05 parts by weight Phenothiazine 0.01 parts by weight Surfactant 2 0.07 parts by weight ----------- ---------------------------

  As the G pigment dispersion 1, “trade name: GT-2” manufactured by Fuji Film Electronics Materials Co., Ltd. was used. As the Y pigment dispersion 1, “trade name: CF Yellow EX3393” manufactured by Mikuni Color Co., Ltd. was used.

[Formation of blue (B) pixels]
Using the colored photosensitive resin composition B1 having the composition shown in Table 5 below on the substrate on which the image K, the pixel R, and the pixel G are formed, heat treatment is performed in the same process as the formation of the black (K) image. Pixel B was formed, and the target color filter A was obtained. The film thickness of the photosensitive resin layer B1 and the coating amount of the pigment are shown below. The film thickness of the photosensitive resin layer R1 and the coating amount of the pigment are shown below. The procedure for preparing the colored photosensitive resin composition is the same as that for the colored photosensitive resin composition K2.
Photosensitive resin film thickness (μm) 1.60
Pigment application amount (g / m ² ) 0.75
C. I. P. B. 15: 6 coating amount (g / m ² ) 0.705
C. I. P. V. 23 coating amount (g / m ² ) 0.045

[Table 5]
--------------------------------------
B pigment dispersion 1 (CIPB15: 6) 8.6 parts by mass B pigment dispersion 2 (CIPB15: 6 + CIPV23) 15 parts by mass Propylene glycol monomethyl ether acetate 28 parts by mass Methyl ethyl ketone 26 parts by mass Binder 4 17 parts by mass DPHA solution 4.0 Parts by mass 2-trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 0.17 parts by mass Phenothiazine 0.02 parts by mass Surfactant 2 0.06 parts by mass ------------------- ------------------

  As the B pigment dispersion 1, “trade name: CF Bull-EX3357” manufactured by Mikuni Color Co., Ltd. was used. As the B pigment dispersion 2, “trade name: CF Bull-EX3383” manufactured by Mikuni Color Co., Ltd. was used.

<Binder 4>
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = 36/22/42 molar ratio random copolymer, molecular weight 38,000) 27 parts by mass-propylene glycol monomethyl ether acetate 73 parts by mass

  Instead of pigment dispersion composition A used for R pigment dispersion 01, R pigment dispersions 02 to 10 were prepared using pigment dispersion compositions B to J, respectively. Then, color filters B to J were prepared in the same manner as the method for manufacturing the color filter A except that R pigment dispersions 02 to 10 were used instead of the R pigment dispersion 01, respectively.

[Production and Evaluation of Liquid Crystal Display]
A liquid crystal display device was prepared using each of the above color filters, and the display characteristics were evaluated.
(Formation of ITO electrode)
The color filter was put in a sputtering apparatus, and 1300 mm thick ITO (indium tin oxide) was vacuum-deposited on the entire surface at 100 ° C., and then annealed at 240 ° C. for 90 minutes to crystallize the ITO to form an ITO transparent electrode.
(Spacer formation)
A spacer was formed on the ITO transparent electrode produced above by the same method as the spacer forming method described in [Example 1] of JP-A-2004-240335.
(Formation of liquid crystal alignment control protrusions)
A liquid crystal alignment control protrusion was formed on the ITO transparent electrode on which the spacer was formed, using the following positive photosensitive resin layer coating solution.
However, the following methods were used for exposure, development, and baking.
A proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) is arranged so that the predetermined photomask is at a distance of 100 μm from the surface of the photosensitive resin layer, and the irradiation energy is 150 mJ / Proximity exposure was performed at cm ² .
Subsequently, a 2.38% tetramethylammonium hydroxide aqueous solution was developed by spraying the substrate at 33 ° C. for 30 seconds on a shower type developing device. In this way, by removing the unnecessary portion (exposed portion) of the photosensitive resin layer by developing and removing the liquid crystal, the liquid crystal alignment control protrusions made of the photosensitive resin layer patterned into a desired shape are formed on the color filter side substrate. A display device substrate was obtained.
Next, the liquid crystal display device substrate on which the liquid crystal alignment control protrusions were formed was baked at 230 ° C. for 30 minutes to form cured liquid crystal alignment control protrusions on the liquid crystal display device substrate.

<Positive photosensitive resin layer coating solution formulation>
・ Positive resist solution (FUJIFILM Electronics
Materials Co., Ltd. FH-2413F): 53.3 parts by mass / Methyl ethyl ketone: 46.7 parts by mass / Megafac F-780F (Dainippon Ink Chemical Co., Ltd.): 0.04 parts by mass

(Creation of liquid crystal display device)
An alignment film made of polyimide was further provided on the liquid crystal display substrate obtained above.
After that, an epoxy resin sealant is printed at a position corresponding to a black matrix outer frame provided around the pixel group of the color filter, and MVA mode liquid crystal is dropped and bonded to the counter substrate. The bonded substrate was heat treated to cure the sealant. Polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. were attached to both surfaces of the liquid crystal cell thus obtained. Next, a backlight of a three-wavelength cold-cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) is constructed and placed on the back side of the liquid crystal cell provided with the polarizing plate. did.

[Production and Evaluation of Liquid Crystal Display]
The liquid crystal display device substrate was taken out from the liquid crystal display device A, and the contrast was measured in the same manner as in Example 1.

  Liquid crystal display devices A to J were produced in the same manner except that the color filter V01 was changed to color filters A to J, respectively, and evaluated in the same manner.

  The color filter and liquid crystal display device produced using the inkjet ink for color filter of the present invention showed high contrast. In addition, it was possible to express black with little leakage light when displaying black, and as a result, it showed high descriptive power.

Claims (10)

In the medium, organic pigment fine particles having an average primary particle diameter of less than 60 nm and a ratio of particles having a primary particle diameter exceeding 60 nm of less than 10% are contained in a concentration of 5% by mass to 30% by mass. A pigment dispersion composition comprising:
The organic pigment fine particles are prepared by mixing an organic pigment solution in which an organic pigment is dissolved in a good solvent and a solvent that is compatible with the good solvent and that is a poor solvent for the organic pigment. Deposited as fine particles,
A pigment dispersion composition, wherein the concentration of the good solvent used at the time of precipitation of organic pigment fine particles contained in the pigment dispersion composition is suppressed to 10 ppm or more and 1000 ppm or less.   The pigment dispersion composition, wherein the concentration of the good solvent contained in the pigment dispersion composition is 30 ppm or more and 500 ppm or less.   The pigment dispersion composition according to claim 1, further comprising a polymer compound having a mass average molecular weight of 1,000 to 100,000.   The pigment dispersion composition according to claim 3, wherein the polymer compound has an acid group in a range of 50 mgKOH / g to 200 mgKOH / g.   A colored photosensitive resin comprising the pigment dispersion composition according to any one of claims 1 to 4, a binder, a monomer or an oligomer, and a photopolymerization initiator or a photopolymerization initiator system. Composition.   The inkjet ink for color filters containing the pigment dispersion composition as described in any one of Claims 1-4, a binder, and a monomer or an oligomer.   A photosensitive resin transfer material, wherein a photosensitive resin layer containing at least the colored photosensitive resin composition according to claim 5 is provided on a temporary support.   A color produced using the colored photosensitive resin composition according to claim 5, the inkjet ink for a color filter according to claim 6, and / or the photosensitive resin transfer material according to claim 7. filter.   A liquid crystal display device comprising the color filter according to claim 8. In the medium, organic pigment fine particles having an average primary particle diameter of less than 60 nm and a ratio of particles having a primary particle diameter exceeding 60 nm of less than 10% are contained in a concentration of 5% by mass to 30% by mass. A method for producing a pigment dispersion composition containing:
An organic pigment solution in which an organic pigment is dissolved in a good solvent and a solvent that is compatible with the good solvent and that is a poor solvent for the organic pigment are mixed, and the organic pigment fine particles are mixed in the mixture. Depositing the organic pigment fine particles in a powder or paste state and dispersing them in the medium to precipitate the organic pigment fine particles contained in the pigment dispersion composition. The manufacturing method of the pigment dispersion composition characterized by making the density | concentration of the said good solvent used into 10 ppm or more and 1000 ppm or less.

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