TWI447178B - Organic pigment composition and preparation method thereof, coloring photosensitive resin composition using the same, color filter - Google Patents

Description

Organic pigment composition and preparation method thereof, coloring photosensitive resin composition using the same, color filter

The present invention relates to an organic pigment composition, a process for producing the same, a colored photosensitive resin composition using the same, and a color filter.

Only the organic pigment in the nanometer-sized particles can be examined, and examples thereof include coatings, inks, toners for electrophotography, inkjet inks, and materials for color filters. Among them, those which are required to be high-performance and practically important are pigments for inkjet inks and pigments for color filters.

Regarding the preparation method of organic particles, there are a gas phase method, a liquid phase method, a laser ablation method, and the like. Among them, the liquid phase method is a method for preparing organic particles which are highly susceptible to the simplicity and productivity.

Patent Document 1 describes an example in which a pigment particle aqueous dispersion is prepared by a liquid phase method. This method is in the final method of aqueous dispersion, and the provision of the organic solvent dispersion is not mentioned. Patent Document 2 describes an example in which an organic solvent dispersion is provided using pigment particles prepared by a liquid phase method. However, the primary particle diameter of the organic pigment particles obtained by this method tends to become large, failing to sufficiently respond to the requirement of micronization.

Regarding the preparation of the nanoparticle by the liquid phase method, a low molecular surfactant and a neutral water-soluble nonionic polymer compound are used for the aggregation of the nanoparticle. Therefore, although the nanoparticles can be dispersed at a high concentration, a large amount of dispersing aid must be used. For example, if the polymer compound having a low viscosity of inkjet is extremely low, it is difficult to directly adopt such techniques.

Further, in response to a request for phase transfer of a nanoparticle to an aqueous solvent system in an aqueous medium, it is known to prepare an aqueous slurry containing a high concentration of pigment, an aqueous paste, a resin or a resin solution, and to mix and stir. A method in which a resin or resin solution replaces the moisture surrounding the pigment. However, in this method, since the particles are once strongly agglomerated in an aqueous medium, the efficiency of coating with a resin is poor, and it becomes difficult to redisperse (see, for example, Patent Documents 3 and 4).

Further, in order to prepare a water-based paste, another method is a method in which the nano pigment particles prepared in an aqueous solvent are directly filtered in a state of primary particles or agglomerated. However, the filtration is time consuming, and the industrial efficiency is poor and complicated.

Although a low molecular anionic or cationic surfactant can also be used as a dispersing agent, dispersion stability may be insufficient due to low molecular weight. There is also an attempt to use a cationic polymer compound to transfer a phase to an ionic liquid without a filtration step of the aqueous dispersion of particles (see, for example, Non-Patent Document 1). However, this method is aimed at low-concentration inorganic particles. The organic pigment is not mentioned, and the final dispersion medium is a non-volatile ionic liquid, and the method described in Non-Patent Document 1 is not suitable for industrial use.

Patent Document 5 discloses a method in which an organic nano pigment particle is aggregated in an aqueous medium and subjected to an extraction operation in a non-aqueous medium. Then, the membrane filter is filtered and separated, and then dispersed in a non-aqueous medium in the presence of an organic polymer. However, since the aggregate at the time of separation is hydrophilic, filtration is time consuming.

Patent Document 1 JP-A-2004-43776

Patent Document 2, JP-A-2004-123853

Patent Document 3 Japanese Patent Laid-Open No. Hei 5-301037

Patent Document 4, JP-A-6-161154

Patent Document 5, JP-A-2007-262378

Non-Patent Document 1 "small", 2006, Vol. 2, No. 7, p. 879-883

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic pigment composition containing nanometer-sized organic pigment microparticles and which can be easily switched between hydrophobicity and hydrophobicity without complicated steps.

An object of the present invention is to provide an organic pigment composition which exhibits high performance and which exhibits high contrast when it is made into a color filter, and a method for producing the same, and provides a colored photosensitive resin composition using the above composition, Color filter.

The object of the present invention is achieved by the following means.

[1] An organic pigment composition characterized by comprising a polymer compound having a repeating unit of the following formula (1) and/or a repeating unit of the formula (2); and an organic pigment fine particle:

(In the formula, A ₁ represents a hydrogen atom or a methyl group; and X ₁ represents a heterocyclic group which has a carbon atom bonded to an NH group).

[2] The organic pigment composition according to [1], wherein the polymer compound further has a repeating unit of the following formula (3) and/or a repeating unit of the formula (4):

(wherein A ₂ represents a hydrogen atom or a methyl group; Y ₁ represents -NH-, -O- or -S-; L represents a single bond or a divalent linking group; Y ₂ represents a hydrogen atom or a basic group; Z ₁ represents An unsaturated heterocyclic group having 1 or 2 nitrogen atoms).

[3] The organic pigment composition according to [1] or [2], wherein the polymer compound further has a repeating unit of the following formula (5) and/or a repeating unit of the formula (6):

(wherein A ₃ and A ₄ each independently represent a hydrogen atom or a methyl group; R ₁ represents an alkyl group; R ₂ represents a hydrogen atom or an alkyl group; and R ₁ and R ₂ may be bonded to each other to form a ring structure group, the ring structure group It may also contain an oxygen atom, a nitrogen atom or a sulfur atom; R ₃ and R ₄ each independently represent a hydrogen atom or an alkyl group; and R ₃ and R ₄ may be bonded to each other to form a ring structure group).

[4] The organic pigment composition according to any one of [1] to [3] wherein the organic pigment fine particles have an average particle diameter in the range of 10 to 100 nm.

[5] The organic pigment composition according to any one of [1] to [4] which is a dispersion in which the organic pigment fine particles are dispersed in a medium.

[6] The organic pigment composition according to any one of [1] to [4] wherein the organic pigment microparticles are aqueous aggregates present in an aqueous medium.

[7] The aqueous agglomerate according to [6], wherein a polymer compound having a mass average molecular weight of 1,000 or more is further present to form an organic pigment composition of a hydrophobic aggregate.

[8] The hydrophobic aggregate as described in [7] is contained in a non-aqueous medium, and the aggregate is deagglomerated to form a redispersed organic pigment composition.

[9] A colored photosensitive resin composition containing at least the organic pigment composition, the binder, the monomer or the oligomer, and the photopolymerization initiator or the photopolymerization initiator system according to [8].

[10] A color filter comprising the colored photosensitive resin composition according to [9].

[11] A process for preparing an organic pigment composition, which is characterized in that a solution of an organic pigment and a polymer compound having a repeating unit of the following formula (1) and/or a repeating unit of the formula (2) is dissolved in a good solvent; And mixing with the medium which is compatible with the good solvent and which is a poor solvent for the organic pigment, and the fine particles of the organic pigment are generated:

(In the formula, A ₁ represents a hydrogen atom or a methyl group; and X ₁ represents a heterocyclic group which has a carbon atom bonded to an NH group).

[12] The method for producing an organic pigment composition according to [11], wherein the polymer compound further has a repeating unit of the following formula (3) and/or a repeating unit of the formula (4):

(wherein A ₂ represents a hydrogen atom or a methyl group; Y ₁ represents -NH-, -O- or -S-; L represents a single bond or a divalent linking group; Y ₂ represents a hydrogen atom or a basic group; Z ₁ represents An unsaturated heterocyclic group having 1 or 2 nitrogen atoms).

[13] The method for producing an organic pigment composition according to [11] or [12], wherein the polymer compound further has a repeating unit of the following formula (5) and/or a repeating unit of the formula (6):

(wherein A ₃ and A ₄ each independently represent a hydrogen atom or a methyl group; R ₁ represents an alkyl group; R ₂ represents a hydrogen atom or an alkyl group; and R ₁ and R ₂ may be bonded to each other to form a ring structure group, the ring structure group It may also contain an oxygen atom, a nitrogen atom or a sulfur atom; R ₃ and R ₄ each independently represent a hydrogen atom or an alkyl group; and R ₃ and R ₄ may be bonded to each other to form a ring structure group).

The organic pigment composition of the present invention contains nanometer-sized organic pigment microparticles and a specific polymer compound, and has an excellent effect of easily switching the composition of the composition without any complicated steps in response to application or manufacturing. effect. Further, by using the organic pigment composition of the present invention, a colored photosensitive resin composition imparting desired properties can be obtained with high efficiency, and the color filter of the present invention using the same can exhibit high contrast in a display device or the like. performance.

The organic pigment composition of the present invention will be described below.

The organic pigment used in the present invention is preferably one formed by a liquid phase method, and may be used singly or in combination of plural or the like.

The organic pigment is not limited to hue, and is, for example, anthraquinone, pirinone, quinacridone, quinacridone oxime, hydrazine, diindolone, benzimidazolone, bisazo condensation, disazo, azo, Indanthrone, indigo, triaryl cation, two Amine, diketopyrrolopyrrole, thiopurine, isoindoline, isoindolinone, pymetrozine or isopurinone compound pigment, or a mixture thereof.

More specifically, there are ruthenium compound pigments such as CI Pigment Red 190 (CI No. 71140), CI Pigment Red 224 (CI No. 71127), CI Pigment Violet 29 (CI No. 71129), and CI Pigment Orange 43 (CI No. 71105). Or CI Pigment Red 194 (CI No. 71100) and other purple ketone compound pigments, CI Pigment Violet 19 (CI No. 73900), CI Pigment Violet 42, CI Pigment Red 122 (CI No. 73915), CI Pigment Red 192, CI Pigment Red 202 (CI No. 73907), CI Pigment Red 207 (CI No. 73900, 73906) or CI Pigment Red 209 (CI No. 73905) quinacridone compound pigment, CI Pigment Red 206 (CI No. 73900/73920), CI Pigment Quinone oxime compound pigment such as Orange 48 (CI No. 73900/73920) or CI Pigment Orange 49 (CI No. 73900/73920), anthrone compound pigment such as CI Pigment Yellow 147 (CI No. 60645), CI Pigment Red 168 (CI No. 59300) and the like ketone compound pigment, CI Pigment Brown 25 (CI No. 12510), CI Pigment Violet 32 (CI No. 12517), CI Pigment Yellow 180 (CI No. 21290), CI Pigment Yellow 181 ( Benzimidazolone compound pigment such as CI No. 11777), CI Pigment Orange 62 (CI No. 11775) or CI Pigment Red 185 (CI No. 12516), CI Pigment Yellow 93 (CI No. 20710), CI Pigment Yellow 9 4 (CI No. 20048), CI Pigment Yellow 95 (CI No. 20034), CI Pigment Yellow 128 (CI No. 20037), CI Pigment Yellow 166 (CI No. 20035), CI Pigment Orange 34 (CI No. 21115), CI Pigment Orange 13 (CI No. 21110), CI Pigment Orange 31 (CI No. 20050), CI Pigment Red 144 (CI No. 20735), CI Pigment Red 166 (CI No. 20730), CI Pigment Red 220 (CI No. 20055), CI Pigment Red A bisazo condensation compound pigment such as 221 (CI No. 20065), CI Pigment Red 242 (CI No. 20067), CI Pigment Red 248, CI Pigment Red 262 or CI Pigment Brown 23 (CI No. 20060), CI Pigment Yellow 13 ( Bisazo compound pigments such as CI No. 21100), CI Pigment Yellow 83 (CI No. 21108) or CI Pigment Yellow 188 (CI No. 21094), CI Pigment Red 187 (CI No. 12486), CI Pigment Red 170 (CI No. 12475) ), CI Pigment Yellow 74 (CI No. 11714), CI Pigment Yellow 150 (CI No. 48545), C. 1. Pigment Red 48 (CI No. 15865), CI Pigment Red 53 (CI No. 15585), CI Pigment Orange 64 ( Anionic compound pigment such as CI No. 12760) or CI Pigment Red 247 (CI No. 15915), an indanthrone compound pigment such as CI Pigment Blue 60 (CI No. 69800), CI Pigment Green 7 (CI No. 74260), CI Pigment Green 36 (CI number 74265), CI Indigo compound pigment such as Green 37 (CI No. 74255), CI Pigment Blue 16 (CI No. 74100), CI Pigment Blue 75 (CI No. 74160: 2) or 15 (CI No. 74160), CI Pigment Blue 56 (CI No. 42800) or a triaryl cation carbon compound pigment such as CI Pigment Blue 61 (CI No. 42765:1), CI Pigment Violet 23 (CI No. 51319) or CI Pigment Violet 37 (CI No. 51345) Compound pigment, amine pigment compound pigment such as CI Pigment Red 177 (CI No. 65300), CI Pigment Red 254 (CI No. 56110), CI Pigment Red 255 (CI No. 561050), CI Pigment Red 264, CI Pigment Red 272 ( CI No. 561150), diketopyrrolopyrrole compound pigment such as CI Pigment Orange 71 or CI Pigment Orange 73, thioindole compound pigment such as CI Pigment Red 88 (CI No. 73312), CI Pigment Yellow 139 (CI No. 56298) , Isoporphyrin compound pigment such as CI Pigment Orange 66 (CI No. 48210), isophthalone compound pigment such as CI Pigment Yellow 109 (CI No. 56284) or CI Pigment Orange 61 (CI No. 11295), CI Pigment Pyridoxal compound pigment such as orange 40 (CI No. 59700) or CI Pigment Red 216 (CI No. 59710), or isopurinone pigment such as CI Pigment Violet 31 (CI No. 60010). Among them, a quinacridone compound pigment, a diketopyrrolopyrrole compound pigment, two a compound pigment, a phthalocyanine compound pigment or an azo compound pigment is preferred, a diketopyrrolopyrrole compound pigment or two Compound pigments are preferred.

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

The organic pigment fine particles in the composition of the present invention can be produced by mixing an organic pigment solution obtained by dissolving an organic pigment in a good solvent with a solvent which is compatible with the good solvent and which is a poor solvent for the organic pigment.

In the present invention, the organic pigment composition preferably contains a composition of the organic pigment fine particles and a specific polymer compound described later, and a dispersion of the organic pigment fine particles (hereinafter referred to as "re-sinking liquid") may be used. A powder composition, agglomerated composition, and a solid composition of the organic pigment fine particles and the specific polymer compound. In this case, the organic pigment composition may contain organic pigment particles and other components other than the specific polymer compound, and the specific polymer compound or the like may coexist independently of the organic pigment particles in the composition, or may be inhaled. Or adsorbed to pigment particles and coexist.

The poor solvent of the organic pigment is not particularly limited as long as it can be dissolved or uniformly mixed with a good solvent for dissolving the organic pigment. The poor solvent of the organic pigment is preferably 0.02% by mass or less based on the organic pigment, and more preferably 0.01% by mass or less. The solubility of the organic pigment in the poor solvent is not particularly limited, and it is considered that the organic pigment generally used is 0.000001% by mass or more. This solubility may also be based on the solubility when dissolved in the presence of an acid or a base. Further, the compatibility or uniformity of the good solvent with the poor solvent is preferably 30% by mass or more, and more preferably 50% by mass or more, with respect to the poor solvent. For the poor solvent, there is no special upper limit for the amount of the good solvent to be dissolved, and it can be actually mixed at any ratio.

The poor solvent is not particularly limited as long as it is an aqueous medium, and examples thereof include an aqueous solvent (for example, water or hydrochloric acid, an aqueous sodium hydroxide solution), an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, an aromatic solvent, and a carbon disulfide solvent. The aliphatic compound solvent, the nitrile compound solvent, the halogen compound solvent, the ester compound solvent, the ionic liquid, the mixed solvent thereof, the aqueous solvent, the alcohol compound solvent, the ketone compound solvent, the ether compound solvent, the ester compound solvent or a mixture thereof is preferably water-based. The solvent, the alcohol compound solvent or the ester compound solvent is more preferable.

The alcohol compound solvent is, for example, methanol, ethanol, isopropanol, n-propanol, 1-methoxy-2-propanol or the like. The ketone compound solvent is, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone. The ether compound solvent is, for example, dimethyl ether, diethyl ether, tetrahydrofuran or the like. The aromatic compound solvent is, for example, benzene, toluene or the like. The aliphatic compound solvent is, for example, hexane or the like. The nitrile compound solvent is, for example, acetonitrile or the like. The halogen compound solvent is, for example, chloroform, dichloromethane, trichloroethylene, iodoform or the like. The ester compound solvent is, for example, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, 2-(1-methoxy)propyl acetate or the like. The ionic liquid is, for example, a 1-but-3-methylimidazolium cation, a salt of PF ₆ ^{- or} the like.

The good solvent is not particularly limited as long as it can dissolve the organic pigment used and is compatible or uniformly mixed with the poor solvent. The solubility in the good solvent of the organic pigment is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. There is no particular upper limit for the solubility of the organic pigment in the good solvent, and it is practical to use 50% by mass or less of the organic pigment generally used. This solubility may also be based on the solubility when dissolved in the presence of an acid or a base. The preferred range of the compatibility or uniformity of the poor solvent with the good solvent is as described above.

The good solvent may, for example, be an aqueous solvent (for example, water, or hydrochloric acid, aqueous sodium hydroxide), an alcohol compound solvent, a guanamine compound solvent, a ketone compound solvent, an ether compound solvent, an aromatic solvent, a carbon disulfide solvent, an aliphatic solvent, a nitrile a compound solvent, an anthraquinone compound solvent, a halogen compound solvent, an ester compound solvent, an ionic liquid, a carboxylic acid compound, a sulfonic acid compound, sulfuric acid, a mixed solvent thereof, an aqueous solvent, an alcohol compound solvent, a ketone compound solvent, an ether compound solvent , an anthraquinone compound solvent, an ester compound solvent, a guanamine compound solvent, a carboxylic acid compound, a sulfonic acid compound, sulfuric acid or a mixture thereof, an aqueous solvent, an alcohol compound solvent, an ester compound solvent, an anthraquinone compound solvent, a guanamine compound The solvent, the carboxylic acid compound, the sulfonic acid compound, and the sulfuric acid are more preferable, and the hydrazine compound solvent, the guanamine compound solvent, the carboxylic acid compound, the sulfonic acid compound, and the sulfuric acid are particularly preferable.

The alcohol compound solvent is, for example, methanol, ethanol, isopropanol, n-propanol, 1-methoxy-2-propanol or the like. The ketone compound solvent is, for example, acetone, methyl ethyl ketone, cyclohexanone or the like. The ether compound solvent is, for example, dimethyl ether, diethyl ether, tetrahydrofuran or the like. The aromatic compound solvent is, for example, nifedipine, chlorobenzene or dichlorobenzene. The aliphatic compound solvent is, for example, hexane or the like. The nitrile compound solvent is, for example, acetonitrile or the like. The solvent of the hydrazine compound is, for example, dimethyl hydrazine, diethyl hydrazine, hexamethylene sulfonium, cyclobutyl hydrazine or the like. The halogen compound solvent is, for example, chloroform, dichloromethane, trichloroethylene, iodoform or the like. The ester compound solvent is, for example, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, 2-(1-methoxy)propyl acetate or the like. The ionic liquid is, for example, a 1-but-3-methylimidazolium cation, a salt of PF ₆ ^{- or} the like. The guanamine compound solvent is, for example, N,N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidone, Ε-caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, Hexaphosphorus triamide and the like. The carboxylic acid compound solvent is, for example, formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, oxalic acid, trifluoroacetic acid, trichloroacetic acid, 2,2-dichloropropionic acid, succinic acid or the like. The sulfonic acid compound is, for example, methyl, sulfonic acid, p-toluenesulfonic acid, sulfuric acid, chlorosulfonic acid, trifluoromethanesulfonic acid

Specific examples of the good solvent and the specific examples of the poor solvent are common, but the same one is not used as a good solvent and a poor solvent, and the relationship with each organic pigment used is good. The solubility is preferably higher than the solubility of the poor solvent. For example, the solubility is preferably 0.2% by mass or more, more preferably 0.5% by mass or more. There is no special upper limit for the difference in solubility between the solvent and the poor solvent, and it is practical to use 50% by mass or less of the organic pigment generally used.

The concentration of the organic pigment solution in which the organic pigment is dissolved in the good solvent is preferably about 1/100 of the saturated concentration of the organic pigment in the good solvent at the time of dissolution.

The preparation conditions of the organic pigment solution are not particularly limited, and the range from atmospheric pressure to subcritical and supercritical conditions can be selected. The temperature under normal pressure is preferably -10 to 150 ° C, more preferably -5 to 130 ° C, and particularly preferably 0 to 100 ° C.

In the present invention, the organic pigment is preferably dissolved under acidic or alkaline conditions. In general, a pigment having a base which can be dissociated in a molecule is basic, and a base which is not dissociated under an alkali exists, and when a plurality of protons in the molecule are easily added to a nitrogen atom, it is acidic. For example, the quinacridone, the diketopyrrolopyrrole, and the disazo condensed compound pigment are alkaline, and the indigo compound pigment is dissolved under acidic conditions.

An inorganic base such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide or barium hydroxide used in the alkaline dissolution, or a trialkylamine, dinonicycloundecene (DBU), metal An organic base such as an alcoholate is preferably an inorganic base.

The amount of the base to be used is not particularly limited as long as it can uniformly dissolve the amount of the pigment, but the inorganic base is preferably 1.0 to 30 mol equivalents with respect to the organic material, more preferably 1.0 to 25 mol equivalents, and 1.0 to 20 mol. The molar equivalent is especially good. The organic base is preferably 1.0 to 100 moles equivalent to the organic material, more preferably 5.0 to 100 moles, and particularly preferably 20 to 100 moles.

It is an inorganic acid such as an acid-based sulfuric acid, hydrochloric acid or phosphoric acid, or an organic acid such as acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid or trifluoromethanesulfonic acid, which is preferably used as an inorganic acid. Sulfuric acid is especially preferred.

The amount of the acid to be used is not particularly limited as long as it can uniformly dissolve the amount of the organic pigment, but it is often used in excess as compared with the base. The inorganic acid and the organic acid are preferably from 3 to 500 mol equivalents, more preferably from 10 to 500 mol equivalents, even more preferably from 30 to 200 mol equivalents, based on the organic material.

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

When organic particles are produced, that is, when organic particles are precipitated and formed, the conditions of the poor solvent are not particularly limited, and the range from normal pressure to subcritical and supercritical conditions can be selected. The temperature under normal pressure is preferably -30 to 100 ° C, more preferably -10 to 60 ° C, and particularly preferably 0 to 30 ° C.

When the organic pigment solution and the poor solvent are mixed, it may be mixed by adding either of them, but it is preferable to add the organic pigment solution to the poor solvent and mix it. In this case, it is preferable to use a poor solvent in a stirred state. . The stirring speed is preferably 100 to 10,000 rpm, more preferably 150 to 8,000 rpm, and particularly preferably 200 to 6,000 rpm. Pumps can also be used when adding, or not. It may be added to the liquid or added externally, and the liquid is preferably added. The mixing ratio of the organic pigment solution to the poor solvent (the good solvent/poor solvent ratio in the organic pigment microparticle re-sinking liquid) is preferably 1/50 to 2/3 by volume, more preferably 1/40 to 1/2, 1 /20~3/8 is especially good. The aqueous medium contains at least 60% by mass of the above aqueous solvent, preferably 80% by mass or more.

When the organic pigment composition is, for example, a dispersion of the re-sinking liquid as described above, the content of the organic pigment fine particles is not particularly limited, but it is preferably in the range of 10 to 40,000 mg for the medium of 1000 ml of the organic pigment fine particles, and is 20 to 30000 mg. The range is better, especially in the range of 50 to 25000 mg.

The preparation scale of the organic pigment fine particles is not particularly limited, but the mixing amount of the poor solvent is preferably from 1 to 1000 L, and the modulation scale of from 1 to 100 L is more preferable.

Regarding the particle size of the organic pigment particles, there is a method of numerically expressing the average size of the group by means of a measurement method, and a mode diameter indicating the maximum value of the distribution is equivalent to the median diameter of the central value of the integral distribution curve. The average diameter (quantity average, length average, area average, mass average, volume average, etc.), etc., in the present invention, unless otherwise stated, the average particle diameter refers to the number average diameter. The average particle diameter of the organic pigment fine particles (primary particles) is a nanometer size, preferably 1 to 200 nm, more preferably 10 to 100 nm, and particularly preferably 10 to 80 nm. The particles formed in the present invention may be crystalline particles or amorphous particles, or may be a mixture of these.

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

The method for measuring the particle diameter of the organic pigment particles includes a microscopic method, a gravimetric method, a light scattering method, a light blocking method, an electric resistance method, an acoustic method, and a dynamic light scattering method, and is preferably a microscopic method or a dynamic light scattering method. Microscopes for microscopy include, for example, a scanning electron microscope, a transmission electron microscope, and the like. The particle measuring device of the dynamic light scattering method is, for example, NANOTRAC UPA-EX150 manufactured by Nikkiso Co., Ltd., DLS-7000 series of dynamic light scattering photometer manufactured by Otsuka Electronics Co., Ltd., LB-400 manufactured by Horiba, Ltd., and the like.

In the present invention, when the organic pigment fine particles are prepared to prepare a dispersion liquid, at least one of the organic pigment solution and the poor solvent may contain a dispersing agent. In this case, the dispersing agent is contained in at least the organic pigment solution (in the present invention, the dispersing agent added at the time of particle precipitation is simply referred to as "dispersing agent", and it is preferably distinguished from the dispersing agent for hydrophobicity described later).

Dispersing agents which can be used are, for example, low molecular or polymeric dispersants of anionic, cationic, zwitterionic, nonionic or pigment derivatives. The amount of the low molecular weight or high molecular weight dispersant added is preferably 10% by mass or more and 1000% by mass or less based on the pigment to be dissolved. 10% by mass or more and 200% by mass or less are more preferable. When the amount of addition is too small, the effect of suppressing the growth and aggregation of the pigment particles is small, and if it is too large, problems such as an increase in viscosity and a poor dissolution tend to occur.

In the present invention, when a dispersion of the organic pigment fine particles is prepared, at least one of the organic pigment solution and the poor solvent may contain a specific polymer compound. At this time, it is preferred to contain a dispersant in at least the organic pigment solution. In the present invention, it is preferred that the specific polymer compound has a dispersant function. Here, the dispersing agent added at the time of particle precipitation is called "dispersing agent", and is distinguished from the dispersing agent for hydrophobicization mentioned later.

In the present invention, the amount of the specific polymer compound having a dispersing agent function is preferably 10% by mass or more and 1000% by mass or less based on the pigment to be dissolved, and more preferably 10% by mass or more and 200% by mass or less. . When the amount is too small, the effect of suppressing the growth of the pigment particles and the strong aggregation between the pigment particles is small, and if it is too large, the viscosity is increased and the dissolution is likely to occur.

In the present invention, the molecular weight of the dispersing agent is preferably 1,000 or more and 200,000 or less by mass average molecular weight, more preferably 3,000 or more and 40,000 or less. When the molecular weight is too small, the effect of suppressing the growth of the pigment particles and the hard aggregation is small, and if it is too large, problems such as an increase in viscosity and a poor dissolution tend to occur. In the present invention, only the molecular weight means the mass average molecular weight, and the mass average molecular weight is a polystyrene-equivalent average molecular weight measured by gel permeation chromatography (carrier: tetrahydrofuran) unless otherwise stated.

The above specific polymer compound is a polymer compound having a repeating unit of the following formula (1) and/or a repeating unit of the formula (2):

In the formula, A ₁ represents a hydrogen atom or a methyl group, and a hydrogen atom is preferred.

X ₁ represents a heterocyclic group bonded to the NH group by a carbon atom thereof. Preferred examples are uracil residues, thiouracil residues, cytosine residues, adenine residues, guanine residues, imidazole residues, benzimidazole residues, thiazole residues, benzothiazole residues, Oxazole residue, benzo Oxazole residue, pyridine residue, pyrimidine residue, hydrazine Residue, pyrazole residue, triazole residue, pyrrole residue, benzimidazolone residue, anthracene residue, quinoline residue, piperidine residue, barbiturate residue, thiobarbital residue More preferred are uracil residues, cytosine residues, adenine residues, guanine residues, benzimidazole residues, benzothiazole residues, benzo Oxazole residue, pyridine residue, pyrimidine residue, hydrazine Residue, triazole residue, benzimidazolone residue, barbiturate residue, thiobarbital residue.

The repeating units of the general formulae (1) and (2) may be hydrophilic or hydrophobic, and have a structure in which interaction with an organic pigment such as hydrogen bonding, π-π interaction, dipole-dipole interaction, etc. good. The stronger these interactions, the higher the adsorption rate of the dispersant to the pigment, and the higher the dispersibility and dispersion stability in the non-aqueous medium.

The repeating units of the formulae (1) and (2) are specifically exemplified below, but the invention is not limited thereto. L1 to 20 are specific examples of the general formula (1), and L21 to 30 are specific examples of the general formula (2).

The specific polymer compound is preferably a polymer compound having a repeating unit of the following formula (3) and/or a repeating unit of the formula (4).

In the formula, A ₂ represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

Y ₁ represents -NH-, -O-, -S-, preferably -NH-, -O-.

L represents a single bond or a divalent linking group. The divalent linking group is preferably an alkylene group having 1 to 8 carbon atoms, an oxiranyl group or an oxypropylene group, and more preferably an alkylene group. Preferred examples of alkylene are methylene, ethyl, propyl, butyl, 2,2-dimethylpropyl, hexyl, heptyl, octyl, and especially carbon atoms. The number of 2 to 4 is an extended ethyl group, a propyl group, a butyl group, and a 2,2-dimethyl propyl group.

Y ₂ represents a hydrogen atom and a basic group. The basic group is a monoalkylamine or a dialkylamine, preferably a dialkylamine. Specific examples of the dialkylamines are dimethylamino, diethylamino, dipropylamino, dibutylamino, dihexylamino, di-2-ethenylamino, dioctylamino, diammonium. And a bis(dodecyl)amino group or the like, preferably a dimethylamino group, a diethylamino group, a dipropylamino group or a dibutylamine group.

Z ₁ represents an unsaturated heterocyclic ring having 1 to 2 nitrogen atoms, preferably an imidazole residue, a pyridine residue, a pyrimidine residue, or a hydrazine. Residues, particularly preferred are imidazole residues, pyrazole residues.

The repeating unit of the general formulae (3) and (4) may be hydrophilic or hydrophobic, but is preferably a structure having a strong acid-base interaction with a dispersing agent for hydrophobicity to be described later. When the dispersing agent for hydrophobicity is acidic, the repeating unit of the general formulae (3) and (4) is preferably basic, and the pKa is preferably 6 or more. When the dispersing agent for hydrophobicity is basic, the repeating unit of the general formulae (3) and (4) is preferably basic, and preferably has a pKa of 5 or less. The stronger the interaction between these acids and bases, the higher the dispersion and dispersion stability in non-aqueous media.

The repeating units of the general formulae (3) and (4) are specifically exemplified below, but the present invention is not limited to these. M1 to 6 are specific examples of the general formula (3), and M7 to 9 are specific examples of the general formula (4).

The specific polymer compound is preferably a polymer compound having a repeating unit of the following formula (5) and/or a repeating unit of the formula (6).

In the formula, A ₃ and A ₄ each independently represent a hydrogen atom or a methyl group, and each of them is preferably a hydrogen atom.

R ₁ represents an alkyl group. Preferred examples of the alkyl group of R ₁ are a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group.

R ₂ represents a hydrogen atom or an alkyl group. Preferred examples of the alkyl group of R ₂ are a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group.

R ₁ and R ₂ may be bonded to each other to form a ring structure, and may also contain an oxygen atom, a nitrogen atom or a sulfur atom. The linking structure is an alkylene group, an oxiranyl group, an propylene oxide group, and an alkyl group is particularly preferred. The alkyl group has an ethyl group, a propyl group, a butyl group, a pentyl group, and more preferably a propyl group or a butyl group.

R ₃ and R ₄ independently represent a hydrogen atom or an alkyl group. The alkyl group of R ₃ and R ₄ is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, decyl, dodecyl, methyl, ethyl, More preferably, propyl and butyl groups.

R ₃ and R ₄ may be bonded to each other to form a ring structure. The linking structure is preferably an alkylene group, an oxiranyl group, an propylene oxide group, an alkylene group or an oxirane group. The alkyl group is preferably a butyl group or a pentyl group. The oxiranyl group may be represented by -(CH ₂ -CH ₂ -O-CH ₂ -CH ₂ ) _n -, and n is preferably 1-4, more preferably 1-2.

The repeating unit of the general formulae (5) and (6) is preferably hydrophilic, and the solubility parameter (SP value) proposed by Oki Tsutomu is used (Japanese Society of Science and Technology Vol. 29, No. 6 (1993) item 249 - 259), the calculation value based repeating units more preferably 20MPa ^1/2. Below this, the dispersant becomes hydrophobic. In the aqueous medium in which the particles are formed, the pigment particles are strongly aggregated, and the aggregation is difficult to be resolved, and the dispersion in the non-aqueous medium is poor.

The repeating units of the formulae (5) and (6) are specifically exemplified below, but the invention is not limited thereto. N1 to 6 are specific examples of the general formula (5), and N7 to 10 are specific examples of the general formula (6).

When the general formulae (1) and (2), (3) and (4), (5) and (6) are merged into one unit α, β, γ, the mass ratio of α, β, γ is α: β. : γ = 0.1 to 50: 0.1 to 60: 30 to 90, and copolymerization is preferred, and more preferably α: β: γ = 5 to 50: 5 to 40: 30 to 90, which are appropriately selected so as to have a total of 100.

The dispersant can be obtained by using a monomer constituting the general formulae (1) to (6), for example, by radical polymerization in a solvent. In the radical polymerization, a radical polymerization initiator can be used, and a chain transfer agent (for example, 2-indole ethanol and dodecyl mercaptan) can be further used. It can also be synthesized by referring to the description of JP-A-2001-31885.

The combination of the general formulae (1) to (6) is preferably a polymer compound having a repeating unit of the formula (1), a repeating unit of the formula (5), and a repeating unit of the formula (3); a polymer compound of a repeating unit of the formula (1), a repeating unit of the formula (6), and a repeating unit of the formula (3); a repeating unit of the formula (1); a repeating unit of the formula (5); a polymer compound having a repeating unit of the formula (4); a polymer compound having a repeating unit of the formula (2), a repeating unit of the formula (5), and a repeating unit of the formula (3); having the formula (2) a repeating unit, a repeating unit of the formula (6), and a repeating unit of the formula (3); a repeating unit of the formula (2), a repeating unit of the formula (5), and a formula (4) a polymer compound of a repeating unit.

More preferably, the combination of the general formulae (1) to (6) is a polymer compound having a repeating unit of the formula (1), a repeating unit of the formula (5), and a repeating unit of the formula (3); a polymer compound of the repeating unit of the formula (2), a repeating unit of the formula (5), and a repeating unit of the formula (3); a repeating unit of the formula (1); a repeating unit of the formula (5); A polymer compound having a repeating unit of the formula (4); a polymer compound having a repeating unit of the formula (2), a repeating unit of the formula (5), and a repeating unit of the formula (4).

Here, preferred examples of the combination of the general formulae (1) to (6) are as follows.

In the present invention, an acid can be added to prepare a water-based aggregate after the preparation of the re-sinking liquid (aqueous dispersion liquid) of the organic pigment fine particles. Alternatively, when preparing an aqueous dispersion of the organic pigment fine particles, an acid may be added to the poor solvent, and a pigment solution may be added thereto to make the organic pigment fine particles a hydrophilic aggregate. It is preferred to obtain an aqueous agglomerate by adding an acid prior to the poor solvent. Here, the "aqueous aggregate" in the present invention means an aggregate in which the aggregate or the surface of the organic pigment fine particles constituting the aggregate is covered with a hydrophilic dispersant. Here, when quantitatively distinguishing between the pro- and the hydrophobicity, the solubility parameter (SP value) theoretical formula proposed by Oki Tsutomu is used (Japanese Society of Science and Technology Vol. 29, No. 6 (1993) 249-259), dispersant When the calculated value is 20 MPa ^1/2 or more, the dispersant is said to be hydrophilic. The hydrophilic aggregate is not particularly limited as long as the primary particles of the organic pigment fine particles are agglomerated by two or more particles, and usually the average particle diameter is about 5 μm, and preferably 0.04 to 10 μm.

The acid used to form the aqueous agglomerate is preferably acetic acid, hydrochloric acid, sulfuric acid or formic acid, more preferably acetic acid or hydrochloric acid. When the pH of the aqueous dispersion is formed when the aqueous aggregate is formed, there is no particular limitation, and it is preferably pH 1 to 6, and pH 2 to 4 is more preferable. The solid content of the aqueous agglomerate is substantially composed of a pigment, and the content of the pigment in the liquid after preparation is, for example, 0.004 to 4% by mass. This concentration is also the same as the non-aqueous aggregates described later.

In the present invention, an organic polymer compound having a mass average molecular weight of 1,000 or more is coexisted with an aqueous agglomerate, and it is preferably a hydrophobic aggregate. (In the future, "an organic polymer compound having a mass average molecular weight of 1,000 or more" or "organic polymer compound" or "a dispersing agent for hydrophobicization".

In the present invention, the organic pigment fine particles present in the aqueous medium can be collectively separated by adding at least one organic polymer compound having a mass average molecular weight of 1,000 or more to form a hydrophobic aggregate. The organic nano-particles present in the aqueous medium are directly filtered by the filter paper and the filter paper is squeezed, and filtration by the filter is also time consuming. As described above, by adding an acid or a base to the poor solvent, the organic pigment fine particles can be obtained as an aqueous aggregate at the time of preparation of the aqueous dispersion of the organic pigment fine particles. However, only in this case, due to the hydrophilicity of the agglutination system, no large aggregates are formed in the aqueous medium, and the filtration is also time consuming due to poor dehydration. Therefore, in the present invention, it is preferred to add the organic polymer compound to make the aqueous agglomerate a non-hydrophilic aggregate (hereinafter, also referred to as "hydrophobic aggregate"). By the addition of the organic polymer compound, the organic pigment fine particles can be made into a large aggregate in an aqueous medium. By this means, the time required for filtration can be shortened, and the filterability can be greatly improved. In the present invention, the term "hydrophobic aggregate" refers to agglomerates in a state in which the aggregate or the surface of the organic pigment fine particles constituting the aggregate is covered with a dispersing agent for hydrophobicization. Here, when quantifying the affinity and hydrophobicity, the solubility parameter (SP value) theoretical formula proposed by Oki Tsutomu (Japanese Society of Science and Technology Vol. 29, No. 6 (1993) 249-259), dispersant is used. When the calculated value is less than 20 MPa ^1/2 , the dispersant is referred to as a dispersing agent for hydrophobicization.

In the present invention, the organic polymer compound is preferably added to the aqueous dispersion containing the hydrophilic aggregate.

The average particle diameter of the hydrophobic aggregate is preferably 10 μm or more, and the larger the better. Below 10 μm, the separation of the aggregate takes time, passes through the filter, and clogs the filter paper or the filter. The so-called average particle diameter is the diameter of the aggregate measured by an optical microscope to observe the aggregate and compared with another standard scale for observation. This so-called diameter system measures the length between the ends of the aggregate, and the longest is defined as the diameter. In the present invention, the agglutination system aggregates two or more primary particles of the nanoparticles which are invisible to the naked eye, and the secondary particles which are aggregated twice or more.

In the present invention, a preferred organic polymer compound has a structural site having affinity for a non-aqueous medium (a repeating unit having a group having affinity for a non-aqueous medium) and a structural site having affinity for the organic pigment microparticle (having The repeating unit of the group having an affinity for the organic pigment fine particles) functions as a compound which disperses the organic pigment fine particles in a non-aqueous medium. The organic polymer compound acts on the hydrophilic aggregate, and the structural portion having affinity for the organic pigment fine particles is coated on the surface of the aqueous aggregate or on the surface of the organic pigment fine particles constituting the aggregate, and as a result, the aggregate or the particles are used for non-aqueous The medium is hydrophobized with an affinity structure.

In the present invention, the organic polymer compound is adsorbed to the aggregated organic pigment fine particles. Therefore, after the steps of filtration, washing, redispersion, etc., the organic polymer compound can function as a dispersing agent directly in the non-aqueous medium, and it is not necessary to add a new dispersing agent. In order to adjust the dispersibility, it is also possible to add a new dispersant afterwards, but it is preferable not to add it from the viewpoint of manufacturing cost.

In the present invention, the organic pigment fine particles constituting the aggregate are preferably agglomerated in a state in which the organic polymer compound is coated, and are not aggregated with such an organic polymer compound, and are more agglomerated than, for example, agglomerates such as hydrochloric acid. It is easier to redisperse after the helium, and the organic pigment particles are more easily deagglomerated into primary particles, and the contrast is increased.

The organic polymer compound may be directly added, but in order to obtain good filterability, it is preferred to dissolve the organic polymer compound in a solvent.

The solvent for dissolving the organic polymer compound is not particularly limited as long as it can be mixed with the aqueous dispersion of the organic pigment fine particles to dissolve the organic polymer compound, and the organic polymer compound itself is not precipitated after the addition.

The solvent for dissolving the organic polymer compound is, for example, an aqueous solvent (for example, water or hydrochloric acid, an aqueous sodium hydroxide solution), an alcohol compound solvent, a guanamine compound solvent, a ketone compound solvent, an ether compound solvent, an aromatic solvent, a carbon disulfide solvent, or the like. An aliphatic compound solvent, a nitrile compound solvent, an anthraquinone compound solvent, a halogen compound solvent, an ester compound solvent, an ionic liquid, a mixed solvent thereof, an aqueous solvent, an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, an anthraquinone compound The solvent, the ester compound solvent, the guanamine compound solvent, the nitrile compound solvent or a mixture thereof is preferably a ketone compound solvent, an ether compound solvent, a nitrile compound solvent or a mixture thereof.

The alcohol compound solvent is, for example, methanol, ethanol, isopropanol, n-propanol, 1-methoxy-2-propanol or the like. The ketone compound solvent is, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or the like. The ether compound solvent is, for example, dimethyl ether, diethyl ether, tetrahydrofuran or the like. The aromatic compound solvent is, for example, benzene, toluene or the like. The aliphatic compound solvent is, for example, hexane or the like. The nitrile compound solvent is, for example, acetonitrile or the like. The halogen compound solvent is, for example, dichloromethane, trichloroethylene or the like. The ester compound solvent is, for example, ethyl acetate, ethyl lactate, 2-(1-methoxy)propyl acetate or the like. The ionic liquid is, for example, a salt of 1-but-3-methylimidazolium and PF ₆ ^{- or} the like.

The amount of the solvent for dissolving the organic polymer compound is not particularly limited as long as it can dissolve the organic polymer compound and form a hydrophobic aggregate which is easy to be filtered, and the complexity of the production and the reduction of the raw material cost are considered. A small amount is probably better. When the aqueous dispersion of the organic pigment fine particles is 100 in terms of mass ratio, the solvent to be added is preferably in the range of 0 to 100, and particularly preferably in the range of 0 to 70. Too much filtering can take a lot of time.

After the organic polymer compound is added, it is preferably stirred in such a manner as to be sufficiently mixed with the aqueous dispersion of the organic pigment fine particles. Stirring and mixing can be carried out by a usual method. The temperature at which the organic polymer compound is added and mixed is not particularly limited, and is preferably from 1 to 100 ° C, more preferably from 5 to 60 ° C. The addition and mixing of the organic polymer compound can be carried out by using any apparatus, for example, a stirring blade or a Raymond mixer.

The amount of the organic polymer compound to be added is preferably 10% by mass or more and 1000% by mass or less based on the pigment, and more preferably 50% by mass or more and 200% by mass or less. When the amount of addition is too small, the effect of the hydrophobicity (non-aqueousization) of the nanoparticles is small, and when it is too large, problems such as an increase in viscosity tend to occur when redispersing. In the present invention, the mass average molecular weight of the organic polymer compound is preferably 1,000 or more. Although there is no special upper limit, it is preferably 3,000,000 or less, and more preferably 300,000 or less.

Specific examples of the organic polymer compound which can be used in the present invention are "Disperbyk-110 (acid group-containing copolymer), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 manufactured by BYK Chemie. (polymer copolymer), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), EFKA 4047, 4050, 4010, 4165 (polyurethane), EFKA 4330, 4340 (block copolymer), EFKA) 4400, 4402 (modified polyacrylate), 5010 (polyester decylamine), 5765 (high molecular weight polycarboxylate), 6220 (fat acid polyester)", AjISPER PB821, PB822 manufactured by Ajinomoto Precision Technology Co., Ltd. "FLOREN TG-710 (urethane ester oligomer)", "POLYFLO No. 50E, No. 300 (propylene oxime copolymer)" manufactured by Kyoeisha Chemical Co., Ltd., "DISPERON KS-860, manufactured by Kwanmoto Chemicals Co., Ltd." 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether ester), DA-703-50, DA-705, DA-725", Kao Corporation "DEMOR RN, N (naphthalenesulfonic acid Fuma) Forest polycondensate), MS, C, SN-B (aromatic condensate of aromatic sulfonate), "HOMOGENO-L-18 (polymeric polycarboxylic acid)", "EMULGEN 920, 930, 935, 985 ( Polyoxyethylene phenyl ether )", "ACETAMIN86 (stearylamine acetate)", "SOLSPERS 55000 (grafted polymer), 13240 (polyesteramine), 3000, 17000, 27000 (polymer with functional part at the end) manufactured by LUPRIZOL Co., Ltd. 24000, 28000, 32000, 38500 (grafted polymer)", NIKKOL T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) manufactured by Nikko Chemical Co., Ltd. Wait.

In the present invention, the known polymer compound may be used singly or in combination of two or more kinds as the organic polymer compound. It is known that the polymer compound may be used in combination with one or more of the organic polymer compounds described below, and the organic polymer compound may be used alone or in combination of two or more.

The organic polymer compound is a polymer compound obtained by copolymerizing at least one of the following monomers (A) to (D), or at least one of the monomers using (A) to (D). The polymer compound of the formula (1) is preferred.

General formula (1)

(In the formula (1), X represents a (1+m)-valent linking group, and S represents a sulfur atom; and Y is a group composed of at least one of the monomer skeletons of the monomers (A) to (B), Z. It is a group consisting of at least one of the monomer skeletons of the monomers (C) to (D); 1+m is 3 to 10, 1 is 0 to 10, and m is 0 to 10.)

(A) a monomer containing at least one of an acidic group and a basic group

(B) a monomer containing a nitrogen-containing heterocycle

(C) Monomers containing oligomers having affinity for non-aqueous media

(D) a monomer containing an oligomer having affinity for organic pigment particles present in an aqueous medium

In the combination of the components (A) to (D), it is preferred to combine the components of (A), (C) or (B) and (C), the components of (A), (B), (C), or ( A), (C), (D) components, or (B), (C), (D) components are better combined, (A), (B), (C), (D) The combination is especially good.

(A) The monomer having at least one of an acidic group and a basic group is a monomer having a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, an amine group, a guanamine group, or a urea group, to obtain an organic polymer. It is preferred that the compound be adsorbed to the organic pigment particles via an acid-base interaction. Specifically, for example, but not limited to these.

(B) A monomer containing a nitrogen-containing heterocyclic ring, containing a benzimidazolone group, a benzimidazolyl group, an anthranilyl group, a uracil group, an acridone group, a naphthyl anthracene group, a carbazolyl group, a pyridine Monomers such as imidazolyl, amber succinimide, benzopyrrolyl, etc., to obtain an organic polymer compound which can be adsorbed by hydrogen bonding interaction, van der Waals interaction, dipole-dipole interaction The construction of organic pigment particles is preferred. Specifically, for example, but not limited to these.

(C) The monomer having an oligomer having affinity for a non-aqueous medium is not particularly limited, and is preferably one which is soluble in a non-aqueous medium used for redispersion later, and has an organic substance in a non-aqueous medium. The dispersion of the pigment particles can be stabilized by the stereoscopic repulsive force.

The single system of (C) comprises a polystyrene skeleton, a polymethyl methacrylate skeleton, a polybutyl methacrylate skeleton, a polyhydroxyethyl methacrylate skeleton, and a polyethyl methacrylate 2-ethyl group. The hexyl ester skeleton, the polyethylene glycol skeleton, the polypropylene glycol skeleton, and the polycaprolactone skeleton are preferred, and contain a polystyrene skeleton, a polymethyl methacrylate skeleton, a polyethylene glycol skeleton, a polypropylene glycol skeleton, and a polycaprolactone. The skeleton is especially good.

This monomer may be a commercially available product or may be a suitable synthesizer.

Specifically, commercially available products include a polystyrene oligomer having a terminal methacrylic acid (Mn=6000, trade name: AS-6, manufactured by East Asia Synthetic Chemical Industry Co., Ltd.), and a terminal methacrylic acid oxime. Polymethyl methacrylate oligomer (Mn=6000, trade name: AA-6, manufactured by East Asia Synthetic Chemical Industry Co., Ltd.), oligomerization of poly(methacrylic acid) n-butyl methacrylate (Mn=6000, trade name: AB-6, manufactured by East Asia Synthetic Chemical Industry Co., Ltd.), polymethyl methacrylate/2-hydroxyethyl methacrylate oligomer with one terminal methacrylic acid ( Mn=7000, trade name: AA-714, manufactured by East Asia Synthetic Chemical Industry Co., Ltd.), a terminal methacrylic acid butyl methacrylate/2-hydroxyethyl methacrylate oligomer (Mn= 7000, trade name: 707S, manufactured by East Asia Synthetic Chemical Industry Co., Ltd., 2-methylhexyl methacrylate/2-hydroxyethyl methacrylate oligomer with methacrylic acid deuterated (Mn=7000) , trade name: AY-707S, AY-714S, East Asia Synthetic Chemical Industry Co., Ltd.), methoxy polyethylene glycol methacrylate (trade name: NK ester M-40G, M-90G, M-230G) (The above East Asian synthetic chemical workers Industry (share) system)); trade name: BLENMER PME-100, PME-200, PME-400, PME-1000, PME-2000, PME-4000 (above Japanese fats and oils)), polyethylene glycol Monomethacrylate (trade name: BLENMER PE-90, PE-200, PE-350, manufactured by Nippon Oil & Fats Co., Ltd.), polypropylene glycol monomethacrylate (trade name: BLENMER PP-500, PP-800, PP-1000, manufactured by Nippon Oil & Fats Co., Ltd., polyethylene glycol polypropylene glycol monomethacrylate (trade name: BLENMER 70PEP-370B, manufactured by Nippon Oil & Fats Co., Ltd.), polyethylene glycol polytetramethylene glycol Monomethacrylate (trade name: BLENMER 55PET-800, manufactured by Nippon Oil & Fats Co., Ltd.), polypropylene glycol polytetramethylene glycol monomethacrylate (trade name: BLENMER NHK-5050, manufactured by Nippon Oil & Fats Co., Ltd.) )Wait.

Specific examples of the synthetic product include 2-ethylhexyloxypolycaprolactone oligomer obtained by ring-opening polymerization of 2-ethylhexanol and ε-caprolactone, and a terminal of a methoxypolyethylene glycol polypropylene glycol random copolymer. An oligomer having a first amine group (trade name: Jeffamine 2005, manufactured by HUNTSMAN Co., Ltd.), a butylene oxide polypropylene glycol oligomer (manufactured by Aldrich Co., Ltd.), or the like, and one of (meth)acryloyloxyethyl isocyanate An oligomer having a polymerizable group at the end.

The monomer of (D) containing an oligomer having affinity for the organic pigment microparticles present in the aqueous medium is not particularly limited to have an affinity for the organic pigment microparticles present in the aqueous medium, and for redispersion It is preferred that the non-aqueous medium has an affinity, that is, a structure having both a hydrophilic portion (a repeating unit having a hydrophilic group) and a hydrophobic portion (a repeating unit having a hydrophobic group). The single system is particularly suitable for both aqueous medium and non-aqueous medium, and can impart hydrophilic aggregate wettability to the organic pigment particles present in the aqueous medium, and can be used in a non-aqueous medium by stereoscopic repulsive force. The structure in which the dispersion of the organic pigment fine particles is stabilized is preferable. The monomer (D) used together with the monomer of (C) is not a monomer of (C), but is preferably a hydrophilic ratio (C).

The single system of (D) contains a polystyrene skeleton, a polymethyl methacrylate skeleton, a polybutyl methacrylate skeleton, a polyhydroxyethyl methacrylate skeleton, and a poly(2-hydroxyethyl methacrylate). The ester skeleton, the polyethylene glycol skeleton, the polypropylene glycol skeleton, and the polycaprolactone skeleton are preferred, and a polyethylene glycol skeleton, a polypropylene glycol skeleton, and a polycaprolactone skeleton are particularly preferable.

This monomer may be a commercially available product or may be a suitable synthesizer.

Specifically, commercially available products include methoxy polyethylene glycol methacrylate (trade name: NK ester M-40G, M-90G, M-230G (manufactured by Toagosei Chemical Co., Ltd.); :BLENMER PME-100, PME-200, PME-400, PME-1000, PME-2000, PME-4000 (manufactured by Nippon Oil & Fat Co., Ltd.), polyethylene glycol monomethacrylate (trade name: BLENMER PE) -90, PE-200, PE-350, manufactured by Nippon Oil & Fats Co., Ltd., polypropylene glycol monomethacrylate (trade name: BLENMER PP-500, PP-800, PP-1000, manufactured by Nippon Oil & Fats Co., Ltd.) , polyethylene glycol polypropylene glycol monomethacrylate (trade name: BLENMER 70PEP-370B, manufactured by Nippon Oil & Fats Co., Ltd.), polyethylene glycol polytetramethylene glycol monomethacrylate (trade name: BLENMER 55PET) -800, manufactured by Nippon Oil & Fats Co., Ltd., polypropylene glycol polytetramethylene glycol monomethacrylate (trade name: BLENMER NHK-5050, manufactured by Nippon Oil & Fats Co., Ltd.).

Specific examples of the synthetic product include an oligomer having a first amine group at one end of a methoxy polyethylene glycol polypropylene glycol random copolymer (trade name: Jeffamine 1000, Jeffamine 2070, manufactured by HUNTSMAN Co., Ltd.), methoxy polyethylene glycol polypropylene glycol An oligomer (manufactured by Aldrich Co., Ltd.) or the like, which is reacted with (meth)acryloyloxyethyl isocyanate to obtain an oligomer having a polymerizable group at one end.

In the polymer compound obtained by copolymerizing at least one of the monomers (A) to (D), the mass ratio is (A): (B): (C): (D) = (0.1 to 60): 0~50): (20~90): (0~60) is better. These mass ratios are appropriately selected so that the sum is 100.

The polymer compound of the formula (1) is a mass ratio (mole ratio) (A): (B): (C): (D) = (0.1 to 6): (0.1 to 5): (1~ 9): (1~6) is preferable, and the mass ratio of these substances is appropriately selected so that the sum is equivalent to the (1+m) valence of X in the formula (1).

The polymer compound obtained by copolymerizing at least one of the monomers (A) to (D) can be obtained by radical polymerization of the monomers (A) to (D), for example, in a solvent. In the radical polymerization, a radical polymerization initiator can be used, and a chain transfer agent (for example, 2-indole ethanol and dodecyl mercaptan) can also be used. The pigment dispersant containing a copolymer can be synthesized by referring to the description of JP-A-2001-31885.

The polymer of the formula (2) and (A) to (D) can be used as the polymer compound of the formula (1) in which at least one of the monomers (A) to (D) is synthesized. Synthesized by the method described in -262378.

General formula (2)

In the above formulae (1) and (2), X represents a (1+m)-valent linking group. 1+m is 3 to 10. The (1+m)-valent linking group represented by X is a nitrogen atom of from 1 to 100, a nitrogen atom of from 0 to 10, an oxygen atom of from 0 to 50, and one to one. The group consisting of 200 hydrogen atoms and 0 to 20 sulfur atoms may further contain an unsubstituted or substituted group.

X in the above formulae (1) and (2) is preferably a carbon atom of from 1 to 60, a nitrogen atom of from 0 to 10, an oxygen atom of from 0 to 50, and one to one. A hydrogen atom of 100 and a sulfur atom of 0 to 20 atoms.

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

Among the above, from the viewpoints of difficulty in obtaining and synthesizing raw materials and solubility in various solvents, the above (r-1), (r-2), (r-10), (r-11), (r) are used. The basis of -16) and (r-17) is preferred.

When the above-mentioned x has a substituent, the substituent has, for example, an alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group or a naphthyl group, and a hydroxyl group or an amine group. a methoxy group having 1 to 6 carbon atoms such as a carboxyl group, a carboxyl group, a sulfonylamino group, an N-decylamino group or an ethoxycarbonyl group, and an alkane having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group. A halogen atom such as an oxy group, a chlorine atom or a bromine group; an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group; or a carbonate group such as a cyano group or a tributyl butyl carbonate;

In the following, a polymer compound obtained by copolymerizing at least one of the monomers (A) to (D), and a polymer of the formula (1) wherein at least one of the monomers (A) to (D) is synthesized is used. Specific examples of the compound are not limited thereto. Wherein Me represents a methyl group and Bu represents a butyl group. R represents -O-CO-CH ₂ -CH ₂ -, which is bonded to the S (sulfur atom) in the repeating unit. In the following specific examples, when each repeating unit is located at the end of the constituent polymer compound, the terminal of the repeating unit is substituted with a hydrogen atom. In P-9 to P-11, the numerical value shown in parentheses [] of the repeating unit indicates the mass ratio of the substance.

The separation method of the hydrophobic aggregate of the organic nanoparticles will be described below.

First, it is preferred to allow the agglutination solution to stand for 0.5 to 2 hours before the separation. Because the aggregates will settle, the supernatant liquid can be decanted, extracted and removed, so that the aggregates are easier to separate in the next step. Further, by performing the centrifugal separation instead of standing, the aggregate may settle more quickly, and the time can be shortened.

The separation method may be a variety of filtration methods, such as limiting filtration, centrifugation, filter paper, filter filtration, and the like.

By ultrafiltration, for example, a method for desalting/concentration of a silver halide emulsion can be employed. The methods described in Research Disclosure No. 10208 (1972), No. 13 122 (1975) and No. 16 351 (1977) are known. The important pressure difference, flow rate, etc. in the operating conditions can be selected by the technique curve of the "Thin Film Utilization Technical Manual", fortunately published in the book (1978), p275, and must be processed in the target organic nanoparticle dispersion. Find the optimum conditions to suppress unwanted agglutination of the particles. The method for replenishing the solvent lost through the film is a batch type in which a constant volume of the solvent is continuously added and an intermittent batch is added, and a constant volume type in which the desalting treatment time is relatively short is preferable. The solvent thus replenished is a pure solvent obtained by ion exchange or distillation, a poor solvent for dispersing agents and dispersing agents may be mixed in pure water, or may be directly added to the organic nanoparticle dispersion.

When the filter is filtered, for example, a pressure filtration device can be used. Preferred filters include filter paper, nano filter, ultrafilter, and the like.

A centrifugal separator for separating organic nanoparticle by centrifugation can be used if any of the organic nanoparticle in the organic nanoparticle dispersion (or organic nanoparticle concentrated extract) can be sedimented. The centrifugal separator includes, for example, a general-purpose device and other continuous centrifugal separators which are provided with a scooping function (a function of sucking up and down the spin, and discharging the outside of the system), and continuously discharging the solid matter.

The centrifugal separation condition is preferably a centrifugal force (a value indicating a centrifugal acceleration applied several times the gravity acceleration) of 50 to 10,000, more preferably 100 to 8,000, and particularly preferably 150 to 6,000. The temperature at the time of centrifugation depends on the solvent type of the dispersion, preferably -10 to 80 ° C, more preferably -5 to 70 ° C, and particularly preferably 0 to 60 ° C.

The desalted aggregates are washed for desalting, dehydration, and removal of excess dispersant. The washing operation can be directly filtered, centrifuged, filtered with filter paper, filter, and directly added with washing liquid. Once the aggregate is taken out, it is re-slurryed in the washing liquid, and then subjected to limit filtration, centrifugal separation, The mixture is separated by filtration through a filter paper, a filter, or the like, and may be washed in combination.

Washing is not only carried out as described above after separation, but also before separation. The agglomerated nano pigment particle dispersion is allowed to stand, and the supernatant liquid is removed, and the washing liquid is added to form a slurry. After re-slurrying, it is allowed to stand, and the supernatant liquid is removed, and the filtration is also possible, but it can also be directly filtered. Washing before separation is because the aggregates are often wet, not only the cleaning efficiency is increased, but also the re-dispersion is easier.

If the cleaning solution can achieve desalting, dehydration, excess dispersing agent, and the removal of the aggregating agent is not particularly limited, specifically, an aqueous solvent (such as water, or hydrochloric acid, aqueous sodium hydroxide), an alcohol compound solvent, a guanamine compound solvent. And a ketone compound solvent, an ether compound solvent, an aromatic compound solvent, a carbon disulfide solvent, an aliphatic compound solvent, a nitrile compound solvent, an anthraquinone compound solvent, a halogen compound solvent, an ester compound solvent, an ionic liquid, a mixed solvent thereof, or the like, preferably It is an aqueous solvent, an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, a nitrile compound solvent, an anthraquinone compound solvent, an ester compound solvent, a guanamine compound solvent or a mixture thereof, an aqueous solvent, an alcohol compound solvent, an ester compound solvent, a nitrile compound The solvent is better.

In the separated hydrophobic aggregate, it is preferred to contain a dispersing agent or a dispersing agent for hydrophobicity in addition to the organic pigment fine particles. The dispersant is preferably coexisted in an amount of 10% by mass or more and 1000% by mass or less based on the pigment. More preferably, it is 10 mass% or more and 200 mass% or less. If the amount is too small or too large, problems such as poor dispersion in a non-aqueous medium are likely to occur. The dispersing agent for hydrophobicity is preferably 10% by mass or more and 1000% by mass or less based on the pigment. More preferably, it is 50 mass% or more and 200 mass% or less. When the amount is too small, the dispersion is poor, and if it is too large, problems such as an increase in viscosity at the time of redispersion tend to occur.

When dispersing the organic pigment fine particles in a non-aqueous medium, the dispersing agent has a function of promoting and maintaining the hydrophobic dispersing agent adsorbed to the organic pigment fine particles. Therefore, when the amount of the dispersant is too small, the dispersing agent for hydrophobicity is detached from the fine particles of the organic pigment, and when it is redispersed in the non-aqueous medium, it is liable to be poorly dispersed. On the other hand, the dispersing agent is hydrophilic, and if the amount is too large, the dispersing agent for hydrophobicity becomes less than the dispersing agent. Therefore, the hydrophobization effect in the aqueous medium may become insufficient, and when it is redispersed in the non-aqueous medium, it may fall into a poor dispersion. In the case of a dispersing agent for hydrophobicity, when the amount is too small, the hydrophobicizing effect of the dispersing agent for hydrophobicity may be insufficient. On the other hand, in a non-aqueous medium, there is a problem of poor dispersion. When the amount of the dispersing agent for hydrophobicity is too large, there is a case where the dispersing agent for excess hydrophobicity which cannot be adsorbed to the organic pigment fine particles is present, and the viscosity may increase when redispersed.

The separated aggregate can be directly redispersed, or the solvent can be redispersed (described later) and then redispersed, and the organic nanoparticle dispersion powder can be dried and then redispersed.

The drying method is not particularly limited, and is lyophilized, dried under reduced pressure, and the like.

The method of freeze-drying is not particularly limited, and any method that can be used in the industry can be used. For example, the refrigerant direct expansion method, the repeated freezing method, the heat medium circulation method, the triple heat exchange method, the indirect heating and freezing method, preferably a refrigerant direct expansion method, an indirect heating and freezing method, and more preferably an indirect heating and freezing method. In either method, it is preferred to perform freeze-drying after pre-freezing. The conditions for pre-freezing are not particularly limited, but the sample to be freeze-dried must be completely frozen.

The indirect heating and freezing method includes a small freeze dryer, an FTS freeze dryer, a LYOVAC freeze dryer, an experimental freeze dryer, a research freeze dryer, a triple heat exchange vacuum freeze dryer, a single cooling freeze dryer, and HULL. The freeze dryer is preferably a small freeze dryer, an experimental freeze dryer, a research freeze dryer, or a single-cooling freeze dryer, and more preferably a small freeze dryer or a single-cooling freeze dryer.

The temperature of the freeze-drying is not particularly limited, and is, for example, -190 to -4 ° C, preferably -120 to -20 ° C, more preferably -80 to -60 ° C. The pressure for freeze-drying is not particularly limited, and may be appropriately selected from, for example, 0.1 to 35 Pa, preferably 1 to 15 Pa, more preferably 5 to 10 Pa. The freeze-drying time is, for example, 2 to 48 hours, preferably 6 to 36 hours, more preferably about 16 to 26 hours. However, these conditions can be appropriately selected. The method of freeze-drying can be referred to, for example, the manual of the preparation machine technical manual: preparation of the mechanical technology research institute, the library, p. 120-129 (September 2000); vacuum manual: Japanese vacuum technology (share), ohm company, p 328-331 (1992); Association of Freezing and Drying Research Association: Ito Takaji, No. 15, p. 82 (1965) and so on.

The apparatus for concentrating the organic nanoparticles by drying under reduced pressure is not particularly limited as long as it can evaporate the solvent of the organic nanoparticle dispersion (or organic nanoparticle concentrated extract). For example, a general-purpose vacuum dryer, a rotary pump, or the like can be used to heat a reduced-pressure drying device while stirring a liquid, and the liquid can be passed through a tube that is heated and decompressed to be continuously dried.

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

According to the production method of the present invention, if necessary, the fine particles of the organic pigment in the aggregated state can be finely dispersed (in the present invention, finely dispersing or redispersing means that the aggregation of the particles in the dispersion is released to improve the degree of dispersion). In the present invention, it is preferred that the hydrophobic aggregate obtained by redispersion is in a non-aqueous medium. (The dispersion thus obtained or the non-aqueous dispersion.)

The above non-aqueous medium means a medium other than the aqueous medium, and a ketone compound solvent, an ester compound solvent, or an aromatic solvent is preferred. Specifically, there are methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, 2-(1-methoxy)propyl acetate, nifedipine, chlorobenzene, dichlorobenzene, among which methyl ethyl ketone, cyclohexanone, acetic acid 2-(1-methoxy)propyl ester or chlorobenzene is preferred.

In order to make the agglomerated organic pigment fine particles into a well-dispersed state which can be rapidly filtered, it is preferred that the organic pigment fine particles are aggregated to obtain a redispersible floc. The flocculation refers to a collection of particles of weak agglomeration (soft agglomeration) which is redispersible. Preferably, both the hydrophilic aggregate and the hydrophobic aggregate are based on flocculation. Thus, the organic pigment fine particles are condensed, and the organic pigment fine particles precipitated in, for example, the aqueous mixed solution can be separated from the medium by rapid filtration or the like. Then, the separated floccule (soft aggregate) is redispersed in an organic solvent suitable for producing a color filter, and an organic solvent-based pigment dispersion composition (non-aqueous dispersion composition) can be produced with high efficiency. In other words, when the mixed solvent of the good solvent and the poor solvent is an aqueous solvent, the dispersion medium (continuous phase) can be switched by replacing the third solvent composed of the organic solvent with high efficiency.

The degree of dispersion by the usual dispersing method is insufficient for microparticulation, and it is necessary to have a method of higher micronization efficiency. The organic particles in such a strong agglomerated state (in the present invention, the aggregated organic particles refer to those in which aggregates such as aggregates are aggregated by a secondary force, and the primary particles are also called agglomerated nanoparticles in the case of nanometer size), by agglutinating organic particles. The particle liquid contains an organic polymer compound having a mass average molecular weight of 1,000 or more, and can be a dispersion in which the organic particles are appropriately finely dispersed. (In the present invention, the agglomerated organic particle liquid refers to a liquid containing agglomerated organic particles, and may be a dispersion. , concentrate, paste, slurry, etc., if it contains agglomerated organic particles.). More specifically, by using the above organic polymer compound, good fine dispersibility (characteristic of achieving uniform fine particle size) and dispersion stability (preservation of uniform fine particles for a long time) when a mixed solution of a good solvent and a poor solvent is precipitated The characteristics of the diameter are maintained after the medium is switched to an organic solvent suitable for the color filter, and a high-performance color filter can be realized. Further, the organic polymer compound can interact with the coloring property of the organic nano pigment particles without hindering the optical characteristics of the color filter, thereby achieving high performance in the color filter.

A method of finely dispersing such a nanoparticle aggregate can be, for example, a method of applying ultrasonic energy by a method of ultrasonic dispersion.

The ultrasonic irradiation device to be used is preferably a function capable of applying an ultrasonic wave of 10 kHz or more, and is, for example, an ultrasonic homogenizer or an ultrasonic cleaner. When the liquid temperature rises during the ultrasonic irradiation, the nanoparticles are thermally aggregated (see Non-Patent Document 1), and the liquid temperature is preferably from 1 to 100 ° C, more preferably from 5 to 60 ° C. The temperature control method can be carried out by controlling the temperature of the dispersion, controlling the temperature of the temperature adjustment layer of the temperature of the dispersion, and the like.

The dispersing machine used when the physical energy is applied to disperse the concentrated organic nanoparticles is not particularly limited, and examples thereof include a kneader, a roll mill, an attritor, a super grinder, a dissolver, a homogenizer, a sand mill, and the like. Dispersing machine. A high pressure dispersion method and a dispersion method using fine beads are also suitable.

A preferred method for preparing the organic nanoparticle dispersion is to knead the colorant in a resin component to a knead dispersion treatment at a viscosity of 10,000 mPa·s or more at 25 ° C, and a higher viscosity of 100,000 mPa·s or more, followed by a desired viscosity. The solvent is added, and the viscosity after the microdispersion treatment to the fine dispersion treatment is 1,000 mPa·s or less, and a method of lower viscosity of 100 mPa·s or less is preferable.

Mechanical two-roller, three-roller, ball mill, drum screen, disperser, kneading machine, kneading extruder, homogenizer, blending machine, single-shaft and double-axis extruder for re-dispersion treatment, etc. Disperse while imparting strong shearing force. Secondly, a solvent is added, mainly using a vertical or horizontal sand mill, a pin mill, a slit mill, an ultrasonic disperser, a high-pressure disperser, etc., and beads made of glass, zirconia, or the like having a particle diameter of 0.1 to 1 mm. Microdispersion treatment. It is also possible to use a fine dispersion of fine beads of 0.1 mm or less.

After the main pigment and the sub-pigment are separately dispersed, the dispersion liquid of the two is mixed and dispersed, and the main pigment and the sub-pigment are dispersed together.

As for the details of the dispersion, T.C. Patton's "Paint Flow and Pigment Dispersion" (published by John Wiley and Sons, Inc., 1964), etc., can be used.

The organic pigment fine particle dispersion after redispersion may be added with a usual pigment dispersant or a surfactant to enhance the dispersibility of the organic pigment fine particles. A variety of compounds can be used as these dispersants, such as indigo derivatives (commercial product EFKA-6745 (manufactured by EFKA)), SOLSPERS 5000 (manufactured by ZENEKA Co., Ltd.); organic siloxane polymer KP341 (Shin-Etsu Chemical Industry) (manufactured by the company), (meth)acrylic (co)polymer POLYFLOW No. 75, No. 90, No. 95 (manufactured by Kyoeisha Oil Chemical Industry Co., Ltd.), W001 (made by Yusho Co., Ltd.), etc. Cationic surfactant; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene phenyl ether, polyethylene glycol dilaurate, poly Nonionic surfactants such as diol distearate and calylide; and anionic surfactants such as W004, W005, W017 (manufactured by Yusho Co., Ltd.); EFKA-46, EFKA-47, EFKA- 47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID 15, DISPERSE AID 9100 (manufactured by SUNOPCO) ) such as polymer dispersants; SOLSPERS 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc. Dispersant (ZENEKA); ADEKAPLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 Electrochemical (share) system and ISONET S-20 (Sanyo Chemical Co., Ltd.). Further, the pigment dispersant described in JP-A-2000-239554, the compound (C) described in Japanese Patent Publication No. Hei 5-72943, and the compound of Synthesis Example 1 described in JP-A-2001-31885 are also applicable.

The organic nanoparticle-dispersed composition after redispersion is such that the organic nanoparticle (primary particle) can be finely dispersed, and the particle diameter is preferably from 1 to 200 nm, more preferably from 2 to 100 nm, and 5 ~50nm is especially good. The Mv/Mn of the particles after redispersion is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, and particularly preferably 1.0 to 1.5.

According to the process of the present invention, although the pigment particles are made to have a small particle size of a nanometer size (for example, 10 to 100 nm), they can be concentrated and redispersed, and can be formed, for example, as a dispersion composition of the organic pigment particles, followed by coloring. A photosensitive resin composition. Therefore, when these compositions are used for a color filter, the optical density is high, the surface uniformity of the filter is excellent, the contrast is high, and image noise is small.

In addition, since the organic pigment fine particles containing the organic pigment fine particle-dispersed composition and the colored photosensitive resin composition can be highly and uniformly dispersed finely, it is possible to exhibit a high coloring concentration with a low film thickness, and to form a thin layer such as a color filter. It becomes possible.

The organic pigment fine particle-dispersed composition and the colored photosensitive resin composition contain a pigment exhibiting a vivid color tone and a high coloring power, and can be used as an image forming material excellent for producing, for example, a color proof or a color filter.

The alkaline developing solution used for the exposure and development of the colored image can be used as an organic nanoparticle-dispersed composition or a colored photosensitive resin composition using an alkaline aqueous solution-soluble binder (adhesive). It can also respond to environmental requirements.

The solvent used for the organic pigment fine particle dispersion composition and the coloring photosensitive resin composition (dispersion medium of the pigment) can be an organic solvent having a suitable drying property, and can satisfy the drying requirement after coating.

[Coloring photosensitive resin composition]

The colored photosensitive resin composition of the present invention contains at least (a) an organic pigment composition, (b) a binder, (c) a monomer or oligomer, and (d) a photopolymerization initiator or a photopolymerization initiator system. Each component of the colored photosensitive resin composition of the present invention will be described below.

(a) Organic pigment composition

The preparation method of the organic pigment composition has been described in detail. The content of the organic nano pigment particles is preferably from 3 to 90% by mass, based on the total solid content in the colored photosensitive resin composition (in the present invention, the total solid content is a total of the components other than the organic solvent), 20 to 80% by weight. The mass % is better, and 25 to 60% by mass is particularly preferable. If the amount is too large, the viscosity of the dispersion rises, which may cause a problem in manufacturing suitability. If it is too small, the tinting strength is insufficient. The organic nano pigment particles having a coloring function have a particle diameter of 0.1 μm or less and preferably 0.08 μm or less. For coloring, it can also be used in combination with a usual pigment, and the pigment can be used as described above. In the present invention, the organic nanoparticle is preferably used as the non-aqueous dispersion of the above organic nanopigment.

(b) Adhesive

The binder in the coloring photosensitive resin composition is preferably a polymer compound having a mass average molecular weight of 1,000 or more. The content of the binder is generally 15 to 50% by mass, and preferably 20 to 45% by mass based on the total solid content of the colored photosensitive resin composition. If the amount is too large, the viscosity of the composition is too high, which is a problem in manufacturing suitability. If it is too small, there is a problem in the formation of a coating film.

(c) monomer or oligomer

The monomer or oligomer contained in the colored photosensitive resin composition of the present invention is preferably a monomer or oligomer having two or more ethylenically unsaturated double bonds and addition polymerization by irradiation with light. Such a monomer or oligomer has at least one ethylenically unsaturated group which can be added to the polymerization, and a compound having a boiling point of 100 ° C or more under normal pressure. Examples thereof include monopentaerythritol hexa(meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate. Acrylate, monofunctional (meth) acrylate; polyethylene glycol di(meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane three (meth) acrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, neopentyl alcohol tri (meth) acrylate Ester, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di(meth) acrylate, trimethylolpropane tris(propylene propylene propylene Ether, tris(propylene oxyethyl) isomeric cyanurate, tris(propylene oxyethyl) cyanurate, glycerol tri(meth) acrylate; trimethylolpropane, glycerol A polyfunctional acrylate or polyfunctional methacrylate esterified with (meth)acrylate after addition of a polyfunctional alcohol to ethylene oxide or propylene oxide. The formula (1) and (2) described in JP-A-10-62986, after the polyfunctional alcohol is added with ethylene oxide or propylene oxide, is (meth)acrylated. Compound.

Further, the urethane acrylates described in Japanese Patent Publication No. Sho-48-41, 193, and JP-A-51-37193, JP-A-48-64183, and JP-A-49-43191 Polyester acrylates described in the publications of Japanese Patent Publication No. Sho 52-30490; and polyfunctional acrylates and methacrylates such as epoxy acrylates of reaction products of epoxy resins and (meth)acrylic acid.

Among them, trimethylolpropane tri(meth)acrylate, neopentyltetrakis(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(methyl) Acrylate is preferred.

In addition, "polymerizable compound B" described in JP-A-11-133600 is also available.

These monomers or oligomers (monomer or oligomer are preferably those having a molecular weight of 200 to 1,000) may be used alone or in combination of two or more kinds, and the total solid content of the colored photosensitive resin composition is generally It is preferably 5 to 50% by mass, and preferably 10 to 40% by mass. If the amount is too large, the control of the developing property is difficult, and it becomes a problem of manufacturing suitability. If it is too small, the hardening power is insufficient at the time of exposure.

(d) Photopolymerization initiator or photopolymerization initiator system

A photopolymerization initiator or a photopolymerization initiator system which is contained in the coloring photosensitive resin composition of the present invention (in the present invention, a photopolymerization initiator refers to a compound which promotes photopolymerization initiation by a combination of plural compounds), Oral polyketalobnyl compound disclosed in the specification of No. 2367660, the sulfonium ether compound described in the specification of U.S. Patent No. 2,448,828, and the aromatic compound substituted by α-hydrocarbon as described in the specification of U.S. Patent No. 2,725,512醯 姻 化合物 , , 美国 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 Benzothiazole compound and trihalo-s-three as described in the '48516 publication Compound, trihalomethyl-three as described in the specification of US Pat. No. 4,239,850 Compound, trihalide, as described in the specification of US Pat. No. 4,212,976 Diazole compounds and the like. Trihalo-s-three Trihalide Diazoles and triaryl imidazole dimers are especially preferred.

In addition, the "polymerization initiator C" described in JP-A-11-133600, the 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)anthracene, O- Benzopyridinyl-4'-(benzoquinone)benzylidene-hexyl-ketooxime, 2,4,6-trimethylbenzenecarbonyl-diphenylphosphine oxide, hexafluorophosphorus-trialkylphenylhydrazine salt, and the like.

These photoinitiators or photoinitiator systems may be used alone or in combination of two or more kinds, and it is especially preferable to use two or more kinds. The display characteristics can be reduced by using at least two kinds of photopolymerization initiators.

The content of the photopolymerization initiator or the photopolymerization initiator system of the total solid content of the colored photosensitive resin composition is usually 0.5 to 20% by mass, preferably 1 to 15% by mass. If the amount is too large, the sensitivity is too high to control. If too little, the exposure sensitivity is too low. The radiation that can be used for exposure is particularly suitable for ultraviolet rays such as g-line or i-line. Based irradiation amount to 5 ~ 1500mJ / cm ² preferably, 10 ~ 1000mJ / cm ² more preferably, 10 ~ 500mJ / cm ² the best.

(other additives) [solvent]

In the colored photosensitive resin composition of the present invention, an organic solvent may be used in addition to the above components. Examples of the organic solvent are not particularly limited, and there are esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, isobutyl acetate, butyl propionate, and isopropyl butyrate. Ester, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl glycolate, ethyl hydroxyacetate, butyl glycolate, ethyl methoxyacetate, methoxyacetate Ester, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, etc. 3-hydroxypropionic acid alkyl ester; methyl 3-methoxypropionate, 3 -ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-hydroxy-2 - methyl methyl propionate, ethyl 2-hydroxy-2-propionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, Ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate, etc.; ethers, for example Ethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methacetin acetate, cecetaxel acetate, diethylene glycol monomethyl ether, propylene glycol methyl ether Butyrate or the like; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclohexanol, 2-heptanone, 3-heptanone, etc.; aromatic hydrocarbons such as toluene, xylene, and the like. Among these solvents, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celecoxib acetate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, 2- Heptanone, cyclohexanone, carbitol acetate, tetracarbitol acetate, propylene glycol methyl ether acetate, etc. are suitable solvents in the present invention. These solvents may be used singly or in combination of two or more.

A solvent having a boiling point of 180 ° C to 250 ° C can be used as necessary. These high boiling solvents can be exemplified as follows. Diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, 3,5,5-trimethyl-2-cyclohexen-1-one, butyl lactate, dipropylene glycol Methyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol diacetate, propylene glycol n-propyl ether acetate, diethylene glycol diethyl ether, 2-ethylhexyl acetate, 3-methoxy-3-methyl acetate Butyl ester, γ-butyrolactone, tripropylene glycol methyl ethyl acetate, dipropylene glycol n-butyl acetate, propylene glycol phenyl ether acetate, 1,3-butylene glycol diacetate.

The content of the solvent is preferably from 10 to 95% by mass based on the total amount of the resin composition.

[Surfactant]

In the color filter used in the past, in order to achieve high color purity, the color of each pixel is rich, and the uneven film thickness of the pixel directly appears as a problem of color spots. Therefore, it is required to improve the film thickness variation at the time of formation (coating) of the photosensitive resin layer which directly affects the film thickness of a pixel.

The color filter of the present invention or the transfer material using the colored photosensitive resin composition of the present invention can be controlled to a uniform film thickness, thereby effectively preventing the application of stains (color spots due to variations in film thickness). It is preferred that the coloring photosensitive resin composition contains an appropriate surfactant.

The surfactants disclosed in JP-A-2003-337424 and JP-A-11-133600 are preferred. The content of the surfactant is preferably 5% by mass or less based on the total amount of the resin composition.

[Thermal polymerization inhibitor]

The colored photosensitive resin composition of the present invention is preferably a thermal polymerization preventing agent. The thermal polymerization inhibitor is, for example, hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-tert-butyl-p-cresol, gallic phenol, cetyl catechol, benzoquinone, 4,4'-sulfur double (3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2-indole benzimidazole, thiophene Wait. The content of the thermal polymerization inhibitor is preferably 1% by mass or less based on the total amount of the resin composition.

[Dyes and pigments for subsidies]

The coloring photosensitive resin composition of the present invention may be added with a coloring agent (dye or pigment) other than the coloring agent (pigment) as necessary. When the pigment in the coloring agent is used, it is preferably uniformly dispersed in the colored photosensitive resin composition. Therefore, the particle size is preferably 0.1 μm or less, particularly preferably 0.08 μm or less.

The dyes and pigments to be used are the pigments described in JP-A-2005-361447 [0068] to [0020], and the pigments described in JP-A-2005-361447 [0068] to [0072]. The coloring agent described in Japanese Patent Publication No. 2005-17521 [0080] to [0088]. The content of the dye or pigment to be used is preferably 5% by mass or less based on the total amount of the resin composition.

[UV absorber]

The colored photosensitive resin composition of the present invention may contain an ultraviolet absorber if necessary. The ultraviolet absorbing agent is a compound described in JP-A-H05-72724, and a salicylate-based, diphenylketone-based, benzotriazole-based, cyanoacrylate-based, nickel-chelating-based, hindered phenol-based, etc. .

Specifically, there are phenyl ruthenate, 4-tert-butylphenyl sulphate, 2,4-di-t-butylbenzene-3', 5'-di-third-4'-hydroxybenzoate, salicylic acid 4-t-butylphenyl ester, 2,4-dihydroxydiphenyl ketone, 2-hydroxy-4-methoxydiphenyl ketone, 2-hydroxy-4-n-octyloxydiphenyl ketone, 2-(2 '-Hydroxy-5'-tolyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-tolyl)-5-chlorobenzotriazole, ethyl-2-cyano -3,3-diphenylacrylate, 2,2'-hydroxy-4-methoxydiphenyl ketone, nickel dibutyldiamine disulfide, bis(2,2,6,6-tetramethyl- 4-pyridine) sebacate, 4-tert-butylphenyl sulphate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethylperidine Condensate, succinic acid-bis(2,2,6,6-tetramethyl-4-piperidine Base, ester, 2-[2-hydroxy-3,5-bis(α,α-dimethyltoluene)phenyl]-2H-benzotriazole, 7-{[4-chloro-6-(di Ethylamine)-5-three -2-yl]amino}-3-benzene oxacin and the like. The content of the ultraviolet absorber is preferably 5% by mass or less based on the total amount of the resin composition.

In addition to the above-mentioned additives, the coloring photosensitive resin composition of the present invention may contain an "adhesive aid" described in JP-A-11-133600, other additives, and the like.

[Coating film of colored photosensitive resin composition]

The content of the coating film using the coloring photosensitive resin composition of the present invention is the same as that described in the previous [Coloring photosensitive resin composition]. The thickness of the coating film using the coloring photosensitive resin composition of the present invention can be appropriately determined depending on the use thereof, and is preferably 0.5 to 5.0 μm, more preferably 1.0 to 3.0 μm. In the coating film using the coloring photosensitive resin composition of the present invention, the (c) monomer or oligomer contained in the coating film is polymerized to form a polymer film of the colored photosensitive resin composition, and color filter having the same can be produced. The film (the color filter is produced as described later). The polymerization of the polymerizable monomer or the polymerizable oligomer can be carried out by photo- (d) photopolymerization initiator or photopolymerization initiator system.

<Color filter and its preparation method>

Next, the color filter of the present invention and a method for producing the same will be described.

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

Hereinafter, the color filter of the present invention will be described in detail by the production method thereof (the method for producing a color filter of the present invention).

The color filter of the present invention is characterized in that it comprises a step of forming a photosensitive film on the substrate directly or via another layer to form a photosensitive film (hereinafter referred to as "photosensitive film forming step". a step of exposing the formed photosensitive film pattern (exposure through a mask) (hereinafter, simply referred to as "exposure step"), and a step of forming a colored pattern by developing the photosensitive film after exposure (hereinafter referred to as a short name) Is the "development step").

Hereinafter, each step in the production method of the color filter of the present invention will be described.

(Photosensitive film forming step)

The photosensitive film forming step is performed by applying (giving) the photocurable composition of the present invention directly or on a substrate having another layer to form a photosensitive film.

The substrate which can be used in this step is, for example, soda glass for a liquid crystal display element, PYREX (registered trademark) glass, quartz glass, and a photoelectric conversion element substrate for a photographic element or the like, to which a transparent conductive film is attached, for example. A germanium substrate or the like, a complementary metal oxide semiconductor (CMOS) or the like. These substrates are sometimes also formed with black stripes that isolate each pixel.

If necessary, an undercoat layer (other layer) for improving the adhesion to the upper layer, preventing the diffusion of the substance, or planarizing the surface of the substrate may be provided on these substrates.

The photocurable composition of the present invention can be applied to a substrate by various coating methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, and screen printing.

The coating film thickness of the photocurable composition is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and particularly preferably 0.2 to 3 μm.

The drying (prebaking) of the photosensitive film coated on the substrate can be carried out at a temperature of 50 to 140 ° C for 10 to 300 seconds using a hot plate, an oven or the like.

(exposure step)

In the exposure step, the photosensitive film formed in the photosensitive film forming step is exposed through a mask having a specific mask pattern, that is, pattern exposure.

In this step, the photosensitive film of the coating film is exposed through a specific mask pattern, and only the portion of the coating film irradiated with light can be hardened.

The radiation that can be used for exposure is preferably ultraviolet rays such as g-line or i-line. The irradiation amount is preferably 5 to 1500 mJ/cm ^{2 , more} preferably 10 to 1000 mJ/cm ^{2 , and most} preferably 10 to 500 mJ/cm ² .

In the case of the color filter-based liquid crystal display device of the present invention, it is preferably 5 to 200 mJ/cm ^{2 in the} above range, more preferably 10 to 150 mJ/cm ^{2 , and most} preferably 10 to 100 mJ/cm ² . When the color filter of the present invention is used for a solid-state imaging device, it is preferably 30 to 1500 mJ/cm ^{2 in the} above range, more preferably 50 to 1000 mJ/cm ^{2 , and most} preferably 80 to 500 mJ/cm ² .

(development step)

Next, after the development processing, the unexposed portion in the exposure step is dissolved in the developing liquid, leaving only the portion which is photohardened. The developing solution can be used if it dissolves the photocurable composition film of the uncured portion and does not dissolve the hardened portion. Specifically, a combination of various organic solvents and an aqueous alkaline solution can be used.

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

The organic solvent may be a solvent which can be used in the preparation of the pigment dispersion composition or the photocurable composition of the present invention.

The alkaline aqueous solution is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, hydrogen. a basic compound such as tetraethylammonium oxide, choline, pyrrole, piperidine or 1,8-dioxabicyclo-[5,4,0]-7-undecene is diluted with pure water to a concentration of 0.001 to 10% by mass. A 0.01 to 1% by mass aqueous alkaline solution is preferred.

When a developing solution composed of such an alkaline aqueous solution is used, it is usually washed with pure water (rinsing) after development.

After the development step, the remaining developer liquid is removed by washing, and dried and then subjected to heat treatment (post-baking).

The post-baking is a heat treatment after the development of the hardening is completed, and is usually performed by a heat hardening treatment at 100 ° C to 240 ° C. When the substrate is a glass substrate or a tantalum substrate, it is preferably 200 to 240 ° C in the above temperature range.

This post-baking treatment can be carried out in a continuous or batch manner by using a heating plate, a convection oven (hot air circulation dryer), a high-frequency heating machine or the like under the conditions of the coating film after development.

The color filter having the desired hue can be produced by repeating the photosensitive film forming step, the exposing step, and the developing step (and, if necessary, heat treatment) described above, depending on the desired number of hue.

When the photocurable composition is formed on the substrate to form a film, the dry thickness of the film is usually 0.3 to 5.0 μm, preferably 0.5 to 3.5 μm, and most preferably 1.0 to 2.5 μm.

The substrate is used for, for example, an alkali-free glass such as a liquid crystal display element, soda glass, PYREX (registered trademark) glass, quartz glass, or a photoelectric conversion element substrate such as a solid-state imaging element, such as a ruthenium substrate. Etc., as well as plastic substrates. Black stripes that isolate each pixel are typically formed on these substrates.

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

The use of the photocurable composition has mainly been explained by the use of the pixels of the color filter, and of course, it is also applicable to the black matrix provided between the pixels of the color filter. A black matrix can be used, and a black coloring agent such as carbon black or titanium black is added to the photocurable composition of the present invention, and is formed by pattern exposure, alkali development, and then post-baking to promote hardening, as in the above-described method for producing a pixel. .

Example

The invention is illustrated in more detail in the following examples, but the invention is not limited thereto.

<Example 1> [Modulation of aqueous dispersion of organic nano pigment particles]

C.I. Pigment Red 254 (45 parts by mass) and the aforementioned exemplified compound O-1 (45 parts by mass) were added to dimethyl hydrazine (DMSO) (953 parts by mass) and stirred. To the solution, a 26% by mass aqueous solution of tetramethylammonium hydroxide (45 parts by mass) was added to prepare a pigment solution A. Further, acetic acid (7.6 parts by mass) was added to water (4000 parts by mass) to prepare a pigment-insoluble solvent B.

The pigment-insoluble solvent B was stirred at 500 rpm with a GK-0222-10 Raymond mixer (trade name) manufactured by Fujisawa Pharmaceutical Co., Ltd. at 30 °C, and a large-capacity pulseless pump of the NP-KX-500 type manufactured by Nippon Precision Science Co., Ltd. (trade name) This pigment solution A was injected into the pigment-insoluble solvent B at a flow rate of 100 mL/min, and injected for 4 minutes and 4 seconds to crystallize the organic nano pigment particles to obtain a hydrophilic aggregate of the organic nano pigment particles.

[Addition of dispersant for hydrophobicization]

A compound (the mass average molecular weight of 8,000) (3 parts by mass) of the following formula (P) is dissolved in acetone (200 parts by mass) as a dispersing agent for hydrophobicity, and is added to the hydrophilic aggregate dispersion of the above organic nanoparticle ( 300 parts by mass), stirred for 0.5 hours. After standing for 0.5 hour, the resulting hydrophobic aggregate was sedimented, and the supernatant was removed by decantation.

(evaluation test)

The following evaluation was performed on the obtained aggregate. The results are shown in Table 1.

(1) Evaluation of the size of primary particles of the organic nano pigment particles constituting the aggregate by a transmission electron microscope.

(2) About 1 part by mass of the agglomerate was taken out, stirred in water/acetone (1:1 volume mixed solution, 100 parts by volume), allowed to stand for 0.5 hour, and decanted to remove the supernatant liquid. This operation was repeated 3 times, and the aggregate was suction-filtered using a filter paper (manufactured by ADVANTEC Co., Ltd., No. 2), and vacuum-dried overnight. The dried pigment solid (10 m parts by mass) was dissolved in DMSO (100 parts by volume), and the absorption spectrum was measured by UV-2500 (trade name, manufactured by Shimadzu Corporation) to determine the mass ratio of the pigment in the pigment solid. The residual ratio of the added dispersant is the adsorption rate.

[Separation ‧ Washing ‧ Drying]

The aggregate was collected by filtration paper (manufactured by ADVANTEC Co., Ltd., No. 2), and washed with water (300 parts by mass). The resulting solid was dried under vacuum at room temperature overnight.

[re-dispersion]

The following non-aqueous solvent 1-methoxy-2-propyl acetate (Formula Q) (4 parts by mass) was added to the organic pigment solid (1 part by mass), and the ultrasonic homogenizer US series (trade name) manufactured by Nippon Seiko Co., Ltd. was used. Ultrasonic irradiation was carried out for 3 hours to obtain a non-aqueous dispersion of organic nano pigment particles (pigment dispersion composition A) using a non-aqueous solvent as a dispersion medium.

(evaluation test) (1) Comparative evaluation

The pigment dispersion composition A obtained by coating was applied onto a glass substrate to a thickness of 2 μm to prepare a sample. The backlight unit is used in a three-wavelength cold cathode tube light source (FWL18EX-N manufactured by Toshiba Optical Technology Co., Ltd.), and the sample is placed on two polarizing plates (SANRITSU (shared) polarizing plate HLC2-2518). Between the two, the amount of transmitted light when the polarization axis is parallel and perpendicular is measured, and the ratio is compared (refer to "The 7th Color Optics Conference of 1990, 512 colors display 10.4" size color filter for TFT-LCD, planting wood, Xiao Guan, Fu Yong, Shan Zhong, etc.). The chromaticity was measured using a color luminance meter (BM-5 manufactured by TOPCON Co., Ltd.). The position of the two polarizing plates, the sample, and the color luminance meter is set at a position of 13 mm from the backlight, and a cylinder having a diameter of 11 mm and a length of 20 mm is disposed at a position of 40 mm to 60 mm, and the light transmitted therethrough is irradiated to the position set at 65 mm. The sample was measured, and the transmitted light was measured by a color luminance meter set at a position of 100 mm through a color luminance meter set at a position of 400 mm. Set the measurement angle of the color luminance meter to 2°. The amount of light of the backlight is set such that the luminance of the two polarizing plates is set to be parallel polarized light up to 1280 cd/m ² without setting the sample. The same evaluation was carried out on the pigment dispersion composition A after one week as an indicator of the stability of the period.

(2) Visual assessment

The pigment dispersion composition A after one week was visually confirmed by the sample for comparative evaluation to confirm the presence or absence of scattering (whether or not). If there is no scattering (if transparent), the pigment particles are sufficiently dispersed in the non-aqueous medium.

<Example 2>

The above-exemplified compound O-1 of Example 1 was changed to O-3, and the operation as in Example 1 was carried out. The evaluation test of Example 1 was carried out with respect to the obtained non-aqueous dispersion of organic nano pigment particles (pigment dispersion composition B). The results are shown in Table 1.

<Example 3>

The above-exemplified compound O-1 of Example 1 was changed to O-10, and the operation as in Example 1 was carried out. The evaluation test of Example 1 was carried out with respect to the obtained non-aqueous dispersion of the organic nano pigment particles (pigment dispersion composition C). The results are shown in Table 1.

<Example 4>

The above-exemplified compound O-1 of Example 1 was changed to O-4, and the operation as in Example 1 was carried out. The evaluation test of Example 1 was carried out with respect to the obtained non-aqueous dispersion of organic nano pigment particles (pigment dispersion composition D). The results are shown in Table 1.

<Comparative Example 1>

The above-exemplified compound O-1 of Example 1 was changed to polyvinylpyrrolidone (K-25 (trade name), manufactured by Wako Pure Chemical Industries, Ltd.), and an aqueous dispersion of organic pigment fine particles was prepared as in Example 1, using a filter ( AD070TEC company H010A047A, trade name) Filtered the hydrophilic agglomerates present therein, and added methacrylic acid/methacrylic acid benzene to the solid which was filtered and dried as in Example 1 (1 part by mass). The methyl ester copolymer (1 part by mass) and 1-methoxy-2-propyl acetate (8 parts by mass) were subjected to ultrasonic irradiation for 3 hours using an ultrasonic homogenizer US series (trade name) manufactured by Nippon Seisakusho Co., Ltd. The following is a non-aqueous dispersion of organic pigment fine particles (pigment dispersion composition E) using a non-aqueous medium as a dispersing agent. The evaluation was performed as in Example 1 except for the filter filtration as described above. The evaluation test of Example 1 was carried out for the pigment dispersion composition E, and the results are shown in Table 1.

As shown by the above results, according to the present invention, a non-aqueous dispersion of organic pigment particles having high dispersibility and dispersion stability can be obtained with high efficiency. This is due to the fact that the adsorption rate of the dispersant is increased, the free dispersant is small, and good fine dispersibility and stability are reproducibly obtained. It is also known that the organic pigment composition of the present invention can greatly enhance the contrast and maintain it for a long time when it is made into a color filter. In the organic pigment composition of the present invention, the "scattering" of the transmitted light is small, and the same amount of the pigment can be used to obtain high chroma, high efficiency and good coloring. Moreover, since the scattering is controlled, the number of coarse particles in the composition is small, which is more favorable for high contrast and display quality improvement.

[Preparation of coloring photosensitive resin composition]

In the pigment dispersion compositions A to E obtained in Examples 1 to 4 and Comparative Example 1, 1000 parts by mass of the following components were added, and the mixture was stirred and mixed to prepare a colored photosensitive resin composition (color resist liquid) of the present invention.

of

[composition]

‧ dipentaerythritol hexaacrylate 80 parts by mass

‧4-[o-bromo-p-N,N-bis(ethoxycarbonyl)amine phenyl]-2,6-di(trichloromethyl)-S-three (Photopolymerization initiator) 30 parts by mass

‧Methyl methacrylate/methacrylic acid (=70/30 [mole ratio]) copolymer (mass average molecular weight: 10,000) propylene glycol monomethyl ether acetate solution (solid content 40%) 200 parts by mass

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

The photocurable composition (color resist liquid) obtained by coating was applied to a glass substrate (manufactured by CORNING Co., Ltd.) of 100 mm × 100 mm, and the color density index x value was 0.650, and dried in an oven at 90 ° C for 60 seconds (pre bake). Then, the coating film was entirely exposed to 200 mJ/cm ² (illuminance: 20 mW/cm ² ), and the exposed coating film was covered with a 1% aqueous solution of an alkali developing solution CDK-1 (manufactured by Fuji Electronics Co., Ltd.), and allowed to stand. 60 seconds. After standing, rinse the developing solution with pure water. Then, the coating film subjected to exposure and development as described above is heat-treated in an oven at 220 ° C for 1 hour (post-baking), and a colored resin film for a color filter is formed on the glass substrate to prepare a colored filter (color filter) Light film).

The R component of each film obtained as measured in Example 1 was compared. The results are shown in Table 2.

From the above results, it was found that the non-aqueous dispersion prepared by using the pigment composition of the present invention was compared with the color filter prepared by coloring the photosensitive resin composition, which was higher than that of the comparative example.

The above-exemplified compound O-1 of Example 1 is changed to compound O-2, compound O-6, compound O-7, compound O-8, compound O-9, compound O-11, compound O-12, compound O- 13. Compound O-14 or compound O-15 was subjected to the operation as in Example 1. As a result, it was confirmed that it had the effects similar to the above-mentioned pigment compositions A to D.

Claims (18)

An organic pigment composition comprising an organic pigment composition of an organic pigment fine particle, wherein a dispersing agent for hydrophobicity having a mass average molecular weight of 1,000 or more represented by the following formula (I) and a specific medium in an aqueous medium are contained The molecular compound and the aqueous aggregate of the organic pigment fine particles coexist to become a hydrophobic aggregate; wherein the specific polymer compound has a repeating unit represented by the following formula (1) and/or a repeat represented by the formula (2) a unit, a repeating unit represented by the following formula (5), and/or a repeating unit represented by the formula (6); Wherein A ₁ represents a hydrogen atom or a methyl group; X ₁ represents a heterocyclic group, and is a uracil residue, a thiouracil residue, a cytosine residue, an adenine residue, a guanine residue, an imidazole residue. , benzimidazole residue, thiazole residue, benzothiazole residue, Oxazole residue, benzo Oxazole residue, pyridine residue, pyrimidine residue, hydrazine Residue, pyrazole residue, triazole residue, pyrrole residue, benzimidazolone residue, anthracene residue, quinoline residue, piperidine residue, barbiturate residue or thiobarbital residue a heterocyclic group bonded to an NH group by a carbon atom thereof; (wherein A ₃ and A ₄ each independently represent a hydrogen atom or a methyl group; R ₁ represents an alkyl group; R ₂ represents a hydrogen atom or an alkyl group; and R ₁ and R ₂ may be bonded to each other to form a ring structure group, the ring structure group It may also contain an oxygen atom, a nitrogen atom or a sulfur atom; R ₃ and R ₄ each independently represent a hydrogen atom or an alkyl group; and R ₃ and R ₄ may be bonded to each other to form a ring structure; a repeating unit represented by the formula (5) And the solubility parameter (SP value) calculated for the repeating unit of the repeating unit represented by the general formula (6) is 20 MPa ^1/2 or more); (In the formula (I), X represents a (l+m)-valent linking group, S represents a sulfur atom; and Y is a group composed of at least one monomer skeleton of the monomers (A) to (B), Z-system a group consisting of at least one monomer skeleton of the monomers (C) to (D); l+m is 3 to 10, l is 0 to 10, m is 0 to 10); (A) contains an acidic group, a monomer having at least one of a basic group, (B) a monomer containing a nitrogen-containing hetero ring, and (C) a monomer containing an oligomer having affinity for a non-aqueous medium, which contains a polystyrene skeleton and a poly Methyl methacrylate skeleton, polybutyl methacrylate skeleton, polyhydroxyethyl methacrylate skeleton, polyethyl 2-ethylhexyl methacrylate skeleton, polyethylene glycol skeleton, polypropylene glycol skeleton, poly A caprolactone skeleton, (D) a monomer containing an oligomer having affinity for organic pigment particles present in an aqueous medium. The organic pigment composition of claim 1, wherein the specific polymer compound further has a repeating unit represented by the following formula (3) and/or a repeating unit represented by the formula (4): (wherein A ₂ represents a hydrogen atom or a methyl group; Y ₁ represents -NH-, -O- or -S-; L represents a single bond or a divalent linking group; Y ₂ represents a hydrogen atom or a basic group; Z ₁ represents An unsaturated heterocyclic group having 1 or 2 nitrogen atoms). The organic pigment composition according to claim 1 or 2, wherein the specific polymer compound is contained in an amount of 10% by mass or more and 1000% by mass or less based on the pigment. The organic pigment composition according to claim 1 or 2, wherein the organic pigment fine particles have an average particle diameter in the range of 10 to 100 nm. An organic pigment composition according to claim 1 or 2, which is a dispersion in which the organic pigment fine particles are dispersed in a medium. The organic pigment composition according to claim 1 or 2, wherein the hydrophobic dispersant is present in an amount of 10% by mass or more and 1000% by mass or less based on the pigment. An organic pigment composition as claimed in claim 2, wherein the general formulae (1) and (2), (3) and (4), (5) and (6) are each integrated into a unit α, β, γ. In the case of mass ratio, α:β:γ=0.1 to 50:0.1 to 60:30 to 90. The organic pigment composition according to claim 1 or 2, wherein the molecular weight of the specific polymer compound is 1,000 or more and 200,000 or less in terms of mass average molecular weight. The organic pigment composition of claim 1 or 2, wherein the solubility parameter (SP value) calculated for the dispersant of the hydrophobic dispersant is less than 20 MPa ^1/2 . The organic pigment composition according to claim 1 or 2, wherein the organic pigment microparticles are a solution obtained by dissolving an organic pigment and the specific polymer compound in a good solvent, and are compatible with the good solvent and The organic pigment is produced by mixing a solvent of a poor solvent. The organic pigment composition according to claim 1 or 2, wherein the hydrophobic aggregate is contained in a non-aqueous medium, and the aggregate is deagglomerated and redispersed. A colored photosensitive resin composition containing at least an organic pigment composition, a binder, a monomer or an oligomer, and a photopolymerization initiator or a photopolymerization initiator system as in claim 11 of the patent application. A color filter characterized by using the colored photosensitive resin composition of claim 12 of the patent application. A process for producing an organic pigment composition characterized by comprising an organic pigment and a repeating unit represented by the following formula (1) and/or a repeating unit represented by the formula (2) and a formula (5) a solution in which a specific polymer compound of the repeating unit and/or the repeating unit represented by the formula (6) is dissolved in a good solvent, and is mixed with a medium which is compatible with the good solvent and which is a poor solvent for the organic pigment. In the case where the fine particles of the organic pigment are formed, the aqueous aggregate of the organic pigment fine particles is contained in the aqueous medium, and then the dispersing agent for hydrophobicity having a mass average molecular weight of 1,000 or more represented by the following formula (I) is coexisted. Become a hydrophobic aggregate: Wherein A ₁ represents a hydrogen atom or a methyl group; X ₁ represents a heterocyclic group, and is a uracil residue, a thiouracil residue, a cytosine residue, an adenine residue, a guanine residue, an imidazole residue. , benzimidazole residue, thiazole residue, benzothiazole residue, Oxazole residue, benzo Oxazole residue, pyridine residue, pyrimidine residue, hydrazine Residue, pyrazole residue, triazole residue, pyrrole residue, benzimidazolone residue, anthracene residue, quinoline residue, piperidine residue, barbiturate residue or thiobarbital residue a heterocyclic group bonded to an NH group by a carbon atom thereof; (wherein A ₃ and A ₄ each independently represent a hydrogen atom or a methyl group; R ₁ represents an alkyl group; R ₂ represents a hydrogen atom or an alkyl group; and R ₁ and R ₂ may be bonded to each other to form a ring structure group, the ring structure group It may also contain an oxygen atom, a nitrogen atom or a sulfur atom; R ₃ and R ₄ each independently represent a hydrogen atom or an alkyl group; and R ₃ and R ₄ may be bonded to each other to form a ring structure; a repeating unit represented by the formula (5) And a repeating unit represented by the formula (6), the solubility parameter (SP value) calculated for the repeating unit is 20 MPa ^1/2 or more); (In the formula (I), X represents a (l+m)-valent linking group, S represents a sulfur atom; and Y is a group composed of at least one monomer skeleton of the monomers (A) to (B), Z-system a group consisting of at least one monomer skeleton of the monomers (C) to (D); l+m is 3 to 10, l is 0 to 10, m is 0 to 10); (A) contains an acidic group, a monomer having at least one of a basic group, (B) a monomer containing a nitrogen-containing hetero ring, and (C) a monomer containing an oligomer having affinity for a non-aqueous medium, which contains a polystyrene skeleton and a poly Methyl methacrylate skeleton, polybutyl methacrylate skeleton, polyhydroxyethyl methacrylate skeleton, polyethyl 2-ethylhexyl methacrylate skeleton, polyethylene glycol skeleton, polypropylene glycol skeleton, poly A caprolactone skeleton, (D) a monomer containing an oligomer having affinity for organic pigment microparticles present in an aqueous medium. The method for producing an organic pigment composition according to claim 14, wherein the specific polymer compound further has a repeating unit represented by the following formula (3) and/or a repeating unit represented by the formula (4): (wherein A ₂ represents a hydrogen atom or a methyl group; Y ₁ represents -NH-, -O- or -S-; L represents a single bond or a divalent linking group; Y ₂ represents a hydrogen atom or a basic group; Z ₁ represents An unsaturated heterocyclic group having 1 or 2 nitrogen atoms). The process for producing an organic pigment composition according to claim 14 or 15, wherein an acid is added to the poor solvent to obtain an aqueous agglomerate. A method of producing an organic pigment composition according to claim 14 or 15, wherein the hydrophobic aggregate is separated by filtration through a filter. The method for producing an organic pigment composition according to claim 14 or 15, wherein the solubility parameter (SP value) calculated for the dispersant of the hydrophobic dispersant is less than 20 MPa ^1/2 .