KR101587073B1 - Organic pigment composition method for producing the same colored photosensitive resin composition using the same and color filter - Google Patents

Abstract

It is possible to efficiently obtain organic nano pigment particle hydrophobic aggregates by isolating the organic nano pigment particles in an aqueous medium as a non-aqueous aggregate capable of easily filtering, without going through a troublesome process, In a non-aqueous medium to prepare a non-aqueous dispersion of organic nano-pigment particles, and to provide a non-aqueous dispersion of organic nano-pigment particles having dispersibility and dispersion stability in a production method for producing a non-aqueous dispersion of organic nano-pigment particles.

(Solution) An organic pigment composition comprising a polymer compound having a repeating unit represented by the following general formula (1) and / or a repeating unit represented by the general formula (2) and organic pigment fine particles.

(Wherein A ₁ represents a hydrogen atom or a methyl group, and X ₁ represents a heterocyclic group connected by a carbon atom.)

Organic pigment composition

Description

TECHNICAL FIELD [0001] The present invention relates to an organic pigment composition, a process for producing the same, a colored photosensitive resin composition using the same, a color filter, and a color filter,

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

Among the fine particles of nanometer size, organic pigments can be used, for example, as paints, printing inks, electrophotographic toners, inkjet inks, and materials for color filters. Of these, pigments for ink-jet inks and pigments for color filters are particularly important in practical use because of their high performance.

Methods for producing organic particles include a vapor phase method, a liquid phase method, and a laser ablation method. Among them, the liquid phase method is attracting attention as a process for producing organic particles excellent in simplicity and productivity.

Patent Document 1 describes an example in which a pigment particle water dispersion is prepared by a liquid phase method. This method is a method to be finally provided as an aqueous dispersion, and there is no mention of a method provided as an organic solvent dispersion. Patent Document 2 discloses an example in which pigment particles prepared by the liquid-phase method are used as an organic solvent dispersion. However, the organic pigment particle obtained by this method tends to have a large primary particle diameter, so that the organic pigment particle can not sufficiently meet the requirement for fine particle formation.

In preparing the nanoparticles in the liquid phase method, a low-molecular surfactant or a neutral, water-soluble nonionic polymer compound is used in order to prevent aggregation of the conventional nanoparticles. Therefore, even if the nanoparticles can be dispersed at a high concentration, a large amount of dispersing aid is required, and when the viscosity is low and the content of the polymer compound is extremely low as in inkjet, it is difficult to apply these techniques as they are.

In addition, in order to meet the requirement to change the phase to a desired solvent system after preparation of nanoparticles in an aqueous medium, an aqueous slurry or an aqueous paste containing a high concentration of pigment is prepared, and a resin or a resin solution is added and mixed and stirred. A flushing method is known in which a resin or a resin solution is used for substitution. However, in this method, once the particles are strongly agglomerated in the aqueous medium, the efficiency of coating by the resin is deteriorated and redispersing becomes difficult (see, for example, Patent Documents 3 and 4).

Another method is to filter the nano-pigment particles, which have been prepared in an aqueous solvent, in the form of primary particles or in a coagulated state in order to produce an aqueous paste. However, filtration takes a long time, which leads to industrial troubles inefficiently.

Further, although low-molecular anionic or cationic surfactants can be used as a dispersant, they are low in molecular weight and sometimes lack dispersion stability. Therefore, there is also attempted a method of converting an aqueous dispersion of particles into an ionic liquid without using a filtration process by using a cationic polymer compound (see, for example, Non-Patent Document 1). However, this method is intended for low-concentration inorganic particles. There is no mention of an organic pigment, and in some cases, the final dispersion medium is a nonvolatile 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 agglomerated in an aqueous medium and an extraction operation is performed by a non-aqueous medium. Then, a membrane filter is filtrated to be isolated, and thereafter, redispersed in a non-aqueous medium in the presence of an organic polymer. However, since the aggregate at the time of isolation is hydrophilic, filtration takes a great deal of time.

[Patent Document 1] Japanese Unexamined Patent Application Publication No. 2004-43776

[Patent Document 2] Japanese Unexamined Patent Application Publication No. 2004-123853

[Patent Document 3] JP-A-5-301037

[Patent Document 4] JP-A-6-161154

[Patent Document 5] Japanese Patent Application Laid-Open No. 2007-262378

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

An object of the present invention is to provide an organic pigment composition containing nanoparticles of organic pigment fine particles and capable of easily switching hydrophilicity and hydrophilicity without a complicated process.

It is another object of the present invention to provide an organic pigment composition having the above characteristics and exhibiting high contrast and high performance when used as a color filter, a process for producing the same, and a colored photosensitive resin composition and a color filter using the composition .

The above-mentioned problems are achieved by the following means.

[1] An organic pigment composition, which comprises a polymer compound having a repeating unit represented by the following general formula (1) and / or a repeating unit represented by the general formula (2) and organic pigment fine particles.

(Wherein A ₁ represents a hydrogen atom or a methyl group, X ₁ represents a heterocyclic group, and the heterocyclic group is bonded to the NH group by the carbon atom thereof.)

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

(A ₂ represents a hydrogen atom or a methyl group in the formula. Y ₁ represents an -NH-, -O- or -S-. L represents a single bond or a divalent connecting group. Y ₂ represents a hydrogen atom or a basic And Z ₁ represents an unsaturated heterocyclic group having one or two nitrogen atoms.

[3] The organic electroluminescent device according to [1] or [2], wherein the polymer compound further comprises a repeating unit represented by the following general formula (5) and / or a repeating unit represented by the general formula (6) Composition.

(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, R ₁ and R ₂ are connected to each other to form a ring structure R ₃ and R ₄ each independently represent a hydrogen atom or an alkyl group, R ₃ and R ₄ are connected to each other to form a ring structure, and the ring structure may contain an oxygen atom, a nitrogen atom or a sulfur atom, You can do it.)

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

[5] The organic pigment composition according to any one of [1] to [4], wherein 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 fine particles are aqueous aggregates present in an aqueous medium.

[7] The organic pigment composition according to [6], further comprising a polymer compound having a mass average molecular weight of 1000 or more in coexistence with the aqueous aggregate to obtain a hydrophobic aggregate.

[8] The organic pigment composition according to [7], wherein the hydrophobic aggregate is contained in a non-aqueous medium, and the agglomerates of the aggregate are released and redispersed.

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

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

[11] A process for producing a colorant, which comprises mixing a solution obtained by dissolving an organic pigment and a polymer compound having a repeating unit represented by the following general formula (1) and / or a repeating unit represented by the general formula (2) in a good solvent, And a medium which becomes a poor solvent for the organic pigment is mixed to produce fine particles of the organic pigment.

(Wherein A ₁ represents a hydrogen atom or a methyl group, X ₁ represents a heterocyclic group, and the heterocyclic group is bonded to the NH group by the carbon atom thereof.)

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

(A ₂ represents a hydrogen atom or a methyl group in the formula. Y ₁ represents an -NH-, -O- or -S-. L represents a single bond or a divalent connecting group. Y ₂ represents a hydrogen atom or a basic And Z ₁ represents an unsaturated heterocyclic group having one or two nitrogen atoms.

[13] The polymer compound according to [11] or [12], wherein the polymer compound further comprises a repeating unit represented by the following general formula (5) and / or a repeating unit represented by the general formula (6) ≪ / RTI >

(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, R ₁ and R ₂ are connected to each other to form a ring structure R ₃ and R ₄ each independently represent a hydrogen atom or an alkyl group, R ₃ and R ₄ are connected to each other to form a ring structure, and the ring structure may contain an oxygen atom, a nitrogen atom or a sulfur atom, You can do it.)

(Effects of the Invention)

INDUSTRIAL APPLICABILITY The organic pigment composition of the present invention contains nano-sized organic pigment fine particles and a specific polymer compound, and can easily switch between the hydrophilicity and hydrophilicity of the composition without complicated processes depending on applications or manufacturing requirements. . Further, by using the organic pigment composition of the present invention, a colored photosensitive resin composition giving desired characteristics can be obtained very efficiently, and the color filter of the present invention using the same can exhibit high performance in a display device and the like with high contrast.

Hereinafter, the organic pigment composition of the present invention will be described.

The organic pigments used in the present invention are preferably those which can be formed into a particle by the liquid phase method, and may be used alone, plural organic pigments, or a combination thereof.

The organic pigments are not limited in color but include, for example, perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimadolone, disazo condensation, disazo, azo, An isoindolinone, an isoindolinone, a pyranthrone or an isobiorentrone compound pigment, or a mixture thereof, and the like can be used in combination. .

More specifically, for example, perylene 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), CI Pigment CI Pigment Violet 19 (CI No. 73900), CI Pigment Violet 42, CI Pigment Red 122 (CI No. 71100), orange 43 (CI No. 71105) or CI Pigment Red 194 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) , Quinacridonequinone compound pigments such as CI Pigment Red 206 (CI No. 73900/73920), CI Pigment Orange 48 (CI No. 73900/73920) or CI Pigment Orange 49 (CI No. 73900/73920) Mentel , Anthanthrone compound pigments such as CI Pigment Red 168 (CI No. 59300), CI Pigment Brown 25 (CI No. 12510), CI Pigment Violet 32 (CI Pigment Red) No. 12517), CI Pigment Yellow 180 (CI No. 21290), CI Pigment Yellow 181 (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 94 (CI No. 20038), CI Pigment Yellow 95 (C.I. CI Pigment Orange 13 (CI No. 21110), CI Pigment Yellow 166 (CI No. 20035), CI Pigment Orange 34 (CI No. 21115), CI Pigment Orange 13 CI Pigment Red 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 221 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 Disazo compound pigments such as Low 13 (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. CI Pigment Yellow 74 (CI No. 11714), CI Pigment Yellow 150 (CI No. 48545), CI Pigment Red 48 (CI No. 15865), CI Pigment Red 53 (CI No. 15585), CI Pigment Azo compound pigments such as Orange 64 (CI No. 12760) or CI Pigment Red 247 (CI No. 15915), indanthrone compound pigments such as CI Pigment Blue 60 (CI No. 69800), CI Pigment Green 7 (CI No. 74260 ), CI Pigment Green 36 (CI No. 74265), Pigment Green 37 (C.I. Phthalocyanine compound pigments such as 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 triarylcarbonium compound pigment such as CI Pigment Blue 61 (CI No. 42765: 1), a diolefin compound pigment such as CI Pigment Violet 23 (CI No. 51319) or CI Pigment Violet 37 (CI No. 51345) , CI Pigment Red 257 (CI No. 56110), CI Pigment Red 255 (CI No. 561050), CI Pigment Red 264, CI Pigment Diketopyrrolopyrrole compound pigments such as Red 272 (CI No. 561150), CI Pigment Orange 71 or CI Pigment Orange 73, thioindigo compound pigments such as CI Pigment Red 88 (CI No. 73312), C.I CI Pigment Yellow 109 (CI No. 56284) or CI Pigment Orange 61 (CI No. 11295), such as Pigment Yellow 139 (CI No. 56298), CI Pigment Orange 66 (CI No. 48210) ), Pyranthrone compound pigments such as CI Pigment Orange 40 (CI No. 59700) or CI Pigment Red 216 (CI No. 59710), or CI Pigment Violet 31 (CI No. 60010) Isobiorantron compound pigments. Among them, quinacridone compound pigments, diketopyrrolopyrrole compound pigments, dioxazine compound pigments, phthalocyanine compound pigments or azo compound pigments are preferable, and diketopyrrolopyrrole compound pigments or dioxazine compound pigments are more preferable.

In the present invention, two or more organic pigments or solid solutions of organic pigments 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 and a solvent having compatibility with the good solvent and a poor solvent with respect to the organic pigment.

In the present invention, the organic pigment composition may be a composition containing organic pigment microparticles and a specific polymer compound described later, and may be a dispersion in which the organic pigment microparticles are produced (hereinafter also referred to as " redeposition solution " ), A powder composition, an aggregating composition, and a solid composition having the organic pigment fine particles and the specific polymer compound. In this case, the organic pigment composition may contain other components than the organic pigment fine particles and the specific polymer compound, and even if the specific polymer compound or the like coexists independently of the organic pigment fine particles separately from the composition, They may be introduced into the fine particles or may be adsorbed and coexist.

The poor solvent of the organic pigment is not particularly limited as long as it is compatible with or can be uniformly mixed with a good solvent for dissolving the organic pigment. As a poor solvent of the organic pigment, the solubility of the organic pigment is preferably 0.02 mass% or less, more preferably 0.01 mass% or less. There is no particular limitation on the solubility of the organic pigment in a poor solvent, but 0.000001 mass% or more is practically considered in view of the organic pigments usually used. The solubility may be the solubility in the presence of an acid or an alkali. The compatibility or homogeneous mixing of the good solvent with the poor solvent is preferably 30% by mass or more, more preferably 50% by mass or more, of the good solvent in the poor solvent. There is no particular upper limit on the amount of dissolution of the good solvent in the poor solvent, but it is practically practically mixed with each other at an arbitrary ratio.

The poor solvent is not particularly limited as long as it is an aqueous medium and includes, for example, an aqueous solvent (for example, water or hydrochloric acid, an aqueous solution of sodium hydroxide), an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, A solvent, an aliphatic compound solvent, a nitrile compound solvent, a halogen compound solvent, an ester compound solvent, an ionic liquid, a mixed solvent thereof, and the like can be mentioned and an aqueous solvent, an alcohol compound solvent, a ketone compound solvent, Or a mixture thereof are preferable, and an aqueous solvent, an alcohol compound solvent or an ester compound solvent is more preferable.

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

Both solvents can dissolve the organic pigment to be used, and are not particularly limited as long as they are compatible with the poor solvent or can be uniformly mixed with the poor solvent. The solubility of the organic pigment in the positive solvent is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. There is no particular upper limit on the solubility of the organic pigment in a good solvent, but it is practically 50% by mass or less in consideration of the organic pigment generally used. The solubility may be the solubility in the presence of an acid or an alkali. The preferred range of compatibility or homogeneous mixing of the poor solvent and the good solvent is as described above.

Examples of the positive solvent include aqueous solvents (e.g., water or hydrochloric acid, aqueous sodium hydroxide solution), alcohol compound solvents, amide compound solvents, ketone compound solvents, ether compounded solvents, aromatic compound solvents, A solvent, a nitrate compound solvent, a sulfoxide compound solvent, a halogen compound solvent, an ester compound solvent, an ionic liquid, a carboxylic acid compound, a sulfonic acid compound, sulfuric acid and a mixed solvent thereof. A ketone compound solvent, an ether compound solvent, a sulfoxide compound solvent, an ester compound solvent, an amide compound solvent, a carboxylic acid compound, a sulfonic acid compound, sulfuric acid or a mixture thereof is preferable, and an aqueous solvent, an alcohol compound solvent, A sulfoxide compound solvent, an amide compound solvent, a carboxylic acid compound, a sulfonic acid Compounds, sulfuric acid is more preferable, and a sulfoxide compound solvent, the amide compound solvent, a carboxylic acid compound, sulfonic acid compound, sulfuric acid is particularly preferred.

Examples of the alcohol compound solvent include methanol, ethanol, isopropanol, n-propanol, 1-methoxy-2-propanol and the like. Examples of the ketone compound solvent include acetone, methyl ethyl ketone, and cyclohexanone. Examples of the ether compound solvent include dimethyl ether, diethyl ether, tetrahydrofuran and the like. Examples of the aromatic compound solvent include nitrobenzene, chlorobenzene, and dichlorobenzene. Examples of the aliphatic compound solvent include hexane and the like. Examples of the nitrile compound solvent include acetonitrile and the like. Examples of the sulfoxide compound solvent include dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, sulfolane, and the like. Examples of the halogen compound solvent include chloroform, dichloromethane, trichlorethylene, iodine, and the like. Examples of the ester compound solvent include ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and 2- (1-methoxy) propyl acetate. Examples of the ionic liquid include salts of 1-butyl-3-methylimidazolium and PF ₆ ^- . Examples of the amide compound solvent include N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, , ε-caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide and hexamethylphosphoric triamide. Examples of the carboxylic acid compound include formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, oxalic acid, trifluoroacetic acid, trichloroacetic acid, 2,2-dichloropropionic acid and squaric acid. Examples of the sulfonic acid compound include methanesulfonic acid, p-toluenesulfonic acid, sulfuric acid, chlorosulfonic acid, and trifluoromethanesulfonic acid.

As specific examples of the good solvent, there is a common one as listed as the poor solvent, but there is no case where the same one as the good solvent and the poor solvent are combined, and the solubility of the good solvent in the poor solvent . For example, the solubility difference is preferably 0.2 mass% or more, and more preferably 0.5 mass% or more. There is no particular upper limit on the difference in solubility in the good solvent and the poor solvent, but it is practically 50% by mass or less in consideration of the commonly used organic pigment.

The concentration of the organic pigment solution obtained by dissolving the organic pigment in the good solvent is preferably in the range of about 1/100 of the saturated concentration of the organic pigment with respect to the good solvent in the dissolution condition.

The conditions for preparing the organic pigment solution are not particularly limited, and the range of the sub-critical and supercritical conditions can be selected from the atmospheric pressure. The temperature at normal pressure is preferably -10 to 150 占 폚, more preferably -5 to 130 占 폚, particularly preferably 0 to 100 占 폚.

In the present invention, the organic pigment is preferably dissolved in acidic or alkaline. Generally, in the case of a pigment having a group dissociable from alkaline in the molecule, acidity is used when there is no alkaline, group dissociated from alkaline, and a lot of nitrogen atoms in the molecule, which are likely to be added with protons. For example, quinacridone, diketopyrrolopyrrole, disazo condensed compound pigments are soluble in alkaline, and phthalocyanine compound pigments are soluble in acidic.

The base used in the case of dissolving in an alkaline state is preferably an inorganic base such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide or barium hydroxide or an organic base such as trialkylamine, diazabicyclo-undecene (DBU) or metal alkoxide Is an inorganic base.

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

The acid used when dissolving in an acid is an inorganic acid such as sulfuric acid, hydrochloric acid or phosphoric acid, or an organic acid such as acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid or trifluoromethanesulfonic acid, but is preferably an inorganic acid. Particularly preferred is sulfuric acid.

The amount of the acid to be used is an amount capable of uniformly dissolving the organic pigment, and although it is not particularly limited, an excess amount of the acid is often used in comparison with the base. Is preferably 3 to 500 molar equivalents, more preferably 10 to 500 molar equivalents, and still more preferably 30 to 200 molar equivalents, relative to the organic material, irrespective of the case of inorganic acids and organic acids.

When an alkali 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 an alkali or acid such as a little water or a lower alcohol may be added to the organic solvent in order to completely dissolve the alkali or acid have. The amount of water or the lower alcohol is preferably 50 mass% or less, more preferably 30 mass% or less, based on the total amount of the organic material solution. Specifically, water, methanol, ethanol, n-propanol, isopropanol, butyl alcohol and the like can be used.

There is no particular limitation on the condition of the poor solvent when the organic particles are produced, that is, when the organic particles are precipitated and formed, and the range from the atmospheric pressure to the subcritical and supercritical conditions can be selected. The temperature at normal pressure is preferably -30 to 100 占 폚, more preferably -10 to 60 占 폚, and particularly preferably 0 to 30 占 폚.

When the organic pigment solution and the poor solvent are mixed, either of them may be added and mixed. However, it is preferable that the organic pigment solution is added to and mixed with a poor solvent, and it is preferable that the poor solvent is stirred. The stirring speed is preferably 100 to 10000 rpm, more preferably 150 to 8000 rpm, and particularly preferably 200 to 6000 rpm. A pump or the like may or may not be used for the addition. In addition, it may be added in the liquid or out of the liquid, but is more preferably added in the liquid. The volume ratio of the organic pigment solution to the poor solvent (preferable solvent / poor solvent ratio in the organic pigment fine particle redeposition solution) is preferably 1/50 to 2/3, more preferably 1/40 to 1/2, 20 to 3/8 is particularly preferable. The aqueous medium contains at least 60 mass% of the aqueous solvent, preferably 80 mass% or more.

When the organic pigment composition is, for example, a dispersion such as the redeposition solution, the content of the organic pigment fine particles is not particularly limited, but it is preferable that the organic pigment fine particles are in the range of 10 to 40,000 mg per 1000 ml of the medium, Is in the range of 20 to 30,000 mg, particularly preferably in the range of 50 to 25000 mg.

The preparation scale at the time of producing the organic pigment fine particles is not particularly limited, but the blending amount of the poor solvent is preferably from 1 to 1000 L, more preferably from 1 to 100 L.

As for the particle size of the organic pigment fine particles, there is a method of expressing the average size of the group by numerical measurement by the measurement method. However, there is a method which is well used. The mode diameter representing the maximum value of the distribution, the median diameter corresponding to the median value of the integral distribution curve, (Number average, length average, area average, mass average, volume average, etc.). In the present invention, unless otherwise specified, the average particle diameter means the number average diameter. The average particle size of the organic pigment fine particles (primary particles) is in the nanometer size, more preferably 1 to 200 nm, further preferably 10 to 100 nm, particularly preferably 10 to 80 nm. The particles to be formed in the present invention may be crystalline particles or amorphous particles or a mixture thereof.

Unless otherwise specified in the present invention, the ratio (Mv / Mn) of the volume average particle diameter (Mv) to the number average particle diameter (Mn) is used as an index showing the monodispersibility of the particles. The monodispersibility (Mv / Mn) of the particles (primary particles) contained in the dispersion used for the method of concentration of the organic pigment fine particles is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, and more preferably 1.0 to 1.5 Is particularly preferable.

Examples of the method for measuring the particle size of the organic pigment fine particles include 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. Microscopic methods and dynamic light scattering method are particularly preferable. Examples of the microscope used in the microscopic method include a scanning electron microscope and a transmission electron microscope. Examples of the particle measuring apparatus by the dynamic light scattering method include Nanotrack UPA-EX150 manufactured by Nikisosa Corporation, DLS-7000 series dynamic light scattering photometer manufactured by Otsuka Denshi Co., Ltd. and LB-400 manufactured by Horiba Seisakusho Co., ).

In the present invention, in preparing the dispersion by precipitating the organic pigment fine particles, a dispersant may be contained in at least one of the organic pigment solution and the poor solvent. At this time, it is preferable that at least the dispersing agent (in the present invention, the dispersing agent to be added to the particulate stone is simply referred to as " dispersing agent "

Examples of usable dispersing agents include anionic, cationic, biponic, nonionic or pigment derivative dispersing agents of low molecular weight or high molecular weight. The addition amount of the low molecular weight or high molecular weight dispersant is preferably 10% by mass or more and 1000% by mass or less based on the dissolved pigment. And more preferably 10 mass% or more and 200 mass% or less. If the addition amount is too small, the effect of inhibiting the growth and agglomeration of the pigment particles is reduced. If the addition amount is too large, problems such as an increase in viscosity and a poor dissolution tend to occur.

In the present invention, a specific polymer compound may be contained in at least one of the organic pigment solution and the poor solvent in preparing the dispersion by precipitating the organic pigment fine particles. At this time, it is preferable that at least a dispersant is contained in the organic pigment solution. In the present invention, it is preferable that a specific polymer compound functions as a dispersant. Here, the dispersant to be added to the particulate silica release is specifically referred to as " dispersant " and may be referred to as a hydrophobic dispersant to be described later.

In the present invention, the addition amount of the specific polymer compound functioning as the dispersing agent is preferably 10 mass% or more and 1000 mass% or less, and more preferably 10 mass% or more and 200 mass% or less, relative to the dissolved pigment. If this amount is too small, the effect of suppressing the aggregation of the pigment particles due to the solidification and solidification between the pigment particles tends to be small, while if the amount is too large, the viscosity tends to rise and the defective solution tends to occur.

The molecular weight of the dispersant in the present invention is preferably from 1,000 to 200,000, more preferably from 3,000 to 40,000, in mass-average molecular weight. If the molecular weight is too small, the effect of suppressing the growth of the pigment particles and the solid agglomeration is lessened. If too large, the problems such as viscosity increase and dissolution failure tend to occur. In the present invention, the term "molecular weight" means the weight average molecular weight, and the mass average molecular weight is an average molecular weight in terms of polystyrene measured by gel permeation chromatography (carrier: tetrahydrofuran) unless otherwise specified.

The specific polymer compound is a polymer compound having a repeating unit represented by the following general formula (1) and / or a repeating unit represented by the general formula (2).

In the formula, A ₁ represents a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

X ₁ represents a heterocyclic group, and the heterocyclic group is bonded to the NH group by the carbon atom thereof. Preferred examples include an aniline residue, a thiouracil residue, a cytosine residue, an adenine residue, a guanine residue, an imidazole residue, a benzimidazole residue, a thiazole residue, a benzothiazole residue, an oxazole residue, a benzoxazole residue, a pyridine residue, A pyrimidine residue, a pyrazine residue, a pyrazole residue, a triazole residue, a pyrrole residue, a benzimidazolone residue, an indole residue, a quinoline residue, a piperidine residue, a barbiturzone residue or a thiobarbiturane residue, A pyrimidine residue, a pyridazine residue, a triazole residue, a benzimadolone residue, a barbiturzone residue, a carbamate residue, a carbamate residue, a carbamate residue, , And thiobarbiturizane.

The repeating units represented by the general formulas (1) and (2) may be hydrophilic or hydrophobic, and may have a structure capable of interacting with organic pigments such as hydrogen bonding, π-π interaction, dipole- . These interactions are strong, and the adsorption rate of the dispersing agent to the pigment is improved, and dispersibility and dispersion stability in the non-aqueous medium are improved.

Specific examples of the repeating units represented by the general formulas (1) and (2) are shown below, but the present 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 further having a repeating unit represented by the following general formula (3) and / or a repeating unit represented by the general formula (4).

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

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

L represents a single bond or a divalent linking group. The divalent linking group is preferably an alkylene group, an ethylene oxide group or a propylene oxide group containing 1 to 8 carbon atoms, and particularly preferably an alkylene group. Preferable examples of the alkylene group include an ethylene group, a propylene group, a propylene group, a butylene group, a 2,2-dimethylpropylene group, a hexylene group, a heptylene group and an octylene group, , Butylene group and 2,2-dimethylpropylene group are particularly preferable.

Y ₂ represents a hydrogen atom or a basic group. Examples of the basic group include monoalkylamines and dialkylamines, and dialkylamines are more preferred. Specific examples of the dialkylamine include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a dihexylamino group, a di-2-ethylhexylamino group, a dioctylamino group, a dodecylamino group and a didodecylamino group. , Diethylamino group, dipropylamino group, and dibutylamino group are more preferable.

Z ₁ represents an unsaturated heterocycle containing 1 to 2 nitrogen atoms, and preferred examples thereof include an imidazole residue, a pyridine residue, a pyrimidine residue and a pyridazine residue. Particularly preferred examples thereof include an imidazole residue and a pyridine residue. .

The repeating units represented by the general formulas (3) and (4) may be hydrophilic or hydrophobic, but it is preferable that the repeating unit represented by the general formulas (3) and (4) has a strong acid-base interaction with a hydrophobic dispersing agent described later. When the hydrophobic dispersant is acidic, the repeating units represented by the general formulas (3) and (4) are preferably basic, and the pKa is preferably 6 or more, particularly preferably 6 or more. When the hydrophobic dispersant is basic, the repeating units represented by the general formulas (3) and (4) are preferably basic and preferably have a pKa of 5 or less. The stronger the acid-base interaction, the better the dispersibility and dispersion stability in the non-aqueous medium.

Specific examples of the repeating units represented by the general formulas (3) and (4) are shown below, but the present invention is not limited thereto. 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 particularly preferably a polymer compound having a repeating unit represented by the following general formula (5) and / or a repeating unit represented by the general formula (6).

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

R ₁ represents an alkyl group. Preferable examples of the alkyl group represented by R ₁ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptylene group and an octyl group.

R ₂ represents a hydrogen atom or an alkyl group. Preferable examples of the alkyl group as R ₂ include 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.

Further, R ₁ and R ₂ may be connected to each other to form a ring structure, or may contain an oxygen atom, a nitrogen atom and a sulfur atom. The linking structure may be an alkylene group, an ethylene oxide group or a propylene oxide group, but an alkylene group is particularly preferable. Examples of the alkylene group include an ethylene group, a propylene group, a butylene group and a pentylene group, but a propylene group and a butylene group are more preferable.

R ₃ and R ₄ independently represent a hydrogen atom or an alkyl group. Examples of the alkyl group for R ₃ and R ₄ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, And a butyl group is more preferable.

R ₃ and R ₄ may be connected to each other to form a ring structure. As the connecting structure, an alkylene group, an ethylene oxide group, and a propylene oxide group are exemplified, but an alkylene group and an ethylene oxide group are more preferable. As the alkylene group, a butylene group and a pentylene group are preferable. The ethylene oxide group may be represented by - (CH ₂ -CH ₂ -O-CH ₂ -CH ₂ ) _n -, and n is preferably 1 to 4, more preferably 1 to 2.

The repeating units represented by the general formulas (5) and (6) are preferably hydrophilic, and the repeating unit represented by the formula (I) of the solubility parameter (SP value) proposed by Oki 1993) 249 to 259}, and the value calculated for the repeating unit is preferably 20 MPa ^1/2 or more. , The dispersing agent becomes hydrophobic and strong aggregation occurs between the pigment particles in the aqueous medium in which the particles are formed, and it becomes difficult to solve the aggregation, resulting in dispersion failure in the non-aqueous medium.

Specific examples of the repeating units represented by the general formulas (5) and (6) are shown below, but the present 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).

In the case of integrating the equations (1), (2), (3), (4), (5) and (6) as one unit α, β and γ, α, β, : β: γ = 0.1 to 50: 0.1 to 60: 30 to 90, more preferably α: β: γ = 5 to 50: 5 to 40:30 to 90, Lt; / RTI >

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

Preferred as the combination of the general formulas (1) to (6) is a polymer having a repeating unit represented by the general formula (1), a repeating unit represented by the general formula (5), and a repeating unit represented by the general formula (3) compound; A polymer compound having a repeating unit represented by the general formula (1), a repeating unit represented by the general formula (6), and a repeating unit represented by the general formula (3); A polymer compound having a repeating unit represented by the general formula (1), a repeating unit represented by the general formula (5), and a repeating unit represented by the general formula (4); A polymer compound having a repeating unit represented by the general formula (2), a repeating unit represented by the general formula (5), and a repeating unit represented by the general formula (3); A polymer compound having a repeating unit represented by the general formula (2), a repeating unit represented by the general formula (6), and a repeating unit represented by the general formula (3); Is a polymer compound having a repeating unit represented by the general formula (2), a repeating unit represented by the general formula (5), and a repeating unit represented by the general formula (4).

Particularly preferable examples of the combination of the general formulas (1) to (6) include the repeating unit represented by the general formula (1), the repeating unit represented by the general formula (5), and the repeating unit represented by the general formula (3) Polymer compound; A polymer chemistry having a repeating unit represented by the general formula (2), a repeating unit represented by the general formula (5), and a repeating unit represented by the general formula (3); A polymer compound having a repeating unit represented by the general formula (1), a repeating unit represented by the general formula (5), and a repeating unit represented by the general formula (4); Is a polymer compound having a repeating unit represented by the general formula (2), a repeating unit represented by the general formula (5), and a repeating unit represented by the general formula (4).

Preferred examples of the combination of the general formulas (1) to (6) are listed below.

In the present invention, an aqueous solution of an organic pigment microparticle is prepared, followed by the addition of an acid to form an aqueous aggregate. Alternatively, in preparing an aqueous dispersion by precipitating organic pigment fine particles, an acid may be added to the poor solvent, and the pigment solution may be added thereto to make the organic pigment fine particles into a hydrophilic aggregate. Particularly, it is preferable to add an acid to a poor solvent to obtain an aqueous aggregate. Here, in the present invention, the term "aqueous aggregate" refers to an aggregate in a state in which the surface of the aggregate or the organic pigment microparticles constituting the aggregate is covered with a hydrophilic dispersing agent. Here, when the hydrophilicity and the affinity are quantitatively distinguished, the theoretical formula of the solubility parameter (SP value) proposed by Oikitsu Toshinobu (Japanese Adhesion Journal Vol. 29, No. 6 (1993) 249-259) When the value calculated for the dispersant is 20 MPa ^{1/2 or} more, the dispersant is said to be hydrophilic. The hydrophilic aggregate is not particularly limited as long as two or more primary particles of the organic pigment microparticles are aggregated, but usually has an average particle diameter of about 5 占 퐉, preferably 0.04 to 10 占 퐉.

The acid used for forming the aqueous aggregate is preferably acetic acid, hydrochloric acid, sulfuric acid or formic acid, more preferably acetic acid or hydrochloric acid. The pH of the aqueous dispersion at the time of formation of the aqueous aggregate is not particularly limited as long as an aggregate is formed, but is preferably pH 1 to 6, and more preferably pH 2 to 4. It is practical that the solid content of the aqueous aggregate is substantially constituted by the pigment, but the content of the pigment in the liquid after preparation is practically 0.004 to 4% by mass, for example. This concentration is the same for the non-aqueous aggregates described later.

In the present invention, it is preferable that an organic polymer compound having a mass average molecular weight of 1000 or more coexists with an aqueous aggregate to obtain a hydrophobic aggregate. (Hereinafter, "organic polymer compound having a mass average molecular weight of 1000 or more" Dispersant "in some cases.)

In the present invention, at least one kind of organic polymer compound having a mass average molecular weight of 1000 or more is added to the organic pigment fine particles present in the aqueous medium to prepare a hydrophobic aggregate, and then the aggregated organic nanoparticles can be isolated. The organic nanoparticles present in the aqueous medium may take a long time to pass through the filter paper or to filter by the filtration filter even if filtration by the filter paper is performed in that state. By adding an acid or an alkali to the poor solvent as described above, the organic pigment fine particles can be obtained as an aqueous aggregate at the time of preparing the aqueous dispersion of the organic pigment fine particles. However, in this case, since the aggregate is hydrophilic, it does not become a large aggregate in the aqueous medium and the dehydration property is also bad, so that it takes a long time to filtrate even if it is filtered. Therefore, in the present invention, it is preferable that the aqueous aggregate is made into a non-hydrophilic aggregate (hereinafter also referred to as " hydrophobic aggregate ") by adding an organic polymer compound. By adding the organic polymer compound, the organic pigment fine particles can be made into a larger aggregate in an aqueous medium. According to this method, the time required for filtration is shortened, and it is possible to greatly improve the filtration property. In the present invention, the term "hydrophobic aggregate" refers to an aggregate in a state in which the surface of the aggregate or the organic pigment microparticles constituting the aggregate is covered with a hydrophobicizing dispersant. Here, when quantifying the affinity and hydrophobicity, it is necessary to calculate the solubility parameter (SP value) theoretical formula {Japanese Adhesion Journal Vol. 29, No. 6 (1993) 249 to 259} proposed by Oki When the value calculated for the dispersant is less than 20 MPa < ^{1/2 &} gt ;, the dispersant is referred to as a hydrophobic dispersant.

In the present invention, the addition of the organic polymer compound is preferably carried out on an aqueous dispersion containing a hydrophilic aggregate.

The hydrophobic aggregate preferably has an average particle diameter of 10 mu m or more, more preferably larger. If it is less than 10 mu m, it takes a long time to isolate the agglomerate, or the filter paper or the filter is escaped or clogged even if it is collected for filtration. The average particle diameter referred to herein is the diameter of an aggregate obtained by observing an aggregate by an optical microscope and measuring the scale separately. Here, the diameter refers to the length of the end of the aggregate, and defines the diameter of the longest portion of the aggregate. The aggregate in the present invention means that two or more primary particles of nanoparticles originally not visible to the naked eye are gathered and grown so as to become secondary particles.

The organic polymer compound in the present invention preferably has a structure moiety (a repeating unit having a group having affinity for a non-aqueous medium) having affinity for a non-aqueous medium and a moiety having affinity for the organic pigment microparticle A repeating unit having a group having affinity to the fine particles), and has a function of dispersing the organic pigment fine particles in a non-aqueous medium. The organic polymer compound acts on the hydrophilic aggregate and the structure site having affinity for the organic pigment microparticles covers the surface of the aqueous aggregate or the surface of the organic pigment microparticles constituting the aggregate and consequently the aggregate or the particles are dispersed in the non- It is hydrophobic by the affinity structural part.

The organic polymer compound in the present invention is adsorbed to the aggregated organic pigment fine particles. Therefore, even after the steps such as filtration, washing and redispersion, the organic polymer compound can act as a dispersant in a non-aqueous medium as it is, so that it is not necessary to add a dispersant. To adjust the dispersibility, a dispersant may be newly added later, but it is preferable not to add the dispersant from the viewpoint of production cost.

Further, the organic pigment fine particles constituting the aggregate of the present invention are preferably aggregated in the state of being coated with the organic polymer compound. Therefore, when the organic pigment fine particles are aggregated without such an organic polymer compound, for example, The subsequent redispersion is easy, the organic pigment fine particles are easily released to primary particles, and the contrast is increased.

The organic polymer compound may be added as it is, but it is preferable to add the organic polymer compound in a solvent in view of obtaining good filterability.

The solvent for dissolving the organic polymer compound is not particularly limited so long as it can be mixed with the organic pigment fine particle aqueous dispersion and the organic polymer compound can be dissolved and the organic polymer compound is not precipitated after the addition.

Examples of the solvent for dissolving the organic polymer compound include aqueous solvents (e.g., water or hydrochloric acid, aqueous sodium hydroxide solution), alcohol compound solvents, amide compound solvents, ketone compound solvents, ether compound solvents, aromatic compound solvents, A solvent, an aliphatic compound solvent, a nitrile compound solvent, a sulfoxide compound solvent, a halogen compound solvent, an ester compound solvent, an ionic liquid, and a mixed solvent thereof. Examples of the solvent include alcohol solvents, ketone compound solvents, ether compounds A solvent, a sulfoxide compound solvent, an ester compound solvent, an amide compound solvent, a nitrile compound solvent or a mixture thereof is preferable, and a ketone compound solvent, an ether compound solvent, a nitrile compound solvent or a mixture thereof is more preferable.

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

The amount of the solvent for dissolving the organic polymer compound is not particularly limited so long as it can dissolve the organic polymer compound and can form hydrophobic agglomerates that can be easily filtered. However, considering the complexity of the production and the reduction of the raw material cost, . When expressed in terms of a mass ratio, when the aqueous dispersion of the organic pigment microparticles is 100, the solvent to be added is preferably in the range of 0 to 100, more preferably in the range of 0 to 70, particularly preferably in the range of 0 to 70. Too much filtration may take a long time.

After the organic polymer compound is added, it is preferable to stir the organic pigment fine particles sufficiently to be mixed with the organic pigment fine particle aqueous dispersion. For stirring mixing, a usual method can be used. The temperature at which the organic polymer compound is added and mixed is not particularly limited, but is preferably 1 to 100 ° C, more preferably 5 to 60 ° C. The addition and mixing of the organic polymer compound may be carried out by any device as long as the respective steps can be preferably carried out. For example, a device such as a stirrer, a radome stirrer or the like can be used.

The addition amount of the organic polymer compound 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. If the amount is too small, the hydrophobicity (non-aqueous) effect of the nanoparticles is reduced. If the amount is too large, problems such as viscosity increase upon re-dispersion tend to occur. In the present invention, the mass average molecular weight of the organic polymer compound is preferably 1000 or more. Although there is no particular upper limit, it is more preferably 3000000 or less, and more preferably 300000 or less.

Specific examples of the organic polymer compound that can be used in the present invention include Disperbyk-110 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 EFKA4047, 4050, 4010, 4165 (polyurethane), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyol), BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) Acrylic acid), 5010 (polyester amide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), Aji Spa PB821 and PB822 manufactured by Ajinomoto Pan Techno Co., -710 (urethane oligomer), Polyflow No.50E, No.300 (acrylic copolymer), DiSparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid ), # 7004 (polyetherester), DA-703-50, DA-705, DA-725 "available from Kao Corporation," demol RN, N (naphthalenesulfonic acid Formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate), homogenol L-18 (polymer polycarboxylic acid), Emulsion 920, 930, 935, 985 (polyoxyethylene (Graft polymer), 13240 (polyester amine), 3000, 17000, and 27000 (having a functional group at the terminal end), " acetaminemethylacetate NIKOL T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Nikko Chemical Co., Ltd., and the like have.

As the organic polymer compound in the present invention, known polymer compounds may be used alone or in combination of two or more. The known polymer compounds may be used in combination with one or more of the organic polymer compounds described below. The organic polymer compounds described below may be used alone or in combination of two or more.

The organic polymer compound may be a polymer compound obtained by copolymerization using at least one of the following monomers (A) to (D), or a polymer compound obtained by copolymerizing at least one of monomers of (A) to (D) (1) are preferable.

(In the general formula (1), X represents a linking group of (1 + m), and S represents a sulfur atom. Y is a group comprising at least one monomer skeleton of the monomers (A) to (B), and Z is a group comprising at least one monomer skeleton of the monomers (C) to (D). l + m is 3 to 10, l 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) a monomer containing an oligomer which is compatible with a non-aqueous medium

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

It is preferable to combine the components (A), (C), (B) and (C) in combination of the components (A) to (D) (A), (B), (C), and (D), it is more preferable to combine the components of (A) It is particularly preferable to combine the components.

Examples of the monomer containing at least one of the acidic group and the basic group of the organic polymer (A) include monomers containing a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, an amino group, an amide group and a urea group, A structure capable of being adsorbed through an acid-base interaction is preferable. Specific examples are shown below, but the present invention is not limited thereto.

Examples of the monomer containing a nitrogen-containing heterocycle of the general formula (B) include benzimidazolone, benzimidazole, anthraquinone, ureasyl, acrido, naphthalimide, A succinimide group, a benzopyrrole group, and the like, and the obtained organic polymer compound can be adsorbed to the organic pigment fine particles through a hydrogen bonding interaction, a van der Waals interaction, a dipole-dipole interaction, or the like. Is preferable. Specific examples are shown below, but the present invention is not limited thereto.

The monomer containing an oligomer having affinity with the non-aqueous medium of (C) is not particularly limited, but it is preferably dissolved in a non-aqueous medium to be used for redispersing described later, and the dispersion of organic pigment fine particles in a non- It is more preferable that the structure is stabilized by the steric repulsion force.

(C) may include a polystyrene skeleton, a polymethyl methacrylate skeleton, a poly-n-butyl methacrylate skeleton, a poly-2-hydroxyethyl methacrylate skeleton, a poly-2-ethylhexyl methacrylate skeleton, A glycol skeleton, a polypropylene glycol skeleton, and a polycaprolactone skeleton, and more preferably a polystyrene skeleton, a polymethyl methacrylate skeleton, a polyethylene glycol skeleton, a polypropylene glycol skeleton, and a polycaprolactone skeleton.

The monomer may be a commercially available product or may be a suitable product.

Specific examples of commercially available products include one-terminal methacryloylated polystyrene oligomer {Mn = 6000, trade name: AS-6, manufactured by Toagosei Kaikako Kogyo Co., Ltd.), one-end methacryloylated polymethyl methacrylate oligomer 6000, trade name: AA-6, manufactured by Toagosei Kaikako Kogyo Co., Ltd.), one end methacryloyl poly-n-butyl acrylate oligomer {Mn = 6000, trade name: AB- (Trade name: AA-714, manufactured by Toagosei Kaikako Kogyo Co., Ltd.), one end terminal methacryloylated polymethyl methacrylate / 2-hydroxyethyl methacrylate oligomer { Methacryloylated polybutyl methacrylate / 2-hydroxyethyl methacrylate oligomer {Mn = 7000, trade name: 707S, manufactured by Toagosei Kaikako Kogyo Co., Ltd.), one end methacryloylated poly (2-ethylhexyl) Methacrylate / 2-hydroxyethyl methacrylate oligomer {Mn = 7000, product (Trade name: AY-707S, AY-714S, manufactured by Toagosei Kaikako Kogyo Co., Ltd.), methoxypolyethylene glycol methacrylate (trade name: NK Ester M-40G, M-90G, M- Manufactured by Kokyo Kogyo Co., Ltd.}; (Manufactured by Nippon Oil & Company, Ltd.), PME-100, PME-200, PME-400, PME-1000, PME-2000 and PME- (Trade name: BREMMER PP-500, PP-800, PP-1000, manufactured by Nippon Oil Co., Ltd.), PE-90, PE-200, PE- }, Polyethylene glycol polypropylene glycol monomethacrylate {trade name: Bremmer 70PEP-370B, manufactured by NOF Corporation), polyethylene glycol poly tetramethylene glycol monomethacrylate {trade name: Bremmer 55PET-800, (Manufactured by Nippon Oil Co., Ltd.) and polypropylene glycol polytetramethylene glycol monomethacrylate (trade name: Blemmer NHK-5050, manufactured by Nippon Oil Co., Ltd.).

Specific examples of the synthetic product include 2-ethylhexyloxypolycaprolactone oligomer obtained by ring-opening polymerization of 2-ethylhexanol and epsilon -caprolactone, methoxypolyethylene glycol polypropylene glycol random copolymer terminated primary amino group oligomer (trade name: Jeffamine 2005 (Manufactured by HUNTSMAN), butoxypolypropylene glycol oligomer (manufactured by Ardrich), and oligomers having a polymerizable group at one end obtained by reacting with (meth) acryloyloxyethyl isocyanate.

The monomer containing an oligomer having affinity with the organic pigment fine particles present in the aqueous medium of the above-mentioned (D) is not particularly limited, but is compatible with the organic pigment fine particles present in the aqueous medium, (That is, a repeating unit having a hydrophilic group) and a hydrophobic region (a repeating unit having a hydrophobic group) are preferable. As the monomer, it is particularly preferable to dissolve in an aqueous medium or a non-aqueous medium. It is possible to impart wettability to the hydrophilic aggregates of the organic pigment microparticles present in the aqueous medium and to control the dispersion of the organic pigment microparticles in the non- It is preferable that it is a structure that can be stabilized. When the monomer (D) is used at the same time as the monomer (C), it is not the same as the monomer (C), and more preferably the hydrophilic monomer (C) is more hydrophilic.

(D) may be a polystyrene skeleton, a polymethyl methacrylate skeleton, a poly-n-butyl methacrylate skeleton, a poly-2-hydroxyethyl methacrylate skeleton, a poly-2-ethylhexyl methacrylate skeleton, A glycol skeleton, a polypropylene glycol skeleton, and a polycaprolactone skeleton, and more preferably a polyethylene glycol skeleton, a polypropylene glycol skeleton, and a polycaprolactone skeleton.

The monomer may be a commercially available product or may be suitably synthesized.

Specific examples of commercially available products include methoxypolyethylene glycol methacrylate (trade names: NK Ester M-40G, M-90G, M-230G (trade name, manufactured by Toagosei Kaikako Kogyo Co., Ltd.); (Manufactured by Nippon Oil & Company, Ltd.), PME-100, PME-200, PME-400, PME-1000, PME-2000 and PME- (Trade name: BREMMER PP-500, PP-800, PP-1000, manufactured by Nippon Oil Co., Ltd.), PE-90, PE-200, PE- }, Polyethylene glycol polypropylene glycol monomethacrylate {trade name: Blemmer 70PEP-370B, manufactured by Nippon Oil Co., Ltd.}, polyethylene glycol polytetramethylene glycol monomethacrylate {trade name: Blumer 55PET-800, (Manufactured by Nippon Oil & Fats Co., Ltd.), and polypropylene glycol polytetramethylene glycol monomethacrylate (trade name: Blemmer NHK-5050, manufactured by Nippon Oil Co., Ltd.).

Specific examples of the synthetic products include methoxypolyethylene glycol polypropylene glycol random copolymer terminated primary amino group oligomers (trade name: Jeffamine 1000, Jeffamine 2070, manufactured by HUNTSMAN), methoxypolyethylene glycol oligomers (manufactured by Ardrich) And an oligomer having a polymerizable group at one end obtained by reacting with an oxyethyl isocyanate.

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

(A): (B): (C): (D) = (0.1 to 6) :( 0.1 to 5) :( 1 to 9) in the mass ratio (molar ratio) ) :( 1 to 6), and these water mass ratios are appropriately selected so that the sum is equivalent to (1 + m) of X in the general formula (1).

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

The polymer compound represented by the general formula (1) synthesized by using at least one of the monomers (A) to (D) can be obtained by reacting a monomer represented by the general formula (2) and (A) Can be synthesized by the method described in Japanese Patent Application Laid-Open No. 2007-262378.

In the general formulas (1) and (2), X represents a linking group of (1 + m). l + m satisfies 3 ~ 10. The (1 + m) linking group represented by X includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms Atoms, and groups of 0 to 20 sulfur atoms, and may be substituted or unsubstituted.

X in the above general formulas (1) and (2) represents an alkyl group having 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 And a group formed by from 0 to 20 sulfur atoms.

The linking group represented by X is preferably an organic linking group, and specific examples (specific examples (r-1) to (r-17)) of the organic linking group are shown below. However, the present invention is not limited thereto.

(R-1), (r-2), (r-10), (r-11), (r-16), (r-17) is preferable.

When X has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, a hydroxyl group, , An acyloxy group having 1 to 6 carbon atoms such as a sulfonamide group, an N-sulfonylamide group and an acetoxy group, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, a halogen atom such as chlorine or bromine , An alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group and a cyclohexyloxycarbonyl group, a carbonic ester group such as a cyano group and t-butylcarbonate, and the like.

A polymer compound obtained by copolymerizing at least one of monomers (A) to (D), a polymer compound represented by formula (1) synthesized using at least one of monomers (A) to (D) But the present invention is not limited thereto. In the following, Me represents a methyl group, and Bu represents a butyl group. R represents -O-CO-CH ₂ -CH ₂ - and is bonded to S (sulfur atom) in the repeating unit by a carbon atom. In the following specific examples, when each repeating unit is located at the end of the polymer compound, the end of the repeating unit is substituted by a hydrogen atom. The numerals below the parentheses [] indicating the repeating units in P-9 to P-11 indicate water mass ratios.

Hereinafter, a method for isolating hydrophobic aggregates of organic nanoparticles will be described.

It is preferable that the solution agglomerated before isolation is left to stand for 0.5 to 2 hours. Since the aggregate is precipitated, the supernatant can be removed by decanting or absorbing, which makes it easier to isolate the aggregate. Further, centrifugal separation is performed instead of centrifugal separation, so that sedimentation of agglomerates can be performed more quickly, and time can be shortened.

As the isolation method, various filtration methods are available, such as limiting filtration, centrifugation, filtration by filtration or filtration.

In the case of ultrafiltration, for example, a method used for desalting / concentration of a silver halide emulsion can be applied. A method described in Research Disclosure No. 10208 (1972), No. 1332 (1975), and No. 16 351 (1977) is known. An important pressure difference or flow rate as an operating condition can be selected with reference to the characteristic curve described in "Membrane Utilization Handbook" published by Saiwa Shobo Publishing Co. (1978), p275 by Haruhiko Oya. However, in processing the desired organic nanoparticle dispersion, It is necessary to find an optimum condition for suppressing the aggregation. In addition, in the method for replenishing the solvent lost from the membrane permeation, there is preferably a batch type (batch type) in which the solvent is added separately and intermittently to the fixed type (continuous type) in which a solvent is continuously added, . The pure water obtained by ion exchange or distillation is used as the solvent to be supplemented in this way, but a poor solvent of the dispersant and the dispersant may be mixed in pure water or may be added directly to the organic nanoparticle dispersion.

Filter filtration may employ, for example, a device such as pressure filtration. Preferable filters include filter paper, nanofilters, ultrafilters, and the like.

A centrifuge used for concentration of organic nanoparticles by centrifugation may be any device as long as it can precipitate organic nanoparticles in an organic nanoparticle dispersion (or organic nanoparticle concentrated extract). Examples of the centrifugal separator include, in addition to a general-purpose apparatus, a skimming function (a function of sucking the supernatant layer during rotation and discharging it out of the system), and a continuous centrifugal separator continuously discharging solids.

The centrifugal separation condition is preferably 50 to 10000, more preferably 100 to 8000, and particularly preferably 150 to 6000 as a centrifugal force (value indicating how many centrifugal acceleration of gravity acceleration is applied). The temperature at the time of centrifugation is preferably from -10 to 80 캜, more preferably from -5 to 70 캜, particularly preferably from 0 to 60 캜, though it depends on the solvent type of the dispersion.

The isolated aggregates may be washed for the purpose of desalting, dewatering, and removal of the excess dispersant. The washing operation may be carried out by limiting filtration, centrifugation, filtration or filtration by filtration, washing by adding the washing liquid as it is, or by once withdrawing the aggregate and reslurrying in the washing liquid, followed by limiting filtration, centrifugation, filtration or filtration Or they may be washed in combination.

The cleaning may be performed not only after isolation as described above but also before isolation. The aggregated nanopigment particle dispersion is allowed to stand to remove the supernatant, and a rinsing liquid is added to effect reslurry. After the reslurry, the solution is allowed to stand to remove the supernatant, and may be filtrated, but may be filtrated as it is. If the cleaning is carried out before isolation, the aggregation is always wet, so that the cleaning efficiency is improved and the re-dispersion described later becomes easier.

The cleaning liquid is not particularly limited as long as it can achieve desalting, dehydration, removal of excess dispersing agent and coagulant, but specifically includes an aqueous solvent (for example, water or hydrochloric acid, an aqueous solution of sodium hydroxide), an alcohol compound solvent, An ether compound solvent, an aromatic compound solvent, a carbon disulfide solvent, an aliphatic compound solvent, a nitrile compound solvent, a sulfoxide compound solvent, a halogen compound solvent, an ester compound solvent, an ionic liquid and a mixed solvent thereof And is preferably an aqueous solvent, an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, a nitrile compound solvent, a sulfoxide compound solvent, an ester compound solvent, an amide compound solvent or a mixture thereof, A compound solvent, and a nitrile compound solvent are preferable.

It is preferable that the isolated hydrophobic aggregates contain a dispersant and a hydrophobic dispersant in addition to the organic pigment fine particles. It is preferable that the dispersing agent coexists at 10 mass% or more and 1000 mass% or less with respect to the pigment. And more preferably 10 mass% or more and 200 mass% or less. If the amount is too small or too large, problems such as dispersion failure in a nonaqueous medium tend to occur. It is preferable that the hydrophobic dispersing agent coexists at 10 mass% or more and 1000 mass% or less with respect to the pigment. More preferably, it is 50 mass% or more and 200 mass% or less. When the amount is too small, dispersion becomes poor, while when it is too large, problems such as increase in viscosity at the time of re-dispersion tend to occur.

The dispersant has a function of promoting and retaining the adsorption of the hydrophobic dispersant to the organic pigment fine particles when the organic pigment fine particles are dispersed in the non-aqueous medium. Therefore, when the amount of the dispersing agent is too small, the hydrophobic dispersing agent may be desorbed from the organic pigment fine particles, resulting in dispersion failure at the time of re-dispersion into the non-aqueous medium. On the other hand, if the dispersing agent is hydrophilic and the amount thereof is too large, the hydrophobic dispersing agent is relatively less as compared with the dispersing agent. Therefore, the hydrophobic effect may become insufficient in an aqueous medium, and in a non-aqueous medium, dispersion failure may occur during redispersion. When the hydrophobic dispersing agent is too small, the effect of hydrophobing by the hydrophobic dispersing agent in an aqueous medium may be insufficient. On the other hand, dispersion failure may occur in a non-aqueous medium. When the amount of the dispersant for hydrophobicization is too large, an extra dispersant for hydrophobicization that can not be adsorbed by the organic pigment fine particles may be generated, and the viscosity may increase during redispersion.

The isolated aggregates may be redispersed as described later, or redispersed by a redispersion solvent (described later), and then redispersion may be carried out after the particles are dried as a powder of the organic nanoparticle dispersion.

The drying method is not particularly limited, and examples thereof include freeze drying and vacuum drying.

The method of freeze-drying is not particularly limited, and any method that can be used by those skilled in the art may be employed. For example, a refrigerant direct expansion method, a redundant freezing method, a heat circulation method, a triple heat exchange method, and an indirect heating freezing method can be mentioned, but preferably a refrigerant direct expansion method, an indirect heating freezing method, It is better to use the method. In either method, it is preferable to perform freeze-drying after preliminary freezing. The conditions of the preliminary freezing are not particularly limited, but it is necessary that the sample to be freeze-dried is frozen uniformly.

Examples of the indirect freezing and freezing method include a small freeze dryer, an FTS freeze dryer, a LYOVAC freeze dryer, a laboratory freeze dryer, a research freeze dryer, a triple heat exchange vacuum freeze dryer, a mono cooling type freeze dryer and a HULL freeze dryer. A small lyophilizer, a laboratory lyophilizer, a research lyophilizer, a mono cooling lyophilizer, more preferably a small lyophilizer or a mono cooling lyophilizer.

The temperature for freeze-drying is not particularly limited, but is, for example, -190 to -4 캜, preferably -120 to -20 캜, more preferably about -80 to -60 캜. The pressure for freeze-drying is not particularly limited and may be suitably selected by those skilled in the art. For example, the pressure is preferably 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 16 to 26 hours. Naturally, these conditions can be appropriately selected by those skilled in the art. The freeze-drying method is described, for example, in "Preparation Machinery Technology Handbook: Preparation of Mechanical Engineering Technology", Chijinshokan, p.120-129 (September 2000); Vacuum Handbook: Japan Vacuum Technology Co., Ltd., Omusa, p. 328-331 (1992); Freezing and Drying Research Meeting: KOJI Ito et al., No.15, p.82 (1965).

The apparatus used for concentration of the organic nanoparticles by reduced-pressure drying is not particularly limited as long as the solvent of the organic nanoparticle dispersion (or the organic nanoparticle concentrated extract) can be evaporated. For example, there can be mentioned a general vacuum dryer and a rotary pump, a device capable of drying under reduced pressure while stirring the liquid, and a device capable of continuously drying by passing the liquid through a tube subjected to heat and pressure reduction.

The drying temperature under reduced pressure 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 decompression is preferably 100 to 100000 Pa, more preferably 300 to 90000 Pa, and particularly preferably 500 to 80000 Pa.

According to the production method of the present invention, it is possible to finely disperse the organic pigment fine particles in a coagulated state if necessary (in the present invention, finely dispersing or redispersing means releasing aggregation of particles in the dispersion to increase dispersibility). In the present invention, it is preferable to redisperse the obtained hydrophobic aggregates in a non-aqueous medium. (The dispersions thus obtained may be referred to as non-aqueous dispersions.)

The non-aqueous medium means a medium other than an aqueous medium, and is preferably a ketone compound solvent, an ester compound solvent or an aromatic compound solvent. Specific examples thereof include methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, 2- (1-methoxy) propyl acetate, nitrobenzene, chlorobenzene and dichlorobenzene. Among these, methyl ethyl ketone, cyclohexanone , 2- (1-methoxy) propyl acetate, and chlorobenzene are preferable.

In order to filter the aggregated organic pigment fine particles rapidly and filter it into a good dispersion state, it is preferable to obtain a flocculated aggregate of organic pigment fine particles to a degree that can be re-dispersed. Here, floc refers to aggregates of fine particles aggregated (weakly aggregated) to the extent that they can be redispersed. It is also preferred that the hydrophilic aggregates and the hydrophobic aggregates are flocs. By making the organic pigment fine particles into flocs, for example, the organic pigment fine particles precipitated in the aqueous liquid mixture can be quickly separated from the medium by filtration or the like. Then, the separated flocs (soft agglomerates) can be re-dispersed in an organic solvent suitable for the production of a color filter to efficiently form an organic solvent-based pigment dispersion composition (non-aqueous dispersion composition). That is, when a mixed solvent of a good solvent and a poor solvent is used for a water-based solvent, it can be efficiently replaced with a third solvent composed of an organic solvent to switch the dispersion medium (continuous phase).

In addition, there is a case that a method of dispersing by using a usual dispersion method is insufficient for fine particle formation and a method of high refining efficiency is further needed. In this strongly agglomerated organic particle (in the present invention, the term "agglomerated organic particle" means that organic particles such as agglomerates are collected by a secondary force, and when the primary particle is a nanometer-sized aggregated nanoparticle ), An organic polymer compound having a mass average molecular weight of 1,000 or more is contained in the aggregated organic particle liquid, whereby a dispersion in which the organic particles are preferably finely dispersed can be obtained (the term "aggregated organic particle liquid" , And it may contain aggregated organic particles even if it is a dispersion, a concentrate, a paste, a slurry, etc.) More specifically, when the organic polymer compound is precipitated in a mixture of a good solvent and a poor solvent (Uniformity, characteristic of realizing minute particle size) and dispersion stability (uniformity, It is possible to achieve high performance in the color filter by maintaining the medium after switching to the organic solvent suitable for the color filter and redispersing the medium. It is possible to realize high performance in the color filter by interacting with the coloring property of the organic nano-pigment fine particles.

As a method of finely dispersing such agglomerates of nanoparticles, for example, a method of dispersing by ultrasonic waves or a method of applying physical energy can be used.

The ultrasonic wave irradiation apparatus to be used preferably has a function of applying an ultrasonic wave of 10 kHz or more, and examples thereof include an ultrasonic homogenizer and an ultrasonic wave cleaner. Since the nanoparticles thermally agglomerate when the liquid temperature rises during the ultrasonic irradiation (see Non-Patent Document 1), the liquid temperature is preferably 1 to 100 占 폚, more preferably 5 to 60 占 폚. The temperature can be controlled by controlling the temperature of the dispersion liquid, or by controlling the temperature of the temperature control layer for controlling the temperature of the dispersion liquid.

The dispersing machine used for dispersing the concentrated organic nanoparticles by adding physical energy is not particularly limited and examples thereof include dispersing machines such as a kneader, a roll mill, an atomizer, a super mill, a dissolver, a homomixer, . In addition, a high-pressure dispersion method or a dispersion method by use of micro-particle beads can also be exemplified as preferable ones.

As a preferable production method of the organic nanoparticle dispersion, the colorant is kneaded and dispersed by a resin component so that the viscosity at 25 ° C after the kneading and dispersing treatment becomes a relatively high viscosity of 10,000 mPa · s or more, preferably 100,000 mPa · s or more, It is preferable to add a solvent and finely disperse the solution so that the viscosity after the micro-dispersion treatment becomes a relatively low viscosity of 1,000 mPa · s or less, preferably 100 mPa · s or less.

The machine used in the redispersion treatment is a two roll, three roll, a ball mill, a trommel, a dispenser, a kneader, a coneerator, a homogenizer, a blender, a single shaft and a biaxial extruder and is dispersed while giving a strong shearing force . Subsequently, a solvent is finely dispersed by beads made of glass or zirconia having a particle size of 0.1 to 1 mm mainly by using a vertical or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, a high pressure disperser or the like . It is also possible to perform fine dispersion treatment using fine particle beads of 0.1 mm or less.

It is also possible to disperse the main pigment and the auxiliary pigment, respectively, and then to mix the dispersions of the two to further disperse the mixture, or to disperse the main pigment and the auxiliary pigment together.

Further, details of dispersion are described in T.C. Patton, " Paint Flow and Pigment Dispersion " (John Wiley and Sons, 1964), and the like may also be used.

To the organic pigment fine particle dispersion after redispersion, a conventional pigment dispersant or a surfactant may be added for the purpose of improving the dispersibility of the organic pigment fine particles. As such dispersants, many kinds of compounds are used. For example, phthalocyanine derivatives {commercial product EFKA-6745 (FPC)}, Solspers 5000 {manufactured by Zeneca Co.}}; (Manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based (co) polymer Polyflow No. 75, No. 90, No. 95 (manufactured by Kyowa Chemical Industry Co., Ltd.) , W001 (manufactured by Yushen Co.), and the like; Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol distearate, polyethylene glycol distearate, sorbitan fatty acid Nonionic surfactants such as esters; Anionic surfactants such as W004, W005 and W017 (manufactured by Yushen Co.); EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401 and EFKA Polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), Disperse AID 6, Disperse Aide 8, Aid 15, and Disperse Aid 9100 (manufactured by San Foo Corporation); (Manufactured by Zeneca Co., Ltd.) such as Sol Spurs 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000 and 28000; (Manufactured by Asahi Denka Kogyo Co., Ltd.) was added to the reaction mixture, and the reaction was carried out in the same manner as in Example 1, And Isonet S-20 (manufactured by Sanyo Chemical Industries, Ltd.). Also, the pigment dispersant described in JP-A-2000-239554, the compound (C) described in JP-A-5-72943, and the compound of SYNTHETIC EXAMPLE 1 described in JP-A-2001-31885 may be preferably used.

In the organic nanoparticle dispersion composition after redispersion, the organic nanoparticles (primary particles) can be finely dispersed particles having a particle size of preferably 1 to 200 nm, more preferably 2 to 100 nm , And particularly preferably from 5 to 50 nm. The Mv / Mn of the particles after re-dispersion is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, particularly preferably 1.0 to 1.5.

According to the manufacturing method of the present invention, the pigment particles can be dispersed in a concentrated material in spite of a minute particle size of nanometer size (for example, 10 to 100 nm), and for example, a dispersion composition of organic pigment fine particles, A photosensitive resin composition may be used. Therefore, when these compositions are used for a color filter, the optical density is high, the uniformity of the filter surface is excellent, the contrast is high, and the noise of the image can be reduced.

Furthermore, since the organic pigment fine particle dispersion composition and the organic pigment fine particles contained in the colored photosensitive composition can be highly and uniformly and finely dispersed, it is possible to exhibit a thin film thickness and a high coloring density. For example, It is possible to make it possible.

In addition, the organic pigment fine particle-dispersed composition and the colored photosensitive resin composition are excellent as an image forming material for producing, for example, color proofing, color filters and the like by containing a bright color tone and a pigment exhibiting high coloring power.

Further, with respect to an alkaline developer used for exposure and development during color image formation, an organic nano-particle dispersion composition and a binder soluble in an alkaline aqueous solution as a binder (binder) can be used in the colored photosensitive resin composition, .

Further, an organic solvent having a proper drying property can be used as a solvent (a dispersion medium of the pigment) used in the organic pigment fine particle-dispersed composition and the colored photosensitive resin composition, so that it is possible to satisfy the requirement even after drying after coating.

[Colored 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) an organic pigment composition

The method of producing the organic pigment composition has already been described in detail. The content of the organic nano pigment particles is preferably from 3 to 90% by mass, more preferably from 20 to 80% by mass, based on the total solid content of the colored photosensitive resin composition (the total solid content in the present invention means the total amount of the composition excluding organic solvent) , And still more preferably from 25 to 60 mass%. If the amount is too large, the viscosity of the dispersion liquid may rise, which may cause problems in manufacturing suitability. If it is too small, the coloring power is not sufficient. As the organic nano pigment particle functioning as a colorant, it is preferable that the particle size is not more than 0.1 탆, particularly not more than 0.08 탆. It may be used in combination with an ordinary pigment for coloring. The pigment described above can be used. In the present invention, the organic nanoparticles are preferably used as the above-mentioned organic nano-pigment non-aqueous dispersion.

(b) a binder

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

(c) a monomer or oligomer

The monomer or oligomer to be contained in the colored photosensitive resin composition of the present invention is preferably a monomer or an oligomer having two or more ethylenically unsaturated double bonds and subject to addition polymerization by light irradiation. Examples of such monomers and oligomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of at least 100 캜 at normal pressure. Examples thereof include monofunctional acrylates such as dipentaerythritol hexa (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate, Rate; (Meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylol ethane triacrylate, trimethylol propane tri (meth) acrylate, trimethylol propane diacrylate, neopentyl glycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (metha) acrylate, dipentaerythritol penta Acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; And multifunctional acrylates or polyfunctional methacrylates such as (meth) acrylates obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as trimethylol propane or glycerin. Also, compounds obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols and then (meth) acrylating them are preferable as shown in the general formulas (1) and (2) described in JP 10-62986 A have.

The urethane acrylates described in JP-A-48-41708, JP-A-50-6034 and JP-A-51-37193; Polyester acrylates described in JP-B-48-64183, JP-A-49-43191 and JP-B-52-30490; Polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid.

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

In addition, the "polymerizable compound B" described in Japanese Patent Application Laid-Open No. 11-133600 may be exemplified as preferable ones.

These monomers or oligomers may be used alone or in combination of two or more of them (monomers or oligomers preferably have a molecular weight of from 200 to 1000), and the content of the colored photosensitive resin composition to the total solid content is generally from 5 to 50 mass% By mass, and preferably from 10 to 40% by mass. When the amount is too large, control of developability becomes difficult, which is a problem in manufacturing suitability.

(d) a photopolymerization initiator or a photopolymerization initiator system

Examples of the photopolymerization initiator or photopolymerization initiator system contained in the colored photosensitive resin composition of the present invention (a photopolymerization initiator in the present invention refers to a mixture which exhibits photopolymerization initiating function by combination of a plurality of compounds) is described in U.S. Patent No. 2367660 Acyloin ether compounds described in the specification of US Patent No. 2448828, aromatic acyloin compounds substituted by? -Hydrocarbon described in US Patent No. 2722512, US Patent Nos. 3046127 and 2951758 disclose polynuclear quinone compounds, combinations of triarylimidazole dimer and p-amino ketone described in U.S. Patent No. 3549367, JP-A-51-48516 , Trihalomethyl-s-triazine compounds described in U.S. Patent No. 4239850 Trihalomethyl-triazine compounds described in the specification, and trihalomethyloxadiazole compounds described in U.S. Patent No. 4212976, and the like. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole and triarylimidazole dimer are preferable.

In addition, as the polymerization initiator C described in JP 11-133600 A, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O- -4 '- (benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyloxide, hexafluorophosphorothio-trialkylphenylphosphonium salt and the like .

These photopolymerization initiators or photopolymerization initiator systems may be used alone or in combination of two or more, but it is particularly preferable to use two or more. When at least two kinds of photopolymerization initiators are used, the display characteristics, particularly, display irregularities can be reduced.

The content of the photopolymerization initiator or the photopolymerization initiator system based on the total solid content of the colored photosensitive resin composition is generally from 0.5 to 20% by mass, and preferably from 1 to 15% by mass. If the amount is too large, the sensitivity becomes too high and control becomes difficult. If it is too small, the exposure sensitivity becomes too low. As the radiation which can be used in exposure, ultraviolet rays such as g line and i line are preferably used. The irradiation dose is preferably 5 to 1500 mJ / cm2, more preferably 10 to 1000 mJ / cm2, and most preferably 10 to 500 mJ / cm2.

(Other additives)

〔menstruum〕

In the colored photosensitive resin composition of the present invention, an organic solvent may be further used in addition to the above components. Examples of the organic solvent include, but are not limited to, esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, Butyl, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-oxypropionic acid alkyl esters such as methyl oxypropionate and ethyl 3-oxypropionate; Methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy- , Methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetonate, ethyl acetoacetate, Methyl carbonate, ethyl 2-oxobutanoate and the like; Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, propylene glycol Methyl ether acetate and the like; Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclohexanol, 2-heptanone, 3-heptanone and the like; Aromatic hydrocarbons such as toluene and xylene. Among these solvents, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethylcarbitol acetate , Butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferably used as the solvent in the present invention. These solvents may be used alone or in combination of two or more kinds.

Further, a solvent having a boiling point of 180 ° C to 250 ° C may be used as needed. The following are examples of these high boiling point solvents. Diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, 3,5,5-trimethyl-2-cyclohexene-1-one, butyl lactate, dipropylene glycol monomethyl ether acetate , Propylene glycol monomethyl ether acetate, propylene glycol diacetate, propylene glycol n-propyl ether acetate, diethylene glycol diethyl ether, 2-ethylhexyl acetate, 3-methoxy-3-methylbutyl acetate, Tripropylene glycol methyl ethyl acetate, dipropylene glycol-n-butyl acetate, propylene glycol phenyl ether acetate, 1,3-butanediol diacetate.

The content of the solvent is preferably 10 to 95% by mass with respect to the total amount of the resin composition.

〔Surfactants〕

There has been a problem in that the color of each pixel becomes thick in order to realize high color purity in a color filter which has been conventionally used and the unevenness of the film thickness of the pixel is recognized as the color unevenness as it is. Therefore, it has been required to improve the film thickness variation at the time of forming (coating) the photosensitive resin layer which directly affects the film thickness of the pixel.

From the viewpoint that 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 have a uniform film thickness and effectively prevent uneven application (color unevenness due to film thickness variation) It is preferred to include a suitable surfactant in the composition.

As the surfactant, surfactants disclosed in JP-A-2003-337424 and JP-A-11-133600 can be preferably exemplified. 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 preferably contains a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl catechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole and phenothiazine. 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 used as adjuvant]

In the colored photosensitive resin composition of the present invention, a colorant (dye, pigment) may be added in addition to the colorant (pigment) as necessary. When a pigment is used in the colorant, it is preferably dispersed uniformly in the colored photosensitive resin composition, and therefore, it is preferable that the particle size is 0.1 탆 or less, particularly 0.08 탆 or less.

Specific examples of the dyes and pigments include pigments described in JP-A-2005-17716, JP-A-2005-361447, JP-A-2005-361447 and JP-A- The colorants described in JP-A-2005-17521 [0080] to [0088] can be preferably used. The content of the dye or pigment to be used as an auxiliary is preferably 5% by mass or less based on the total amount of the resin composition.

[Ultraviolet absorber]

The colored photosensitive resin composition of the present invention may contain an ultraviolet absorber if necessary. Examples of the ultraviolet absorber include salicylate, benzophenone, benzotriazole, cyanoacrylate, nickel chelate, hindered amine and the like in addition to the compounds described in JP-A-5-72724.

Specific examples thereof include phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ', 5'-di- -Butylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano- -Diphenyl acrylate, 2,2'-hydroxy-4-methoxybenzophenone, nickel dibutyldithiocarbamate, bis (2,2,6,6-tetramethyl-4- pyridine) 4-t-butylphenyl salicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinic acid-bis (2,2,6,6-tetramethyl- Benzyltriazole, 7 - {[4-chloro-6- ((2-hydroxy- Diethylamino) -5-triazin-2-yl] amino} -3-phenyl coumarin and the like The can. The content of the ultraviolet absorber is preferably 5% by mass or less based on the total amount of the resin composition.

In addition, in the colored photosensitive resin composition of the present invention, in addition to the above-mentioned additives, " adhesion improvers " and other additives described in JP-A-11-133600 may be incorporated.

[Coated film of colored photosensitive resin composition]

The contained components in the coating film using the colored photosensitive resin composition of the present invention are the same as those described in the section of [colored photosensitive resin composition]. The thickness of the coated film using the colored photosensitive resin composition of the present invention may be appropriately determined depending on the application, but is preferably 0.5 to 5.0 탆, more preferably 1.0 to 3.0 탆. In the coating film using the colored photosensitive resin composition of the present invention, a color filter having the polymerized film of the colored photosensitive resin composition by polymerizing the monomer (c) or the oligomer contained therein can be produced The polymerization of the polymerizable monomer or the polymerizable oligomer can be performed by irradiating (d) a photopolymerization initiator or a photopolymerization initiator system by light irradiation.

≪ Color filter and manufacturing method thereof &

Next, the color filter of the present invention and its manufacturing method will be described.

The color filter of the present invention is characterized by having a coloring pattern formed 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 through a manufacturing method thereof (a method of manufacturing a color filter of the present invention).

The process for producing a color filter of the present invention is a process for producing a color filter comprising the steps of forming a photosensitive film by applying the photocurable composition of the present invention directly or through another layer on a substrate (hereinafter abbreviated as "photosensitive film forming process" (Hereinafter referred to as " exposure step " as appropriate) for pattern-exposing a photosensitive film to light (exposure through a mask) and a step of developing a photosensitive film after exposure to form a colored pattern ).

Each step in the method of manufacturing a color filter of the present invention will be described below.

(Photosensitive film forming step)

In the photosensitive film formation step, the photosensitive film of the present invention is applied (applied) directly or on a substrate having another layer to form a photosensitive film.

Examples of the substrate that can be used in the present process include soda glass, Pyrex (registered trademark) glass, quartz glass and a photoelectric conversion element substrate used for an imaging device or the like to which a transparent conductive film is attached, For example, a silicon substrate or a complementary metal oxide semiconductor (CMOS) may be used. These substrates may be formed with black stripes for isolating each pixel.

Further, a primer layer (another layer) may be formed on these substrates in order to improve adhesion with the upper layer, prevent diffusion of the material, or planarize the surface of the substrate, if necessary.

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

The coating thickness of the photocurable composition is preferably 0.1 to 10 占 퐉, more preferably 0.2 to 5 占 퐉, and still more preferably 0.2 to 3 占 퐉.

Drying (prebaking) of the photosensitive film applied on the substrate can be performed in a hot plate, an oven or the like at a temperature of 50 to 140 캜 for 10 to 300 seconds.

(Exposure step)

In the exposure step, the photosensitive film formed in the photosensitive film formation step is exposed through a mask having a predetermined mask pattern, that is, pattern exposure is performed.

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

As the radiation which can be used in exposure, ultraviolet rays such as g line and i line are preferably used. The irradiation dose is preferably 5 to 1500 mJ / cm2, more preferably 10 to 1000 mJ / cm2, and most preferably 10 to 500 mJ / cm2.

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

(Developing step)

Subsequently, by performing development processing, the unexposed portion in the exposure process is eluted into the developer, leaving only the photo-cured portion. Any developer may be used as long as it dissolves the film of the photocurable composition in the uncured portion and does not dissolve the cured portion. Concretely, a combination of various organic solvents or an alkaline aqueous solution can be used.

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

Examples of the organic solvent include the above-mentioned solvents that can be used when preparing the pigment dispersion composition or photo-curable composition of the present invention.

Examples of the alkaline aqueous solution include aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Alkaline compounds such as ammonium hydroxide, choline, pyrrole, piperidine and 1,8-diazabicyclo- [5,4,0] -7-undecene in an amount of 0.001 to 10% by mass, preferably 0.01 To 1% by mass is preferably used as the developing solution.

When a developing solution comprising such an alkaline aqueous solution is used, it is generally rinsed (cleaned) with pure water after development.

After the development process, the excess developer is washed away, dried, and then heat-treated (post-baked).

The post baking is a post-development heat treatment for making the curing to be complete, and the heat curing treatment is usually performed at 100 to 240 캜. When the substrate is a glass substrate or a silicon substrate, it is preferably 200 DEG C to 240 DEG C in the above temperature range.

This post-baking treatment can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation type drier), a high frequency heater or the like so that the coated film after development is in the above condition.

By repeating the photosensitive film forming step, the exposure step, and the developing step (and, if necessary, the heat treatment) described above for the desired number of colors, a color filter having a desired color is produced.

When the photo-curable composition is applied to a substrate to form a film, the dry thickness of the film is generally from 0.3 to 5.0 占 퐉, preferably from 0.5 to 3.5 占 퐉, and most preferably from 1.0 to 2.5 占 퐉.

Examples of the substrate include a photoelectric conversion element substrate used for a non-alkali glass used for a liquid crystal display element, a soda glass, a Pyrex (registered trademark) glass, a quartz glass, A silicon substrate, and a plastic substrate. On these substrates, a black stripe for isolating each pixel is usually formed.

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

It is needless to say that the use of the photo-curable composition has mainly been described mainly on the use of color filters in pixels, but it is also applicable to a black matrix formed between pixels of a color filter. The black matrix is subjected to pattern exposure and alkali development in the same manner as the above-described method for producing a pixel except that a black colorant such as carbon black or titanium black is added to the photo-curable composition of the present invention as a coloring agent, Can be formed by accelerating the curing.

(Example)

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not construed as being limited thereto.

≪ Example 1 >

[Preparation of aqueous nano-pigment particle aqueous dispersion]

C. I. Pigment Red 254 (45 parts by mass) and the above exemplified compound O-1 (45 parts by mass) were added to dimethylsulfoxide (DMSO) (953 parts by mass) and stirred. A pigment aqueous solution A was prepared by adding a 26 mass% aqueous solution of tetramethylammonium hydroxide (45 mass parts) to this solution. On the other hand, water (4000 parts by mass) to which acetic acid (7.6 parts by mass) was added was prepared as pigment-insoluble solvent B.

The pigment-insoluble solvent B was added to the pigment-insoluble solvent B with stirring at 500 rpm at 30 ° C by Gamma-type GK-0222-10 (trade name) manufactured by Seiyakuko G. Fujisawa, -KX-500 type high capacity non-pulsating pump (trade name) at a flow rate of 100 mL / min for 4 minutes and 4 seconds to crystallize the organic nano pigment particles to obtain hydrophilic aggregates of the organic nano pigment particles.

[Addition of dispersant for hydrophobicity]

(3 parts by mass) represented by the following formula (P) as a dispersant for hydrophobicization was dissolved in acetone (200 parts by mass) and dissolved in a dispersion (300 parts by mass) of the hydrophilic agglomerate of the above organic nanoparticles And the mixture was stirred for 0.5 hours. The resultant was allowed to stand for 0.5 hour to precipitate the resulting hydrophobic aggregates, and the supernatant was removed by decanting.

(Evaluation test)

The obtained aggregates were subjected to the following evaluations. The results are shown in Table 1.

(1) The size of the primary particles of the organic nano pigment particles constituting the agglomerate was evaluated by a transmission electron microscope.

(2) About 1 part by mass of the aggregate was withdrawn and stirred in water / acetone (1: 1 volume mixture, 100 parts by volume) for 0.5 hour, and the supernatant was removed by decantation. This operation was repeated three times in total, and the resulting aggregate was filtered through a filter paper (No. 2, manufactured by ADVANTEC Co., Ltd.) by a nutsche, and vacuum-dried overnight. The dried pigment solids (10 parts by mass) were dissolved in DMSO (100 parts by volume) and the absorption spectrum was measured by UV-2500 (trade name, manufactured by Shimadzu Seisakusho Co., Ltd.), and the mass ratios of the pigments in the pigment solids were obtained , And the residual ratio of the added dispersant was defined as the adsorption rate.

[Isolation, washing, drying]

The above-mentioned aggregate was collected by filtration with a filter paper (ADVANTEC, No. 2), and washed with water (300 parts by mass). The obtained solid was vacuum dried overnight at room temperature.

[Redistribution]

The following non-aqueous solvent 1-methoxy-2-propyl acetate (formula Q) (4 parts by mass) was added to this organic pigment solid (1 part by mass), and an ultrasonic homogenizer US series (manufactured by Nippon Seimitsu Co., (Pigment Dispersion Composition A) was obtained by conducting ultrasonic irradiation for 3 hours using a non-aqueous solvent as a dispersion medium.

(Evaluation test)

(1) Contrast evaluation

The obtained pigment dispersion composition A was coated on a glass substrate to a thickness of 2 占 퐉 to prepare a sample. A polarizing plate (polarizer HLC2-2518 manufactured by Sankyo Co., Ltd.) was used as a backlight unit in which a diffusion plate was provided on a three-wavelength cold cathode tube light source (FWL18EX-N manufactured by Toshiba Latech Co., Ltd.) The amount of transmitted light when the polarization axis was parallel and vertical was measured, and the ratio was used as the contrast ("7th Color Optics Conference, 1990, color filter for 512 color display 10.4" size TFT-LCD, The color positions of the two polarizers, the sample and the chromaticity luminance meter were measured by using a backlight (see, for example, Kobunshi, Fukunaga, Yamanaka) A cylindrical polarizing plate was placed at a position of 13 mm from the center and a rod having a diameter of 11 mm and a length of 20 mm at a position of 40 mm to 60 mm was placed and irradiated to a measurement sample provided at a position of 65 mm, The light was set at a position of 400 mm through a polarizing plate provided at a position of 100 mm The measurement angle of the color luminance meter was set at 2 DEG. The light quantity of the backlight was adjusted so that the luminance when the two polarizing plates were placed on the parallel Nicole without sample was set to 1280 cd / m < 2 > The same evaluation was also made on the pigment dispersion composition A after one week, and the result was regarded as an index of stability with elapsed time.

(2) Visual evaluation

The sample used for the contrast evaluation of the pigment-dispersed composition A after one week was visually confirmed, and the presence or absence of scattering (whether it was transparent or not) was confirmed. If there is no scattering (if transparent), it can be said that the pigment particles are sufficiently dispersed in the non-aqueous medium.

≪ Example 2 >

The same operation as in Example 1 was carried out by changing the above-mentioned Exemplary Compound O-1 of Example 1 to O-3. The obtained organic nano pigment particle non-aqueous dispersion (Pigment dispersion composition B) was subjected to the same evaluation test as in Example 1. The results are shown in Table 1.

≪ Example 3 >

The same operation as in Example 1 was carried out by changing the above-mentioned Exemplary Compound O-1 of Example 1 to O-10. The obtained organic nano pigment particle non-aqueous dispersion (Pigment Dispersion Composition C) was subjected to the same evaluation test as in Example 1. The results are shown in Table 1.

<Example 4>

The same operation as in Example 1 was carried out by changing the above-mentioned Exemplary Compound O-1 of Example 1 to O-4. The obtained organic nano pigment particle non-aqueous dispersion (Pigment dispersion composition D) was subjected to the same evaluation test as in Example 1. The results are shown in Table 1.

&Lt; Comparative Example 1 &

Exemplary Compound O-1 of Example 1 was changed to polyvinylpyrrolidone {K-25 (trade name), manufactured by Wako Pure Chemical Industries, Ltd.), and the organic pigment aqueous dispersion prepared in the same manner as in Example 1 The hydrophilic agglomerates were filtered with a filter (H010A047A, trade name, manufactured by ADOBAN TECH CO., LTD.), Filtered, and washed and dried in the same manner as in Example 1 to obtain a solid (1 part by mass). Methacrylic acid / methacrylic acid Benzyl copolymer (1 part by mass) and 1-methoxy-2-propyl acetate (8 parts by mass) were added. Ultrasonic waves were irradiated for 3 hours using a Nisshin Seisakusho Ultrasonic Humogizer US series Thereby obtaining an organic pigment fine particle non-aqueous dispersion (Pigment Dispersion Composition E) containing the following non-aqueous solvent as a dispersant. Evaluation was carried out in the same manner as in Example 1, except that filter filtration was performed as described above. The evaluation results of the pigment dispersion composition E were evaluated in the same manner as in Example 1. The results are shown in Table 1.

As shown in the above results, according to the present invention, it was possible to efficiently obtain a non-aqueous dispersion of organic nano pigment particles having high dispersibility and dispersion stability. This is considered to be because the adsorption rate of the dispersing agent is improved and the dispersibility of the glass is decreased, so that good fine dispersion and stability are reproducibly obtained. Further, it can be seen that the organic pigment composition of the present invention can remarkably improve the contrast when it is used as a color filter, and can maintain this for a long period of time. Further, in the present invention, "scattering" of the transmitted light in the organic pigment composition is small, and even when the same amount of pigment is used, high chromaticity can be obtained, and efficient and good coloring can be achieved. Further, it is understood that the number of coarse particles in the composition is reduced in that scattering is suppressed, thereby contributing to a higher contrast and a higher display quality of the color filter even more effectively.

[Preparation of colored photosensitive resin composition]

The following composition was further added to 1000 parts by mass of the pigment-dispersed compositions A to E obtained in Examples 1 to 4 and Comparative Example 1, followed by stirring and mixing to prepare a colored photosensitive resin composition (color resist solution) of the present invention.

〔Furtherance〕

· Dipentaerythritol hexaacrylate ... 80 parts by mass

· 4- [o-Bromo-p-N, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine (photopolymerization initiator) 30 parts by mass

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

· 1-Methoxy-2-propyl acetate ... 490 parts by mass

The obtained photo-curable composition (color resist solution) was applied onto a glass substrate (1737, made by Corning) having a size of 100 mm x 100 mm so as to have an x value of 0.650 which is an index of color density and dried in an oven at 90 캜 for 60 seconds Pre-baking). Thereafter, the entire surface of the coated film was exposed at 200 mJ / cm 2 (roughness 20 mW / cm 2), and the coated film after the exposure was covered with a 1% aqueous solution of alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.) Stopped. After stopping, pure water was dispersed in a shower and the developer was washed away. Then, the coated film, which was exposed and developed as described above, was heat-treated in an oven at 220 캜 for 1 hour (post baking) to form a colored resin film for a color filter on a glass substrate, .

Table 2 shows the results of measurement of the contrast of the R component of each film obtained in the same manner as in Example 1. [

As can be seen from the results, the color filter prepared from the non-aqueous dispersion prepared using the pigment composition of the present invention through the colored photosensitive resin composition exhibited a higher contrast than that of the comparative example.

Further, the above-mentioned Exemplary Compound O-1 of Example 1 was dissolved in a solvent of a compound O-2, a compound O-6, a compound O-7, a compound O-8, a compound O- -13, the compound O-14 or the compound O-15, and the same operation as in Example 1 was carried out. As a result, it was confirmed that the same effects as those of the above-mentioned pigment compositions A to D were obtained.

Claims (17)

An organic pigment composition containing organic pigment fine particles, which comprises a polymer compound having a repeating unit represented by the following general formula (1) and / or a repeating unit represented by the general formula (2) and an aqueous pigment containing an organic pigment fine particle in an aqueous medium Characterized in that a hydrophobic dispersing agent having a mass average molecular weight of 1000 or more represented by the following general formula (I) is coexisted with the agglomerate to obtain a hydrophobic agglomerate.

(Wherein A ₁ represents a hydrogen atom or a methyl group, X ₁ represents a heterocyclic group, and the heterocyclic group is bonded to the NH group by the carbon atom thereof.)

(Wherein X represents a linking group of (1 + m), S represents a sulfur atom, Y represents a group comprising at least one monomer skeleton of the monomers of (A) to (B) M is from 3 to 10, l is from 0 to 10, and m is from 0 to 10. The monomer (A) and the monomer (B) (A) a monomer containing at least one of an acidic group and a basic group (B) a monomer containing a nitrogen-containing heterocycle (C) a monomer containing an oligomer having affinity with a non-aqueous medium, wherein the polystyrene skeleton, the polymethyl methacrylate skeleton, the poly-n-butyl methacrylate skeleton, the poly- Poly-2-ethylhexyl methacrylate skeleton, polyethylene glycol skeleton, polypropylene glycol skeleton and polycaprolactone skeleton. (D) a monomer containing an oligomer having affinity with the organic pigment fine particles present in the aqueous medium The organic pigment composition according to claim 1, wherein the average particle diameter of the organic pigment fine particles is in the range of 10 to 100 nm. The organic pigment composition according to claim 1, wherein the polymer compound further has a repeating unit represented by the following general formula (5) and / or a repeating unit represented by the general formula (6).

(Wherein A ₃ and A ₄ represents a hydrogen atom or a methyl group independently. R ₁ represents an alkyl group having 1 ~ 8. R ₂ represents a hydrogen atom or an alkyl group having a carbon number of ₁ ~ 8. R 1 and R ₂ may be connected to each other to form a ring structure, and the ring structure may contain an oxygen atom, a nitrogen atom or a sulfur atom, R ₃ and R ₄ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms R ₃ and R ₄ may be connected to each other to form a cyclic structure group.) 4. The organic pigment composition according to claim 3, wherein the average particle diameter of the organic pigment fine particles is in the range of 10 to 100 nm. The organic pigment composition according to claim 1, wherein the polymer compound further has a repeating unit represented by the following general formula (3) and / or a repeating unit represented by the general formula (4).

(A ₂ represents a hydrogen atom or a methyl group in the formula. Y ₁ represents an -NH-, -O- or -S-. L represents a single bond or a divalent connecting group. Y ₂ represents a hydrogen atom or a basic And Z ₁ represents an unsaturated heterocyclic group having one or two nitrogen atoms. 6. The organic pigment composition according to claim 5, wherein the average particle diameter of the organic pigment fine particles is in the range of 10 to 100 nm. The organic pigment composition according to claim 5, wherein the polymer compound further has a repeating unit represented by the following general formula (5) and / or a repeating unit represented by the general formula (6).

(Wherein A ₃ and A ₄ represents a hydrogen atom or a methyl group independently. R ₁ represents an alkyl group having 1 ~ 8. R ₂ represents a hydrogen atom or an alkyl group having a carbon number of ₁ ~ 8. R 1 and R ₂ may be connected to each other to form a ring structure, and the ring structure may contain an oxygen atom, a nitrogen atom or a sulfur atom, R ₃ and R ₄ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms R ₃ and R ₄ may be connected to each other to form a cyclic structure group.) 8. The organic pigment composition according to claim 7, wherein the average particle diameter of the organic pigment fine particles is in the range of 10 to 100 nm. delete delete delete 9. An organic pigment composition characterized by containing the hydrophobic aggregate according to any one of claims 1 to 8 in a non-aqueous medium, releasing aggregation of the aggregate and redispersing it. A colored photosensitive resin composition comprising at least the organic pigment composition according to claim 12, a binder, a monomer or oligomer, and a photopolymerization initiator or a photopolymerization initiator system. A color filter comprising the colored photosensitive resin composition according to claim 13. A solution prepared by dissolving a polymer compound having an organic pigment and a repeating unit represented by the following general formula (1) and / or a repeating unit represented by the general formula (2) in a good solvent is compatible with both solvents, The medium for the pigment to be a poor solvent is mixed to produce the fine particles of the organic pigment, and the aqueous pigment and the water-soluble polymer are mixed with the aqueous pigment and the organic pigment fine particles in an aqueous medium containing hydrophobicization agent having a mass average molecular weight of 1000 or more represented by the following general formula (I) And a dispersing agent coexist to form a hydrophobic agglomerate.

(Wherein A ₁ represents a hydrogen atom or a methyl group, X ₁ represents a heterocyclic group, and the heterocyclic group is bonded to the NH group by the carbon atom thereof.)

(Wherein X represents a linking group of (1 + m), S represents a sulfur atom, Y represents a group comprising at least one monomer skeleton of the monomers of (A) to (B) M is from 3 to 10, l is from 0 to 10, and m is from 0 to 10. The monomer (A) and the monomer (B) (A) a monomer containing at least one of an acidic group and a basic group (B) a monomer containing a nitrogen-containing heterocycle (C) a monomer containing an oligomer having affinity with a non-aqueous medium, wherein the polystyrene skeleton, the polymethyl methacrylate skeleton, the poly-n-butyl methacrylate skeleton, the poly- Poly-2-ethylhexyl methacrylate skeleton, polyethylene glycol skeleton, polypropylene glycol skeleton and polycaprolactone skeleton. (D) a monomer containing an oligomer having affinity with the organic pigment fine particles present in the aqueous medium The method of producing an organic pigment composition according to claim 15, wherein the polymer compound further has a repeating unit represented by the following general formula (3) and / or a repeating unit represented by the general formula (4).

(A ₂ represents a hydrogen atom or a methyl group in the formula. Y ₁ represents an -NH-, -O- or -S-. L represents a single bond or a divalent connecting group. Y ₂ represents a hydrogen atom or a basic And Z ₁ represents an unsaturated heterocyclic group having one or two nitrogen atoms. The organic pigment composition according to claim 15 or 16, wherein the polymer compound further comprises a repeating unit represented by the following general formula (5) and / or a repeating unit represented by the general formula (6) Way.

(Wherein A ₃ and A ₄ each independently represent a hydrogen atom or a methyl group, R ₁ represents an alkyl group having 1 to 8 carbon atoms, R ₂ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ₁ and R ₂ may be connected to each other to form a ring structure, and the ring structure may contain an oxygen atom, a nitrogen atom or a sulfur atom, R ₃ and R ₄ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms R ₃ and R ₄ may be connected to each other to form a cyclic structure group.)