JP2009287002A - Pigment-dispersed composition, photo-setting composition using the same, color filter and method for producing the same, inkjet ink, and production method of pigment-dispersed composition - Google Patents

Abstract

（Ｒ^１は水素原子またはメチル基、Ｊは−ＣＯ−、−ＣＯＯ−、−ＣＯＮＲ^４−、−ＯＣＯ−、メチレン基、フェニレン基、または−Ｃ_６Ｈ_４ＣＯ−基、Ｒ^４は水素原子、アルキル基、アリール基、またはアラルキル基、Ｗは単結合または２価の連結基、Ｒ^２は水素原子、あるいは置換もしくは無置換の、アルキル基またはアリール基、Ｒ^３は水素原子または置換基）
【選択図】なしA pigment dispersion composition containing fine pigment particles and having excellent dispersibility and stability.
A pigment dispersion composition comprising a polymer compound having a repeating unit represented by the general formula (1) or a repeating unit represented by a tautomer structure thereof, and pigment fine particles.

(R ¹ is a hydrogen atom or a methyl group, J is —CO—, —COO—, —CONR ⁴ —, —OCO—, a methylene group, a phenylene group, or —C ₆ H ₄ CO— group, and R ⁴ is a hydrogen atom. , An alkyl group, an aryl group, or an aralkyl group, W is a single bond or a divalent linking group, R ² is a hydrogen atom, or a substituted or unsubstituted alkyl group or aryl group, and R ³ is a hydrogen atom or a substituent)
[Selection figure] None

Description

  The present invention relates to a pigment dispersion composition, a photocurable composition using the same, a color filter and a method for producing the same, an inkjet ink, and a method for producing the pigment dispersion composition.

Conventionally, pigments have a clear color tone, high tinting strength, and weather resistance, and have been widely used in many fields. Among these pigments, those that are practically important are generally those of fine particles, and a clear color tone and high coloring power can be obtained by preventing the pigment from agglomerating and making it finer.
Such fine organic pigments can be used as, for example, paints, printing inks, electrophotographic toners, inkjet inks, color filters, and the like, and are very important compounds. Among them, high performance is required, and particularly important in practical use include inkjet pigments and color filter pigments.

  Conventionally, dyes have been used for coloring materials for ink jet inks, but there are problems in terms of water resistance and light resistance, and pigments having high water resistance and light resistance have been used. An image obtained with a pigment ink has the advantage of being excellent in light resistance and water resistance as compared with an image obtained with a dye-based ink. However, it is difficult to uniformly refine (ie, monodisperse) a nanometer size that can be infiltrated into the voids on the paper surface, and there is a problem of poor adhesion to paper.

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

  However, as the pigment is further refined, the pigment dispersion often exhibits high viscosity. For this reason, when this pigment dispersion is prepared on an industrial scale, it becomes difficult to take out the pigment dispersion from a disperser, it cannot be transported by a pipeline, and further, it is gelled during storage. It could become unusable.

  Therefore, in order to obtain a pigment dispersion or colored photosensitive composition having excellent fluidity and dispersibility, surface treatment of the organic pigment is performed (for example, see Patent Documents 1 and 2), or various dispersants are used. (For example, refer to Patent Documents 3, 4, and 5). However, the organic pigment dispersions prepared by these methods have not yet been sufficiently satisfactory in terms of dispersibility and fluidity.

JP-A-11-269401 Japanese Patent Laid-Open No. 11-302553 JP-A-8-48890 JP 2000-239554 A JP 2007-9117 A

  An object of the present invention is to provide a pigment dispersion composition containing fine pigment particles and having excellent dispersibility and stability. Further, the pigment dispersion composition of the present invention has characteristics suitable as a color material for a color filter, and can be efficiently produced on an industrial scale. Furthermore, the present invention is a pigment dispersion composition that is produced using a pigment dispersion composition having the above-described properties and has high contrast and can exhibit high display performance in a liquid crystal display device, and a photocurable composition using the same. An object of the present invention is to provide a color filter and a method for producing the same, an inkjet ink, and a method for producing a pigment dispersion composition.

The above object has been achieved by the following means.
(1) A pigment dispersion composition comprising a polymer compound having a repeating unit represented by the following general formula (1) or a repeating unit represented by a tautomer structure thereof, and pigment fine particles.

(R ¹ represents a hydrogen atom or a methyl group. J represents —CO—, —COO—, —CONR ⁴ —, —OCO—, a methylene group, a phenylene group, or a —C ₆ H ₄ CO— group. ⁴ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, W represents a single bond or a divalent linking group, R ² represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted group. Represents an aryl group, and R ³ represents a hydrogen atom or a substituent.
(2) The pigment dispersion composition according to (1), wherein the general formula (1) is a repeating unit represented by the following general formula (1A) or a tautomer structure thereof.

(R ¹ , R ² , and R ³ have the same meaning as in general formula (1). W ¹ represents an alkylene group.)
(3) The polymer compound comprises at least a monomer comprising a repeating unit represented by the general formula (1) or the general formula (1A) or a repeating unit represented by a tautomer structure thereof, and ethylene at the terminal. The pigment dispersion composition according to (1) or (2), which is a graft copolymer obtained by copolymerizing a polymerizable oligomer having a polymerizable unsaturated double bond.
(4) The pigment fine particles may contain at least one of a pigment solution obtained by dissolving an organic pigment in a good solvent and a precipitation solvent that is compatible with the good solvent and that is a poor solvent for the organic pigment. The pigment dispersion according to any one of (1) to (3), wherein a molecular compound is contained, and the organic pigment is deposited by mixing the pigment solution and a precipitation solvent. Composition.
(5) The pigment dispersion composition according to any one of (1) to (3), wherein the pigment fine particles are prepared by pulverizing a pigment with a mechanical force.
(6) A photocurable composition comprising the pigment dispersion composition according to any one of (1) to (5), containing a photopolymerizable compound and a photopolymerization initiator.
(7) The photocurable composition as described in (6), further comprising an alkali-soluble resin.
(8) The photocurable composition as described in (6) or (7), which is for producing a color filter.
(9) A color filter having a colored pattern obtained by coating and curing the photocurable composition according to (8) directly or through another layer on a substrate.
(10) A photosensitive film forming step of forming a photosensitive film by applying the photocurable composition according to (8) directly or via another layer to a substrate, and a pattern on the formed photosensitive film And a color pattern forming step of forming a color pattern by sequentially performing exposure and development.
(11) An inkjet ink comprising organic pigment fine particles in the composition according to any one of (1) to (5) contained in a medium containing a polymerizable monomer and / or a polymerizable oligomer. .
(12) The inkjet ink as described in (11), which is for producing a color filter.
(13) When the organic pigment is precipitated and formed by mixing a pigment solution obtained by dissolving an organic pigment in a good solvent and a precipitation solvent that is compatible with the good solvent and that is a poor solvent for the organic pigment. A method for producing a pigment dispersion composition, wherein at least one of the pigment solution and the precipitation solvent contains a polymer compound containing a repeating unit represented by the following general formula (1).

(R ¹ represents a hydrogen atom or a methyl group. J represents —CO—, —COO—, —CONR ⁴ —, —OCO—, a methylene group, a phenylene group, or a —C ₆ H ₄ CO— group. ⁴ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, W represents a single bond or a divalent linking group, R ² represents a hydrogen atom, or a substituted or unsubstituted alkyl group or aryl group. R ³ represents a hydrogen atom or a substituent.)
(14) The polymer compound includes at least a monomer that forms the repeating unit represented by the general formula (1) or a tautomer structure thereof, and an ethylenically unsaturated double bond at the terminal. (13) The method for producing a pigment dispersion composition according to (13), wherein the polymer is a graft copolymer obtained by copolymerizing a polymerizable oligomer having a molecular weight.

  The pigment dispersion composition of the present invention contains fine pigment particles, is excellent in dispersibility and stability, and has characteristics suitable as a color material for a color filter. Further, according to the production method of the present invention, it is possible to efficiently produce the pigment dispersion composition having the above excellent characteristics and its color filter. Furthermore, the above-described pigment dispersion composition of the present invention or the photocurable composition or ink jet thereof can be suitably used for the production of a color filter, and the color filter of the present invention produced using them can be displayed with high contrast. High display performance can be exhibited when used by being incorporated in an apparatus.

  Examples of the pigment forming the pigment fine particles to be contained in the pigment dispersion composition of the present invention include perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, and tria. Reel carbonium, dioxazine, aminoanthraquinone, diketopyrrolopyrrole, indigo, thioindigo, isoindoline, isoindolinone, pyranthrone or isoviolanthrone compound pigment, or a mixture thereof.

  More specifically, for example, perylene compound pigments such as Pigment Red 190, Pigment Red 224, and Pigment Violet 29, Perinone Compound Pigments such as Pigment Orange 43, and Pigment Red 194, Pigment Violet 19, Pigment Violet 42, Pigment Red 122, and Pigment Quinacridone compound pigments such as red 192, pigment red 202, pigment red 207, or pigment red 209, quinacridone quinone compound pigments such as pigment red 206, pigment orange 48, or pigment orange 49, anthraquinone compound pigments such as pigment yellow 147, pigment red 168 Anthrone compound pigments, Pigment Brown 25, Pigment Buy Benzimidazolone compound pigments such as Let 32, Pigment Orange 36, Pigment Yellow 120, Pigment Yellow 180, Pigment Yellow 181, Pigment Orange 62, or Pigment Red 185, Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128 Pigment Yellow 166, Pigment Orange 34, Pigment Orange 13, Pigment Orange 31, Pigment Red 144, Pigment Red 166, Pigment Red 220, Pigment Red 221, Pigment Red 242, Pigment Red 248, Pigment Red 262, Pigment Brown 23, etc. Disazo condensation compound pigment, Pigment Yellow 13, Pigment Yellow 83 or Pigment Yellow 188 or other disazo compound pigments, Pigment Red 187, Pigment Red 170, Pigment Yellow 74, Pigment Yellow 150, Pigment Red 48, Pigment Red 53, Pigment Orange 64, or Pigment Red 247, Pigment Blue 60 and other indanthrone compound pigments, Pigment Green 7, Pigment Green 36, Pigment Green 37, Pigment Blue 16, Pigment Blue 75, and Pigment Blue 15 and other phthalocyanine compound pigments, Pigment Blue 56, and Pigment Blue 61 Dioxadi such as triarylcarbonium compound pigment, pigment violet 23, or pigment violet 37 Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 272, Pigment Orange 71, and Pigment Orange 73, etc. Diketopyrrolopyrrole Compound Pigment, Pigment Red 88 Thioindigo compound pigments such as Pigment Yellow 139 and Pigment Orange 66, isoindoline compound pigments such as Pigment Yellow 109 and Pigment Orange 61, and pyranthrone compound pigments such as Pigment Orange 40 and Pigment Red 216 Alternatively, an isoviolanthrone compound pigment such as Pigment Violet 31 may be used. Among these, quinacridone, benzimidazolone, azo, phthalocyanine, dioxazine, anthraquinone, and diketopyrrolopyrrole compound pigments are preferable, and quinacridone, benzimidazolone, phthalocyanine, and dioxazine compound pigments are more preferable. These organic pigments may be used alone or in combination of two or more.

[Build-up pigment fine particles (first embodiment)]
The pigment dispersion composition of the present invention preferably contains build-up pigment fine particles. The build-up pigment fine particles are, for example, an organic pigment solution in which an organic pigment is dissolved in a good solvent, a solvent that is compatible with the good solvent and is a poor solvent for the organic pigment (hereinafter referred to as this solvent). [Organic pigment poor solvent] or simply [poor solvent]) is preferably mixed (hereinafter referred to as "reprecipitation method"). The dispersion containing the organic nanoparticles obtained at this time is sometimes referred to as “re-precipitation liquid of organic pigment fine particles” or simply “re-precipitation liquid”.

The poor solvent for the organic pigment is not particularly limited as long as it is compatible with or uniformly mixed with a good solvent for dissolving the organic pigment. As a poor solvent for the organic pigment, the solubility of the organic pigment is preferably 0.02% by mass or less, and more preferably 0.01% by mass or less. Although there is no particular lower limit to the solubility of the organic pigment in the poor solvent, 0.000001% by mass or more is practical in consideration of a commonly used organic pigment. This solubility may be the solubility when dissolved in the presence of an acid or alkali. In addition, the compatibility or uniform mixing property of the good solvent and the poor solvent is preferably 30% by mass or more, more preferably 50% by mass or more, with respect to the poor solvent. There is no particular upper limit to the amount of good solvent dissolved in the poor solvent, but it is practical to mix them in an arbitrary ratio.
The poor solvent is not particularly limited as long as it is an aqueous medium. For example, an aqueous solvent (for example, water, hydrochloric acid, sodium hydroxide aqueous solution), alcohol compound solvent, ketone compound solvent, ether compound solvent, aromatic compound solvent , Carbon disulfide solvent, aliphatic compound solvent, nitrile compound solvent, halogen compound solvent, ester compound solvent, ionic liquid, mixed solvent thereof, and the like, aqueous solvent, alcohol compound solvent, ketone compound solvent, ether compound solvent , Ester compound solvents, or mixtures thereof are preferred, and aqueous solvents, alcohol compound solvents, or ester compound solvents are more preferred.

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

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

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

Examples of the 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. Examples of the nitrile compound solvent include acetonitrile. 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, trichloroethylene, iodoform, and the like. Examples of the ester compound solvent include ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, 2- (1-methoxy) propyl acetate and the like. The ionic liquids, for example, 1-butyl-3-methylimidazolium and PF ₆ ^-, etc. and salts thereof. Examples of the amide compound solvent include N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, formamide, N -Methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like. 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, squaric acid, and the like. Examples of the sulfonic acid compound include methanesulfonic acid, p-toluenesulfonic acid, sulfuric acid, chlorosulfonic acid, trifluoromethanesulfonic acid, and the like.

  There are some common examples of those listed as specific examples of good solvents and those listed as poor solvents, but the same solvents are not combined as good solvents and poor solvents. It is sufficient that the solubility in is sufficiently higher than the solubility in a poor solvent. For example, the solubility difference is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. Although there is no particular upper limit to the difference in solubility between the good solvent and the poor solvent, it is practical that the difference is 50% by mass or less in consideration of a commonly used organic pigment.

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

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

  The organic pigment is preferably dissolved uniformly in a good solvent, but it is also preferable to dissolve it in an acidic or alkaline manner. In general, in the case of a pigment having an alkaline and dissociable group in the molecule, alkali is used, and when there is no alkaline and dissociable group and there are many nitrogen atoms in the molecule that are prone to add protons, acidity is used. For example, quinacridone, diketopyrrolopyrrole, disazo condensation compound pigments are alkaline, and phthalocyanine compound pigments are acidic.

  Bases used for alkaline dissolution are inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide or barium hydroxide, or trialkylamine, tetraalkylammonium hydroxide, diazabicyclo. Organic bases such as undecene (DBU), metal alkoxides, preferably tetraalkylammonium hydroxide (eg, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, sodium methoxide, potassium-t-butoxide) and inorganic Base (eg, sodium hydroxide, potassium hydroxide).

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

  Acids used for acidic dissolution are inorganic acids such as sulfuric acid, hydrochloric acid, or phosphoric acid, or organic acids such as formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, or trifluoromethanesulfonic acid. An inorganic acid is preferable. Particularly preferred are formic acid, methanesulfonic acid and sulfuric acid.

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

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

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

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

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

[Breakdown Pigment Fine Particles (Second Embodiment)]
As another preferred embodiment, the pigment dispersion composition of the present invention preferably contains fine pigment particles (breakdown pigment fine particles) produced by pulverizing a pigment with a mechanical force. In that case, it can obtain by mixing various solvents, resin, varnish etc. if necessary, and disperse | distributing with a horizontal sand mill, a vertical sand mill, an annular bead mill, an attritor, etc. The specific polymer compound (specific polymer) and other pigment dispersants to be described later may be dispersed after mixing all components. First, the pigment and the specific polymer compound (specific polymer), etc. Alternatively, only the pigment or only the pigment and the pigment dispersant may be dispersed, and then another component may be added and dispersed again.
Also, before dispersing with a horizontal sand mill, vertical sand mill, annular bead mill, attritor, etc., pre-dispersion using a kneader mixer such as a kneader, 3-roll mill, solid dispersion with 2-roll mill, etc., or pigment A synergist having a basic group and / or a dispersant may be treated. Moreover, a disperser and a mixer such as a high speed mixer, a homomixer, a ball mill, a roll mill, a stone mill, and an ultrasonic disperser can be used.

  In the pigment dispersion composition of the present invention, the concentration of the organic pigment particles is not particularly limited. For example, in the embodiment using the build-up pigment fine particles (first embodiment), the aqueous medium is used for reprecipitation of the organic pigment fine particles. The organic pigment fine particles are preferably in the range of 10 to 40,000 mg, more preferably in the range of 20 to 30000 mg, and particularly preferably in the range of 50 to 25000 mg with respect to 1000 ml. On the other hand, in the embodiment using the breakdown pigment fine particles (second embodiment), it is preferable that the organic pigment fine particles are contained in the range of 1 g to 500 g with respect to 1000 ml of the dispersion medium in the dispersion after pulverization. Is in the range of 10 g to 400 g, particularly preferably in the range of 50 g to 300 g. In the present invention, the pigment dispersion composition may be a liquid composition such as the reprecipitation liquid, or may be a paste composition, a powder composition, a solid composition, or the like.

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

  In the present invention, the ratio (Mv / Mn) of the volume average particle diameter (Mv) and the number average particle diameter (Mn) is used as an index representing the monodispersity of the particles unless otherwise specified. The monodispersity of the particles (primary particles) contained in the organic pigment fine particle dispersion used in the organic pigment fine particle concentration method, that is, Mv / Mn is preferably 1.0 to 2.0, and preferably 1.0 to 2.0. 1.8 is more preferable, and 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 microscope method, a weight method, a light scattering method, a light blocking method, an electric resistance method, an acoustic method, and a dynamic light scattering method. Is particularly preferred. Examples of the microscope used for the microscopy include a scanning electron microscope and a transmission electron microscope. Examples of the particle measuring apparatus based on the dynamic light scattering method include Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd., Dynamic Light Scattering Photometer DLS-7000 series manufactured by Otsuka Electronics Co., Ltd., and LB-400 manufactured by Horiba, Ltd. Product name).

In the present invention, in preparing the dispersion liquid by depositing the organic pigment fine particles in the first embodiment, a dispersant may be contained in at least one of the organic pigment solution and the poor solvent. Alternatively, this dispersant may be added before or after pulverization in the second embodiment. In the first embodiment, at least a dispersant in the organic pigment solution (in the present invention, the dispersant added at the time of particle precipitation is simply referred to as “dispersant” or “dispersant for reprecipitation”, which will be described later. It may preferably be distinguished from “hydrophobizing dispersant”).
As a dispersant that can be used, for example, a low molecular or high molecular dispersant of anionic, cationic, amphoteric, nonionic or pigment derivative can be used. The addition amount of the low molecular weight or high molecular dispersant is preferably 10% by mass or more and 1000% by mass or less with respect to the dissolved pigment. Furthermore, 10 mass% or more and 200 mass% or less are more preferable. When the amount is too small, the effect of suppressing the growth and aggregation of the pigment particles is reduced. When the amount is too large, problems such as an increase in viscosity and poor dissolution are likely to occur.

  The molecular weight of the polymer dispersant is preferably 1,000 to 200,000 in terms of number average molecular weight. Furthermore, 3,000 or more and 40,000 or less are more preferable. If the molecular weight is too low, the effect of suppressing the growth and strong aggregation of the pigment particles is reduced. If the molecular weight is too high, problems such as an increase in viscosity and poor dissolution tend to occur. In addition, the high molecular compound in this invention points out the thing of 1000 or more in a number average molecular weight.

  The polymer dispersant is nonionic, specifically, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene glycol, polypropylene glycol, polyacrylamide, polydimethylaminopropyl acrylamide, vinyl alcohol-vinyl acetate copolymer. Polymer, polyvinyl alcohol-partial formalized product, polyvinyl alcohol-partial butyralized product, vinylpyrrolidone-vinyl acetate copolymer, vinylpyrrolidone-dimethylaminopropylacrylamide, vinylpyrrolidone-vinylpyridine copolymer, vinylpyrrolidone-vinylimidazole copolymer Polymer, polyethylene oxide / propylene oxide block copolymer, polyethylene oxide / propylene oxide random copolymer, etc. Among them, polyvinylpyrrolidone, polydimethylaminopropylacrylamide, vinylpyrrolidone-dimethylaminopropylacrylamide, vinylpyrrolidone-vinylpyridine copolymer, vinylpyrrolidone-vinylimidazole copolymer, polyethylene oxide / propylene oxide block copolymer, A polyethylene oxide / propylene oxide random copolymer is preferred.

Examples of anionic substances include polyacrylates, polyvinyl sulfates, polybenzene sulfonates, condensed naphthalene sulfonates, cellulose derivatives, and starch derivatives. Among these, polybenzene sulfonate and condensed naphthalene sulfonate are more preferable.
These anionic ones can be obtained by copolymerizing an anionic monomer, but they may be copolymerized with not only the anionic monomer itself but also a nonionic monomer. Specific examples of the nonionic monomer include vinyl pyrrolidone, styrene, naphthalene, styryl methyl chloride, vinyl imidazole, vinyl pyridine, acrylamide, vinyl amide, dimethylaminopropyl acrylamide, and the like.

As the cationic compound, a polymer compound having a quaternary ammonium moiety is particularly preferable. Poly (methacryloxyalkylammonium salt), poly (methacryloxyarylammonium salt), poly (acryloxyalkylammonium salt), poly (acrylic) Oxyarylammonium salts), poly (diallylammonium salts), polystyrylmethyleneimidazolium salts, polystyrylmethylenepyridinium salts, and the like. In addition, natural polymers such as alginate, gelatin, albumin, casein, gum arabic, tragacanth gum, and lignin sulfonate can also be used.
As the amphoteric one, copolymers of those mentioned above as anionic and cationic are preferable.

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

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

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

The amphoteric one is a dispersant having both an anionic group part in the molecule of the anionic dispersant and a cationic group part in the molecule of the cationic dispersant.
Nonionic ones include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, etc. Can do. Among these, polyoxyethylene alkyl aryl ether is preferable. These nonionic dispersants can be used alone or in combination of two or more.

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

  In the said 1st embodiment, when preparing the organic pigment solution dissolved in the good solvent, it is also preferable to coexist the pigment dispersant containing an amino group. In the second embodiment, it may be added before and after pulverization. Here, the amino group includes a primary amino group, a secondary amino group, and a tertiary amino group, and the number of amino groups may be one or more. A pigment derivative compound in which a substituent having an amino group is introduced into the pigment skeleton, or a polymer compound having a monomer having an amino group as a polymerization component may be used. Examples thereof include, for example, compounds described in JP-A Nos. 2000-239554, 2003-96329, 2001-31885, JP-A-10-339949, and JP-B-5-72943. However, it is not limited to these.

In the present invention, after preparing an aqueous dispersion of organic pigment fine particles, an acid may be added to form a hydrophilic aggregate. In preparing the aqueous dispersion by precipitating the organic pigment fine particles, in the first embodiment, an acid is added to a poor solvent, and the pigment solution is added thereto to make the organic pigment fine particles as hydrophilic aggregates. It is preferable to obtain. In particular, it is preferable to obtain a hydrophilic aggregate by adding an acid to a poor solvent. Here, the “hydrophilic aggregate” in the present invention refers to an aggregate in a state where the surface of the aggregate or the organic pigment fine particles constituting the aggregate is coated with a hydrophilic dispersant. Here, a value calculated for the dispersant using the theoretical formula of solubility parameter (SP value) proposed by Toshinao Okitsu (Journal of the Adhesion Society of Japan Vol. 29, No. 6 (1993) 249-259) 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 fine particles are aggregated, but usually has an average particle diameter of about 5 μm, preferably 0.04 to 10 μm.
The acid used for forming the hydrophilic 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 forming the hydrophilic aggregate is not particularly limited as long as the aggregate is formed, but is preferably pH 1 to 6, more preferably pH 2 to 4.

  The pigment dispersion composition of the present invention comprises a polymer compound (hereinafter referred to as a specific polymer) containing the organic pigment fine particles and a repeating unit represented by the following general formula (1) or a repeating unit having a tautomer structure thereof. May also be included). In the first embodiment, the specific polymer is preferably used as a pigment dispersant (dispersant for reprecipitation). In the second embodiment, the specific polymer is used as a dispersant added before or after pulverization. It is preferable. This dispersant is particularly preferably used as a dispersant exhibiting not only Van-der-Wals interactions but also hydrogen bonding interactions. And by having a thiobarbitur group having a high affinity for the pigment, a stable dispersion can be obtained because the adsorptivity with the pigment is good. Further, since it is a polymer compound having a specific repeating structural unit, a steric repulsion effect of the polymer chain can be expected, and dispersion stabilization by this can be achieved.

Here, tautomerism will be described. Tautomerism is reversible interconversion between isomers, and is a phenomenon in which hydrogen atoms are rearranged mainly by proton rearrangement. In addition, tautomers refer to those in which interconvertible structural isomers can reach an equilibrium state in which both isomers can coexist at a high rate of isomerization. A common example occurs by a rearrangement reaction of a hydrogen atom, or proton, involving the conversion of a single bond and a double bond. The rate of isomerization and the equilibrium ratio vary depending on the temperature, pH, liquid phase or solid phase, and in the case of a solution, the type of solvent. Even when equilibrium is reached for several hours to several days, it is often referred to as tautomerism.
In the present invention, the chemical structure (part) showing the tautomerism in the polymer compound is referred to as tautomer structure (part), and tautomerization in the repeating unit represented by the general formula (1) is performed. The chemical structure (tautomer structure) obtained by the reaction is as shown in the following formulas (a) to (h).

  In the present invention, the “substituent” may be any group that can be substituted. For example, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aryloxy group, Heterocyclic oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, arylsulfonyloxy group, Heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic sulfonamide group, aryl sulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonylamino group, Aryloxycarbonylamino group, heterocycle Xoxycarbonylamino group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic thio group, arylthio group, hydroxy group, cyano group, sulfo group, carboxyl group, aliphatic oxyamino group, aryloxyamino group, carbamoylamino group, sulfo group Examples include a famoylamino group, a halogen atom, a sulfamoylcarbamoyl group, a carbamoylsulfamoyl group, a dialiphatic oxyphosphinyl group, and a diaryloxyphosphinyl group.

  The specific polymer used in the present invention is a heterocyclic group-containing polymer compound containing a repeating unit represented by the following general formula (1) or a repeating unit having a tautomer structure as described above. As described above, it is possible to stabilize the dispersion of the pigment dispersion composition by using the steric repulsion effect between the pigment and the polymer chain by using the polymer compound having the specific repeating structural unit. It is as follows.

In general formula (1), R ¹ represents a hydrogen atom or a methyl group.
In General Formula (1), J represents —CO—, —COO—, —CONR ⁴ —, —OCO—, a methylene group, a phenylene group, or —C ₆ H ₄ CO—. Of these, J is preferably -CO-, a phenylene group, or a benzoyl group. R ⁴ is a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an n-hexyl group, an n-octyl group, a 2-hydroxyethyl group), an aryl Represents a group (for example, a phenyl group), preferably a hydrogen atom, a methyl group, or an ethyl group.

W represents a single bond or a divalent linking group. Examples of the divalent linking group include a linear, branched or cyclic alkylene group, an aralkylene group, and an arylene group, and these may have a substituent.
The alkylene group represented by W is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms. For example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an octylene group, a decylene group, and the like can be given. Among them, a methylene group, an ethylene group, a propylene group, and the like are particularly preferable.
The aralkylene group represented by W is preferably an aralkylene group having 7 to 13 carbon atoms, and examples thereof include a benzylidene group and a cinnamylidene group.
The arylene group represented by W is preferably an arylene group having 6 to 12 carbon atoms, and examples thereof include a phenylene group, a cumenylene group, a mesitylene group, a tolylene group, and a xylylene group, and among them, a phenylene group is particularly preferable.

During divalent linking group represented by ^{W, -NR 7 -, - NR} 7 R 8 -, - COO -, - OCO -, - O -, - SO 2 NH -, - NHSO 2 -, - NHCOO-, -OCONH-, or a group derived from a heterocyclic ring (a divalent group formed by removing two hydrogen atoms from a heterocyclic compound) may be interposed as a bonding group. R ⁷ and R ⁸ each independently represent hydrogen or an alkyl group, and preferred examples include hydrogen, a methyl group, an ethyl group, and a propyl group.
Among the linking groups represented by W, a single bond or an alkylene group is preferable, and a single bond, a methylene group, an ethylene group, or a 2-hydroxypropylene group is particularly preferable.

S is a sulfur atom.
R ² represents a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group. Among these, a hydrogen atom, a methyl group, an ethyl group, a 2-ethylhexyl group, or a phenyl group is preferable.
R ³ represents a hydrogen atom or a substituent.
Among them, the substituent represented by R ³ preferably has a structure represented by the following general formula (7).

R ²³ represents a substituted or unsubstituted aromatic ring or a heteroatom-containing (eg, oxygen atom, sulfur atom, nitrogen atom) heterocycle. Among them, the structure of the aromatic ring and the heterocyclic ring is preferably a 5-membered to 6-membered monocyclic or bicondensed ring. Among them, benzene ring, pyridine ring, pyrimidine ring, imidazole ring, isoxazole ring, oxazole ring, thiazole ring, pyrazole ring, triazole ring, tetrazole ring, benzimidazole ring, benzthiazole ring, benzoxazole ring, benzisoxazole ring A benzothiazole thiadiazole ring is preferred.
It is preferable that the general formula (1) is further represented by the general formula (1A). In General Formula (1A), W ¹ represents an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms. For example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an octylene group, a decylene group and the like can be mentioned, and among them, a methylene group is particularly preferable. R < ¹ > -R < ³ > is synonymous with General formula (1).

  Hereinafter, preferred specific examples of the repeating unit represented by the general formula (1) will be given, but the present invention is not limited thereto. In addition, the structure given in this specific example is an example of possible tautomeric structures, and other tautomeric structures can be taken.

  The specific polymer to be contained in the pigment dispersion composition of the present invention is a copolymer of the monomer that forms the repeating unit represented by the general formula (1) or a repeating unit having a tautomer structure thereof and other monomers. A polymer is preferred. Examples of other copolymerizable monomers include unsaturated carboxylic acids (eg, (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid), unsaturated sulfonic acids (eg, 2-acrylamide-2) -Methyl-propanesulfonic acid, etc.), aromatic vinyl compounds (eg, styrene, α-methylstyrene, 4-tbutylstyrene, N, N-dimethyl-4-vinylbenzamide, N, N-dipropyl 4-vinylbenzamide, N, N-dioctyl 4-vinylbenzamide, vinyltoluene, 2-vinylpyridine, 4-vinylpyridine, N-vinylimidazole, etc.), (meth) acrylic acid alkyl esters (eg, methyl (meth) acrylate, ethyl (meth)) Acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, etc.), (Meth) acrylic acid alkyl aryl esters (eg, benzyl (meth) acrylate), (meth) acrylic acid substituted alkyl esters (eg, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, etc.), carboxylic acid vinyl esters (Eg, vinyl acetate and vinyl propionate), vinyl cyanide (eg, (meth) acrylonitrile and α-chloroacrylonitrile), and aliphatic conjugated dienes (eg, 1,3-butadiene and isoprene). Among these, unsaturated carboxylic acids, aromatic vinyl compounds, (meth) acrylic acid alkyl esters, and (meth) acrylic acid alkyl aryl esters are preferable, and unsaturated carboxylic acids and aromatic vinyl compounds are more preferable.

  The specific polymer is a repeating unit represented by the general formula (1) or a repeating unit having a tautomer structure thereof, and at least one of the following general formulas (4), (5), and (6). It is preferable that it is a copolymer compound containing the above repeating unit.

In the general formula (4), R ¹⁷ represents a hydrogen atom or a methyl group.
In the general formula (4), R ¹⁸ represents a substituted or unsubstituted aryl group. Of these, a phenyl group, a tbutylphenyl group, an N, N-dimethylbenzamide group, and a naphthalene group are preferable.
In General Formula (5), R ¹⁹ represents a hydrogen atom or a methyl group.
In the general formula (5), R ²⁰ represents a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group. Among these, a hydrogen atom, a methyl group, an ethyl group, an n-butyl group, a t-butyl group, a 2-hydroxyethyl group, a dimethylaminoethyl group, a benzyl group, an adamantyl group, a glycidyl group, a cyclohexyl group, and a 2-ethylhexyl group are preferable. .
In general formula (6), R ²¹ represents a hydrogen atom or a methyl group.
In the general formula (6), R ²² represents a substituted or unsubstituted alkyl group or aryl group. Of these, a methyl group, an ethyl group, an n-butyl group, and a dimethylaminopropyl group are preferable.

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

Moreover, it is preferable that this macromonomer has the number average molecular weight (Mn) of polystyrene conversion in the range of 1000-10000, and the range of 2000-9000 is especially preferable.
The polymer chain portion is a homopolymer or copolymer formed from at least one monomer selected from the group consisting of alkyl (meth) acrylate, styrene and derivatives thereof, acrylonitrile, vinyl acetate and butadiene, or polyethylene oxide. Polypropylene oxide and polycaprolactone are generally used.
The polymerizable oligomer is preferably an oligomer represented by the following general formula (2).

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

  The polymerizable oligomer is preferably not only a polymerizable oligomer represented by the general formula (2) but also a polymerizable oligomer represented by the following general formula (3).

In the general formula (3), R ¹³ represents a hydrogen atom or a methyl group, and R ¹⁴ represents an alkylene group having 1 to 8 carbon atoms. Q represents ^{-OR 15} or -OCOR ^16. Here, R ¹⁵ and R ¹⁶ represent a hydrogen atom, an alkyl group, or an aryl group. n represents 2 to 200. ]
In the general formula (3), R ¹³ represents a hydrogen atom or a methyl group. R ¹⁴ represents an alkylene group having 1 to 8 carbon atoms. Among them, an alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 2 to 3 carbon atoms is more preferable. Q represents ^{-OR 15} or -OCOR ^16. Here, R ¹⁵ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a phenyl group substituted with an alkyl group having 1 to 18 carbon atoms. R ¹⁶ represents an alkyl group having 1 to 18 carbon atoms. Moreover, n represents 2-200, 5-100 are preferable and 10-100 are especially preferable.

Examples of the polymerizable oligomer represented by the general formula (3) include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, and polytetramethylene glycol monomethacrylate. These may be commercially available products or may be appropriately synthesized.
The polymerizable monomer represented by the general formula (3) is also available as a commercial product as described above, and as a commercial product, methoxypolyethylene glycol methacrylate (trade names: NK ester M-40G, M-90G, M -230G (manufactured by Shin-Nakamura Chemical Co., Ltd.); trade names: Blemmer PME-100, PME-200, PME-400, PME-1000, PME-2000, PME-4000 (above, NOF Corporation) Manufactured)), polyethylene glycol monomethacrylate (trade names: Blemmer PE-90, PE-200, PE-350, manufactured by NOF Corporation), polypropylene glycol monomethacrylate (trade names: Blemmer PP-500, PP-800, PP-1000, manufactured by NOF Corporation), polyethylene glycol polypropylene glycol mono Tacrylate (trade name: Blemmer 70PEP-350B, manufactured by NOF Corporation), polyethylene glycol polytetramethylene glycol monomethacrylate (trade name: BREMMER 55PET-800, manufactured by NOF Corporation), polypropylene glycol polytetramethylene glycol mono Methacrylate (trade name: Bremer NHK-5050, manufactured by NOF Corporation), and the like.
In addition to the polymerizable oligomers represented by the general formulas (2) and (3), polycaprolactone monomers are also preferable. Examples of commercially available products include polycaprolactone monomethacrylate (trade names: Plaxel FM2D, FM3, FM5, FA1DDM, FA2D, Daicel Chemical). Kogyo Co., Ltd.).

  The specific polymer contained in the pigment dispersion composition of the present invention may be a copolymer with a monomer having a nitrogen atom. Specific examples of the monomer having a nitrogen atom include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, 1- (N, N-dimethylamino) -1, 1- Dimethylmethyl (meth) acrylate, N, N-dimethylaminohexyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diisopropylaminoethyl (meth) acrylate, N, N-di-n- Butylaminoethyl (meth) acrylate, N, N-di-i-butylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, piperidinoethyl (meth) acrylate, 1-pyrrolidinoethyl (meth) acrylate, N, N -Methyl-2-pyrrolidylaminoethyl (meth) acrylate DOO and N, N- methylphenyl aminoethyl (meth) acrylate (or (meth) acrylates);

Dimethyl (meth) acrylamide, diethyl (meth) acrylamide, diisopropyl (meth) acrylamide, di-n-butyl (meth) acrylamide, di-i-butyl (meth) acrylamide, morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide and N, N-methylphenyl (meth) acrylamide (above (meth) acrylamides);
2- (N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, N-diethylamino) ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth) acrylamide, 3- (N , N-dimethylamino) propyl (meth) acrylamide, 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylamide and 6- (N, N-diethylamino) hexyl (meth) acrylamide (above) Aminoalkyl (meth) acrylamides);
p-vinylbenzyl-N, N-dimethylamine, p-vinylbenzyl-N, N-diethylamine, p-vinylbenzyl-N, N-dihexylamine (above vinylbenzylamines);
N, N-dimethyl-4-vinylbenzamide, N, N-dipropyl-4-vinylbenzamide, N, N-dioctyl 4-vinylbenzamide (above vinylbenzamides); and 2-vinylpyridine, 4-vinylpyridine, N- Mention may be made of vinylimidazoles. Among these, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, 3- (N, N-diethylamino) propyl (meth) acrylamide, 3- (N, N- Dimethylamino) propyl (meth) acrylamide, N, N-dimethyl-4-vinylbenzamide, N, N-dioctyl 4-vinylbenzamide, 2-vinylpyridine, 4-vinylpyridine and N-vinylimidazole are preferred.

The specific polymer in the present invention has a repeating unit represented by the general formula (1), and further has the general formulas (4), (5), (6), the polymerizable oligomer (macromonomer), and nitrogen. It is preferably a copolymer comprising at least one repeating unit selected from atom-containing monomers (may be selected in duplicate).
It is preferable that the copolymer has a repeating unit represented by the general formula (1) in a range of 2 to 70% by mass (particularly 5 to 30% by mass) of all repeating units. When it has a repeating unit represented by General formula (4), it is preferable to have in the range of 10-90 mass% (especially 30-90 mass%) of all the repeating units. When it has a repeating unit represented by General formula (5), it is preferable to have in the range of 2-50 mass% (especially 5-30 mass%) of all the repeating units. When it has a repeating unit represented by General formula (6), it is preferable to have in the range of 2-50 mass% (especially 5-30 mass%) of all the repeating units. When it has a unit given from the above-mentioned polymerizable oligomer (macromonomer), it is preferred to have in the range of 30-80 mass% (especially 50-80 mass%) of all repeating units. It is preferable to have a repeating unit derived from a monomer having a nitrogen-containing group in a range of 2 to 80% by mass (particularly 5 to 50% by mass) of all repeating units.

  Furthermore, when using other monomer copolymerizable with these, it is preferable to have the repeating unit derived from this monomer in the range of 2-50 mass% of all the repeating units, and to have in the range of 5-30 mass%. Is particularly preferred. The weight average molecular weight (Mw) of the copolymer is preferably in the range of 1,000 to 200,000, and particularly preferably in the range of 10,000 to 100,000. In the present invention, unless otherwise specified, the molecular weight of the polymer compound or polymer refers to the weight average molecular weight, and is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (carrier: tetrahydrofuran).

Although the example of the said specific copolymer containing the repeating unit represented by General formula (1) or the repeating unit which has the tautomer structure is shown below, this invention is not restrict | limited to these.
(1) Monomer / Styrene / Methacrylic Acid Copolymer Providing Component M-1 (2) Monomer / Terminal Methacryloylated Polymethyl Methacrylate Copolymer / Methacrylic Acid Copolymer (3) Providing Component M-1 ) Monomer / terminal methacryloylated polymethylmethacrylate copolymer / dimethylaminopropylacrylamide copolymer to give component M-1 (4) Monomer / terminal methacryloylated polystyrene / methacrylic acid copolymer to give component M-1 (5) Monomer / terminal methacryloylated polybutylmethacrylate / methacrylic acid copolymer providing the above component M-1 (6) Monomer / terminal (meth) acryloylated polyethylene glycol polypropylene glycol / methacrylic providing the above component M-1 Acid copolymer ( ) Monomer / terminal (meth) acryloylated polyethylene glycol / methacrylic acid copolymer providing the above component M-1 (8) Monomer / terminal (meth) acryloylated polypropylene glycol / methacrylic acid copolymer providing the above component M-1 Polymer (9) Monomer / Terminal Methacryloylated Polycaprolactone / Methacrylic Acid Copolymer Providing Component M-1 (10) Monomer / Terminal Methacryloylated Polystyrene / Methacrylic Acid / Dimethylaminopropyl Providing Component M-1 Acrylamide copolymer

(11) Monomer / terminal methacryloylated polymethyl methacrylate copolymer that provides the constituent component M-1 (12) Monomer / styrene / dimethylaminopropylacrylamide copolymer that provides the constituent component M-1 (13) The constituent component Monomer that gives M-1 / N, N-dimethyl-4-vinylbenzamide / methacrylic acid copolymer (14) Monomer that gives the above component M-1 / 4-tbutylstyrene / methacrylic acid copolymer (15) Monomer / Methacrylic acid / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (16) for Providing Component M-3 Monomer / Methacrylic Acid / Polyethylene Glycol Mono (meth) acrylate Copolymer (17) for Providing Component M-4 ) Monomer / methacrylic acid / providing the above component M-5 End-methacryloylated polycaprolactone copolymer (18) Monomer that gives component M-2 / 3- (N, N-dimethylamino) propylacrylamide / terminal methacryloylated polymethylmethacrylate copolymer (19) Component M Monomer to give -6 / 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate copolymer (20) Monomer to give the above component M-7 / Methacrylic acid / Terminal methacryloylated polymethyl Methacrylate / polyethylene glycol mono (meth) acrylate copolymer

(21) Monomer giving the above component M-8 / 2- (N, N-dimethylamino) ethyl (meth) acrylate / N, N-dimethyl-4-vinylbenzamide (22) giving the above component M-9 Monomer / 4-vinylpyridine / terminal methacryloylated polymethylmethacrylate copolymer (23) Monomer / terminal methacryloylated polybutylmethacrylate / N-vinylimidazole copolymer (24) above component M giving the component M-10 -11 monomer / methacrylic acid / terminated methacryloylated poly n-butyl methacrylate copolymer (25) Monomer / acrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (26) Monomer / Styrene / Meta to give Component M-13 Rylic acid copolymer (27) Monomer / methacrylic acid / terminal methacryloylated polymethylmethacrylate copolymer (28) Monomer / methacrylic acid / terminal methacryloylated polystyrene to give constituent M-6 Copolymer (29) Monomer that provides the above component M-3 / 3- (N, N-dimethylamino) propylacrylamide / terminated methacryloylated polymethyl methacrylate copolymer (30) Monomer that provides the above component M-3 / N, N-dimethyl-4-vinylbenzamide / methacrylic acid copolymer

(31) Monomer / 4-vinylpyridine / terminal methacryloylated polystyrene copolymer providing the above component M-7 (32) Monomer / methacrylic acid / terminal methacryloylated polymethyl methacrylate copolymer providing the above component M-7 (33) Monomer / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer that provides the constituent component M-8 (34) Monomer / styrene / methacrylic acid / methacrylic acid methyl ester copolymer that provides the constituent component M-1 (35) Monomer / styrene / butyl methacrylate copolymer that provides the above component M-1 (36) Monomer / methacrylic acid tbutyl ester / methacrylic acid copolymer that provides the above component M-2 (37) Monomer / Styrene / 4- giving component M-3 Butylstyrene copolymer (38) Monomer that provides component M-1 / styrene / butylacrylamide copolymer (39) Monomer that provides component M-5 / methylacrylamide / methacrylic acid copolymer (40) Monomer giving component M-6 / methacrylic acid methyl ester / ethyl acrylamide (41) Monomer giving component M-1 / benzyl methacrylate / isopropyl acrylamide / styrene

  Such a specific polymer can be obtained by radical polymerization of a monomer in a solvent. At that time, a radical polymerization initiator is generally used, but in addition to the initiator, a chain transfer agent (eg, 2-mercaptoethanol and dodecyl mercaptan) may be added and synthesized.

In the pigment dispersion composition of the present invention, the specific polymer may be one kind or a combination of two or more kinds. The content of the specific polymer in the pigment dispersion is in the range of 0.1 to 1000 parts by mass with respect to 100 parts by mass of the organic pigment in order to further improve the uniform dispersibility and storage stability of the organic pigment. It is preferably in the range of 1 to 500 parts by mass, and more preferably in the range of 10 to 250 parts by mass. If this amount is too small, the dispersion stability of the organic pigment fine particles may not be improved. In the pigment dispersion composition of the present invention, the specific polymer may be present in the composition independently of the organic pigment fine particles, or may be incorporated into the organic pigment fine particles. Or you may adsorb | suck to organic pigment fine particles, and may exist in the state which combined these.
In addition to the specific polymer, other pigment dispersants can be used in combination with the pigment dispersion of the present invention as long as the effects are not impaired. The addition amount is preferably 50% by mass or less of the specific polymer.

  In the said 1st embodiment, it is preferable to contain the said 3rd solvent different from any of the said good solvent and poor solvent used for precipitation of pigment fine particles in the liquid mixture after pigment fine particle precipitation. Although the kind of 3rd solvent is not specifically limited, It is preferable that it is an organic solvent, for example, an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, an aliphatic compound solvent is preferable, an ester compound solvent, an aromatic compound solvent or Aliphatic compound solvents are more preferred, and ester compound solvents are particularly preferred. The third solvent may be a pure solvent based on the above solvent or a mixed solvent composed of a plurality of solvents. At this time, it is preferable to incorporate the polymer compound having a mass average molecular weight of 1000 or more into the third solvent and introduce it together to redisperse the pigment fine particle concentrate or its powder. In addition, not only the above-mentioned third solvent but also a solvent different from both the good solvent and the poor solvent, which is a medium of the composition, including a fourth solvent described later, is referred to as “third”. Solvent of

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

  Of these, ethyl lactate, ethyl acetate, and ethanol are preferable, and ethyl lactate is more preferable. These may be used alone or in combination of two or more. The third solvent is not the same as the first solvent or the second solvent.

  The timing of the addition of the third solvent is not particularly limited as long as it is after the pigment fine particles are precipitated, but a part of the solvent of the mixed liquid in which the pigment fine particles are precipitated is previously removed (concentrated) (first removal), and then It is preferable to add to. That is, it is preferable that the third solvent is used as a substitution solvent, and the solvent component consisting of the first solvent and the second solvent in the dispersion liquid in which the pigment fine particles are precipitated is substituted with the third solvent.

  In addition, when a pigment dispersion composition to be described later is used, after the first solvent removal step (first removal), the third solvent is added to replace the solvent, and the second solvent removal step ( It is preferable to remove the solvent by the second removal) and pulverize. And a binder and / or a solvent can be added after that, and it can be set as a desired pigment dispersion composition. The amount of the third solvent added is not particularly limited, but is preferably 100 to 300,000 parts by mass, and more preferably 500 to 10,000 parts by mass with respect to 100 parts by mass of the pigment fine particles.

  The pigment fine particles can be used, for example, in a dispersed state in a vehicle. The vehicle refers to a portion of a medium in which a pigment is dispersed when it is in a liquid state, a portion that is liquid and binds to the pigment to harden a coating film (binder). And a component (organic solvent) to be dissolved and diluted. In the present invention, the binder used for nanoparticle formation and the binder used for redispersion may be the same or different.

  The pigment fine particle concentration of the dispersion composition of the pigment fine particles after redispersion is appropriately determined according to the purpose, but preferably the pigment fine particles are preferably 2 to 30% by mass with respect to the total amount of the dispersion composition. More preferably, it is 20 mass%, and it is especially preferable that it is 5-15 mass%. In the case of dispersing in the vehicle as described above, the amount of the binder and dissolved dilution component is appropriately determined depending on the type of the organic pigment and the like, but the binder is 1 to 30% by mass with respect to the total amount of the dispersion composition. Preferably, it is 3-20 mass%, More preferably, it is 5-15 mass%. It is preferable that a dissolution dilution component is 5-80 mass%, and it is more preferable that it is 10-70 mass%.

  The organic pigment fine particles in the present invention are preferably subjected to a predetermined treatment / operation in the dispersion composition to form soft aggregates of fine particles. Here, soft agglomeration is an agglomeration that is weak enough to be redispersed as necessary, and the soft agglomerates are sometimes called flocs. In this way, for example, organic pigment fine particles precipitated in an aqueous dispersion composition can be quickly separated by filtration or the like. Then, the separated soft agglomerates can be re-dispersed in an organic solvent suitable for production of a color filter, and an organic solvent-based dispersion composition can be efficiently obtained. That is, when the mixed solvent of the good solvent and the poor solvent is an aqueous solvent, the dispersion medium (continuous phase) can be switched by efficiently replacing it with a third solvent made of an organic solvent. The average particle size of the aggregate is not particularly limited, but is preferably 0.5 to 500 μm and preferably 5 to 100 μm in consideration of the filterability described above and redispersibility in the third solvent in the subsequent step. More preferred.

As a method of redispersing the pigment fine particles (floc) in such a soft aggregation state, for example, a dispersion method using ultrasonic waves or a method of applying physical energy can be used. The ultrasonic irradiation device used preferably has a function capable of applying an ultrasonic wave of 10 kHz or higher, and examples thereof include an ultrasonic homogenizer and an ultrasonic cleaner. When the liquid temperature rises during ultrasonic irradiation, thermal aggregation of the nanoparticles occurs, so the liquid temperature is preferably 1 to 100 ° C, more preferably 5 to 60 ° C. The temperature control method can be performed by controlling the dispersion temperature, controlling the temperature of the temperature adjusting layer that controls the temperature of the dispersion, or the like.
The disperser used when dispersing the pigment fine particles by applying physical energy is not particularly limited, and examples include dispersers such as a kneader, roll mill, atrider, super mill, dissolver, homomixer, and sand mill. It is done. In addition, a high-pressure dispersion method and a dispersion method using fine particle beads are also preferable.

  The photocurable composition of the present invention is preferably the following colored photosensitive resin composition. The colored photosensitive resin composition (pigment-dispersed photoresist) contains the organic pigment fine particles and a monomer or oligomer (polymerizable compound), and preferably further contains a binder and a photopolymerization initiator or photopolymerization initiator system. Hereinafter, each component of the colored photosensitive resin composition will be described.

  The organic pigment fine particles and the method for producing the powder have already been described in detail. The content of the pigment fine particles in the colored photosensitive resin composition is preferably 3 to 90% by mass with respect to the total solid content (in the present invention, the total solid content refers to the total composition excluding the organic solvent). 20-80 mass% is more preferable, and 25-60 mass% is further more preferable. If this amount is too large, the viscosity of the dispersion increases, which may cause problems in production suitability. If the amount is too small, the coloring power is not sufficient. Moreover, you may use it in combination with a normal pigment for toning. As the pigment, those described above can be used.

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

Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in Japanese Patent Publication No. 52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid.
Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.
In addition, “polymerizable compound B” described in JP-A-11-133600 can also be mentioned as a preferable example.

  Monomers or oligomers may be used alone or in admixture of two or more. The content of the colored photosensitive resin composition with respect to the total solid content is generally 5 to 50% by mass, and 10 to 40% by mass. Is preferred. If this amount is too large, it becomes difficult to control the developability, which causes a problem in production suitability. If the amount is too small, the curing power at the time of exposure is insufficient.

  As the binder, a binder having an acidic group is preferable, and it can be added at the time of preparing an inkjet ink for a color filter or a colored photosensitive resin composition, but at the time of producing the pigment fine particle dispersion composition or at the time of forming pigment fine particles. It is also preferable to add. It is also possible to add a binder to both or one of the poor solvent for adding the organic pigment solution and the organic pigment solution to form pigment fine particles. Alternatively, it is also preferable to add a binder solution when forming fine pigment particles in a separate system.

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

  The binder may be used singly or may be used in the state of a composition used in combination with a normal film-forming polymer, and the addition amount relative to 100 parts by mass of pigment nanoparticles is generally 10 to 200 parts by mass. And 25-100 mass parts is preferable.

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

  As a photopolymerization initiator or a photopolymerization initiator system (in the present invention, a photopolymerization initiator system refers to a mixture that exhibits a photopolymerization initiation function by a combination of a plurality of compounds), US Pat. No. 2,367,660 Vicinal polyketaldonyl compounds disclosed in US Pat. No. 2,448,828, acyloin ether compounds described in US Pat. No. 2,448,828, α-hydrocarbon-substituted fragrances described in US Pat. No. 2,722,512 Group acyloin compounds, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, combinations of triarylimidazole dimers described in US Pat. No. 3,549,367 and p-amino ketones, Benzothiazole compounds and trihalomethyl-s-triazines described in Japanese Patent No. 51-48516 Compound, trihalomethyl are described in U.S. Patent No. 4239850 - triazine compounds include U.S. Patent trihalomethyl oxadiazole compounds described in No. 4,212,976 specification or the like. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable.

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

  The photopolymerization initiator or the photopolymerization initiator system 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, display characteristics, particularly display unevenness, can be reduced. The content of the photopolymerization initiator or the photopolymerization initiator system with respect to the total solid content of the colored photosensitive resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass. If this amount is too large, the sensitivity becomes too high and control becomes difficult. If the amount is too small, the exposure sensitivity becomes too low.

  In the colored photosensitive resin composition, in addition to the above components, an organic solvent for preparing a resin composition (fourth solvent) may be further used. Examples of the fourth solvent include, but are not limited to, esters, ethers, and ketones. Among these, 1,3-butylene glycol diacetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl Carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferably used. These solvents may be used alone or in combination of two or more. Moreover, the solvent whose boiling point is 180 to 250 degreeC can be used if needed. As for content of a 4th solvent, 10-95 mass% is preferable with respect to the resin composition whole quantity.

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

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

  In addition to the colorant (pigment), a colorant (dye or pigment) can be added to the colored photosensitive resin composition as necessary. In the case of using a pigment among the colorants, it is desirable that the pigment is uniformly dispersed in the colored photosensitive resin composition. Therefore, the particle diameter is preferably 0.1 μm or less, particularly 0.08 μm or less. Specific examples of the dye or pigment include the colorant described in JP-A-2005-17716 [0038] to [0040] and JP-A-2005-361447 [0068] to [0072]. And the colorants described in JP-A-2005-17521 [0080] to [0088] can be suitably used. The content of the auxiliary dye or pigment is preferably 5% by mass or less based on the total amount of the resin composition.

  The colored photosensitive resin composition may contain an ultraviolet absorber as necessary. Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, nickel chelate-based, hindered amine-based compounds and the like in addition to the compounds described in JP-A-5-72724. As for content of a ultraviolet absorber, 5 mass% or less is preferable with respect to the resin composition whole quantity.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The liquid crystal display device provided with the color filter of the present invention has a high contrast and excellent descriptive power such as black spots, and is particularly preferably a VA system. It can also be suitably used as a large-screen liquid crystal display device such as a notebook personal computer display or a television monitor. The color filter of the present invention can be used for a CCD device and exhibits excellent performance.

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

(Synthesis Example 1)
(Synthesis of Monomer M-1)
45.28 parts of 2-thiobarbituric acid and 13.82 parts of sodium hydroxide are dissolved in 200 parts of dimethyl sulfoxide and heated to 25 ° C. To this, 57.53 parts of chloromethylstyrene is dropped, and the mixture is further heated and stirred at 55 ° C. for 5 hours. After heating and stirring, 150 parts of methanol and 150 parts of distilled water are added to the reaction solution and stirred for 1 hour. Subsequently, this solution is poured into 2000 parts of distilled water while stirring, and the resulting precipitate is filtered and washed. As a result, 80.1 parts of monomer M-1 was obtained.
(Synthesis of polymer P-1)
The following monomer solution was introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), heated while flowing nitrogen into the flask, heated to 78 ° C., and stirred for 30 minutes. To do. Then, the following initiator solution is added to said liquid, and it heat-stirs at 78 degreeC for 2 hours. The following initiator solution is further added after heating and stirring, and the operation of heating and stirring at 78 ° C. for 2 hours is repeated twice in total. After the last 2 hours of stirring, the mixture is subsequently heated and stirred at 90 degrees for 2 hours. The obtained reaction solution was poured into 1500 parts of isopropanol while stirring, and the resulting precipitate was collected by filtration and dried by heating to obtain graft polymer P-1.
(Monomer solution)
-Monomer M-1 2.0 parts-Styrene 16.0 parts-Methacrylic acid 2.0 parts-1-Methyl-2-pyrrolidone 46.67 parts (initiator solution)
2.2'-azobis (isobutyric acid) dimethyl (V-601 manufactured by Wako Pure Chemical Industries, Ltd.)
0.6 parts 1-methyl-2-pyrrolidone 2 parts

(Synthesis Example 2)
(Synthesis of polymer P-2)
V-601 added to the initiator solution after changing to styrene used in Synthesis Example 1 to polymethyl methacrylate having a methacryloyl group at the end (number average molecular weight 6000, AA-6 (trade name) manufactured by Toa Gosei Chemical Co., Ltd.) A graft polymer P-2 was obtained in the same manner as in Synthesis Example 1 except that the amount of was changed to 0.1 part.

(Synthesis Examples 3-43)
Polymers P-3 to P-41, T-1, and T-2 were obtained in the same manner as in Synthesis Example 1 except that the monomer composition and the initiator composition shown in Synthesis Example 1 were changed to Table 1.

AS-6: One-end methacryloylated polystyrene oligomer (Mn = 6000, manufactured by Toa Gosei Chemical Co., Ltd.),
AA-6: One-terminal methacryloylated polymethyl methacrylate oligomer (Mn = 6000, manufactured by Toa Gosei Chemical Co., Ltd.)
AB-6: One-terminal methacryloylated poly-n-butyl methacrylate oligomer (Mn = 6000, manufactured by Toa Gosei Chemical Co., Ltd.)
M-90G: NK ester M-90G (trade name), methoxypolyethylene glycol methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
PME-1000; Bremer PME-1000 (trade name), methoxypolyethylene glycol methacrylate (manufactured by NOF Corporation)),
PE-350; Bremer PE-350 (trade name), polyethylene glycol monomethacrylate (manufactured by NOF Corporation)
PP-1000; Bremmer PP-1000 (trade name), polypropylene glycol monomethacrylate (manufactured by NOF Corporation)
PEP-350B; BLEMMER 70PEP-350B (trade name), polyethylene glycol polypropylene glycol monomethacrylate (manufactured by NOF Corporation),
FM5: Plaxel FM5 (trade name), polycaprolactone monomethacrylate (manufactured by Daicel Chemical Industries, Ltd.)

MAA; methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
St: Styrene (Wako Pure Chemical Industries, Ltd.)
DMAPAAm; dimethylaminopropylacrylamide (Wako Pure Chemical Industries, Ltd.)
DMAEA; dimethylaminoethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
DMVBAm; N, N-dimethyl-4-vinylbenzamide tBuSt; 4-tbutylstyrene (manufactured by Tokyo Chemical Industry Co., Ltd.)
VPy; 4-vinylpyridine VIm; N-vinylimidazole AA; acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
NMP; 1-methyl-2-pyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.)
MMA: Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
BMA: Butyl methacrylate (manufactured by Wako Pure Chemical Industries)
tBMA: t-butyl methacrylate (Wako Pure Chemical Industries, Ltd.)
BAAm: Butylacrylamide (Wako Pure Chemical Industries, Ltd.)
EAAm: Ethylacrylamide (Wako Pure Chemical Industries, Ltd.)
MAAm: Methylacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.)
BnMA; benzyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
iPrMA: Isopropyl methacrylate (Wako Pure Chemical Industries, Ltd.)

<Examples and comparative examples using build-up pigment fine particles>
Example 1
To 1000 ml of dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.) as the first solvent, 35.9 ml of 26% aqueous solution of tetramethylammonium hydroxide, pigment C.I. I. Pigment Red 254 (Irgaphor Red BT-CF, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) 50 g and Polymer P-1, 50.0 g were added to prepare Pigment Solution 1. Separately, 1000 ml of water containing 16 ml of 1 mol / l hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared as the second solvent.
Here, the temperature of the solution was controlled at 5 ° C., and the pigment solution 1 was added to 1000 ml of the second solvent water stirred at 500 rpm with a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). By using a 500 type large capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.), 100 ml is injected from a liquid feed pipe having a flow path diameter of 1.1 mm at a flow rate of 400 ml / min to form organic pigment fine particles. A pigment nanoparticle dispersion liquid 1 was prepared.
Using the H-112 type centrifugal filter (trade name) manufactured by Kokusan Co., Ltd. and the P89C type cloth (trade name) manufactured by Shikishima Canvas Co., Ltd. Concentration was performed at 5000 rpm for 90 minutes, the solvent was removed from the pigment dispersion, and the solvent was reduced (first concentration / removal step) and dried at 80 ° C. for 12 hours to obtain powder V-1 composed of flocs of organic pigment fine particles.
Using the organic pigment fine particle powder V-1, the following composition was prepared, and motor mill M-50 (manufactured by Eiger Japan Co., Ltd.) was used with zirconia beads having a diameter of 0.65 mm at a peripheral speed of 9 m / s. The pigment dispersion composition 1 was produced by time dispersion.

Organic pigment fine particle powder V-1 20.2 g
Solsperse 39000 10.0g
1-methoxy-2-propyl acetate (PGMEA) 100.0 g

Examples 2 to 41 (Comparative Examples 1 and 2)
In Example 1, pigment dispersion compositions 2 to 41 (Examples 2 to 41), C ₁ and C ₂ (comparison) except that the composition of each agent used was changed to that shown in the table below. Examples 1, 2) were prepared. However, the redispersant refers to a dispersant used when redispersing the dried organic pigment powder V in 1-methoxy-2-propylacetate, and it is not used when it is blank.
However, when the first solvent is methanesulfonic acid / formic acid, 2000 ml of methanesulfonic acid (manufactured by Wako Pure Chemical Industries) and 500 ml of formic acid (manufactured by Wako Pure Chemical Industries) are heated to 60 ° C. as the first solvent to dissolve the pigment. A liquid was prepared. Moreover, when using the dispersing agent for re-dispersion, the following composition was prepared using the powder of each produced organic pigment fine particle, and a motor mill M-50 (made by Eiger Japan) had a diameter of 0.65 mm. By using zirconia beads and dispersing for 2 hours at a peripheral speed of 9 m / s, a pigment dispersion composition was obtained.

(Example 42)
As the first solvent, while heating 2500 ml of methanesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.) to 80 ° C., pigment C.I. I. Pigment violet 23 (manufactured by Clariant, Hostaperm Violet RL-NF) 112.5 g and polymer P-1 80.0 g were added to prepare a pigment solution 42.
Separately, 2000 ml of water containing 20 ml of 1 mol / l sodium hydroxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared as the second solvent.
Here, the temperature of the solution was controlled at 25 ° C., and the pigment solution 1 at 80 ° C. was added to the second solvent stirred at 500 rpm with a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). Infusion was performed using a KX-500 large capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.). The flow path diameter and supply port diameter of the liquid supply pipe for the pigment solution 42 are set to 2.2 mm, the supply port is placed in the second solvent, and the organic pigment particles are formed by injecting 220 ml at a flow rate of 200 ml / min. Liquid 42 was prepared.
The pigment dispersion prepared by the above procedure was concentrated at 3000 rpm for 90 minutes using a H-110A type centrifugal filter manufactured by Kokusan Co., Ltd. and a P89C type cloth manufactured by Shikishima Canvas Co., Ltd. Minutes were removed and reduced (first concentration / removal step) and dried at 80 ° C. for 12 hours to obtain a powder V-42 composed of flocs of fine organic pigment particles.
The following composition was prepared using the organic pigment fine particle powder V-42, and the motor mill M-50 (manufactured by Eiger Japan Co., Ltd.) was used with zirconia beads having a diameter of 0.65 mm and a peripheral speed of 9 m / s. The pigment dispersion composition 42 was produced by time dispersion.

19.6 g of the organic pigment fine particle powder V-42
Solsperse 39000 10.0g
1-methoxy-2-propyl acetate 100.0 g

(Example 43) (Comparative Example 3)
In Example 42, pigment dispersion compositions 43 (Example 43) and C ₃ (Comparative Example 3) were prepared in the same manner except that the component composition of each agent used was changed to that shown in the table below. However, the redispersant refers to a dispersant used when redispersing the dried organic pigment powder V in 1-methoxy-2-propylacetate, and it is not used when it is blank.

(Evaluation)
1. Average particle diameter The particle diameter of the pigment particles was determined by using a transmission electron microscope (JEM-2010, trade name, manufactured by JEOL Ltd.) using a sample obtained by dropping and drying the pigment dispersion composition on a mesh covered with a support film. The observation was performed at an acceleration voltage of 100 kV. Subsequently, 100 or more of the measured photographic particles were subjected to image processing one by one, and the average particle size was obtained. The pigment dispersion composition used was subjected to two levels immediately after preparation and after standing for 1 week.

2. Viscosity (flowability)
The viscosity at 25 ° C. of each pigment dispersion composition was measured using a viscometer (manufactured by Toki Sangyo Co., Ltd., RE80, trade name) and evaluated according to the following criteria.
A: Less than 50 mPa · s B: 50 mPa · s or more, less than 200 mPa · s C: 200 mPa · s or more As described above, the pigment dispersion composition used was subjected to two levels immediately after preparation and after standing at room temperature for 1 week.
3. Measurement of contrast Each of the obtained pigment dispersion compositions was applied on a glass substrate so as to have a thickness of 2 μm, thereby preparing a sample. As a backlight unit, a three-wavelength cold cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) with a diffusion plate installed was used, and two polarizing plates (polarizing plates HLC2-2518 manufactured by Sanritsu Co., Ltd.) were used. ), The amount of transmitted light when the polarization axis is parallel and vertical is measured, and the ratio is defined as the contrast (“1990 Seventh Color Optical Conference, 512-color display 10. 4 ”size TFT-LCD color filter, planting, Koseki, Fukunaga, Yamanaka etc.). Two polarizing plates, a sample, and a color luminance meter are installed at a position 13 mm from the backlight, a polarizing plate at a position 40 mm to 60 mm, a cylinder 11 mm in diameter and 20 mm in length, and light transmitted through this. Was measured on a color luminance meter installed at a position of 400 mm through a polarizing plate installed at a position of 100 mm. The measurement angle of the color luminance meter was set to 2 °. The amount of light of the backlight was set so that the luminance when the two polarizing plates were installed in parallel Nicol was 1280 cd / m ² without the sample being installed. The obtained contrast measurement results are shown in Table 3. As before, the pigment dispersion composition used was subjected to two levels immediately after preparation and after standing at room temperature for 1 week.

  From the table, the pigment dispersion composition having a polymer compound containing a repeating unit represented by the general formula (1) or a tautomer structure thereof is excellent in dispersion stability, and the viscosity increase with time and the formation of pigment aggregates are It was hardly seen.

<Examples and comparative examples using breakdown pigment fine particles>
(Example 44)
The components of the following composition A are mixed, and using a homogenizer, the rotational speed is 3,000 r. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
[Composition A]
・ C. I. Pigment Red 254 ... 90 parts I. Pigment Red 177 10 parts Specific polymer P-2 45 parts 1-methoxy-2-propyl acetate 855 parts Subsequently, the mixed solution obtained above is further added to 0.3 mmφ Disperse for 6 hours with a bead disperser disperse mat (manufactured by GETZMANN) using zirconia beads, and then further using a high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.) Dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ . This dispersion treatment was repeated 10 times to obtain a red pigment dispersion composition 44. When the particle size of the pigment fine particles at this time was measured using Nanotrack UPA-EX150 (trade name) manufactured by Nikkiso Co., Ltd., the volume average particle size was 67 nm.

Examples 45 to 62 (Comparative Examples 4 and 5)
In Example 44, red pigment dispersion compositions 45 to 62, C ₄ and C ₅ were obtained in the same manner as in Example 44, except that the specific polymer P-2 was replaced with the specific polymers described in the table. Was prepared.

(Example 63)
In Example 44, a green pigment was obtained in the same manner as in Example 44, except that the red pigment dispersion composition was replaced with a pigment dispersion composition obtained using a mixed solution containing a green pigment of the following composition B. A dispersion composition 63 was obtained.
[Composition B]
・ C. I. Pigment Green 36 ... 60 copies I. Pigment Yellow 150 ... 40 parts-Specific Polymer P-2 ... 45 parts-1-Methoxy-2-propyl acetate ... 855 parts

(Examples 64-81) (Comparative Examples 6 and 7)
In Example 63, green pigment dispersion compositions 64-81, C ₆ and C ₇ were used in the same manner as in Example 63, except that the specific polymer P-2 was replaced with the specific polymers described in the table. Was prepared.

(Example 82)
In Example 44, except that the red pigment dispersion composition was replaced with a blue pigment dispersion composition obtained by using a mixed solution containing a blue pigment of the following composition C, A pigment dispersion composition 82 was obtained.
[Composition C]
・ C. I. Pigment Blue 15; 6 ... 85 parts I. Pigment Violet 23 15 parts Specific polymer P-2 45 parts 1-methoxy-2-propyl acetate 855 parts

(Examples 83 to 100) (Comparative Examples 8 and 9)
In Example 82, blue pigment dispersion compositions 83 to 100, C ₈ and C ₉ were used in the same manner as in Example 82 except that the specific polymer P-2 was replaced with the specific polymers described in the table. Was prepared.

  From the table, all of the pigment dispersion compositions of Examples 44 to 100 having a polymer compound containing a repeating unit represented by the general formula (1) or a tautomer structure thereof are excellent in dispersion stability and Little thickening or formation of pigment aggregates was observed. Also, regarding the particle size, in Examples 44 to 100, there was almost no change between immediately after dispersion and one week, but in Comparative Examples 4 to 9, aggregates were formed and a part of the sediment was confirmed. Concomitantly, the contrast is at a level that does not cause any practical problems in Examples 44 to 100, but in Comparative Examples 4 to 9, it was difficult to apply the pigment dispersion and measurement was impossible.

Claims (14)

A pigment dispersion composition comprising: a polymer compound having a repeating unit represented by the following general formula (1) or a repeating unit represented by a tautomer structure thereof; and pigment fine particles.

(R ¹ represents a hydrogen atom or a methyl group. J represents —CO—, —COO—, —CONR ⁴ —, —OCO—, a methylene group, a phenylene group, or a —C ₆ H ₄ CO— group. ⁴ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, W represents a single bond or a divalent linking group, R ² represents a hydrogen atom, or a substituted or unsubstituted alkyl group or aryl group. R ³ represents a hydrogen atom or a substituent.) The pigment dispersion composition according to claim 1, wherein the general formula (1) is a repeating unit represented by the following general formula (1A) or a tautomer structure thereof.

(R ¹ , R ² , and R ³ have the same meaning as in general formula (1). W ¹ represents an alkylene group.)   The polymer compound is at least a monomer having a repeating unit represented by the above general formula (1) or general formula (1A) or a tautomer structure thereof, and an ethylenically unsaturated group at the terminal. The pigment dispersion composition according to claim 1 or 2, which is a graft copolymer obtained by copolymerizing a polymerizable oligomer having a double bond.   The polymer compound is added to at least one of a pigment solution obtained by dissolving the organic pigment in a good solvent and a precipitation solvent that is compatible with the good solvent and is a poor solvent for the organic pigment. The pigment dispersion composition according to any one of claims 1 to 3, wherein the organic pigment is deposited by mixing the pigment solution and a solvent for precipitation.   The pigment dispersion composition according to any one of claims 1 to 3, wherein the pigment fine particles are prepared by pulverizing a pigment with a mechanical force.   A photocurable composition, wherein the pigment dispersion composition according to any one of claims 1 to 5 contains a photopolymerizable compound and a photopolymerization initiator.   Furthermore, alkali-soluble resin was contained, The photocurable composition of Claim 6 characterized by the above-mentioned.   The photocurable composition according to claim 6 or 7, wherein the photocurable composition is for producing a color filter.   A color filter comprising a colored pattern obtained by applying and curing the photocurable composition according to claim 8 directly or via another layer on a substrate.   A photosensitive film forming step of forming a photosensitive film by applying the photocurable composition according to claim 8 directly or via another layer to the substrate, and pattern exposure and development on the formed photosensitive film And a colored pattern forming step of forming a colored pattern by sequentially performing the steps.   An inkjet ink comprising organic pigment fine particles in the composition according to any one of claims 1 to 5 contained in a medium containing a polymerizable monomer and / or a polymerizable oligomer.   The inkjet ink according to claim 11, which is for producing a color filter. When the organic pigment is precipitated and formed by mixing a pigment solution obtained by dissolving an organic pigment in a good solvent and a precipitation solvent that is compatible with the good solvent and that is a poor solvent for the organic pigment. A method for producing a pigment dispersion composition, wherein a polymer compound containing a repeating unit represented by the following general formula (1) is contained in at least one of a solution and a solvent for precipitation.

(R ¹ represents a hydrogen atom or a methyl group. J represents —CO—, —COO—, —CONR ⁴ —, —OCO—, a methylene group, a phenylene group, or a —C ₆ H ₄ CO— group. ⁴ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, W represents a single bond or a divalent linking group, R ² represents a hydrogen atom, or a substituted or unsubstituted alkyl group or aryl group. R ³ represents a hydrogen atom or a substituent.)   Polymerization in which the polymer compound has at least a repeating unit represented by the above general formula (1) or a repeating unit represented by a tautomer structure thereof and an ethylenically unsaturated double bond at the terminal. The method for producing a pigment dispersion composition according to claim 13, which is a graft copolymer obtained by copolymerizing a functional oligomer.