KR20080070578A - Color filter, liquid crystal display device having the same and orgarnic pigment dispersions used therein, inkjet ink for color filter, colored photosensitive resin composition and photosensitive resin transfer material - Google Patents

Abstract

A color filter is provided to realize high contrast, to exhibit high color description power when the color filter is used in a display device, and to keep excellent display performance for a long time by suppressing color stains. A color filter has pigment particles contained in at least one color pixel of the color filter. The pigment particles have an average particle size of 40 nm or smaller. A ratio of particles having a particle size of 50 nm or larger to the total pigment particles is 1% or greater. An organic pigment dispersion comprises (a) pigment nanoparticles obtained by mechanically grinding a bulk body of organic pigment, and (b) pigment nanoparticles precipitated by mixing an organic pigment solution having an organic pigment dissolved in a good solvent, with a solvent which is compatible with the good solvent and is a poor solvent for the organic pigment.

Description

COLOR FILTER, LIQUID CRYSTAL DISPLAY DEVICE HAVING THE SAME AND ORGARNIC PIGMENT DISPERSIONS USED THEREIN Color filter, liquid crystal display device having the same and organic pigment dispersion used therein, ink jet ink for color filter, color photosensitive resin composition and photosensitive resin transfer material , INKJET INK FOR COLOR FILTER, COLORED PHOTOSENSITIVE RESIN COMPOSITION AND PHOTOSENSITIVE RESIN TRANSFER MATERIAL}

The present invention relates to a color filter, a liquid crystal display device having the same, an organic pigment dispersion used therein, an ink jet ink for a color filter, a color photosensitive resin composition, and a photosensitive resin transfer material.

As one of nanotechnology, research is being conducted to miniaturize particles to a range of 10 to 100 nm. The nano-size effect is to bring about new characteristics that were not previously expected.

In this regard, in the field of organic pigments, for example, the application of the nanotechnology is progressing in paints, printing inks, electrophotographic toners, inkjet inks, color filters and the like. Particularly, the color filter pigments and inkjet inks are the most advanced technology areas for coping with high performance, and the results are expected.

 When it comes to color filters, thinning is expected, and it holds the key of high pixel of digital camera and high sensitivity of CCD sensor. In recent years, organic pigments have been used as color materials for color filters, but their thicknesses depend largely on the particle diameter of organic pigments. At the nanometer size level and without monodisperse stable pigment particles, this problem cannot be overcome. In addition, a new manufacturing method with high design freedom and low price, which manufactures color filters using inkjet technology, has been considered. However, no pigment fine particles are yet suitable and exhibit sufficient performance.

Regarding the method for miniaturizing organic particles, it has been common to carry out using a disperser such as a roll mill, a ball mill, an attritor, and the like (see Non-Patent Document 1 and the like). In addition, in recent years, a gas phase method, a liquid phase method, and a laser ablation method have been studied. Especially, the liquid phase method attracts attention as a manufacturing method of organic particle | grains excellent in simplicity and productivity (refer patent document 1, 2).

Moreover, the method of mixing a good solvent solution and a poor solvent solution of a pigment and depositing pigment particle in recent years is developed (patent document 3). By using the pigment particles, high contrast of the color filter is intended.

[Patent Document 1] Japanese Patent Application Laid-Open No. 6-79168

[Patent Document 2] Japanese Patent Application Laid-Open No. 2004-91560

[Patent Document 3] International Patent Publication No. 2006/121016

[Non-Patent Document 1] Pigment Dispersion Technology-Surface Treatment and Dispersant Usage and Dispersibility Evaluation-Technical Information Society 1999

In color filters, not only high contrast but also excellent display performance when used in a display device or the like is required to be maintained for as long as possible.

Accordingly, an object of the present invention is to provide a color filter capable of realizing high contrast, exhibiting high color rendering power when used in a display device, suppressing color spots, and maintaining excellent display performance for a long time, and an organic pigment dispersion used therein. It is done. In addition, an object of the present invention is to provide an ink jet ink for a color filter containing the excellent organic pigment dispersion, a coloring photosensitive resin composition, a photosensitive resin transfer material, a color filter using the same, and a liquid crystal display device having the same.

The above object of the present invention has been achieved by the following means.

(1) Pigment particles contained in at least one color pixel of the color filter, wherein the average particle diameter of the pigment particles is 40 nm or less, and the ratio of the number of particles having a particle diameter of 50 nm or more is 1% or more of all pigment particles. The color filter characterized by the above-mentioned.

(2) The color filter according to (1), wherein the particle size distribution of the pigment particles contained in the pixel is provided with two or more maximum values.

(3) The color filter according to (1) or (2), wherein the particle size distribution of the pigment particles contained in the pixel has a maximum value at a particle size of 30 nm or less.

(4) The color filter according to any one of (1) to (3), wherein the number of particles having a particle diameter of 50 nm or more is 5% or more of all pigment particles in the pigment particles contained in the pixel.

(5) pigment nanoparticles (a) obtained by mechanically pulverizing a bulk body of an organic pigment, and

An organic pigment solution in which an organic pigment is dissolved in a good solvent and a pigment nanoparticle (b), which are mixed with the good solvent and mixed with a solvent which is a poor solvent with the organic pigment, are precipitated. Organic pigment dispersions.

(6) The organic pigment dispersion according to (5), wherein the pigment nanoparticle (b) is contained in an amount of 1% by mass or more of all pigment particles.

(7) The organic pigment dispersion according to (5) or (6), wherein the pigment nanoparticle (b) is contained in an amount of 3% by mass to 95% by mass of all the pigment particles.

(8) In any one of (5)-(7), the average particle diameter of all the pigment particles of the said pigment nanoparticles (a) and (b) shall be 40 nm or less, and the number of particle | grains whose particle diameter is 50 nm or more may be used. An organic pigment dispersion comprising a ratio of 1% or more of all pigment particles.

(9) The pigment nanoparticle (b) according to any one of (5) to (8), wherein the pigment nanoparticle (b) is a nanoparticle obtained by removing a single amount of a solvent to obtain a powder and redispersing the powder. Organic pigment dispersions.

(10) The organic pigment dispersion according to any one of (5) to (9), wherein the pigment nanoparticles (b) are nanoparticles obtained in the coexistence of a polymer compound having a mass average molecular weight of 1000 or more.

(11) The organic pigment dispersion according to any one of (5) to (10), wherein the mass compound having a molecular weight of 1,000 or more is a compound represented by the following general formula (1).

일반식(1)

General formula (1)

[In general formula, R <^1> represents a (m + n) valent coupling group and R <^2> represents a single bond or a bivalent coupling group. A ¹ has a group selected from the group consisting of an acidic group, a basic group having a nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group and a hydroxyl group Monovalent organic group or monovalent organic group containing the organic pigment | dye structure or heterocycle which may have a substituent is shown. However, n piece A <^1> may mutually be same or different. m represents a number from 1 to 8, n represents a number from 2 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer compound residue.]

(12) The organic pigment dispersion according to any one of (5) to (11), which is used for a color filter having any of blue, green and red colors.

(13) An ink jet ink for color filters, comprising the organic pigment dispersion according to any one of (5) to (12).

(14) The coloring photosensitive resin composition containing the organic pigment dispersion, binder, monomer, or oligomer in any one of (5)-(12).

(15) The photosensitive resin transfer material formed on the support body by the layer which has the coloring photosensitive resin composition as described in (14).

(16) A color filter in which the organic pigment dispersion according to any one of (5) to (12) is contained in at least one of an R pixel, a G pixel, and a B pixel.

(17) A color filter produced by using any one of the inkjet ink according to (13), the coloring photosensitive resin composition according to (14), and the photosensitive resin transfer material according to (15).

(18) A liquid crystal display device comprising the color filter according to (15) or (16).

The color filter of the present invention exhibits high contrast and exhibits high color rendering power when used in a liquid crystal display device, and its vivid image quality is maintained even when used for a long time, resulting in an excellent effect of suppressing color spots.

 In addition, according to the organic pigment dispersion of the present invention and the inkjet ink for color filters, the coloring photosensitive resin composition and the photosensitive resin transfer material containing the same, the excellent color filter can be mass-produced with good efficiency.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

As a preferred embodiment of the color filter of the present invention, the average particle diameter of the pigment particles contained in at least one color pixel is 40 nm or less, and the ratio of the number of particles having a particle diameter of 50 nm or more is 1% or more of all pigment particles. It can be mentioned. At this time, a high performance color filter containing the pigment nanoparticles (a) and the pigment nanoparticles (b) described later can be obtained as another embodiment. However, when the color filter is used in a display device or the like, the display performance can be excellent for a long time. It is preferable to make the average particle diameter of a pigment particle into 40 nm or less as mentioned above, and to make it 30 nm or less as mentioned above, in order to hold | maintain over time, to satisfy | fill balanced performance required, and to satisfy the demand of higher contrast. More preferred. Although there is no restriction | limiting in particular in the lower limit of the average particle diameter of the said pigment particle, Usually, you may be 5 nm or more. In the color filter of the present invention, among all the pixels of the R pixel, the G pixel, and the B pixel, it is particularly preferable that the pigment particles contained therein have a proportion of particles having an average particle diameter and a particle diameter of 50 nm or more.

Moreover, in the said particle | grain, it is preferable to have 2 or more local maximums in the particle size distribution which took the number of particle | grains on the vertical axis | shaft, and the particle diameter (particle size corresponded to a sphere) on the horizontal axis | shaft. In addition, in the particle size distribution, the smallest local maximum is preferably 30 nm or less, more preferably 25 nm or less, and particularly preferably 20 nm or less.

As mentioned above, in the color filter of this embodiment, although the ratio of the number of the particle | grains whose particle diameter is 50 nm or more in the pigment particle contained in at least 1 pixel exists 1% or more of all the pigment particles, it is more than 5%. It is preferable and it is especially preferable that it is 10% or more. Although there is no restriction | limiting in particular in the upper limit of the said ratio, Usually, it shall be 50% or less.

The particle size of the organic particles can be quantified by a survey method to express the average size of the population. However, the particle size of the organic particles is often used, and the mode particle size, which represents the maximum value of the distribution, the median particle size corresponding to the median of the integral distribution curve, and the average of various types. There are particle diameters (number average, length average, area average, mass average, volume average, etc.), and in the present invention, the average particle diameter refers to the number average particle diameter (Mn) unless otherwise specified. The pigment fine particles may be crystalline particles or amorphous particles, or may be a mixture or a solid solution thereof. Moreover, when two or more types of organic particles are mixed and it is a mixture or a solid solution, the layer which consists of another substance is formed uniformly on the surface of a particle, or it is a particle | grain of a core-cell structure, it is used preferably.

In addition, in this invention, as an index which shows the monodispersibility of particle | grains, the ratio (Mv / Mn) of volume average particle diameter (Mv) and number average particle diameter (Mn) is used unless there is particular restriction. It is preferable that monodispersity, ie Mv / Mn, of a pigment fine particle (primary particle) is 1.0-2.0, It is more preferable that it is 1.0-1.8, It is especially preferable that it is 1.0-1.5.

As a measuring method of the particle diameter of organic particle | grains, a microscopic method, a mass method, a light scattering method, the light blocking method, an electrical resistance method, an acoustic method, and a dynamic light scattering method are mentioned, A microscope method and a dynamic light scattering method are especially preferable. As a microscope used for a microscopic method, a scanning electron microscope, a transmission electron microscope, etc. are mentioned, for example. As a particle measuring apparatus by the dynamic light scattering method, the Nikkiso company Nanotrac UPA-EX150, the Otsuka Denshi company dynamic light scattering photometer DLS-7000 series, etc. are mentioned, for example.

Next, the organic pigment dispersion which can be used suitably for manufacture of a color filter including the thing of embodiment mentioned above is demonstrated.

The organic pigment dispersion of the present invention is a pigment dispersion containing pigment nanoparticles (a) and pigment nanoparticles (b). In the present invention, "pigment dispersion" means that the pigment particles are dispersed in the medium, and may be a liquid composition or a solid composition, a photosensitive transfer material and a color filter having a dispersion of the pigment, an inkjet ink, a pigment dispersion resist, and a pigment. It means to include the pixel part of.

Organic pigments are not limited to the color, for example, perylene compound pigments, perinone compound pigments, quinacridone compound pigments, quinacridone quinone compound pigments, anthraquinone compound pigments, anthrone compound pigments, benzimida Zolon compound pigments, disazo condensed compound pigments, disazo compound pigments, azo compound pigments, indanthone compound pigments, phthalocyanine compound pigments, triarylcarbonium compound pigments, dioxazine compound pigments, amino anthraquinone compound pigments, diketopyrrolopyrrole And compound pigments, thioindigo compound pigments, isoindolin compound pigments, isoindolinone compound pigments, pyrantrone compound pigments, isobioanthrone compound pigments, and mixtures thereof.

Among them, quinacridone compound pigments, diketopyrrolopyrrole compound pigments, dioxazine compound pigments, phthalocyanine compound pigments or azo compound pigments are preferred, and diketopyrrolopyrrole compound pigments, dioxazine compound pigments and phthalocyanine compound pigments are more preferred. desirable.

In the production method of the present invention, two or more organic pigments or a solid solution of organic pigments may be used in combination, or may be used in combination with ordinary dyes.

Pigment nanoparticle (a) (hereinafter referred to as " breakdown pigment nanoparticle ") is a particle obtained by mechanically pulverizing a bulk body of organic pigment and downsizing to nanometer size. Here, the bulk of organic pigment means pigment solids whose diameter becomes 1 micrometer or more when it converts into a sphere. The nanoparticles after grinding may be dispersed in a medium or may be separated as solid powder. In the present invention, "nanoparticle" refers to a particle having a nanometer size, which is also referred to as "particulate".

Breakdown pigment nanoparticles can be produced by conventional methods. As a specific manufacturing apparatus, a ball mill, a bead mill, a roll mill, a colloid mill, a disper, a homogenizer, an ultrasonic disperser, etc. are mentioned, for example. Among these dispersers, the bead mill which can manufacture productivity and a fine dispersion, and can use a fine dispersion medium is especially preferable.

As such a bead mill, For example, a horizontal dienomill (made by Shinmaru Enterprises company), an ultra-biscomill (made by IMEX company), a spike mill (made by Inoue Seisakujo company); Vertical dry mills (manufactured by Draiswerke Co.), sand mills (manufactured by Canfecatate Ryota Co.) and the like. As a dispersion medium used at the time of dispersion, a dispersion medium made of ceramics or steel, such as zirconia and alumina, is mentioned, for example. Among these, the zirconia dispersion medium excellent in abrasion resistance is especially preferable.

 In addition, the method of kneading vigorously with two rolls or balm mixer while heating the pigment and the solid resin, and kneading the mixture of water-soluble inorganic salts such as pigment and salt with a small amount of aqueous solvent with kneader, etc. And so-called salt milling methods in which an inorganic salt and a solvent are washed with water and dried to obtain a fine pigment.

 Pigment nanoparticle (b) (hereinafter referred to as "build-up pigment nanoparticle") is an organic pigment solution in which an organic pigment is dissolved in a good solvent, and is compatible with the good solvent and poor solvent with respect to an organic pigment. It is nanoparticle which mixed and precipitated the solvent (henceforth this solvent is called a "poor solvent"). It is necessary that there is a sufficient difference in the solubility of the organic pigment in the merging of the poor solvent and the good solvent, and it is necessary to select a preferable one in accordance with the organic pigment.

Although the poor solvent is not specifically limited, It is preferable that the solubility of organic pigment is 0.02 mass% or less, and it is more preferable that it is 0.01 mass% or less. There is no particular lower limit to the solubility of the organic pigment in the poor solvent, but considering the organic pigments usually used, 0.000001 mass% or more is practical. This solubility may be solubility when melt | dissolved in presence of an acid or an alkali. The compatibility or homogeneity of the good solvent and the poor solvent is preferably 30% by mass or more, more preferably 50% by mass or more in the poor solvent.

As a poor solvent, for example, an aqueous solvent (for example, water or hydrochloric acid, an aqueous sodium hydroxide solution), an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, an aromatic compound solvent, a carbon disulfide solvent, an aliphatic compound solvent, a nitrile compound solvent A halogen solvent, an ester compound, an ionic liquid, a mixed solvent thereof, and the like, and an aqueous solvent, an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, an ester compound solvent, or a mixture thereof is preferable. 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. As a ketone compound solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are mentioned, for example. As an ether compound solvent, dimethyl ether, diethyl ether, tetrahydrofuran, etc. are mentioned, for example. As an aromatic compound solvent, benzene, toluene, etc. are mentioned, for example. As an aliphatic compound solvent, hexane etc. are mentioned, for example. As a nitrile compound solvent, acetonitrile etc. are mentioned, for example. As a halogen compound solvent, dichloromethane, trichloroethylene, etc. are mentioned, for example. As an ester compound solvent, ethyl acetate, ethyl lactate, 2- (1-methoxy) propyl acetate, etc. are mentioned, for example. The ionic liquid includes, for example, 1-butyl-3-methylimidazolium and PF ₆ ^-, and the like salts.

When precipitation-generating organic particles, there are no particular restrictions on the conditions of the poor solvent, and a range of subcritical and supercritical conditions can be selected at normal pressure. As for temperature at normal pressure, -30-100 degreeC is preferable, -10-60 degreeC is more preferable, and 0-30 degreeC is especially preferable.

 A good solvent can dissolve the organic pigment used, and if it is compatible with the said poor solvent or mixed uniformly, it will not specifically limit. It is preferable that the solubility of an organic pigment is 0.2 mass% or more, and, as for the solubility with respect to the good solvent of an organic pigment, it is more preferable that it is 0.5 mass% or more. Although there is no upper limit in the solubility with respect to the good solvent of an organic pigment, it is practical that it is 50 mass% or less considering the organic pigment normally used. This solubility may be solubility when melt | dissolved in presence of an acid or an alkali. The preferred range of compatibility or homogeneous mixing of the poor solvent and the good solvent is as described above.

As a good solvent, for example, 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 an aliphatic compound solvent , Nitrile compound solvents, sulfoxide compound solvents, halogenated solvents, ester compound solvents, ionic liquids, mixed solvents thereof, and the like.Aqueous solvents, alcohol compound solvents, ketone compound solvents, ether compound solvents, sulfoxide compound A solvent, an ester compound solvent, an amide compound solvent or a mixture thereof is preferable, and an aqueous solvent, an alcohol compound solvent, an ester compound solvent, a sulfoxide compound solvent or an amide compound solvent is preferable, and an aqueous solvent, a sulfoxide compound solvent or an amide compound is preferred. Solvents are more preferred, and sulfoxide compound solvents or amide compound solvents are particularly preferred. desirable.

Examples of the sulfoxide compound solvent include dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, sulfolane and the like. As the amide compound solvent, for example, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone , (epsilon) -caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide, and the like.

In addition, the concentration of the organic pigment solution in which the organic pigment is dissolved in the good solvent is preferably in the range of saturation concentration to about 1/100 of the good solvent of the organic pigment under the conditions of dissolution.

 There is no restriction | limiting in particular in the preparation condition of an organic pigment solution, A range of subcritical and supercritical conditions can be selected at normal pressure. The temperature at normal pressure is preferably -10 to 150 ° C, more preferably -5 to 130 ° C, particularly preferably 0 to 100 ° C.

Although it is common to what is listed as a specific example of a good solvent and what is listed as a poor solvent, the same thing is not combined as a good solvent and a poor solvent, and the solubility with respect to a good solvent is poor with respect to each organic pigment to be used. It is good to be sufficiently higher than the solubility with respect to, for example, it is preferable that the solubility difference is 0.2 mass% or more, and it is more preferable that it is 0.5 mass% or more. Although there is no upper limit in particular in the difference in solubility with respect to a good solvent and a poor solvent, when considering the organic pigment which can be used normally, it is practically 50 mass% or less.

When the organic pigment is uniformly dissolved in a good solvent, it may be dissolved in acid or alkaline. In general, in the case of a pigment having an alkaline-dissociable group in a molecule, it is preferable to dissolve in alkaline, and in the case of a pigment having a large number of nitrogen atoms in a molecule to which protons are easy to be added without a group that decomposes in alkali, it is preferable to dissolve in acid. desirable. However, whether to be dissolved in acid or alkaline may be selected in consideration of not only the solubility of the pigment but also the characteristics of the atomic groups used as the color filter, and is not particularly limited. For example, quinacridone compound pigments and diketopyrrole compound pigments. And disazo condensation compound pigments are easy to dissolve in alkali, and phthalocyanine compound pigments are easy to dissolve in acid.

The base used for dissolving in alkaline is inorganic base such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide or barium hydroxide, or organic base such as trialkylamine, diazabicycloundecene (DBU), metal alkoxide, etc. But preferably inorganic base.

The amount of the base to be used is an amount which can dissolve the pigment uniformly and is not particularly limited, but in the case of inorganic bases, it is preferably 1.0 to 30 molar equivalents, more preferably 1.0 to 25 molar equivalents, more preferably relative to organic pigments. Preferably it is 1.0-20 molar equivalent. In the case of an organic base, Preferably it is 1.0-100 mol equivalent with respect to an organic pigment, More preferably, it is 5.0-100 mol equivalent, More preferably, it is 20-100 mol equivalent.

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

The amount of acid to be used is an amount capable of uniformly dissolving the organic pigment, and is not particularly limited, but is often used in excess in comparison with the base. Regardless of the case of the inorganic acid and the organic acid, the amount is preferably 3 to 500 molar equivalents, more preferably 10 to 500 molar equivalents, and even more preferably 30 to 200 molar equivalents based on the organic pigment.

When alkali or acid is mixed with an organic solvent and used as a good solvent for organic pigments, in order to completely dissolve the alkali or acid, a solvent having high solubility in alkali or acid, such as some water or lower alcohol, is added to the organic solvent. can do. 50 mass% or less is preferable with respect to the organic pigment solution whole quantity, and, as for the quantity of water and lower alcohol, 30 mass% or less is more preferable. Specifically, water, methanol, ethanol, n-propanol, isopropanol, butyl alcohol, etc. can be used.

It is preferable that it is 0.5-80.0 mPa * s, and, as for the viscosity of an organic pigment solution, it is more preferable that it is 1.0-50.0 mPa * s.

It is preferable that the difference between the pH of the organic pigment solution and the poor solvent is 5 or more. It is more preferable if it is 7 or more, and 10 or more are especially preferable.

 When mixing an organic pigment solution and a poor solvent, you may add and mix both, but it is preferable to classify and mix an organic pigment solution in a poor solvent, and it is preferable that the poor solvent is stirred at that time. As for stirring speed, 100-10000rpm is preferable, 150-8000rpm is more preferable, 200-6000rpm is especially preferable. A pump etc. can also be used for addition and it is not necessary to use it. In addition, although addition may be carried out in liquid or extra liquid, addition in liquid is more preferable. It is also preferable to continuously feed the liquid into the pump through the supply pipe. 0.1-200 mm is preferable and, as for the internal diameter of a supply pipe, 0.2-100 mm is more preferable. As a speed | rate supplied in a liquid from a supply line, 1-10000 ml / min is preferable, and 5-5000 ml / min is more preferable.

The particle diameter of the organic nanoparticles to be precipitated can be controlled by adjusting the Reynolds number in accordance with the mixing of the organic pigment solution and the poor solvent. Here, Reynolds number is a dimensionless number representing the state of fluid flow and is represented by the following equation.

         Re = ρUL / μ... Formula (1)

In Equation (1), Re denotes Reynolds number, ρ denotes the density of the organic pigment solution [kg / m 3], and U denotes the relative velocity [m / s] when the organic pigment solution and the poor solvent meet each other. And L denote an equivalent diameter [m] of a flow path or a supply port where the organic pigment solution and the poor solvent meet each other, and μ denotes the viscosity coefficient [Pa · s] of the organic pigment solution.

Equivalent diameter L means the diameter of the equivalent circular pipe when an equivalent circular pipe is assumed with respect to the opening diameter and the flow path of an arbitrary cross section piping. The equivalent diameter L is expressed by the following formula (2) when the cross-sectional area of the pipe is A, the wetting circumference length (outer) of the pipe, or the outer circumference of the flow path is p.

L = 4A / p... Formula (2)

It is preferable to inject the organic pigment solution into the poor solvent through the pipe to form particles. When a circular pipe is used for the pipe, the equivalent diameter matches the diameter of the circular pipe. For example, the equivalent diameter can be adjusted by changing the opening diameter of the liquid supply port. Although the value of equivalent diameter L is not specifically limited, For example, it is the same as the preferable internal diameter of the supply opening mentioned above.

The relative speed U when the good solvent solution and the poor solvent of the organic pigment meet is defined as the relative speed in the vertical direction with respect to the plane of the portion where they meet. That is, for example, in the case where a good solvent solution of organic pigment is injected and mixed into a stationary poor solvent, the rate injected from the supply port is equal to the relative speed U. Although the value of the relative speed U is not specifically limited, For example, it is preferable to set it as 0.5-100 m / s, and it is more preferable to set it as 1.0-50 m / s.

The density ρ of the organic pigment solution is a value determined by the kind of material selected, but it is practical that the range of the material suitably used in the production method of the present invention is, for example, 0.8 to 2.0 kg / m 3. In addition, although the viscosity coefficient mu of an organic pigment solution is a value determined by the material used, an environmental temperature, etc., the preferable range is the same as the preferable viscosity of the organic pigment solution mentioned above.

 The smaller the Reynolds number Re, the easier it is to form laminar flow, and the larger the value of Reynolds number Re, the easier it is to form turbulent flow. For example, the Reynolds number can be adjusted to 60 or more to obtain and control the particle diameter of the organic nanoparticles, preferably 100 or more, more preferably 150 or more. Although there is no upper limit in particular in Reynolds number, it is preferable because it can obtain and control favorable organic nanoparticles by adjusting to the range of 100000 or less, for example. Alternatively, the conditions may be such that the Reynolds number is improved so that the average particle diameter of the obtained nanoparticles is 60 nm or less. In this case, the Reynolds number is usually increased within the above range to obtain organic nanoparticles having a smaller particle size.

The mixing ratio of the organic pigment solution and the poor solvent (ratio of good solvent / poor solvent in the organic fine particle precipitate) is preferably 1/50 to 2/3 by volume ratio, more preferably 1/40 to 1/2, and more preferably 1 / 20-3 / 8 are especially preferable.

When the organic fine particles are precipitated, the concentration of the pigment nanoparticles (b) in the dispersion is not particularly limited, but the organic particles are preferably in the range of 10 to 40000 mg, more preferably in the range of 20 to 30000 mg per 1000 ml of the solvent. It is the range of 50-25000 mg especially preferably.

In addition, although the preparation scale in producing a pigment nanoparticle is not specifically limited, It is preferable that the mixing amount of a poor solvent is 10-2000 L of preparation scale, and it is more preferable that it is 50-1000 L of preparation scale.

When depositing the build-up pigment nanoparticles, it is preferable to contain a dispersant. Although the process of containing a dispersing agent is not specifically limited, It is preferable to add a dispersing agent to both or one side of an organic pigment solution and a poor solvent, and to contain it. It is also preferable to add the dispersant solution when forming the pigment nanoparticles in a system different from the above two solutions. It is also preferable to use the pigment particle previously surface-treated with a dispersing agent, and the pigment particle may be surface-treated so that adsorption of a dispersing agent may be promoted. The dispersant has the effect of (1) rapidly adsorbing onto the precipitated pigment surface to form fine nanoparticles, and (2) preventing these particles from agglomerating again.

As the dispersant, for example, an anionic, cationic, zwitterionic, nonionic or pigment derivative low molecular or polymeric dispersant may be used. On the other hand, the molecular weight of the polymer dispersant can be used without limitation as long as it can be dissolved in a solution uniformly, but preferably has a molecular weight of 1,000 to 2,000,000, more preferably 5,000 to 1,000,000, even more preferably 10,000 to 500,000, 10,000 to 100,000 This is particularly preferred. Specific examples of the polymer dispersant include polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, polyvinyl alcohol- partial form Maleic acid, polyvinyl alcohol-part butyralide, vinylpyrrolidone-vinyl acetate copolymer, polyethylene oxide / propylene oxide block copolymer, polyacrylate, polyvinyl sulfate, poly (4-vinylpyridine) salt, Polyamide, polyallylamine salt, condensed naphthalene sulfonate, cellulose derivative, starch derivative and the like. In addition, natural polymers such as alginate, gelatin, albumin, casein, arabian rubber, tragagant rubber and lignin sulfonate can also be used. Especially, polyvinylpyrrolidone is preferable. These polymers can be used individually by 1 type or in combination of 2 or more types. These dispersants can be used individually or in combination. Dispersants for use in dispersing pigments are described in detail on pages 29-46 of "Pigment Dispersion Stabilization and Surface Treatment Technology and Evaluation" (Chemical Information Association, December 2001).

As an anionic acid (anionic surfactant), N-acyl-N-alkyltaurine salt, a fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinic acid salt, alkyl phosphate ester salt, naphthalene Sulfonic acid formalin condensate, polyoxyethylene alkyl sulfate ester salt and the like. Especially, N-acyl-N-alkyltaurine salt is preferable. As the N-acyl-N-alkyl taurine salt, those described in JP-A-3-273067 are preferable. These anionic component acidic agents can be used individually or in combination of 2 or more types.

Cationic component acids (cationic surfactants) include quaternary ammonium salts, alkoxylated polyamines, aliphatic amine polyglycol ethers, aliphatic amines, diamines and polyamines derived from aliphatic amines and aliphatic alcohols, imidazolines derived from fatty acids and their cations Salts of sexual substances are included. These cationic component acidic agents can be used individually or in combination of 2 or more types.

 The zwitterionic acidic acid is a dispersant having an anionic group portion of the anionic component acidic acid and a cationic group portion of the cationic component acidic acid in the molecule.

 As nonionic acidic acid (nonionic surfactant), 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. are mentioned. Especially, polyoxyethylene alkyl aryl ether is preferable. These nonionic acidic acid can be used individually or in combination of 2 or more types.

Pigment derivative type dispersant is a derivative derived from organic pigments and produced by chemical modification of its parent structure, or pigment derivatives obtained by the pigmentation reaction of a pigment derivative type dispersant or a chemical modified pigment precursor. Defined as a body dispersant. For example, sugar-containing pigment derivative type dispersant, piperidyl-containing pigment derivative type dispersant, naphthalene or perylene derivative pigment derivative type dispersant, pigment derivative type dispersant having a functional group linked to the pigment parent structure through a methylene group, chemical formula into polymer Pigment parent structure, pigment derivative dispersant having sulfonic acid group, pigment derivative dispersant having sulfonamide group, pigment derivative dispersant having ether group or pigment derivative dispersant having carboxylic acid group, carboxylic acid ester group or carboxamide group, etc. There is this.

It is also preferable to use the pigment dispersant containing an amino group as a dispersing agent. The amino group may include a primary amino group, a secondary amino group, and a tertiary amino group, and the number of amino groups may be one or plural. The pigment derivative compound which introduce | transduced the substituent which has an amino group in a pigment skeleton, or the polymer compound which made into the polymerization component the monomer which has an amino group may be sufficient. As an example of these, Unexamined-Japanese-Patent No. 2000-239554, 2003-96329, 2001-31885, Unexamined-Japanese-Patent No. 10-339949, Unexamined-Japanese-Patent No. 5-72943, Although the compound etc. of Paragraph 0047 of Unexamined-Japanese-Patent No. 2006-129714, Paragraph 0018 of the International Publication No. 2006/121017 pamphlet-0033, etc. are mentioned, It is not limited to these.

In order to further improve the homogeneous dispersibility and storage stability of the pigment nanoparticles, the content of the dispersant is preferably in the range of 0.1 to 1000 parts by mass with respect to 100 parts by mass of the pigment, more preferably in the range of 1 to 500 parts by mass. More preferably, it is the range of 5-20 mass parts. The improvement of the dispersion stability of pigment nanoparticles which are less than 0.1 mass part may not be seen. In addition, a dispersing agent may be used individually or may be used in combination of several things.

After the build-up pigment nanoparticles are precipitated as pigment nanoparticles, it is preferable to reduce or remove the solvent content of the dispersion liquid containing the precipitated particles (hereinafter, this process is referred to as a "concentration / removal process"). has exist). As a result, nanoparticle concentrates or powders suitable for color filter coating liquids and inkjet inks can be produced on an industrial scale.

The concentration and removal step is not particularly limited. For example, a form in which the extraction solvent is added and mixed with the pigment nanoparticle dispersion liquid to concentrate the extraction of the pigment nanoparticles onto the extraction solvent, and the filter is filtered and used to form the concentrated nanoparticle liquid. , Precipitated and concentrated pigment nanoparticles by centrifugation, desalted concentration by ultrafiltration, form using spray drying, sublimation of solvent by vacuum freeze drying, concentration under reduced pressure without heating And a form in which the solvent is dried by condensation, a combination of them, and the like. Among these, the form is concentrated by centrifugation, spray drying is used, and the form is dried and concentrated by reduced pressure without heating. desirable.

The extraction solvent used for the concentrated extraction is not particularly limited, but is not substantially mixed with the dispersion solvent of the pigment nanoparticle dispersion (for example, an aqueous solvent) (in the present invention, a material that is not substantially mixed has a low compatibility). 50 mass% or less of melt | dissolution is preferable, and 30 mass% or less is more preferable. Although there is no restriction | limiting in particular in this melt | dissolution amount, it is practical that it is 1 mass% or more in consideration of the solubility of a normal solvent), and after mixing It is preferable that it is a solvent which forms an interface, if left still. In addition, the extraction solvent is preferably a solvent in which the pigment nanoparticles cause weak coagulation (a floc which can be re-dispersed even without adding a high shear force such as milling or high-speed stirring) in the extraction solvent. Such a state is preferable in that it is possible to wet the desired pigment nanoparticles with an extraction solvent without causing strong agglomeration to change the particle size and to easily remove a dispersion solvent such as water by filter filtration or the like. The extraction solvent is preferably an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent or an aliphatic compound solvent, more preferably an ester compound solvent, an aromatic compound solvent or an aliphatic compound solvent, and particularly preferably an ester compound solvent.

As an ester compound solvent, 2- (1-methoxy) propyl acetate, ethyl acetate, ethyl lactate, etc. are mentioned, for example. As an alcohol compound solvent, n-butanol, isobutanol, etc. are mentioned, for example. As an aromatic compound solvent, benzene, toluene, xylene, etc. are mentioned, for example. As an aliphatic compound solvent, n-hexane, cyclohexane, etc. are mentioned, for example. The extraction solvent may be a pure solvent of the above-mentioned preferred solvent or a mixed solvent of a plurality of solvents.

The amount of the extraction solvent is not particularly limited as long as the pigment nanoparticles can be extracted, but is preferably smaller than the pigment nanoparticle dispersion in consideration of concentration and extraction. When this is expressed by volume ratio, the extraction solvent added when the pigment nanoparticle dispersion is 100 is preferably in the range of 1 to 100, more preferably in the range of 10 to 90, and particularly preferably in the range of 20 to 80. Too many requires enormous time for concentration, and too little, insufficient extraction results in nanoparticles remaining in the dispersion solvent.

After the extraction solvent is added, it is preferable to stir and mix so as to be in sufficient contact with the dispersion. Stirring mixing can use a conventional method. Although there is no restriction | limiting in particular in the temperature at the time of adding and mixing an extraction solvent, It is preferable that it is 1-100 degreeC, and it is more preferable that it is 5-60 degreeC. The addition and mixing of the extraction solvent may be any device as long as the respective steps can be preferably carried out, but for example, a separation lot type device can be used.

In case of ultrafiltration, for example, a method used for desalting / concentrating a silver halide emulsion may be applied. Research Disclosure No. 10208 (1972), No. 13 122 (1975) and No. 16 351 (1977) are known. Pressure differentials and flow rates that are important as operating conditions can be selected by referring to the characteristic curves described in Oyaharuhiko, "Technology for Use of Membrane Handbook", Saiwaisho Publication (1978), page 275, while treating the desired pigment nanoparticle dispersion. In order to suppress aggregation of particles, it is necessary to find out the optimum conditions. In addition, in the method of replenishing the solvent lost by the membrane permeation, there are two types of batch formulas which are added continuously and a batch formula which is added intermittently, but a formula having a relatively short desalting time is preferable. Pure water obtained by ion exchange or distillation is used as the solvent to be supplemented in this way. However, the poor solvent of the dispersant and the dispersant may be mixed in the pure water, or may be added directly to the pigment nanoparticle dispersion.

Ultrafiltration membranes are already equipped as modules such as flat, spiral, cylindrical, aerial sand, hollow fiber, etc. Asahi Kasei Co., Ltd., Daisel Kagaku Co., Ltd., Toray Co., Ltd., Nitoden Co., Ltd. Although commercially available from Kousa and the like, a spiral type or an aerial sand type is preferable from the viewpoint of the total film area and the cleaning property. In addition, although the fractional molecular weight used as an index of the boundary value of the component which can permeate a membrane needs to be determined by the molecular weight of the dispersing agent used, it is preferable that it is 5,000 or more and 50,000 or less, and it is more preferable that it is 5,000 or more and 15,000 or less.

The device for filter filtration may be, for example, a device such as pressure filtration. As a preferable filter, a nano filter, an ultra filter, etc. are mentioned. It is preferable to remove the dispersion solvent left by filter filtration and to further concentrate the pigment nanoparticles in the concentrated extract liquid to obtain the concentrated nanoparticle liquid.

Freeze-drying is not specifically limited, Any thing may be used as long as it is a conventional method. For example, a refrigerant direct expansion method, a redundant freezing method, a fruit circulation method, a triple heat exchange method, and an indirect heating freezing method may be mentioned. It is good to use the method. In either method, it is preferable to perform freeze drying after prefreezing. The conditions for preliminary freezing are not particularly limited, but the sample to be lyophilized needs to be frozen evenly.

The apparatus of the indirect heating freezing method may include a small freeze dryer, an FTS freeze dryer, a LYOVAC freeze dryer, an experimental freeze dryer, a research freeze dryer, a triple heat exchange vacuum freeze dryer, a monocooled freeze dryer, and a HULL freeze dryer. Small freeze dryer, experimental freeze dryer, research freeze dryer, mono-cooling freeze dryer, more preferably small freeze dryer, mono-cooling freeze dryer.

The temperature of the lyophilization is not particularly limited, but is, for example, -190 to -4 ° C, preferably -120 to -20 ° C, more preferably about -80 to -60 ° C. The pressure of the lyophilization is not particularly limited and can be appropriately selected by those skilled in the art. For example, the pressure is preferably 0.1 to 35 Pa, preferably 1 to 15 Pa, more preferably about 5 to 10 Pa. The freeze drying time is, for example, 2 to 48 hours, preferably 6 to 36 hours, more preferably about 16 to 26 hours. However, these conditions can be suitably selected by those skilled in the art. For freeze-drying methods, see, for example, the Pharmaceutical Machinery Technology Handbook: The Society of Pharmaceutical Machinery Technology Studies, Chijin Shokan, pp. 120-129 (September 2000); The Vacuum Handbook: Japan Vacuum Technology Co., Ltd., Omsa, pp. 328-331 ( 1992); Journal of Freezing and Drying Research: Itokoji et al., No. 15, p. 82 (1965).

The centrifugal separator may be any device as long as it can precipitate pigment nanoparticles. For example, in addition to the general-purpose apparatus, a skimming function (a function of sucking the symbol layer during rotation and discharging it out of the system) is added, and a continuous centrifuge for continuously discharging solids.

The centrifugal conditions are preferably 50-10000, more preferably 100-8000, particularly preferably 150-6000 as the centrifugal force (a value indicating how many times the centrifugal acceleration will be applied). Although the temperature at the time of centrifugation depends on the kind of solvent of a dispersion liquid, -10-80 degreeC is preferable, -5-70 degreeC is more preferable, 0-60 degreeC is especially preferable.

Drying under reduced pressure is not particularly limited as long as the solvent can be evaporated. For example, a general-purpose vacuum dryer and a rotary pump, the apparatus which can dry-pressure-drying, stirring a liquid, the apparatus which can be continuously dried by passing a liquid in a heat-decompression pipe | tube, etc. are mentioned.

30-230 degreeC is preferable, 35-200 degreeC is more preferable, and 40-180 degreeC of the heating reduced pressure drying temperature is especially preferable. 100-100000 Pa is preferable, as for the pressure at the time of pressure reduction, 300-90000 Pa is more preferable, 500-80000 Pa is especially preferable.

Moreover, you may dry by the following forms. For example, as a dryer using hot air, a drum dryer, a multi-tube dryer, a cylindrical dryer, etc. are suitably used as a dryer using heat conduction such as a shelf dryer, a band dryer, a stirring dryer, a fluidized bed dryer, a spray dryer, an airflow dryer, and the like. . In addition, depending on the solvent composition, it is also possible to use a freeze dryer or an infrared dryer.

Among these means, a spray dryer (for example, COC-12 manufactured by Owara Kakouki Co., Ltd.) and a fluidized bed dryer (for example, Narakikai Seisaku Co., Ltd.) from the viewpoint of being suitable for obtaining powder dried directly from the dispersion. Sosa product MSD-100) is particularly preferably used. In addition, a plurality of drying means may be combined to form a pigment powder having a low residual solvent amount. For example, a process of completely drying the pigment dispersion preconcentrated with a cylindrical dryer in a drum dryer may be used. have.

There is no restriction | limiting in particular as long as it is possible to evaporate a solvent about drying conditions and materials, such as a pigment and a dispersing agent, will not denature. In addition, for the purpose of increasing the drying rate, it is possible to incorporate means such as reduced pressure, stirring and multistage, depending on the type of the dryer.

Although the quantity which reduces or removes a solvent content is not specifically limited, In the form which reduces a solvent content, it is preferable to remove 50 mass% or more of a total solvent volume, and it is more preferable to remove 75 mass% or more. In the form of removing the amount of solvent, it is preferable to remove 80 mass% or more of the total amount of solvent, and it is more preferable to remove 90 mass% or more.

When the solvent content is decreased by the concentration and removal step, the water content in the remaining dispersion is not particularly limited, but is preferably 0.01 to 3% by mass, more preferably 0.01 to 1% by mass. At this time, for example, it is preferable to remove the solvent content by the above-mentioned drying method and to make the powder of pigment nanoparticles, for example, to make the content rate of solid content into 50-100 mass%, and to make 70-100 mass% More preferred.

 The concentration / removal step may be performed a plurality of times. For example, the concentration and removal step may be performed both before and after addition of the third solvent described later.

The build-up pigment nanoparticles are preferably obtained by redispersing organic particles in agglomerated state by the concentration and removal process. The organic particles concentrated by the above-mentioned form may cause aggregation. As a result, rapid filter filtration and the like are possible, and some may be excessively aggregated in consideration of the number of times of separation. In such a case, in order to obtain a good dispersion state again, it is preferable to obtain the above-mentioned pigment fine particles with a flux. Here, the fluke refers to an aggregate of fine particles which are weakly coagulated (coagulated) to a degree capable of redispersion. By using such pigment fine particles as a flux, for example, organic pigment fine particles precipitated in an aqueous liquid mixture can be quickly separated from the medium by filtration or the like. The separated fluke (soft aggregate) can be redispersed in an organic solvent suitable for the production of a color filter to obtain a pigment dispersion composition (non-aqueous dispersion composition) of an organic solvent having good efficiency. That is, when the mixed solvent of the good solvent and the poor solvent is an aqueous solvent, it can be efficiently replaced with a third solvent made of an organic solvent to change the dispersion medium (continuous phase). Although the average particle diameter of a fluke is not specifically limited, It is preferable that it is 0.5-500 micrometers in consideration of the filterability mentioned above, and it is more preferable that it is 5-100 micrometers. In addition, in this invention, the solvent different from any of the said good solvent (1st solvent) and the said poor solvent (2nd solvent) is named generically "third solvent."

 However, the redispersion of the agglomerated particles is insufficient in the usual dispersing method. Also in such strong aggregated organic particles (in the present invention, the aggregated organic particles are those in which organic particles such as aggregates are gathered by a secondary force, and also referred to as aggregated nanoparticles when the primary particles have a size of nm). Organic particles can be preferably re-dispersed by containing, for example, a polymer compound having a mass average molecular weight of 1000 or more described below in the particle liquid (agglomerated organic particle liquid in the present invention refers to containing agglomerated organic particles in a liquid, Dispersions, concentrates, pastes, slurries, etc. may be included in the aggregated organic particles). In detail, the use of the above-described polymer compound results in good microdispersibility (uniformly small particle size is realized) and dispersion stability (uniformly fine particle size is maintained for a long time when precipitated in a mixed solution of a good solvent and a poor solvent). This medium is retained even after the medium is converted to an organic solvent suitable for the color filter and redispersed, thereby realizing high performance in the color filter. In addition, it is possible to realize high performance in color filters and liquid crystal displays in which the polymer compound interacts with the colorability of the organic pigment fine particles without disturbing the optical properties of the color filter.

It is preferable that the said high molecular compound is a high molecular compound represented by following General formula (1).

일반식(1)

General formula (1)

In the general formula (1), A ¹ is an acidic group, a basic group having a nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and The monovalent organic group which has group selected from the hydroxyl group, or the monovalent organic group containing the organic pigment | dye structure or heterocycle which may have a substituent is shown. n pieces of A ¹ may be the same or different.

The Specifically, A ¹ is not particularly limited, wherein, for example, a "monovalent organic group having an acidic group", a carboxylic acid group, a sulfonic acid group, a mono sulfuric acid ester group, a phosphate group, monophosphate ester group, boric acid group, etc. The monovalent organic group which has is mentioned. Further, having, for example, an amino group (-NH ₂₎ a monovalent organic group, a substituted imino group ^{(-NHR 8, -NR 9 R 10} ) having a "monovalent organic group having a basic group having a nitrogen atom" Monovalent organic groups, where R ⁸ and R ⁹ And each R ¹⁰ independently represents an alkyl group having 1 to 20 carbon atoms, an alkyl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms), and a guanidyl group represented by the following general formula (a1). A valent organic group (In general formula (a1), R ^a1 and R ^a2 each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms.), Monovalent organic group which has an amidinyl group represented by the following general formula (a2) [In general formula (a2), R ^a3 and R ^a4 are respectively independently C1-C20 alkyl group, C6-C20 aryl group, Or an aralkyl group having 7 to 30 carbon atoms.

As the "monovalent organic group having a urea group", for example, -NHCONHR ¹⁵ (wherein R ¹⁵ is a hydrogen atom, an alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, or 7 to 30 carbon atoms) And an aralkyl group).

As the "monovalent organic group having a urethane group", for example, -NHCOOR ¹⁶ , -OCONHR ¹⁷ (wherein R ¹⁶ and R ¹⁷ are each independently an alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms) Or an aralkyl group having 7 to 30 carbon atoms).

Examples of the "monovalent organic group having a group having a coordinating oxygen atom" include a group having an acetylacetonate group, a group having a crown ether, and the like.

Examples of the "monovalent organic group having a hydrocarbon group having 4 or more carbon atoms" include an alkyl group having 4 or more carbon atoms (e.g., an octyl group, a dodecyl group, etc.), an aryl group having 6 or more carbon atoms (e.g., a phenyl group, a naphthyl group, etc.), and a carbon number 7 The aralkyl group (for example, benzyl group etc.) mentioned above is mentioned. Although there is no upper limit in carbon number at this time, it is preferable that it is 30 or less.

Examples of the "monovalent organic group having an alkoxysilyl group" include groups having a trimethoxysilyl group, a triethoxysilyl group, and the like.

As said "monovalent organic group which has an epoxy group", group which has glycidyl group etc. is mentioned, for example.

As said "monovalent organic group which has an isocyanate group", 3-isocyanate propyl group etc. are mentioned, for example.

As said "monovalent organic group which has a hydroxyl group", 3-hydroxypropyl group etc. are mentioned, for example.

It is preferable that it is a monovalent organic group which has an acidic group, a basic group which has a nitrogen atom, a urea group, or a C4 or more hydrocarbon group as said A <^1> .

The organic pigment structure or heterocycle is not particularly limited. More specifically, the organic pigment structure may be, for example, a phthalocyanine compound, an insoluble azo compound, an azolake compound, an anthraquinone compound, a quinacridone compound, or a dioxazine compound. , Diketopyrrolopyrrole compounds, anthrapyridine compounds, anthrone compounds, indanthrone compounds, flavantron compounds, perinone compounds, perylene compounds, thioindigo compounds, and the like. As the heterocycle, for example, thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole , Triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindolin, isoindolinone, benzimidazolone , Succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridon, anthraquinone and the like.

In addition, the said organic pigment | dye structure or heterocyclic ring may have substituent T, As said substituent T, a C6-C16 aryl group, such as a C1-C20 alkyl group, such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group, for example. And C1-C6 alkoxy groups such as acyloxy groups such as acetoxy groups, methoxy groups and ethoxy groups, halogen atoms such as chlorine and bromine, methoxycarbonyl groups, ethoxycarbonyl groups and cyclohexyloxycarbonyl groups Carbonate ester groups, such as a C2-C7 alkoxycarbonyl group, a cyano group, and t-butyl carbonate, a hydroxyl group, an amino group, a carboxyl group, sulfonamide group, and N-sulfonylamide group, etc. are mentioned.

In addition, A <^1> can be represented by following General formula (4).

일반식(4)

General formula (4)

In the general formula (4), B ¹ is an acid group, a basic group having a nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group And an organic pigment structure or a heterocyclic ring which may have a group or a substituent selected from a hydroxyl group, and R ¹⁸ represents a single bond or a monovalent organic or inorganic linking group. a1 represents a 1 ~ 5, a1 of B ¹ may be the same or different to Fig. In group represented by General formula (4), a preferable aspect is the same as that of A <^1> .

R <^18> represents a single bond or an a1 + monovalent coupling group, and a1 represents 1-5. The linking group R ¹⁸ includes a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. You may have more. R ¹⁸ is preferably an organic linking group.

R ^{18 As a} specific example, the following structural unit or a group formed by merging the structural units may be mentioned. On the other hand, the linking group R ¹⁸ is the substituent may have a T.

In said general formula (1), R <^1> represents a (m + n) valent coupling group. m + n satisfies 3-10.

The (m + n) valence group represented by R ^{1 is} composed of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. The group to be included is included and may have a substituent even if it is unsubstituted. R ¹ is preferably an organic linking group.

As a specific example of R <^1> , group (May form a ring structure) comprised by combining the group of said (t-1)-(t-34) or its plurality is mentioned. When the connecting group R ¹ has a substituent, examples of the substituent there may be mentioned the above-described substituent T.

R ² represents a single bond or a divalent linking group. R ² includes a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms and 0 to 20 sulfur atoms, and further has a substituent even if unsubstituted You may be. As a specific example of R <^2> , the group comprised by combining the said t-3-5, 7-18, 22-26, 32, 34 or its plurality is mentioned. R ² preferably has a sulfur atom at the linking position with R ¹ . When said R <^2> has a substituent, the said substituent T is mentioned as said substituent.

M represents 1-8 in the said General formula (1). As m, 1-5 are preferable, 1-3 are more preferable, and 1-2 are especially preferable.

In addition, n represents 2-9. As n, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

In General Formula (1), P ¹ represents a polymer compound residue (polymer skeleton) and can be appropriately selected from ordinary polymers and the like.

Among the polymers, the polymer skeleton structure includes polymers or copolymers of vinyl monomers, ester compound polymers, ether compound polymers, urethane compound polymers, amide compound polymers, epoxy compound polymers, silicone compound polymers and modified or copolymers thereof [for example, At least one selected from the group consisting of a polyether / polyurethane copolymer, a copolymer of a polyether / vinyl monomer polymer, and the like (random copolymer, block copolymer, graft copolymer, etc.) may be used. More preferably at least one selected from the group consisting of polymers or copolymers of vinyl monomers, ester compound polymers, ether compound polymers, urethane compound polymers and modified or copolymers thereof, and particularly preferred are polymers or copolymers of vinyl monomers. .

In addition, the polymer is preferably soluble in an organic solvent. When the affinity with an organic solvent is low, for example, when used as a pigment dispersant, the affinity with a dispersion medium may become weak and it may become impossible to ensure the adsorption layer sufficient for dispersion stabilization.

In addition, P ¹ preferably has a sulfur atom at the linking position with R ¹ .

Among the polymer compounds represented by the general formula (1), polymer compounds represented by the following general formula (2) are more preferable.

일반식(2)

General formula (2)

In the said General formula (2), A <^2> is the same as A <^1> in the said General formula (1), and its specific and preferable aspect is also the same. In addition, A ² may have a substituent and the said substituent T can be illustrated.

In the said General formula (2), R <^3> represents a (x + y) valent coupling group. R <^3> is the same as R <^1>, and its preferable range is also the same. Wherein R ³ is a x + y valence group, but the value of x and its preferred range are equal to n in General Formula (1), the value of y and its preferred range are equal to m, the value of x + y and The preferred range is equal to m + n.

It is preferable that the coupling group represented by R <^3> is an organic coupling group, and the preferable and specific example of this organic coupling group is shown below. However, this invention is not limited by these.

Among the above, from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents, (r-1), (r-2), (r-10), (r-11), and (r-16) and (r-17) are preferable.

Moreover, when said R <^3> has a substituent, the said substituent T is mentioned as said substituent.

In the said General formula (2), R <^4> and R <^5> represents a single bond or a bivalent coupling group each independently.

As a "bivalent coupling group" represented by said R <^4> , R <^5> , you may have a substituent, and it is a linear, branched or cyclic alkylene group, arylene group, or aralkylene group, -O-, -S-, -C (= O ), -N (R ¹⁹ )-, -SO-, -SO _2- , -CO _2- , or -N (R ²⁰ ) SO ₂ -or a divalent group in which two or more groups thereof are combined is preferable. R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Especially, it is preferable that it is an organic coupling group.

Examples of the R ⁴ a straight-chain or branched alkylene group or an aralkyl group, -O-, -C (= O) -, -N (R 19) -, -SO 2 -, -CO 2 - or -N (R ²⁰ ) SO ₂ -or a divalent group in which two or more groups thereof are combined is more preferable, and a linear or branched alkylene group or aralkylene group, -O-, -C (= O)-, -N (R ¹⁹ )- Or -CO ₂ -or a divalent group in which two or more groups thereof are combined is particularly preferable.

Examples of the R ⁵ a single bond, a linear or branched alkylene group, an aralkyl group, -O-, -C (= O) -, -N (R 19) -, -SO 2 -, -CO 2 - , or -N (R ²⁰ ) SO ² -or a divalent group in which two or more groups thereof are combined is more preferable, and a linear or branched alkylene group, aralkylene group, -O-, -C (= 0)-, -N (R ¹⁹ )-or -CO ₂ -or divalent groups in which two or more groups thereof are combined are particularly preferred.

Moreover, when said R <^4> , R <^5> has a substituent, the said substituent T is mentioned as said substituent.

In addition, P <^2> in General formula (2) represents a high molecular skeleton, and can be selected suitably from a normal polymer. About a preferable form of a polymer, it is the same as P <^1> in the said General formula (1), and its preferable form is also the same.

Among the polymer compounds represented by the general formula (2), in particular, R ³ is the specific examples (r-1), (r-2), (r-10), (r-11), (r-16) or (r-17), R ⁴ is a single bond, a straight chain or a branched alkylene group or an aralkylene group, -O-, -C (= O)-, -N (R ¹⁹ )-or -CO ₂ -or these the group is a divalent organic group having combined two or more, R ⁵ is a single bond, an ethylene group, a propylene group or the following general formula (sa) or a linking group represented by (sb), polymer or copolymer of the P ^second vinyl monomers , A polymer compound having an ester compound polymer, an ether compound polymer, a urethane polymer or a modified product thereof, y of 1 to 2 and x of 3 to 6 is particularly preferable. In addition, in the following group, R <^21> represents a hydrogen atom or a methyl group, and l represents 1 or 2.

Although the mass average molecular weight of the said high molecular compound is 1000 or more, 3000-100000 are preferable as a mass average molecular weight, 5000-80000 are more preferable, 7000-60000 are especially preferable. When the mass average molecular weight is in the above range, the effect of a plurality of functional groups introduced at the ends of the polymer is sufficiently exerted, thereby exhibiting excellent performance of adsorption to the solid surface, micelle formation ability, and surfactant activity, and achieving good dispersibility and dispersion stability. can do.

In the present invention, the molecular weight refers to a mass average molecular weight unless otherwise specified. Examples of the method for measuring the molecular weight include a chromatography method, a viscosity method, a light scattering method, a sedimentation rate method and the like, but in the present invention, polystyrene measured by gel permeation chromatography method (carrier: tetrahydrofuran) is not particularly limited. The mass average molecular weight in terms of weight is used.

The specific example of the compound represented by General formula (1) is shown below. However, this invention is not limited at all by these specific examples.

The high molecular compound represented by the said General formula (1) or (2) can be synthesize | combined, for example by the following each method.

1. An acid halide or a plurality of functional groups (A ¹ in the above general formula) having a polymer having a functional group selected from a carboxyl group, a hydroxyl group, an amino group, etc. introduced into the terminal, and a plurality of functional groups (A ¹ or A ² in the above general formula) or an alkyl halide or a plurality of functional groups having an a ²⁾ (a method of reacting a polymer such as an isocyanate having a ¹ or a ²⁾ in the formula.

2. A method for making a Mike addition reaction between a polymer having a carbon-carbon double bond introduced at its terminal and a mercaptan having a plurality of functional groups (A ¹ or A ² in the general formula).

3. A method in which a polymer having a carbon-carbon double bond introduced at its terminal and a mercaptan having a plurality of functional groups (A ¹ or A ² in the general formula) are reacted in the presence of a radical generator.

4. A method in which a polymer having a plurality of mercaptans introduced at its terminal and a functional group (A ¹ or A ² in the general formula) having introduced a carbon-carbon double bond are reacted in the presence of a radical generator.

5. A method of radical polymerization of a vinyl monomer with a mercaptan compound having a plurality of functional groups (A ¹ or A ² in the general formula) as a chain transfer agent.

Especially, 2, 3, 4, 5 are preferable, 3, 4, and 5 are more preferable, and 5 is especially preferable for the ease of synthesis. On the other hand, the contents described in paragraphs 0184 to 0216 of Japanese Patent Application No. 2006-129714 can be referred to for the synthesis method thereof.

As the polymer compound having a molecular weight of 1000 or more, a polymer compound having the following acidic group (hereinafter sometimes referred to as "acid group-containing polymer compound") may be used, and the polymer compound is preferably a polymer compound having a carboxyl group. More preferably, a copolymer compound containing at least one of repeating units derived from (A) a compound having a carboxyl group and at least one of repeating units derived from a compound having (B) a carboxylic acid ester group.

It is preferable that it is a repeating unit represented by the following general formula (I) as a repeating unit derived from the compound which has the said (A) carboxyl group, It is more preferable that it is a repeating unit derived from acrylic acid or methacrylic acid, The said (B) carbon It is preferable that it is a repeating unit represented by the following general formula (II) as a repeating unit derived from the compound which has an acid ester group, It is more preferable that it is a repeating unit represented by the following general formula (IV), Benzyl acrylate and benzyl methacryl Particular preference is given to repeating units introduced in the rate, phenethyl acrylate, phenethyl methacrylate, 3-phenylpropyl acrylate or 3-phenylpropyl methacrylate.

In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ₂ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R <_3> represents group represented by the following general formula (III). R ₄ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxy group, a hydroxyalkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms. R ₅ and R ₆ each represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. i represents the number of 1-5. R ₇ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R <_8> represents group represented by the following general formula (V). R ₉ represents an alkyl group having 2 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms. R ₁₀ and R ₁₁ represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. j represents the number of 1-5.

Further, as the polymerization ratio of the repeating unit derived from the compound having (A) carboxyl group and the repeating unit derived from the compound having (B) carboxylic acid ester group, the quantity of the total number of repeating units of repeating unit (A) It is preferable that ratio is 3-40, and it is more preferable that it is 5-35.

The polymer compound may be either water-soluble or oil-soluble, and may be water-soluble or oil-soluble. The method of adding the polymer compound may be a solution dissolved in an aqueous solvent or an organic solvent, may be in a solid state, or may be a combination thereof. As a method for adding to a solution dissolved in a solvent, for example, a method of adding to a coagulated organic particle liquid in a state of dissolving in a solvent such as a solvent of coagulated organic particle liquid, or in a state dissolved in another solvent compatible with a solvent of coagulated organic particle liquid. The method of adding is mentioned. Although the density | concentration of the high molecular compound in the case of adding to the solution melt | dissolved in the solvent is not restrict | limited, 1-70 mass% is preferable, 2-65 mass% is more preferable, 3-60 mass% is especially preferable.

The polymer compound may be added at the time of precipitation of the pigment nanoparticles, before or after the concentration, at the time of concentration or before or after the dispersion of the aggregated organic particles after the concentration, or before or after these steps and after the completion of these steps. Moreover, you may divide and add in multiple times. In the production method of the present invention, the polymer compound having a mass average molecular weight of 1000 or more may be contained in the composition as a binder to be described later. For example, the organic fine particle precipitate is concentrated and then added when the aggregated organic particles are finely dispersed. Do.

The amount of the polymer compound added is preferably 0.1 to 1000 parts by mass, more preferably 5 to 500 parts by mass, and particularly preferably 10 to 300 parts by mass with respect to 100 parts by mass of the pigment.

A polymer compound having a molecular weight of 1000 or more, and for example, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate Copolymer, Polyvinyl Alcohol-Partial Formalate, Polyvinyl Alcohol- Partial Butyralate, Vinyl Pyrrolidone-Vinyl Acetate Copolymer, Polyethylene Oxide / Propylene Oxide Block Copolymer, Polyamide, Cellulose Derivative, Starch Derivative Etc. can be mentioned. In addition, natural polymer compounds such as arginate, gelatin, albumin, casein, arabian rubber, tragacanth rubber, and lignin sulfonate can also be used. Moreover, polyvinyl sulfate, condensation naphthalene sulfonic acid, etc. are mentioned as a high molecular compound which has an acidic group.

As a high molecular compound which has a carboxyl group, polyacrylic acid, polymethacrylic acid, the cellulose derivative which has a carboxyl group in a side chain, etc. are mentioned, for example. As a copolymer compound containing at least 1 type of the repeating unit derived from the compound which has (A) carboxyl group, and (B) the repeating unit derived from the compound which has the carboxylic acid ester group, Unexamined-Japanese-Patent No. 59-44615. Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Publication No. 59-53836 and Japanese Patent Publication No. 59-71048 Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like as described in the publications. Further preferred examples include acrylic acid-acrylic acid ester copolymers, methacrylic acid-acrylic acid ester copolymers, acrylic acid-methacrylic acid ester copolymers and methacrylic acid-methacrylic acid ester copolymers described in US Pat. And polyporous polymers of acrylic acid or methacrylic acid, acrylic acid ester or methacrylic acid ester and other vinyl compounds.

Examples of vinyl compounds include styrene or substituted styrene (for example, vinyltoluene, vinylethylbenzene), vinylnaphthalene or substituted vinylnaphthalene, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, and the like. And styrene is preferred.

Only 1 type may be used for the high molecular compound of 1000 or more molecular weight, may be used for it combining 2 or more types, and may be used together with the compound of molecular weight less than 1000.

 The build-up pigment nanoparticles are preferably obtained by precipitating the pigment nanoparticles and then containing a third solvent. Although the kind of the third solvent is not particularly limited, it is preferably an organic solvent, for example, an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, an aliphatic compound solvent, a ketone compound solvent, and an ester compound solvent or ketone. Compound solvents are particularly preferred.

As an ester compound solvent, 2- (1-methoxy) propyl acetate, ethyl acetate, ethyl lactate, etc. are mentioned, for example. As an alcohol compound solvent, methanol, ethanol, n-butanol, isobutanol, etc. are mentioned, for example. As an aromatic compound solvent, benzene, toluene, xylene, etc. are mentioned, for example. As an aliphatic compound solvent, n-hexane, cyclohexane, etc. are mentioned, for example. As a ketone compound solvent, methyl ethyl ketone, acetone, cyclohexanone, etc. are mentioned, for example.

Especially, ethyl lactate, ethyl acetate, acetone, and ethanol are preferable, and ethyl lactate is more preferable. These may be used individually by 1 type and may use 2 or more types together.

The addition of the third solvent is not particularly limited as long as it is after precipitation of the pigment nanoparticles, but is preferably added after the above-described concentration / removal process. In the case of the pigment dispersion composition to be described later, it is preferable to add a third solvent after the first concentration and removal step, and reduce or remove the solvent component by the second concentration and removal step. Then, a binder and / or a solvent can be added and it can be set as a desired pigment dispersion composition.

Although the addition amount of a 3rd solvent is not specifically limited, It is preferable that it is 100-30000 mass parts with respect to 100 mass parts of pigment nanoparticles, and it is more preferable that it is 500-10000 mass parts.

The organic pigment dispersion of the present invention contains the breakdown pigment nanoparticle (a) and the buildup pigment nanoparticle (b) produced as described above. The form which mixes both is not specifically limited, The composition of each pigment nanoparticle may be prepared separately, and may be mixed, or may be mixed as powder. Although the mixing ratio of both is not specifically limited, It is preferable that buildup pigment nanoparticle (b) is 1 mass% or more with respect to the total amount of both particles, and it is more preferable that it is 3-95 mass%.

In the organic pigment dispersion of the present invention, the average particle size of all the pigment particles of the pigment nanoparticles (a) and (b) is 40 nm or less, and the ratio of the number of particles having a particle diameter of 50 nm or more is 1% of the total pigment particles. The above-mentioned thing is preferable, It is more preferable to set it as 5% or more, It is especially preferable to set it as 10% or more. Although there is no restriction | limiting in particular in the upper limit of the said ratio, Usually, it shall be 50% or less. At this time, the average particle diameter is more preferably 30 nm or less. Although there is no restriction | limiting in particular in the lower limit of the said average particle diameter, Usually, it shall be 5 nm or more. It is preferable to have two or more local maximums when the particle size distribution is measured about all the said pigment fine particles. Moreover, in the same particle size distribution, it is preferable that the minimum maximum value is 30 nm or less, It is more preferable that it is 25 nm or less, It is especially preferable that it is 20 nm or less.

By using at least one of an R pigment, a G pixel, and a B pixel of the color filter, for example, by using the organic pigment dispersion having the particle size distribution as described above, the color filter of the above-described preferred embodiment can be obtained.

Here, in the above-mentioned organic pigment dispersion, the average particle diameter, monodispersibility of the pigment particle, its preferable range, and those measuring methods are the same as that described about the color filter of the said preferable embodiment.

The concentration in the organic pigment dispersion of the pigment nanoparticles (a) and (b) is appropriately determined according to the purpose, but preferably it is 2-30 mass% with respect to the total amount of the organic pigment dispersion, and 4-20 mass It is more preferable that it is%, and it is especially preferable that it is 5-15 mass%.

Pigment nanoparticles can be used, for example in the state disperse | distributed in the vehicle. The vehicle refers to a part of a medium in which pigments are dispersed when in a liquid state, and includes a part (binder) that binds to the liquid pigment to harden the coating film and a component (organic solvent) that dissolves and dilutes the film. . In addition, the binder used when forming a nanoparticle and the binder used for redispersion may be same or different.

In the case of dispersing in the vehicle as described above, the amount of the binder and the dissolved dilution component is appropriately determined according to the type of organic pigment, etc., but the binder is preferably 1-30 mass%, preferably 3-20 mass%, based on the total amount of the dispersion composition. More preferably, it is especially preferable that it is 5-15 mass%. It is preferable that it is 5-80 mass%, and, as for a dissolved dilution component, it is more preferable that it is 10-70 mass%.

In the above-concentrated nanoparticle liquid, in order to enable rapid filter filtration as described above, it is preferable to aggregate the pigment nanoparticles by concentration, and to concentrate and aggregate by centrifugation or drying. . As a method of redispersing such aggregated nanoparticles, for example, a dispersion method by ultrasonic waves or a method of adding physical energy can be used. The ultrasonic irradiation apparatus used preferably has a function capable of applying an ultrasonic wave of 10 kHz or more, and examples thereof include an ultrasonic homogenizer and an ultrasonic cleaner. When the liquid temperature rises during ultrasonic irradiation, thermal coagulation of nanoparticles occurs (see Pigment Dispersion Technology-Surface Treatment and Dispersant Usage and Dispersibility Evaluation-Technical Information Association 1999). It is preferable, and 5-60 degreeC is more preferable. The temperature control method can be carried out by controlling the dispersion liquid temperature, controlling the temperature of the temperature adjusting layer for controlling the dispersion temperature, and the like.

There is no restriction | limiting in particular as a disperser used when disperse | distributing the concentrated pigment nanoparticle by physical energy, For example, dispersers, such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill, are mentioned. Can be. Moreover, a high pressure dispersion method and the dispersion method by use of microparticle beads are mentioned as a preferable thing.

The coloring photosensitive resin composition of this invention contains the said organic pigment dispersion, a monomer or oligomer, and a binder.

Although the organic pigment dispersion containing the pigment nanoparticles (a) and (b) has already been described in detail, in the coloring photosensitive resin composition, the total content of the pigment nanoparticles (a) and (b) is the total solid content thereof. In the present invention, the total solid content is preferably 3 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 25 to 60% by mass with respect to the total composition of the composition excluding the organic solvent. When this amount is too large, the viscosity of a dispersion liquid may rise, and it may become a problem in manufacturing suitability. When too small, the coloring power is not enough. As microparticles | fine-particles which function as a coloring agent, it is preferable that it is 0.1 micrometer or less in particle size, and especially 0.08 micrometer or less in particle diameter. Moreover, you may use it, combining with a normal pigment for coloring.

As a monomer or oligomer, it is preferable to have two or more ethylenically unsaturated double bonds and to add-polymerize by light irradiation. As such a compound, the compound which has at least 1 addition-polymerizable ethylenically unsaturated group in a molecule, and whose boiling point is 100 degreeC or more at normal pressure is mentioned. Examples thereof 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. Acrylates; Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) arc acrylate, trimethylol ethane triacrylate, trimethylol propane tri (meth) acrylate, trimethylol propane diacrylate, neopentyl glycol di (meth ) Acrylic acid, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol 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 (meth) acrylate to ethylene oxide or propylene oxide to polyfunctional alcohols such as trimethylolpropane and glycerin. Furthermore, as described in General Formulas (1) and (2) in Japanese Patent Application Laid-Open No. 10-62986, a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated is also preferred. Can be mentioned. Here, "(meth) acrylate" means containing acrylate and methacrylate, and "(meth) acrylic acid" means containing acrylic acid and methacrylic acid.

Urethane acrylates described in Japanese Patent Application Laid-Open No. 48-41708, Japanese Patent Application Laid-open No. 50-6034 and Japanese Patent Application Laid-open No. 51-37193; Polyester acrylates described in JP-A-48-64183, JP-A-49-43191 and JP-A-52-30490; Polyfunctional acrylates and methacrylates, such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid, are mentioned.

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 Unexamined-Japanese-Patent No. 11-133600 is also mentioned as a preferable thing.

As for an oligomer, the thing of the molecular weight 200-1000 is preferable, You may use individually or in mixture of 2 or more types, As for content with respect to the total solid of the inkjet ink for color filters, 5-50 mass% is common, 10-40 mass% Is preferred. When this amount is too large, control of developability becomes difficult and becomes a problem in manufacturing suitability. When too small, hardening power will become inadequate at the time of exposure.

As the binder, a binder having an acidic group is preferable and may be added when preparing an inkjet ink for a color filter or a colored photosensitive resin composition, but may also be added when preparing the pigment nanoparticle dispersion composition or when forming the pigment nanoparticles. desirable. A binder may be added to both or one of the poor solvents in order to add the organic pigment solution and the organic pigment solution to produce pigment nanoparticles. Or it is also preferable to add a binder solution when forming a pigment nanoparticle by a separate system. As a binder, the alkali-soluble polymer which has polar groups, such as a carboxylic acid group and a carboxylate group, in a side chain is preferable. Examples include Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, and Japanese Patent Publication No. 59-53836 Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like described in Japanese Patent Application Laid-Open No. 59-71048 Can be mentioned. Moreover, the cellulose derivative which has a carboxylic acid group, a carboxylate, etc. in a side chain can also be mentioned, In addition, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used conveniently. Moreover, as a particularly preferable example, the copolymer of benzyl (meth) acrylate and (meth) acrylic acid described in US Patent No. 4,139,391, and the polycopolymer of benzyl (meth) acrylate, (meth) acrylic acid, and another monomer are mentioned. Can be. These polar binder polymers may be used alone, or may be used in a state of a composition used in combination with a conventional film-forming polymer, and the amount of addition to 100 parts by mass of pigment nanoparticles is generally 10 to 200 parts by mass, and 25 100 mass parts is preferable.

Moreover, in order to improve crosslinking efficiency, you may have a polymeric group in a side chain, UV curable resin, a thermosetting resin, etc. are also useful. Examples of the polymer containing these polymerizable groups are exemplified below, but are not limited as long as alkali-soluble groups such as COOH groups, OH groups, and ammonium groups are included. An epoxy ring having a OH group reactivity in a copolymer of, for example, 2-hydroxyethyl acrylate having an OH group and a monomer such as, for example, methacrylic acid and an acrylic or vinyl compound copolymerizable with these, containing a COOH group; Compounds having a carbon-carbon unsaturated bond group, for example, compounds obtained by reacting a compound such as glycidyl acrylate can be used. In the reaction with OH, in addition to the epoxy ring, a compound having an acid anhydride and an isocyanate group and having an acryloyl group can also be used. In addition, reactants obtained by reacting a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring disclosed in Japanese Patent Application Laid-Open No. Hei 6-102669 and Japanese Patent Application Laid-Open Hei 6-1938 are reacted with a saturated or unsaturated polybasic anhydride. Can be used. As a compound having an alkali solubilizer and a carbon-carbon unsaturated group such as COOH, for example, DIANAL NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer6173 (COOH-containing Polyurethane acrylic oligmer, Diamond Shamrock Co. Ltd.), Biscot R -264, KS Resist 106 (all from Osaka Yuuki Kagaku Kogo Co., Ltd.), CYCLOMER P Series, Placcel CF200 Series (all from Daisel Kagaku Kogo Co., Ltd.), Ebecryl 3800 (from Daicel UCB Co., Ltd.) Etc. can be mentioned.

As the binder resin, an organic polymer having a water-soluble atomic group in a part of the side chain can be used. The binder resin is a linear organic polymer which is compatible with the monomer, and is an organic solvent and an alkali-soluble (preferably one that can be developed with a weak alkaline aqueous solution). As said alkali-soluble resin, the polymer which has a carboxylic acid in a side chain, for example, Unexamined-Japanese-Patent No. 59-44615, Japan Patent Publication 54-34327, Japan Patent Publication 58-12577, Japan Patent Publication 54 Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid such as those described in -25957, Japanese Patent Laid-Open No. 59-53836, and Japanese Patent Laid-Open No. 59-71048 Copolymers, partially esterified maleic acid copolymers, and the like, and an acidic cellulose derivative having a carboxylic acid in the side chain thereof may be mentioned. As said alkali-soluble resin, what added the acid anhydride to the polymer which has a hydroxyl group, etc. are useful. Especially among these, the benzyl (meth) acrylate / (meth) acrylic acid copolymer, the benzyl (meth) acrylate / (meth) acrylic acid, and the polypolymer of another monomer are preferable specifically ,. As the alkali-soluble resin, at least one acid component monomer selected from at least (i) maleic anhydride (MAA), acrylic acid (AA), methacrylic acid (MA), and formic acid (FA), and (ii) alkylpolyoxyethylene Copolymers consisting of (meth) acrylate and (iii) benzyl (meth) acrylate (hereinafter sometimes referred to as "copolymer A") can be used.

Examples of the copolymer A include (i) an acid component monomer, (ii) alkyl polyoxyethylene (meth) acrylate (Acr (EO) n: CH ₃ (OC ₂ H ₄ ) nOCOC (R) = CH ₂ ), (Iii) The composition mass ratio of benzyl (meth) acrylate (Bz (M) A) is preferably 10 to 25/5 to 25/50 to 85, more preferably 15 to 20/5 to 20/60 to 80 This is preferred. Moreover, as polystyrene conversion mass mean molecular weight (Mw) by GPC of the said copolymer, Preferably it is 3,000-50,000, More preferably, it is 5,000-30,000.

(i) Alkali solubility and solubility to a solvent will hardly fall when the composition mass ratio of an acid component monomer exists in the said range. Moreover, when the composition mass ratio of (ii) alkyl polyoxyethylene (meth) acrylate (Acr (EO) n: CH ₃ (OC ₂ H ₄ ) nOCOC (R) = CH ₂ ) is in the above range, the liquid of the composition Since it is easy to spread on a board | substrate and the dispersibility of a coloring agent does not fall easily, the effect of this invention can be effectively achieved. (Iii) When the composition mass ratio of benzyl (meth) acrylate (Bz (M) A) is in the above range, the solubility of the colorant and the alkali developability of the coating film are less likely to decrease.

On the other hand, the repeating number n of polyoxyethylene (EO) n of the above-mentioned (ii) alkyl polyoxyethylene (meth) acrylate (Acr (EO) n: CH ₃ (OC ₂ H ₄ ) nOCOC (R) = CH ₂ ) 2-15 are preferable, 2-10 are more preferable, and 4-10 are especially preferable. When the repetition number n is in the above range, development residues are less likely to occur after development with an alkali developing solution, fluidity decreases as a coating liquid of the composition, and coating nonuniformity can be prevented, and uniformity and liquid of the coating film thickness can be prevented. It is possible to prevent the liquid savinig from deteriorating.

The binder polymers having these polar groups may be used alone or in a state of a composition used in combination with an ordinary film-forming polymer, and the amount of addition to 100 parts by mass of pigment nanoparticles is generally 10 to 200 parts by mass, and 25 100 mass parts is preferable.

When the binder is a high molecular compound, the number of acidic groups in the high molecular compound is not particularly limited, but when the number of repeating units included in one molecule is 100, the repeating unit having an acidic group is preferably 5 to 100, 10 It is more preferable that it is -100. In addition, in terms of the polymerization ratio of the repeating unit derived from the compound having a carboxyl group and the repeating unit derived from the compound having a carboxylic acid ester group, the mole% of the repeating unit (1) is 5 to 40. It is preferable that it is preferable that repeating unit (2) is 40-90, and it is preferable that repeating units other than repeating unit (1) or (2) are 25 or less. Moreover, 3000-1 million are preferable, as for the molecular weight of the high molecular compound of the alkali-soluble binder which has an acidic group, 4000-200000 are more preferable, 5000-80000 are especially preferable.

In addition, the above-described polymer compound having a mass average molecular weight of 1000 or more can be preferably used, and the content thereof is generally 15 to 50% by mass, and preferably 20 to 45% by mass, based on the total solids of the colored photosensitive resin composition. When this amount is too large, the viscosity of the composition becomes too high, which is a problem in terms of manufacturability. When too small, there exists a problem in formation of a coating film.

As a photoinitiator or a photoinitiator type | system | group (in this invention, a photoinitiator system refers to the polymerization initiator composition which expresses the function of photoinitiator by merging of several compound), the bisinal polyketaldo disclosed in the specification of US2367660. Neyl Compound, Acyloin Ether Compound Described in US Patent No. 2448828, Aromatic Acyloin Compound Substituted with α-Hydrocarbon as Described in US Patent No. 2722512, US Patent No. 3046127 and No. 2951758 Multinuclear Quinone Compounds Described in the Specification, Triarylimidazole Dimers Described in US Pat. No. 3549367 and p-Aminoketones; Benzothiazole Compounds and Trihalomethyl in JP-A-51-48516 -s-triazine compound, trihalomethyl-triazine compound described in US Patent No. 4239850, US Patent No. 4212976 Trihaloalkyl described in the books and the like can be mentioned methyl oxadiazole compound. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole and triarylimidazole dimers are preferable.

In addition, "polymerization initiator C" described in Japanese Patent Laid-Open No. 11-133600, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O- as an oxime system Benzoyl-4 '-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyl oxide, hexafluorophosphoro-trialkylphenylphosphonium salt, etc. are also exemplified as preferred. can do.

Although these photoinitiators or photoinitiator system may be individual or it may mix and use 2 or more types, It is preferable to use 2 or more types especially. By using at least two photopolymerization initiators, display characteristics, especially display stains, can be reduced.

As for content of the photoinitiator or photoinitiator system with respect to the total solid of a coloring photosensitive resin composition, 0.5-20 mass% is common, and 1-15 mass% is preferable. If this amount is too large, the sensitivity becomes too high and control becomes difficult. When too small, exposure sensitivity will become low too much. Especially as radiation which can be used at the time of exposure, ultraviolet rays, such as g line | wire and i line | wire, are preferable. 5-1500mJ / cm <2> is preferable, 10-1000mJ / cm <2> of an irradiation amount is more preferable, 10-500mJ / cm <2> is especially preferable.

In the coloring photosensitive resin composition of this invention, you may use an organic solvent further than the said component. Examples of the organic solvent are not particularly limited, but esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, Butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-oxypropionate alkyl esters, such as methyl 3-oxypropionate and ethyl 3-oxypropionate; Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2 Methyl methoxypropionate, 2-methoxy ethylpropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy-2-methylpropionate, 2-oxy-2- Ethyl methyl propionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, Ethyl 2-oxobutyrate and the like; Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, propylene glycol methyl Ether acetate and the like; Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclohexanol, 2-heptanone, 3-heptanone and the like; Aromatic hydrocarbons, for example, toluene, xylene and the like. Of these solvents, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethylcarbitol acetate , Butylcarbitol acetate, propylene glycol methyl ether acetate, and the like are suitably used as the solvent in the present invention. These solvents may be used alone or in combination of two or more thereof.

Moreover, the solvent whose boiling point is 180 degreeC-250 degreeC can be used as needed. The following are illustrated as these high boiling point solvents. Diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, 3,5,5-trimethyl-2-cyclohexen-1-one, butyl lactate, dipropylene glycol monomethyl ether acetate , Propylene glycol monomethyl ether acetate, propylene glycol diacetate, propylene glycol-n-propyl ether acetate, diethylene glycol diethyl ether, 2-ethylhexyl acetate, 3-methoxy-3-methylbutyl acetate, γ-butyl lactone , Tripropylene glycol methyl ethyl acetate, dipropylene glycol -n-butyl acetate, propylene glycol phenyl ether acetate, 1,3-butanediol diacetate.

As for content of a solvent, 10-95 mass% is preferable with respect to coloring photosensitive resin composition whole quantity.

In the color filter used conventionally, in order to realize high color purity, the color of each pixel became dark and there existed a problem that the nonuniformity of the film thickness of a pixel is recognized as a color spot as it is. For this reason, there has been a demand for quantification of film thickness variations that directly affect the film thickness of pixels.

In the color filter of this invention, it is preferable to contain a suitable surfactant in a coloring photosensitive resin composition from a viewpoint of being able to control to uniform film thickness, and effectively preventing the color stain by a change in film thickness.

As said surfactant, surfactant disclosed by Unexamined-Japanese-Patent No. 2003-337424 and Unexamined-Japanese-Patent No. 11-133600 is mentioned as a preferable thing. As for content of surfactant, 5 mass% or less is preferable with respect to resin composition whole quantity.

It is preferable that the coloring photosensitive resin composition of this invention contains a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, hydoquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thio Bis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine, and the like. . As for content of a thermal-polymerization inhibitor, 1 mass% or less is preferable with respect to coloring photosensitive resin composition whole quantity.

The coloring photosensitive resin composition of this invention can add a coloring agent (dye, pigment) other than the said coloring agent (pigment) as needed. When using a pigment in a coloring agent, it is preferable to disperse | distribute uniformly in a coloring photosensitive resin composition, and for that reason, it is preferable that particle diameter is 0.1 micrometer or less, especially 0.08 micrometer or less.

As a dye or a pigment, specifically, the pigment | dye material as described in Unexamined-Japanese-Patent No. 2005-17716-[0038]-[0040], or Unexamined-Japanese-Patent No. 2005-361447-[0072] The pigment described and the coloring agent of Unexamined-Japanese-Patent No. 2005-17521-[0088] can be used preferably. As for content of the dye or pigment used supplementally, 5 mass% or less is preferable with respect to coloring photosensitive resin composition whole quantity.

The coloring photosensitive resin composition of this invention can contain a ultraviolet absorber as needed. As a ultraviolet absorber, salicylate type, benzophenone type, benzotriazole type, cyanoacrylate type, nickel chelate type, hindered amine type, etc. are mentioned other than the compound of Unexamined-Japanese-Patent No. 5-72724.

Specifically, phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ', 5'-di-t-4'-hydroxybenzoate, 4-t -Butylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2'-hydroxy Hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3 -Diphenylacrylate, 2,2'-hydroxy-4-methoxybenzophenone, nickel dibutyldithiocarbamate, bis (2,2,6,6-tetramethyl-4-pyridine) -sebacate, 4-t-butylphenylsalicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethylpiperizine condensate, succinic acid-bis (2,2,6,6-tetramethyl-4- Piperidenyl) -ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- (diethyl Amino) -5-triazin-2-yl] amino} -3-phenylcoumarin and the like The can. As for content of a ultraviolet absorber, 5 mass% or less is preferable with respect to coloring photosensitive resin composition whole quantity.

In addition, in the coloring photosensitive resin composition of this invention, the "adhesion adjuvant" of Unexamined-Japanese-Patent No. 11-133600, other additives, etc. can be contained in addition to the said additive.

The coloring photosensitive resin composition of this invention can be made into the inkjet ink for color filters by adjusting the composition timely. At this time, it is preferable to control the ink temperature so that the variation in viscosity is within ± 5%. It is preferable that the viscosity at the time of injection is 5-25 mPa * s, It is more preferable that it is 8-22 mPa * s, It is especially preferable that it is 10-20 mPa * s (The viscosity in this invention is 25 degreeC in particular, unless it restrict | limits especially). Value when). In addition to the setting of the injection temperature, the viscosity can be adjusted by adjusting the type and amount of the components to be contained in the ink. The said viscosity can be measured by normal apparatuses, such as a conical flat rotational viscometer and an E-type viscometer, for example.

In addition, the surface tension of the ink at the time of injection is preferably from 15 to 40 mN / m from the viewpoint of improving the flatness of the pixel (the surface tension in the present invention is a value at 23 ° C unless otherwise limited). More preferably, it is 20-35 mN / m, Most preferably, it is 25-30 mN / m. Surface tension can be adjusted with addition of surfactant and the kind of solvent. The surface tension is, for example, a well-known surface tension measuring device (Kyowa Kaimen Kagaku Co., Ltd., CBVP-Z), a fully automatic type electro surface tension meter ESB-V (Kyowa Kagaku Co., Ltd.), etc. It can measure by a platinum plate method using a measuring instrument.

The ink jet ink for color filter of the present invention is a method of continuously spraying charged ink and controlling it by an electric field, intermittently spraying ink using a piezoelectric element, heating the ink and spraying intermittently using the foaming. Various methods, such as the method of making it, can be used.

In addition, regarding the inkjet method used for forming each pixel, conventional methods such as a method of thermosetting ink, a photocuring method, and a method of dropping a transparent aqueous phase layer on a substrate in advance and dropping can be used.

Ordinary water can be applied to the inkjet head (hereinafter, simply referred to as a head), and a continuous type or a drop-on-demand type can be used. Among the required extraction types, the thermal head is preferably a shape having movable sides as described in Japanese Patent Application Laid-open No. Hei 9-323420 for discharging. As the piezo head, for example, heads described in European Patent A 277,703 and European Patent A 278,590 can be used. The head preferably has a temperature control function so as to manage the temperature of the ink. It is preferable to set the injection temperature so that the viscosity at the time of injection becomes 5-25 mPa * s, and to control the ink temperature so that the fluctuation range of a viscosity may be within +/- 5%. Moreover, it is preferable to operate at 1-500 kHz as a drive frequency.

Furthermore, after forming each pixel, the heating process of heat processing (so-called baking process) may be included. That is, the board | substrate which has a layer which photopolymerized by light irradiation is heated in an electric furnace, a dryer, etc., or an infrared lamp is irradiated. The heating temperature and time depend on the composition of the photosensitive deep color composition or the thickness of the formed layer, but generally from about 10 to about 120 minutes at about 120 ° C to about 250 ° C in terms of obtaining sufficient solvent resistance, alkali resistance and ultraviolet absorbance. It is preferable to heat.

The pattern shape of the color filter thus formed is not particularly limited, and may be a stripe shape, a lattice shape, or a delta array shape, which is a general black matrix shape.

In this invention, the manufacturing method which creates a partition beforehand and prepares an ink in the part enclosed by the said partition before the pixel formation process using the inkjet ink for color filters mentioned above is preferable. The barrier rib may be any type, but in the case of producing a color filter, the barrier rib is preferably a barrier rib having a light shielding function having a black matrix function (hereinafter, simply referred to as a "barrier rib"). The partition wall can be produced by the same material and method as those of the usual black matrix for color filters. For example, paragraphs [0021] to [0074] of Japanese Patent Laid-Open No. 2005-3861, or the black matrix described in paragraphs [0012] to [0021] of Japanese Patent Laid-Open No. 2004-240039, and Japanese Patent Paragraph Nos. [0015]-[0020] of Unexamined-Japanese-Patent No. 2006-17980, black-matrix for inkjets, etc. of Paragraph No.-0009-[0044] of Unexamined-Japanese-Patent No. 2006-10875 are mentioned.

Although it can be set as a coating film using said coloring photosensitive resin composition, the thickness can be suitably determined, It is preferable that it is 0.5-5.0 micrometers, and it is more preferable that it is 1.0-3.0 micrometers. In the coating film using this coloring photosensitive resin composition, the oligomer contained therein can be superposed | polymerized and the color filter which has it as a polymerization film of a coloring photosensitive resin composition can be manufactured (The manufacture of a color filter is mentioned later.). The polymerization of the polymerizable monomer or the polymerizable oligomer can be carried out by actuating the photopolymerization initiator or the photopolymerization initiator system by light irradiation.

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

The coating method for the substrate of the colored photosensitive resin composition is excellent in spin coating in that a thin film having a thickness of 1 to 3 μm can be uniformly applied with high precision, and can be widely used in the production of color filters. However, in recent years, in order to further increase the manufacturing efficiency and manufacturing cost in accordance with the enlargement and mass production of liquid crystal display devices, slit coating suitable for coating a large area substrate with a wider width than spin coating has been used for the production of color filters. On the other hand, the slit coating is superior to the spin coating from the viewpoint of liquid storage, and a uniform coating film can be obtained with a smaller amount of coating liquid.

The slit coating has a slit having a width of several tens of microns at the tip and a constant relative speed between the substrate and the coating head, while maintaining the clearance of the substrate at several 10 to several hundred microns with the application head having a length corresponding to the application width of the rectangular substrate. It is a coating method to apply a coating liquid supplied from a slit to a board | substrate at a predetermined discharge amount. This slit coating has less liquid loss than (1) spin coating, (2) cleaning process is reduced to prevent the coating liquid from scattering, and (3) there is no reincorporation into the dispersed liquid component coating film. 4) Since there is no time for the rotation to start and stop, the tack time can be shortened, and (5) it has the advantage of easy application to a large substrate. Due to these advantages, slit coating is suitable for the production of color filters for large screen liquid crystal display devices, and is expected as an advantageous coating method even in reducing the amount of coating liquid.

Since the slit coating forms a coating film having a much larger area than the spin coating, it is necessary to maintain a certain relative speed between the coater and the coated object when discharging the coating liquid from a wide slit outlet. For this reason, the favorable fluidity | liquidity is calculated | required by the coating liquid used for the slit coating system. In addition, the slit coating is particularly required to maintain a constant condition of the coating liquid supplied to the substrate in the slit of the coating head throughout the coating width. If liquid properties such as fluidity and viscoelastic properties of the coating liquid are insufficient, coating unevenness tends to occur, and it becomes difficult to keep the coating thickness constant in the coating width direction, resulting in a problem that a uniform coating film cannot be obtained.

 For these reasons, many attempts have been made to improve the fluidity or viscoelastic properties of the coating liquid in order to obtain a uniform coating film without any nonuniformity. However, as described above, there are proposed means for lowering the molecular weight of the polymer, selecting a polymer having excellent solubility in the solvent, selecting various solvents for controlling the evaporation rate, or using a surfactant. All were not enough to improve the problem mentioned above.

It is preferable to form the photosensitive resin transfer material of this invention using the photosensitive resin transfer material described in Unexamined-Japanese-Patent No. 5-72724, ie, the integrated film. As an example of a structure of the said integral film, the structure which laminated | stacked the support body / thermoplastic resin layer / intermediate | middle layer / photosensitive resin layer / protective film in this order is mentioned, As a photosensitive resin transfer material of this invention, the said coloring photosensitive resin composition is photosensitive. What formed as a resin layer is preferable.

In the photosensitive resin transfer material of the present invention, it is necessary to have plasticity and not have significant deformation, shrinkage, or elongation even under pressure or under pressure and heating. Examples of such a branched member include polyethylene terephthalate film, triacetic cellulose film, polystyrene film, polycarbonate film, and the like, and biaxially stretched polyethylene terephthalate film is particularly preferable.

As a component used for a thermoplastic resin layer, the organic polymer material of Unexamined-Japanese-Patent No. 5-72724 is preferable, and the softening point by the Vicat method (specifically, the softening point measurement method by the American material test method ASTMD1235) is weak. Particular preference is given to being selected from organic polymeric materials of up to 80 ° C. Specific examples include 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; Polyvinyl chloride copolymers, polyvinylidene chloride, vinylidene chloride copolymers, polystyrene, styrene and styrene copolymers such as styrene and (meth) acrylic acid esters or saponified products thereof, polyvinyltoluene, vinyltoluene and (meth) acrylic acid esters or their Vinyl toluene copolymer such as saponified product, poly (meth) acrylic acid ester, (meth) acrylic acid ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer nylon, copolymer nylon, N-alkoxy methylated nylon, N And organic polymers such as polyamide resins such as -dimethylaminoylated nylon.

In the photosensitive resin transfer material of this invention, it is preferable to form an intermediate | middle layer in order to prevent mixing of components at the time of apply | coating a some coating layer and the storage after application | coating. As the intermediate layer, Japanese Patent Laid-Open No. 5-72724 is described as a "separation layer". It is preferable to use an oxygen barrier film having an oxygen blocking function, and in this case, the sensitivity is increased when exposing and the time load of the exposure machine is increased. Decreases and productivity improves.

As said oxygen barrier film, it is preferable to show low oxygen permeability and to disperse or dissolve in water or aqueous alkali solution, and to select suitably from a normal thing. Of these, particularly preferred is the combination of polyvinyl alcohol and polyvinylpyrrolidone.

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

In the photosensitive resin transfer material of the present invention, a coating liquid (a coating liquid for thermoplastic resin layer) in which an additive of a thermoplastic resin layer is dissolved on a base member is dried, and a thermoplastic resin layer is formed by drying. It can produce by apply | coating and drying the solution of the intermediate | middle layer material which consists of a solvent which does not melt a resin layer, and apply | coats, dries, and forms the photosensitive resin layer with the solvent which does not dissolve an intermediate layer after that.

In addition, by preparing a sheet having a thermoplastic resin layer and an intermediate layer formed on the branch support and a sheet having a photosensitive resin layer formed on a protective film, and bonding the intermediate layer and the photosensitive resin layer to each other, It is also possible to prepare a sheet in which a thermoplastic resin layer is formed on a sheet and a sheet in which a photosensitive resin layer and an intermediate layer are formed on a protective film, and to be bonded to each other such that the thermoplastic resin layer and the intermediate layer are in contact with each other.

In the photosensitive resin transfer material of the present invention, the film thickness of the photosensitive resin layer is preferably 1.0 to 5.0 µm, more preferably 1.0 to 4.0 µm, particularly preferably 1.0 to 3.0 µm. In addition, although it is not specifically limited, As a preferable film thickness of other layers, a support body is 15-100 micrometers, a thermoplastic resin layer is 2-30 micrometers, an intermediate layer is 0.5-3.0 micrometers, and a protective film is 4-40 micrometers generally. desirable.

In addition, in the said manufacturing method, although application | coating can be performed by a normal coating apparatus etc., in this invention, it is preferable to carry out by the coating apparatus (slit coater) using the slit-shaped nozzle demonstrated previously. Preferable specific examples of the slit coater are as described above.

The color filter of this invention can be used as what is excellent in contrast. In the present invention, the contrast refers to the ratio of the amount of transmitted light when the polarization axes are parallel and perpendicular between two polarizing plates ("7th Color Optical Conference of 1990, 512 Color Display for 10.4" Size TFT-LCD Color filters, Ueki, Ozeki, Fukunaga, Yamanaka ", etc.).

The high contrast of the color filter indicates that the contrast of the contrast when combined with the liquid crystal can be increased, which is a very important performance for the liquid crystal monitor to be replaced by the CRT. It is preferable that the contrast of the color filter of this invention is 3000 or more in monochromatic color, It is more preferable that it is 5000 or more, It is especially preferable that it is 7000 or more. In the color filter which has R pixel, G pixel, and B pixel, and formed the black matrix as needed, it is preferable that it is 3000 or more, It is more preferable that it is 5000 or more, It is especially preferable that it is 6000 or more. The present invention has the feature of realizing such a high contrast.

When the color filter of the present invention is used for a television, the chromaticity of all the single colors of red (R), green (G), and blue (B) by the F10 light source are the values shown in the following table (hereinafter, " It is preferable that it is the range within 5 within the difference (DELTA) E of the target chromaticity ", It is more preferable that it is within 3, It is especially preferable that it is within 2.

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

In the present invention, the chromaticity is measured by a microscopic spectrophotometer (Olympus Co., Ltd .; OSP100 or 200), calculated as a result of 2 degrees F10 light source field of view, and represented by the xyY value of the xyz colorimeter. In addition, the difference of target chromaticity is represented by the color difference of La * b * color system.

The liquid crystal display device provided with the color filter of this invention uses the color filter of this invention excellent in contrast, and is excellent in description power, such as a black finish. It can also be used suitably also as a large screen liquid crystal display device, such as a notebook monitor and a television monitor.

EXAMPLE

Hereinafter, although this invention is demonstrated in more detail based on an Example, this invention is not limited and interpreted by this.

(Example, Comparative Example 1)

Pigment Dispersion Composition A

 15.0 ml of dimethyl sulfoxide (from Wako Pure Chemical Industries, Ltd.), 75.0 ml of sodium methoxide 28% methanol solution, 50 g of pigment CIPigment Red 254 (Irgphor Red BT-CF, trade name, manufactured by Chiba Specialty Chemicals Co., Ltd.) and poly 90.0 g of vinyl pyrrolidone (K-30, a brand name, Wako Pure Chemical Industries Ltd.) was added, and pigment solution A (density: 1.0 kg / m <2>) was prepared. The viscosity was measured for this pigment solution A using Viscomate VM-10A-L (brand name, the product made by CBC Materials), and the viscosity when the liquid temperature of pigment solution A was 25.0 degreeC was 18.0 mPa * s. In contrast, 2000 ml of water containing 20 ml of 1 mol / L hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared as a poor solvent.

Here, NP-KX-500 type pigment solution A was added to 2000 ml of poor solvent water which temperature-controlled at 25 degreeC, and stirred at 500 rpm by GK-0222-10 type Ramond stirrer (brand name, the product made by Fujisawa Yakuhin Kogyo Co., Ltd.). It injected | threw-in using the large capacity | capacitance-free pump (brand name, the Nippon Seimitsu Chemical Co., Ltd. product). The flow path diameter and supply diameter of the liquid feed pipe of the pigment solution A were 0.8 mm, the feed port was put in a poor solvent, and injected at a flow rate of 100 ml / min to form organic pigment particles, thereby preparing a pigment dispersion A. The number average particle diameter Mn and monodispersity (Mv / Mn) of the pigment nanoparticles in this pigment dispersion A were measured using Nanotrac UPA-EX150 (trade name, manufactured by Nikkiso Corporation). The results are shown in Table 1 below.

Pigment Dispersion A prepared in the above procedure was concentrated at 5000 rpm for 90 minutes using H-112 centrifugal filter manufactured by Kokusan Co., Ltd. and P89C filter cloth manufactured by Shikishima Canvas Co., Ltd. to recover the pigment nanoparticle concentrate paste. It was. It was 17.2 mass% when the paste pigment content rate was measured using the 8453 type spectrophotometer by Agilent.

Next, 13.8 g of the pigment nanoparticle concentrate paste, 5 g of ethyl lactate, 0.1 g of pigment dispersant A synthesized according to Japanese Patent Application Laid-Open No. 2000-239554, methacrylic acid / benzyl methacrylic acid copolymer (molar ratio 28/72). The mass average molecular weight: 30,000 and the solution which added 5.94 g of 40% 1-methoxy- 2-propyl acetate solution) were added, and it stirred at 1500 rpm 60 minutes with the resolver. Thereafter, 25.0 cc of ethyl acetate was added, and further stirred at 500 rpm for 10 minutes with a dissolver to obtain a dispersion.

The obtained dispersion liquid was filtered using a FP-010 filter manufactured by Sumitomo Denco Fine Polymer Co., Ltd. to obtain a paste-like concentrated pigment liquid A (nano pigment concentration 32.2% by mass).

The pigment dispersion composition A of the following composition was prepared using the said paste-form concentrated pigment liquid A.

20.0 g of the concentrated pigment liquid A

1,3 butylene glycol diacetate 44.3 g

The pigment dispersion composition A having the composition was dispersed at a circumferential speed of 9 m / s for 1 hour using a motor mill M-50 (manufactured by Aiger Japan) using zirconia beads having a diameter of 0.65 mm.

Pigment Dispersion Composition B

In the preparation of the pigment dispersion composition A, the same procedure was followed except that the methacrylic acid / benzyl methacrylic acid copolymer was replaced by an equivalent mass to the exemplary polymer compound C-1 of the general formula (1) of the present invention, Pigment dispersion composition B containing pigment nanoparticles was prepared.

Pigment Dispersion Composition C

In the preparation of pigment dispersion composition B, all the same was carried out until the concentrated pigment solution was prepared. Instead of using a filter for filtration, the concentrated solution was transferred to a branch-type fresco and evaporated at 70 ° C. Drying under reduced pressure for 1.5 hours yielded a dry powder C (nano pigment concentration 45.3% by mass) of the pigment nanoparticles.

Using the said powder C, the pigment dispersion composition C of the following composition was prepared.

14.2 g of the powder C

1,3-butylene glycol diacetate 50.1 g

Pigment Dispersion Composition D

The pigment dispersion composition D of the following composition was prepared as follows.

Pigment (Pigment Red 254) 6.43g

Sodium chloride 64.0g

Pigment Dispersant A 0.6g

Methacrylic acid / benzyl methacrylate copolymer * 5.94 g

  * Molar ratio 28/72, mass average molecular weight: 30,000,

     40% 1-methoxy-2-propyl acetate solution

 Sodium chloride, powder of pigment (Pigment Red 254), and methacrylic acid / benzyl methacrylic copolymer were placed in a twin kneader in a 1,3 butylene glycol diacetate solution and kneaded at 80 ° C. for 10 hours. After kneading, the mixture was extracted with 700 parts by mass of 1% aqueous hydrochloric acid solution at 80 ° C, and after stirring for 1 hour, filtration, hot water washing, drying, and pulverization, and 2.4 g of 1,3 butylene glycol diacetate was added and mixed with 1 g of the pulverized product. . The pigment composition was dispersed using a motor mill M-50 (manufactured by Aiger Japan) with zirconia beads having a diameter of 0.65 mm for 1 hour at a circumferential speed of 9 m / s to obtain a pigment dispersion composition D.

Pigment Dispersion Compositions E and F

The pigment dispersion composition was the same except that the pigment Cigigment Red 254 used in the production of the pigment dispersion composition C and D was replaced with the pigment CIPigment Red 177 (Cromophtal Red A2B, trade name, product of Chiba Specialty Chemicals Co., Ltd.). E and F were produced respectively.

Pigment Dispersion Composition G ~ J

 Pigment dispersion composition G was changed in the same manner except that pigment Cigigment Red 254 used in the production of pigment dispersion compositions A to D was replaced with pigment CIPigment Green 36 (Rionol Green 6YK, trade name, manufactured by Toyo Ink Seijo Co., Ltd.). ~ J was produced respectively.

Pigment Dispersion Compositions K and L

Pigment dispersion compositions K and L are the same except that pigment CIPigment Red 177 used in the production of pigment dispersion compositions E and F is replaced with pigment CIPigment Yellow 150 (Bayplast Yellow 5GN 01, trade name, manufactured by Bayer Corporation). Were produced respectively.

Pigment Dispersion Composition M

7 g of Pigment CIPigment Violet 23 (Hostaperm Violet RL-NF, trade name, product of Clariant) contains 12 g of polyvinylpyrrolidone (product of Wako Pure Chemical Industries, Ltd., K30, molecular weight 40,000) and heated to 85 ° C. It dissolved in 140 ml of methanesulfonic acid, and obtained the pigment solution M. When the viscosity was measured using Viscomate VM-10A-L (brand name, the product made by CBC Materials), the viscosity when the liquid temperature of the pigment solution M is 85.0 degreeC is 17.3 mPa * s. Separately, 1500 ml of water containing 10 ml of 1 mol / L sodium hydroxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared as a poor solvent.

Here, NP-KX-500 type pigment solution M was put into 1000 ml of poor solvent water which temperature-controlled at 85 degreeC, and stirred at 500 rpm by GK-0222-10 type Ramond stirrer (brand name, the product made by Fujisawa Yakuhin Kogyo Co., Ltd.). It injected | threw-in using the large capacity | capacitance-free pump (brand name, the Nippon Seimitsu Chemical Co., Ltd. product). A pigment dispersion M was prepared by forming an organic pigment particle by placing the feed port in a poor solvent with a flow path diameter and a feed diameter of 0.8 mm of the feed pipe of the pigment solution M, and injecting 100 ml at a flow rate of 100 ml / min. About the pigment nanoparticles in this pigment dispersion liquid, the number average particle diameter Mn and monodispersity (Mv / Mn) were measured using NanotracUPA-EX150 (brand name, the product of Nikkiso Corporation). The results are shown in Table 1 below.

Furthermore, the pigment dispersion liquid M was transferred to the branch flask, and the pigment nanoparticle dry powder M (pigment concentration 55.4 mass%) was obtained by drying under reduced pressure at 70 degreeC for 1.5 hours by the evaporator.

Next, a solution obtained by adding 0.1 g of the pigment dispersant A to 50.0 cc of ethyl lactate was added to 14.5 g of the pigment nanoparticle powder M, and stirred at 1500 rpm for 80 minutes with a dissolver to obtain a pigment dispersion composition M.

<Production of Pigment Dispersion Composition N>

Pigment C.I.Pigment Violet 23 7.0g

12 g of polyvinylpyrrolidone (product made by Wako Pure Chemical Industries, Ltd., K30, molecular weight 40,000)

Ethyl lactate 50.0cc

Into the above composition, the mixture of the pigment dispersant A, the pigment (Pigment Violet 23), the polyvinylpyrrolidone 6g, and the methacrylic acid / benzyl methacrylic acid copolymer were added and stirred in a diethylene glycol monobutyl ether acetate solution. To obtain a mixed solution. Next, this mixed solution was dispersed for 9 hours at a circumferential speed of 9 m / s using zirconia beads having a diameter of 0.65 mm with a motor mill M-50 (manufactured by Aiger Japan).

Pigment Dispersion Composition O

Pigment dispersion composition was made in the same manner except that Pigment CIPigment Blue 15: 6 (Rionol Green ES, trade name, manufactured by Toyo Ink Co., Ltd.) was used in place of Pigment Cigigment Green 36 used in preparing Pigment Dispersion Composition H. O was produced.

Pigment Dispersion Composition P

The pigment dispersion composition P was produced in the same manner except that C.I. Pigment Blue 15: 6 was used in place of the pigment C.I.Pigment Violet 23 used in the preparation of the pigment dispersion composition N.

Pigment Dispersion Composition AA

In preparing the pigment dispersion composition A, when preparing the pigment dispersion A, the flow path, the flow path diameter and the supply diameter of the liquid supply pipe for feeding the pigment solution A is 0.5 mm, and the flow rate to be injected is 200 ml / min. Was the same as the pigment composition A to produce a pigment dispersion composition AA.

Pigment Dispersion Composition D ⁺ , F ⁺ >

In preparation of the raw material dispersion compositions D and F, pigment dispersion compositions D ⁺ and F ⁺ were produced in the same manner except that the processing time of the motor mill was changed from 1 hour to 4 hours.

Pigment Dispersion Average particle diameter (nm) Monodispersity (Mv / Mn) A 35 1.31 B 33 1.33 C 33 1.32 D 48 1.56 E 37 1.35 F 46 1.53 G 36 1.35 H 30 1.36 I 31 1.35 J 44 1.62 K 40 1.33 L 49 1.60 M 35 1.32 N 51 1.44 O 39 1.30 P 49 1.45 AA 22 1.32 D ⁺ 37 1.61 F ⁺ 36 1.58

<Production of color filter and liquid crystal display device using ink jet ink>

[Production of Photosensitive Transfer Material]

The coating liquid for thermoplastic resin layers which consists of following formula H1 was apply | coated and dried using the slit-shaped nozzle on the 75-micrometer-thick polyethylene terephthalate film support body. Next, the coating liquid for intermediate | middle layers which consists of following prescription P1 was apply | coated and dried. Further, a resin composition K1 having light shielding properties, which is formed by the following composition, is applied and dried, and the thermoplastic resin layer having a dry film thickness of 15 µm, the intermediate layer having a dry film thickness of 1.6 µm, and the dry film thickness are formed on the support. A resin layer having a light shielding property of 2.4 μm was formed, and a protective film (thickness 12 μm polypropylene film) was pressed.

In this way, a photosensitive resin transfer material integrally formed with the branch member, the thermoplastic resin layer, the intermediate layer (oxygen barrier film) and the light-shielding resin layer was produced, and the sample name was named photosensitive resin transfer material K1.

[Coating solution for thermoplastic resin layer: prescription H1]

-------------------------------------------------- ---------------------------

Methanol 11.1 parts by mass

6.4 parts by mass of propylene glycol monomethyl ether acetate

  Daisel Kagaku Co., Ltd. product, MMPG-Ac (we use the same material as follows)

52.4 parts by mass of methyl ethyl ketone

Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymer ratio (molar ratio) = 55 / 11.7 / 4.5 / 28.8, molecular weight 100,000, Tg ≒ 70 ° C.) 5.83 parts by mass

3.6 parts by mass of styrene / acrylic acid copolymer (copolymerization ratio (molar ratio) = 63/37, molecular weight = 10,000, Tg ≒ 100 ° C.)

9.1 parts by weight of 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd.)

Surfactant 1 0.54 parts by mass

-------------------------------------------------- ---------------------------

＊ The composition of surfactant 1 (Megafac F-780-F (product of Dainippon Ink & Chemical Co., Ltd.))

C ₆ F ₁₃ CH ₂ CH ₂ OCOCH = CH ₂ : 40 parts by mass,

H (OCH (CH ₃ ) CH ₂ ) ₇ OCOCH = CH ₂ : 55 parts by mass and

H (OCH ₂ CH ₂ ) ₇ OCOCH = CH ₂ : 5 parts by mass of copolymer (molecular weight 30,000) 30 parts by mass

70 parts by mass of methyl ethyl ketone

[Coating liquid prescription for intermediate layer (oxygen barrier layer): P1]

-------------------------------------------------- ---------------------------

Polyvinyl alcohol .... 32 parts by mass

  (PVA205 (reduction rate = 88%); Kuraray Co., Ltd.)

Polyvinylpyrrolidone ... 14.9 parts by mass

  (PVP, K-30; product made by ISP Japan)

Methanol ... 429 parts by mass

Distilled water ... 524 parts by mass

-------------------------------------------------- ---------------------------

[Resin composition K1]

-------------------------------------------------- ---------------------------

K pigment dispersion 1 (carbon black) 30 parts by mass

Propylene glycol monomethyl ether acetate 7.3 parts by mass

Methyl ethyl ketone 34 parts by mass

8.6 parts by mass of cyclohexanone

Binder 1 14 parts by mass

5.8 parts by mass of DPHA liquid

Polymerization initiator A (2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) amino-3'-bromophenyl] -s-triazine) 0.22 mass part

Phenothiazine 0.006 parts by mass

Surfactant 1 0.058 parts by mass

-------------------------------------------------- ---------------------------

The resin composition K1 having light shielding properties was first measured by taking K pigment dispersion 1 and propylene glycol monomethyl ether acetate, mixed at a temperature of 24 ° C. (± 2 ° C.), stirring at 150 rpm for 10 minutes, and then methyl ethyl ketone, Cyclohexanone, binder 1, phenothiazine, DPHA solution, polymerization initiator A, and surfactant 1 were measured and taken, added in this order at a temperature of 25 ° C (± 2 ° C), and at a temperature of 40 ° C (± 2 ° C). It obtained by stirring for 30 minutes at 150 rpm.

<K Pigment Dispersion 1>

Carbon black

    (Product made by Degussa, trade name Nipex35) 13.1 parts by mass

0.65 parts by mass of the above pigment dispersant A

6.72 parts by mass of polymer 1 (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 370,000)

79.53 parts by mass of propylene glycol monomethyl ether acetate

＊ The composition of binder 1

27 parts by mass of polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 40,000)

Propylene glycol monomethyl ether acetate 73 parts by mass

＊ The composition of DPHA liquid

76 parts by weight of dipentaerythritol hexaacrylate (containing MEHQ 500ppm, made by Nihon Kayaku Co., Ltd., trade name: KAYARAD DPHA)

24 parts by mass of propylene glycol monomethyl ether acetate

[Formation of partition wall having light shielding property]

The glass cleaner liquid which adjusted the alkali free glass substrate to 25 degreeC was wash | cleaned with the rotating brush which has nylon hair, mounting for 20 second by shower, and after pure shower washing, a silane coupling liquid (N-((amino ethyl)) γ) -0.3 mass% aqueous solution of aminopropyltrimethoxysilane, brand name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was mounted for 20 seconds by a shower, followed by pure shower cleaning. This board | substrate was heated at 100 degreeC for 2 minutes with the board | substrate preheater.

 After peeling off the protective film of the said photosensitive resin transfer material K1, the board | substrate heated at 100 degreeC for 2 minutes using the laminator (The Hitachi Industries Co., Ltd. product type (Lamic II type)), the rubber roller temperature 130 degreeC, linear pressure 100N / It laminated at cm and conveyance speed 2.2m / min.

After peeling off the supporting member, the exposure mask surface and the mask were placed in a vertical state with a substrate and a mask (a quartz exposure mask having an image pattern) vertically with a proximity type exposure machine (manufactured by Hitachi High-Technology Engineering Co., Ltd.) having an ultra-high pressure mercury lamp. The distance between thermoplastic resin layers was set to 200 micrometers, and pattern exposure was carried out by exposure amount 100mPa / cm <2>. The radius of curvature of the convex angle at the side of the partition which has light shielding property was 0.6 micrometer in the part corresponding to the boundary line of a pixel and a partition which has light shielding shape in a mask form.

Next, triethanolamine-based developer (30% of triethanolamine-containing, trade name: T-PD2, and Fuji Shashin Film Co., Ltd.) was diluted with pure water 12 times (mixing T-PD2 in a ratio of 1 part to 11 parts of pure water). Solution), followed by shower development at 50 DEG C for 30 seconds at a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer (oxygen barrier layer).

Sodium carbonate developer (0.38 mol / l sodium chloride, 0.47 mol / l sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer containing, brand name: T-CD1, Fujishashin Film Using a liquid diluted 5 times with pure water), shower at 29 ° C for 30 seconds at 0.15 MPa cone nozzle pressure to develop a resin layer having light shielding properties, and patterning a pixel barrier (light shielding property). Partition wall pattern).

Subsequently, a rotating brush having a shower head and a nylon hair at 20 ° C. at 33 ° C. with a cone nozzle pressure of 0.02 MPa using a cleaning agent (a liquid diluted 10-fold with pure water brand name “T-SD3 (manufactured by Fujishashin Film Co., Ltd.)”). The debris was removed, and a partition having light shielding properties was obtained. Thereafter, the substrate was post-exposured with light of 500 mPa / cm 2 with ultra-high pressure mercury lamp on the side of the resin layer, followed by heat treatment at 240 ° C. for 50 minutes.

[Plasma Waste Hydration Treatment]

Thereafter, plasma waste hydration was performed by the following method.

The plasma coupling hydration process was performed on the said board | substrate with which the light shielding partition was formed, using the cathode coupling type parallel flat type plasma processing apparatus.

Gas Used: CF ₄

Gas flow rate: 80sccm

Pressure: 40 Pa

RF power: 50W

Processing time: 30sec

[Preparation of Inkjet Ink for Color Filter]

The inkjet ink for color filters was prepared with the following prescription.

About mixing of each component of the said Table 1r, 1g, 1b, the pigment and the polymeric dispersant were first thrown in and mixed with a part of solvent, and it stirred using three rolls and a bead mill, and obtained the pigment dispersion. On the other hand, the other compounding components were thrown into the remainder of the solvent, stirred, and dispersed to obtain a monomer solution. And the pigment dispersion liquid or pigment dispersion composition was added little by little in the monomer solution, and it fully stirred with the dissolver, and the inkjet ink for color filters was prepared.

[Pixel formation]

First, the color filter 101 was produced using R ink 1, G ink 1, and B ink 1 described above. At this time, the inkjet head used SE-128 manufactured by Dimatix, and the Apollo II manufactured by Dimatix. The inkjet head is mounted on an automatic two-dimensional moving stage (KS211-200, manufactured by Surugasei Mitsukikei Co., Ltd.), and the discharge is controlled by the discharge control apparatus while moving the stage so that a predetermined amount of ink is discharged into the gap between the partition walls. Motivated.

Here, the three colors of ink of the substrate are filled in separate heads, and each head is fixed on the XY stage so that the three heads are independently controlled by the discharge control device so that each ink reaches a predetermined position. It was.

The ink composition is discharged until the desired concentration is reached, dried by heating at 100 ° C. for 2 minutes in a hot plate, and then baked in a 230 ° C. oven for 30 minutes to completely cure the partition and the pixels to produce a color filter. It was.

[Production of liquid crystal display device]

The liquid crystal display device was manufactured using the produced color filter 101, and the display characteristics were evaluated.

(ITO electrode formation)

The glass substrate on which the color filter was formed was placed in a spatter device, and ITO (Indium Tin Oxide) having a thickness of 1300 에서 at 100 ° C. was vacuum-deposited at 100 ° C., followed by annealing at 240 ° C. for 90 minutes to form ITO transparent electrodes. .

(Formation of spacer)

The spacer was formed on the above-mentioned ITO transparent electrode by the method similar to the spacer formation method of [Example 1] of Unexamined-Japanese-Patent No. 2004-240335.

(Formation of projection for liquid crystal alignment control)

Using the following coating liquid for positive photosensitive resin layers, the processus | protrusion for liquid crystal orientation control was formed on the ITO transparent electrode in which the said spacer was formed.

However, the following method used the exposure, image development, and baking process.

Proximate photodetector (made by Hitachi High-Tech Engineering Co., Ltd.) is arranged so that a predetermined photomask may be at a distance of 100 µm from the surface of the photosensitive resin layer, and the irradiation energy is 150 mPa / cm 2 by the ultra-high pressure mercury lamp through the photomask. Proximity exposure.

Subsequently, a 2.38% aqueous tetramethylammonium hydroxide solution was developed by spraying the substrate onto the substrate at 33 DEG C for 30 seconds in a shower developing device. In this way, the unnecessary part (exposure part) of the photosensitive resin layer was image-removed, and the board | substrate for liquid crystal display devices in which the liquid crystal orientation control protrusion which consists of the photosensitive resin layer patterned in the desired shape on the color filter side board | substrate was formed.

Next, the liquid crystal display control projections were formed on the liquid crystal display control substrate by baking the liquid crystal display device substrate having the liquid crystal alignment control projections at 230 ° C. for 30 minutes.

<Coating solution prescription for positive photosensitive resin layer>

Positive resist liquid (FH-2413F manufactured by FUJIFILM Electronics Alz Corporation): 53.3 parts by mass

Methyl ethyl ketone: 46.7 parts by mass

Megafac F-780F (from Dainippon Ink & Chemical Co., Ltd.): 0.04 parts by mass

(Making of liquid crystal display device)

An alignment film made of polyimide was further formed on the obtained liquid crystal display substrate.

Thereafter, an epoxy resin sealing agent was printed at a position corresponding to the black matrix outline formed around the pixel group of the color filter, the liquid crystal for MVA mode was added dropwise, and the bonded substrate was bonded to the opposing substrate. The heat treatment cured the sealing agent. The polarizing plate HLC2-2518 by Sanlitz Corporation was stuck on both surfaces of the liquid crystal cell obtained in this way. Next, a backlight of a three-wavelength cold cathode tube light source (F18L18EX-N manufactured by Toshiba Laitech Co., Ltd.) was configured and placed on the side of the liquid crystal cell on which the polarizing plate was formed to be a liquid crystal display device 101.

The liquid crystal display devices 102 to 108 were produced in the same manner as in the liquid crystal display device 101 except that the R ink 1 used in the production of the liquid crystal display device 101 was changed to the R inks 2 to 8, respectively.

The liquid crystal display devices 109 to 113 were produced in the same manner as the liquid crystal display device 101 except that the G ink 1 of the liquid crystal display device 101 was changed to the G ink 2 to 6, respectively.

The liquid crystal display devices 114 to 116 were produced in the same manner as the liquid crystal display device 101 except that the B ink 1 of the liquid crystal display device 101 was changed to the B ink 2 to 4, respectively.

In addition, the R ink 1, the G ink 1, and the B ink 1 of the liquid crystal display device 101 are replaced with the R ink 4, the G ink 4, and the B ink 3, respectively, to replace the liquid crystal display device 117 with R ink 6, G ink 6, and B ink. The liquid crystal display 118 was manufactured by replacing with ink 1.

 The details of the inkjet ink used in the produced liquid crystal display color filter are shown in Tables 5 to 8 together with the evaluation results.

<Evaluation of Inks and Liquid Crystal Display Devices>

[Measurement of Contrast and Light Resistance of Ink]

The contrast and light resistance of inkjet ink, R ink 1-8, G ink 1-6, and B ink 1-4 were measured as follows.

Each of the obtained inks was coated on a glass substrate to have a thickness of 2 μm to prepare a sample. As a backlight unit, the thing which installed the diffuser plate with the three wavelength cold cathode tube light source (FF # L18EX-N by Toshiba Laitech Co., Ltd.) is used, and the polarizing plate With this sample in between, the amount of transmitted light when the polarization axes were parallel and perpendicular was measured, and the ratio was called contrast ("7th Color Optical Conference of 1990, 512 Color Display 10.4" Size for TFT-LCD "). Color filter, Ueki, Ozeki, Fukunaga, Yamanaka ", etc.) A color luminance meter (BM-5, manufactured by Topcon, Inc.) was used for color measurement. Two polarizers, a sample, and an installation position of the color luminance meter In the position of 13mm from the backlight, a polarizing plate is placed at a position of 40mm to 60mm, and a cylinder having a diameter of 11mm and a length of 20mm is irradiated to the measurement sample provided at the position of 65mm. We let polarizing plate installed in position pass and install in position of 400mm The measurement angle of the color luminance meter was set to 2 ° The light intensity of the backlight was set so that the luminance when two polarizing plates were installed in parallel nicol without a sample installed was set to 1280 cd / m2. It was.

The sample was irradiated with a high-pressure mercury lamp of 90 mW / cm 2 for 24 hours, and the color difference before and after irradiation was measured and used as an index of light resistance. In addition, in this invention, chromaticity is measured with a microspectral spectrophotometer (Olympus Co., Ltd. product: OSP100 or 200), and it calculates as a result of 2 degrees of F10 light source visual fields, and shows it as the xxyY value of a xyz colorimeter. The difference in chromaticity is represented by the color difference of the La * b * color system. The smaller this color difference is, the more preferable.

The results are shown in Tables 2-4.

In addition, the particle diameter of the pigment particle contained about each ink was diluted using the ion exchanger so that a pigment concentration might be in the range of 1 to 5 weight%, and was measured using the DLS-7000 by Otsuka Denshi Co., Ltd. product. It was. The obtained particle size distribution is plotted by taking the number of longitudinal axis particles (ratio of the total number of pigment particles (%)) at intervals of 2 nm in the horizontal axis particle size, and the particle size having the maximum value, the number of the maximum value, and the total particle size of 50 nm or more. The ratio (%) of the number to the pigment particles was obtained and the results are shown in Tables 2a to 4a.

[Display Characteristics Test of Liquid Crystal Display]

The display characteristics of each of the produced liquid crystal display devices were evaluated from the viewpoints of (1) illuminance after continuous display, (2) descriptive power of a specific color, and (3) presence or absence of color stain when a specific color was displayed in a single color.

(1) For the illuminance after continuous display, the produced liquid crystal display device is displayed for 1000 hours continuously, and the illuminance of specific color light (the illuminance of red display in the case of red light) is 400mm on the screen of the liquid crystal display device in the dark room. The illuminometer UV-M10-S (manufactured by Oak Seisakusho Co., Ltd.) was set at a measurement angle of 2 ° and measured, and the relative values before and after the test of each Example and Comparative Example (light intensity after test / light intensity before test) were measured. ) Is shown in Tables 5 to 8 together with the contrast data of the pigment dispersion composition.

(2) Descriptive power of a specific color and (3) Color spots when a specific color was displayed in a single color were evaluated by ten panelists, and the average of ten people was evaluated by the following step evaluation.

(2) depiction of each color

5: Description is excellent

4: There is no problem in description (good)

3: Somewhat lacks description (usually)

2: There is a lack of description (somewhat bad)

1: Color reproduction is poor (very bad)

(3) red stain

5: no stain at all

4: I do not mind a dirt (good)

3: a little dirt is felt (usually)

2: We can clearly recognize stain (slightly worse)

1: stains are remarkable (very bad)

Evaluation items (1) to (3) were evaluated for liquid crystal display devices 101 to 108 in red (Table 5), liquid crystal display devices 101 and 109 to 113 for green (Table 6), and liquid crystal display devices 101 and 114 to 116. The comparative evaluation (Table 7) was carried out in blue. In addition, the liquid crystal display devices 101, 117, and 118 were evaluated by red, green, blue, and gray (Table 8), and are represented by the average value of each result.

ink Pigment Dispersion Composition b ratio * Contrast Light resistance (color difference) R1 D + F 0 4200 4.6 R2 A + F 90 9600 2.2 R3 B + F 90 9900 2.0 R4 C + F 90 9800 2.1 R5 B + E 100 11200 2.3 R6 C + E 100 10500 2.4 R7 D ⁺ + F ⁺ 0 8500 3.1 R8 AA + F 90 12500 2.1

* B ratio: The ratio (mass%) of the buildup pigment nanoparticle (b) in all the pigment particles.

ink Pigment Dispersion Composition b ratio Contrast Light resistance (color difference) G1 J + L 0 4200 3.8 G2 G + L 51 9600 2.0 G3 H + L 51 9900 1.9 G4 I + L 51 9800 2.0 G5 H + K 100 9800 2.1 G6 I + K 100 9900 2.2

ink Pigment Dispersion Composition b ratio Contrast Light resistance (color difference) B1 N + P 0 4200 4.8 B2 M + P 4 9600 2.1 B3 N + O 96 9900 2.2 B4 M + O 100 9800 2.3

Continuation of Table 2 ink Pigment Dispersion Composition Average particle diameter (nm) Number of maximums Particle Ratio over 50nm (%) R1 D + F 48 One 37 R2 A + F 41 2 4 R3 B + F 36 2 23 R4 C + F 35 2 3 R5 B + E 35 One 0 R6 C + E 34 One 0 R7 D ⁺ + F ⁺ 38 One 31 R8 AA + F 25 2 4

Continuation of Table 3 ink Pigment Dispersion Composition Average particle diameter (nm) Number of maximums Particle Ratio over 50nm (%) G1 J + L 46 One 42 G2 G + L 42 2 11 G3 H + L 39 2 9 G4 I + L 39 2 10 G5 H + K 35 One 0 G6 I + K 34 One 0

Continuation of Table 4 ink Pigment Dispersion Composition Average particle diameter (nm) Number of maximums Particle Ratio over 50nm (%) B1 N + P 50 One 42 B2 M + P 48 2 38 B3 N + O 41 2 One B4 M + O 39 One 0

R optical evaluation Display Ink used evaluation R G B Roughness ratio (%) Portrayal Stain 101 R1 G1 B1 110 2.0 1.5 102 R2 〃 〃 101 4.7 4.6 103 R3 〃 〃 102 4.8 5.0 104 R4 〃 〃 101 4.7 4.8 105 R5 〃 〃 104 4.5 1.9 106 R6 〃 〃 105 4.9 2.5 107 R7 〃 〃 104 4.2 4.0 108 R8 〃 〃 101 5.0 4.9

G light evaluation Display Ink used evaluation R G B Roughness ratio (%) Portrayal Stain 101 R1 G1 B1 108 1.3 1.9 109 〃 G2 〃 102 4.9 4.8 110 〃 G3 〃 102 4.9 4.9 111 〃 G4 〃 101 5.0 4.8 112 〃 G5 〃 109 5.0 2.4 113 〃 G6 〃 111 4.9 2.1

B optical evaluation Display Ink used evaluation R G B Roughness ratio (%) Portrayal Stain 101 R1 G1 B1 109 1.5 1.2 114 〃 〃 B2 102 4.6 4.7 115 〃 〃 B3 102 4.8 4.8 116 〃 〃 B4 107 4.9 2.1

Gray light evaluation Display Ink used evaluation R G B Roughness ratio (%) Portrayal Stain 101 R1 G1 B1 107 1.8 1.5 117 R4 G4 B3 102 5.0 5.0 118 R6 G6 B4 106 5.0 1.9

It was found from the above results that the ink containing the build-up pigment nanoparticles (b) exhibits high contrast (see inks R2 to 6, 8, G2 to 6, and B2 to 4 in Tables 2 to 4).

The ink of the present invention which uses the breakdown pigment nanoparticle (a) and the buildup pigment nanoparticle (b) together also exhibits excellent display performance when the liquid crystal display device is used, and has a long display performance, portrayal power, and color. By suppressing unevenness (refer to display devices 102 to 104, 108 to 111, 114, 115, and 117 in Tables 5 to 8), it was found that excellent display performance with good balance could be realized.

In particular, in the case of B ink, even if the content of the build-up pigment nanoparticles (b) is very small, the display performance is significantly increased in contrast and the liquid crystal display device (ink B2). In addition, it was found that the above-described excellent effect was also exhibited by containing the dried-up pigment nanoparticles once dried (inks R4, G4, and B2).

Moreover, ink R3, R4, R7, R8 which contains the ink R7 which consists only of a breakdown pigment, and which the average particle diameter of the pigment particle contained was 40 nm or less and the ratio of the number of the particle | grains of 50 nm or more particle diameter was 1% or more , G3 and G4 exhibited sufficient contrast and exhibited good balance and excellent balance performance (display devices 103, 104, 107, 108, 110 and 111). In addition, the ink R8 and the liquid crystal display 108 using the same having an average particle diameter of 30 nm or less and having two maximum values in the particle size distribution, and having a ratio of the number of particles having a particle size of 50 nm or more to 1% or more in contrast and description power Higher performance.

(Example, Comparative Example 2)

<Production of Color Filter and Liquid Crystal Display Using Color Photosensitive Resin Composition>

[Formation of black (K) image]

The alkali free glass substrate was washed with a UV cleaner, and then brush-washed with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.

The substrate was cooled and warmed at 23 ° C., and then coated with a photosensitive resin composition K2 having a composition shown in Table 9a with a glass substrate coater (FAS Asia, trade name: MH-1600) having a slit nozzle. Subsequently, a part of the solvent was dried with VCD (vacuum drying apparatus; manufactured by Tokyo Okagyo Co., Ltd.) for 30 seconds to remove fluidity of the coating layer, and then prebaked at 120 ° C. for 3 minutes to color a film having a thickness of 2.4 μm. The layer K2 of the photosensitive resin composition was obtained. On the other hand, the preparation procedure of the coloring photosensitive resin composition K2 is the same as that of the preceding resin composition K1.

K Pigment Dispersion 2 25 parts by mass Propylene Glycol Monomethyl Ether Acetate 8.0 parts by mass Methyl ethyl ketone 53 parts by mass Binder 1 9.1 parts by mass Hydroquinone monomethyl ether 0.002 parts by mass DPHA liquid 4.2 parts by mass Polymerization Initiator A 0.16 parts by mass Surfactants 1 0.044 parts by mass

The distance between the exposure mask surface and the photosensitive resin layer in a state in which a substrate and a mask (a quartz exposure mask having an image pattern) are placed vertically with a proximal exposure machine (manufactured by Hitachi Hi-Tech Density Engineering Co., Ltd.) having an ultra-high pressure mercury lamp. Was set to 200 µm, and the pattern was exposed to an exposure dose of 300 mPa / cm 2.

Next, pure water was sprayed from a shower nozzle to uniformly wet the surface of the photosensitive resin layer K1, and then used as a KOH-based developer (KOH, containing a nonionic surfactant, trade name: CDK-1, manufactured by FUJIFILM Electronics). Shower development was carried out at 80 ° C. for 80 seconds at a flat nozzle pressure of 0.04 MPa to obtain a patterned image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultra-high pressure washing nozzle to remove debris to obtain an image K of black (K). Then, it heat-processed at 220 degreeC for 30 minutes.

<K Pigment Dispersion 2>

Carbon black (brand name: Nipex 35, manufactured by Degussa Japan) 13.1 parts by mass

0.65 parts by mass of dispersant (compound 2J)

Benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 370,000

6.72 parts by mass

79.53 parts by mass of propylene glycol monomethyl ether acetate

[Adjustment of Pigment Dispersion Composition]

Except for using propylene glycol monomethyl ether acetate in place of the 1,3-butylene glycol diacetate used in the pigment dispersion compositions C to F, I to L, and M to P prepared in Example 1, all were the same. Pigment dispersion compositions C2 to F2, I2 to L2, and M2 to P2 were prepared.

[Formation of red (R) pixel]

On the substrate on which the image K was formed, a pixel R having completed the heat treatment was formed in the same process as the formation of the black (K) image using a coloring photosensitive resin composition having the composition shown in Table 9b. The film thickness of the said photosensitive resin layer and the application amount of a pigment are shown below. On the other hand, the preparation procedure of the coloring photosensitive resin composition is the same as that of the said coloring photosensitive resin composition K2.

Photosensitive resin film thickness (μm) 1.80

Pigment Coating Amount (g / ㎡) 1.13

C.I.P.R.254 Coating amount (g / ㎡) 1.08

C.I.P.R.177 Coating volume (g / ㎡) 0.12

Color photosensitive resin composition R21 R Pigment Dispersion V 45.5 parts by mass Propylene Glycol Monomethyl Ether Acetate 7.6 parts by mass Methyl ethyl ketone 35 parts by mass Binder 2 0.7 parts by mass DPHA liquid 4.3 parts by mass Polymerization Initiator B 0.12 parts by mass Polymerization Initiator A 0.05 parts by mass Phenothiazine 0.01 parts by mass Surfactant 2 0.06 parts by mass

 <R Pigment Dispersion V>

Pigment dispersion composition D 90 parts by mass

Pigment dispersion composition F 10 parts by mass

 <Surfactant 2>

30 parts by mass of the following compound 1

70 parts by mass of methyl ethyl ketone

Compound 1

(n = 6, x = 55, y = 5, Mw = 33940, Mw / Mn = 2.55, PO: propylene oxide, ED: ethylene oxide)

<Polymerization Initiator B>

2-trichloromethyl- (p-styrylstyryl) 1,3,4-oxadiazole

[Formation of Green (G) Pixel]

On the substrate on which the image K and the pixel R were formed, a colored photosensitive resin composition having the composition shown in Table 9c was used to form a pixel G after the heat treatment was completed in the same process as the formation of the black (K) image. The film thickness of the said photosensitive resin layer and the application amount of a pigment are shown below. On the other hand, the preparation procedure of the coloring photosensitive resin composition is the same as that of the coloring photosensitive resin composition K2.

Photosensitive resin film thickness (㎛) 1.75

Pigment Coating Amount (g / ㎡) 2.10

C.I.P.G.36 Coating Amount (g / ㎡) 1.47

C.I.P.Y.150 Coating volume (g / ㎡) 0.63

Color-sensitive resin composition G21 G Pigment Dispersion W 43 parts by mass Propylene Glycol Monomethyl Ether Acetate 29 parts by mass Methyl ethyl ketone 26 parts by mass Cyclohexanone 1.3 parts by mass Binder 1 2.5 parts by mass DPHA liquid 3.5 parts by mass Polymerization Initiator B 0.12 parts by mass Polymerization Initiator A 0.05 parts by mass Phenothiazine 0.01 parts by mass Surfactant 2 0.07 parts by mass

<G Pigment Dispersion W>

Pigment dispersion composition J 70 parts by mass

Pigment dispersion composition L 30 parts by mass

 [Formation of blue (B) pixel]

 On the substrate on which the image K, the pixel R, and the pixel G are formed, a colored photosensitive resin composition composed of the composition shown in Table 9d is used, and a pixel B which has been heat-treated in the same process as the formation of the black (K) image is formed. To obtain the desired color filter A. The film thickness of the said photosensitive resin layer and the application amount of a pigment are shown below. On the other hand, the preparation procedure of the coloring photosensitive resin composition is the same as that of the coloring photosensitive resin composition K2.

Photosensitive resin film thickness (μm) 1.60

Pigment Coating Amount (g / ㎡) 0.75

C.I.P.B.15: 6 Coating amount (g / ㎡) 0.705

C.I.P.V.23 Coating amount (g / ㎡) 0.045

Color photosensitive resin composition B21 B Pigment Dispersion X 23.6 parts by mass Propylene Glycol Monomethyl Ether Acetate 28 parts by mass Methyl ethyl ketone 26 parts by mass Binder 3 17 parts by mass DPHA liquid 4.0 parts by mass Polymerization Initiator B 0.17 parts by mass Phenothiazine 0.02 parts by mass Surfactant 2 0.06 parts by mass

B Pigment Dispersion X

Pigment dispersion composition N 94 parts by mass

Pigment dispersion composition P 6 parts by mass

 <Binder 3>

Benzyl methacrylate / methacrylic acid / methyl methacrylate = 36/22/42 molar ratio random copolymer, molecular weight 38.27 parts by mass

Propylene glycol monomethyl ether acetate 73 parts by mass

The color filter 201 was produced as mentioned above. On the other hand, the color dispersion composition used was changed as shown in Table 9e below to produce color filters 202 and 203, respectively.

Display R Color photosensitive resin (pigment dispersion composition) b ratio G Color photosensitive resin (pigment dispersion composition) b ratio B Color photosensitive resin (pigment dispersion composition) b ratio 201 R21 (D + F) 0% G21 (J + L) 0% B21 (N + P) 0% 202 R22 (C + F) 90% G22 (I + L) 70% B22 (M + P) 6% 203 R23 (C + E) 100% G23 (I + K) 100% B23 (M + O) 100%

 [Production and Evaluation of Liquid Crystal Display Device]

 The liquid crystal display devices 201, 202, and 203 were manufactured using the color filters 201, 202, and 203, respectively, to evaluate the display characteristics.

(ITO electrode formation)

The glass substrate on which the color filter was formed was placed in a spatter apparatus, and ITO (Indium Tin Oxide) having a thickness of 1300 에서 at 100 ° C. was vacuum-deposited at 100 ° C., and then annealed at 240 ° C. for 90 minutes to form ITO transparent electrodes.

(Formation of spacer)

The spacer was formed on the above-mentioned ITO transparent electrode by the method similar to the spacer formation method of [Example 1] of Unexamined-Japanese-Patent No. 2004-240335.

(Formation of projection for liquid crystal alignment control)

The liquid crystal alignment control protrusion was formed on the ITO transparent electrode on which the spacer was formed using the coating solution for the positive photosensitive resin layer described below.

 However, the following method used the exposure, image development, and baking process.

Proximate photodetector (made by Hitachi Hi-Tech Engineering Co., Ltd.) is arranged so that a predetermined photomask may be 100 micrometers from the surface of the photosensitive resin layer, and the irradiation energy is 150 mPa / cm <2> by an ultra-high pressure mercury lamp through the said photomask. Proximity exposure.

Subsequently, a 2.38% tetramethylammonium hydroxide aqueous solution was developed while spraying onto the substrate at 33 DEG C for 30 seconds in a shower developing device. In this way, the unnecessary part (exposure part) of the photosensitive resin layer was image-removed, and the board | substrate for liquid crystal display devices with which the process liquid crystal orientation control protrusion which consists of the photosensitive resin layer patterned in the desired shape on the color filter side board | substrate was obtained.

Next, the liquid crystal display control projections were formed on the liquid crystal display control substrate by baking the liquid crystal display device substrate having the liquid crystal alignment control projections at 230 ° C. for 30 minutes.

<Coating solution prescription for positive photosensitive resin layer>

Positive resist liquid (FH-2413F, manufactured by FUJIFILM Electronics Alz Corporation): 53.3 parts by mass

Methyl ethyl ketone: 46.7 parts by mass

Megafac F-780F (product of Dainippon Ink & Chemicals Co., Ltd.): 0.04 parts by mass

(Production of LCD)

An alignment film made of polyimide was further formed on the obtained liquid crystal display substrate. Thereafter, an epoxy resin sealing agent was printed at a position corresponding to the black matrix outline formed around the pixel group of the color filter, and the liquid crystal for MVA mode was dropped, bonded to the counter substrate, and then bonded. The substrate was heat treated to cure the sealing agent. The polarizing plate HLC2-2518 by Sanrittsu Corporation was stuck on both surfaces of the liquid crystal cell obtained in this way. Next, a backlight of a three-wavelength cold cathode tube light source (FＷL18EX-N manufactured by Toshiba Laitech Co., Ltd.) was configured, and placed on the side of the liquid crystal cell in which the polarizing plate was formed to be a liquid crystal display device.

The produced liquid crystal display devices 201, 202, and 203 were evaluated in the same manner as in Example 1 (1) roughness ratio, (2) descriptive power, and (3) color stain. As a result, the liquid crystal display device 201 was inferior in any of (1) roughness ratio, (2) descriptive power, and (3) color spots, and the liquid crystal display device 203 was inferior in (1) light intensity ratio and (3) color spots. .

On the other hand, the liquid crystal display device 202 had good results in any of (1) roughness ratio, (2) descriptive power, and (3) color stain.

As a result, even when the color filter was manufactured using the coloring photosensitive resin composition, it was found that the organic pigment dispersion of the present invention has a good balance between high display characteristics and high display durability.

(Example and Comparative Example 3)

The photosensitive resin transfer material was prepared by the same method as that of the photosensitive transfer material K1 except that the resin composition K1 when the colored photosensitive resin composition K1 was prepared in Example 1 was changed to the colored photosensitive resins R21, G21, and B21 in Example 2, respectively. R301, G301, and B301 were produced.

[Formation of black (K) image]

 By using the photosensitive resin transfer material K1 in the same manner as in Example 1, a patterned pixel barrier (border pattern having light shielding properties) was obtained.

[Formation of red (R) pixel]

Using the photosensitive resin transfer material R301, a red R pixel R was obtained by heat treatment in the same process as the photosensitive resin transfer material K1. However, the exposure amount was 40 mPa / cm <2> and the image development by the sodium carbonate developer was 35 degreeC 35 second. The film thickness of the said photosensitive resin layer and the coating amount of pigment (C.I.P.R.254 and C.I.P.R.177) are shown below.

Photosensitive resin film thickness (㎛) 2.00

Pigment Coating Amount (g / ㎡) 1.00

C.I.P.R.254 Coating amount (g / ㎡) 0.90

C.I.P.R.177 Coating amount (g / ㎡) 0.10

 The board | substrate which formed this image K and the pixel R was again wash | cleaned with a brush as mentioned above, and after pure shower cleaning, it sent to the board | substrate preliminary heating apparatus without using a silane coupling liquid.

[Formation of Green (G) Pixel]

Using the photosensitive resin transfer material G301, the pixel G of green (G) that had been heat-treated in the same process as the photosensitive resin transfer material R301 was obtained. However, the exposure amount was 40 mPa / cm <2> and the image development by the sodium carbonate type developing solution was 34 degreeC 45 second. The film thickness of the said photosensitive resin layer and the coating amount of pigment (C.I.P.G.36 and C.I.P.Y.150) are shown in the following table.

Photosensitive resin film thickness (㎛) 2.00

Pigment Coating Amount (g / ㎡) 1.90

C.I.P.G.36 Coating amount (g / ㎡) 1.24

C.I.P.Y.150 Coating amount (g / ㎡) 0.68

 The board | substrate which formed this image K, the pixel R, and the pixel G was again wash | cleaned with a brush as mentioned above, and after pure shower washing, it sent to the board | substrate preliminary heating apparatus, without using a silane coupling liquid.

[Formation of blue (B) pixel]

Using the photosensitive resin transfer material B301, a pixel B of blue (B) obtained by heat treatment in the same process as the photosensitive resin transfer material R301 was obtained. However, the exposure amount was 30 mPa / cm <2> and the image development by the sodium carbonate type developing solution was 36 degreeC 40 second. The film thickness of the said photosensitive resin layer and the coating amount of pigment (C.I.P.B.15: 6 and C.I.P.V.23) are shown below.

Photosensitive resin film thickness (㎛) 2.00

Pigment Coating Amount (g / ㎡) 0.76

C.I.P.B.15: 6 Coating amount (g / ㎡) 0.70

C.I.P.V.23 Coating amount (g / ㎡) 0.06

The board | substrate which formed this pixel R, the pixel G, the pixel B, and the image K was baked at 240 degreeC for 50 minutes, and the color filter 301 was obtained.

Regarding the method for producing the color filter 301, the colored photosensitive resins R-21, G-21, and B-21 used when the photosensitive resin transfer materials R301, G301, and B301 were produced were R-22, G-22, and B-, respectively. The color filter 302 changed to 22 and the color filter 303 changed to R-23, G-23, and B-23 were produced. Using this color filter, liquid crystal display devices 301, 302, and 303 were produced in the same manner as in Example 1.

The produced liquid crystal display devices 301, 302, and 303 were evaluated in the same manner as in Example 1 (1) roughness ratio, (2) descriptive power, and (3) color stain. As a result, the liquid crystal display device 301 was inferior in any of (1) roughness ratio, (2) descriptive power, and (3) color stain, and the liquid crystal display device 303 was inferior in (1) light intensity ratio and (3) color stain. .

On the other hand, the liquid crystal display device 302 had good results in any of (1) roughness ratio, (2) descriptive power, and (3) color stain.

As a result, even when the color filter was produced using the photosensitive resin transfer material, it was found that the organic pigment dispersion of the present invention exhibits a good balance between high display characteristics and high display durability.

Claims (18)

Pigment particles contained in at least one color pixel of the color filter, wherein the average particle diameter of the pigment particles is 40 nm or less, and the ratio of the number of particles having a particle size of 50 nm or more is 1% or more of all pigment particles. Characteristic color filter. The method of claim 1, The particle size distribution of the pigment particle contained in the said pixel WHEREIN: The color filter characterized by having two or more maximum values. The method according to claim 1 or 2, The particle size distribution of the pigment particle contained in the said pixel WHEREIN: The color filter which has a maximum value below 30 nm of particle diameters, The color filter characterized by the above-mentioned. The method according to any one of claims 1 to 3, The pigment filter contained in the said pixel WHEREIN: The number of particle | grains whose particle diameter is 50 nm or more is made to be 5% or more of all the pigment particles, The color filter characterized by the above-mentioned. Pigment nanoparticles (a) which mechanically grind | pulverized the bulk body of organic pigment; And An organic pigment dispersion comprising a pigment nanoparticle (b) obtained by mixing an organic pigment solution in which an organic pigment is dissolved in a good solvent and a solvent which is compatible with the good solvent and becomes a poor solvent with respect to the organic pigment. The method of claim 5, wherein An organic pigment dispersion comprising the pigment nanoparticle (b) in an amount of 1% by mass or more of all pigment particles. The method according to claim 5 or 6, An organic pigment dispersion comprising the pigment nanoparticle (b) in an amount of 3% by mass to 95% by mass of all pigment particles. The method according to any one of claims 5 to 7, The average particle diameter of all the pigment particles of the said pigment nanoparticles (a) and (b) was 40 nm or less, and the ratio of the number of particle | grains whose particle diameter is 50 nm or more was 1% or more of all pigment particles, The organic characterized by the above-mentioned. Pigment dispersions. The method according to any one of claims 5 to 8, The pigment nanoparticle (b) is an organic pigment dispersion, characterized in that the nanoparticles obtained by removing a single amount of the solvent to a powder, and redispersing the powder. The method according to any one of claims 5 to 9, The pigment nanoparticles (b) is an organic pigment dispersion, characterized in that the nanoparticles obtained under the coexistence of a polymer compound having a mass average molecular weight of 1000 or more. The method according to any one of claims 5 to 10, An organic pigment dispersion, wherein the polymer compound having a mass average molecular weight of 1000 or more is a compound represented by the following General Formula (1).

General formula (1) [In general formula, R <^1> represents a (m + n) valent coupling group and R <^2> represents a single bond or a bivalent coupling group. A ¹ is a group selected from the group consisting of an acidic group, a basic group having a nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group and a hydroxyl group The monovalent organic group which has the monovalent organic group which has, or the organic pigment structure or heterocycle which may have a substituent is shown. However, n piece A <^1> may mutually be same or different. m represents a number from 1 to 8, n represents a number from 2 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer compound residue.] The method according to any one of claims 5 to 11, An organic pigment dispersion, which is used for a color filter having any one of blue, green and red colors. An ink jet ink for color filters, comprising the organic pigment dispersion according to any one of claims 5 to 12.  The coloring photosensitive resin composition containing the organic pigment dispersion, binder, monomer, or oligomer of any one of Claims 5-12.  The photosensitive resin transfer material in which the layer which has the coloring photosensitive resin composition of Claim 14 was formed on a support body. A color filter in which the organic pigment dispersion according to any one of claims 5 to 12 is contained in at least one of an R pixel, a G pixel, and a B pixel.  The color filter produced using any one of the inkjet ink of Claim 13, the coloring photosensitive resin composition of Claim 14, and the photosensitive resin transfer material of Claim 15. A liquid crystal display device comprising the color filter according to claim 15.