JP5385511B2 - Color filter and liquid crystal display device including the same - Google Patents

Description

The present invention relates to a color filter, liquid crystal display equipment having the same.

  As one of nanotechnology, research for reducing the size of particles to the range of 10 to 100 nm is underway. It is intended to bring out new characteristics that could not be predicted by the nano-size effect.

  In this regard, in the field of organic pigments, for example, the application of the nanotechnology is being promoted in paints, printing inks, electrophotographic toners, inkjet inks, color filters, and the like. In particular, with regard to color filter pigments and inkjet inks thereof, efforts have been made to improve performance as a state-of-the-art technology field, and the results are expected.

  Regarding color filters, thinning is desired, and the key to increasing the pixel count of digital cameras and the sensitivity of CCD sensors is the key. In recent years, an organic pigment has been used as a color material for a color filter, and its thickness largely depends on the particle diameter of the organic pigment. The above problem cannot be overcome without nanometer-sized levels and monodisperse stable pigment particles. Furthermore, a new manufacturing method with a high degree of design freedom and a low cost, in which a color filter is manufactured using an ink jet technique, is being studied. However, there are still no pigment fine particles that are suitable for this and perform sufficiently.

  Regarding the method for refining organic particles, conventionally, it has been common to use a disperser such as a roll mill, a ball mill, or an attritor (see Non-Patent Document 1, etc.). In addition, recently, a gas phase method, a liquid phase method, a laser ablation method and the like have been studied. Among these, the liquid phase method has attracted attention as a method for producing organic particles having excellent simplicity and productivity (see Patent Documents 1 and 2).

  Recently, a method has been developed in which pigment particles are precipitated by mixing a good solvent solution and a poor solvent solution of the pigment (Patent Document 3). The pigment particles are used to increase the contrast of the color filter.

JP-A-6-79168 JP 2004-91560 A International Publication No. WO2006 / 121016 Pamphlet Pigment Dispersion Technology-Surface Treatment and Use of Dispersing Agents and Dispersibility Evaluation-Technical Information Association 1999

Color filters are required not only to achieve high contrast but also to maintain excellent display performance for as long as possible when used in display devices and the like.
LCD The present invention achieves a high contrast, exhibit high color descriptive power when used in a display device, yet having a Re color filter及benefactor capable of long-term maintaining display performance with excellent suppressing color unevenness An object is to provide a display device.

（式中、Ｒ^１は、（ｍ＋ｎ）価の連結基を表し、Ｒ^２は単結合あるいは２価の連結基を表す。Ａ^１は、酸性基、窒素原子を有する塩基性基、ウレア基、ウレタン基、配位性酸素原子を有する基、炭素数４以上の炭化水素基、アルコキシシリル基、エポキシ基、イソシアネート基、および水酸基からなる群より選ばれる基を有する１価の有機基、または置換基を有してもよい有機色素構造もしくは複素環を含有する１価の有機基を表す。ただし、ｎ個のＡ^１は互いに同一であっても、異なっていてもよい。ｍは１〜８の数を表し、ｎは２〜９の数を表し、ｍ＋ｎは３〜１０を満たす。Ｐ^１は高分子化合物残基を表す。）
（１２）青色、緑色、及び赤色のいずれかの色を持つ画素を具備する（１）〜（１１）のいずれか１項に記載のカラーフィルタ。
（１３）（１）〜（１２）のいずれかに記載のカラーフィルタを備えた液晶表示装置。
The above object of the present invention has been achieved by the following means.
(1) In pigment particles contained in at least one color pixel of a color filter, 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% of all pigment particles. % Or more of color filters,
In the particle size distribution of the pigment particles contained in the pixel, it has two or more maximum values,
A color filter having a maximum value in a particle size distribution of 30 nm or less in a particle size distribution of pigment particles contained in the pixel.
(2) The pigment constituting the pigment particles is preferably a quinacridone compound pigment, a diketopyrrolopyrrole compound pigment, a dioxazine compound pigment, a phthalocyanine compound pigment, or an azo compound pigment, a diketopyrrolopyrrole compound pigment, a dioxazine compound pigments, and the color filter according to the phthalocyanine compound selected from pigments or al the group consisting (1).
(3) Pigment nanoparticles (a) obtained by mechanically pulverizing a bulk body of an organic pigment, an organic pigment solution in which the organic pigment is dissolved in a good solvent, and the above-mentioned good solvent. Pigment nanoparticles (b) deposited by mixing with a solvent as a solvent
The color filter as described in (1) or (2), wherein
(4) Any one of (1) to (3), wherein in the pigment particles contained in the pixel, the number of particles having a particle size of 50 nm or more is 5% or more of the total pigment particles. Item 1. A color filter according to item 1.
(5) The volume average particle size (Mv) and the number average particle size (Mn) of the pigment particles are defined, and the monodispersity (Mv / Mn) is 1.0 to 2.0. The color filter according to any one of (4).
(6) The color filter according to any one of (3) to (5), wherein the pigment nanoparticles (b) are contained in an amount of 1% by mass or more based on the total pigment particles.
(7) The color filter according to any one of (3) to (6), wherein the pigment nanoparticle (b) is contained in an amount of 3% by mass to 95% by mass based on all pigment particles.
(8) The average particle diameter of all 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% or more of all pigment particles. (3) The color filter according to any one of (7) to (7).
(9) Any one of (3) to (8), wherein the pigment nanoparticles (b) are nanoparticles obtained by removing the solvent once to obtain powder and redispersing the powder. Item 1. A color filter according to item 1.
(10) The color filter according to any one of (1) to (9), further comprising a polymer compound having a mass average molecular weight of 1000 or more.
(11) The color filter as described in (10), wherein the polymer compound having a mass average molecular weight of 1000 or more is a compound represented by the following general formula (1).

(In the formula, R ¹ represents an (m + n) -valent linking group, R ² represents a single bond or a divalent linking group. A ¹ represents an acidic group, a basic group having a nitrogen atom, a urea group, A monovalent organic group having 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, or a hydroxyl group, or a substituent Represents a monovalent organic group containing an organic dye structure or a heterocyclic ring which may have a group, provided that n A ^{1 s} may be the same as or different from each other, and m is 1 to 8. And n represents a number of 2 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer compound residue.)
(12) The color filter according to any one of (1) to (11), including a pixel having any one color of blue, green, and red.
(13) A liquid crystal display device comprising the color filter according to any one of (1) to (12).

〔式中、Ｒ^１は、（ｍ＋ｎ）価の連結基を表し、Ｒ^２は単結合あるいは２価の連結基を表す。Ａ^１は、酸性基、窒素原子を有する塩基性基、ウレア基、ウレタン基、配位性酸素原子を有する基、炭素数４以上の炭化水素基、アルコキシシリル基、エポキシ基、イソシアネート基、および水酸基からなる群より選ばれる基を有する１価の有機基、または置換基を有してもよい有機色素構造もしくは複素環を含有する１価の有機基を表す。ただし、ｎ個のＡ^１は互いに同一であっても、異なっていてもよい。ｍは１〜８の数を表し、ｎは２〜９の数を表し、ｍ＋ｎは３〜１０を満たす。Ｐ^１は高分子化合物残基を表す。〕
（１２）青色、緑色、及び赤色のいずれかの色を持つカラーフィルタに用いることを特徴とする（５）〜（１１）のいずれか１項に記載の有機顔料分散物。
（１３）（５）〜（１２）のいずれか１項に記載の有機顔料分散物からなるカラーフィルタ用インクジェットインク。
（１４）（５）〜（１２）のいずれか１項に記載の有機顔料分散物と、バインダーと、モノマーもしくはオリゴマーとを含有する着色感光性樹脂組成物。
（１５）（１４）記載の着色感光性樹脂組成物を有する層を仮支持体上に設けた感光性樹脂転写材料。
（１６）Ｒ画素、Ｇ画素、及びＢ画素の少なくとも一つに（５）〜（１２）のいずれか１項に記載の有機顔料分散物を含有させたカラーフィルタ。
（１７）（１３）に記載のインクジェットインク、（１４）に記載の着色感光性樹脂組成物、および（１５）に記載の感光性樹脂転写材料のいずれかを用いて作製したことを特徴とするカラーフィルタ。
（１８）（１５）または（１６）に記載のカラーフィルタを備えた液晶表示装置。

[Wherein, R ¹ represents a (m + n) -valent linking group, and R ² represents a single bond or a divalent linking group. 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 A monovalent organic group having a group selected from the group consisting of a hydroxyl group, or a monovalent organic group containing an organic dye structure or a heterocyclic ring which may have a substituent. However, n pieces of A ¹ may be the same as or different from each other. m represents a number of 1 to 8, n represents a number of 2 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer compound residue. ]
(12) The organic pigment dispersion as described in any one of (5) to (11), which is used for a color filter having any one color of blue, green, and red.
(13) An inkjet ink for a color filter comprising the organic pigment dispersion according to any one of (5) to (12).
(14) A colored photosensitive resin composition comprising the organic pigment dispersion according to any one of (5) to (12), a binder, and a monomer or oligomer.
(15) A photosensitive resin transfer material provided with a layer having the colored photosensitive resin composition according to (14) on a temporary support.
(16) A color filter comprising the organic pigment dispersion described in any one of (5) to (12) in at least one of an R pixel, a G pixel, and a B pixel.
(17) It is produced using any one of the inkjet ink described in (13), the colored photosensitive resin composition described in (14), and the photosensitive resin transfer material described in (15). Color filter.
(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, exhibits high color rendering power when used in a liquid crystal display device, and maintains its clear image quality even when used for a long period of time, thereby suppressing color unevenness. Excellent effect .

Hereinafter, the present invention will be described in detail.
As a preferred embodiment of the color filter of the present invention, the average particle diameter of 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% of the total pigment particles. The above is mentioned. At this time, as another embodiment, pigment nanoparticles (a) and pigment nanoparticles (b), which will be described later, can be contained to obtain a high-performance color fill, but when the color filter is used in a display device or the like. In order to maintain excellent display performance for as long as possible, satisfy the required performance in a balanced manner, and meet the increasing demand for higher contrast, the average particle size of the pigment particles is as described above. The thickness is preferably 40 nm or less, and more preferably 30 nm or less. In the color filter of the present invention, among all the R pixels, G pixels, and B pixels, the pigment particles contained therein have the above average particle size and the proportion of particles having a particle size of 50 nm or more. It is preferable.
Further in the above pigment particles, particle count on the vertical axis, the particle size distribution was taken particle size (equivalent spherical diameter) on the horizontal axis, that have a maximum value of two or more. Further in the above-mentioned particle size distribution, it is assumed that the smallest maximum value is 30nm or less, more preferably a 25nm or less, particularly preferably 20nm or less.
As described above, in the color filter of this embodiment, the ratio of the number of particles having a particle diameter of 50 nm or more in the pigment particles included in at least one pixel is 1% or more of the total pigment particles. % Or more is more preferable, and 10% or more is particularly preferable.

Regarding the particle size of organic particles, there is a method of expressing the average size of the population by quantifying by a measurement method. Median diameter, various average diameters (number average, length average, area average, mass average, volume average, etc.), etc. In the present invention, unless otherwise specified, the average particle diameter is the number average. It refers to the particle size (Mn). The pigment fine particles may be crystalline particles, amorphous particles, or a mixture thereof.
Further, in the present invention, the ratio (Mv / Mn) of the volume average particle diameter (Mv) and the number average particle diameter (Mn) is used as an index representing the monodispersity of the particles unless otherwise specified. The monodispersity of the pigment fine particles (primary particles), that is, Mv / Mn, is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, and 1.0 to 1. 5 is particularly preferred.
Examples of the method for measuring the particle size of the organic particles include microscopy, mass method, light scattering method, light blocking method, electrical resistance method, acoustic method, and dynamic light scattering method. Particularly preferred. Examples of the microscope used for the microscopy include a scanning electron microscope and a transmission electron microscope. Examples of the particle measuring apparatus by the dynamic light scattering method include Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd. and Dynamic Light Scattering Photometer DLS-7000 series manufactured by Otsuka Electronics Co., Ltd.

Next, an organic pigment dispersion that can be suitably used for producing a color filter including those of the above-described embodiments will be described.
The organic pigment dispersion of the present invention is a pigment dispersion containing pigment nanoparticles (a) and pigment nanoparticles (b). In the present invention, the “pigment dispersion” refers to a dispersion of pigment particles in a medium, which may be a liquid composition or a solid composition, a pigment dispersion, an ink-jet ink, a pigment. It is used to mean including a dispersion resist, a photosensitive transfer material having a pigment, and a pixel portion of a color filter.

  Organic pigments are not limited in hue, for example, perylene compound pigments, perinone compound pigments, quinacridone compound pigments, quinacridone quinone compound pigments, anthraquinone compound pigments, anthanthrone compound pigments, benzimidazolone compound pigments, disazo condensation Compound pigment, disazo compound pigment, azo compound pigment, indanthrone compound pigment, phthalocyanine compound pigment, triarylcarbonium compound pigment, dioxazine compound pigment, aminoanthraquinone compound pigment, diketopyrrolopyrrole compound pigment, thioindigo compound pigment, isoindoline compound And pigments, isoindolinone compound pigments, pyranthrone compound pigments, isoviolanthrone compound pigments, and mixtures thereof.

Among these, quinacridone compound pigments, diketopyrrolopyrrole compound pigments, dioxazine compound pigments, phthalocyanine compound pigments, or azo compound pigments are preferable, and diketopyrrolopyrrole compound pigments, dioxazine compound pigments, and phthalocyanine compound pigments are more preferable.
In the production method of the present invention, two or more kinds of organic pigments or solid solutions of organic pigments can be used in combination, or can be used in combination with ordinary dyes.

  The pigment nanoparticle (a) (hereinafter, this particle is also referred to as “breakdown pigment nanoparticle”) is a particle that is mechanically pulverized into a nanometer size by pulverizing a bulk body of an organic pigment. Here, the bulk of the organic pigment refers to a solid pigment having a diameter of 1 micrometer or more when converted into a sphere. The pulverized nanoparticles may be dispersed in the medium or separated as a solid powder. In the present invention, “nanoparticles” refer to nanometer-sized particles, which are sometimes referred to as “fine particles”.

  Breakdown pigment nanoparticles can be produced by conventional methods. Specific examples of the production apparatus include a ball mill, a bead mill, a roll mill, a colloid mill, a disper, a homogenizer, and an ultrasonic disperser. Among these dispersers, a bead mill capable of using a fine dispersion medium is particularly preferable in producing productivity and a fine dispersion.

  Examples of such bead mills include a horizontal dyno mill (manufactured by Shinmaru Enterprises), an ultra visco mill (manufactured by Imex), a spike mill (manufactured by Inoue Seisakusho); a vertical dry mill (manufactured by Dries Velke). , Sand mill (made by Campe Household Paint Co., Ltd.), etc. Examples of the dispersion medium used in the dispersion include ceramic or steel dispersion media such as zirconia and alumina. Among these, a dispersion medium made of zirconia having excellent wear resistance is particularly preferable.

  In addition, a method of kneading strongly with a two-roll or Banbury mixer while heating the pigment and solid resin, a mixture of a water-soluble inorganic salt such as a pigment and salt with a small amount of an aqueous solvent, and a kneader Examples of the so-called salt milling method include obtaining a fine pigment by strongly kneading and then removing the inorganic salt and solvent by washing and drying.

  The pigment nanoparticle (b) (hereinafter, this particle is also referred to as “build-up pigment nanoparticle”) has an organic pigment solution in which an organic pigment is dissolved in a good solvent, and is compatible with the good solvent. The organic pigment is a nanoparticle deposited by mixing with a solvent which is a poor solvent (hereinafter, this solvent is referred to as “poor solvent”). The combination of the poor solvent and the good solvent needs to have a sufficient difference in solubility of the organic pigment, and it is necessary to select a preferable one according to the organic pigment. Any one can be selected.

  Although a poor solvent is not specifically limited, It is preferable that the solubility of an organic pigment is 0.02 mass% or less, and it is more preferable that it is 0.01 mass% or less. Although there is no particular lower limit to the solubility of the organic pigment in the poor solvent, 0.000001% by mass or more is practical in consideration of a commonly used organic pigment. This solubility may be the solubility when dissolved in the presence of an acid or alkali. In addition, the compatibility or uniform mixing property of the good solvent and the poor solvent is preferably 30% by mass or more, more preferably 50% by mass or more, with respect to the poor solvent.

  Examples of the poor solvent include an aqueous solvent (for example, water or hydrochloric acid, an aqueous sodium hydroxide solution), an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, an aromatic compound solvent, a carbon disulfide solvent, an aliphatic compound solvent, Examples thereof include nitrile compound solvents, halogen compound solvents, ester compound solvents, ionic liquids, and mixed solvents thereof, and aqueous solvents, alcohol compound solvents, ketone compound solvents, ether compound solvents, ester compound solvents, or mixtures thereof are preferable. An aqueous solvent, an alcohol compound solvent or an ester compound solvent is more preferable.

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

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

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

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

  Examples of the sulfoxide compound solvent include dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, sulfolane and the like. Examples of the amide compound solvent include N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, formamide, N -Methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like.

In addition, the concentration of the organic pigment solution in which the organic pigment is dissolved in the good solvent is preferably a saturated concentration of the organic pigment with respect to the good solvent under the dissolution conditions or a range of about 1/100 of this.
There are no particular limitations on the conditions for preparing the organic pigment solution, and a range from normal pressure to subcritical and supercritical conditions can be selected. The temperature at normal pressure is preferably −10 to 150 ° C., more preferably −5 to 130 ° C., and particularly preferably 0 to 100 ° C.

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

  When the organic pigment is uniformly dissolved in a good solvent, it may be dissolved acidic or alkaline. In general, in the case of a pigment having an alkaline and dissociable group in the molecule, it is preferable that the pigment dissolves in an alkaline manner, and in the case of a pigment having a large number of nitrogen atoms in the molecule where there is no alkaline dissociable group and protons are easily added, It is preferable to dissolve in. However, it is not particularly limited to select whether it dissolves acidic or alkaline in consideration of not only the solubility of the pigment but also the characteristics of the color filter. For example, a quinacridone compound pigment The diketopyrrole compound pigment, the disazo condensation compound pigment, and the like may be alkaline and easily dissolved, and the phthalocyanine compound pigment may be acidic and easily dissolved.

  Bases used for alkaline dissolution are inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, or barium hydroxide, or trialkylamine, diazabicycloundecene (DBU), An organic base such as a metal alkoxide is preferable, but an inorganic base is preferable.

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

The acid used for the acid dissolution 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 preferably It is an inorganic acid. Particularly preferred is sulfuric acid.
The amount of the acid used is an amount capable of uniformly dissolving the organic pigment, and is not particularly limited, but is often used in an excessive amount as compared with the base. Regardless of the inorganic acid or organic acid, it is preferably 3 to 500 molar equivalents, more preferably 10 to 500 molar equivalents, and further preferably 30 to 200 molar equivalents with respect to the organic pigment.

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

  The viscosity of the organic pigment solution is preferably 0.5 to 80.0 mPa · s, and more preferably 1.0 to 50.0 mPa · s.

  The difference in pH between the organic pigment solution and the poor solvent is preferably 5 or more. 7 or more is more preferable, and 10 or more is particularly preferable.

  When mixing the organic pigment solution and the poor solvent, either of them may be added and mixed, but it is preferable to jet the organic pigment solution into the poor solvent and mix, and the poor solvent is stirred at that time. It is preferable that the The stirring speed is preferably 100 to 10,000 rpm, more preferably 150 to 8000 rpm, and particularly preferably 200 to 6000 rpm. A pump or the like may be used for the addition, or it may not be used. Moreover, although addition in a liquid or addition outside a liquid may be sufficient, addition in a liquid is more preferable. Further, it is preferable to continuously supply the liquid into the liquid through a supply pipe. The inner diameter of the supply pipe is preferably 0.1 to 200 mm, more preferably 0.2 to 100 mm. As a speed | rate supplied into a liquid from a supply pipe | tube, 1-1000 ml / min is preferable and 5-5000 ml / min is more preferable.

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

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

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

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

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

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, more preferably 1/40 to 1/2, and 1 / 20 to 3/8 is particularly 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 40,000 mg, more preferably 20 to 1000 ml with respect to 1000 ml of the solvent. It is in the range of 30000 mg, particularly preferably in the range of 50-25000 mg.
Moreover, the preparation scale at the time of producing | generating a pigment nanoparticle is although it does not specifically limit, It is preferable that the mixing amount of a poor solvent is a 10-2000L preparation scale, and it is more preferable that it is a 50-1000L preparation scale.

  When depositing build-up pigment nanoparticles, it is preferable to contain a dispersant. The step of incorporating the dispersant is not particularly limited, but it is preferable to add the dispersant to the organic pigment solution and / or the poor solvent. Further, it is also preferable to add the dispersant solution at the time of forming the pigment nanoparticles in a system different from the above two solutions. It is also preferable to use pigment particles that have been surface-treated with a dispersant in advance, and the pigment particles may be subjected to a surface treatment that can promote adsorption of the dispersant. The dispersant (1) has a function of quickly adsorbing on the surface of the deposited pigment to form fine nanoparticles and (2) preventing these particles from aggregating again.

  As the dispersant, for example, an anionic, cationic, amphoteric, nonionic or pigment derivative low molecular or high molecular dispersant can be used. The molecular weight of the polymer dispersant can be used without limitation as long as it can be uniformly dissolved in a solution, but preferably has a molecular weight of 1,000 to 2,000,000, and 5,000 to 1,000,000. 000 is more preferable, 10,000 to 500,000 is more preferable, and 10,000 to 100,000 is particularly preferable. Specifically, as the polymer dispersant, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, polyvinyl alcohol-partial formalized product, Polyvinyl alcohol-partially butyralized product, vinyl pyrrolidone-vinyl acetate copolymer, polyethylene oxide / propylene oxide block copolymer, polyacrylate, polyvinyl sulfate, poly (4-vinylpyridine) salt, polyamide, polyallylamine salt, Examples include condensed naphthalene sulfonate, cellulose derivatives, starch derivatives and the like. In addition, natural polymers such as alginate, gelatin, albumin, casein, gum arabic, tonganto gum and lignin sulfonate can also be used. Of these, polyvinylpyrrolidone is preferable. These polymers can be used alone or in combination of two or more. These dispersants can be used alone or in combination. The dispersant used for dispersing the pigment is described in detail on pages 29 to 46 of “Pigment dispersion stabilization and surface treatment technology / evaluation” (Chemical Information Association, issued in December 2001).

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

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

The amphoteric dispersant is a dispersant having both an anion group part in the molecule of the anionic dispersant and a cationic group part in the molecule of the cationic dispersant.
Nonionic dispersants (nonionic surfactants) include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, Examples thereof include glycerin fatty acid esters. Of these, polyoxyethylene alkylaryl ether is preferable. These nonionic dispersants can be used alone or in combination of two or more.

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

  It is also preferable to use a pigment dispersant containing an amino group as the dispersant. Here, the amino group includes a primary amino group, a secondary amino group, and a tertiary amino group, and the number of amino groups may be one or more. A pigment derivative compound in which a substituent having an amino group is introduced into the pigment skeleton, or a polymer compound having a monomer having an amino group as a polymerization component may be used. Examples of these include, for example, JP-A Nos. 2000-239554, 2003-96329, 2001-31885, JP-A-10-339949, JP-B-5-72943, and JP-A-2006-129714. The compounds described in Paragraphs 0047 to 0113 of the document and Paragraphs 0018 to 0033 of the pamphlet of International Publication No. WO2006 / 121017 can be mentioned, but are not limited thereto.

  In order to further improve the uniform 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 weight, more preferably 100 parts by weight of the pigment. Is in the range of 1 to 500 parts by weight, more preferably in the range of 5 to 20 parts by weight. If the amount is less than 0.1 parts by mass, the dispersion stability of the pigment nanoparticles may not be improved. Moreover, a dispersing agent may be used independently or may be used in combination of multiple 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 containing the precipitated particles (hereinafter, this step is referred to as “concentration / removal step”). Sometimes it is.) As a result, it is possible to produce nanoparticle concentrates and powders suitable for color filter coating liquids and inkjet inks on an industrial scale.

  The concentration / removal step is not particularly limited. For example, an aspect in which an extraction solvent is added to and mixed with the pigment nanoparticle dispersion liquid, and the pigment nanoparticles are concentrated and extracted into the extraction solvent phase, and an aspect in which the concentrated nanoparticle liquid is filtered through a filter or the like. , A mode in which pigment nanoparticles are precipitated and concentrated by centrifugation, a mode in which desalting is concentrated by ultrafiltration, a mode in which spray drying is used, a mode in which the solvent is sublimated by vacuum freeze drying, and a solvent by heating to reduced pressure Examples include a mode of drying and concentrating, a mode of combining them, and a mode of concentrating by centrifugation, a mode of using spray drying, and a mode of drying and concentrating the solvent by heating or decompressing.

  The extraction solvent used for the concentration extraction is not particularly limited, but it is not substantially mixed with the dispersion solvent (for example, aqueous solvent) of the pigment nanoparticle dispersion (in the present invention, it is not compatible) The dissolution amount is preferably 50% by mass or less, more preferably 30% by mass or less, and there is no particular lower limit to the dissolution amount, but it is 1% by mass or more considering the solubility of ordinary solvents. It is practical.) A solvent that forms an interface when allowed to stand after mixing is preferable. In addition, this extraction solvent is a solvent that generates weak aggregation (floc that can be redispersed without applying high shearing force such as milling or high-speed stirring) in which the pigment nanoparticles can be redispersed in the extraction solvent. Is preferred. In such a state, the dispersion of a dispersion solvent such as water can be easily removed by filter filtration or the like while the target pigment nanoparticles are wetted with the extraction solvent without causing strong aggregation that changes the particle size. This is preferable. 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.

  Examples of the ester compound solvent include 2- (1-methoxy) propyl acetate, ethyl acetate, and ethyl lactate. Examples of the alcohol compound solvent include n-butanol and isobutanol. Examples of the aromatic compound solvent include benzene, toluene, xylene and the like. Examples of the aliphatic compound solvent include n-hexane and cyclohexane. Further, the extraction solvent may be a pure solvent based on the above preferred solvent or a mixed solvent composed 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 represented by volume ratio, when the pigment nanoparticle dispersion liquid is 100, the extraction solvent to be added is preferably in the range of 1 to 100, more preferably in the range of 10 to 90, and 20 to 80. The range of is particularly preferable. If it is too much, it will take a lot of time for concentration, and if it is too little, extraction will be insufficient and nanoparticles will remain in the dispersion solvent.
After adding the extraction solvent, it is preferable to stir and mix so as to be in sufficient contact with the dispersion. A normal method can be used for stirring and mixing. Although there is no restriction | limiting in particular in the temperature when 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. Any device may be used for adding and mixing the extraction solvent as long as each step can be preferably performed. For example, a separation funnel type device can be used.

  In the case of ultrafiltration, for example, a method used for desalting / concentration of a silver halide emulsion can be applied. Research Disclosure No. 10208 (1972), no. 13 122 (1975) and no. 16 351 (1977) is known. The pressure difference and flow rate that are important as operating conditions can be selected with reference to the characteristic curve described in Haruhiko Oya's “Membrane Utilization Technology Handbook”, Koshobo Publishing, (1978), p275. In order to process the particles, it is necessary to find an optimum condition in order to suppress the aggregation of particles. There are two methods for replenishing the solvent that is lost due to membrane permeation: a constant volume method in which the solvent is continuously added and a batch method in which the solvent is intermittently added, but the desalting time is relatively short. The formula is preferred. As the solvent to be replenished, pure water obtained by ion exchange or distillation is used. However, a dispersant, a poor solvent for the dispersant may be mixed in pure water, or directly into the pigment nanoparticle dispersion. It may be added.

  Ultrafiltration membranes, such as flat plate type, spiral type, cylindrical type, hollow fiber type and hollow fiber type, which are already incorporated as modules, are available from Asahi Kasei Corporation, Daicel Chemical Co., Ltd., Toray Industries, Inc. ( Although it is commercially available from Nitto Denko Corporation, a spiral type or a hollow fiber type is preferred from the viewpoint of the total membrane area and detergency. In addition, the molecular weight cut off as an index of the threshold value of the component that can permeate the membrane needs to be determined from the molecular weight of the dispersant used, but preferably 5,000 or more and 50,000 or less, More preferred is 5,000 or more and 15,000 or less.

  As the filter filtration device, for example, a device such as pressure filtration can be used. Preferred filters include nanofilters and ultrafilters. It is preferable to remove the remaining dispersion solvent by filter filtration and further concentrate the pigment nanoparticles in the concentrated extract to obtain a concentrated nanoparticle solution.

  Freeze drying is not particularly limited, and any method may be adopted as long as it is a normal method. For example, a refrigerant direct expansion method, an overlap refrigeration method, a heat medium circulation method, a triple heat exchange method, and an indirect heating freezing method can be mentioned, preferably a refrigerant direct expansion method, an indirect heating freezing method, more preferably an indirect heating freezing method. It is good to use. In any method, it is preferable to perform freeze-drying after preliminary freezing. The pre-freezing conditions are not particularly limited, but it is necessary that the sample to be freeze-dried is completely frozen.

  Indirect heating freezing equipment includes small freeze dryer, FTS freeze dryer, LYOVAC freeze dryer, experimental freeze dryer, research freeze dryer, triple heat exchange vacuum freeze dryer, mono-cooling freeze dryer , HULL freeze dryers, preferably small freeze dryers, laboratory freeze dryers, research freeze dryers, monocooling freeze dryers, more preferably small freeze dryers, monocooling freeze dryers Should be used.

  Although the temperature of freeze-drying is not specifically limited, For example, it is -190--4 degreeC, Preferably it is -120--20 degreeC, More preferably, it is about -80--60 degreeC. The pressure for lyophilization is not particularly limited, and can be appropriately selected by those skilled in the art. The freeze-drying time is, for example, 2 to 48 hours, preferably 6 to 36 hours, and more preferably about 16 to 26 hours. However, these conditions can be appropriately selected by those skilled in the art. Regarding the freeze-drying method, for example, Formulation Machine Technology Handbook: Formulation Machine Technology Study Group, Jinshokan, p. 120-129 (September 2000); Vacuum Handbook: Japan Vacuum Technology Co., Ltd., Ohm, p. 328-331 (1992); Journal of the Research Group on Freezing and Drying: Koji Ito et al. 15, p. 82 (1965) or the like.

Any device may be used as the centrifuge as long as it can precipitate the pigment nanoparticles. For example, in addition to a general-purpose device, a device having a skimming function (a function of sucking a supernatant layer during rotation and discharging it out of the system), a continuous centrifuge that continuously discharges solid matter, and the like can be given.
Centrifugation conditions are preferably 50 to 10000, more preferably 100 to 8000, and particularly preferably 150 to 6000 in terms of centrifugal force (a value representing how many times the gravitational acceleration is applied). Although the temperature at the time of centrifugation is based on the solvent seed | species of a dispersion liquid, -10-80 degreeC is preferable, -5-70 degreeC is more preferable, 0-60 degreeC is especially preferable.

The 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, an apparatus that can be heated and reduced in pressure while stirring the liquid, and an apparatus that can be continuously dried by passing the liquid through a heated and reduced pressure tube.
The heating and drying temperature is preferably 30 to 230 ° C, more preferably 35 to 200 ° C, and particularly preferably 40 to 180 ° C. The pressure during decompression is preferably 100 to 100,000 Pa, more preferably 300 to 90,000 Pa, and particularly preferably 500 to 80,000 Pa.
Moreover, you may dry by the following aspects. For example, as dryers using hot air, shelf dryers, band dryers, stirring dryers, fluidized bed dryers, spray dryers, air dryers, etc., dryers using heat conduction are drum dryers, multiple dryers, etc. A tube dryer, a cylindrical dryer or the like is preferably used. Depending on the solvent composition, a freeze dryer or an infrared dryer can be used.
Among these means, a spray dryer (for example, COC-12 manufactured by Okawara Chemical Co., Ltd.), a fluidized bed dryer (for example, Okawara Kako Co., Ltd.) from the viewpoint that it is suitable for obtaining a dry powder directly from the dispersion. Nara Machinery Co., Ltd. MSD-100) is particularly preferably used. In addition, a plurality of drying means may be used in combination to prepare a pigment powder with a small amount of residual solvent. For example, a pigment dispersion pre-concentrated with a cylindrical dryer is completely dried with a drum dryer. Processes such as obtaining powder can be used.
The drying conditions are not particularly limited as long as the solvent can be evaporated and materials such as pigments and dispersants are not denatured. Further, for the purpose of increasing the drying speed, it is possible to combine means such as depressurization, stirring and mixing and multi-stage depending on the type of dryer.

The amount to reduce or remove the solvent content is not particularly limited, but in an embodiment in which the solvent content is reduced, it is preferable to remove 50% by mass or more of the total solvent content, and more preferably 75% by mass or more. In the embodiment of removing the solvent, it is preferable to remove 80% by mass or more of the total solvent, and more preferably 90% by mass or more.
When the solvent content is reduced by the concentration / removal step, the water content in the remaining dispersion is not particularly limited, but is preferably 0.01 to 3% by mass, and preferably 0.01 to 1% by mass. It is more preferable. At this time, for example, it is preferable to remove the solvent component by the above drying method or the like to obtain pigment nanoparticle powder. For example, the solid content is preferably 50 to 100% by mass, and 70 to 100% by mass. More preferably.
The concentration / removal step may be performed a plurality of times, for example, preferably performed both before and after the addition of the third solvent described later.

The build-up pigment nanoparticles are preferably obtained by redispersing the organic particles in an aggregated state by the concentration / removal step. The organic particles concentrated by the above-described embodiment may be agglomerated. As a result, rapid filter filtration or the like is possible, and the aggregated state may be given in consideration of separation and recovery. In such a case, in order to obtain a good dispersion state again, it is preferable to form a floc that is weakly aggregated to such an extent that it can be redispersed in the concentrate.
However, in order to redisperse the above-mentioned aggregated particles, a normal dispersion method may be insufficient. Even in the organic particles in such an agglomerated state, the organic particles can be suitably redispersed by containing, for example, the following polymer compound having a mass average molecular weight of 1000 or more.

  The polymer compound is preferably a polymer compound represented by the following 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, or an alkoxysilyl group. , A monovalent organic group having a group selected from an epoxy group, an isocyanate group and a hydroxyl group, or a monovalent organic group containing an organic dye structure or a heterocyclic ring which may have a substituent. The n A ¹ may be the same or different.
Specifically, A ¹ is not particularly limited, and examples of the “monovalent organic group having an acidic group” include a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, Examples thereof include monovalent organic groups having a monophosphate ester group, a boric acid group, and the like. Examples of the “monovalent organic group having a basic group having a nitrogen atom” include, for example, a monovalent organic group having an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R). ¹⁰ ) having a monovalent organic group (wherein R ⁸ , R ⁹ , and R ¹⁰ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a carbon number) A monovalent organic group having a guanidyl group represented by the following general formula (a1) [in the general formula (a1), R ^a1 and R ^a2 are each independently carbon; It represents 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. A monovalent organic group having an amidinyl group represented by the following general formula (a2) [in the general formula (a2), R ^a3 and R ^a4 are each independently an alkyl group having 1 to 20 carbon atoms, carbon An aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 30 carbon atoms is represented. And the like.

As the “monovalent organic group having a urea group”, for example, —NHCONHR ¹⁵ (wherein R ¹⁵ is a hydrogen atom, 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).
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 having 1 to 20 carbon atoms, 6 carbon atoms). Or an aryl group having 20 or less 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 acetylacetonato group and a group having a crown ether.
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 (for example, octyl group, dodecyl group, etc.) and an aryl group having 6 or more carbon atoms (for example, phenyl Group, a naphthyl group, etc.), an aralkyl group having 7 or more carbon atoms (for example, a benzyl group) and the like. At this time, there is no upper limit to the number of carbon atoms, but it is preferably 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.
Examples of the “monovalent organic group having an epoxy group” include a group having a glycidyl group.
Examples of the “monovalent organic group having an isocyanate group” include a 3-isocyanatopropyl group.
Examples of the “monovalent organic group having a hydroxyl group” include a 3-hydroxypropyl group.

A ¹ is preferably a monovalent organic group having an acidic group, a basic group having a nitrogen atom, a urea group, or a hydrocarbon group having 4 or more carbon atoms.

  The organic dye structure or heterocyclic ring is not particularly limited. More specifically, examples of the organic dye structure include phthalocyanine compounds, insoluble azo compounds, azo lake compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds, Examples include diketopyrrolopyrrole compounds, anthrapyridine compounds, ansanthrone compounds, indanthrone compounds, flavanthrone compounds, perinone compounds, perylene compounds, and thioindigo compounds. Examples of the heterocyclic ring include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, Examples include morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, and anthraquinone.

  The organic dye structure or the heterocyclic ring may have a substituent T. Examples of the substituent T include alkyl groups having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. Aryl groups having 6 to 16 carbon atoms such as groups, acyloxy groups having 1 to 6 carbon atoms such as acetoxy groups, alkoxy groups having 1 to 6 carbon atoms such as methoxy groups and ethoxy groups, halogen atoms such as chlorine and bromine, C2-C7 alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, carbonate groups such as cyano group and t-butyl carbonate, hydroxyl group, amino group, carboxyl group, sulfonamide group, N -A sulfonylamide group etc. are mentioned.

Also, the A ¹ can be represented by the following general formula (4).

In the general formula (4), B 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, or an alkoxysilyl group. Represents an organic dye structure or a heterocyclic ring optionally having a substituent selected from an epoxy group, an isocyanate group, and a hydroxyl group, and R ¹⁸ represents a single bond or an a1-valent organic or inorganic linking group. . a1 represents 1 to 5, a1 amino ^{B 1} represents may be the same or different. Preferred embodiments of the group represented by the general formula (4) has the same meaning as the A ^1.

R ¹⁸ represents a single bond or an a1 + 1 valent linking group, and a1 represents 1 to 5. The linking group R ¹⁸ is 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 may be unsubstituted or may further have a substituent. R ¹⁸ is preferably an organic linking group.

Specific examples of R ¹⁸ include the following structural units or groups formed by combining the structural units. The linking group R ¹⁸ may have the substituent T.

In the general formula (1), R ¹ represents an (m + n) -valent linking group. m + n satisfies 3-10.
Examples of the (m + n) -valent linking group represented by R ¹ include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and A group consisting of 0 to 20 sulfur atoms is included, which may be unsubstituted or may further have a substituent. R ¹ is preferably an organic linking group.

Specific examples of R ¹ include the groups (which may form a ring structure) configured by combining the groups (t-1) to (t-34) or a plurality thereof. . When the linking group R ¹ has a substituent, examples of the substituent include the substituent T described above.

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. It may be unsubstituted or may further have a substituent.
Specific examples of R ² include groups formed by combining the groups of t-3 to 5, 7 to 18, 22 to 26, 32, and 34, or a plurality thereof. R ² preferably has a sulfur atom at the position of connection with R ¹ . When R ² has a substituent, examples of the substituent include the substituent T.

In said general formula (1), m represents 1-8. As m, 1-5 are preferable, 1-3 are more preferable, and 1-2 are especially preferable.
N represents 2-9. n is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.

In the general formula (1), P ¹ represents a polymer compound residue (polymer skeleton) and can be appropriately selected from ordinary polymers.
Among polymers, in order to constitute a polymer skeleton, a vinyl monomer polymer or copolymer, ester compound polymer, ether compound polymer, urethane compound polymer, amide compound polymer, epoxy compound polymer, silicone compound polymer, and these Modified product or copolymer [for example, polyether / polyurethane copolymer, copolymer of polyether / vinyl monomer, etc. (any of random copolymer, block copolymer, graft copolymer) May be included). Is preferably selected from the group consisting of vinyl monomer polymers or copolymers, ester compound polymers, ether compound polymers, urethane compound polymers, and modified products or copolymers thereof. At least one kind is more preferred, and a polymer or copolymer of vinyl monomers is particularly preferred.
Furthermore, the polymer is preferably soluble in an organic solvent. If the affinity with the organic solvent is low, for example, when used as a pigment dispersant, the affinity with the dispersion medium is weakened, and it may not be possible to secure a sufficient adsorption layer for stabilizing the dispersion.
Also, P ¹ preferably has a sulfur atom in the coupling position with R ^1.

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

In the general formula (2), A ² has the same meaning as A ¹ in the general formula (1), the same applies its specific preferred embodiment. A ² may have a substituent, and examples thereof include the substituent T.

In the general formula (2), R ³ represents a (x + y) -valent linking group. R ³ has the same meaning as R ¹ , and the preferred range is also the same. At this time, R ³ is an x + y-valent linking group, but the value of x and its preferred range are the same as n in formula (1), the value of y and its preferred range are the same as m, and x + y The value of and the preferred range thereof are the same as m + n.

The linking group represented by R ³ is preferably an organic linking group, and preferred specific examples of the organic linking group are shown below. However, the present invention is not limited to these.

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

Further, when the above R ³ has a substituent, the substituent T can be cited as the substituent.

In the general formula (2), R ⁴ and R ⁵ each independently represents a single bond or a divalent linking group.
The “divalent linking group” represented by R ⁴ and R ⁵ is a linear, branched, or cyclic alkylene group, arylene group, or aralkylene group, which may have a substituent, — O -, - S -, - C (= O) -, - N (R 19) -, - SO -, - SO 2 -, - CO 2 -, or _{^{-N (R 20) SO 2 -}} , or they A divalent group in which two or more groups are combined is preferable (the R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Of these, an organic linking group is preferred.

As R ⁴ , a linear or branched alkylene group or aralkylene 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 of these groups are combined is more preferable, and a linear or branched alkylene group or aralkylene group, —O—, —C (═O) —, —N (R ¹⁹ ) —, —CO ₂ —, or a divalent group in which two or more of these groups are combined is particularly preferable.

R ⁵ is a single bond, straight chain or branched alkylene group, aralkylene 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 of these groups are combined is more preferable. A linear or branched alkylene group, an aralkylene group, —O—, —C (= O) —, —N (R ¹⁹ ) —, or —CO ₂ —, or a divalent group in which two or more of these groups are combined is particularly preferable.

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

P ² in the general formula (2) represents a polymer skeleton and can be appropriately selected from ordinary polymers and the like. The preferred embodiment of the polymer, has the same meaning as P ¹ in Formula (1), the same applies to its preferred embodiment.

Among the polymer compounds represented by the general formula (2), in particular, R ³ represents the specific examples (r-1), (r-2), (r-10), (r-11), (r -16) or (r-17), wherein R ⁴ is a single bond, linear or branched, alkylene group or aralkylene group, —O—, —C (═O) —, —N (R ¹⁹ ) -, or -CO 2 _-, or a divalent organic group formed by combining two or more of these groups, R ⁵ is a single bond, an ethylene group, a propylene group, or the following general formula (s-a) or A linking group represented by (s-b), wherein P ² is a polymer or copolymer of a vinyl monomer, an ester compound polymer, an ether compound polymer, a urethane polymer, or a modified product thereof, y Is a polymer compound in which x is 1 to 2 and x is 3 to 6. There. In the following groups, R ²¹ represents a hydrogen atom or a methyl group, and l represents 1 or 2.

The mass average molecular weight of the polymer compound is 1000 or more, preferably 3000 to 100,000, more preferably 5000 to 80000, and particularly preferably 7000 to 60000 in terms of mass average molecular weight. When the mass average molecular weight is within the above range, the effects of the multiple functional groups introduced at the polymer ends are sufficiently exhibited, and the performance of adsorbing to a solid surface, micelle forming ability, and surface activity is excellent. Good dispersibility and dispersion stability can be achieved.
In the present invention, the molecular weight means a mass average molecular weight unless otherwise specified. Examples of the molecular weight measuring method include chromatography, viscosity, light scattering, sedimentation rate, etc. In the present invention, unless otherwise specified, polystyrene measured by gel permeation chromatography (carrier: tetrahydrofuran). The converted mass average molecular weight is used.

  Specific examples of the compound represented by the general formula (1) are shown below. However, the present invention is not limited to these specific examples.

The polymer compound represented by the general formula (1) or (2) can be synthesized, for example, by the following methods.
1. A polymer in which a functional group selected from a carboxyl group, a hydroxyl group, an amino group and the like is introduced at the terminal, an acid halide having a plurality of functional groups (A ¹ or A ² in the general formula), or a plurality of functional groups ( A method in which an alkyl halide having A ¹ or A ² ) in the general formula or an isocyanate having a plurality of functional groups (A ¹ or A ² in the general formula) is polymerized.
2. A method in which a polymer having a carbon-carbon double bond introduced at the terminal and a mercaptan having a plurality of functional groups (A ¹ or A ² in the above general formula) are subjected to a Michael addition reaction.
3. A method in which a polymer having a carbon-carbon double bond introduced at a terminal thereof and a mercaptan having a plurality of functional groups (A ¹ or A ² in the above general formula) are reacted in the presence of a radical generator.
4). A method of reacting a polymer having a plurality of mercaptans introduced at its terminal and a functional group having a carbon-carbon double bond introduced (A ¹ or A ² in the above general formula) in the presence of a radical generator.
5. A method of radical polymerization of a vinyl monomer using a mercaptan compound having a plurality of functional groups (A ¹ or A ² in the above general formula) as a chain transfer agent.
Of these, 2, 3, 4, 5 are preferable, 3, 4, 5 are more preferable, and 5 is particularly preferable because of ease of synthesis. As for these synthesis methods, the contents described in paragraphs 0184 to 0216 of Japanese Patent Application No. 2006-129714 can be referred to.

In addition, as a polymer compound having a molecular weight of 1000 or more, a polymer compound having the following acidic group (hereinafter, this compound may be referred to as “acidic group-containing polymer compound”) may be used. It is preferably a polymer compound having a group, and (A) at least one repeating unit derived from a compound having a carboxyl group and (B) at least one repeating unit derived from a compound having a carboxylic ester group. More preferred are copolymer compounds containing seeds.
The repeating unit derived from the compound (A) having a carboxyl group is preferably a repeating unit represented by the following general formula (I), preferably a repeating unit derived from acrylic acid or methacrylic acid. More preferably, the repeating unit derived from the compound (B) having a carboxylic acid ester group is preferably a repeating unit represented by the following general formula (II), and represented by the following general formula (IV). A repeating unit is more preferable, and a repeating unit derived from benzyl acrylate, benzyl methacrylate, phenethyl acrylate, phenethyl methacrylate, 3-phenylpropyl acrylate, or 3-phenylpropyl methacrylate is particularly preferable.

式中、Ｒ_１は水素原子又は炭素原子数１〜５のアルキル基を表す。Ｒ_２は水素原子又は炭素原子数１〜５のアルキル基を表す。Ｒ_３は下記一般式（ＩＩＩ）で表される基を表す。Ｒ_４は水素原子、炭素原子数１〜５のアルキル基、ヒドロキシ基、炭素原子数１〜５のヒドロキシアルキル基、又は炭素原子数６〜２０のアリール基を表す。Ｒ_５及びＲ_６はそれぞれ水素原子又は炭素原子数１〜５のアルキル基を表す。ｉは１〜５の数を表す。Ｒ_７は水素原子又は炭素原子数１〜５のアルキル基を表す。Ｒ_８は下記一般式（Ｖ）で表される基を表す。Ｒ_９は炭素原子数２〜５のアルキル基又は炭素原子数６〜２０のアリール基を表す。Ｒ_１０及びＲ_１１は水素原子又は炭素原子数１〜５のアルキル基を表す。ｊは１〜５の数を表す。
また、（Ａ）カルボキシル基を有する化合物から導かれた繰り返し単位と、前記（Ｂ）カルボン酸エステル基を有する化合物から導かれた繰り返し単位との重合比率としていえば、繰り返し単位（Ａ）の全繰り返し単位数に対する数量比％が３〜４０であることが好ましく、５〜３５であることがより好ましい。

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 a 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 a 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 a number from 1 to 5;
Further, in terms of the polymerization ratio of the repeating unit derived from the compound having (A) a carboxyl group and the repeating unit derived from the compound having the (B) carboxylic ester group, all of the repeating units (A) The quantity ratio% to the number of repeating units is preferably 3 to 40, more preferably 5 to 35.

The polymer compound may be water-soluble or oil-soluble, and may be water-soluble and oil-soluble. The polymer compound may be added by a solution in an aqueous solvent or an organic solvent, a solid state, or a combination thereof. As a method of adding in a solution dissolved in a solvent, for example, a method of adding to an aggregated organic particle liquid in a state dissolved in the same solvent as the solvent of the aggregated organic particle liquid, compatible with the solvent of the aggregated organic particle liquid, The method of adding in the state melt | dissolved in a different solvent is mentioned. The concentration of the polymer compound when added in a solution dissolved in a solvent is not particularly limited, but is preferably 1 to 70% by mass, more preferably 2 to 65% by mass, and particularly preferably 3 to 60% by mass.
The polymer compound may be added at any time during or after the precipitation of pigment nanoparticles, during or after concentration, when or after the dispersion of aggregated organic particles after concentration, or after the completion of these steps. It may be added, or may be added in a plurality of times. In the production method of the present invention, a 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, after concentrating the organic fine particle deposit, finely dispersing the aggregated organic particles It is preferable to add to.

The addition amount of the polymer compound 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. preferable.
In addition to the above compounds, the polymer compound having a molecular weight of 1000 or more, for example, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, polyvinyl alcohol -Partially formalized product, polyvinyl alcohol-partially butyralized product, vinylpyrrolidone-vinyl acetate copolymer, polyethylene oxide / propylene oxide block copolymer, polyamide, cellulose derivative, starch derivative and the like. In addition, natural polymer compounds such as alginate, gelatin, albumin, casein, gum arabic, tonganto gum and lignin sulfonate can also be used. Examples of the polymer compound having an acidic group include polyvinyl sulfate and condensed naphthalene sulfonic acid.

Examples of the polymer compound having a carboxyl group include polyacrylic acid, polymethacrylic acid, and cellulose derivatives having a carboxyl group in the side chain. A copolymer compound containing (A) at least one repeating unit derived from a compound having a carboxyl group and (B) at least one repeating unit derived from a compound having a carboxylic ester group is disclosed in 59-44615, JP-B 54-34327, JP-B 58-12577, JP-B 54-25957, JP-A 59-53836, and JP-A 59-71048. Examples thereof include methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, and partially esterified maleic acid copolymers. Further, as particularly preferred examples, acrylic acid-acrylic acid ester copolymers, methacrylic acid-acrylic acid ester copolymers, acrylic acid-methacrylic acid ester copolymers, methacrylic acid-described in US Pat. No. 4,139,391 are described. Examples include methacrylic acid ester copolymers, and multi-component copolymers 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 (eg, vinyl toluene, vinyl ethyl benzene), vinyl naphthalene or substituted vinyl naphthalene, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, and the like, and styrene is preferred.

  Only one type of polymer compound having a molecular weight of 1000 or more may be used, or two or more types may be used in combination, or a compound having a molecular weight of less than 1000 may be used in combination.

  The build-up pigment nanoparticles are preferably obtained by precipitating the pigment nanoparticles and then containing a third solvent. Although the kind of 3rd solvent is not specifically limited, It is preferable that it is an organic solvent, for example, an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, an aliphatic compound solvent, a ketone compound solvent is preferable, an ester compound solvent, a ketone Compound solvents are particularly preferred.

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

  Of these, ethyl lactate, ethyl acetate, acetone, and ethanol are preferable, and ethyl lactate is more preferable. These may be used alone or in combination of two or more.

The addition of the third solvent is not particularly limited as long as it is after the precipitation of the pigment nanoparticles, but is preferably added after the concentration / removal step described above. Further, when a pigment dispersion composition to be described later is used, after the first concentration / removal step, a third solvent is added, and the solvent content is reduced or removed by the second concentration / removal step. Is preferred. And a binder and / or a solvent can be added after that, and it can be set as a desired pigment dispersion composition.
The addition amount of the third solvent is not particularly limited, but is preferably 100 to 300,000 parts by mass, and more preferably 500 to 10,000 parts by mass with respect to 100 parts by mass of the pigment nanoparticles.

  The organic pigment dispersion of the present invention contains breakdown pigment nanoparticles (a) and buildup pigment nanoparticles (b) prepared as described above. The mode of mixing both is not particularly limited, and the composition of each pigment nanoparticle may be prepared and mixed separately, or may be mixed as a powder. The mixing ratio of the two is not particularly limited, but the build-up pigment nanoparticles (b) are preferably 1% by mass or more, more preferably 3 to 95% by mass with respect to the total amount of both particles.

  In the organic pigment dispersion of the present invention, the average particle size of all 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 size of 50 nm or more is 1% of all pigment particles. % Or more, more preferably 5% or more, and particularly preferably 10% or more. At this time, the average particle diameter is more preferably 30 nm or less. It is preferable to have two or more maximum values when the particle size distribution is measured for all the pigment fine particles. In the same particle size distribution, the minimum maximum value is preferably 30 nm or less, more preferably 25 nm or less, and particularly preferably 20 nm or less.

By using, for example, at least one R pixel, G pixel, and B pixel of the color filter using the organic pigment dispersion having the particle size distribution as described above, the color filter of the preferred embodiment described above is obtained. be able to.
In the organic pigment dispersion described above, the average particle diameter, monodispersibility and preferred range of the pigment particles, and the measurement method thereof are the same as those described for the color filter of the preferred embodiment.

  The concentration of the pigment nanoparticles (a) and (b) in the organic pigment dispersion is appropriately determined depending on the purpose, and preferably 2 to 30% by mass with respect to the total amount of the organic pigment dispersion, It is more preferably 4 to 20% by mass, and particularly preferably 5 to 15% by mass.

The pigment nanoparticles can be used, for example, in a dispersed state in a vehicle. The vehicle refers to a portion of a medium in which a pigment is dispersed when it is in a liquid state, a portion that is liquid and binds to the pigment to harden a coating film (binder). And a component (organic solvent) to be dissolved and diluted. In addition, the binder used at the time of nanoparticle formation and the binder used for redispersion may be the same or different.
In the case of dispersing in the vehicle as described above, the amount of the binder and dissolved dilution component is appropriately determined depending on the type of the organic pigment and the like, but the binder is 1 to 30% by mass with respect to the total amount of the dispersion composition. Preferably, it is 3-20 mass%, More preferably, it is 5-15 mass%. It is preferable that a dissolution dilution component is 5-80 mass%, and it is more preferable that it is 10-70 mass%.

In the concentrated and extracted nanoparticle liquid, as described above, in order to enable rapid filter filtration, the pigment nanoparticles are preferably aggregated by concentration, and concentrated by centrifugation or drying. Aggregation is preferred. As a method of redispersing such aggregated nanoparticles, for example, a dispersion method using ultrasonic waves or a method of applying physical energy can be used. The ultrasonic irradiation device used preferably has a function capable of applying an ultrasonic wave of 10 kHz or higher, and examples thereof include an ultrasonic homogenizer and an ultrasonic cleaner. When the liquid temperature rises during ultrasonic irradiation, thermal aggregation of the nanoparticles occurs (pigment dispersion technique—surface treatment and use of dispersant and evaluation of dispersibility—see Technical Information Association 1999), so the liquid temperature is 1 to 100 ° C. It is preferable to set it as 5-60 degreeC. The temperature control method can be performed by controlling the dispersion temperature, controlling the temperature of the temperature adjusting layer that controls the temperature of the dispersion, or the like.
There are no particular restrictions on the dispersing machine used to disperse the concentrated pigment nanoparticles by applying physical energy, for example, kneader, roll mill, atrider, super mill, dissolver, homomixer, sand mill, etc. Machine. Further, a high-pressure dispersion method and a dispersion method using fine particle beads are also preferable.

The colored photosensitive resin composition of the present invention contains the above organic pigment dispersion, monomer or oligomer, and binder.
The organic pigment dispersion containing the pigment nanoparticles (a) and (b) has already been described in detail. In the colored photosensitive resin composition, the total content of the pigment nanoparticles (a) and (b) is 3-90 mass% is preferable with respect to total solid content (in this invention, total solid means the composition sum total except an organic solvent), 20-80 mass% is more preferable, 25-60 mass% is preferable. Is more preferable. If this amount is too large, the viscosity of the dispersion increases, which may cause problems in production suitability. If the amount is too small, coloring power is not sufficient. The fine particles functioning as the colorant preferably have a particle size of 0.1 μm or less, particularly 0.08 μm or less. Moreover, you may use it in combination with a normal pigment for toning.

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

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

  The oligomer preferably has a molecular weight of 200 to 1000, and may be used alone or in combination of two or more. The content of the ink for a color filter based on the total solid content is generally 5 to 50% by mass, 10-40 mass% is preferable. If this amount is too large, it becomes difficult to control the developability, which causes a problem in production suitability. If the amount is too small, the curing power at the time of exposure is insufficient.

  As the binder, a binder having an acidic group is preferable, and it can be added at the time of preparing the inkjet ink for color filter or the colored photosensitive resin composition, but when producing the pigment nanoparticle dispersion composition, or pigment nanoparticle It is also preferable to add at the time of formation. It is also possible to add a binder to both or one of the poor solvent for adding the organic pigment solution and the organic pigment solution to form pigment nanoparticles. Alternatively, it is also preferable to add the binder solution in a separate system when forming the pigment nanoparticles. The binder is preferably an alkali-soluble polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-57-36. A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer as described in JP-A-59-71048 Etc. Moreover, the cellulose derivative which has a carboxylic acid group, carboxylate, etc. in a side chain can also be mentioned, In addition to this, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. As particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate and (meth) acrylic acid are used. And multi-component copolymers with other monomers. These binder polymers having a polar group may be used alone or in the form of a composition used in combination with a normal film-forming polymer. -200 mass parts is common, 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 useful. Examples of polymers containing these polymerizable groups are shown below, but are not limited to the following as long as they contain an alkali-soluble group such as a COOH group, OH group, and ammonium group and a carbon-carbon unsaturated bond. Reactive with OH groups in copolymers of OH groups such as 2-hydroxyethyl acrylate, COOH groups such as methacrylic acid, and monomers such as acrylic or vinyl compounds copolymerizable therewith A compound obtained by reacting a compound having an epoxy ring with a carbon-carbon unsaturated bond group, for example, 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, an isocyanate group, and an acryloyl group can also be used. Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring disclosed in JP-A-6-102669 and JP-A-6-1938 can be used as a saturated or unsaturated polybasic acid anhydride. A reaction product obtained by reacting a product can also be used. Examples of compounds having both an alkali-solubilizing group such as COOH and a carbon-carbon unsaturated group are Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing Polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co. Ltd.,). Viscoat R-264, KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), etc. Can be mentioned.

Furthermore, as the binder resin, an organic high molecular polymer having a water-soluble atomic group in a part of the side chain can be used. The binder resin is a linear organic high molecular polymer that is compatible with the monomer, and is soluble in an organic solvent and alkali (preferably developable with a weak alkaline aqueous solution). Examples of the alkali-soluble resin include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-sho 59-53836, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer as described in JP-A-59-71048, There are partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also included. As the alkali-soluble resin, those obtained by adding an acid anhydride to a polymer having a hydroxyl group are also useful. In particular, among these, specifically, a benzyl (meth) acrylate / (meth) acrylic acid copolymer and a multi-component copolymer of benzyl (meth) acrylate / (meth) acrylic acid / and other monomers are preferable. The alkali-soluble resin includes at least (i) at least one acid component monomer selected from maleic anhydride (MAA), acrylic acid (AA), methacrylic acid (MA), and fumaric acid (FA), and (ii) It is possible to use a copolymer (hereinafter referred to as “copolymer A”) composed of ()) alkylpolyoxyethylene (meth) acrylate and (iii) benzyl (meth) acrylate.
As the combination of the copolymer A, (i) acid component monomer, (ii) alkyl polyoxyethylene (meth) acrylate (Acr (EO) n: CH ₃ (OC ₂ H ₄ ) nOCOC (R) ═CH ₂ ) And (iii) The composition mass ratio of benzyl (meth) acrylate (Bz (M) A) is preferably 10-25 / 5-25 / 50-85, more preferably 15-20 / 5-20 / 60- 80 is preferred. The polystyrene-reduced mass average molecular weight (Mw) by GPC of the copolymer is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.

(I) When the compositional mass ratio of the acid component monomer is within the above range, alkali solubility and solubility in a solvent are unlikely to decrease. In addition, 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, Since the liquid easily spreads on the substrate and the dispersibility of the colorant is hardly lowered, the effect of the present invention can be effectively achieved. (Iii) When the compositional mass ratio of benzyl (meth) acrylate (Bz (M) A) is in the above range, the dispersion stability of the colorant, the solubility in the composition, and the alkali development suitability of the coating film decrease. Hateful.
Incidentally, the (ii) alkylpolyoxyethylene (meth) acrylate repeating number n of the polyoxyethylene (EO) n of _{(Acr (EO) n CH 3} (OC 2 H 4) nOCOC (R) = CH 2) is 2-15 are preferable, 2-10 are still more preferable, and 4-10 are especially preferable. When the above repeating number n is in the above range, a development residue is less likely to occur after development with an alkaline developer, the fluidity of the composition as a coating solution can be prevented, and coating unevenness can be prevented. It is possible to prevent the thickness uniformity and the liquid-saving property from decreasing.
These binder polymers having a polar group may be used alone or in the form of a composition used in combination with a normal film-forming polymer. -200 mass parts is common, and 25-100 mass parts is preferable.

When the binder is a polymer compound, the number of acidic groups in the polymer compound is not particularly limited, but when the number of repeating units contained in one molecule is 100, the number of repeating units having an acidic group is 5 It is preferable that it is -100, and it is more preferable that it is 10-100. Further, the polymerization ratio of the repeating unit derived from the compound having (1) carboxyl group and the repeating unit derived from the compound having (2) carboxylic acid ester group is the mole of repeating unit (1). % Is preferably 5 to 40, the repeating unit (2) is preferably 40 to 90, and the repeating unit other than the repeating unit (1) or (2) is preferably 25 or less. The molecular weight of the alkali-soluble binder polymer compound having an acidic group is preferably 3000 to 1000000, more preferably 4000 to 200000, and particularly preferably 5000 to 80000.
In addition, the above-described polymer compound having a mass average molecular weight of 1000 or more can also be preferably used, and the content thereof is generally 15 to 50% by mass with respect to the total solid content of the colored photosensitive resin composition. 20-45 mass% is preferable. If the amount is too large, the viscosity of the composition becomes too high, causing a problem in production suitability. If the amount is too small, there is a problem in forming a coating film.

  As the photopolymerization initiator or the photopolymerization initiator system (in the present invention, the photopolymerization initiator system refers to a polymerization initiation composition that exhibits a photopolymerization initiation function by a combination of a plurality of compounds). A vicinal polyketaldonyl compound disclosed in US Pat. No. 2,367,660, an acyloin ether compound described in US Pat. No. 2,448,828, and an α-hydrocarbon described in US Pat. No. 2,722,512 Aromatic acyloin compounds, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, and triarylimidazole dimers described in US Pat. No. 3,549,367 in combination with p-aminoketone Benzothiazole compounds described in Japanese Patent Publication No. 51-48516 and trihalomethyl-s-to Azine compounds, U.S. trihalomethyl patents listed in the 4239850 Pat - triazine compound include a trihalomethyl oxadiazole compounds described in U.S. Pat. No. 4,212,976. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable.

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

These photopolymerization initiators or photopolymerization initiator systems may be used singly or as a mixture of two or more, but it is particularly preferable to use two or more. When at least two kinds of photopolymerization initiators are used, display characteristics, particularly display unevenness, can be reduced.
The content of the photopolymerization initiator or the photopolymerization initiator system with respect to the total solid content of the colored photosensitive resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass. If this amount is too large, the sensitivity becomes too high and control becomes difficult. If the amount is too small, the exposure sensitivity becomes too low. The radiation that can be used for exposure is particularly preferably ultraviolet rays such as g-line and i-line. Irradiation dose is preferably 5~1500mJ / cm ^2, more preferably ^{10~1000mJ / cm 2, 10~500mJ / cm} 2 is particularly preferred.

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

Moreover, the solvent whose boiling point is 180 to 250 degreeC can be used if needed. Examples of these high-boiling solvents include the following. 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 di Acetate, propylene glycol-n-propyl ether acetate, diethylene glycol diethyl ether, 2-ethylhexyl acetate, 3-methoxy-3-methylbutyl acetate, γ-butyllactone, tripropylene glycol methyl ethyl acetate, dipropylene glycol-n-butyl acetate, Propylene glycol phenyl ether acetate, 1, - butanediol diacetate.
As for content of a solvent, 10-95 mass% is preferable with respect to the coloring photosensitive resin composition whole quantity.

Conventionally used color filters have a problem that the color of each pixel becomes dark in order to achieve high color purity, and the film thickness unevenness of the pixel is recognized as color unevenness as it is. For this reason, improvement in film thickness variation that directly affects the film thickness of the pixel has been demanded.
In the color filter of the present invention, an appropriate surfactant can be contained in the colored photosensitive resin composition from the viewpoint of being able to control to a uniform film thickness and effectively preventing color unevenness due to film thickness fluctuation. preferable.
Preferred examples of the surfactant include surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600. The content of the surfactant is preferably 5% by mass or less with respect to the total amount of the resin composition.

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

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

The colored photosensitive resin composition of the present invention may contain an ultraviolet absorber as necessary. Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, nickel chelate-based, hindered amine-based compounds and the like in addition to the compounds described in JP-A-5-72724.
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-5′-methylphenyl) benzotriazole, 2- (2 '-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3-diphenyl acrylate, 2,2'-hydroxy-4-methoxybenzophenone, nickel Dibutyldithiocarbamate, bis (2,2,6,6-tetramethyl-4-pyridine) -Sebakei 4-t-butylphenyl salicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethylpiperidine 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- (diethylamino) -5-triazine- 2-yl] amino} -3-phenylcoumarin and the like. As for content of a ultraviolet absorber, 5 mass% or less is preferable with respect to the coloring photosensitive resin composition whole quantity.

  In addition, the colored photosensitive resin composition of the present invention may contain “adhesion aid” described in JP-A No. 11-133600, other additives and the like in addition to the above additives.

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

As the spraying of the inkjet ink for the color filter of the present invention, a method in which charged ink is continuously ejected and controlled by an electric field, a method in which ink is ejected intermittently using a piezoelectric element, and ink is heated and foamed is used. Then, various methods such as a method of intermittent injection can be employed.
In addition, regarding the ink jet method used for forming each pixel, a normal method such as a method of thermally curing ink, a method of photocuring, or a method of ejecting droplets after forming a transparent image receiving layer on a substrate in advance. Can be used.

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

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

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

  It can be set as a coating film using said coloring photosensitive resin composition, Although the thickness can be defined suitably, it is preferable that it is 0.5-5.0 micrometers, 1.0-3.0 micrometers. It is more preferable that In the coating film using this colored photosensitive resin composition, the oligomer contained therein is polymerized to form a polymerized film of the colored photosensitive resin composition, and a color filter having the same can be produced (of the color filter). The production will be described later.) Polymerization of the polymerizable monomer or polymerizable oligomer can be carried out by allowing a photopolymerization initiator or a photopolymerization initiator system to act upon irradiation with light.

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

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

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

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

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

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

  In the photosensitive resin transfer material of the present invention, the temporary support is required to be flexible and not to cause significant deformation, shrinkage or elongation even under pressure or under pressure and heating. is there. Examples of such a temporary support include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, a polycarbonate film, etc. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.

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

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

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

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

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

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

The color filter of the present invention can be used as one having excellent contrast. In the present invention, the contrast represents the ratio of the amount of transmitted light between two polarizing plates when the polarization axis is parallel and vertical (“1990 Seventh Color Optical Conference, 512-color display 10.4”). "Refer to" Color TFT for size TFT-LCD, Ueki, Koseki, Fukunaga, Yamanaka "etc.).
The high contrast of the color filter means that the bright and dark discrimination when combined with the liquid crystal can be increased, which is a very important performance in order to replace the liquid crystal display with a CRT. The contrast of the color filter of the present invention is monochromatic and is preferably 3000 or more, more preferably 5000 or more, and particularly preferably 7000 or more. In a color filter having R pixels, G pixels, and B pixels, and provided with a black matrix as necessary, it is preferably 3000 or more, more preferably 5000 or more, and particularly preferably 6000 or more. The present invention has a feature capable of realizing such a high contrast.

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

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

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

  The liquid crystal display device provided with the color filter of the present invention uses the color filter of the present invention which is excellent in contrast, and is excellent in descriptive power such as black spots. It can also be suitably used as a large-screen liquid crystal display device such as a notebook personal computer display or a television monitor.

EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, this invention is limited to this and is not interpreted.
(Example / Comparative Example 1)
<Pigment dispersion composition A>
To 1500 ml of dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.), 75.0 ml of 28% sodium methoxide methanol solution, pigment C.I. I. Pigment Red 254 (Irgaphor Red BT-CF, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) 50 g, and polyvinylpyrrolidone (K-30, trade name, manufactured by Wako Pure Chemical Industries, Ltd.) 90.0 g were added. Pigment solution A (density: 1.0 kg / m ² ) was prepared. As a result of measuring the viscosity of this pigment solution A using Viscomate VM-10A-L (trade name, manufactured by CBC Materials), the viscosity when the liquid temperature of the pigment solution A is 25.0 ° C. is 18. 0 mPa · s. Separately, 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, the temperature of the solution was controlled at 25 ° C., and the pigment solution A was added to 2,000 ml of poor solvent water stirred at 500 rpm by a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). Injection was performed using a large-capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.). By setting the flow path diameter and supply port diameter of the liquid supply pipe of the pigment solution A to 0.8 mm, putting the supply port in a poor solvent, and injecting at a flow rate of 100 ml / min, organic pigment particles are formed, and the pigment dispersion A Was prepared. For the pigment nanoparticles in this pigment dispersion A, the number average particle diameter Mn and the monodispersity (Mv / Mn) were measured using Nanotrac UPA-EX150 (trade name, manufactured by Nikkiso Co., Ltd.). The results are shown in Table 1-1 below.

  The pigment dispersion A prepared by the above procedure was concentrated at 5000 rpm for 90 minutes using a H-112 type centrifugal filter manufactured by Kokusan Co., Ltd. and a P89C type cloth manufactured by Shikishima Canvas Co., Ltd., and the resulting pigment was obtained. The nanoparticle concentrated paste was recovered. The pigment content of the paste was measured using an Agilent 8453 type spectrophotometer and found to be 17.2% by mass.

  Next, 13.8 g of the above pigment nanoparticle concentrated paste, 0.1 g of pigment dispersant A synthesized in accordance with JP-A 2000-239554 in 50.0 cc of ethyl lactate, a methacrylic acid / benzyl methacrylate copolymer (molar ratio 28 / 72, mass average molecular weight: 30,000, 40% 1-methoxy-2-propyl acetate solution) 5.94 g was added, and the mixture was stirred with a dissolver at 1500 rpm for 60 minutes. Thereafter, 25.0 cc of ethyl acetate was added, and the mixture was further stirred with a dissolver at 500 rpm for 10 minutes to obtain a dispersion.

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

Using the paste-like concentrated pigment liquid A, a pigment dispersion composition A having the following composition was prepared.
20.0 g of the paste-like concentrated pigment liquid A
1,3 Butylene glycol diacetate 44.3g

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

<Pigment dispersion composition B>
In preparing the pigment dispersion composition A, the build-up pigment was exactly the same except that the methacrylic acid / benzyl methacrylate copolymer was replaced with the exemplified polymer compound C-1 of the general formula (1) of the present invention at an equal mass. A pigment dispersion composition B containing nanoparticles was prepared.

<Pigment dispersion composition C>
The preparation of the pigment dispersion composition B was carried out in exactly the same manner before the preparation of the paste-like concentrated pigment liquid. Instead of performing filtration using a filter, the liquid before concentration was transferred to an eggplant-shaped flask and 70 By drying under reduced pressure for 1.5 hours at ° C., a dry powder C of pigment nanoparticles (nanopigment concentration: 45.3% by mass) was obtained.

Using the powder C, a pigment dispersion composition C having the following composition was prepared.
14.2 g of the powder C
1,3 Butylene glycol diacetate 50.1g

<Pigment dispersion composition D>
A pigment dispersion composition D having 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, a pigment (Pigment Red 254) powder, and a methacrylic acid / benzyl methacrylate copolymer were charged in a 1,3-butylene glycol diacetate solution in a double-arm kneader and kneaded at 80 ° C. for 10 hours. After kneading, it was taken out into 700 parts by mass of 1% hydrochloric acid aqueous solution at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized, and then 2.4 g of 1,3 butylene glycol diacetate was added to 1 g of the pulverized product and mixed. . The pigment composition was dispersed with a motor mill M-50 (manufactured by Eiger Japan) using zirconia beads having a diameter of 0.65 mm at a peripheral speed of 9 m / s for 1 hour to obtain a pigment dispersion composition D. .

<Pigment dispersion composition E, F>
The pigment C.D. used for preparing the pigment dispersion compositions C and D was used. I. Pigment Red 254 is pigment C.I. I. Pigment dispersion compositions E and F were prepared in exactly the same manner except that they were replaced with CI Pigment Red 177 (Chromophthal Red A2B, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.).

<Pigment dispersion compositions G to J>
Pigment C. used in preparing the pigment dispersion compositions A to D I. Pigment Red 254 is a pigment C.I. I. Pigment dispersion compositions G to J were prepared in exactly the same manner except that they were replaced with Pigment Green 36 (Rionol Green 6YK, trade name, manufactured by Toyo Ink Manufacturing Co., Ltd.).

<Pigment dispersion composition K, L>
Pigment C. used in preparing pigment dispersion compositions E and F I. Pigment Red 177 is a pigment C.I. I. Pigment dispersion compositions I and J were prepared in exactly the same manner except that CI Pigment Yellow 150 (Bayplast Yellow 5GN 01, trade name, manufactured by Bayer Co., Ltd.) was used.

<Pigment dispersion composition M>
Pigment C.I. I. 7 g of Pigment Violet 23 (Hostaperm Violet RL-NF, trade name, manufactured by Clariant) containing 12 g of polyvinylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd., K30, molecular weight 40,000) and heated to 85 ° C. A pigment solution M was obtained by dissolving in 140 ml of methanesulfonic acid. As a result of measuring the viscosity using Viscomate VM-10A-L (trade name, manufactured by CBC Materials), the viscosity when the liquid temperature of the pigment solution M was 85.0 ° C. was 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, the temperature of the solution was controlled at 85 ° C., and the pigment solution M was added to 1000 ml of poor solvent water stirred at 500 rpm by a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). Injection was performed using a large-capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.). By setting the flow path diameter and supply port diameter of the liquid supply pipe of the pigment solution M to 0.8 mm, placing the supply port in a poor solvent, and injecting 100 ml at a flow rate of 100 ml / min, organic pigment particles are formed, and the pigment dispersion liquid M was prepared. The number average particle diameter Mn and the monodispersity (Mv / Mn) of the pigment nanoparticles in the pigment dispersion were measured using Nanotrac UPA-EX150 (trade name, manufactured by Nikkiso Co., Ltd.). The results are shown in Table 1-1 below.

  Further, the pigment dispersion M was transferred to an eggplant-shaped flask and dried under reduced pressure at 70 ° C. for 1.5 hours with an evaporator to obtain pigment nanoparticle dry powder M (pigment concentration 55.4% by mass).

  Next, a solution obtained by adding 0.1 g of the pigment dispersant A to 50.0 cc of ethyl lactate is 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. It was.

<Preparation of Pigment Dispersion Composition N>
Pigment C.I. I. Pigment Violet 23 7.0g
Polyvinylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd., K30, molecular weight 40,000) 12 g
Ethyl lactate 50.0cc

  In the diethylene glycol monobutyl ether acetate solution, the pigment dispersant A, the pigment (Pigment Violet 23) powder, 6 g of polyvinyl pyrrolidone, and a methacrylic acid / benzyl methacrylate copolymer were added to the diethylene glycol monobutyl ether acetate solution and stirred. A liquid was obtained. Next, this mixed liquid was dispersed with a motor mill M-50 (manufactured by Eiger Japan) for 9 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

<Pigment dispersion composition O>
Pigment C. used in preparing the pigment dispersion composition H I. Pigment Green 36 instead of Pigment Green 36 I. Pigment dispersion composition O was prepared in exactly the same manner except that CI Pigment Blue 15: 6 (Rionol Green ES, trade name, manufactured by Toyo Ink Co., Ltd.) was used.

<Pigment dispersion composition P>
Pigment C. used in preparation of pigment dispersion composition N I. Pigment Violet 23 instead of C.I. I. Pigment dispersion composition P was prepared in exactly the same manner except that CI Pigment Blue 15: 6 was used.

<Pigment dispersion composition AA>
In the preparation of the pigment dispersion composition A, when preparing the pigment dispersion A, the flow path and flow path diameter and supply port diameter of the liquid feed pipe for feeding the pigment solution A are set to 0.5 mm, and the injection flow rate is 200 ml / min. Except for the above, a pigment dispersion composition AA was produced in the same manner as in the pigment composition A.
<Pigment dispersion composition D ⁺ , F ⁺ >
In the preparation of the raw material dispersion compositions D and F, pigment dispersion compositions D + and F + were prepared in exactly the same manner except that the processing time of the motor mill was changed from 1 hour to 4 hours.

[Table 1-1]
----------------------------------
Pigment dispersion average particle size (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 inkjet ink>
[Production of photosensitive transfer material]
On a 75 μm thick polyethylene terephthalate film temporary support, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Further, a light-shielding resin composition K1 having the following composition is applied and dried, and a thermoplastic resin layer having a dry film thickness of 15 μm and an intermediate layer having a dry film thickness of 1.6 μm are formed on the temporary support. Then, a light-shielding resin layer having a dry film thickness of 2.4 μm was provided, and a protective film (12 μm thick polypropylene film) was pressure-bonded.
Thus, a photosensitive resin transfer material in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the light-shielding resin layer were integrated was prepared, and the sample name was designated as photosensitive resin transfer material K1. .

[Coating liquid for thermoplastic resin layer: Formulation H1]
---------------------------------------
-Methanol 11.1 parts by mass-Propylene glycol monomethyl ether acetate 6.4 parts by mass Daicel Chemical Industries, Ltd., MMPG-Ac (the same material is also used below)
Methyl ethyl ketone 52.4 parts by massMethyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymer ratio (molar ratio) = 55 / 11.7 / 4.5 / 28.8, molecular weight 10 10,000, Tg≈70 ° C.) 5.83 parts by mass. Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 63/37, molecular weight = 10,000, Tg≈100 ° C.) 3.6 parts by mass. 2,2-bis [4- (methacryloxypolyethoxy) phenyl]
Propane (manufactured by Shin-Nakamura Chemical Co., Ltd.) 9.1 parts by mass / surfactant 1 0.54 parts by mass --------------------- -----------------

* The composition of surfactant 1 (Megafac F-780-F (manufactured by Dainippon Ink & Chemicals, Inc.)) is: C ₆ F ₁₃ CH ₂ CH ₂ OCOCH = CH ₂ : 40 parts by mass and 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
Copolymer (molecular weight 30,000) 30 parts by mass / methyl ethyl ketone 70 parts by mass

[Coating liquid formulation for intermediate layer (oxygen barrier layer): P1]
---------------------------------------
-Polyvinyl alcohol ... 32.2 parts by mass (PVA205 (saponification rate = 88%); manufactured by Kuraray Co., Ltd.)
・ Polyvinylpyrrolidone ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 14.9 parts by mass (PVP, K-30; manufactured by ISP Japan Co., Ltd.)
・ 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 Cyclohexanone 8.6 parts by mass Binder 1 14 parts by mass DPHA solution 5.8 parts by mass Polymerization initiator A (2 , 4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) amino-3'-bromophenyl] -s-triazine)
0.22 parts by mass Phenothiazine 0.006 parts by mass Surfactant 1 0.058 parts by mass ----------------------------- ----------

  The resin composition K1 having a light-shielding property is obtained by weighing K pigment dispersion 1 and propylene glycol monomethyl ether acetate, mixing at a temperature of 24 ° C. (± 2 ° C.), stirring for 10 minutes at 150 rpm, and then methyl ethyl ketone and cyclohexanone. , Binder 1, phenothiazine, DPHA solution, polymerization initiator A and surfactant 1 are weighed and added in this order at a temperature of 25 ° C. (± 2 ° C.), and at a temperature of 40 ° C. (± 2 ° C.) at 150 rpm for 30 minutes. Obtained by stirring.

<K pigment dispersion 1>
Carbon black (Degussa, trade name Nipex 35) 13.1 parts by mass Pigment dispersant A 0.65 parts by mass Polymer 1 (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 37,000) 6.72 parts by mass / propylene glycol monomethyl ether acetate 79.53 parts by mass

* Composition of binder 1 is polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio
Random copolymer of, molecular weight 40,000) 27 parts by mass, propylene glycol monomethyl ether acetate 73 parts by mass

* DPHA liquid composition: Dipentaerythritol hexaacrylate (containing polymerization inhibitor MEHQ 500 ppm, Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76 parts by mass Propylene glycol monomethyl ether acetate 24 parts by mass

[Formation of light-blocking partition walls]
The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% by mass aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.

After peeling off the protective film of the photosensitive resin transfer material K1, a substrate heated at 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)), a rubber roller temperature of 130 ° C., a wire Lamination was performed at a pressure of 100 N / cm and a conveyance speed of 2.2 m / min.
After peeling off the temporary support, exposure is performed with a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp with the substrate and mask (quartz exposure mask with image pattern) standing vertically. The distance between the mask surface and the thermoplastic resin layer was set to 200 μm, and pattern exposure was performed with an exposure amount of 100 mJ / cm ² . The mask shape is a lattice shape, and the radius of curvature of the corner protruding toward the light-shielding partition wall in the portion corresponding to the boundary line between the pixel and the light-shielding partition wall is 0.6 μm.

Next, a triethanolamine developer (containing 30% triethanolamine, trade name: T-PD2, manufactured by Fuji Photo Film Co., Ltd. 12 times with pure water (1 part of T-PD2 and 11 parts of pure water) The resulting mixture was diluted with a mixture) at 30 ° C. for 50 seconds at a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer (oxygen barrier layer).
Subsequently, sodium carbonate developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% sodium dibutylnaphthalene sulfonate, anionic surfactant, antifoaming agent, stabilizer included , Trade name: T-CD1, manufactured by Fuji Photo Film Co., Ltd. diluted 5 times with pure water) and shower-developed at 29 ° C. for 30 seconds with a cone type nozzle pressure of 0.15 MPa to have a light shielding property Was developed to obtain a patterning separation wall (a partition wall pattern having a light shielding property).

Subsequently, using a detergent (trade name “T-SD3 (manufactured by Fuji Photo Film Co., Ltd.)” diluted 10 times with pure water), a shower and nylon hair at 33 ° C. for 20 seconds and a cone type nozzle pressure of 0.02 MPa. Residue was removed with a rotating brush having a light shielding property to obtain a light-shielding partition. Thereafter, the substrate was further post-exposed with light of 500 mJ / cm ^{2 with} an ultra-high pressure mercury lamp from the resin layer side, and then heat treated at 240 ° C. for 50 minutes.

[Plasma water repellency treatment]
Thereafter, plasma water repellency treatment was performed by the following method.
Plasma water repellency treatment was performed on the substrate on which the light-shielding partition walls were formed using a cathode coupling parallel plate type plasma processing apparatus under the following conditions.
Gas used: CF ₄
Gas flow rate: 80sccm
Pressure: 40Pa
RF power: 50W
Processing time: 30 sec

[Preparation of inkjet ink for color filter]
An inkjet ink for a color filter was prepared according to the following formulation.

  Regarding the mixing of the components in Tables 1-R, 1-G, and 1-B, first, the pigment and the polymer dispersant are charged into a part of the solvent, mixed, and stirred using a three-roll and bead mill. Thus, a pigment dispersion was obtained. On the other hand, other compounding components were added to the remainder of the solvent, and were dissolved and dispersed by stirring to obtain a monomer solution. Then, while adding the pigment dispersion or the pigment dispersion composition little by little to the monomer solution, the mixture was sufficiently stirred with a dissolver to prepare an inkjet ink for a color filter.

[Pixel formation]
First, the color filter 101 was produced using the R ink 1, G ink 1, and B ink 1 described above. At this time, the inkjet head used SE-128 made from Dimatix, and the discharge control apparatus used Apollo II made from Dimatix. An inkjet head is mounted on an automatic two-dimensional moving stage (KS211-200 manufactured by Suruga Seiki), and the stage is moved from the head by the discharge control device while moving the stage so that a predetermined amount of ink is discharged into the gap of the partition wall produced above. The discharge was synchronized.
Here, the three colors of ink described above are filled in different heads, each head is fixed on the XY stage, and the three heads are ejected by the ejection control device so that each ink lands on a predetermined position. Were controlled independently.
For droplet ejection, the ink composition is discharged until the desired concentration is reached, heated and dried on a hot plate at 100 ° C. for 2 minutes, and then baked in an oven at 230 ° C. for 30 minutes to completely cure both the partition walls and pixels. A color filter was prepared.

[Production of liquid crystal display devices]
A liquid crystal display device was manufactured using the manufactured color filter 101, and display characteristics were evaluated.
(Formation of ITO electrode)
The glass substrate on which the color filter is formed is put into a sputtering apparatus, and 1300 mm thick ITO (indium tin oxide) is vacuum-deposited on the entire surface at 100 ° C., and then annealed at 240 ° C. for 90 minutes to crystallize the ITO. A transparent electrode was formed.
(Spacer formation)
A spacer was formed on the ITO transparent electrode prepared above by the same method as the spacer forming method described in [Example 1] of JP-A-2004-240335.
(Formation of liquid crystal alignment control protrusions)
A liquid crystal alignment control protrusion was formed on the ITO transparent electrode on which the spacer was formed, using the following positive photosensitive resin layer coating solution.
However, the following methods were used for exposure, development, and baking.
A proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) is arranged so that the predetermined photomask is at a distance of 100 μm from the surface of the photosensitive resin layer, and the irradiation energy is 150 mJ / Proximity exposure was performed at cm ² .
Subsequently, a 2.38% tetramethylammonium hydroxide aqueous solution was developed by spraying it on a substrate at 33 ° C. for 30 seconds in a shower type developing device. In this way, by removing the unnecessary portion (exposed portion) of the photosensitive resin layer by developing and removing the liquid crystal, the liquid crystal alignment control protrusions made of the photosensitive resin layer patterned into a desired shape are formed on the color filter side substrate. A display device substrate was obtained.
Next, the liquid crystal alignment control projection on which the liquid crystal alignment control protrusion was formed was baked at 230 ° C. for 30 minutes to form a cured liquid crystal alignment control protrusion on the liquid crystal display substrate.
<Positive photosensitive resin layer coating solution formulation>
・ Positive resist solution (FUJIFILM Electronics
FH-2413F manufactured by Materials Co., Ltd.): 53.3 parts by mass / methyl ethyl ketone: 46.7 parts by mass / Megafac F-780F (manufactured by Dainippon Ink & Chemicals, Inc.): 0.04 parts by mass ( Creation of liquid crystal display device)
An alignment film made of polyimide was further provided on the liquid crystal display substrate obtained above.
After that, an epoxy resin sealant is printed at a position corresponding to a black matrix outer frame provided around the pixel group of the color filter, and MVA mode liquid crystal is dropped and bonded to the counter substrate. The bonded substrate was heat treated to cure the sealant. A polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached to both surfaces of the liquid crystal cell thus obtained. Next, a backlight of a three-wavelength cold-cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) is constructed and arranged on the side of the liquid crystal cell provided with the polarizing plate. did.

Liquid crystal display devices 102 to 108 were produced in exactly the same manner as the liquid crystal display device 101, except that the R ink 1 used for producing the liquid crystal display device 101 was changed to R inks 2 to 8, respectively. 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 G inks 2 to 6, respectively.
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 B inks 2 to 4, respectively.
Further, the R ink 1, G ink 1, and B ink 1 of the liquid crystal display device 101 are replaced with R ink 4, G ink 4, and B ink 3, respectively, and the liquid crystal display device 117 is further replaced with R ink 6, G ink 6, and B ink. A liquid crystal display device 118 was produced by replacing with ink 1.
The breakdown of the inkjet ink used for the color filter of the produced liquid crystal display device is shown in Tables 1-5 to 1-8 together with the evaluation results.

<Evaluation of ink and liquid crystal display device>
[Measurement of ink contrast and light resistance]
The contrast and light resistance of the inkjet ink, R ink 1 to 8, G ink 1 to 6, and B ink 1 to 4 were measured as follows.

Each of the obtained inks was applied on a glass substrate so as to have a thickness of 2 μm, thereby preparing a sample. As the backlight unit, a three-wavelength cold cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) with a diffusion plate installed was used, and two polarizing plates (polarizing plates HLC2-2518 manufactured by Sanritsu Co., Ltd.) were used. ), The amount of transmitted light when the polarization axis is parallel and vertical is measured, and the ratio is defined as the contrast (“1990 Seventh Color Optical Conference, 512-color display 10. 4 ”size TFT-LCD color filter, planting, Koseki, Fukunaga, Yamanaka etc.). A color luminance meter (BM-5 manufactured by Topcon Corporation) was used for the measurement of chromaticity. Two polarizing plates, a sample, and a color luminance meter are installed at a position 13 mm from the backlight, a polarizing plate at a position 40 mm to 60 mm, a cylinder 11 mm in diameter and 20 mm in length, and light transmitted through this. Was measured on a color luminance meter installed at a position of 400 mm through a polarizing plate installed at a position of 100 mm. The measurement angle of the color luminance meter was set to 2 °. The amount of light of the backlight was set so that the luminance when the two polarizing plates were installed in parallel Nicol was 1280 cd / m ² without the sample being installed.
This sample was irradiated with a 90 mW / cm ² high-pressure mercury lamp for 24 hours, and the color difference before and after the irradiation was measured to provide an index of light resistance. In the present invention, the chromaticity is measured with a microspectrophotometer (manufactured by Olympus Optical Co., Ltd .; OSP100 or 200), calculated as a result of the F10 light source field of view of 2 degrees, and expressed as an xyY value in the xyz color system. The difference in chromaticity is represented by the color difference of the La ^* b ^* color system. The smaller the color difference, the better.
The results are shown in Tables 1-2 to 1-4.

  In addition, for each ink, the particle size of the pigment particles contained is diluted with ion-exchanged water so that the pigment concentration is in the range of 1 to 5% by weight, and DLS-7000 manufactured by Otsuka Electronics Co., Ltd. is used. And measured. The obtained particle size distribution is plotted by taking the number of particles on the vertical axis (ratio (%) with respect to the number of all pigment particles) every 2 nm on the horizontal axis, and the maximum particle size, the number of maximum values, and the particle size. The ratio (%) of the number of particles of 50 nm or more to the total pigment particles was determined, and the results are shown in Tables 1-2a to 1-4a.

[Display characteristics test of liquid crystal display]
Display characteristics of each liquid crystal display device produced were evaluated in terms of (1) illuminance after continuous display, (2) descriptive power of a specific color, and (3) presence or absence of color unevenness when a specific color was displayed in a single color. did.

(1) Regarding the illuminance after continuous display, the produced liquid crystal display device is displayed continuously for 1000 hours, and the illuminance of the specific color light (in the case of red light, the illuminance of the light when red is displayed) is displayed in the dark room. Measure the illuminance meter UV-M10-S (manufactured by Oak Manufacturing Co., Ltd.) at a measurement angle of 2 ° at a position of 400 mm on the screen of the apparatus. The values (illuminance after the test / illuminance before the test) are shown in Tables 1-5 to 1-8 together with the contrast data of the pigment dispersion composition.

(2) Descriptive power of a specific color, (3) Color unevenness when a specific color is displayed in a single color was evaluated by 10 panelists, and an average of 10 people was used as an evaluation value in the following stage evaluation.

(2) Descriptive power of each color 5: Excellent description 4: No problem in description (good)
3: Description is slightly unsatisfactory (normal)
2: The picture is unsatisfactory (somewhat bad)
1: Color reproduction is poor (very bad)
(3) Red color unevenness 5: No unevenness is seen at all 4: Unevenness is not noticed (good)
3: Unevenness is felt slightly (normal)
2: Unevenness can be clearly recognized (slightly bad)
1: Unevenness is noticeable (very bad)

  Regarding the evaluation items (1) to (3), the liquid crystal display devices 101 to 108 are evaluated in red (Table 1-5), the liquid crystal display devices 101 and 109 to 113 are green (Table 1-6), and the liquid crystal display device 101, About 114-116, blue comparative evaluation (Table 1-7) was performed. Further, the liquid crystal display devices 101, 117, and 118 were evaluated in red, green, blue, and gray (Table 1-8), and the average values of the respective results were shown.

[Table 1-2]
--------------------------------------
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: Ratio (mass%) of build-up pigment nanoparticles (b) in all pigment particles

[Table 1-3]
--------------------------------------
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
--------------------------------------

[Table 1-4]
--------------------------------------
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
--------------------------------------

[Table 1-2a] Continuation of Table 1-2 ------------------------------------ −
Ink Pigment dispersion composition Average particle size Number of maximum values 50 nm or more
(Nm) Particle ratio (%)
--------------------------------------
R1 D + F 48 1 37
R2 A + F 41 2 4
R3 B + F 36 2 23
R4 C + F 35 2 3
R5 B + E 35 1 0
R6 C + E 34 1 0
R7 D ⁺ + F ⁺ 38 1 31
R8 AA + F 25 2 4
--------------------------------------

[Table 1-3a] Continuation of Table 1-3 ------------------------------------ −
Ink Pigment dispersion composition Average particle size Number of maximum values 50 nm or more
(Nm) Particle ratio (%)
--------------------------------------
G1 J + L 46 1 42
G2 G + L 42 2 11
G3 H + L 39 2 9
G4 I + L 39 2 10
G5 H + K 35 1 0
G6 I + K 34 1 0
--------------------------------------

[Table 1-4a] Table 1-4 continued ------------------------------------ −
Ink Pigment dispersion composition Average particle size Number of maximum values 50 nm or more
(Nm) Particle ratio (%)
--------------------------------------
B1 N + P 50 1 42
B2 M + P 48 2 38
B3 N + O 41 2 1
B4 M + O 39 1 0
----------------------------------

[Table 1-5] R light evaluation -------------------------------------
Display device Ink used Evaluation
R GB Illuminance ratio (%) Descriptive power Color unevenness ------------------------------------ −
101 R1 G1 B1 110 2.0 1.5
102 R2 〃 １０１ 101 4.7 4.6
103 R3 〃 １０２ 102 4.8 5.0
104 R4 〃 １０１ 101 4.7 4.8
105 R5 〃 １０４ 104 4.5 1.9
106 R6 〃 １０５ 105 4.9 2.5
107 R7 〃 １０４ 104 4.2 4.0
108 R8 〃 １０１ 101 5.0 4.9
--------------------------------------

[Table 1-6] G light evaluation -------------------------------------
Display device Ink used Evaluation
R GB Illuminance ratio (%) Descriptive power Color unevenness ------------------------------------ −
101 R1 G1 B1 108 1.3 1.9
109 〃 G2 １０２ 102 4.9 4.8
110 Ｇ G3 １０２ 102 4.9 4.9
111 Ｇ G4 １０１ 101 5.0 4.8
112 〃 G5 １０９ 109 5.0 2.4
113 Ｇ G6 〃 111 4.9 2.1
--------------------------------------

[Table 1-7] B light evaluation -------------------------------------
Display device Ink used Evaluation
R GB Illuminance ratio (%) Descriptive power Color unevenness ------------------------------------ −
101 R1 G1 B1 109 1.5 1.2
114 〃 Ｂ B2 102 4.6 4.7
115 〃 〃 B3 102 4.8 4.8
116 〃 Ｂ B4 107 4.9 2.1
--------------------------------------

[Table 1-8] Gray light evaluation -------------------------------------
Display device Ink used Evaluation
R GB Illuminance ratio (%) Descriptive power Color unevenness ------------------------------------ −
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
--------------------------------------

From the above results, it can be seen 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 1-2 to 1-4). .
The ink of the present invention using the breakdown pigment nanoparticle (a) and the buildup pigment nanoparticle (b) in combination exhibits excellent display performance when used as a liquid crystal display device for a long time. Realizes display suitability, descriptive power, and suppression of color unevenness (see display devices 102-104, 108-111, 114, 115, 117 in Tables 1-5 to 1-8), and can achieve well-balanced display performance. I understand that.
In particular, in the B ink, even when the content of the build-up pigment nanoparticles (b) was small, the contrast and the display performance in the liquid crystal display device were significantly increased (ink B2). Moreover, it turns out that said outstanding effect is exhibited also by including the build-up pigment nanoparticle once dried (ink R4, G4, B2).

  In addition, the ink R3, R4, including the ink R7 composed only of the breakdown pigment, the average particle diameter of the contained 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. R7, R8, G3, and G4 showed sufficient contrast and balanced performance with excellent display characteristics (display devices 103, 104, 107, 108, 110, and 111). Furthermore, in the ink R8 having an average particle size of 30 nm or less, two maximum values in the particle size distribution, and the ratio of the number of particles having a particle size of 50 nm or more being 1% or more, and the liquid crystal display device 108 using the ink R8, Higher performance in contrast and descriptive power.

(Example / Comparative Example 2)
<Preparation of color filter and liquid crystal display device using colored photosensitive resin composition>
[Formation of black (K) image]
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., it is described in Table 2-1 below on a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. A colored photosensitive resin composition K2 having the composition: Subsequently, a part of the solvent was dried by VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to obtain a film thickness of 2. A layer K2 of a colored photosensitive resin composition having a thickness of 4 μm was obtained. In addition, the preparation procedure of the colored photosensitive resin composition K2 is the same as the procedure of the previous resin composition K1.

[Table 2-1]
--------------------------------------
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 solution 4.2 parts by mass Polymerization initiator A 16 parts by mass Surfactant 1 0.044 parts by mass ----------------------------------- −

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

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

(Preparation of pigment dispersion composition)
Except for using propylene glycol monomethyl ether acetate instead of 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, Pigment dispersion compositions C2 to F2, I2 to L2, and M2 to P2 were prepared.
[Formation of red (R) pixels]
Using the colored photosensitive resin composition having the composition described in Table 2-2 below on the substrate on which the image K was formed, a heat-treated pixel R was formed in the same process as the formation of the black (K) image. . The film thickness of the photosensitive resin layer and the coating amount of the pigment are shown below. The procedure for preparing the colored photosensitive resin composition is the same as that for the colored photosensitive resin composition K2.
Photosensitive resin film thickness (μm) 1.80
Pigment coating amount (g / m ² ) 1.13
C. I. P. R. 254 coating amount (g / m ² ) 1.08
C. I. P. R. 177 coating amount (g / m ² ) 0.12

[Table 2-2] Colored 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 solution 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>
-The following compound 1 30 mass parts-Methyl ethyl ketone 70 mass parts

＜重合開始剤Ｂ＞
・２−トリクロロメチル−（ｐ−スチリルスチリル）１，３，４−オキサジアゾール

<Polymerization initiator B>
2-Trichloromethyl- (p-styrylstyryl) 1,3,4-oxadiazole

[Formation of green (G) pixels]
Using a colored photosensitive resin composition having the composition described in Table 2-3 below on the substrate on which the image K and the pixel R are formed, the heat-treated pixel G is processed in the same process as the formation of the black (K) image. Formed. The film thickness of the photosensitive resin layer and the coating amount of the pigment are shown below. The procedure for preparing the colored photosensitive resin composition is the same as that for the colored photosensitive resin composition K2.
Photosensitive resin film thickness (μm) 1.75
Pigment application amount (g / m ² ) 2.10
C. I. P. G. 36 coating amount (g / m ² ) 1.47
C. I. P. Y. 150 coating amount (g / m ² ) 0.63

[Table 2-3] Colored photosensitive resin composition G21
--------------------------------------
G pigment dispersion W 43 parts by weight Propylene glycol monomethyl ether acetate 29 parts by weight Methyl ethyl ketone 26 parts by weight Cyclohexanone 1.3 parts by weight Binder 1 2.5 parts by weight DPHA solution 3.5 parts by weight Polymerization initiator B 0.12 parts by weight 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) pixels]
A colored photosensitive resin composition having the composition described in Table 2-4 below is used for the substrate on which the image K, the pixel R, and the pixel G are formed, and heat treatment is performed in the same process as the formation of the black (K) image. The finished pixel B was formed, and the target color filter A was obtained. The film thickness of the photosensitive resin layer and the coating amount of the pigment are shown below. The procedure for preparing the colored photosensitive resin composition is the same as that for the colored photosensitive resin composition K2.
Photosensitive resin film thickness (μm) 1.60
Pigment application amount (g / m ² ) 0.75
C. I. P. B. 15: 6 coating amount (g / m ² ) 0.705
C. I. P. V. 23 coating amount (g / m ² ) 0.045

[Table 2-4] Colored photosensitive resin composition B21
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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 solution 4.0 parts by mass Polymerization initiator B 0.17 parts by mass Phenothiazine 0.02 parts by mass Interface Activator 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>
-Random copolymer of benzyl methacrylate / methacrylic acid / methyl methacrylate = 36/22/42 molar ratio, molecular weight 38,000 27 parts by mass-propylene glycol monomethyl ether acetate 73 parts by mass

The color filter 201 was produced as described above. On the other hand, color filters 202 and 203 were produced by changing the pigment dispersion composition to be used as shown in Table 2-5 below.
[Table 2-5]
--------------------------------------
Display device R colored photosensitive resin G colored photosensitive resin B colored photosensitive resin
(Pigment dispersion composition) (Pigment dispersion composition) (Pigment dispersion composition)
b ratio b ratio b ratio -------------------------------------
201 R21 G21 B21
(D + F) (J + L) (N + P)
0% 0% 0%
--------------------------------------
202 R22 G22 B22
(C + F) (I + L) (M + P)
90% 70% 6%
--------------------------------------
203 R23 G23 B23
(C + E) (I + K) (M + O)
100% 100% 100%
--------------------------------------

[Production and Evaluation of Liquid Crystal Display]
Liquid crystal display devices 201, 202, and 203 were produced using color filters 201, 202, and 203, respectively, and display characteristics were evaluated.
(Formation of ITO electrode)
The glass substrate on which the color filter is formed is put into a sputtering apparatus, and 1300 mm thick ITO (indium tin oxide) is vacuum-deposited on the entire surface at 100 ° C., and then annealed at 240 ° C. for 90 minutes to crystallize the ITO. A transparent electrode was formed.
(Spacer formation)
A spacer was formed on the ITO transparent electrode prepared above by the same method as the spacer forming method described in [Example 1] of JP-A-2004-240335.
(Formation of liquid crystal alignment control protrusions)
A liquid crystal alignment control protrusion was formed on the ITO transparent electrode on which the spacer was formed, using the following positive photosensitive resin layer coating solution.
However, the following methods were used for exposure, development, and baking.
A proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) is arranged so that the predetermined photomask is at a distance of 100 μm from the surface of the photosensitive resin layer, and the irradiation energy is 150 mJ / Proximity exposure was performed at cm ² .
Subsequently, a 2.38% tetramethylammonium hydroxide aqueous solution was developed by spraying it on a substrate at 33 ° C. for 30 seconds in a shower type developing device. In this way, by removing the unnecessary portion (exposed portion) of the photosensitive resin layer by developing and removing the liquid crystal, the liquid crystal alignment control protrusions made of the photosensitive resin layer patterned into a desired shape are formed on the color filter side substrate. A display device substrate was obtained.
Next, the liquid crystal alignment control projection on which the liquid crystal alignment control protrusion was formed was baked at 230 ° C. for 30 minutes to form a cured liquid crystal alignment control protrusion on the liquid crystal display substrate.
<Positive photosensitive resin layer coating solution formulation>
・ Positive resist solution (FUJIFILM Electronics
FH-2413F manufactured by Materials Co., Ltd.): 53.3 parts by mass / methyl ethyl ketone: 46.7 parts by mass / Megafac F-780F (manufactured by Dainippon Ink & Chemicals, Inc.): 0.04 parts by mass ( Production of liquid crystal display device)
An alignment film made of polyimide was further provided on the liquid crystal display substrate obtained above.
After that, an epoxy resin sealant is printed at a position corresponding to a black matrix outer frame provided around the pixel group of the color filter, and MVA mode liquid crystal is dropped and bonded to the counter substrate. The bonded substrate was heat treated to cure the sealant. Polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. were attached to both surfaces of the liquid crystal cell thus obtained. Next, a backlight of a three-wavelength cold cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) was constructed and placed on the back side of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display device. .

The manufactured liquid crystal display devices 201, 202, and 203 were evaluated in the same manner as in Example 1 for (1) illuminance ratio, (2) descriptive power, and (3) color unevenness. As a result, the liquid crystal display device 201 is inferior in any of (1) illuminance ratio, (2) descriptive power, and (3) color unevenness, and the liquid crystal display device 203 is inferior in (1) illuminance ratio and (3) color unevenness. Was inferior.
On the other hand, the liquid crystal display device 202 showed good results in any of (1) illuminance ratio, (2) descriptive power, and (3) color unevenness.
From these results, it can be seen that the organic pigment dispersion of the present invention exhibits a well-balanced performance that achieves both high display characteristics and high display durability even when a color filter is produced using the colored sensitive resin composition. .

(Example / Comparative Example 3)
Except for changing the resin composition K1 used for preparing the colored photosensitive resin composition K1 in Example 1 to the colored photosensitive resins R21, G21, and B21 in Example 2, respectively, the same as the preparation of the photosensitive transfer material K1. By the method, photosensitive resin transfer materials R301, G301, and B301 were produced.
[Formation of black (K) image]
In the same manner as in Example 1, a pattern separation wall (a partition pattern having a light shielding property) was obtained using the photosensitive resin transfer material K1.

[Formation of red (R) pixels]
Using the photosensitive resin transfer material R301, a heat-treated red (R) pixel R was obtained in the same process as the photosensitive resin transfer material K1. However, the exposure amount was 40 mJ / cm ² , and development with a sodium carbonate developer was 35 ° C. for 35 seconds. The film thickness of the photosensitive resin layer and the coating amount of the pigments (CIPR 254 and CIPR 177) are shown below.
Photosensitive resin film thickness (μm) 2.00
Pigment coating amount (g / m ² ) 1.00
C. I. P. R. 254 coating amount (g / m ² ) 0.90
C. I. P. R. 177 coating amount (g / m ² ) 0.10
The substrate on which the image K and the pixel R were formed was again cleaned with a brush as described above, and after pure water shower cleaning, the substrate was sent to a substrate preheating device without using a silane coupling liquid.

[Formation of green (G) pixels]
Using the photosensitive resin transfer material G301, a heat-treated green (G) pixel G was obtained in the same process as the photosensitive resin transfer material R301. However, the exposure amount was 40 mJ / cm ² , and development with a sodium carbonate developer was 34 ° C. and 45 seconds. The film thickness of the photosensitive resin layer and the coating amount of pigment (CIPG36 and CIPY150) are shown in the table below.
Photosensitive resin film thickness (μm) 2.00
Pigment coating amount (g / m ² ) 1.90
C. I. P. G. 36 coating amount (g / m ² ) 1.24
C. I. P. Y. 150 coating amount (g / m ² ) 0.68
The substrate on which the image K, the pixel R, and the pixel G were formed was again cleaned with a brush as described above, and after pure water shower cleaning, the silane coupling liquid was not used and the substrate was sent to a substrate preheating device.

[Formation of blue (B) pixels]
Using the photosensitive resin transfer material B301, a heat-treated blue (B) pixel B was obtained in the same process as the photosensitive resin transfer material R301. However, the exposure amount was 30 mJ / cm ² , and development with a sodium carbonate developer was 36 ° C. for 40 seconds. The film thickness of the photosensitive resin layer and the coating amounts of pigments (CIPB15: 6 and CIPVV23) are shown below.
Photosensitive resin film thickness (μm) 2.00
Pigment application amount (g / m ² ) 0.76
C. I. P. B. 15: 6 coating amount (g / m ² ) 0.70
C. I. P. V. 23 coating amount (g / m ² ) 0.06
The substrate on which the pixel R, pixel G, pixel B, and image K were formed was baked at 240 ° C. for 50 minutes to obtain a color filter 301.

The colored photosensitive resins R-21, G-21, and B-21 used in preparing the photosensitive resin transfer materials R301, G301, and B301 are respectively R-22, The color filter 302 changed to G-22 and B-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 manufactured liquid crystal display devices 301, 302, and 303 were evaluated in the same manner as in Example 1 for (1) illuminance ratio, (2) descriptive power, and (3) color unevenness. As a result, the liquid crystal display device 301 is inferior in any of 1) illuminance ratio, (2) descriptive power, and (3) color unevenness, while the liquid crystal display device 303 is inferior in (1) illuminance ratio and (3) color unevenness. It was inferior.
On the other hand, the liquid crystal display device 302 showed good results in any of (1) illuminance ratio, (2) descriptive power, and (3) color unevenness.
From these results, it can be seen that the organic pigment dispersion of the present invention exhibits a well-balanced performance that balances high display characteristics and high display durability even when a color filter is produced using a photosensitive resin transfer material. .

Claims (13)

In the pigment particles contained in at least one color pixel of the color filter, 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 the total pigment particles A color filter characterized by
In the particle size distribution of the pigment particles contained in the pixel, it has two or more maximum values,
A color filter having a maximum value in a particle size distribution of 30 nm or less in a particle size distribution of pigment particles contained in the pixel. The pigment constituting the pigment particles is preferably a quinacridone compound pigment, a diketopyrrolopyrrole compound pigment, a dioxazine compound pigment, a phthalocyanine compound pigment, or an azo compound pigment, a diketopyrrolopyrrole compound pigment, a dioxazine compound pigment, and the color filter according to claim 1 selected from the group consisting phthalocyanine compound pigment or al. Pigment nanoparticles (a) obtained by mechanically pulverizing a bulk body of an organic pigment, an organic pigment solution obtained by dissolving an organic pigment in a good solvent, and the poor solvent for the organic pigment. Pigment nanoparticles (b) deposited by mixing with a solvent
The color filter according to claim 1 or 2, further comprising:   4. The pigment particles contained in the pixel, wherein the number of particles having a particle size of 50 nm or more is 5% or more of all pigment particles. Color filter.   The volume average particle diameter (Mv) and the number average particle diameter (Mn) of the pigment particles are defined, and the monodispersity (Mv / Mn) is 1.0 to 2.0. 2. The color filter according to item 1.   The color filter according to any one of claims 3 to 5, wherein the pigment nanoparticles (b) are contained in an amount of 1% by mass or more based on the total pigment particles.   The color filter according to any one of claims 3 to 6, wherein the pigment nanoparticles (b) are contained in an amount of 3% by mass to 95% by mass based on the total pigment particles.   The average particle diameter of all 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% or more of the total pigment particles, The color filter according to any one of claims 3 to 7.   9. The pigment nanoparticle (b) according to any one of claims 3 to 8, wherein the pigment nanoparticle (b) is a nanoparticle obtained by removing the solvent once to obtain a powder and redispersing the powder. Color filter.   Furthermore, the color filter of any one of Claims 1-9 containing a high molecular compound with a mass mean molecular weight 1000 or more. The color filter according to claim 10, wherein the polymer compound having a mass average molecular weight of 1000 or more is a compound represented by the following general formula (1).

[Wherein, R ¹ represents a (m + n) -valent linking group, and R ² represents a single bond or a divalent linking group. 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 A monovalent organic group having a group selected from the group consisting of a hydroxyl group, or a monovalent organic group containing an organic dye structure or a heterocyclic ring which may have a substituent. However, n pieces of A ¹ may be the same as or different from each other. m represents a number of 1 to 8, n represents a number of 2 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer compound residue. ]   The color filter according to any one of claims 1 to 11, further comprising a pixel having any one color of blue, green, and red. A liquid crystal display device comprising the color filter according to claim 1.