JP5224785B2 - Method for producing organic pigment nanoparticles - Google Patents

Description

  The present invention relates to a method for producing organic nanoparticles, organic nanoparticles obtained thereby, inkjet ink for color filter containing the same, colored photosensitive resin composition, photosensitive resin transfer material, and color filter using them The present invention relates to a liquid crystal display device and a CCD device.

In recent years, efforts have been made to reduce the size of particles. In particular, research is being conducted to reduce the size to a nanometer size that is difficult to produce by a pulverization method or the like, for example, in the range of 10 to 100 nm. Furthermore, attempts have been made to reduce the size to nanometer size and to make monodisperse particles.
It has been pointed out that such nanometer-sized microparticles are located in the middle between normal bulk particles and molecules and atoms, and have a size region that has not existed before, and can bring out new characteristics that could not be expected. In addition, if the monodispersity is increased, the properties of nanoparticles can be stabilized, and the potential of such nanoparticles is expected in various fields. Biochemistry, new materials, electronic devices, light-emitting displays Research is growing in a wide range of fields such as devices, printing, and medicine.
In particular, organic particles made of an organic compound have a high potential as a functional material because the organic compound itself has diversity. For example, polyimide is used in many fields because it is a chemically and mechanically stable material such as heat resistance, solvent resistance, and mechanical properties, and has excellent electrical insulation. And it is expected to be applied to a wider field by making polyimide fine particles and combining the material characteristics and shape characteristics. For example, it has been proposed to use finely divided polyimide as an additive for powder toner for image formation (Patent Document 1).

Further, regarding organic pigments among organic particles, for example, paints, printing inks, electrophotographic toners, inkjet inks, color filters, and the like can be used. These are now important compounds that are indispensable in daily life. Among them, high performance is required, and pigments for inkjet ink and pigments for color filters are particularly important in practical use.
Conventionally, dyes have been used for coloring materials for ink jet inks, but there are problems in terms of water resistance and light resistance, and pigments have been used to improve them. An image obtained with the pigment ink has an advantage of being excellent in light resistance and water resistance as compared with an image obtained with a dye-based ink. However, it is difficult to increase the monodispersity at a nanometer size that can penetrate into the voids on the paper surface, and the adhesion to paper is poor.
In addition, with the increase in the number of pixels in a digital camera, it is desired to reduce the thickness of color filters used for optical elements such as CCD sensors and display elements. An organic pigment is used for the color filter. However, since the thickness of the filter greatly depends on the particle diameter of the organic pigment, it is desired to produce fine particles having a nanometer size level and being monodispersed and stable.

On the other hand, regarding the improvement of the dispersibility of particles, the dispersion of organic pigments is conventionally carried out industrially using various dispersers (roll mill, ball mill, attritor, etc.), but by making the particles finer The viscosity may increase. If the viscosity increases, it becomes difficult to take out from the disperser, it cannot be transported by pipeline, or it becomes gelled during storage and becomes unusable. In order to solve these problems, a dispersing agent that aids dispersion and a polymer that stabilizes dispersion are added, but a sufficient effect is not obtained (see Non-Patent Document 1, etc.).
In addition, in order to improve the dispersibility of organic pigment dispersions for color filters, polymers and pigment dispersants that can provide both the properties of alkali developability and dispersion stability necessary for the production of color filters are added. (Patent Document 2). However, these methods do not satisfy the requirements because dispersion takes time and the viscosity increases.

  Regarding the method for producing organic particles, a gas phase method (a method in which a sample is sublimated in an inert gas atmosphere and the particles are collected on a substrate), a liquid phase method (for example, a sample dissolved in a good solvent under stirring conditions or Reprecipitation method to obtain fine particles by injecting into a poor solvent with controlled temperature), laser ablation method (method of refining particles by irradiating a sample to a sample dispersed in a solution and ablating) It has been studied. Among these, the liquid phase method has attracted attention as a method for producing organic particles having excellent simplicity and productivity (Patent Document 3).

Organic particles produced by this liquid phase method can adjust the crystal form and particle surface properties by adjusting the precipitation conditions with the solvent type, injection speed, temperature, etc., and the crystal form of the quinacridone pigment is adjusted with a poor solvent type Is described (Patent Document 4).
And the improvement of the dispersibility of the pigment particle prepared by the said liquid phase method is tried, and the example which prepared the pigment particle aqueous dispersion by the liquid phase method is described (patent document 5). However, this method is a method of finally making an aqueous dispersion, and no mention is made of a method of making an organic solvent dispersion. Further, there is a method of precipitating a pigment by dissolving the pigment in a basic compound and / or a basic solution and then adding a liquid neutral compound and / or an acidic compound, or a neutral liquid and / or an acidic liquid. (Patent Document 6). However, the organic pigment particles obtained by this method have a large primary particle size and have not fully met the demand for fine particles. In addition, a method for controlling the dispersibility of the generated fine particles by controlling the fluid flow state is disclosed (Patent Document 7), and the pH is changed by allowing the microchannel to pass as a laminar flow with a low Reynolds number. Means have been proposed. However, the level required for color filters for liquid crystal display devices has not been sufficiently satisfied.

JP-A-11-237760 JP 2000-239554 A JP-A-6-79168 JP 2004-91560 A JP 2004-43776 A JP 2004-123853 A JP 2005-307154 A Pigment Dispersion Technology-Surface Treatment and Use of Dispersing Agents and Dispersibility Evaluation-Technical Information Association 1999

An object of the present invention is to provide a method for producing a dispersion containing organic pigment nanoparticles having high dispersion stability and a nano-size and a sharp particle size distribution peak. Specifically, an object of the present invention is to provide a method for producing an organic pigment nanoparticle dispersion liquid having high contrast, exhibiting excellent display characteristics, excellent durability, and suitable for producing a high-quality color filter.

（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。）
（７）前記高分子化合物が下記一般式（２）で表されることを特徴とする（６）に記載の有機顔料ナノ粒子分散液の製造方法。

（式中、Ｒ^３は、（ｘ＋ｙ）価の連結基を表す。Ｒ^４およびＲ^５は、各々独立に単結合または２価の連結基を表す。Ａ^２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、ｘ個のＡ^２は互いに同一であっても、異なっていてもよい。ｙは１〜８の数を表し、ｘは２〜９の数を表し、ｘ＋ｙは３〜１０を満たす。Ｐ^２は高分子化合物残基を表す。）
（８）前記高分子化合物を有機顔料１００質量部に対して０．１〜１０００質量部で含有させることを特徴とする（５）〜（７）のいずれか１項に記載の有機顔料ナノ粒子分散液の製造方法。
（９）前記有機顔料がピロロピロール化合物顔料であることを特徴とする（１）〜（８）のいずれか１項に記載の有機顔料ナノ粒子分散液の製造方法。
（１０）前記ピロロピロール化合物顔料がＣ．Ｉ．ピグメントレッド２５４、Ｃ．Ｉ．ピグメントレッド２５５、Ｃ．Ｉ．ピグメントレッド２６４、及びＣ．Ｉ．ピグメントレッド２７２のいずれかであることを特徴とする（９）に記載の有機顔料ナノ粒子分散液の製造方法。
（１１）前記有機顔料がフタロシアニン化合物顔料であることを特徴とする（１）〜（８）のいずれか１項に記載の有機顔料ナノ粒子分散液の製造方法。
（１２）前記フタロシアニン化合物顔料がＣ．Ｉ．ピグメントグリーン３６、Ｃ．Ｉ．ピグメントグリーン７、及びＣ．Ｉ．ピグメントブルー１５：６のいずれかであることを特徴とする（１１）に記載の有機顔料ナノ粒子分散液の製造方法。
（１３）前記有機顔料がジオキサジン化合物顔料であることを特徴とする（１）〜（８）のいずれか１項に記載の有機顔料ナノ粒子分散液の製造方法。
（１４）前記ジオキサジン化合物顔料がＣ．Ｉ．ピグメントバイオレット２３またはＣ．Ｉ．ピグメントバイオレット３７であることを特徴とする（１３）に記載の有機顔料ナノ粒子分散液の製造方法。
（１５）前記有機顔料ナノ粒子を、前記貧溶媒が１０Ｌ以上のスケールで析出させることを特徴とする（１）〜（１４）のいずれか１項に記載の有機顔料ナノ粒子分散液の製造方法。
The above problems have been achieved by the following means.
(1) an organic Pigments solution of an organic Pigments in a good solvent for the above is a good solvent miscible and the organic Pigments represented a solvent which is a poor solvent by the following equation (1) that the Reynolds number is a process for the preparation of organic pigment nanoparticles Ru precipitated mixed nanoparticles of the organic pigment average particle size in the 60nm or less under conditions of 60 or more,
A method for producing an organic pigment nanoparticle dispersion, wherein the organic pigment solution is jetted from a supply pipe and mixed into the poor solvent under stirring.
Re = ρUL / μ Equation (1)
(In Formula (1), Re represents a Reynolds number, [rho represents the density of the organic Pigments solution, U is represents the relative speed at which meet the organic Pigments solution and the poor solvent, L represents an organic Pigment solution represents the equivalent diameter of the flow path or feed port portion and a poor solvent meet, mu denotes the viscosity coefficient of the organic Pigment solution.)
(2) The method of producing organic pigment nanoparticle dispersion of the Reynolds number placing serial to 100 or more (1).
( 3 ) The method for producing an organic pigment nanoparticle dispersion liquid according to (1) or (2), wherein the Reynolds number is 2500 or less.
(4) Any one of (1) to (3), wherein the mixing ratio of the organic pigment solution and the poor solvent (ratio of good solvent / poor solvent) is 1/50 to 2/3 by volume. The manufacturing method of the organic pigment nanoparticle dispersion liquid as described in an item.
( 5 ) The method for producing an organic pigment nanoparticle dispersion according to any one of (1) to (4), wherein the dispersion contains a polymer compound having a molecular weight of 1000 or more.
( 6 ) The method for producing an organic pigment nanoparticle dispersion liquid according to (5), wherein the polymer compound is 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.)
( 7 ) The method for producing an organic pigment nanoparticle dispersion liquid according to (6), wherein the polymer compound is represented by the following general formula (2).

(In the formula, R ³ represents a (x + y) -valent linking group. R ⁴ and R ⁵ each independently represents a single bond or a divalent linking group. A ² has an acidic group or a nitrogen atom. 1 having a group selected from the group consisting of a basic group, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group Represents a monovalent organic group containing a divalent organic group or an organic dye structure or a heterocyclic ring which may have a substituent, provided that x A ² may be the same or different from each other. Y represents a number of 1 to 8, x represents a number of 2 to 9, and x + y satisfies 3 to 10. P ² represents a polymer compound residue.
( 8 ) The organic pigment nanoparticles according to any one of ( 5) to (7), wherein the polymer compound is contained in an amount of 0.1 to 1000 parts by mass with respect to 100 parts by mass of the organic pigment. A method for producing a dispersion .
( 9 ) The method for producing an organic pigment nanoparticle dispersion liquid according to any one of ( 1) to (8), wherein the organic pigment is a pyrrolopyrrole compound pigment.
( 10 ) The pyrrolopyrrole compound pigment is C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264, and C.I. I. The method for producing an organic pigment nanoparticle dispersion liquid according to (9), which is any one of CI Pigment Red 272.
( 11 ) The method for producing an organic pigment nanoparticle dispersion liquid according to any one of ( 1) to (8), wherein the organic pigment is a phthalocyanine compound pigment.
( 12 ) The phthalocyanine compound pigment is C.I. I. Pigment green 36, C.I. I. Pigment green 7, and C.I. I. Pigment Blue 15: 6 method of producing an organic pigment nanoparticle dispersion of placing serial in (11) to be either.
( 13 ) The method for producing an organic pigment nanoparticle dispersion liquid according to any one of ( 1) to (8), wherein the organic pigment is a dioxazine compound pigment.
( 14 ) The dioxazine compound pigment is C.I. I. Pigment violet 23 or C.I. I. The method for producing an organic pigment nanoparticle dispersion liquid according to ( 13) , which is CI Pigment Violet 37.
( 15 ) The method for producing an organic pigment nanoparticle dispersion according to any one of (1) to (14), wherein the organic pigment nanoparticles are precipitated on a scale in which the poor solvent is 10 L or more. .

According to the production method of the present invention, organic pigment nanoparticles having a nanometer size, a sharp particle size distribution peak, and excellent dispersion stability are controlled on an industrial production scale by controlling the particle size. Can be manufactured automatically. And if the dispersion liquid of the organic pigment nanoparticle which has such an excellent characteristic is used , the contrast of a color filter can be improved, generation | occurrence | production of a precipitate can be suppressed, and durability can be improved.
In addition, the liquid crystal display device and the CCD device using the color filter having the high performance described above exhibit excellent display characteristics without color unevenness and excellent long-term display durability.

Hereinafter, the present invention will be described in detail.
The organic material used in the method of producing organic pigment nanoparticles of the present invention are organic pigments. Hereinafter, organic pigment nanoparticles are simply referred to as organic nanoparticles, and organic pigments are referred to as organic materials.

  The organic pigment is not limited in hue, for example, perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, triarylcarbonium , Dioxazine, aminoanthraquinone, diketopyrrolopyrrole, thioindigo, isoindoline, isoindolinone, pyranthrone or isoviolanthrone compound pigment, or a mixture thereof.

  More specifically, for example, C.I. I. Pigment red 190 (C.I. No. 71140), C.I. I. Pigment red 224 (C.I. No. 71127), C.I. I. Perylene compound pigments such as C.I. Pigment Violet 29 (C.I. No. 71129); I. Pigment orange 43 (C.I. No. 71105), or C.I. I. Perinone compound pigments such as C.I. Pigment Red 194 (C.I. No. 71100); I. Pigment violet 19 (C.I. No. 73900), C.I. I. Pigment violet 42, C.I. I. Pigment red 122 (C.I. No. 73915), C.I. I. Pigment red 192, C.I. I. Pigment red 202 (C.I. No. 73907), C.I. I. Pigment Red 207 (C.I. No. 73900, 73906) or C.I. I. Pigment Red 209 (C.I. No. 73905), a quinacridone compound pigment; I. Pigment red 206 (C.I. No. 73900/73920), C.I. I. Pigment orange 48 (C.I. No. 73900/73920), or C.I. I. Quinacridonequinone compound pigments such as CI Pigment Orange 49 (C.I. No. 73900/73920); I. Anthraquinone compound pigments such as C.I. Pigment Yellow 147 (C.I. No. 60645); I. Anthanthrone compound pigments such as CI Pigment Red 168 (C.I. No. 59300); I. Pigment brown 25 (C.I. No. 12510), C.I. I. Pigment violet 32 (C.I. No. 12517), C.I. I. Pigment yellow 180 (C.I. No. 21290), C.I. I. Pigment yellow 181 (C.I. No. 11777), C.I. I. Pigment orange 62 (C.I. No. 11775), or C.I. I. Benzimidazolone compound pigments such as CI Pigment Red 185 (C.I. No. 12516); I. Pigment yellow 93 (C.I. No. 20710), C.I. I. Pigment yellow 94 (C.I. No. 20038), C.I. I. Pigment yellow 95 (C.I. No. 20034), C.I. I. Pigment yellow 128 (C.I. No. 20037), C.I. I. Pigment yellow 166 (C.I. No. 20035), C.I. I. Pigment orange 34 (C.I. No. 21115), C.I. I. Pigment orange 13 (C.I. No. 21110), C.I. I. Pigment orange 31 (C.I. No. 20050), C.I. I. Pigment red 144 (C.I. No. 20735), C.I. I. Pigment red 166 (C.I. No. 20730), C.I. I. Pigment red 220 (C.I. No. 20055), C.I. I. Pigment red 221 (C.I. No. 20065), C.I. I. Pigment red 242 (C.I. No. 20067), C.I. I. Pigment red 248, C.I. I. Pigment red 262, or C.I. I. Disazo condensed compound pigments such as CI Pigment Brown 23 (C.I. No. 20060); I. Pigment yellow 13 (C.I. No. 21100), C.I. I. Pigment yellow 83 (C.I. No. 21108), or C.I. I. Disazo compound pigments such as CI Pigment Yellow 188 (C.I. No. 21094); I. Pigment red 187 (C.I. No. 12486), C.I. I. Pigment red 170 (C.I. No. 12475), C.I. I. Pigment yellow 74 (C.I. No. 11714), C.I. I. Pigment yellow 150 (C.I. No. 48545), C.I. I. Pigment red 48 (C.I. No. 15865), C.I. I. Pigment red 53 (C.I. No. 15585), C.I. I. Pigment orange 64 (C.I. No. 12760), or C.I. I. Azo compound pigments such as CI Pigment Red 247 (C.I. No. 15915), C.I. I. Indanthrone compound pigments such as C.I. Pigment Blue 60 (C.I. No. 69800); I. Pigment green 7 (C.I. No. 74260), C.I. I. Pigment green 36 (C.I. No. 74265), C.I. I. Pigment green 37 (C.I. No. 74255), C.I. I. Pigment blue 16 (C.I. No. 74100), C.I. I. Pigment blue 75 (C.I. No. 74160: 2), C.I. I. Pigment Blue 15: 6 (C.I. No. 74160), or C.I. I. Phthalocyanine compound pigments such as C.I. Pigment Blue 15: 3 (C.I. No. 74160); I. Pigment blue 56 (C.I. No. 42800), or C.I. I. Pigment Blue 61 (C.I. No. 42765: 1) and the like triarylcarbonium compound pigments, C.I. I. Pigment violet 23 (C.I. No. 51319) or C.I. I. Pigment Violet 37 (C.I. No. 51345) and other dioxazine compound pigments, C.I. I. Aminoanthraquinone compound pigments such as C.I. Pigment Red 177 (C.I. No. 65300); I. Pigment red 254 (C.I. No. 56110), C.I. I. Pigment Red 255 (C.I. No. 561050), C.I. I. Pigment red 264, C.I. I. Pigment red 272 (C.I. No. 561150), C.I. I. Pigment orange 71, or C.I. I. Diketopyrrolopyrrole compound pigments such as C.I. Pigment Orange 73; I. Thioindigo compound pigments such as C.I. Pigment Red 88 (C.I. No. 7313); I. Pigment yellow 139 (C.I. No. 56298), C.I. I. Pigment Orange 66 (C.I. No. 48210), an isoindoline compound pigment such as C.I. I. Pigment yellow 109 (C.I. No. 56284), C.I. I. Pigment yellow 185 (C.I. No. 56290), or C.I. I. Pigment Orange 61 (C.I. No. 11295) and the like, an inindolinone compound pigment such as C.I. I. Pigment Orange 40 (C.I. No. 59700), or C.I. I. Pyranthrone compound pigments such as C.I. Pigment Red 216 (C.I. No. 59710); I. Quinophthalone pigments such as CI Pigment Yellow 138; I. And isoviolanthrone compound pigments such as CI Pigment Violet 31 (60010). 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.

  According to the production method of the present invention, fine particles of a nanometer-sized diketopyrrolopyrrole compound pigment (hereinafter sometimes simply referred to as “pyrrolopyrrole compound pigment”) can be obtained with a sharp particle size distribution. . In addition, when the pigment fine particles are used in a color filter, desired color purity and high contrast can be achieved at the same time, and the light resistance is excellent, and the occurrence of protrusions can be suppressed. And the liquid crystal display device provided with the color filter is excellent in blackness and red descriptive power, and display unevenness is suppressed.

  Among the above diketopyrrolopyrrole compound pigments, C.I. I. P. R. 254, 255, 264 are preferred, and C.I. I. P. R. 254 is more preferable from the viewpoint of the absorption spectrum. C. I. P. R. As 254, commercially available products such as Irgaphor Red B-CF, Chromophthal DPP Red BO, Irgadin DPP Red BO, and Microlen DPP RED BP can be used. C. I. P. R. As 255, Croftal Coral Red C, Irgadin DPP Red 5G, or the like can be used. C. I. P. R. As H.264, Hostepperum Rubin D3B LP2615, Irgadin DPP Rubin TR, or the like can be used.

As a colorant for blue pixels of color filters in recent years, C.I. I. P. B. 15: 6 (phthalocyanine compound pigment) has come to be frequently used, and as a result, the color purity of color filters has increased. However, a light source such as a cold-cathode tube, which is a light source frequently used in liquid crystal display devices, emits a little light on the long wave side of the blue light emission peak, which makes the chromaticity inferior to NTSC.
The problem is that C.I. I. P. V. It can be improved by adding a dioxazine compound pigment represented by 23 or 37 (for example, about 5%). Although it is conceivable to improve contrast and further improve display characteristics with this color filter having high color purity, satisfactory results cannot be obtained by the conventional bead dispersion method or salt milling method.
On the other hand, according to the production method of the present invention, the dioxazine compound pigment can be obtained as a nano-sized pigment having a uniform particle size distribution. The dispersion containing the dioxazine compound pigment fine particles can be made excellent in stability over time. Therefore, the color filter used therefor can achieve both high color purity and high contrast, and is excellent in light resistance. In addition, the liquid crystal display device provided with the color filter is excellent in depiction and reproducibility of black spots and blue, and display unevenness can be suppressed. Note that C.I. I. P. V. As 23, commercially available products such as Cromofine Violet RE, Fastgen Super Violet BBL, Helio Fast Violet EB, Microlith Violet RL-WA, and Sanyo Fast Violet BLD can be used. C. I. P. V. As 37, it is possible to use commercially available products such as Chromophthal Violet B and Microlith Violet B-A.

  In addition to the phthalocyanine compound pigments mentioned above, examples of pigments for color filters include pigments described on pages 300 to 314 of “Encyclopedia of Pigments” published by Asakura Shoten on September 25, 2000, among which pigment blue 15 : 6, Pigment Green 7 and Pigment Green 36 are preferable from the viewpoint of the absorption spectrum.

  The phthalocyanine compound pigment is structurally chemically stable and excellent in heat resistance and light resistance. Furthermore, it has high coloring power and is used as a basic pigment for the B and G pixels of the color filter. It was expected that when these pigments were made into fine particles, the contrast was improved and the display characteristics were further improved. However, satisfactory results were not obtained by the conventional bead dispersion method or salt milling method. On the other hand, according to the production method of the present invention, even a phthalocyanine compound pigment can be obtained as a nanometer-sized pigment having a uniform particle size distribution, and can be used as a good pixel material for a color filter. .

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 dye that can be used in the present invention is not particularly limited, and ordinary dyes can be used for color filters. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 The dyes disclosed in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like can be used.
The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene-based, phthalocyanine-based, benzopyran-based and indigo-based dyes can be used.

In the case of a resist system that performs water or alkali development, an acid dye and / or a derivative thereof may be suitably used from the viewpoint of completely removing the binder and / or dye in the light non-irradiated part by development.
In addition, a direct dye, a basic dye, a mordant dye, an acid mordant dye, an azoic dye, a disperse dye, an oil-soluble dye, a food dye, and / or a derivative thereof can be usefully used.
The acidic dye is not particularly limited as long as it has an acidic group such as sulfonic acid or carboxylic acid, but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, other in the composition. It is selected in consideration of all the required performances such as interaction with the components, light resistance and heat resistance.

Although the specific example of the said acidic dye is given to the following, it is not limited to these. For example, acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 45, 62, 70, 74, 80, 83 , 86, 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1; acid chroma violet K; acid Fuchsin; acid green 1, 3 , 5, 9, 16, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116, 184, 243; Food Yellow 3; and derivatives of these dyes.
Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; C.I. I. Acid dyes such as Solvent orange 45; Rhodamine B, Rhodamine 110, and derivatives of these dyes are also preferably used.

  In addition, polydiacetylene, polyimide, or the like may be used as a high-molecular organic material such as an azo dye, a cyanine dye, a merocyanine dye, or a coumarin dye as an organic dye.

Next, precipitation formation of organic nanoparticles will be described.
In the production method of the present invention, the organic nanoparticle (in the present invention, “nanoparticle” means a nanometer-sized particle, sometimes referred to as “fine particle”) is an organic material solution in which an organic material is dissolved in a good solvent. And a solvent that is compatible with the good solvent and that is a poor solvent for the organic material (hereinafter, this solvent may be referred to as “poor solvent for organic material” or simply “poor solvent”). (Hereinafter, this method is sometimes referred to as “fine particle precipitation method”). The dispersion containing the organic nanoparticles obtained at this time is referred to as “organic fine particle precipitation solution” or “organic nanoparticle dispersion”. "Liquid" etc.)). The combination of the poor solvent and the good solvent needs to have a sufficient difference in the solubility of the organic material, and it is necessary to select a preferable one according to the material. Any choice is possible.
The poor solvent for the organic material is not particularly limited as long as it is compatible with or uniformly mixed with a good solvent for dissolving the organic material. As a poor solvent for the organic material, the solubility of the organic material is preferably 0.02% by mass or less, and more preferably 0.01% by mass or less. Although there is no particular lower limit to the solubility of the organic material in the poor solvent, 0.000001% by mass or more is practical in consideration of a commonly used organic material. This solubility may be the solubility when dissolved in the presence of an acid or alkali. In addition, the compatibility or uniform mixing property of the good solvent and the poor solvent is preferably 30% by mass or more, more preferably 50% by mass or more, with respect to the poor solvent. There is no particular upper limit to the amount of good solvent dissolved in the poor solvent, but it is practical to mix them in an arbitrary ratio.
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, mixed solvents thereof, and aqueous solvents, alcohol compound solvents, ketone compound solvents, ether compound solvents, ester compound solvents, or mixtures thereof. Preferably, 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.

Next, a good solvent that dissolves the organic material will be described.
The good solvent is not particularly limited as long as it can dissolve the organic material to be used and is compatible with or uniformly mixed with the poor solvent. The solubility of the organic material in a good solvent is such that the solubility of the organic material is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. Although there is no particular upper limit to the solubility of the organic material in the good solvent, it is practical that it is 50% by mass or less in consideration of a commonly used organic material. 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 material solution in which the organic material is dissolved in the good solvent is preferably a saturated concentration of the organic material with respect to the good solvent in the dissolution condition or a range of about 1/100 of this.
The conditions for preparing the organic material solution are not particularly limited, 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.

  Here, there are things in common between those listed as specific examples of good solvents and those listed as poor solvents, but they do not combine the same as good solvents and poor solvents, and in relation to each organic material adopted The solubility in the good solvent should be sufficiently higher than the solubility in the poor solvent. For example, the solubility difference is preferably 0.2% by mass or more, more preferably 0.5% by mass or more. There is no particular upper limit to the difference in solubility between the good solvent and the poor solvent, but it is practical that it is 50% by mass or less in consideration of a commonly used organic material.

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

  Bases used for alkaline dissolution are inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, or barium hydroxide, or trialkylamine, 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 relative to the organic material, more preferably 1 0.0 to 25 molar equivalents, more preferably 1.0 to 20 molar equivalents. In the case of an organic base, it is preferably 1.0 to 100 molar equivalents, more preferably 5.0 to 100 molar equivalents, still more preferably 20 to 100 molar equivalents relative to the organic material.

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

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

There 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 viscosity of the organic material solution is preferably 0.5 to 80.0 mPa · s, and more preferably 1.0 to 50.0 mPa · s.
In the present invention, when mixing the organic material solution and a poor solvent, you mixed chromatic equipment cost solution jets poor solvent. Situations that der the poor solvent is stirred at that time. 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. In this invention, it is preferable to supply continuously in a liquid with a pump through a supply pipe | tube. 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.

In the production method of the present invention, the particle size of the organic nanoparticles formed by precipitation is controlled by adjusting the Reynolds number when mixing the organic material solution and the poor solvent. 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 material solution, and U represents the relative velocity [m / s] when the organic material solution and the poor solvent meet. L represents the equivalent diameter [m] of the flow path or supply port where the organic material solution and the poor solvent meet, and μ represents the viscosity coefficient [Pa · s] of the organic material solution.

In the present invention, the equivalent diameter L refers to the diameter of an equivalent circular pipe when assuming an opening diameter of a pipe having an arbitrary cross-sectional shape or a circular pipe equivalent to a 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)
In the present invention, it is preferable to form particles by injecting an organic material solution into a poor solvent through a pipe, and when a circular pipe is used for the pipe, the equivalent diameter matches the diameter of the circular pipe. For example, it is equivalent by changing the opening diameters of the supply ports 14a of the apparatus shown in FIGS. 1-1 to 1-4 described later, the supply ports 24a and 25a of the apparatus of FIG. 2, and the supply ports 32a and 33a of the apparatus shown in FIG. The diameter can be adjusted. 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 velocity U when the good solvent solution and the poor solvent of the organic material meet is defined by the relative velocity in the direction perpendicular to the surface of the portion where both meet. That is, for example, when a good solvent solution of an organic material 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 material solution is a value determined by the type of material selected, and is, for example, 0.8 to 2.0 kg / m ³ in the range of materials preferably used in the production method of the present invention. That is practical. Further, the viscosity coefficient μ of the organic material solution is also a value determined by the material used, the environmental temperature, and the like, but its preferred range is synonymous with the preferred viscosity of the organic material 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. In the production method of the present invention, the Reynolds number can be adjusted to 60 or more to control the particle size of the organic nanoparticles, and is preferably 100 or more, more preferably 150 or more. Although there is no upper limit to the number of Reynolds nozzles of the present invention, in consideration of the fact that the control of the Reynolds number can greatly affect the performance of the particles after formation, the Reynolds number can be adjusted within a range of 3500 or less to achieve good organic nanometers. It is preferable to obtain particles by controlling, more preferably 3000 or less, and particularly preferably 2500 or less. Further, in the manufacturing method of the present invention, that the average particle size of the obtained nanoparticles controls the Reynolds number as a 60nm or less, more preferably 40nm or less, to control the Reynolds number such that the 30nm or less Particularly preferred.

The mixing ratio of the organic material solution and the poor solvent (good solvent / poor solvent ratio in the organic fine particle deposit) is preferably 1/50 to 2/3, more preferably 1/40 to 1/2, and 1 / 20 to 3/8 is particularly preferable.
The concentration of the organic fine particle deposition liquid is not particularly limited as long as the organic particles can be generated, but the organic particles are preferably in the range of 10 to 40,000 mg, more preferably in the range of 20 to 30000 mg with respect to 1000 ml of the dispersion solvent. Especially preferably, it is the range of 50-25000 mg.
Moreover, the preparation scale at the time of producing | generating an organic 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.

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, but as a common use, the mode diameter indicating the maximum value of the distribution, the median value of the integral distribution curve 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. The diameter. The average particle size of the organic nanoparticles (primary particles) is nanometer size, and the average particle size is particularly preferably in the above range . The particles formed by the production method of the present invention may be crystalline particles, amorphous particles, or a mixture thereof.
In the present invention, the ratio (Mv / Mn) of the volume average particle diameter (Mv) and the number average particle diameter (Mn) is used as an index representing the monodispersity of the particles unless otherwise specified. The monodispersity of organic nanoparticles (primary particles), that is, Mv / Mn, is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, and 1.0 to A ratio of 1.5 is particularly preferred.
Examples of the method for measuring the particle size of organic particles include microscopy, gravimetric 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.

[Dispersant]
In the method for producing organic nanoparticles of the present invention, it is preferable to contain a dispersant when preparing the organic nanoparticle dispersion. The step of containing the dispersant is not particularly limited, but it is preferable to add the dispersant to the organic material solution and / or the poor solvent. Moreover, it is also preferable to add a dispersing agent solution at the time of formation of organic 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 a dispersant that can be used, for example, a low molecular or high molecular dispersant of anionic, cationic, amphoteric, nonionic or pigment derivative can be used. The 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.

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

As the dispersant used in the production method of the present invention, it is preferable to use at least one selected from compounds represented by the following general formulas (D1), (D3), and formula (D4).
<1. Compound represented by general formula (D1)>

  In general formula (D1), A represents a component capable of forming an azo dye together with XY. A can be arbitrarily selected as long as it is a compound capable of forming an azo dye by coupling with a diazonium compound. Specific examples of A will be shown below, but the present invention is not limited thereto.

  In general formula (D1), X represents a single bond or a group selected from divalent linking groups represented by structural formulas of the following formulas (i) to (v).

  In General Formula (D1), Y represents a group represented by the following General Formula (D2).

In general formula (D2), Z represents a lower alkylene group. Z can be represented as — (CH ₂ ) _b —, wherein b represents an integer of 1 to 5, preferably 2 or 3. In General Formula (D2), —NR ₂₁ represents a lower alkylamino group or a 5- to 6-membered saturated heterocyclic group containing a nitrogen atom. The _{-NR 21,} when a lower alkyl amino group _is represented as _{-N (C r H 2r + 1} ) 2, r represents an integer of 1 to 4, preferably represents 1 or 2. When —NR ₂₁ represents a 5- to 6-membered saturated heterocyclic group containing a nitrogen atom, any heterocyclic group represented by the following structural formula is preferable.

In the general formula (D2), Z and —NR ₂₁ may each have a lower alkyl group or an alkoxy group as a substituent. In the general formula (D2), a represents 1 or 2, preferably 2.

  Specific examples of the compound represented by the general formula (D1) are shown below, but the present invention is not limited to these specific examples.

  The compound represented by the general formula (D1) can be synthesized by, for example, a method described in JP-A No. 2000-239554.

<2. Compound represented by general formula (D3)>

In general formula (D3),
Q is an anthraquinone compound dye, azo compound dye, phthalocyanine compound dye, quinacridone compound dye, dioxazine compound dye, anthrapyrimidine compound dye, ansanthrone compound dye, indanthrone compound dye, flavanthrone compound dye, pyranthrone compound dye, perinone compound It represents an organic dye residue selected from a dye, a perylene compound dye, and a thioindigo compound dye. Among them, an azo compound dye or a dioxazine compound dye is preferable, and an azo compound dye is more preferable.
X ₁ represents —CO—, —CONH—Y ₂ —, —SO ₂ NH—Y ₂ —, or —CH ₂ NHCOCH ₂ NH—Y ₂ —, and is —CO— or —CONH—Y ₂ —. It is preferable.
Y ₂ represents an alkylene group or an arylene group that may have a substituent, and among them, phenylene, toluylene, or hexylene is preferable, and phenylene is more preferable.
R ₁₁ and R ₁₂ may each independently form a substituted or unsubstituted alkyl group or a heterocyclic group containing at least a nitrogen atom with R ₁₁ and R ₁₂ . Of these, a methyl group, an ethyl group, a propyl group, or a pyrrolidinyl group including a nitrogen atom is preferable, and an ethyl group is more preferable.
Y ₁ represents —NH— or —O—.
Z ₁ represents a hydroxyl group or a group represented by the general formula (D3a). However, when n1 is 1, it may be —NH—X ₁ -Q. m1 represents the integer of 1-6, and 2-3 are preferable. n1 represents the integer of 1-4, and 1-2 are preferable.

In General Formula (D3a), Y ₃ represents —NH— or —O—, and m1, R ₁₁ , and R ₁₂ have the same meaning as those in General Formula (D3).

  More specifically, the compound represented by the general formula (D3) is represented by the following general formula, for example.

In general formulas (D3-1) to (D3-6), Q, m1, n1, R ₁₁ , and R ₁₂ have the same meanings as those in general formula (D3). Specific examples of the compound represented by formula (D3) are shown below, but the present invention is not limited thereto. In the formula, Cu-Pc represents copper phthalocyanine.

Compound represented by the general formula (D3), for example R ₁₁ and alcohol compounds having amine compound with R ₁₁ and R ₁₂ having the R ₁₂ and reacted with a halogenated triazine compound, a dye compound resulting intermediate Can be obtained by reacting. The description in Japanese Patent Publication No. 5-72943 can also be referred to.

<3. Pigment Dispersant Containing Graft Copolymer>
In the method for producing organic nanoparticles of the present invention, it is also preferable to use a dispersant containing a graft copolymer having an amino group and an ether group and containing other components appropriately selected as necessary.
The graft copolymer has at least an amino group and an ether group, and may contain other monomers as copolymer units.
As a mass average molecular weight of the said graft copolymer, 3000-100000 are preferable and 5000-50000 are more preferable. When the mass average molecular weight is less than 3000, aggregation of the organic nanoparticles cannot be prevented and the viscosity may increase. When it exceeds 100,000, the solubility in an organic solvent is insufficient, and the viscosity is May rise.

  The graft copolymer includes (i) a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal, (ii) a monomer having an amino group and an ethylenically unsaturated double bond, and (iii) an ether group. It is preferable that it contains at least a polymerizable monomer having a copolymer unit and, if necessary, (iv) another monomer as a copolymer unit.

  The content of these copolymer units in the graft copolymer is preferably (i) 15 to 98% by mass of the polymerizable oligomer, more preferably 25 to 90% by mass, (Ii) The amino group-containing monomer is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, and (iii) the polymerizable monomer having an ether group is 1 to 70% by mass. It is preferably 5 to 60% by mass.

  If the content of the polymerizable oligomer is less than 15% by mass, a steric repulsion effect as a dispersant may not be obtained, and aggregation of organic nanoparticles may not be prevented. In some cases, the proportion of the monomer is reduced, the adsorption ability to the organic particles is lowered, and the dispersibility is not sufficient. When the content of the nitrogen-containing monomer is less than 1% by mass, the adsorption ability with respect to the organic particles is lowered and the dispersibility may not be sufficient. When the content exceeds 40% by mass, the ratio of the polymerizable oligomer is decreased. For this reason, the steric repulsion effect as a dispersant cannot be obtained, and aggregation of organic particles may not be sufficiently prevented. When the content of the polymerizable monomer having an ether group is less than 1% by mass, the development suitability in the production of a color filter or the like may not be sufficient, and when it exceeds 70% by mass, the ability as a dispersant. May decrease.

(I) Polymerizable oligomer The polymerizable oligomer (hereinafter sometimes referred to as “macromonomer”) is an oligomer having a terminal group having an ethylenically unsaturated double bond at the terminal. In the present invention, among the polymerizable oligomers, it is preferable to have a group having the ethylenically unsaturated double bond only at one of both ends of the oligomer.

  The oligomer is generally a homopolymer formed from at least one monomer selected from, for example, alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, styrene, acrylonitrile, vinyl acetate, and butadiene. Examples of the copolymer include alkyl (meth) acrylate homopolymers or copolymers, polystyrene, and the like. In the present invention, these oligomers may be substituted with a substituent, and the substituent is not particularly limited, and examples thereof include a halogen atom.

  Preferred examples of the group having an ethylenically unsaturated double bond include a (meth) acryloyl group and a vinyl group. Among these, a (meth) acryloyl group is particularly preferred.

  In the present invention, among the polymerizable oligomers, oligomers represented by the following general formula (E6) are preferable.

In the general formula (E6), R ⁶¹ and R ⁶³ represent a hydrogen atom or a methyl group. R ⁶² represents an alkylene group which may be substituted by an alcoholic hydroxyl group having 1 to 8 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms. Y ⁶ represents a phenyl group, a phenyl group having an alkyl group having 1 to 4 carbon atoms, or —COOR ⁶⁴ (where R ⁶⁴ is an alcoholic hydroxyl group having 1 to 6 carbon atoms, or an alkyl which may be substituted with a halogen atom). A phenyl group or —COOR ¹⁶⁴ (wherein R ¹⁶⁴ may be substituted with an alcoholic hydroxyl group having 1 to 4 carbon atoms). Represents a good alkyl group). q represents 20-200.

  Specific examples of the polymerizable oligomer include poly-2hydroxyethyl (meth) acrylate, polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, poly-i-butyl (meth) acrylate, and those A copolymer which is a copolymer and has a (meth) acryloyl group bonded to one molecular end is preferable.

  The polymerizable oligomer may be a commercially available product or an appropriately synthesized product. Examples of the commercially available product include a one-end methacryloylated polystyrene oligomer (Mn = 6000, trade name: AS-6). , Manufactured by Toa Gosei Chemical Co., Ltd.), one-end methacryloylated polymethyl methacrylate oligomer (Mn = 6000, trade name: AA-6, manufactured by Toa Gosei Chemical Co., Ltd.), one-end methacryloylated poly-n -Butyl acrylate oligomer (Mn = 6000, trade name: AB-6, manufactured by Toa Gosei Chemical Co., Ltd.), one-end methacryloylated polymethyl methacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7000, trade name: AA) -714, manufactured by Toa Gosei Chemical Co., Ltd.), one-end methacryloylated polybutylmethacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7000, trade name: 707S, manufactured by Toa Gosei Chemical Co., Ltd.), one-end methacryloylated poly-2-ethylhexyl methacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7000) And trade names: AY-707S, AY-714S, manufactured by Toagosei Chemical Co., Ltd.), and the like.

  Preferred specific examples of the polymerizable oligomer in the present invention include at least one oligomer selected from a polymer of alkyl (meth) acrylate and a copolymer of alkyl (meth) acrylate and polystyrene, A number average molecular weight is 1000-20000, and what has a (meth) acryloyl group at the terminal is mentioned.

(Ii) Amino group-containing monomer As the amino group-containing monomer, for example, at least one selected from compounds represented by the following general formula (E2) is preferably exemplified.

In the general formula (E2), R ²¹ represents a hydrogen atom or a methyl group. R ²² represents an alkylene group having 1 to 8 carbon atoms, and among these, an alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 2 to 3 carbon atoms is particularly preferable.

X ² represents —N (R ²³ ) (R ²⁴ ), —R ²⁵ N (R ²⁶ ) (R ²⁷ ). ^{Wherein, R 23} and ^{R 24} represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 6 carbon atoms. R ²⁵ represents an alkylene group having 1 to 6 carbon atoms, and R ²⁶ and R ²⁷ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

Among the above, R ²³ and R ²⁴ in —N (R ²³ ) (R ²⁴ ) are preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and —R ²⁵ —N (R ²⁶ ) (R ^{R 25} of ²⁷⁾ is preferably an alkylene group having 2 to 6 carbon ^{atoms, R 26} and ^{R 27,} preferably an alkyl group having 1 to 4 carbon atoms. m2 and n2 represent 1 or 0, and m2 = 1 and n2 = 1 or m2 = 1 and n2 = 0 are preferable (that is, corresponding to monomers represented by the following general formulas (E3) and (E4)) To do).

  In the present invention, among the monomers represented by the general formula (E2), at least one selected from monomers represented by any of the following general formulas (E3) and (E4) is preferable.

In the general formula (E3), R ³¹ has the same meaning as R ²¹ . R ³² has the same meaning as R ²² . X ³ has the same meaning as X ² .

In the general formula (E4), R ⁴¹ has the same meaning as R ²¹ . X ⁴ is synonymous with X ² , and —N (R ⁴³ ) (R ⁴⁴ ) (where R ⁴³ and R ⁴⁴ are synonymous with R ²³ and R ²⁴ ), or —R ⁴⁵ —. N (R ⁴⁶ ) (R ⁴⁷ ) (where R ⁴⁵ , R ⁴⁶ and R ⁴⁷ have the same meanings as R ²⁵ , R ²⁶ and R ²⁷ , respectively) is preferable.

  Specific examples of the monomer represented by the general formula (E2) include dimethyl (meth) acrylamide, diethyl (meth) acrylamide, diisopropyl (meth) acrylamide, di-n-butyl (meth) acrylamide, and di-i-butyl. (Meth) acrylamide, morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide and N, N-methylphenyl (meth) acrylamide (above (meth) acrylamides); (N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, N-diethylamino) ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth) acrylamide, 3- (N, N -Dimethylamino) propyl (meth) acrylic 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylamide, 6- (N, N-diethylamino) hexyl (meth) acrylamide (aminoalkyl (meth) acrylamides) and the like. It is mentioned as preferable.

(Iii) Polymerizable monomer having an ether group Suitable examples of the polymerizable monomer having an ether group include at least one selected from monomers represented by the following general formula (E1).

In the general formula (E1), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² represents an alkylene group having 1 to 8 carbon atoms. Among them, an alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 2 to 3 carbon atoms is more preferable. X ¹ represents —OR ¹³ or —OCOR ¹⁴ . Here, R ¹³ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a phenyl group substituted with an alkyl group having 1 to 18 carbon atoms. R ¹⁴ represents an alkyl group having 1 to 18 carbon atoms. Moreover, m3 represents 2-200, 5-100 are preferable and 10-100 are especially preferable.

  The polymerizable monomer having an ether group is not particularly limited as long as it has an ether group and is polymerizable, and can be appropriately selected from ordinary ones. For example, polyethylene glycol mono (meth) Examples include acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, polytetramethylene glycol monomethacrylate, etc., and these may be commercially available products or may be appropriately synthesized. Good. Examples of the commercially available products include methoxypolyethylene glycol methacrylate (trade names: NK esters M-40G, M-90G, M-230G (manufactured by Toa Gosei Chemical Co., Ltd.); trade names: BLEMMER PME-100, PME. -200, PME-400, PME-1000, PME-2000, PME-4000 (manufactured by Nippon Oil & Fats Co., Ltd.)), polyethylene glycol monomethacrylate (trade names: BLEMMER PE-90, PE-200, PE- 350, manufactured by NOF Corporation), polypropylene glycol monomethacrylate (trade names: BLEMMER PP-500, PP-800, PP-1000, manufactured by NOF Corporation), polyethylene glycol polypropylene glycol monomethacrylate (trade name) : Bremmer 70PEP-370B, Japan Manufactured by Yushi Co., Ltd.), polyethylene glycol polytetramethylene glycol monomethacrylate (trade name: Blemmer 55PET-800, manufactured by Nippon Oil & Fats Co., Ltd.), polypropylene glycol polytetramethylene glycol monomethacrylate (trade name: Blemmer NHK-5050) , Manufactured by Nippon Oil & Fats Co., Ltd.).

(Iv) Other monomer The graft copolymer may further contain the other monomer as a copolymer unit, and the other monomer is not particularly limited and is appropriately selected depending on the purpose. For example, aromatic vinyl compounds (eg, styrene, α-methylstyrene and vinyltoluene), (meth) acrylic acid alkyl esters (eg, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl) (Meth) acrylate and i-butyl (meth) acrylate), (meth) acrylic acid alkylaryl ester (eg, benzyl (meth) acrylate), glycidyl (meth) acrylate, carboxylic acid vinyl ester (eg, vinyl acetate and propionic acid) Vinyl), vinyl cyanide (eg, (meth) acrylonitrile and And α-chloroacrylonitrile), aliphatic conjugated dienes (eg, 1,3-butadiene and isoprene), (meth) acrylic acid, and the like. Among these, unsaturated carboxylic acid, (meth) acrylic acid alkyl ester, (meth) acrylic acid alkyl aryl ester, and carboxylic acid vinyl ester are preferable.

  As content of this other monomer in the said graft copolymer, 5-70 weight% is preferable, for example. When the content is less than 5% by weight, the physical properties of the coating film may not be controlled, and when it exceeds 70% by weight, the ability as a dispersant may not be sufficiently exhibited.

As a preferred specific example of the graft copolymer,
(11) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,
(12) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminal methacryloylated polystyrene copolymer,

(13) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / methyl (meth) acrylate-terminated methacryloylated polystyrene copolymer,
(14) a copolymer of a copolymer of 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminal methacryloylated methyl (meth) acrylate and 2-hydroxyethyl methacrylate,
(15) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminated methacryloylated methyl methacrylate and 2-hydroxyethyl methacrylate copolymer,
(16) a copolymer of a copolymer of 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminal methacryloylated methyl methacrylate and 2-hydroxyethyl methacrylate,

(17) 3- (N, N-dimethylamino) propylacrylamide / polypropylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,
(18) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol polypropylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,
(19) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol polytetramethylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,
(20) 3- (N, N-dimethylamino) propylacrylamide / polypropylene glycol polytetramethylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer, and the like.
Among these, (11), (14), and (18) are preferable, and a compound represented by the following formula (D4) is more preferable. In formula (D4), Me represents a methyl group.

  The graft copolymer can be obtained, for example, by radical polymerization of the components to be the copolymer units in a solvent. In the radical polymerization, a radical polymerization initiator can be used, and a chain transfer agent (eg, 2-mercaptoethanol and dodecyl mercaptan) can be further used. JP-A-2001-31885 can be referred to for the pigment dispersant containing the graft copolymer.

  In order to further improve the uniform dispersibility and storage stability of the organic nanoparticles, the content of the dispersant is preferably in the range of 0.1 to 1000 parts by mass, more preferably 100 parts by mass 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 organic nanoparticles may not be improved. Moreover, a dispersing agent may be used independently or may be used in combination of multiple things.

  In order to further improve the uniform dispersibility and storage stability of the organic particles, the content of the dispersant is preferably in the range of 0.1 to 1000 parts by mass, more preferably 100 parts by mass of the organic particles. 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 organic nanoparticles may not be improved.

[manufacturing device]
In the production method of the present invention, a preferred embodiment of the production apparatus used for forming the organic nanoparticles will be described, but the present invention is not construed as being limited thereto.

(Manufacturing device example 1)
FIG. 1-1 is a schematic view of a production apparatus used as an embodiment in the production method of the present invention. In FIG. 1, the organic material solution is continuously supplied into the container 11 through the supply pipe 14. Here, a poor solvent 11a is contained in the container 11, and the bulk poor solvent is always convected by the action of stirring.
FIG. 1-2 is a schematic view of a production apparatus used as another more preferable embodiment of the present invention. In the production apparatus of FIG. 1-1, a mixing chamber (stirring region) 13 is provided in a container 11. The mixing chamber 13 is provided below the surface of the poor solvent, and the inside thereof is filled with the poor solvent. The bulk poor solvent in the reaction vessel 11 is always convected by the agitation action in the mixing chamber 13 so as to cross the mixing chamber 13 from below to above (in the direction of the arrow in the figure).

  1-3 is an enlarged partial cross-sectional view schematically showing the mixing chamber 13 in an enlarged manner as an embodiment of the manufacturing apparatus of FIG. 1-2. The organic material solution is supplied into the mixing chamber 13 through the supply pipe 14 from the supply port 14a. The mixing chamber 13 is formed by a casing 17 composed of a rectangular cylinder having a constant cross-sectional area, the upper end of the casing 17 is an open end (open portion), and a circular hole 18 is provided at the lower end. The poor solvent is connected to the bulk poor solvent outside the stirring region (in the configuration shown in the drawing, the region other than the mixing chamber 13 in the poor solvent 11a is outside the stirring region and is also referred to as the non-stirring region). It has become. Here, the organic material solution supply pipe 14 is provided in a wall constituting the lower end of the casing 17 and opens toward the circular hole. A stirring blade 12 is provided in the mixer 13. The stirring blade is attached to a shaft 15 and is rotated by a motor 16. The rotation of the stirring blade 12 causes the poor solvent to constantly circulate through the circular hole 18 in the mixer 13 from below to above.

The stirring blade 12 provided in the mixing chamber 13 must produce a desired mixing strength in the mixing chamber. This mixing strength is presumed to be an important operating factor for the size of the droplet when the organic pigment solution is mixed.
In addition, the stirring blade 12 is formed by organic nanoparticles generated in the mixing space remaining in the mixing chamber 13, so that the stirring blade 12 is combined with other organic nanoparticles to become larger particles, or an organic material supplied to the mixing chamber 13. In order to prevent large particles from being generated by exposure to a solution, the organic nanoparticles that have been generated can be quickly extracted and quickly discharged out of the mixing chamber 13. preferable.
As long as the said objective is achieved as the stirring blade 12, what kind of thing may be sufficient, for example, a turbine type, a fan turbine type, etc. may be used.
Moreover, it is preferable that the casing 17 is comprised by the square cylinder as mentioned above. By doing in this way, the angle of the casing 17 disturbs the flow created by the stirring blade 12, and the mixing effect can be further enhanced without requiring an additional material such as a baffle plate.

  1-4 is an enlarged partial cross-sectional view of a mixer having two stirring blades (mixing stirring blade 19a and discharging stirring blade 19b) in the mixing chamber as another embodiment of the manufacturing apparatus of FIG. 1-2. is there. By providing two stirring blades in this way, the ability to control the mixing strength and the ability to discharge the generated organic pigment particles to the outside of the mixer can be selected independently. It is possible to operate by setting the circulation amount to a desired value independently.

(Manufacturing device example 2)
FIG. 2 is a cross-sectional view schematically showing another embodiment of the production apparatus used in the production method of the present invention. In FIG. 2, the organic material solution and the poor solvent are continuously supplied into the agitation tank 21a through the supply pipes 24 and 25 and the supply ports 24a and 25a, respectively. The organic material particles generated in the agitation tank 21a remain in the agitation tank 21a, so that the organic material particles are combined with other organic pigment particles to become larger particles or exposed to the organic material solution supplied from the supply ports 24a and 25b. The generated organic material particle dispersion is quickly drawn out from the discharge pipe 23 so that the large particles are not generated due to the large particles.

FIG. 3 is a sectional view schematically showing still another embodiment of the apparatus used in the production method of the present invention. In the manufacturing apparatus of FIG. 3, the stirring device 50 includes two supply pipes 32 and 33 having supply ports 32 a and 33 a through which an organic material solution and a poor solvent flow, respectively. And it comprises a pair of stirring blades 41 and 42 as stirring means for controlling the stirring state of the liquid in a cylindrical stirring tank 38 having a liquid discharge port 36 for discharging the mixed liquid after the stirring process. .
The agitation tank 38 includes a cylindrical tank body 39 whose central axis is directed in the vertical direction, and a seal plate 40 serving as a tank wall that closes the upper and lower opening ends of the tank body 39. The agitation tank 38 and the tank body 39 are made of a nonmagnetic material having excellent magnetic permeability. The two liquid supply ports 32 and 33 are provided at positions near the lower end of the tank body 39, and the liquid discharge port 36 is provided at a position near the upper end of the tank body 39.

  Then, the pair of stirring blades 41 and 42 are disposed apart from the upper and lower ends facing each other in the stirring tank 38 and are driven to rotate in opposite directions. Each of the stirring blades 41 and 42 constitutes a magnetic coupling C with an external magnet 46 disposed outside the tank wall (seal plate 40) in which the respective stirring blades 41 and 42 are close to each other. That is, the blades 41 and 42 are coupled to the external magnets 46 by magnetic force, and are rotated in opposite directions by driving the external magnets 46 with independent motors 48 and 49.

A pair of stirring blades 41 and 42 arranged opposite to each other in the tank 38 allows the stirring flows having different directions to flow into the tank 38 as indicated by the wavy arrow (X) and the solid arrow (Y) in FIG. Form. And since the stirring flow which each stirring blade 41 and 42 forms differs in the flow direction, it collides with each other, the high speed turbulent flow which accelerates | stimulates stirring in the tank 38 is produced | generated in the tank 38, Is prevented from becoming steady, and even when the rotation speed of the stirring blades 41 and 42 is increased, the formation of a cavity around the rotation axis of the stirring blades 41 and 42 is prevented, and at the same time, the stirring action is sufficiently achieved. Therefore, it is possible to prevent a disadvantage that a steady flow that flows in the tank 38 along the inner peripheral surface of the stirring tank 38 is formed. Therefore, the processing speed can be easily improved by increasing the speed of rotation of the stirring blades 41 and 42. Further, at this time, the liquid flow in the tank 38 becomes steady, and liquid with insufficient stirring and mixing is obtained. It is possible to prevent discharge and prevent deterioration in processing quality.
In addition, since the stirring blades 41 and 42 in the stirring tank 38 are connected to the motors 48 and 49 disposed outside the stirring tank 38 by the magnetic coupling C, the rotating shaft is attached to the tank wall of the stirring tank 38. Since there is no need for insertion, the stirring tank 38 can be made into a closed container structure without the insertion part of the rotating shaft, so that leakage of the stirred and mixed liquid to the outside of the tank can be prevented and at the same time the lubricating liquid (seal for the rotating shaft) It is possible to prevent deterioration in processing quality due to mixing of the liquid) into the liquid in the tank 38 as an impurity.

In the production method of the present invention, the production apparatus having these configurations can be used to produce organic nanoparticles not only in a batch method but also in a continuous flow method, and can be used for mass production. In addition, since the generated organic nanoparticle dispersion liquid is quickly discharged, the ratio of the organic material solution and the poor solvent liquid supplied into the stirring tank can be always kept constant. For this reason, it becomes possible to make the solubility of the organic material of a dispersion liquid constant from the time of manufacture start to the end of manufacture, and it is possible to stably manufacture monodisperse organic nanoparticles.
Furthermore, the liquid flow in the tank becomes steady and the organic nanoparticle dispersion liquid with insufficient stirring and mixing is prevented from being discharged, and the lubricating liquid (seal liquid) for the rotating shaft is an impurity in the tank. By preventing mixing in the liquid, monodispersed organic nanoparticles can be produced more stably.

(Manufacturing device example 3)
As a device used in the production method of the present invention, a production method in which stirring is performed using blades having shearing force, which is still another embodiment, will be described.
The shearing force referred to in the present invention is a shearing force exerted on the droplets (droplets) generated by the stirring blade after the organic material solution is mixed in the poor solvent.
The shape of the stirring section that can be used in the present invention is not particularly limited as long as it can be subjected to a high shearing force, but generally includes paddle blades, turbine blades, screw blades, fowler blades, etc., preferably dissolver blades, An agitating, emulsifying, and dispersing machine of an agitating part composed of a turbine part that can rotate and a fixed stator part that is positioned with a slight gap around it is preferable.
The dissolver blade is a special stirring blade having a function capable of forming a high shearing force. One example of the dissolver blade is schematically shown in a front view in FIG. 4-1, and a drawing substitute photograph is shown in FIG. 4-2.
Further, an apparatus having a stirring unit composed of a rotatable turbine unit as shown in FIG. 5 and a fixed stator unit positioned with a slight gap around the turbine unit is also preferably used. Examples of the disperser include Hiscotron manufactured by Microtech / Nichion Co., Ltd. and T.K. K homomixer, ULTRA-TURRAX manufactured by IKA Corporation.

  The stirring speed varies depending on the viscosity of the poor solvent, the temperature, the type of surfactant and the amount added, but is preferably 100 to 10000 rpm, more preferably 150 to 8000 rpm, and particularly preferably 200 to 6000 rpm. If the rotational speed is too low, the stirring effect is not sufficiently exhibited. Conversely, if the rotational speed is too high, bubbles are involved in the poor solvent, which is not preferable.

[concentrated]
In the method for producing organic nanoparticles of the present invention, it is possible to produce a concentrated solution suitable for color filter coating liquid and ink-jet ink on an industrial scale by desalting and concentrating the organic nanoparticle dispersion liquid. It is.
Below, the concentration method is demonstrated.
The concentration method is not particularly limited as long as the organic nanoparticle liquid can be concentrated. For example, an extraction solvent is added to and mixed with the organic nanoparticle dispersion, and the organic nanoparticles are concentrated and extracted into the extraction solvent phase. The solution is filtered through a filter or the like to obtain a concentrated nanoparticle solution, the method is to concentrate and concentrate organic nanoparticles by centrifugation, the method is to desalinate and concentrate by ultrafiltration, and the solvent is sublimated by vacuum lyophilization. The method of concentrating, the method of drying and concentrating the solvent by heating or pressure reduction, etc. are preferable. Or a combination thereof is very preferably used.
The concentration of the organic nanoparticles after concentration is preferably 1 to 100% by mass, more preferably 5 to 100% by mass, and particularly preferably 10 to 100% by mass.

Hereinafter, a method of concentration extraction will be described.
The extraction solvent used for the concentration extraction is not particularly limited, but does not substantially mix with the dispersion solvent (for example, an aqueous solvent) of the organic nanoparticle dispersion (in the present invention, substantially does not mix) This means that the solubility is low, preferably 50% by mass or less, and more preferably 30% by mass or less, although there is no particular lower limit to this amount, it is 1% by mass or more considering the solubility of ordinary solvents. However, it is preferably a solvent that forms an interface when allowed to stand after mixing. 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 organic nanoparticles can be redispersed in the extraction solvent. Is preferred. In such a state, it is possible to easily remove the dispersion solvent such as water by filter filtration or the like while wetting the target organic nanoparticles 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 organic nanoparticles can be extracted, but is preferably smaller than the organic nanoparticle dispersion in consideration of concentration and extraction. When this is shown by volume ratio, when the organic 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 by referring 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 organic nanoparticle dispersion. It may be added.

  The apparatus for performing ultrafiltration permeates the tank containing the fatty acid silver dispersion, the circulation pump for circulating the dispersion in the tank, and the by-product inorganic salt in the dispersion introduced by the circulation pump. It is preferable to have an ultrafiltration module that removes as water. The dispersion from which the permeated water is separated is returned to the tank again, and the same operation can be repeated until the predetermined purpose of removing the by-product inorganic salt is achieved. Further, this apparatus is preferably provided with a replenishment pure water measurement flow meter used for replenishing a certain amount of solvent lost by permeate as pure water, and determines the replenishment amount of pure water. It is preferable that a flow meter for measuring permeated water used in is installed. Moreover, it is preferable that a reverse cleaning pump for introducing water for diluting the permeated water is installed.

  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.

  In order to separate the dispersion solvent from the organic nanoparticle dispersion and the concentrated extract, it is preferable to filter. 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 organic nanoparticles in the concentrated extract to obtain a concentrated nanoparticle solution.

  The method of lyophilization is not particularly limited, and any method that can be used by those skilled in the art may be adopted. 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 of lyophilization is not particularly limited, and can be appropriately selected by those skilled in the art. For example, the pressure may be 0.1 to 35 Pa, preferably 1 to 15 Pa, and more preferably about 5 to 10 Pa. 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.

The centrifugation will be described below.
The centrifuge used for concentration of the organic nanoparticles by centrifugation may be any device as long as it can precipitate the organic nanoparticles in the organic nanoparticle dispersion (or the organic nanoparticle concentrated extract). As a centrifuge, for example, in addition to a general-purpose device, a device with a skimming function (a function of sucking the supernatant layer during rotation and discharging it out of the system) or continuous centrifugation for continuously discharging solid matter Machine.
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 will be described below.
The apparatus used for concentration of the organic nanoparticles by drying under reduced pressure is not particularly limited as long as the solvent of the organic nanoparticle dispersion (or organic nanoparticle concentrated extract) 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.

According to the concentration method as described above, the organic nanoparticles can be efficiently concentrated from the organic nanoparticle dispersion. Regarding the concentration ratio, for example, when the concentration of the nanoparticles in the organic nanoparticle dispersion as a raw material is 1, the concentration in the concentrated organic nanoparticle paste is preferably about 100 to 3000 times, more preferably about 500 to 2000 times. Can be concentrated.
[Fine dispersion]
According to the production method of the present invention, the organic particles in an agglomerated state can be finely dispersed, for example, by concentration or the like, if necessary (in the present invention, fine dispersion means the particles in the dispersion liquid). It means to release the agglomeration and increase the degree of dispersion).
The organic particles contained in the organic particle liquid concentrated by the extraction solvent, centrifugation, and drying described above are usually aggregated by the concentration. At this time, in order to enable rapid filter filtration and obtain a good dispersion state again, it is preferable to obtain flocs aggregated to such an extent that they can be redispersed. For this reason, the degree of dispersion using an ordinary dispersion method is insufficient for the formation of fine particles, and a method with higher micronization efficiency is required. Even in such an aggregated organic particle (in the present invention, an aggregated organic particle is a particle in which organic particles such as an aggregate are gathered by a secondary force. When the primary particle is nanometer size, the aggregated nanoparticle The organic particles are suitably finely dispersed by containing a polymer compound having a mass average molecular weight of 1000 or more or a substantially water-insoluble polymer compound in the aggregated organic particle liquid or the pigment dispersion liquid. (In the present invention, the agglomerated organic particle liquid refers to a liquid containing the agglomerated organic particles in the liquid, and even if the agglomerated organic particles are contained even in a dispersion, a concentrated liquid, a paste, a slurry, etc.) Good.)

The polymer compound having a molecular weight of 1000 or more is preferably a water-insoluble polymer compound. Here, substantially water-insoluble means that the solubility in water at 20 ° C. is preferably 0.5% by mass or less, more preferably 0.01% by mass or less.
The polymer compound having a molecular weight of 1000 or more or the water-insoluble 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 (where R ¹⁵ is an alkyl group having 1 to 20 hydrogen atoms, an aryl group having 6 to 20 carbon atoms, or Represents 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.

  Although the mass average molecular weight of the polymer compound used in the production method of the present invention is 1000 or more, the mass average molecular weight is preferably 3000 to 100,000, more preferably 5000 to 80000, and particularly preferably 7000 to 60000. 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.

The polymer compound represented by the general formula (1) (including those represented by the general formula (2)) is not particularly limited, but can be synthesized by the following method. Of the following synthesis methods, the following synthesis methods such as 2, 3, 4, 5 and the like are more preferable, and the following synthesis methods such as 3, 4, 5, and the like are particularly preferable because of ease of synthesis.
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.

  Among the above, the polymer compound (preferably the polymer compound represented by the general formula (2)) used in the production method of the present invention is synthesized, for example, by any one of the above methods 2, 3, 4, and 5. However, from the viewpoint of ease of synthesis, it is more preferable to synthesize by the above method 5.

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

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.

（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 ₁ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

（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 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 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 are And each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, i represents a number of 1 to 5)

（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 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。
本発明の製造方法において分子量とは、特に断らない限り、質量平均分子量をいう。分子量の測定方法としては、クロマトグラフィー法、粘度法、光散乱法、沈降速度法等が挙げられるが、本発明では、特に断らない限りゲルパーミエーションクロマトグラフィー法（キャリア：テトラヒドロフラン）により測定したポリスチレン換算の質量平均分子量を用いる。

(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 1 Represents a number of ~ 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.
In the production method of 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.

The polymer compound having a molecular weight of 1000 or more may be added in a solution dissolved in an aqueous solvent or an organic solvent, in 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 addition of the polymer compound having a molecular weight of 1000 or more is performed during or after the precipitation of organic nanoparticles, during or after concentration, during or after the dispersion of aggregated organic particles after concentration, These may be added at any time, or may be added in multiple portions. In the production method of the present invention, a polymer compound having a mass average 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 at this time.

The addition amount of the polymer compound having a molecular weight of 1000 or more is preferably 0.1 to 1000 parts by mass, more preferably 5 to 500 parts by mass, and more preferably 10 to 300 parts by mass, when the organic nanoparticles are 100 parts by mass. Part is particularly preferred.
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.

  In the method for producing organic nanoparticles of the present invention, the dispersion of organic nanoparticles preferably contains 60% by mass or more of an organic solvent, and more preferably 65% by mass or more. There is no restriction | limiting in particular as an organic solvent, It can select suitably from normal things. For example, an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, an aliphatic compound solvent, and a ketone compound solvent are preferable, and an ester compound solvent and a ketone compound solvent are particularly preferable. These may be used alone or in combination of two or more.

  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. Examples of the ketone compound solvent include methyl ethyl ketone, acetone, and cyclohexanone.

[Organic nanoparticle dispersion composition]
Next, the aspect which makes a composition when organic nanoparticles are used for a color filter, an inkjet ink, etc. is demonstrated in detail, for example. The organic nanoparticles can be used, for example, in a state dispersed in a vehicle. The vehicle refers to a portion of a medium in which a pigment is dispersed when it is in a liquid state, a portion that is liquid and binds to the pigment to harden a coating film (binder). And a component (organic solvent) to be dissolved and diluted. In the present invention, the binder used at the time of nanoparticle formation and the binder used for redispersion may be the same or different, and may be distinguished as a nanoparticle-forming binder and a redispersion binder, respectively. .
The concentration of the organic nanoparticles in the dispersion composition of the organic nanoparticles after redispersion is appropriately determined according to the purpose, but preferably the organic nanoparticles are 2 to 30% by mass with respect to the total amount of the dispersion composition. More preferably, it is 4-20 mass%, and it is especially preferable that it is 5-15 mass%. In the case of being dispersed by the vehicle as described above, the amount of the binder and the dissolved and diluted component is appropriately determined depending on the kind of the organic material, etc. 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 above-described concentrated and extracted nanoparticle liquid, as described above, in order to enable rapid filter filtration, the organic nanoparticles are preferably aggregated by concentration, and concentrated by centrifugation or drying. Aggregation is preferred.
As a method for finely dispersing 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 organic 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 organic particles contained in the organic particle liquid concentrated by the extraction solvent, centrifugation, and drying described above are usually aggregated by the concentration. At this time, in order to enable rapid filter filtration and obtain a good dispersion state again, it is preferable to obtain pigment fine particles as floc. Here, the floc means an aggregate of fine particles that have been weakly aggregated (soft aggregated) to such an extent that they can be redispersed. By making the pigment fine particles floc in this way, for example, the organic pigment fine particles deposited in an aqueous mixed liquid can be quickly separated from the medium by filtration or the like. Thereafter, the flocs are aggregated and re-dispersed in an organic solvent suitable for production of a color filter, whereby an organic solvent-based pigment dispersion composition (non-aqueous dispersion composition) can be efficiently produced. That is, when the mixed solvent of the good solvent and the poor solvent is an aqueous solvent, the dispersion medium (continuous phase) can be switched by efficiently replacing it with a third solvent made of an organic solvent. The average particle size of the floc is not particularly limited, but is preferably 0.5 to 500 μm and more preferably 5 to 100 μm in view of the filterability described above. In the present invention, solvents different from both the good solvent (first solvent) and the poor solvent (second solvent) are collectively referred to as “third solvent”.

<1> Dispersion Method As a preferred method for producing the organic nanoparticle dispersion composition, the viscosity at 25 ° C. after kneading and dispersing the colorant with the resin component is 10,000 mPa · s or more, preferably 100,000 mPa · s or more. So that the viscosity after the fine dispersion treatment is 1,000 mPa · s or less, preferably 100 mPa · s or less. A method of fine dispersion treatment is preferred.
The machines used in the kneading and dispersing treatment are two rolls, three rolls, ball mills, tron mills, dispersers, kneaders, kneaders, homogenizers, blenders, single and twin screw extruders, etc., which disperse while giving a strong shearing force. . Next, a solvent was added, and a vertical or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, a high pressure disperser, etc. were used, and it was made of glass having a particle diameter of 0.1 to 1 mm, zirconia, or the like. Fine dispersion with beads. Furthermore, it is possible to perform a fine dispersion treatment using fine particle beads of 0.1 mm or less. It is also possible to omit the kneading and dispersing process. In that case, beads are dispersed with a pigment, a dispersant or a surface treatment agent, and the acrylic copolymer and solvent in the present invention.
It is also possible to disperse the main pigment and the complementary pigment separately, and then mix the dispersions of the two to add further dispersion treatment, or to disperse the main pigment and the complementary pigment together.
For details on kneading and dispersing, see T.W. C. It is also described in “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964), and this method may be used.

<2> Examples of Dispersing Agent A normal pigment dispersant or surfactant can be added to the organic nanoparticle dispersion composition for the purpose of improving the dispersibility of the organic nanoparticles. As these dispersants, many kinds of compounds are used. For example, a phthalocyanine derivative (commercially available product EFKA-6745 (manufactured by Efka)), Solsperse 5000 (manufactured by Geneca), organosiloxane polymer KP341 ( Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl Nonionic surfactants such as ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; anionic surfactants such as W004, W005, W017 (manufactured by Yusho); EFKA- 46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), Disperse Aid 6, Polymer dispersing agents such as ISPERSIDE 8, DISPERSIDE 15 and DISPERSIDE 9100 (manufactured by San Nopco); Solsols such as Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 Dispersant (manufactured by Zeneca); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka Co., Ltd.) and Isonet S-20 (Sanyo Kasei Co., Ltd.). Further, the pigment dispersant described in JP 2000-239554 A, the compound (C) described in JP-B-5-72943, the compound of Synthesis Example 1 described in JP 2001-31885 A, and the like are also preferably used. Can be used.
It is also preferable to use again the compound shown in the section of [Dispersant] as a dispersant used at the time of redispersion when forming organic nanoparticles.

  In the organic nanoparticle-dispersed composition, the re-dispersed organic nanoparticles (primary particles) can be finely dispersed particles, and the particle size can be preferably 1 to 200 nm, and 2 to 100 nm. More preferred is 5 to 50 nm. Further, the Mv / Mn of the particles after redispersion is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, and 1.0 to 1.5. Is particularly preferred.

According to the production method of the present invention, for example, pigment particles contained in an organic nanoparticle dispersion composition or a colored photosensitive resin composition described later can be reduced to a nanometer size (for example, 10 to 100 nm). Regardless, it can be concentrated and redispersed. For this reason, when used in a color filter, the optical density is high, the filter surface is excellent in uniformity, the contrast is high, and the image noise can be reduced.
Furthermore, the organic nanoparticles contained in the organic nanoparticle dispersion composition and the colored photosensitive composition can be finely dispersed in a highly and uniform manner, so that a high color density can be achieved with a thin film thickness. For example, a color filter or the like can be thinned.
In addition, the organic nanoparticle dispersion composition and the colored photosensitive resin composition are excellent as an image forming material for producing, for example, a color proof or a color filter by including a pigment exhibiting a clear color tone and high coloring power. ing.
Furthermore, for an alkaline developer used for exposure / development in the formation of a colored image, an organic nanoparticle dispersion composition, a colored photosensitive resin composition, a binder (binder) soluble in an alkaline aqueous solution It can be used and can meet environmental requirements.
In addition, organic solvents with adequate drying properties can be used as the solvent (pigment dispersion medium) used in the organic nanoparticle dispersion composition and the colored photosensitive resin composition, and satisfy the requirements in terms of drying after coating. can do.

[Inkjet ink for color filter]
The inkjet ink for a color filter of the present invention contains (a) organic nanoparticles and (b) a polymerizable monomer and / or a polymerizable oligomer. Ink ink for color filter containing (a) organic nanoparticles, (b) polymerizable monomer and / or polymerizable oligomer, (c) binder, and (d) photopolymerization initiator or photopolymerization initiator system Or it is good also as a coloring photosensitive resin composition. Hereinafter, the components (a) to (d) will be described.

(A) Organic nanoparticles The method for producing organic nanoparticles has already been described in detail. The content of the organic nanoparticles is 3 to 90% by mass with respect to the total solid content (in the present invention, the total solid content means the total composition excluding the organic solvent) in the inkjet ink for a color filter. Preferably, 20-80 mass% is more preferable, and 25-60 mass% is further more preferable. If this amount is too large, the viscosity of the dispersion increases, which may cause problems in production suitability. If the amount is too small, the coloring power is not sufficient. 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.

(B) Polymerizable monomer and / or polymerizable oligomer The polymerizable monomer and / or polymerizable oligomer contained in the inkjet ink for a color filter of the present invention has two or more ethylenically unsaturated double bonds, light It is preferable that addition polymerization is carried out by irradiation. 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.

  These polymerizable monomers and / or polymerizable oligomers preferably have a molecular weight of 200 to 1,000, and may be used alone or in admixture of two or more. The content of the ink for a color filter with respect to the total solid content is 5 -50 mass% is common and 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.

(C) Binder As the binder, an acid group-containing binder is preferable, and it can be added during the preparation of the color filter inkjet ink or the colored photosensitive resin composition. Or it is also preferable to add at the time of organic nanoparticle 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 organic nanoparticles. Or it is also preferable to add a binder solution at the time of formation of organic nanoparticles by another system. The binder is preferably an alkali-soluble polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-57-36. A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer as described in JP-A-59-71048 Etc. Moreover, the cellulose derivative which has a carboxylic acid group, carboxylate, etc. in a side chain can also be mentioned, In addition to this, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. As particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate and (meth) acrylic acid are used. And multi-component copolymers with other monomers. These binder polymers having a polar group may be used alone or in the form of a composition used in combination with an ordinary film-forming polymer, and the amount added to 100 parts by mass of the organic nanoparticles is 10%. -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 an alkali (preferably one that can be developed 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 an ordinary film-forming polymer, and the amount added to 100 parts by mass of the organic nanoparticles is 10%. -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 15 to 50 mass with respect to the total solid content of the inkjet ink for color filter or the colored photosensitive resin composition. % Is general and 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.

(D) Photopolymerization initiator or photopolymerization initiator system The photopolymerization initiator or photopolymerization initiator system contained in the inkjet ink for a color filter of the present invention (in the present invention, the photopolymerization initiator system is a plurality of compounds). As a polymerization initiator composition that exhibits a photopolymerization initiation function in combination.), A vicinal polyketaldonyl compound disclosed in US Pat. No. 2,367,660 is described in US Pat. No. 2,448,828. Acyloin ether compounds, aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, polynuclear quinones described in US Pat. Nos. 3,046,127 and 2,951,758 Compound, a combination of triarylimidazole dimer and p-aminoketone described in US Pat. No. 3,549,367 In addition, a benzothiazole compound and a trihalomethyl-s-triazine compound described in JP-B-51-48516, a trihalomethyl-triazine compound described in U.S. Pat. No. 4,239,850, and U.S. Pat. The described trihalomethyloxadiazole compounds and the like can be mentioned. 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 color filter inkjet ink 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.

(Other additives)
〔solvent〕
In the inkjet ink for a color filter 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 Ren glycol 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 inkjet ink for color filters whole quantity.

[Surfactant]
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, it is preferable to contain an appropriate surfactant in the inkjet ink for a color filter from the viewpoint of being able to control to a uniform film thickness and effectively preventing color unevenness due to film thickness fluctuation. .
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.

(Thermal polymerization inhibitor)
The inkjet ink for a color filter 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 inkjet ink for color filter.

[Dyes and pigments used auxiliary
In the ink for a color filter of the present invention, a colorant (dye or pigment) can be added as needed in addition to the colorant (pigment) as long as the effects of the present invention are not impaired. In the case of using a pigment among the colorants, it is desirable that the pigment is uniformly dispersed in the ink-jet ink for a color filter. Therefore, the particle size 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 color filter ink-jet ink.

[Ultraviolet absorber]
The inkjet ink for a color filter of the present invention can 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. The content of the ultraviolet absorber is preferably 5% by mass or less with respect to the total amount of the inkjet ink for color filter.

  In addition, the inkjet ink for a color filter 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-mentioned additives.

In addition, the inkjet ink for a color filter 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-mentioned additives.
In the inkjet ink for color filter of the present invention, 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.

[Blowing inkjet ink for color filter]
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. to the point of obtaining sufficient solvent resistance, alkali resistance, and ultraviolet absorbance. Heating at about 250 ° C. for about 10 minutes to about 120 minutes is preferred.
The pattern shape of the color filter thus formed is not particularly limited, and may be a general black matrix shape such as a stripe shape, a lattice shape, or a delta arrangement. May be.

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

[Coating film of colored photosensitive resin composition]
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, (c) the monomer or 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. (The production of the color filter will be described later). Polymerization of the polymerizable monomer or polymerizable oligomer can be carried out by allowing (d) a photopolymerization initiator or a photopolymerization initiator system to act upon irradiation with light.

(Slit nozzle)
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.

[Photosensitive resin transfer material]
Next, the photosensitive resin transfer material of the present invention will be described.
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 provided with a photosensitive resin by using the above-mentioned colored photosensitive resin composition.

(Temporary support)
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.

(Thermoplastic resin layer)
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.

(Middle layer)
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.

(Protective film)
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.

(Method for producing photosensitive resin transfer 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, the slit-shaped nozzle already demonstrated in the item of the coating film of a coloring photosensitive resin composition was used. It is preferable to use a coating apparatus (slit coater). Preferred specific examples of the slit coater are the same as described above.

[Color filter]
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.

  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.

(Photosensitive resin layer)
The color filter of the present invention can be produced by a method such as a method in which a photosensitive resin layer is formed on a substrate, and exposure and development are repeated for the number of colors. If necessary, the boundary may be divided by a black matrix.
In the above production method, the method for forming the photosensitive resin layer on the substrate includes (a) a method of applying each of the colored photosensitive resin compositions with a normal coating apparatus or the like, and (b) the above-described method. Examples thereof include a method of using a photosensitive resin transfer material and affixing with a laminator.

(A) Application by coating apparatus When the color filter of the present invention is produced, a normal coating apparatus can be used for coating the colored photosensitive resin composition. The slit coater described in the section of [Coating film] can be suitably used. The preferred specific example of the slit coater is the same as described above. When the photosensitive resin layer is formed by coating, the film thickness is preferably 1.0 to 3.0 μm, more preferably 1.0 to 2.5 μm, and particularly preferably 1.5 to 2.5 μm.

(B) Affixing with a laminator A photosensitive resin transfer material of the present invention is used to press-bond or bond a photosensitive resin layer formed in a film shape with a roller or flat plate heated and / or pressurized on a substrate to be described later. It can be attached by thermocompression bonding. Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From this point of view, it is preferable to use the method described in JP-A-7-110575. In addition, the preferable film thickness in the case of forming the photosensitive resin layer with the photosensitive resin transfer material of the present invention is the same as the preferable film thickness described in the section of [Photosensitive resin transfer material].

(substrate)
In the present invention, as the substrate on which the color filter is formed, for example, a transparent substrate is used, a glass plate such as a soda glass plate having a silicon oxide film on its surface, a low expansion glass, a non-alkali glass, a quartz glass plate, or the like. And a plastic film.
Moreover, the said board | substrate can make favorable adhesion | attachment with a coloring photosensitive resin composition or the photosensitive resin transfer material by giving a coupling process previously. As the coupling treatment, a method described in JP 2000-39033 A is preferably used. In addition, although it does not necessarily limit, as a film thickness of a board | substrate, 700-1200 micrometers is generally preferable and 500-1100 micrometers is especially preferable.

(Oxygen barrier membrane)
In the color filter of the present invention, when the photosensitive resin layer is formed by applying a colored photosensitive resin composition, an oxygen-blocking film can be further provided on the photosensitive resin layer, thereby improving the exposure sensitivity. Can be up. Examples of the oxygen blocking film include those already described in the section of (Interlayer) of [Photosensitive resin transfer material]. Although not particularly limited, the thickness of the oxygen blocking film is generally preferably 0.5 to 3.0 μm.

(Exposure and development)
A predetermined mask is disposed above the photosensitive resin layer formed on the substrate, and then exposed from above the mask through the mask, the thermoplastic resin layer, and the intermediate layer, and then developed with a developer. By repeating this process for the number of colors, the color filter of the present invention can be obtained.
Here, the light source for the exposure can be appropriately selected and used as long as it can irradiate light in a wavelength region capable of curing the photosensitive resin layer (for example, 365 nm, 405 nm, etc.). Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. As an exposure amount, it is about 5-200 mJ / cm < ² > normally, Preferably it is about 10-100 mJ / cm < ² >.

Moreover, there is no restriction | limiting in particular as said developing solution, Normal developing solutions, such as a thing of Unexamined-Japanese-Patent No. 5-72724, can be used. The developer is preferably one in which the photosensitive resin layer exhibits a dissolution type development behavior. For example, a developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L is preferable. A small amount of a miscible organic solvent may be added.
Examples of organic solvents miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, and benzyl alcohol. , Acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like. The concentration of the organic solvent is preferably 0.1% by mass to 30% by mass.
Further, a normal surfactant can be further added to the developer. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.

As a development method, methods such as paddle development, shower development, shower & spin development, and dip development can be used.
Here, the shower development will be described. The uncured portion can be removed by spraying a developer onto the exposed photosensitive resin layer by shower. In addition, it is preferable to spray an alkaline liquid having low solubility of the photosensitive resin layer by a shower or the like before development to remove the thermoplastic resin layer, the intermediate layer, or the like. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like.
The liquid temperature of the developer is preferably 20 ° C. to 40 ° C., and the pH of the developer is preferably 8 to 13.

In addition, when manufacturing the color filter of the present invention, as described in JP-A No. 11-248922 and Japanese Patent No. 3255107, a base is formed by overlapping the colored photosensitive resin composition forming the color filter, It is preferable from the viewpoint of cost reduction that a transparent electrode is formed thereon and a spacer is formed by further stacking projections for split orientation.
When the colored photosensitive resin composition is sequentially applied and stacked, the film thickness becomes thin each time the coating is performed due to the leveling of the coating solution. For this reason, it is preferable to overlap the four colors of K (black), R, G, and B, and further overlap the divisional alignment protrusions. On the other hand, in the case of using a transfer material having a thermoplastic resin layer, it is preferable that three or two colors be overlapped because the thickness is kept constant.
Further, the size of the base is preferably 25 μm × 25 μm or more, and particularly preferably 30 μm × 30 μm or more, from the viewpoint of preventing deformation of the photosensitive resin layer when the transfer material is laminated and laminating and maintaining a certain thickness.

[Liquid Crystal Display]
The liquid crystal display device of the present invention uses the color filter of the present invention having excellent 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.

[CCD device]
The CCD device of the present invention comprises a color filter produced using organic nanoparticles obtained by the production method of the present invention. Hereinafter, each material used for making the CCD device of the present invention will be described first.
The alkali-soluble resin used in the CCD device is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, as described in JP-A-59-53836 and JP-A-59-71048, There are maleic acid copolymers, partially esterified maleic acid copolymers, and the like, and similarly there are acidic cellulose derivatives having a carboxylic acid in the side chain. In addition, a polymer in which an acid anhydride is added to a polymer having a hydroxyl group is also useful. Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers with benzyl (meth) acrylate / (meth) acrylic acid / and other monomers are preferred. In addition, 2-hydroxyethyl methacrylate, polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like are also useful as the water-soluble polymer.

  Further, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl described in JP-A-7-140654 Methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc. It is done. As addition amount in the curable composition of the said alkali-soluble resin, 5-90 mass% is preferable with respect to the composition total mass, More preferably, it is 10-60 mass%.

  The polymerizable monomer is preferably a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure.

  Compounds having at least one addition-polymerizable ethylenically unsaturated group and a boiling point of 100 ° C. or higher at normal pressure include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth). Monofunctional acrylates and methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, (Acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, and then (meth) acrylate after addition of ethylene oxide or propylene oxide, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034 And urethane acrylates as described in JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid can be mentioned. Furthermore, the Japan Adhesion Association Vol. 20, no. 7, what is introduced as a photocurable monomer and oligomer on pages 300 to 308 can also be used.

  Moreover, the compound shown by the following general formula (B-1) or (B-2) can also be used.

{Wherein (B-1), (B -2), B are each _{independently, - (CH 2 CH 2 O} ) - and _{- (CH 2 CH (CH 3} ) O) - represents one of; Each X independently represents any one of an acryloyl group, a methacryloyl group and a hydrogen atom, and in the formula (B-1), the total of the acryloyl group and the methacryloyl group is 5 or 6, and the formula (B -2) is 3 or 4, each n independently represents an integer of 0-6, and the sum of each n is 3-24; m is each independently 0-6 It represents an integer, and the total of each m is 2-16. }

  These polymerizable monomers can be used in any ratio as long as they can form a coating film having adhesiveness upon irradiation with radiation. The amount used is usually 5 to 90% by mass, preferably 10 to 50% by mass, based on the total solid content of the composition.

  As the colorant, various dyes, inorganic pigments or organic pigments can be used singly or in combination.

  There is no restriction | limiting in particular in dye, A well-known dye can be used for color filters conventionally. For example, JP-A 64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, Toho 2592207, U.S. Pat. No. 4,808,501, U.S. Pat. No., U.S. Pat. No. 505950, U.S. Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, etc. Can be used. As chemical structure, dyes such as pyrazole azo, anilino azo, triphenyl methane, anthraquinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine are used. it can. In particular, since the curable composition can be cured at a relatively low temperature, even a dye that is inferior in heat resistance compared to a pigment can be used at a high temperature during post-baking to impart durability to the cured film. It is possible to reduce problems such as decomposition even when exposed to water.

  Examples of inorganic pigments are metal compounds such as metal oxides and metal complex salts. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony And composite oxides of the above metals.

  Examples of organic pigments include C.I. I. Pigment Yellow 11, 24, 31, 53, 83, 85, 99, 108, 109, 110, 138, 139, 150, 151, 154, 167, 185, C.I. I. Pigment Orange 36, 38, 43, 71, C.I. I. PigmentRed 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 224, 242, 254, C.I. I. PigmentViolet 19, 23, 32, 39, C.I. I. Pigment Blue 1, 2, 15, 16, 22, 60, 66, 15: 3, 15: 6, C.I. I. PigmentGreen 7, 36, 37, C.I. I. Pigment Brown 25, 28, C.I. I. Pigment Black 1, 7 and carbon black.

  These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples are shown below. As the red pigment, an anthraquinone pigment, perylene pigment alone or a mixture of at least one of them with a disazo yellow pigment or an isoindoline yellow pigment is used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177 and perylene pigments include C.I. I. Pigment Red 155, and C.I. I. Pigment yellow 83 or C.I. I. Good mixing with Pigment Yellow 139. The mass ratio of the red pigment to the yellow pigment is preferably from 100: 5 to 100: 50. In this range, the light transmittance from 400 nm to 500 nm can be suppressed, and the color purity can be increased, which is preferable.

  As the green pigment, a halogenated phthalocyanine pigment alone or a mixture with a disazo yellow pigment, a quinophthalone yellow dye or an isoindoline yellow pigment is used. I. Pigment Green 7, 36, 37 and C.I. I. Mixing with pigment yellow 83, 138, 139 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 100. Within this range, light transmittance from 400 nm to 450 nm can be suppressed, and good color purity can be obtained.

  As the blue pigment, a phthalocyanine pigment alone or a mixture with a dioxazine purple pigment is used. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 50. Within this range, the light transmittance from 400 nm to 420 nm can be suppressed and the color purity can be increased.

  Further, a pigment-containing photosensitive resin having good dispersibility and dispersion stability by using a powdered processed pigment in which the above pigment is finely dispersed in an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate copolymer, an ethyl cellulose resin, or the like. Can be obtained.

  Further, as the pigment for the black matrix, carbon, titanium oxide, iron oxide, alone or a mixture thereof is used, and the case of carbon and titanium oxide is preferable. The mass ratio is preferably in the range of 100: 5 to 100: 40. Within this range, the light transmittance at long wavelengths is small, and the dispersion stability is also good.

  Examples of the solvent include 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, and lactic acid. 3 such as ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate -Oxypropionic acid alkyl esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxypropion Ethyl, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy-2- Methyl methyl propionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, Methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like: ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether Ter, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and the like; aromatic hydrocarbons such as toluene and xylene.

  Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, 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. The addition amount of the solvent is usually 60 to 90% by mass, preferably 70 to 90% by mass in the composition.

  These solvents may be used alone or in combination of two or more.

  Furthermore, a sensitizer can be used in combination. Specific examples thereof include 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-anthrone, and 9,10-anthraquinone. 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyryl Examples thereof include ketones, p- (dimethylamino) phenyl-p-methylstyryl ketone, benzoanthrone, and benzothiazole compounds described in Japanese Patent Publication No. 51-48516.

  It can be prepared by mixing and dispersing the above main components and other additives used as necessary using various mixers and dispersers.

  A general manufacturing method of a color filter used in a CCD device is as follows. The step of applying and drying the composition (color resist solution) of the present invention on a substrate, the step of pattern exposure of the resulting dry coating film with an i-line stepper, the step of alkali development after exposure, and the step of heat treatment A color filter is obtained by sequentially performing the above steps and successively repeating the above steps for each color (three colors or four colors) to produce a cured film.

  More specifically, the above curable composition is applied onto a suitable substrate by a spinner or the like so that the film thickness upon drying is generally 0.1 to 5 μm, preferably 0.2 to 2 μm. And left in an oven at 85 ° C. for 2 minutes to obtain a smooth coating film.

  The substrate is not particularly limited, but is a glass plate, a plastic plate, an aluminum plate, a base material for electronic parts such as a silicon wafer for an image pickup device, a transparent resin plate, a resin film, a cathode ray tube display surface, a light receiving surface for image sensing feeling. Wafers with solid-state image sensors such as CCD, BBD, CID, BASIS, contact image sensors using thin film semiconductors, liquid crystal display surfaces, color electrophotographic photoreceptors, substrates for electrochromy (EC) display devices Etc. Further, it is preferable to perform a high adhesion treatment to improve the adhesion to the color filter layer on the substrate. Specifically, a pattern of the curable composition may be formed after thinly coating with a silane coupling agent or the like on the substrate in advance, or a silane coupling agent may be included in the curable composition in advance.

  In addition, when there exists a level | step difference on a board | substrate, after applying the planarization film | membrane for eliminating the level | step difference and smoothing a coating surface on a board | substrate, the curable composition of this invention can be apply | coated. . For example, an image sensor such as a CCD is composed of a photoelectric conversion unit (photodiode) that generates electrons on a silicon substrate according to the amount of received light, and a read gate unit for outputting the generated electrons. If light hits the gate part, it causes noise and accurate data is not output.Therefore, a light shielding film layer is formed on the top of the readout gate part, and there is a step between the photodiode part without the light shielding film layer. It may have occurred. When a color resist is applied on such a step and a color filter is directly formed, the optical path length becomes long, so that the image becomes dark and the light condensing property becomes inferior. In order to improve this, it is preferable to form a transparent flattening film between the CCD and the color filter in order to fill the step. Examples of the material for the flattening film include a photo-curable resist solution, a thermosetting resin such as an acrylic type and an epoxy type.

  After applying the photocurable composition, pre-baking is usually performed to evaporate the solvent and obtain a dry coating film. Examples of the pre-baking method include reduced-pressure drying, indirect heating drying using high-temperature air, direct heating drying using a hot plate or the like (about 80 to 140 ° C., 50 to 200 seconds), and the like. In addition, post-baking is performed in order to sufficiently cure the pattern obtained after development to increase the mechanical strength and form a permanent film. For example, when a three-color filter is manufactured, the first formed pattern is then subjected to application, exposure, and development of another color resist solution twice. At this time, post-baking is performed so as not to cause pattern omission due to color mixing with the applied resist solution, exposure, and development. This post-baking uses the same method as pre-baking, but is performed at a higher temperature and for a longer time than the pre-baking conditions. For example, in the case of indirect heating by an oven, the heating is performed at about 180 to 250 ° C. for about 0.5 to 2 hours, and in the case of direct heating by a hot plate, the heating is performed at about 180 to 250 ° C. for about 2 to 10 minutes.

  Although the light source for exposure is not particularly limited, i-line of a mercury lamp can be cited as a light source that has a remarkable effect on the pattern forming property. The feature of the present invention is particularly remarkable in the production of a color filter for an image sensor in which i-line, which is one of the line spectrum of a mercury lamp, is used from an appropriate aspect of the process, but it can also be used for an LCD. Of course.

  There is no restriction | limiting in particular in the developing solution used for image development of a curable composition, A normal developing solution can be used. Of these, organic alkaline developers of quaternary ammonium salts such as tetramethylammonium hydroxide (TMAH) are preferred.

  As the polymerization initiator, a normal photopolymerization initiator can be used. Specifically, the vicinal polykettle aldonyl compound described in US Pat. No. 2,367,660, the α described in US Pat. Nos. 2,367,661 and 2,367,670 Carbonyl compounds, acyloin ethers described in US Pat. No. 2,448,828, aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, US Polynuclear quinone compounds described in Patent Nos. 3,046,127 and 2,951,758, and triallylimidazole dimer / p-aminophenyl ketone described in US Pat. No. 3,549,367. Examples thereof include benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-B 51-48516.

  The content of the photopolymerization initiator (including the above-described ordinary photopolymerization initiator) in the dye-containing negative curable composition is 0.01 to 50 with respect to the solid content (mass) of the radical polymerizable monomer. % By mass is preferable, 1 to 30% by mass is more preferable, and 1 to 20% by mass is particularly preferable. When the content is in the above range, sufficient polymerization and curing can be performed, and the polymerization does not proceed easily, and the polymerization rate increases but the molecular weight does not decrease and the film strength does not decrease.

Moreover, a sensitizer and a light stabilizer can be used in combination with the above photopolymerization initiator.
Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, and 2-ethyl-9-anthrone. 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2- Methoxyxanthone, 2-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyryl ketone, p- (dimethyl Amino) phenyl-p-methylstyryl ketone Examples include benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, tinuvin 1130, 400, and the like. It is done.

  According to the production method of the present invention, it is possible to efficiently obtain organic nanoparticles miniaturized to a nanometer size, and further to obtain organic nanoparticles that are nano-sized and highly monodispersed. Further, according to the production method of the present invention, when preparing an organic particle dispersion, nanoparticles can be obtained by concentrating as necessary, and even aggregated particles in the concentrate can be efficiently dispersed. Organic nanoparticles can be obtained. Furthermore, according to the production method of the present invention, organic nanoparticles suitable for color filter coating liquids and inkjet inks and dispersions thereof can be produced on an industrial scale. In addition, the color filter using the organic nanoparticles of the present invention has the desired color purity and high contrast, is excellent in weather resistance, and its liquid crystal display device is black and has good reproducibility and improved display unevenness. There is an excellent effect of being able to.

The present invention will be described below in more detail based on examples, but the present invention is not limited thereto.
Example 1
(Example 1-1)
1000 ml of dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.), 50.0 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.) 85.0 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. 2 mPa · s. Separately, 1500 ml of water containing 16 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 1500 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.). NP-KX-500 Injection was performed using a large-capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.). The pigment solution A has a flow path diameter and a supply port diameter of 0.8 mm, the supply port is placed in a poor solvent, and 100 ml is injected at a flow rate of 100 ml / min to form organic pigment particles. A was prepared. The number average particle diameter Mn and monodispersity (Mv / Mn) of this pigment dispersion were measured using Nanotrac UPA-EX150 (trade name, manufactured by Nikkiso Co., Ltd.). The results are shown in Table 1-A below.

The pigment nanoparticle dispersion prepared in the above procedure was concentrated for 90 minutes at 5000 rpm using an H-112 type centrifugal filter manufactured by Kokusan Co., Ltd. and a P89C type cloth manufactured by Shikishima Canvas Co., Ltd. The pigment nanoparticle concentrated paste was recovered.
It was 16.4 mass% when the pigment content rate of the paste was measured using the Agilent 8453 type | mold spectrophotometer. 0.1 g of Pigment Dispersant A (Exemplary Compound (7.) of Compound Represented by General Formula (D1)) Synthesized in accordance with JP-A-2000-239554 with 50.0 cc of ethyl lactate, and polymer compound C-1 The solution added with 2.6 g is added to 14.5 g of the pigment nanoparticle concentrated paste, stirred at 1500 rpm for 60 minutes with a dissolver, then added with 25.0 cc of ethyl acetate, and further stirred at 500 rpm for 10 minutes with a dissolver. By using a FP-010 type filter manufactured by Sumitomo Electric Fine Polymer, Inc., a pasty concentrated pigment liquid A (nano pigment concentration of 35.8% by mass) was obtained.

Using the paste-like concentrated pigment liquid A, a pigment dispersion composition A having the following composition was prepared.
The paste-like concentrated pigment liquid A 18.0 g
1,3 Butylene glycol diacetate 46.3g

  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.

(Example 1-2)
Similar to Example 1-1, except that the flow path diameter and the supply port diameter of the liquid supply pipe when injecting the pigment solution A in Example 1-1 were changed to 0.50 mm and the injection flow rate was changed to 50 ml / min. Thus, a pigment dispersion composition B was prepared. The number average particle diameter and monodispersity of the pigment dispersion B prepared at that time were measured in the same manner as in Example 1-1.

(Example 1-3)
A pigment dispersion composition C was prepared in the same manner as in Example 1-1 except that the injection flow rate when injecting the pigment solution A in Example 1-1 was changed to 50 ml / min. The number average particle diameter and monodispersity of the pigment dispersion C prepared at that time were measured in the same manner as in Example 1-1.

(Example 1-4)
Similar to Example 1-1, except that the flow path diameter and the supply port diameter of the liquid feed pipe when injecting the pigment solution A in Example 1-1 were changed to 2.20 mm and the injection flow rate was changed to 400 ml / min. Thus, a pigment dispersion composition D was prepared. The number average particle diameter and monodispersity of the pigment dispersion D prepared at that time were measured in the same manner as in Example 1-1.

(Example 1-5)
Similar to Example 1-1, except that the flow path diameter and the supply port diameter of the liquid feeding pipe when injecting the pigment solution A in Example 1-1 were changed to 10.0 mm and the injection flow rate was changed to 1000 ml / min. Thus, a pigment dispersion composition E was prepared. The number average particle diameter and monodispersity of the pigment dispersion E prepared at that time were measured in the same manner as in Example 1-1.

(Example 1-6)
Instead of the polymer compound C-1 used in preparing the pigment dispersion A, 5.75 g of a methacrylic acid / benzyl methacrylate copolymer (molar ratio 28/72 mass average molecular weight 30,000 40% 1-methoxy-2 -Pigment dispersion composition F was prepared in the same manner as in Example 1-1 except that the amount of 1,3-butylene glycol diacetate was changed to 42.85 g. The number average particle diameter and monodispersity of the pigment dispersion F prepared at that time were measured in the same manner as in Example 1-1.

(Example 1-7)
Instead of the NP-KX-500 type large-capacity non-pulsating pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.) used in the preparation of Pigment Dispersion A, a high-pressure pump (Maruyama Excel Co., Ltd .; manufactured by MNT6107) was used. The pigment dispersion composition was the same as in Example 1-1 except that the flow path diameter and the supply port diameter of the liquid feeding pipe when the pigment solution A was injected were changed to 0.8 mm and the injection flow rate was changed to 1800 ml / min. Q was prepared. The number average particle diameter and monodispersity of the pigment dispersion Q prepared at that time were measured in the same manner as in Example 1-1.

(Example 1-8)
A pigment dispersion composition R was prepared in exactly the same manner as in Example 1-1 except that the injection speed at the time of injecting the pigment solution A in preparing the pigment dispersion Q was 1500 ml / min. The number average particle diameter and monodispersity of the pigment dispersion R prepared at that time were measured in the same manner as in Example 1-1.

(Comparative Example 1-1)
The same as Example 1-1 except that the flow path diameter and the supply port diameter of the liquid supply pipe when injecting the pigment solution A in Example 1-1 were changed to 0.25 mm and the injection flow rate was changed to 5 ml / min. Thus, a pigment dispersion composition G was prepared. The number average particle diameter and monodispersity of the pigment dispersion G prepared at that time were measured in the same manner as in Example 1-1.

(Comparative Example 1-2)
Similar to Example 1-1, except that the flow path diameter and the supply port diameter of the liquid supply pipe when injecting the pigment solution A in Example 1-1 were changed to 0.50 mm and the injection flow rate was changed to 20 ml / min. Thus, a pigment dispersion composition H was prepared. The number average particle diameter and monodispersity of the pigment dispersion H prepared at that time were measured in the same manner as in Example 1-1.

(Comparative Example 1-3)
A pigment dispersion composition I having the following composition was prepared using a bead mill disperser as described below.
Pigment (Pigment Red 254) 6.43g
Pigment dispersant A 0.26g
Polyvinylpyrrolidone 7.10g
Methacrylic acid / benzyl methacrylate copolymer * 14.9 g
(* Molar ratio 28/72, mass average molecular weight: 30,000,
40% 1-methoxy-2-propyl acetate solution)
1,3 Butylene glycol diacetate 35.80 g

(Comparative Example 1-4)
A pigment dispersion composition J having the following composition was prepared as follows.
Pigment (Pigment Red 254) 6.43g
Sodium chloride 64.0g
Methacrylic acid / benzyl methacrylate copolymer * 14.9 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 500 parts by mass of 1% aqueous hydrochloric acid 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) for 1 hour at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm. A pigment dispersion composition J was obtained.

The obtained pigment dispersion compositions A to J, Q, and R were each applied onto a glass substrate so as to have a thickness of 2.0 μm, thereby preparing samples. As a backlight unit, a three-wavelength cold cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) with a diffusion plate installed was used, and two polarizing plates (polarizing plates HLC2-2518 manufactured by Sanritsu Co., Ltd.) were used. ), The amount of transmitted light when the polarization axis is parallel and vertical is measured, and the ratio is defined as the contrast (“1990 Seventh Color Optical Conference, 512-color display 10. 4 ”size TFT-LCD color filter, planting, Koseki, Fukunaga, Yamanaka etc.). 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 number average particle diameters and monodispersities of the pigment dispersions A to J, Q, and R are shown in Table 1-A together with the Reynolds number at the time of particle formation determined by the formula (1), and the pigment dispersion compositions A to J The contrast is shown in Table 1-B. Unlike the comparative example, the particles (Examples 1-1 to 1-8) produced by the production method of the present invention have a small particle size, good monodispersibility, and extremely high dispersion contrast. You can see that Furthermore, among Examples 1-1 to 1-8, pigment dispersion compositions (Examples 1-1 to 1-5 and 7, 8) using the compound represented by the general formula (1) It can be seen that the contrast value is high. In Examples 1-1 to 1-5 and 7, 8, 1-1, 2, 4, 5, 7, and 8 having a Reynolds number of 100 or more have a smaller particle size. Further, among Examples 1-1, 2, 4, 5, 7, and 8, Examples 1-1, 2, 4, 5, and 8 having a Reynolds number of 2500 or less, and monodispersity is further good. It turns out that it shows high light resistance.

(Example 2)
(Example 2-1)
<Production of liquid crystal display device>
[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. Furthermore, a light-shielding resin composition K1 having the composition described in Table 2-A below is applied and dried, and a thermoplastic resin layer having a dry film thickness of 15 μm on the temporary support and a dry film thickness is formed. A 1.6 μm intermediate layer and a light-shielding resin layer having a dry film thickness of 2.4 μm were 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 solution for thermoplastic resin layer: Formulation H1
Methanol 11.1 parts by mass Propylene glycol monomethyl ether acetate 6.4 parts by mass Methyl ethyl ketone 52.4 parts by mass Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) )
= 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, 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 (made 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.))
_{· C 6 F 13 CH 2 CH} 2 OCOCH = CH 2: 40 parts by weight and _{H (OCH (CH 3) CH} 2) 7 OCOCH = CH 2: 55 parts by mass of _{H (OCH 2 CH 2) 7} OCOCH = CH 2 : With 5 parts by mass
Copolymer (molecular weight 30,000) 30 parts by mass / methyl ethyl ketone 70 parts by mass

* Coating solution 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

[Table 2-A]
--------------------------------------
K pigment dispersion 1 25 parts by weight Propylene glycol monomethyl ether acetate 8.0 parts by weight Methyl ethyl ketone 53 parts by weight Binder 1 9.1 parts by weight Hydroquinone monomethyl ether 0.002 parts by weight DPHA solution 4.2 parts by weight Polymerization initiator A 0. 16 parts by mass Surfactant 1 0.044 parts by mass ----------------------------------- −

  The resin composition K1 having a light-shielding property is first weighed K pigment dispersion 1 and propylene glycol monomethyl ether acetate, mixed at a temperature of 24 ° C. (± 2 ° C.) and stirred at 150 rpm for 10 minutes, and then binder 1 and hydroquinone monomethyl. Ether, DPHA liquid, polymerization initiator A (2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethyl) amino-3′-bromophenyl] -s-triazine), Surfactant 1 was weighed out, added in this order at a temperature of 25 ° C. (± 2 ° C.), and stirred at a temperature of 40 ° C. (± 2 ° C.) at 150 rpm for 30 minutes.

Of the compositions described in Table 2-A,
* The composition of K pigment dispersion 1 is
Carbon black (Degussa, trade name Special Black 250) 13.1 parts by mass Pigment dispersant A 0.65 parts by mass Polymer (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

* The 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

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

  The surfactant 1 is the same as the surfactant 1 used in the thermoplastic resin layer coating solution H1.

[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, with a triethanolamine developer (2.5% triethanolamine-containing, nonionic surfactant-containing, polypropylene-based antifoamer-containing, trade name: T-PD1, manufactured by Fuji Photo Film Co., Ltd.) Shower development was performed at 30 ° C. for 50 seconds and 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 (0.06 mol / liter sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer, trade name: Using T-CD1, Fuji Photo Film Co., Ltd., shower developing at 29 ° C. for 30 seconds and cone-type nozzle pressure of 0.15 MPa, developing a light-shielding resin layer, and patterning separation wall (a partition wall pattern having a light-shielding property) )

Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent and stabilizer, trade name “T-SD1 (manufactured by Fuji Photo Film Co., Ltd.)”), 33 ° C., 20 seconds, cone type Residue removal was performed with a rotary brush having a shower and nylon hair at a nozzle pressure of 0.02 MPa 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 ink-jet ink for a color filter was prepared according to the following formulation with reference to Example 1 of JP-A-2002-201387.

  Regarding the mixing of each component in Table 2-B, first, the pigment and the polymer dispersant were added to a part of the solvent, mixed, and stirred using a three roll and bead mill to obtain a pigment dispersion. On the other hand, other blending components were added to the remainder of the solvent, and dissolved and dispersed by stirring to obtain a binder solution. Then, while adding the pigment dispersion or the pigment dispersion composition little by little to the binder solution, the mixture was sufficiently stirred with a dissolver to prepare an inkjet ink for a color filter.

[Pixel formation]
The R ink 1, G ink 1, and B ink 1 obtained above were first ejected into a recess surrounded by a light-shielding partition as follows using a piezo type head. And the color filter of this invention was obtained as follows.
The head has a nozzle density of 150 per 25.4 mm, and has 318 nozzles. By fixing these two nozzles in the nozzle row direction with a shift of 1/2 the nozzle interval, 25 heads are arranged on the substrate in the nozzle array direction. . 300 drops per 4 mm.
The head and ink are controlled so that the vicinity of the ejection portion is 50 ± 0.5 ° C. by circulating hot water in the head.
Ink ejection from the head is controlled by a piezo drive signal applied to the head, and ejection of 6 to 42 pl per drop is possible. In this embodiment, the head is moved while the glass substrate is conveyed at a position 1 mm below the head. More drops. The conveyance speed can be set in the range of 50 to 200 mm / s. The piezo drive frequency can be up to 4.6 kHz, and the droplet ejection amount can be controlled by these settings.

Each of R, G, and B is desired by controlling the conveying speed and the driving frequency so that the coating amount of the pigment is 1.1 g / m ² , 1.8 g / m ² , and 0.75 g / m ^2. R, G, and B inks were ejected into the recesses corresponding to R, G, and B.
The ejected ink is conveyed to an exposure unit and exposed by an ultraviolet light emitting diode (UV-LED). NCCU033 (trade name) manufactured by Nichia Corporation was used as the UV-LED. This LED outputs ultraviolet light having a wavelength of 365 nm from one chip. When a current of about 500 mA is applied, light of about 100 mW is emitted from the chip. A plurality of these are arranged at intervals of 7 mm, and a power of 0.3 W / cm ² can be obtained on the surface. The exposure time after the droplet ejection and the exposure time can be changed according to the medium transport speed and the distance between the head and the LED transport direction. After landing, the film was dried at 100 degrees for 10 minutes and then exposed.
Depending on the setting of the distance and the conveyance speed, the exposure energy on the medium can be adjusted between 0.01 and 15 J / cm ² . The exposure energy was adjusted according to the conveyance speed.
A spectroradiometer URS-40D (trade name) manufactured by USHIO ELECTRIC CO., LTD. Was used for measurement of these exposure power and exposure energy, and a value obtained by integrating the wavelength between 220 nm and 400 nm was used.
The glass substrate after droplet ejection was baked in an oven at 230 ° C. for 30 minutes, so that both the light-shielding partition and each pixel were completely cured.

[Production of liquid crystal display devices]
A liquid crystal display device was produced using the produced color filter (referred to as color filter A), 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 configured and arranged on the back side of the liquid crystal cell provided with the polarizing plate. did.

  The color filters B to J, Q are exactly the same as the color filter A and the liquid crystal display device A, except that the R ink 1 used for manufacturing the liquid crystal display device A from the color filter A is changed to R inks 2 to 12, respectively. , R and liquid crystal display devices B to J, Q, R were produced.

<Evaluation of ink and liquid crystal display device>
[Measurement of contrast]
The contrast of the inkjet inks A to J, Q, and R was measured in the same manner as in Example 1.
[Long time display test of liquid crystal display]
The produced liquid crystal display device is continuously displayed for 1000 hours, and the illuminance meter UV-M10-S [Co., Ltd.] is placed at a position of 400 mm on the screen of the liquid crystal display device in the dark room. ) (Oak Manufacturing Co., Ltd.) was set and measured at a measurement angle of 2 °, and the relative value (illuminance after test / illuminance before test) before and after the test of each example and comparative example was determined as the pigment dispersion composition. Table 2-C shows the contrast data.
From the results, it can be seen that the ink-jet ink for color filter of the present invention shows not only high contrast but also excellent long-term display resistance as a color filter of a liquid crystal display device.

(Example 3)
(Example 3-1)
The pigment dispersion composition A was mixed with other components so as to have the composition shown in Table 3-1 below to prepare a colored photosensitive resin composition A for color filters.

[Table 3-1]
--------------------------------------
Pigment dispersion composition A 44.5 parts by mass Propylene glycol monomethyl ether acetate 7.6 parts by mass Methyl ethyl ketone 37 parts by mass Binder 2 0.7 parts by mass DPHA solution 3.8 parts by mass 2-Trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 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 ----------- --------------------------

<Binder 2>
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = random copolymer of 38/25/37 molar ratio, molecular weight 40,000) 27 parts by mass ・ Propylene glycol monomethyl ether acetate 73 parts by mass <Surfactant 2>
・ The following structure 1 30 mass parts ・ Methyl ethyl ketone 70 mass parts

Colored photosensitive resin compositions B to J, Q, and R for color filters were prepared in the same manner as above except that pigment dispersion compositions B to J, Q, and R were used instead of pigment dispersion composition A, respectively. did.
The colored photosensitive composition for producing the color filter was applied on a glass substrate using a spin coater and dried at 100 ° C. for 2 minutes to form a film having a thickness of about 2 μm. Next, the film was exposed to an ultrahigh pressure mercury lamp under a nitrogen stream, and then developed with a 1% aqueous sodium carbonate solution. The results of measuring the contrast of the R component and the light resistance of each film obtained in the same manner as in Example 1 are shown in Table 3-B below.
[Table 3-B]
Sample Contrast Light resistance (color difference)
----------------------------------
Colored photosensitive resin composition A 18000 2.0
Colored photosensitive resin composition B 16000 1.9
Colored photosensitive resin composition C 15500 1.9
Colored photosensitive resin composition D 17500 2.0
Colored photosensitive resin composition E 16000 2.0
Colored photosensitive resin composition F 13000 2.1
Colored photosensitive resin composition G 8000 1.5
Colored photosensitive resin composition H 6400 1.2
Colored photosensitive resin composition I 6800 4.2
Colored photosensitive resin composition J 6000 1.8
Colored photosensitive resin composition Q 15000 2.0
Colored photosensitive resin composition R 17000 1.9
----------------------------------

  As shown in Table 3-B, colored photosensitive resin compositions A to F, Q, and R using organic particles dispersed and formed as nanometer-sized particles by the production method of the present invention are comparative samples G. Compared with ~ J, the contrast and light resistance were extremely excellent. Samples A to E, Q, and R using the polymer compound represented by the general formula (1) showed more excellent results in both the contrast and the light resistance among the examples. .

(Example 3-2)
[Preparation of color filter (preparation by application using slit nozzle)]
[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 3-2 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 4 μm photosensitive resin layer K2 was obtained. In addition, the adjustment procedure of the colored photosensitive resin composition K2 is the same as the procedure of the previous resin composition K1.

[Table 3-2]
--------------------------------------
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 3 9.1 parts by mass Hydroquinone monomethyl ether 0.002 parts by mass DPHA liquid 4.2 parts by mass Polymerization initiator A 0. 16 parts by mass 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-dispersing agent (compound 2J below) 0.65 parts by mass-polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio
Random copolymer of, molecular weight 37,000) 6.72 parts by mass / propylene glycol monomethyl ether acetate 79.53 parts by mass

<Binder 3>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio
Random copolymer, molecular weight 38,000) 27 parts by mass / propylene glycol monomethyl ether acetate 73 parts by mass

[Formation of red (R) pixels]
Using the colored photosensitive resin composition R1 having the composition described in Table 3-3 below on the substrate on which the image K is formed, the heat-treated pixel R is formed in the same process as the formation of the black (K) image. did. The film thickness of the photosensitive resin layer R1 and the coating amount of the pigment are shown below. The procedure for adjusting 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 coating amount (g / m ² ) 1.00
C. I. P. R. 254 coating amount (g / m ² ) 0.80
C. I. P. R. 177 coating amount (g / m ² ) 0.20

[Table 3-3]
--------------------------------------
R pigment dispersion A 40 parts by mass R pigment dispersion 2 (CIPR177) 4.5 parts by mass Propylene glycol monomethyl ether acetate 7.6 parts by mass Methyl ethyl ketone 37 parts by mass Binder 2 0.7 parts by mass DPHA solution 3.8 parts by mass 2 -Trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 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 A>
-23 parts by mass of paste-like concentrated pigment liquid A (CIPR 254) of Example 1-1-0.8 parts by mass of dispersant (the compound 2J)-Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio
Random copolymer of, molecular weight 30,000) 8 parts by mass / propylene glycol monomethyl ether acetate 68.2 parts by mass <R pigment dispersion 2>
・ C. I. P. R. 177 (Product name: Chromophthal Red A2B,
Ciba Specialty Chemicals Co., Ltd.) 18 parts by mass Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio)
Random copolymer, molecular weight 30,000) 12 parts by mass / 70 parts by mass of propylene glycol monomethyl ether acetate

[Formation of green (G) pixels]
In the same process as the formation of the black (K) image, the heat-treated pixel is formed using the colored photosensitive resin composition G1 having the composition described in Table 3-4 below on the substrate on which the image K and the pixel R are formed. G was formed. The film thickness of the photosensitive resin layer G1 and the coating amount of the pigment are shown below. The procedure for adjusting 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 ) 1.92
C. I. P. G. 36 coating amount (g / m ² ) 1.34
C. I. P. Y. 150 coating amount (g / m ² ) 0.58

[Table 3-4]
--------------------------------------
G pigment dispersion 1 (CIPG 36) 28 parts by mass Y pigment dispersion 1 (CIPI 150) 15 parts by mass Propylene glycol monomethyl ether acetate 29 parts by mass Methyl ethyl ketone 26 parts by mass Cyclohexanone 1.3 parts by mass Binder 3 2.5 parts by mass DPHA solution 3 0.5 part by mass 2-trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 0.12 parts by mass Polymerization initiator A 0.05 parts by mass Phenothiazine 0.01 parts by mass Surfactant 2 0.07 parts by mass ----------- --------------------------

  As the G pigment dispersion 1, “trade name: GT-2” manufactured by Fuji Film Electronics Materials Co., Ltd. was used. As the Y pigment dispersion 1, “trade name: CF Yellow EX3393” manufactured by Mikuni Color Co., Ltd. was used.

[Formation of blue (B) pixels]
In the same process as the formation of the black (K) image, using the colored photosensitive resin composition B1 having the composition described in Table 3-5 below on the substrate on which the image K, the pixel R, and the pixel G are formed. A heat-treated pixel B was formed to obtain a target color filter A. The film thickness of the photosensitive resin layer B1 and the coating amount of the pigment are shown below. The film thickness of the photosensitive resin layer R1 and the coating amount of the pigment are shown below. The procedure for adjusting 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 3-5]
--------------------------------------
B pigment dispersion 1 (CIPB15: 6) 8.6 parts by mass B pigment dispersion 2 (CIPB15: 6 + CIPV23) 15 parts by mass Propylene glycol monomethyl ether acetate 28 parts by mass Methyl ethyl ketone 26 parts by mass Binder 4 17 parts by mass DPHA solution 4.0 Parts by mass 2-trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 0.17 parts by mass Phenothiazine 0.02 parts by mass Surfactant 2 0.06 parts by mass ------------------- ------------------

  As the B pigment dispersion 1, “trade name: CF Bull-EX3357” manufactured by Mikuni Dye Co., Ltd. was used. As the B pigment dispersion 2, “trade name: CF Bull-EX3383” manufactured by Mikuni Color Co., Ltd. was used.

<Binder 4>
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = 36/22/42 molar ratio random copolymer, molecular weight 38,000) 27 parts by mass-propylene glycol monomethyl ether acetate 73 parts by mass

  Instead of the concentrated pigment liquid A used in the R pigment dispersion A, R pigment dispersions B to F, Q, and R were prepared using concentrated pigment liquids B to F, Q, and R, respectively. Then, the color filters B to F, Q, and R were prepared in the same manner as the above-described method for producing the color filter A except that R pigment dispersions B to F, Q, and R were used instead of the R pigment dispersion A, respectively. Produced.

In contrast to the method for producing the color filter A, the paste-like concentrated pigment liquid A used for the R pigment dispersion A was changed to the pigment dispersion compositions G to J, and color filters G to J were produced.
The results of measuring the contrast and light resistance of each color filter in the same manner as in Example 1 are shown in Table 3-C. Moreover, about the R pixel part of color filter AJ, Q, and R, the presence or absence of the deposit was observed with the magnification of 500 times using the optical microscope (the Olympus Corporation make, MX-50). Any foreign matter or deposits that are not observed in the pixel or at the edge of the pixel are made uniform with no precipitate, and foreign matter or deposits that are observed in the pixel or at the edge of the pixel are found to be uniform. did. The results are shown in Table 3-C.

[Table 3-C]
Color filter Contrast Light resistance (color difference) Presence or absence of precipitation -------------------------------------
A 10500 1.9 No precipitation
B 9700 1.9 No precipitation
C 9000 1.9 No precipitation
D 9900 2.0 No precipitation
E 8800 2.0 No precipitation
F 8500 2.0 No precipitation
G 6800 1.5 No precipitation
H 6200 1.2 No precipitation
I 7000 4.3 Precipitation
J 4700 1.8 Precipitation
Q 7000 2.0 No precipitation
R 8900 1.9 No precipitation
--------------------------------------

  From the above results, it can be seen that the color filters A to F, Q, and R of the present invention exhibit extremely high contrast and light resistance with respect to the comparative specimens G to J. If the color difference is different by 2 or more, it can be distinguished depending on the viewer. This difference is further enlarged by long-term use (for example, one year or more), and becomes a significant difference on the display screen. The color filters of the present invention were all good color filters with high contrast and no precipitates. On the other hand, the color filter of the comparative example had a low contrast and a precipitate, which was a level that did not satisfy practical requirements. In addition, the specimens A to E, Q, and R using the polymer compound represented by the general formula (1) show a higher contrast among the examples, and there is no precipitate and light resistance. Was also excellent.

(Example 3-3)
[Production and Evaluation of Liquid Crystal Display]
A liquid crystal display device was produced using the color filters A to J, Q, and R, and the 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.) 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. .

[Production and Evaluation of Liquid Crystal Display]
In the same manner as the color filter A, a liquid crystal display device was produced using the color filters G to J, Q, and R, and the display characteristics were evaluated.

  Compared to the liquid crystal display device using the color filter of the comparative example, the liquid crystal display device using the color filter of the present invention is excellent in blackness and red descriptive power and exhibits good display characteristics without display unevenness. confirmed.

(Example 3-4)
[Production of color filter (production by lamination of photosensitive resin transfer material)]
[Production of photosensitive resin transfer material]
On a polyethylene terephthalate film temporary support having a thickness of 75 μm, a coating solution for a thermoplastic resin layer having the following formulation H2 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P2 was applied and dried. Furthermore, the colored photosensitive resin composition K2 is applied and dried, and a thermoplastic resin layer having a dry film thickness of 14.6 μm, an intermediate layer having a dry film thickness of 1.6 μm, and a dry layer are dried on the temporary support. A photosensitive resin layer having a film thickness of 2.4 μm was provided, and a protective film (12 μm thick polypropylene film) was pressure-bonded.
In this way, a photosensitive resin transfer material K3 in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the black (K) photosensitive resin layer were integrated was produced.

<Coating liquid for thermoplastic resin layer: Formulation H2>
Methanol 11.1 parts by mass Propylene glycol monomethyl ether acetate 6.36 parts by mass Methyl ethyl ketone 52.4 parts by mass Methyl methacrylate / 2-ethylhexyl acrylate / benzyl
Methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55 / 11.7 / 4.5 / 28.8,
Molecular weight: 90,000, Tg: about 70 ° C.) 5.83 parts by mass. Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio))
= 63/37, molecular weight: 10,000, Tg: about 100 ° C.) 13.6 parts by mass. Compound obtained by dehydration condensation of 2 equivalents of bisphenol A and pentaethylene glycol monomethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.,
Product name: 2,2-bis [4- (methacryloxypolyethoxy)
Phenyl] propane) 9.1 parts by mass / surfactant 2 0.54 parts by mass

<Intermediate layer coating solution: prescription P2>
・ PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.,
Degree of saponification = 88%, degree of polymerization 550) 32.2 parts by mass / polyvinylpyrrolidone (manufactured by ASP Japan Co., Ltd.)
K-30) 14.9 parts by mass, 524 parts by mass of distilled water, 429 parts by mass of methanol

  Next, the colored photosensitive resin compositions K101 and G101 having the compositions described in Tables 3-6 to 3-8 below are used as the colored photosensitive resin composition K2 used in the production of the photosensitive resin transfer material K3. Photoresin transfer materials R101, G101, and B101 were prepared in the same manner as described above except that they were changed to B101 and B101. In addition, the preparation method of colored photosensitive resin composition R101, G101, and B101 is based on the preparation method of the said colored photosensitive resin composition R1, G1, and B1, respectively.

[Table 3-6] R101
--------------------------------------
R pigment dispersion A 40 parts by mass R pigment dispersion 2 (CIPR177) 4.5 parts by mass Propylene glycol monomethyl ether acetate 7.6 parts by mass Methyl ethyl ketone 37 parts by mass Binder 2 0.8 parts by mass DPHA solution 4.4 parts by mass 2 -Trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 0.14 parts by weight Polymerization initiator A 0.06 parts by weight Phenothiazine 0.01 parts by weight Additive 1 0.52 parts by weight Surfactant 2 0.06 parts by weight ---- ----------------------------------

[Table 3-7] G101
--------------------------------------
G pigment dispersion 1 (CIPG36) 28 parts by mass Y pigment dispersion 1 (CIPI150) 15 parts by mass Propylene glycol monomethyl ether acetate 29 parts by mass Methyl ethyl ketone 26 parts by mass Cyclohexanone 1.3 parts by mass Binder 3 3.0 parts by mass DPHA solution 4 .3 parts by mass 2-trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 0.15 parts by mass Polymerization initiator A 0.06 parts by mass Phenothiazine 0.01 parts by mass Surfactant 2 0.07 parts by mass ----------- --------------------------

[Table 3-8] B101
--------------------------------------
B pigment dispersion 1 (CIPB15: 6) 8.6 parts by mass B pigment dispersion 2 (CIPB15: 6 + CIPV23) 15 parts by mass Propylene glycol monomethyl ether acetate 28 parts by mass Methyl ethyl ketone 26 parts by mass Binder 4 18.5 parts by mass DPHA solution 4 .3 parts by mass 2-trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 0.17 parts by mass Phenothiazine 0.02 parts by mass Surfactant 2 0.06 parts by mass ------------------- ------------------

  In addition, among the compositions described in Table 3-6, the additive 1 used was a phosphate ester special activator (Takamoto Kasei Co., Ltd., trade name: HIPLAAD ED152).

[Formation of black (K) image]
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 with a substrate preheating device and sent to the next laminator.
After peeling off the protective film of the photosensitive resin transfer material K2, a substrate heated to 100 ° C. using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)), rubber roller temperature 130 ° C., linear pressure Lamination was performed at 100 N / cm ² and a conveyance speed of 2.2 m / min.
After peeling the temporary support at the interface with the thermoplastic resin layer, the substrate and mask (quartz exposure mask with image pattern) are used with a proximity-type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp. ) Was set vertically, the distance between the exposure mask surface and the thermoplastic resin layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 70 mJ / cm ² .

Next, 30 ° C. in a triethanolamine developer (containing 2.5% triethanolamine, nonionic surfactant, polypropylene antifoam, trade name: T-PD1, manufactured by Fuji Photo Film Co., Ltd.) The thermoplastic resin layer and the intermediate layer were removed by shower development with a flat nozzle pressure of 0.04 MPa for 50 seconds.
Subsequently, sodium carbonate developer (0.06 mol / liter sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalene sulfonate, anionic surfactant, antifoaming agent, stabilizer contained, trade name: T -CD1, manufactured by Fuji Photo Film Co., Ltd.), shower development was performed at 29 ° C. for 30 seconds and a cone type nozzle pressure of 0.15 MPa to develop the photosensitive resin layer to obtain a patterning image.
Continuing detergent (phosphate, silicate, nonionic surfactant, defoaming agent, stabilizer, trade name "T-SD1 (Fuji Photo Film Co., Ltd.)" or sodium carbonate / phenoxyoxyethylene surfactant Containing the product name “T-SD2 (manufactured by Fuji Photo Film Co., Ltd.)”, removing the residue with a rotating brush having a shower and nylon bristles at 33 ° C. for 20 seconds and a cone type nozzle pressure of 0.02 MPa. An image of K) was obtained. Thereafter, the substrate was further post-exposed with light of 500 mJ / cm ² from the resin layer side with an ultra-high pressure mercury lamp and then heat-treated at 220 ° C. for 15 minutes.
The substrate on which this image K was formed was again cleaned with a brush as described above, and after pure water shower cleaning, the silane coupling solution was not used and was sent to a substrate preheating device.

[Formation of red (R) pixels]
Using the photosensitive resin transfer material R101, heat-treated red (R) pixels R were obtained in the same process as the photosensitive resin transfer material K2. 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 R101 and the coating amount of 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 ) 0.80
C. I. P. R. 177 coating amount (g / m ² ) 0.20
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 G101, heat-treated green (G) pixels G were obtained in the same process as the photosensitive resin transfer material R101. 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 G101 and the coating amounts of pigments (CIPG36 and CIPY150) are shown below.
Photosensitive resin film thickness (μm) 2.00
Pigment application amount (g / m ² ) 1.92
C. I. P. G. 36 coating amount (g / m ² ) 1.34
C. I. P. Y. 150 coating amount (g / m ² ) 0.58
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 B101, heat-treated blue (B) pixels B were obtained in the same process as the photosensitive resin transfer material R101. 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 B101 and the coating amount of the pigment (CIPB15: 6 and CIPVV23) are shown below.
Photosensitive resin film thickness (μm) 2.00
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
The substrate on which the pixel R, the pixel G, the pixel B, and the image K were formed was baked at 240 ° C. for 50 minutes to obtain a color filter A1.

  The R pigment dispersion A was changed to R pigment dispersions B to F, Q, and R, respectively, with respect to the method for producing the color filter A1, and color filters B1 to F1, Q1, and R1 were produced.

  The R pigment dispersion A was changed to the pigment dispersion compositions G to J, respectively, with respect to the method for producing the color filter A1, and color filters G1 to J1 were produced.

Table 3-D shows the results obtained by measuring the contrast, color difference, and presence of precipitates of the obtained color filters A1 to J1, Q1, and R1 in the same manner as in Example 3-2.
[Table 3-D]
Color filter Contrast Weather resistance (color difference) Presence or absence of precipitation -------------------------------------
A1 11000 1.9 No precipitation
B1 9800 1.9 No precipitation
C1 9000 1.9 No precipitation
D1 10000 2.0 No precipitation
E1 9100 2.0 No precipitation
F1 9000 1.9 No precipitation
G1 6500 1.5 Little precipitation H1 6000 1.2 No precipitation
I1 7100 4.2 Precipitation
J1 4500 1.8 Precipitation
Q1 9500 1.8 No precipitation
R1 9800 1.8 No precipitation
--------------------------------------

  From the above Table 3-D, by using the production method of the present invention in which organic particles are dispersed and formed as nano-sized particles, the contrast is extremely high, the light resistance is excellent, and the generation of precipitates is suppressed, so that the R pixel. It can be seen that the color filters A1 to F1, Q1, and R1 with no unevenness in the portions can be obtained. In addition, the color filters A1 to E1, Q1, and R1 using the polymer compound represented by the general formula (1) show a higher contrast among the examples, and there are no precipitates and good weather resistance. Showed sex.

(Example 3-5)
[Production and Evaluation of Liquid Crystal Display]
A liquid crystal display device was produced using the color filters A1 to F1 in the same manner as in Example 3-3, and the display characteristics were evaluated.

In the same manner as the color filter A1, a liquid crystal display device was manufactured using the color filters G1 to J1, Q1, and R1, and display characteristics were evaluated.
Compared to the liquid crystal display device using the color filter of the comparative example, the liquid crystal display device using the color filter of the present invention is excellent in blackness and red descriptive power, and has good display characteristics without display unevenness. It was confirmed.

Example 4
Pigment dispersion compositions K and L were prepared by using Pigment Green 36 and Pigment Blue 15: 6 in place of Pigment Red 254 in the preparation of Pigment Dispersion Composition A in Example 1-1.
In the preparation of the liquid crystal display device of Example 2-1, in place of pigment PG36 and PB15: 6 in the preparation of G ink 1 and the preparation of B ink 1, pigment dispersion compositions K and L were used, respectively, and benzyl methacrylate-methacrylic acid G ink 2 and B ink 2 were prepared by reducing the amount of diethylene glycol monobutyl ether acetate so that the pigment concentration was not changed except for the acid copolymer. The effects of using G ink 2 instead of G ink 1 and B ink 2 instead of B ink 1 were manifested in the same manner as R inks 1 to 6 in Example 2, respectively.

(Example 5)
(Example 5-1)
<Preparation of pigment dispersion composition M>
[Preparation of pigment dispersion]
To 1000 ml of methanesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.), C.I. I. Pigment Violet 23 (Hostaperm Violet RL-NF manufactured by Clariant) 50 g was added to prepare a pigment solution M. As a result of measuring the viscosity of this pigment solution M using Viscomate VM-10A-L (trade name, manufactured by CBC Materials), the viscosity when the liquid temperature of the pigment solution M was 45.0 ° C. was 24.degree. 0 mPa · s. Separately from this, 1600 ml of water was prepared as a poor solvent.
Here, the temperature of the solution was controlled at 25 ° C., and the pigment solution M was added to 1600 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.). NP-KX-500 Organic pigment particles are formed by injecting 100 ml at a flow rate of 70 ml / min from a liquid feed pipe having a channel diameter of 0.25 mm using a large-capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.) Dispersion M was prepared. The number average particle diameter Mn and monodispersity (Mv / Mn) of this pigment dispersion were measured using Nanotrac UPA-EX150 (trade name, manufactured by Nikkiso Co., Ltd.). Mn 29 nm, Mv / Mn 1.27 Met. Note that the Reynolds number under this condition is 248.
The pigment nanoparticle dispersion prepared by the above method was concentrated at 3000 rpm for 90 minutes using an H-122 type centrifugal filter manufactured by Kokusan Co., Ltd. and a P89C type cloth manufactured by Shikishima Canvas Co., Ltd. The pigment nanoparticle concentrated paste was recovered.
The pigment content of the paste was measured using an Agilent 8453 type spectrophotometer and found to be 14.5% by mass.
By adding 50.0 cc of ethyl lactate to 18.0 g of the above pigment nanoparticle preparation paste, stirring at 1500 rpm for 60 minutes with a dissolver, and then filtering using a FP-010 type filter manufactured by Sumitomo Electric Fine Polymer, paste form Concentrated pigment liquid M (nanopigment concentration 31% by mass) was obtained.

[Preparation of pigment dispersion composition M]
Using the paste, a pigment dispersion composition M having the following composition was prepared.
20.8 g of the paste-like concentrated pigment liquid M
Pigment dispersant A 0.6g
6.4 g of compound C-16 of general formula (1)
16.7 g of 1-methoxy-2-propyl acetate
The pigment dispersant A was synthesized according to Japanese Patent Laid-Open No. 2000-239554.
The pigment dispersion composition having the above composition was dispersed for 180 minutes using an ultrasonic homogenizer (Branson Co., Ltd .; Sony Fire 450).

<Preparation of pigment dispersion composition N>
C. of Pigment Dispersion Composition G in Comparative Example 1-1 I. Pigment Red 254 is C.I. I. Pigment dispersion composition N was prepared in exactly the same manner except that it was changed to CI Pigment Violet 23.

<Preparation of pigment dispersion composition P>
In preparing the pigment dispersion composition M of the present invention, after preparing the paste-like concentrated pigment liquid M, 43.7 g of ethyl lactate was added to 20.8 g of the concentrated pigment liquid M (nano-pigment concentration 31%), and an ultrasonic homogenizer. A pigment dispersion composition P was obtained by dispersing for 180 minutes using (Branson (manufactured); Sony Fire 450).

  The contrasts of the pigment dispersion compositions M, N, and P were measured in the same manner as in Example 1. As a result, they were 22000, 9500, and 15000, respectively. The pigment dispersion prepared by the production method of the present invention was compared with the conventional pigment dispersion composition N. It can be seen that the compositions M and P achieve a clearly high contrast. In particular, it can be seen that the pigment dispersion composition M using the water-insoluble polymer compound C-16 can provide high contrast.

(Example 5-2)
In the production of the color filter by the photosensitive resin transfer material laminate in Example 3, the B pigment dispersions 1 and 2 were prepared as C.I. I. Pigment blue 15: 6 and C.I. I. A combination of B pigment dispersion 1 and pigment dispersion composition M, a combination of B pigment dispersion 1 and pigment dispersion composition N, and further B pigment dispersion 1 and pigment dispersion so that the content of pigment violet 23 is the same. A liquid crystal display device was produced using the color filter replaced by the combination of the composition P. When the pigment dispersion M or P of the present invention was used, the liquid crystal display device was black compared with the case where the pigment dispersion N was used. There was a noticeable improvement in the power of drawing and blue.

(Example 6)
In the process of mixing the pigment solution with the poor solvent, the pigment dispersion composition A is the same as the pigment dispersion composition A of Example 1-1 except that the amount of the pigment and solvent used is 10 times and 100 times. −10 and A-100 were prepared, and the contrast was measured in the same manner as in Example 1.
Table 6 shows the evaluation results of the contrast of the produced pigment dispersion composition.
[Table 6]
Sample Contrast ---------------------------
Pigment dispersion composition A 19500
Pigment dispersion composition A-10 19600
Pigment dispersion composition A-100 20300
-------------------------------
From the results of Table 6, according to the organic nanoparticles obtained by the production method of the present invention, it is possible to produce a high-contrast pigment dispersion composition, maintaining its excellent characteristics even when scaled up in the production of nanoparticles, Furthermore, it turns out that it can improve. Thereby, according to the manufacturing method of this invention, in manufacture of an organic nanoparticle, it turns out that high quality and high productivity can be made compatible.

(Example 7)
(Comparative Example 7-1)
[Production of CCD device]
(Preparation of pigment dispersion for CCD)
Pigment dispersion liquid (1)... Green G, (2)... Blue B, (3)... Red using the pigment dispersion composition F obtained in Comparative Example 1 with the following formulation R was prepared.
Pigment dispersion (1)
・ C. I. P. G. 36 95 parts by mass-C.I. I. P. G. 7 30 parts by mass I. P. Y. 139 45 parts by mass-PLAAD ED151 (manufactured by Enomoto Kasei Co., Ltd.) 20 parts by mass-Benzyl methacrylate / methacrylic acid copolymer 25 parts by mass (copolymerization molar ratio 70:30, mass average molecular weight 30,000)
Propylene glycol monomethyl ether acetate 625 parts by mass Pigment dispersion (2)
・ C. I. P. B. 15: 6 125 parts by mass-C.I. I. P. V. 23 20 parts by mass-PLAAD ED151 (manufactured by Enomoto Kasei Co., Ltd.) 40 parts by mass-Benzyl methacrylate / methacrylic acid copolymer 25 parts by mass (copolymerization molar ratio 70:30, mass average molecular weight 30,000)
Propylene glycol monomethyl ether acetate 790 parts by mass Pigment dispersion (3)
Pigment dispersion composition I 600 parts by weight Dispersant C-16 40 parts by weight benzyl methacrylate / methacrylic acid copolymer 25 parts by weight (copolymerization molar ratio 70:30, weight average molecular weight 30,000)
・ 345 parts by mass of propylene glycol monomethyl ether acetate

(Preparation of colored resin composition)
The following composition was uniformly mixed with a stirrer for each 200 parts by mass of the pigment dispersion of each color obtained from the above to prepare a colored resin composition for a color filter for each color.
<Composition>
・ 35 parts by mass of benzyl acrylate / methacrylic acid copolymer (copolymerization molar ratio = 70/30, mass average molecular weight 30,000)
-38 parts by mass of dipentaerythritol pentaacrylate-120 parts by mass of propylene glycol monomethyl ether acetate-40 parts by mass of ethyl-3-ethoxypropionate-4 parts by mass of halomethyltriazine-based initiator (photopolymerization initiator product name TAZ107 Midori Chemical Co., Ltd.)

(Production of color filters and CCD devices)
The following composition was mixed with a stirrer to prepare a planarizing film resist solution.
〔composition〕
165 parts by mass of benzyl acrylate / methacrylic acid copolymer (copolymerization molar ratio = 70/30, mass average molecular weight 30,000)
-65 parts by weight of dipentaerythritol pentaacrylate-138 parts by weight of propylene glycol monomethyl ether acetate-123 parts by weight of ethyl-3-ethoxypropionate-3 parts by weight of a halomethyltriazine-based initiator (photopolymerization initiator product name TAZ107 Midori Chemical Co., Ltd.)
The obtained flattening resist solution was uniformly applied by spin coating onto a 6-inch silicon wafer on which photodiodes were formed. In spin coating, the coating rotation speed was adjusted so that the film thickness would be about 1.5 μm when the surface temperature of the coating film was heated using a hot plate under the condition of 100 ° C. × 120 seconds after coating.
Then, it was placed in an oven at 220 ° C. for 1 hour to cure the coating film, and a planarizing film was formed so as to uniformly cover the surface of the photodiode formed on the silicon wafer.

  Next, for each color, in order of G, R, and B, the above-described colored resin composition for color filter is applied on the flattening film, and 100 parts by weight is applied to the flattening film resist solution preparation and dried (prebaked). Pattern exposure, alkali development, rinsing, and curing drying (post-baking) were performed to form a colored resin film, and a color filter was produced on a silicon wafer with a photodiode.

The pattern exposure was performed at 500 mJ / cm <2> using an i-line stepper (trade name: FPA-3000i5 +, manufactured by Canon Inc.) through a 2 [mu] m mask pattern.
Further, for alkali development, after performing paddle development for 60 seconds at room temperature using a 40% by mass aqueous solution of an organic alkaline developer (trade name: CD-2000, manufactured by Fuji Film Electronics Materials Co., Ltd.). Then, it was rinsed with pure water in a spin shower for 20 seconds, and further washed with pure water. Thereafter, water droplets were blown with high-temperature air, the substrate was naturally dried to obtain a pattern, and then post-baked on a hot plate at a surface temperature of 200 ° C. for 5 minutes.

  When the CCD device obtained as described above is mounted on a digital camera and an image of a color chart with a KODAK gray scale is taken under the same light source and observed on a monitor, image fluctuations and red color unevenness are observed. It was done.

(Example 7-1)
A CCD device produced in exactly the same manner as in Comparative Example 7-1 except that Pigment Dispersion Composition A was used instead of Pigment Dispersion Composition I used in Comparative Example 7-1 was mounted on a digital camera, and the same evaluation was made. As a result, a uniform and smooth color image with little fluctuation was obtained. Further, it was confirmed that an image with little fluctuation was obtained in the same manner even when the pigment dispersion compositions B to F were used.

(Example 8)
C. used in Example 1 I. In place of Pigment Red 254, C.I. I. When carried out using CI Pigment Red 255, 264, and 272, it was confirmed that the effects of the present invention were similarly exhibited.

Example 9
C. used in Example 4 I. In place of Pigment Green 36, C.I. I. Even when CI Pigment Green 7 was used, it was confirmed that the effects of the present invention were similarly exhibited.

(Example 10)
C. used in Example 5 I. In place of Pigment Violet 23, C.I. I. It was confirmed that even when CI Pigment Violet 37 was used, the effects of the present invention were similarly expressed.

It is sectional drawing which shows schematically the preferable embodiment of the manufacturing apparatus used for the manufacturing method of this invention. It is sectional drawing which shows schematically another preferable embodiment of the manufacturing apparatus used for the manufacturing method of this invention. It is an expanded sectional view which shows roughly a mixing chamber by a partial cross section as one embodiment of the manufacturing apparatus of FIGS. It is an expanded sectional view which shows roughly a mixing chamber by a partial cross section as another embodiment of the manufacturing apparatus of FIGS. 1-2. It is sectional drawing which shows schematically another preferable embodiment of the manufacturing apparatus used for the manufacturing method of this invention. It is sectional drawing which shows schematically still another preferable embodiment of the manufacturing apparatus used for the manufacturing method of this invention. It is a front view which shows roughly an example of the dissolver stirring blade used for the manufacturing method of this invention. 4 is a drawing-substituting photograph of the dissolver stirring blade shown in FIG. 4-1. It is sectional drawing which shows roughly an example of the stirring part comprised from the turbine part which can be used for the manufacturing method of this invention, and the fixed stator part located in the circumference | surroundings with a slight gap. .

Explanation of symbols

11 Container 11a Liquid tank (solvent)
11b Liquid level 12 Stirring blade 13 Mixing chamber 14 Supply pipe 14a Supply port 15 Shaft 16 Motor 17 Casing (mixing chamber wall)
18 holes (circular holes)
19a, 19b Stirring blade 21 Container (outer wall of stirring tank)
21a stirring tank 22 stirring blade 23 discharge pipe 24, 25 supply pipe 24a, 25a supply port 26 shaft 50 stirring device 32, 33 supply pipe 32a, 33a supply port 36 discharge port 40 seal plate 41, 42 stirring blade 46 external magnet 48, 49 Motor 61 Disc part 62 Blade 63 Shaft 74 Rotating turbine part 75 Fixed stator part

Claims (15)

Organic Pigment solution of an organic Pigments in a good solvent, the Reynolds number with respect to the above is a good solvent miscible and the organic Pigments represented a solvent which is a poor solvent by the following equation (1) there a method for producing organic pigment nanoparticles Ru precipitated with an average particle size of nano particles of the organic pigments were mixed under conditions of 60 or higher 60nm or less,
A method for producing an organic pigment nanoparticle dispersion, wherein the organic pigment solution is jetted from a supply pipe and mixed into the poor solvent under stirring.
Re = ρUL / μ Equation (1)
(In Formula (1), Re represents a Reynolds number, [rho represents the density of the organic Pigments solution, U is represents the relative speed at which meet the organic Pigments solution and the poor solvent, L represents an organic Pigment solution represents the equivalent diameter of the flow path or feed port portion and a poor solvent meet, mu denotes the viscosity coefficient of the organic Pigment solution.) The method for producing an organic pigment nanoparticle dispersion according to claim 1, wherein the Reynolds number is 100 or more. The method for producing an organic pigment nanoparticle dispersion according to claim 1 or 2 , wherein the Reynolds number is 2500 or less. The organic pigment solution according to any one of claims 1 to 3 , wherein the mixing ratio of the organic pigment solution and the poor solvent (ratio of good solvent / poor solvent) is 1/50 to 2/3 by volume. A method for producing a pigment nanoparticle dispersion . The method for producing an organic pigment nanoparticle dispersion liquid according to any one of claims 1 to 4 , wherein the dispersion liquid contains a polymer compound having a molecular weight of 1000 or more. The said high molecular compound is represented by following General formula (1), The manufacturing method of the organic pigment nanoparticle dispersion liquid of Claim 5 characterized by the above-mentioned.

[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 method for producing an organic pigment nanoparticle dispersion liquid according to claim 6 , wherein the polymer compound is represented by the following general formula (2).

[Wherein R ³ represents a (x + y) -valent linking group. R ⁴ and R ⁵ each independently represents a single bond or a divalent linking group. A ² 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, x A ² may be the same or different. y represents a number of 1 to 8, x represents a number of 2 to 9, and x + y satisfies 3 to 10. P ² represents a polymer compound residue. ] The method for producing an organic pigment nanoparticle dispersion liquid according to any one of claims 5 to 7 , wherein the polymer compound is contained in an amount of 0.1 to 1000 parts by mass with respect to 100 parts by mass of the organic pigment. . The said organic pigment is a pyrrolopyrrole compound pigment, The manufacturing method of the organic pigment nanoparticle dispersion liquid of any one of Claims 1-8 characterized by the above-mentioned. The pyrrolopyrrole compound pigment is C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264, and C.I. I. The method of producing an organic pigment nanoparticle dispersion liquid according to claim 9 , which is any one of CI Pigment Red 272. The method for producing an organic pigment nanoparticle dispersion liquid according to any one of claims 1 to 8, wherein the organic pigment is a phthalocyanine compound pigment. The phthalocyanine compound pigment is C.I. I. Pigment green 36, C.I. I. Pigment green 7, and C.I. I. The method of producing an organic pigment nanoparticle dispersion liquid according to claim 11 , which is any one of CI Pigment Blue 15: 6. The method for producing an organic pigment nanoparticle dispersion liquid according to any one of claims 1 to 8, wherein the organic pigment is a dioxazine compound pigment. The dioxazine compound pigment is C.I. I. Pigment violet 23 or C.I. I. It is a pigment violet 37, The manufacturing method of the organic pigment nanoparticle dispersion liquid of Claim 13 characterized by the above-mentioned. The method for producing an organic pigment nanoparticle dispersion liquid according to any one of claims 1 to 14 , wherein the organic pigment nanoparticles are precipitated on a scale in which the poor solvent is 10 L or more.

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