KR101390760B1

KR101390760B1 - Pigment dispersion composition, colored photosensitive resin composition and photosensitive resin transfer material using the same, and color filter, liquid crystal display and ccd device using the same

Info

Publication number: KR101390760B1
Application number: KR1020070054143A
Authority: KR
Inventors: 코이치 스기하라; 미츠토시 타나카; 히데노리 타카하시; 케이스케 마츠모토
Original assignee: 후지필름 가부시키가이샤
Priority date: 2006-06-02
Filing date: 2007-06-01
Publication date: 2014-05-02
Also published as: TW200806754A; CN101081943A; KR20070115802A

Abstract

Provided is a pigment dispersion composition having a low water content, which contains sharp organic pigment nano-particles having a nano-sized particle diameter distribution peak with stable dispersibility. Also provided is a colored photosensitive resin composition excellent in stability using the above pigment dispersion composition and having high contrast, an ink jet ink for a color filter, and a photosensitive resin transfer material. Also provided is a color filter, a liquid crystal display device, and a CCD device that exhibit high stability and excellent display characteristics with high contrast.

Wherein the ratio of particles having a primary particle size of less than 15 nm in the organic pigment nanoparticles is less than 10%, the proportion of particles having a particle size exceeding 60 nm is less than 10%, the water content is less than 0.01 mass % To 5% by mass of the pigment.

Description

TECHNICAL FIELD [0001] The present invention relates to a pigment dispersion composition, a colored photosensitive resin composition using the pigment dispersion composition, and a photosensitive resin transfer material, and a color filter, a liquid crystal display device, and a CCD device using the same. BACKGROUND ART , LIQUID CRYSTAL DISPLAY AND CCD DEVICE USING THE SAME}

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a preferred embodiment of a production apparatus used for producing the pigment dispersion composition of the present invention. Fig.

2 is a cross-sectional view schematically showing another preferred embodiment of a production apparatus usable for producing the pigment dispersion composition of the present invention.

Fig. 3 is an enlarged partial cross-sectional view schematically showing a mixing chamber as a partial cross-section as one embodiment of the manufacturing apparatus of Fig. 2;

Fig. 4 is an enlarged partial cross-sectional view schematically showing a mixing chamber as a partial cross-section as another embodiment of the manufacturing apparatus of Fig. 2;

5 is a cross-sectional view schematically showing another preferred embodiment of a production apparatus usable for producing the pigment dispersion composition of the present invention.

6 is a cross-sectional view schematically showing another preferred embodiment of a production apparatus usable for producing the pigment dispersion composition of the present invention.

7 is a front view schematically showing an example of a dissolver stirring blade which can be used in the production of the pigment dispersion composition of the present invention.

Fig. 8 is a photograph for showing the diolzer stirring wing shown in Fig. 7; Fig.

9 is a cross-sectional view schematically showing an example of a stirring part composed of a rotatable turbine part used for manufacturing the pigment dispersion composition of the present invention and an immobilized stator part positioned with a gap therebetween.

Fig. 10 is an explanatory view showing an example of the configuration of an ultrafiltration apparatus used for producing the pigment dispersion composition of the present invention. Fig.

DESCRIPTION OF THE REFERENCE SYMBOLS

11 vessel 11a basin (solvent)

11b liquid surface 12 stirring blade

13 Mixing room 14 Feeder

14a Supply pipe opening 15 Shaft

16 Motor 17 Casing (Mixed Wall)

18 hole (circular hole) 19a, 19b stirring blade

21 vessel (stirring vessel outer wall) 21a stirring vessel

22 stirring wing 23 discharge pipe

24a, 24b Supply pipe 25 shaft

50 stirring device 32, 33 supply port

36 outlet 40 sealing plate

41, 42 stirring blade 46 outer magnet

48, 49 Motor 61 Disk section

62 Wings 63 Shaft

74 rotatable turbine section 75 A fixed stator section

81 Container for storing dispersion 82 Circulation pump

83 Ultrafiltration module 84 Replenishment Flow meter for pure measurement

85 Flow meter for permeate measurement 86 Reverse flow pump

The present invention relates to a pigment dispersion composition, a colored photosensitive composition using the same, and a photosensitive resin transfer material, and a color filter, a liquid crystal display, and a CCD device using the same.

In recent years, countermeasures for reducing the particle size have been made. Particularly, research is being conducted to reduce the size to a nanometer size (for example, in the range of 10 to 100 nm) which is difficult to manufacture by a pulverization method, a precipitation method, or the like. It has also been attempted to make particles having a high particle size in nanometer size and a high dispersibility (monodispersibility in the present invention refers to the degree of aggregation of particle diameters).

The size of such nanometer size particulates is in the size range that is conventionally located in the middle of larger bulk particles, smaller molecules or atoms. It has been pointed out that such nanometer-sized particles can lead to new properties that have not been anticipated so far. Further, if the monodispersity can be increased, the characteristics can be stabilized. Therefore, the possibility that such nanoparticles are possessed is expected in various fields, and research is vigorous in a wide range of fields such as biochemistry, new materials, electronic devices, light emitting display devices, printing, and medical care.

Particularly, the organic nanoparticles composed of the 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 material chemically and mechanically stable such as heat resistance, solvent resistance, and mechanical properties, and has excellent electrical insulation. In addition, polyimide has been made into fine particles and has been used in many fields by combining characteristics and shapes having polyimide. For example, proposals have been made in which fine particles of polyimide are used as additives for powdery toner for image formation (Patent Document 1).

Among organic nanoparticles, organic pigments can be enumerated as applications, for example, paints, printing inks, electrophotographic toners, inkjet inks, and color filters. These have become an indispensable compound in life today. Of these pigments, pigments for ink-jet inks and pigments for color filters are of particular importance in practical use because of their high performance.

Conventional dyes can be used for the color material of the ink-jet ink. However, the dyes have problems in terms of water resistance and light resistance. Pigments could be used to improve it. The image obtained by the pigment ink has an advantage of being excellent in light resistance and water resistance as compared with an image by a dye-based ink. However, it is difficult to increase the monodispersity in the nanometer size that can be absorbed in the space of the paper surface, and the adhesion to paper is poor.

In addition, with the increase in the size of a digital camera, it is expected that a color filter used as an optical element such as a CCD sensor or a display element is thinned. Organic pigments are used for color filters. Since the thickness of the filter depends largely on the particle diameter of the organic pigment, it is expected to produce fine particles that are stable at a nanometer size level and stable in monodisperse.

The organic particles can be produced by a vapor phase method (a method in which a sample is sublimated in an inert gas atmosphere to recover particles on a substrate), a liquid phase method (for example, a sample dissolved in a good solvent is injected into a poor solvent (A method in which fine particles are obtained by irradiating a laser beam onto a sample dispersed in a solution to polish the particles) and the like have been studied. In addition, a production example in which monodispersion is attempted at a desired size by these methods has been reported. Among them, the liquid phase method has attracted attention as a process for producing organic particles excellent in simplicity and productivity (see Patent Documents 2 and 3, etc.). The organic particles prepared by this liquid phase method can adjust the crystal form and properties of the particle surface by adjusting the precipitation conditions by the solvent species, injection rate, temperature, and the like. Patent Document 3 discloses that the crystal form of the quinacridone pigment is a poor solvent An example of adjustment is described.

On the other hand, regarding the improvement of the dispersibility of particles, conventionally, dispersion of organic pigments has been industrially carried out using various dispersing machines (roll mill, ball mill, attritor, etc.). In this case, there are cases where the viscosity is increased by making the particles finer. If the viscosity is increased, it becomes difficult to take out from the dispersing machine, the transportation by the pipeline can not be performed, or the gel becomes gained during storage and becomes unusable. In order to solve these problems, a dispersant for stabilizing dispersion and a polymer for stabilizing dispersion have been added, but sufficient effect can not be obtained (see Non-Patent Document 1, etc.). In order to improve the dispersibility of the organic pigment dispersion for color filters, a polymer or a pigment dispersant capable of imparting both alkali development properties and dispersion stability necessary for the production of color filters is added (see, for example, Patent Document 4). However, in these methods, it takes time to disperse and does not satisfy the demand for reasons such as an increase in viscosity.

An example in which the pigment particles produced by the liquid phase method are used and the dispersibility is improved is also reported. However, they can not sufficiently cope with the requirement of monodisperse nanoparticles. For example, Patent Document 5 is a method of providing an aqueous dispersion, and there is no mention of a method provided as an organic solvent dispersion. The method disclosed in Patent Document 6 has a larger primary particle diameter. In Patent Document 7, the specifications regarding the pigment particle size and distribution are disclosed, but the water content is not considered, and storage stability is poor and contrast can not be sufficiently obtained. In Patent Document 8, the specification of the water content is disclosed only for the dispersant, the particle size is not considered, the storage stability is poor, and the contrast can not be sufficiently obtained.

[Patent Document 1] JP-A-11-237760

[Patent Document 2] JP-A-6-79168

[Patent Document 3] JP-A-2004-91560

[Patent Document 4] JP-A-2000-239554

[Patent Document 5] Japanese Unexamined Patent Application Publication No. 2004-43776

[Patent Document 6] Japanese Unexamined Patent Application Publication No. 2004-123853

[Patent Document 7] JP-A-2002-328215

[Patent Document 8] JP-A-2002-241640

[Non-Patent Document 1] Pigment Dispersion Technique - Surface Treatment and Usage of Dispersant and Evaluation of Dispersibility - Technical Information Association 1999

An object of the present invention is to provide a pigment dispersion composition with a low water content containing sharp organic pigment nano-particles having a particle diameter distribution peak at a nanometer size with high dispersion stability, and also has excellent stability using the above pigment dispersion composition, The present invention also provides a colored photosensitive resin composition having a high contrast, an inkjet ink for a color filter, and a photosensitive resin transferring material, and a color filter, a liquid crystal display, and a CCD It is intended to provide a device.

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

(1) A pigment dispersion composition containing organic pigment particles and an organic solvent, wherein the organic pigment particles have a primary particle size of less than 10% (number%) and a particle size of less than 15 nm Is less than 10% (number%), and the water content of the composition is 0.01% by mass to 5% by mass.

(2) The pigment dispersion composition according to (1), wherein the organic pigment particles are nanoparticles formed by mixing a solution of an organic pigment dissolved in a good solvent and a poor solvent of the organic pigment compatible with the solvent.

(3) The pigment dispersion composition according to (1) or (2) above, wherein the water content is 3 mass% or less.

(4) The pigment dispersion composition according to the above (1) or (2), wherein the water content is 1 mass% or less.

(5) The pigment dispersion composition according to any one of (1) to (4) above, which contains a compound represented by the following general formula (1)

Wherein R ¹ represents a linking group of (m + n), and R ² represents a single bond or a divalent linking group. A ¹ is selected from the group consisting of an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a radial oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group and a hydroxyl group Or a monovalent organic group containing an organic pigment structure or a heterocyclic ring which may have a substituent. However, n A ^{1 s} may be the same or different. 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.]

(6) The pigment dispersion composition according to any one of (1) to (5), wherein the pigment dispersion composition is an inkjet ink.

(7) A pigment dispersion composition comprising the pigment dispersion composition according to any one of (1) to (6), a polyfunctional monomer having at least two ethylenically unsaturated double bonds, and a photopolymerization initiator or a photopolymerization initiator system Sensitive resin composition.

(8) A photosensitive resin residue material comprising at least a photosensitive resin layer containing the colored photosensitive resin composition according to (7) above on a branched support.

(9) A color filter comprising the colored photosensitive resin composition according to (7) and / or the photosensitive resin transfer material according to (8) above.

(10) A liquid crystal display device comprising the color filter according to (9).

(11) The liquid crystal display device according to (10), wherein the liquid crystal display device is a VA type.

(12) A CCD device comprising the color filter according to (9).

The pigment dispersion composition of the present invention contains organic pigment nanoparticles and an organic solvent, wherein the proportion of particles having a primary particle size of less than 15 nm in the organic pigment nanoparticles is less than 10% (number%), more than 60 nm (%) Is less than 10% (number%) and the water content is 0.01% by mass to 5% by mass (hereinafter, when only the percentage of particles is described, to be.)

In the present invention, the proportion of particles having a primary particle size of less than 15 nm is more preferably less than 7%, and particularly preferably less than 5%.

If the ratio of the particles of less than 15 nm is 10% or more, heat resistance and light resistance may be deteriorated.

In the present invention, the proportion of particles having a primary particle size exceeding 60 nm is preferably less than 7%, particularly preferably less than 5%.

When the ratio of the particles exceeding 60 nm is 10% or more, there is a possibility that the contrast is lowered, which is not preferable.

In the present invention, the water content is preferably 3 mass% or less, more preferably 0.01 mass% to 3 mass%, still more preferably 1 mass% or less, and particularly preferably 0.01 mass% to 1 mass%.

If the water content is higher than 5% by mass, stability tends to deteriorate, which is not preferable. Further, in order to lower the moisture content to less than 0.01% by mass, it takes a lot of energy cost to dehydrate the solvent to be used, so that it is not preferable to lower the water content to less than 0.01% by mass in view of industrial production.

The organic pigment that can be used in the present invention is not particularly limited as long as it can form particles by the re-precipitation method, and may be used alone, or a plurality of organic pigments may be used in combination.

The organic pigments are not limited in color but include pigments such as perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimidazolone, disazo condensation, disazo, azo , Indanthrone, phthalocyanine, triarylcarbonium, dioxazine, aminoanthraquinone, diketopyrrolopyrrole, thioindigo, isoindoline, isoindolinone, pyranthrone or isoviolanthrone compound pigments, or mixtures thereof Lt; / RTI >

More specifically, for example, C.I. Pigment Red 190 (C.I. No. 71140), C.I. Pigment Red 224 (C.I. No. 71127), C.I. Pigment Violet 29 (C.I. No. 71129), C.I. Pigment Orange 43 (C.I. No. 71105), or C.I. Pigment Red 194 (C.I. No. 71100), C.I. Pigment Violet 19 (C.I. No. 73900), C.I. Pigment Violet 42, C.I. Pigment Red 122 (C.I. No. 73915), C.I. Pigment Red 192, C.I. Pigment Red 202 (C.I. No. 73907), C.I. Pigment Red 207 (C.I. No. 73900, 73906), or C.I. Quinacridone compound pigments of Pigment Red 209 (C.I. No. 73905), C.I. Pigment Red 206 (C.I. No. 73900/73920), C.I. Pigment Orange 48 (C.I. No. 73900/73920), or C.I. Pigment Orange 49 (C.I. No. 73900/73920), C.I. Anthraquinone compound pigments such as Pigment Yellow 147 (CI No. 60645), C.I. Pigment Red 168 (C.I. No. 59300), C.I. Pigment Brown 25 (C.I. No. 12510), C.I. Pigment Violet 32 (CI No. 12517), C.I. Pigment Yellow 180 (CI No. 21290), C.I. Pigment Yellow 181 (CI No. 11777), C.I. Pigment Orange 62 (C.I. No. 11775), or C.I. Benzimidazolone compound pigments such as Pigment Red 185 (C.I. No. 12516), C.I. Pigment Yellow 93 (CI No. 20710), C.I. Pigment Yellow 94 (C.I. No. 20038), C.I. Pigment Yellow 95 (C.I. No. 20034), C.I. Pigment Yellow 128 (C.I. No. 20037), C.I. Pigment Yellow 166 (C.I. No. 20035), C.I. Pigment Orange 34 (C. I. No. 21115), C.I. Pigment Orange 13 (C.I. No. 21110), C.I. Pigment Orange 31 (CI No. 20050), C.I. Pigment Red 144 (CI No. 20735), C.I. Pigment Red 166 (C. I. No. 20730), C.I. Pigment Red 220 (C.I. No. 20055), C.I. Pigment Red 221 (C.I. No. 20065), C.I. Pigment Red 242 (C.I. No. 20067), C.I. Pigment Red 248, C.I. Pigment Red 262, or C.I. Disazo condensed compound pigments such as Pigment Brown 23 (C.I. No. 20060), C.I. Pigment Yellow 13 (CI No. 21100), C.I. Pigment Yellow 83 (CI No. 21108), or C.I. Disazo compound pigments such as Pigment Yellow 188 (C.I. No. 21094), C.I. Pigment Red 187 (CI No. 12486), C.I. Pigment Red 170 (C.I. No. 12475), C.I. Pigment Yellow 74 (CI No. 11714), C.I. Pigment Yellow 150 (CI No. 48545), CI Pigment Red 48 (CI No. 15865), C.I. Pigment Red 53 (C. I. No. 15585), C.I. Pigment Orange 64 (C.I. No. 12760), or C.I. Pigment Red 247 (C.I. No. 15915), C.I. Indanthrone compound pigments such as Pigment Blue 60 (C.I. No. 69800), C.I. Pigment Green 7 (C. I. No. 74260), C.I. Pigment Green 36 (C. I. No. 74265), C.I. Pigment Green 37 (C.I. No. 74255), C.I. Pigment Blue 16 (C.I. No. 74100), C.I. Phthalocyanine compound pigments such as Pigment Blue 75 (C.I. No. 74160: 2) or 15 (C.I. No. 74160), C.I. Pigment Blue 56 (C.I. No. 42800), or C.I. Pigment Blue 61 (C.I. No. 42765: 1), C.I. Pigment Violet 23 (C.I. No. 51319), or C.I. Pigment Violet 37 (C.I. No. 51345), C.I. Aminoanthraquinone compound pigments such as Pigment Red 177 (C.I. No. 65300), C.I. Pigment Red 254 (C.I. No. 56110), C.I. Pigment Red 255 (C.I. No. 561050), C.I. Pigment Red 264, C.I. Pigment Red 272 (C.I. No. 561150), C.I. Pigment Orange 71, or C.I. Diketopyrrolopyrrole compound pigments such as Pigment Orange 73, C.I. Pigment Red 88 (C.I. No. 73312), C.I. Pigment Yellow 139 (C.I. No. 56298), C.I. Isoindoline compound pigments such as Pigment Orange 66 (C.I. No. 48210), C.I. Pigment Yellow 109 (C.I. No. 56284), or C.I. Isoindolinone compound pigments such as Pigment Orange 61 (CI No. 11295), C.I. Pigment Orange 40 (C.I. No. 59700), or C.I. Pyranthrone compound pigments such as Pigment Red 216 (C.I. No. 59710), or C.I. Pigment Violet 31 (60010), and other isoviolanthrone compound pigments. Among them, quinacridone compound pigments, diketopyrrolopyrrole compound pigments, dioxazine compound pigments, phthalocyanine compound pigments, or azo compound pigments are preferable, and diketopyrrolopyrrole compound pigments or dioxazine compound pigments are more preferable.

Hereinafter, the diketopyrrolopyrrole compound pigment or the dioxazine compound pigment will be described in more detail.

C.I.P.R. Since the pyrrolopyrrole compound pigment represented by 254, 255, and 264 has an absorption region suitable for increasing the color purity of the red pixel constituting the color filter and can broaden the color reproduction region, its use in the color filter is tested have. However, conventional pigments do not comply with demands such as color purity and contrast. For example, a good color filter can not be obtained in the ink jet ink described in Japanese Patent Application Laid-Open No. 2003-336001, a bead dispersion or a method obtained by a method by salt milling.

According to the present invention, nano-sized pyrrolopyrrole compound pigment microparticles can be obtained in a sharp particle diameter distribution. In addition, when the pigment fine particles are used in a color filter, a desired color purity and high contrast can be achieved at the same time, and furthermore, the light resistance is excellent and the occurrence of precipitates can be suppressed. Further, the liquid crystal display device provided with this color filter is excellent in black sharpness and red coloring power, and display unevenness is suppressed.

In the diketopyrrolopyrrole compound pigments, CIPR254 (a compound represented by the following formula (Z)), 255 (a compound represented by the following formula (W)), 264 (a compound represented by the following formula ) Is preferable, and CIPR254 is more preferable in terms of absorption spectrum. It is also possible to use commercially available products such as Irgaphor Red B-CF, Cromophtal DPP Red BO, Irgazin DPP Red BO, and Microlen DPP Red BP as CI P.254. As C.I.P.R. 255, Cromophtal Coral Red C, Irgazin DPP Red 5G and the like can be used. HostPaper Rubin D3B LP2615, Irgazin DPP Rubin TR, and the like can be used as C.I.P.R.264.

Next, the dioxazine compound pigment will be described. Recently, coloring agents such as C.I.P.B. 15: 6 has been used, and the color purity of the color filter has been increased accordingly. However, a light source such as a cold cathode tube, which is a light source widely used for a liquid crystal display device, has a slight light emission on the longer wavelength side of the blue emission peak, and thus the chromaticity is inferior to NTSC.

This problem is addressed by C.I.P.V. 23, and 37 (for example, about 5%). Although it is considered that the contrast is improved and the display characteristics are further improved by the color filter of high color purity, satisfactory results can not be obtained by the conventional bead dispersion method or salt milling method.

On the other hand, according to the method for producing a pigment dispersion composition of the present invention, the dioxazine compound pigment can be obtained as a nano-sized pigment having a constant particle diameter distribution. The dispersion liquid containing the dioxazine compound pigment microparticles can be said to be excellent in stability over time. Therefore, a color filter using this 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 the description and reproducibility of black sharpness, blue, and can suppress display unevenness. It is possible to use all 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 as C.I.P.V.23. As C.I.P.V.37, it is possible to use all commercially available products such as Cromophtal Violet B and Microlith Violet B-A.

As the pigment dispersing composition of the present invention, a combination of two or more organic pigments or a solid solution of an organic pigment may be used.

Examples of the organic dye include azo dyes, cyanine dyes, merocyanine dyes, and keratin dyes. As the polymer organic material, for example, polydiacetylene, polyimide and the like are listed.

In the present invention, the organic pigment nanoparticles are prepared by mixing an organic pigment solution prepared by dissolving an organic pigment in a good solvent and a solvent which has compatibility with the good solvent and which becomes a poor solvent for the organic pigment (hereinafter, (This is sometimes referred to as " re-impregnation "). In this case, the organic pigment nanoparticles containing the organic pigment nanoparticles The dispersion liquid may be referred to as " organic particle re-precipitation liquid "). Here, " good solvent " means a solvent having a high solubility with respect to an organic pigment, and " poor solvent " means a solvent having a low solubility with respect to an organic pigment. The positive and negative solvents used in the present invention are required to have solubility differences of sufficient organic pigments to produce the organic pigment nanoparticles, and solvents that satisfy this requirement may be used in combination.

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

Examples of the poor solvent include water-soluble solvents (e.g., water or hydrochloric acid, aqueous sodium hydroxide solution), alcohol compound solvents, ketone compound solvents, ether compound solvents, aromatic compound solvents, carbon disulfide solvents, aliphatic compound solvents, An alcohol compound, a ketone compound solvent, an ether compound solvent, an ester compound solvent, or a mixture thereof are preferable, and an aqueous solvent, an ester compound solvent, an ester compound solvent, an ionic liquid, 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 solvent for the ether compound include dimethyl ether, diethyl ether, tetrahydrofuran and the like. Examples of the aromatic compound solvent include benzene, toluene, and the like. Examples of the aliphatic solvent include hexane and the like. Examples of the nitrile compound solvent include acetonitrile and the like. Examples of the halogen compound solvent include dichloromethane, trichlorethylene, and the like. Examples of the ester compound solvent include ethyl acetate, ethyl lactate, and 2- (1-methoxy) propyl acetate. Examples of the ionic liquid include salts of 1-butyl-3-methylimidazolium and PF ₆ ^- .

Next, a good solvent for dissolving the organic pigment will be described.

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

Examples of the positive solvent include aqueous solvents (e.g., water or hydrochloric acid, aqueous sodium hydroxide solution), alcohol compound solvents, amide compound solvents, ketone compound solvents, ether compound solvents, aromatic compound solvents, carbon disulfide solvents, A solvent solvent, a sulfoxide compound solvent, a halogen compound solvent, an ester compound solvent, an ionic liquid, and a mixed solvent thereof, and examples thereof include aqueous solvents, alcohol compound solvents, ketone compound solvents, ether compound solvents, sulfoxide compound solvents, The solvent is preferably an aqueous solvent, an alcohol compound solvent, an ester compound solvent, a sulfoxide compound solvent or an amide compound solvent, and an aqueous solvent, a sulfoxide compound solvent or an amide compound solvent is preferable. More preferably, the solvent or the solvent DE 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,慣 -caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide and hexamethylphosphoric triamide.

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

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

In the present invention, the organic pigment should be uniformly dissolved in a good solvent, but it is also preferable to dissolve it in an acidic or alkaline solution. Generally, in the case of a pigment having an alkaline dissociable group in its molecule, acidity is used when it has alkaline, and there are no dissociated groups in the alkaline state and thus many nitrogen atoms are likely to be added to the proton. For example, quinacridone, diketopyrrolopyrrole, disazo condensed compound pigments are soluble in alkaline and phthalocyanine compound pigments are soluble in acid.

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

The amount of the base to be used is an amount that can uniformly dissolve the pigment and is not particularly limited. In the case of an inorganic base, it is preferably 1.0 to 30 molar equivalents, more preferably 1.0 to 25 molar equivalents, 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 50 to 100 molar equivalents, and even more preferably 20 to 100 molar equivalents with respect to the organic pigment.

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

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

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

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

When the organic pigment solution and the poor solvent are mixed, any of them may be added and mixed. It is preferable that the organic pigment solution is added to and mixed with the poor solvent, and it is preferable that the poor solvent is stirred. The stirring speed is preferably 100 to 10000 rpm, more preferably 150 to 8000 rpm, and particularly preferably 200 to 6000 rpm. A pump or the like may or may not be used for the addition. In addition, it may be added to the liquid, or may be added outside the liquid.

The volume ratio of the organic pigment solution to the poor solvent (the ratio of the good solvent to the poor solvent in the solution of the organic particles) is preferably 1/50 to 2/3, more preferably 1/40 to 1/2, ~ 3/8 is particularly preferred.

The concentration of the organic particle repellent solution is not particularly limited as long as it can form organic particles, but the organic pigment nanoparticles are preferably in the range of 10 to 40,000 mg, more preferably 20 to 30,000 mg per 1000 mL of the dispersion solvent , Particularly preferably from 50 to 25000 mg.

The production scale for producing the organic pigment nanoparticles is not particularly limited, but it is preferably a production scale having a mixed amount of the poor solvent of 10 to 200 OL, more preferably a production scale of 50 to 100 OL.

With regard to the particle diameter of the organic pigment nanoparticles, there is a method of expressing the average size of the population by numerical measurement by a measurement method. However, the well-known method is a mode diameter indicating the maximum value of the distribution, a median diameter corresponding to the median diameter of the integral distribution curve , Average diameter (number average, length average, area average, weight average, volume average, etc.), and in the present invention, unless otherwise specified, the average particle diameter means the number average diameter. The average particle diameter of the organic pigment nanoparticles (primary particles) is in the nanometer size, and the average particle diameter is preferably 1 nm to 1 μm, more preferably 1 to 200 nm, still more preferably 2 to 100 nm, And particularly preferably from 5 to 80 nm. The particles formed in the method for producing a pigment dispersion composition of the present invention may be crystalline particles or amorphous particles or a mixture thereof.

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

Examples of the method for measuring the particle diameter of the organic pigment nanoparticles include a microscopic method, a gravimetric method, a light scattering method, a light blocking method, an electric resistance method, an acoustic method, and a dynamic light scattering method, and microscopic method and dynamic light scattering method are particularly preferable. Examples of the microscope used in the microscopic method include a scanning electron microscope and a transmission electron microscope. As a particle measuring apparatus by the dynamic light scattering method, for example, Nikkiso Co., Ltd. NANO RACK UPA-EX150, 0tsuka Electronics Co., Ltd. Ltd. Dynamic light scattering photometer DLS-7000 series.

The pigment dispersion composition of the present invention preferably contains a dispersant. The step of adding a dispersant to the pigment dispersion composition is not particularly limited, but it is preferable that a dispersant is added to both or one of the organic pigment solution and the poor solvent. It is also preferable that the dispersant solution is added at the time of forming the organic nanoparticles in a different system from the nutrient solution. It is also preferable to use pigment particles previously subjected to a surface treatment with a dispersant, and the pigment particles may be subjected to surface treatment capable of promoting adsorption of the dispersant. The dispersant has the function of (1) rapidly adsorbing onto the surface of the precipitated pigment to form fine nano particles, and (2) inhibiting the aggregation of these particles again.

As the dispersant that can be used, for example, a low molecular weight or polymer dispersant of anionic, cationic, amphoteric, nonionic or pigment derivative can be used. The molecular weight of the polymer dispersant is not particularly limited as long as it can be uniformly dissolved in a solution. The molecular weight is preferably 1,000 to 2,000,000, more preferably 5,000 to 1,000,000, still more preferably 10,000 to 500,000, Is particularly preferable. Specific examples of the polymer dispersing agent include polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol acetate vinyl copolymer, polyvinyl alcohol-partial formaldehyde, Polyvinyl pyrrolidone-vinyl acetate copolymer, polyethylene oxide / propylene oxide block copolymer, polyacrylate, polyvinylsulfate, poly (4-vinylpyridine) salt, polyamide, Polyallylamine salts, condensed naphthalenesulfonic acid salts, cellulose derivatives, and starch derivatives. Natural polymers such as alginate, gelatin, albumin, casein, gum arabic, tragacanth gum, and ligninsulfonic acid salt may also be used. Among them, polyvinyl pyrrolidone is preferable. These polymers may be used singly or in combination of two or more. These dispersants may be used alone or in combination. The dispersing agent used for dispersing the pigment is described in detail in pages 29 to 46 of "Pigment dispersion stabilization and surface treatment technology and evaluation" (issued by Japan Chemical Information Association, December 2001).

Examples of the anionic dispersing agent (anionic surfactant) include N-acyl-N-alkyl taurine salts, fatty acid salts, alkylsulfuric acid ester salts, alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, dialkylsulfosuccinic acid salts, alkylphosphoric acid ester salts, Sulfonic acid formalin condensate, polyoxyethylene alkyl sulfate ester salt, and the like. Among them, N-acyl-N-alkyltaurine salts are preferable. As the N-acyl-N-alkyltaurine salt, those described in Japanese Patent Application Laid-Open No. 3-273067 are preferable. These anionic dispersants may be used alone or in combination of two or more.

Examples of the cationic dispersant (cationic surfactant) include quaternary ammonium salts, alkoxylated polyamines, aliphatic amine polyglycol ethers, aliphatic amines, diamines and polyamines derived from aliphatic amines and aliphatic alcohols, imidazolines derived from fatty acids, Salts of the sex hormones. These cationic dispersants may be used alone or in combination of two or more.

The amphoteric dispersant is a dispersant having both an anionic group portion of the anionic dispersant in the molecule and a cationic portion of the cationic dispersant in the molecule together in the molecule.

Examples of nonionic dispersants (nonionic surfactants) include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamine, glycerin fatty acid Esters, and the like. Of these, polyoxyethylene alkyl aryl ethers are preferred. These nonionic dispersants may be used alone or in combination of two or more.

The pigment derivative-type dispersant is defined as a pigment derivative-type dispersant which is derived from an organic pigment as a parent substance and which is prepared by chemically modifying the parent group, or a pigment derivative-type dispersant obtained by pigmentation reaction of a chemically modified pigment precursor. For example, a pigment-containing pigment derivative-dispersant, a pigment-containing pigment derivative-dispersant, a naphthalene- or perylene-derived pigment derivative-type dispersant, a pigment derivative-type dispersant having a functional group connected to the pigment-friend group through a methylene group, A pigment derivative component having a sulfonic acid group, a pigment derivative component having a sulfonamide group, a pigment derivative component having an ether group, or a pigment derivative component having a carboxylic acid group, a carboxylic acid ester group or a carboxyamide group.

In the case of producing the pigment dispersion composition of the present invention, it is preferable to coexist with a pigment dispersing agent containing an amino group when preparing an organic pigment solution dissolved in both solvents. 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 plural. A pigment derivative compound in which a substituent having an amino group is introduced into a pigment skeleton or a polymer compound having a monomer having an amino group as a polymerization component may be used. Examples of these compounds include compounds described in JP-A Nos. 2000-239554, 2003-96329, 2001-31885, JP-A-10-339949, and JP-A-5-72943 But are not limited thereto.

The dispersing agent having an amino group used in the method for producing a pigment dispersion composition of the present invention is not limited to this, but may be at least one selected from the compounds represented by the following general formulas (D1), (D3) and (D4) Can be used.

<1. The compound represented by the general formula (D1)

In the general formula (D1), A represents a component capable of forming an azo dye together with X-Y. The A may 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 the above-mentioned A are shown below, but the present invention is not limited thereto at all.

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

In the general formula (D1), Y represents a group represented by the following general formula (D2).

In the general formula (D2), Z represents a lower alkylene group. Z is represented by - (CH ₂ ) _b -, wherein b represents an integer of 1 to 5, preferably 2 or 3. In the general formula (D2), -NR ₂₁ represents a 5 to 6 membered saturated heterocyclic group comprising a lower alkyl group, or a nitrogen atom. When -NR ₂₁ represents a lower alkylamino group, it is represented by -N (C _r H _{2r + 1} ) ₂ , r represents an integer of 1 to 4, preferably 1 or 2. When -NR ₂₁ represents a saturated 5- to 6-membered heterocyclic group containing a nitrogen atom, any one of the heterocyclic groups represented by the following structural formulas is preferable.

Z and -NR ₂₁ in the general formula (D2) each may 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 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 the method described in, for example, JP-A-2000-239554.

<2. The compound represented by the general formula (D3)

In formula (D3), Q represents an anthraquinone compound dye, an azo compound dye, a phthalocyanine compound dye, a quinacridone compound dye, a dioxazine compound dye, an anthrapyrimidine compound dye, an anthanthrone compound dye, A pyranthrone compound dye, a pyranthrone compound dye, a pyranthrone compound dye, a pyranthrone compound dye, a pyranthrone compound dye, a perinone compound dye, a perylene compound dye, a perylene compound dye and a thioindigo compound dye. Among them, azo compound dye or dioxazine compound dye is preferable. More preferably a compound dye.

X ₁ represents -CO-, -CONH-Y ₂ -, -SO ₂ NH-Y ₂ - or -CH ₂ NHCOCH ₂ NH-Y ₂ -, and is preferably -CO- or -CONH-Y ₂ - .

Y ₂ represents an alkylene group or an arylene group which may have a substituent, and among them, phenylene, toluene or hexylene is preferable, and phenylene is more preferable.

R ₁₁ and R ₁₂ each independently represent a substituted or unsubstituted alkyl group or a heterocyclic group containing at least a nitrogen atom as R ₁₁ and R ₁₂ . Among them, a methyl group, an ethyl group, a propyl group, or a pyrrolidinyl group containing 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 formula (D3a), or -NH-X ₁ -Q when n1 is 1. m1 represents an integer of 1 to 6, preferably 2 to 3; n1 represents an integer of 1 to 4, preferably 1 to 2;

In the general formula (D3a), Y ₃ represents -NH- or -O-, m1, R ₁₁ and R ₁₂ are the same meaning as those in formula (D3).

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

Further, with respect to Formula (D3-1) ~ (D3-6), Q, m1, n1, R 11, R 12 is the same meaning as those in formula (D3). Specific examples of the compound represented by formula (D3) are listed below, but the present invention is not limited thereto.
Also, in the formula, Cu-Pc represents copper phthalocyanine.

The compound represented by the general formula (D3), for example, R _11, and an alcohol compound having an amine and R ₁₁ and R ₁₂ having the R ₁₂ is reacted with a halogenated triazine compound, can be obtained by reacting a dye compound of the obtained intermediate have. Also, reference may be made to the specification of Japanese Patent Publication No. Hei 5-72943.

<3. Pigment Dispersant Containing Graft Copolymer>

In the method for producing a pigment dispersion composition 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 other monomers and the like may be contained as a copolymer unit.

The weight average molecular weight (Mw) of the graft copolymer is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000. If the weight average molecular weight (Mw) is less than 3,000, the aggregation of the organic nanoparticles can not be inhibited and the viscosity may increase. If the weight average molecular weight (Mw) is more than 100000, the solubility in organic solvents becomes insufficient and the viscosity increases . The weight average molecular weight is a polystyrene reduced weight average molecular weight measured by gel permeation chromatography (carrier: tetrahydrofuran).

(Ii) a monomer having an amino group and an ethylenically unsaturated double bond; and (iii) a polymerizable monomer having an ether group as a copolymer unit, wherein the polymerizable oligomer has an ethylenically unsaturated double bond at the terminal thereof, , And (iv) other monomers as copolymerized units, if necessary.

The content of these copolymer units in the graft copolymer is preferably (i) 15 to 98% by mass, more preferably 25 to 90% by mass, and most preferably (ii) More preferably 5 to 30 mass%, and (iii) the polymerizable monomer having an ether group is preferably 1 to 70 mass%, more preferably 5 to 60 mass% Is more preferable.

If the content of the polymerizable oligomer is less than 15 mass%, the effect of steric repulsion as a dispersing agent can not be obtained and the aggregation of the organic nanoparticles can not be prevented in some cases. When the content exceeds 98 mass%, the ratio of the nitrogen- There is a case in which the adsorption ability to organic particles is lowered and the dispersibility is insufficient. If the content of the nitrogen-containing monomer is less than 1% by mass, the adsorption capability to organic particles may deteriorate and the dispersibility may not be sufficient. When the content is more than 40% by mass, the proportion of the polymerizable oligomer is reduced, It is impossible to obtain a three-dimensional repulsive effect as the organic nanoparticles, so that the aggregation of the organic nanoparticles can not be sufficiently prevented. If the content of the polymerizable monomer having an ether group is less than 1% by mass, the developing property may not be sufficient when a color filter or the like is produced. When the content is more than 70% by mass, the ability as a dispersant may decrease.

(i) a polymerizable oligomer

The polymerizable oligomer (hereinafter sometimes referred to as "macromonomer") is an oligomer having a group having an ethylenically unsaturated double bond at the terminal thereof. In the present invention, among the above-mentioned polymerizable oligomers, those having a group having an ethylenically unsaturated double bond at only one side of both ends of the oligomer are preferable.

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

As the group having an ethylenically unsaturated double bond, for example, a (meth) acryloyl group and a vinyl group are preferably exemplified. Among them, a (meth) acryloyl group is particularly preferable.

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

In the above 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 with 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 (wherein R ⁶⁴ represents an alkyl group having 1 to 6 carbon atoms, an alkyl group which may be substituted with halogen, a phenyl group, An arylalkyl group), and is preferably a phenyl group or -COOR ⁶⁴ (wherein R ⁶⁴ represents an alkyl group which may be substituted with an alcoholic hydroxyl group having 1 to 4 carbon atoms). q represents 20 to 200;

Specific examples of the polymerizable oligomer include poly-2-hydroxyethyl (meth) acrylate, polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, Acrylate, a copolymer thereof and a (meth) acryloyl group bonded to one of the molecular terminals is preferable.

The above-mentioned polymerizable oligomer may be a commercially available product or may be suitably synthesized. Examples of commercially available products include commercially available end-capped methacryloylated polystyrene oligomer (Mn = 6000, trade name: AS-6, manufactured by Toagosei Chemical Industry Co., Ltd.). Terminal methacryloylated polymethyl methacrylate oligomer (Mn = 6000, trade name: AA-6, manufactured by Toagosei Chemical Industry Co., Ltd.), one end methacryloyl poly-n-butyl acrylate (Manufactured by Toagosei Chemical Industry Co., Ltd.), an end-capped methacryloylated polymethyl methacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7000, trade name: AB- Terminal methacryloylated polybutyl methacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7000, trade name: 707S, manufactured by Toagosei Chemical Industry Co., Ltd.) , Ltd.), one end methacryloyl chloride Li 2-ethylhexyl methacrylate / 2-hydroxyethyl methacrylate oligomer: include (Mn = 7000, trade name AY-707S, AY-714S, Toagosei Chemical Industry Co., Ltd., Ltd.) are exemplified.

Preferred examples of the polymerizable oligomer in the present invention include at least one oligomer selected from the group consisting of a polymer of alkyl (meth) acrylate and a copolymer of alkyl (meth) acrylate and polystyrene, and has a number average molecular weight of 1000 To 20000, and (meth) acryloyl groups at the terminals.

(ii) an amino group-containing monomer

As the amino group-containing monomer, at least one member selected from the 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 ). Here, R ²³ and R ²⁴ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. 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.

The ^{one, -N (R 23) (R} 24) in R ²³ and R ²⁴ is a hydrogen atom or a 1-4C alkyl group or a phenyl group preferred, and ^{-R 25 -N (R 26) (} R 27) in R ²⁵ is preferably an alkylene group having 2 to 6 carbon atoms, and R ²⁶ and R ²⁷ are preferably an alkyl group having 1 to 4 carbon atoms. m2 and n2 represent 1 or 0, and m2 = 1 or n2 = 1 or m2 = 1 and n2 = 0 (i.e., corresponding to monomers represented by the following formulas (E3) and (E4) .

In the present invention, among the monomers represented by the general formula (E2), at least one selected from the monomers represented by any one 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 the same as X ² and is -N (R ⁴³ ) (R ⁴⁴ ) (wherein R ⁴³ and R ⁴⁴ are the same as R ²³ and R ²⁴ ), or -R ⁴⁵ -N ⁴⁶ ) (R ⁴⁷ ) (wherein R ⁴⁵ , R ⁴⁶ and R ⁴⁷ are the same as R ²⁵ , R ²⁶ and R ²⁷ , respectively).

Specific examples of the monomer represented by the general formula (E2) include dimethyl (meth) acrylamide, diethyl (meth) acrylamide, diisopropyl (meth) acrylamide, di- (Meth) acrylamide, N-methylpyrrolidyl (meth) acrylamide, N, N-methylphenyl (meth) acrylamide, Metha) acrylamide (above, (meth) acrylamides); (Meth) acrylamide, 2- (N, N-dimethylamino) ethyl (meth) acrylamide, 2- (Meth) acrylamide, 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylamide, 6- Diethylamino) hexyl (meth) acrylamide (above, aminoalkyl (meth) acrylamides), and the like.

(iii) a polymerizable monomer having an ether group

As the polymerizable monomer having an ether group, for example, at least one kind selected from monomers represented by the following formula (E1) is preferably listed.

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, 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 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. Also, m3 represents 2 to 200, preferably 5 to 100, and particularly preferably 10 to 100.

The polymerizable monomer having an ether group is not particularly limited as long as it has an ether group and can be polymerized, and can be appropriately selected from ordinary ones. Examples thereof include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono Polyethylene glycol polypropylene glycol mono (meth) acrylate, and polytetramethylene glycol monomethacrylate. These may be commercially available products or suitably synthesized products. As commercial products, methoxypolyethylene glycol methacrylate (trade name: NK ESTER M-40G, M-90G, M-230G (manufactured by Toagosei Chemical Industry Co., Ltd.), BLENMER PME- (Trade name: BLENMER PE-90, PE-200, PE-200, PME-400, PME-1000, PME-2000 and PME-4000 manufactured by Nippon Yushi Co., Ltd.), polyethylene glycol monomethacrylate 350, manufactured by Nippon Yushi Co., Ltd.), polypropylene glycol monomethacrylate (trade name: BLENMER PP-500, PP-800, PP-1000, manufactured by Nippon Yushi Co., Ltd.), polyethylene glycol polypropylene glycol (Manufactured by Nippon Yushi Co., Ltd.), polyethylene glycol polytetramethylene glycol monomethacrylate (trade name: BLENMER 55PET-800, manufactured by Nippon Yushi Co., Ltd.), and polypropylene glycol monomethacrylate (trade name: BLENMER 70PEP- Polypropylene glycol polytetramethylene glycol monomethacrylate (trade name: BLENMER NHK-5050, manufactured by Nippon Yushi Co., Ltd.) ) Are listed.

(iv) Other monomers

The graft copolymer may further contain other monomers as a copolymer unit. The other monomers are not particularly limited and may be appropriately selected according to the purpose. Examples thereof include aromatic vinyl compounds (e.g., styrene, Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate and i-butyl (meth) (Meth) acrylates such as benzyl (meth) acrylate, glycidyl (meth) acrylate, carboxylic acid vinyl esters (such as vinyl acetate and vinyl propionate) Acrylonitrile and? -Chloroacrylonitrile), aliphatic conjugated dienes (e.g., 1,3-butadiene and isoprene), (meth) acrylic acid, and the like. Of these, unsaturated carboxylic acids, alkyl (meth) acrylates, alkylaryl (meth) acrylate esters and carboxylic acid vinyl esters are preferred.

The content of the other monomer in the graft copolymer is preferably 5 to 70% by mass, for example. When the content is less than 5 mass%, the physical properties of the coating film may not be controlled. When the content is more than 70 mass%, the ability as a dispersant may not be sufficiently exhibited.

As specific preferred examples of the graft copolymer,

(11) A copolymer comprising a copolymer of 3- (N, N-dimethylamino) propyl acrylamide / polyethylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth)

(12) A polystyrene resin composition comprising 3- (N, N-dimethylamino) propyl acrylamide / polyethylene glycol mono (meth) acrylate / end methacryloylated polystyrene copolymer,

(13) A method for producing a polymethacrylate copolymer of 3- (N, N-dimethylamino) propyl acrylamide / polyethylene glycol mono (meth) acrylate / methyl (meth)

(14) A copolymer of a copolymer of methyl (meth) acrylate and 2-hydroxyethyl methacrylate of 3- (N, N-dimethylamino) propyl acrylamide / polyethylene glycol mono Copolymers,

(15) Copolymers of copolymers of 3- (N, N-dimethylamino) propyl acrylamide / polyethylene glycol mono (meth) acrylate / terminal methacryloyl methyl methacrylate and 2-hydroxyethyl methacrylate ,

(16) Copolymer of a copolymer of 3- (N, N-dimethylamino) propyl acrylamide / polyethylene glycol mono (meth) acrylate / terminal methacryloyl methyl methacrylate and 2-hydroxyethyl methacrylate ,

(17) A copolymer comprising a copolymer of 3- (N, N-dimethylamino) propyl acrylamide / polypropylene glycol mono (meth) acrylate / end methacrylated polymethyl (meth)

(18) A copolymer comprising a copolymer of 3- (N, N-dimethylamino) propyl acrylamide / polyethylene glycol polypropylene glycol mono (meth) acrylate / terminal methacrylate polymethyl (meth)

(19) A copolymer comprising a copolymer of 3- (N, N-dimethylamino) propyl acrylamide / polyethylene glycol polytetramethylene glycol mono (meth) acrylate / terminal methacrylate polymethyl (meth)

(20) 3- (N, N-dimethylamino) propyl acrylamide / polypropylene glycol polytetramethylene glycol mono (meth) acrylate / terminal methacrylated polymethyl (meth) acrylate copolymer.

Among them, (11), (14) and (18) are preferable, and the compound represented by the following formula (D4) is more preferable. In the formula (D4), Me represents a methyl group.

The graft copolymer can be obtained by radical polymerization of the components as the respective copolymer units, for example, in a solvent. In the radical polymerization, a radical polymerization initiator can be used, and a chain transfer agent (e.g., 2-mercaptoethanol and dodecyl mercaptan) can be further used. For a pigment dispersant containing a graft copolymer, reference may be made to the disclosure of JP-A-2001-31885.

The content of the dispersant is preferably in the range of 0.1 to 1000 parts by mass, more preferably in the range of 1 to 500 parts by mass, and still more preferably in the range of 1 to 500 parts by mass, relative to 100 parts by mass of the pigment, in order to further improve the uniform dispersibility and storage stability of the organic particles. Preferably 5 to 20 parts by mass. If the amount is less than 0.1 part by mass, the dispersion stability of the organic nanoparticles may not be improved. The dispersant may be used alone or in combination of a plurality of dispersants.

[Manufacturing apparatus]

Preferred embodiments of the production apparatus used in the production of the pigment dispersion composition of the present invention will be described, but the present invention is not limited thereto.

(Manufacturing Apparatus Example 1)

1 is a preferred embodiment of a production apparatus used for producing the pigment dispersion composition of the present invention. In Fig. 1, the organic material solution is continuously supplied into the container 11 by the supply pipe 14. Here, in the vessel 11, a poor solvent 11a is accommodated, and the bulk bean solvent can always be convected by the stirring action.

Fig. 2 is a schematic view of another preferred embodiment of the production apparatus used in the production of the pigment dispersion composition of the present invention. In the production apparatus of Fig. 1, a mixing chamber (agitation region) 13 is provided in the vessel 11 . The mixing chamber (13) is provided below the liquid surface of the poor solvent, and the inside thereof is filled with the poor solvent. In addition, the bulk bean solvent in the reaction vessel 11 is always allowed to be convected in the mixing chamber 13 from below to above (in the direction of the arrow in the figure) by the stirring action in the mixing chamber 13 .

3 is an enlarged partial sectional view schematically showing the mixing chamber 13 as an embodiment of the manufacturing apparatus of Fig. The organic pigment solution is supplied from the supply pipe 14 into the mixing chamber 13. The mixing chamber 13 is formed by a casing 17 having a rectangular cross section with a constant cross section and the upper end of the casing 17 is formed as an open end and the lower end thereof is formed with a circular hole 18, 13) outside the stirring area (in the case of the constitution shown in the figure, the area other than the stirring area of the mixing chamber 13 among the poor solvent 11a is also referred to as the outside of the stirring area) . Here, the organic material solution supply pipe 14 is formed in the wall constituting the lower end of the casing 17 and opens toward the circular hole. A stirrer blade 12 is formed in the mixer 13 and the stirring blade is attached to the shaft 15 and rotated by the motor 16. By the rotation of the stirring blades 12, the poor solvent passes through the circular hole 18 and circulates within the mixer 13 constantly from below to upward.

The stirring blades 12 provided in the mixing chamber 13 should produce desired mixing strength in the mixing chamber. It is presumed that this mixing strength is an important operational factor for the size of the droplet (droplet) when the organic pigment solution is incorporated.

The agitating blades 12 are formed in such a manner that the organic nanoparticles generated in the mixing space stay in the mixing chamber 13 so that they can be combined with other organic nanoparticles to become larger particles, It is preferable to select the organic nanoparticles having the ability to quickly take out the produced organic nanoparticles and to quickly discharge them out of the mixing chamber 13 so that large particles are not formed due to exposure to the solution.

The stirring vane 12 may be of any type, for example, a turbine type, a fan turbine type, or the like may be used if the above object is achieved.

It is preferable that the casing 17 is constituted by a rectangular barrel as described above. By doing so, the flow formed by the stirring vane 12 is shaken by the angle of the casing 17, and it is not necessary to add additives such as a baffle plate, so that the mixing effect can be further enhanced.

Fig. 4 is an enlarged partial cross-sectional view of a mixer in which two mixing blades in the mixing chamber (mixing mixing blades 19a, discharge mixing blades 19b) are another embodiment of the manufacturing apparatus of Fig. 2; By providing two stirring blades in this manner, it is possible to independently select the ability to control the mixing intensity and the ability to discharge the generated organic pigment particles to the outside of the mixer, so that the mixing strength and the circulation amount can be independently set to desired values Lt; / RTI >

(Manufacturing Apparatus Example 2)

5 is a cross-sectional view schematically showing another embodiment of the production apparatus used for producing the pigment dispersion composition of the present invention. In Fig. 5, the organic material solution and the poor solvent are continuously supplied into the stirring tank 21a by the supply pipes 24a and 24b, respectively. The organic material particles generated in the agitating tank 21a stay in the agitating tank 21a to be combined with other organic pigment particles to become larger particles or exposed to the organic material solution supplied from the supply pipes 24a and 24b The resulting organic material particle dispersion liquid is quickly taken out from the discharge pipe 23 so that large particles do not form and large particles are generated.

6 is a cross-sectional view schematically showing still another embodiment of the apparatus used for producing the pigment dispersion composition of the present invention. 6, the stirring device 50 includes two liquid supply ports 32 and 33 for introducing the organic material solution and a poor solvent, respectively, and a liquid discharge port 36 for discharging the mixed liquid after the stirring process And a pair of stirring blades 41 and 42 which are stirring means for controlling the stirring state of the liquid in the stirring tank 38 by rotationally driving the stirring tank 38 in the stirring tank 38 Respectively.

The stirring tank 38 is constituted by a tubular main body 39 having a central axis oriented in the up and down direction and a sealing plate 40 composed of a tubular wall closing the upper and lower open ends of the tub main body 39. The stirring tank 38 and the bath main body 39 are formed of a nonmagnetic material having excellent investment property. The two liquid supply ports 32 and 33 are provided at the lower end of the bath main body 39 and the liquid discharge port 36 is provided at the position of the upper end of the bath main body 39.

Then, the pair of stirring blades 41 and 42 are arranged at the upper and lower ends opposite to each other in the stirring tank 38, and are rotationally driven in mutually opposite directions. Each of the stirring blades 41 and 42 constitutes a magnetic coupling C and an external magnet 46 disposed outside the crude wall (sealing plate 40) where the stirring blades 41 and 42 are close to each other. That is, each of the vanes 41 and 42 is connected to each of the external magnets 46 by a magnetic force, and the external magnets 46 are rotated by the independent motors 48 and 49 to rotate in opposite directions.

A pair of stirring vanes 41 and 42 disposed in the tank 38 in opposing relation to each other is provided with an agitating flow of different directions in the tank 38 as indicated by an arrow X indicated by a broken line and an arrow Y indicated by a solid line in FIG. . Since the agitation flows formed by the respective stirring vanes 41 and 42 are different from each other in the flow direction, they generate high-speed turbulence in the tank 38 that collides with each other to promote stirring in the tank 38, It is possible to prevent a cavity from being formed around the rotation axis of the stirring vanes 41 and 42 even when the rotation speed of the stirring vanes 41 and 42 is increased, It is possible to prevent the occurrence of disadvantage that a steady stream flowing in the tank 38 along the inner circumferential surface of the stirring tank 38 is formed. Therefore, the speed of rotation of the stirring vanes 41, 42 can be easily increased, and the flow of liquid in the tank 38 is normalized at that time so that liquid with insufficient stirring and mixing is discharged So that the degradation of the processing quality can be prevented.

Since the stirring vanes 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, It is not necessary to insert the rotating shaft into the crude wall of the stirring vessel 38. This makes it possible to make the stirring vessel 38 a sealed container structure without the insertion passage portion of the rotating shaft, It is possible to prevent the degradation of the processing quality due to the mixing of the lubricant (sealing liquid) or the like into the liquid in the tank 38 as impurities.

In the production of the pigment dispersion composition of the present invention, organic nanoparticles can be produced not only by the batch method but also by the continuous flow method using the production apparatus having these constitutions, and can cope with mass production. In addition, since the resulting dispersion of organic nanoparticles is rapidly discharged, it becomes possible to always keep the ratio of the organic solvent solution and the poor solvent solution supplied into the stirring tank constant. Therefore, it is possible to make the solubility of the organic material in the dispersion constant from the start to the end of the production, and monodisperse organic nanoparticles can be stably produced.

In addition, the flow of the liquid in the tank is normalized to prevent the dispersion of the organic nanoparticle dispersion liquid from being insufficiently stirred, and the lubricant (sealing liquid) or the like for the rotation shaft is prevented from being mixed with the liquid in the tank as impurities, The organic nanoparticles can be prepared more stably.

(Manufacturing Apparatus Example 3)

As a device used in the production of the pigment dispersion composition of the present invention, a production method of stirring by using a wing having a shear force, which is another embodiment, will be described.

The shear force referred to in the present invention is a shearing force applied to a droplet (droplet) generated after a stirring blade is mixed with an organic solvent solution.

The shape of the agitating portion usable in the present invention is not particularly limited as long as it is a form capable of applying a high shear force, and generally includes a paddle blade, a turbine blade, a screw blade, a pfaudler blade blade, An agitating, emulsifying and dispersing unit of a stirring portion constituted by a solenoid blade, a rotatable turbine portion and a fixed stator portion located at a certain interval therearound is preferable.

The dissolver blade is a special stirring blade having a function of forming a high shear force. An example thereof is shown in a schematic front view in Fig. 7, and a photograph of the drawing is shown in Fig.

It is also preferable to use an apparatus having an agitating portion constituted by a rotatable turbine portion and a stationary stator portion located at a slight interval therearound as shown in Fig. 9, and as the agitating, emulsifying and dispersing device, For example, Micro-Tech Nichion Co., Ltd. Product of HISC0RON, Tokushu Kika Kogyo Co. T.K homomixer of the product, and ULTRA-TURRAX of the IKA product.

The stirring speed may vary depending on the viscosity of the poor solvent, the temperature, and the kind or amount of the surfactant, but is preferably 100 to 10000 rpm, more preferably 150 to 8000 rpm, and particularly preferably 200 to 6000 rpm. If the number of revolutions is too low, the stirring effect is not sufficiently exhibited. On the other hand, if the number of revolutions is too high, bubbles are generated in a poor solvent, which is not preferable.

In the method for producing a pigment dispersion composition of the present invention, by concentrating the organic nanoparticle dispersion liquid by desalting, it is possible to produce a concentrate suitable for a color filter coating liquid or an inkjet ink on an industrial scale.

Hereinafter, the concentration method will be described.

The concentration method is not particularly limited as long as the organic nanoparticle solution can be concentrated. For example, an extraction solvent is added to and mixed with the organic nanoparticle dispersion, the organic nanoparticles are concentrated and extracted on the extraction solvent, A method of concentrating the organic nanoparticles by centrifugation and concentration, a method of concentrating desalting by ultrafiltration, a method of sublimating and concentrating the solvent by vacuum freeze drying, a method of heating Or a method of drying and concentrating the solvent by reduced pressure is preferable. Or a combination thereof, and the like are very preferably used.

In the process of passing the low moisture content pigment dispersion composition of the present invention, when the concentration process of the water dispersion has elapsed, the moisture content of the concentrated wet cake is usually 15% by mass to 95% by mass, but 30% By mass, more preferably 50% by mass to 85% by mass.

If the moisture content of the wet cake is less than 15% by mass, the pigment particles may form an irreversible aggregate and may be unable to disperse. In addition, if the moisture content of the wet cake exceeds 95 mass%, a large amount of organic solvent may be required in a later step.

In the process of obtaining the pigment dispersion composition having a low water content of the present invention, the solvent concentrate of the pigment may be roughened. The concentration of the pigment in the solvent concentrate is usually 10% by mass to 70% by mass, but is preferably 15% by mass to 60% by mass, and more preferably 20% by mass to 50% by mass. The water content in the concentrate is preferably 50% by mass or less based on the pigment, more preferably 30% by mass or less, and particularly preferably 10% by mass or less based on the pigment.

The water content can be measured by any known method, but in the present invention, the water content was measured by the Karl Fischer method (Experimental Chemistry Lecture 15 (lower) Analytical Chemistry P. 241).

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 and extraction will be described.

The extraction solvent used for the concentration and extraction is not particularly limited, but is not substantially mixed with a dispersion solvent (for example, an aqueous solvent) of the organic nanoparticle dispersion (in the present invention, It is preferable that the dissolution amount is not less than 50% by mass, more preferably not more than 30% by mass. The solubility of the solvent is not particularly limited, but it is practically at least 1% The extracting solvent is preferably a solvent which forms an interface with the organic nanoparticles in the presence of a weak coagulation capable of redispersing the organic nanoparticles in the extraction solvent (a floc which can be redispersed without applying a high shearing force such as milling or high- It is preferable that the solvent is a solvent to be produced. In such a state, strong coagulation for changing the particle size is not caused, It is preferable in that the nanoparticles are wetted in an extraction solvent and the dispersion solvent such as water can be easily removed by filter filtration etc. As the extraction solvent, an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, an aliphatic compound A solvent, an ester compound solvent, an aromatic compound solvent or an aliphatic compound solvent is more preferable, and an ester compound solvent is particularly preferable.

Examples of the ester compound solvent include 2- (1-methoxy) propyl acetate, ethyl acetate, ethyl lactate and the like. 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, cyclohexane, and the like. Further, the extraction solvent may be a pure solvent by the above-mentioned preferable solvent or a mixed solvent by a plurality of solvents.

The amount of the extraction solvent is not particularly limited as long as the organic nanoparticles can be extracted, but it is preferably smaller than the organic nanoparticle dispersion in consideration of concentration and extraction. When this is expressed as a volume ratio, when the organic nanoparticle dispersion is taken as 100, the extraction solvent added is preferably in the range of 1 to 100, more preferably in the range of 10 to 90, and particularly preferably in the range of 20 to 80 . If it is too much, enormous time is required for the concentration, and if it is too small, the extraction is insufficient and the nanoparticles remain in the dispersion solvent.

After the extraction solvent is added, it is preferable to stir and mix so as to sufficiently contact with the dispersion. For stirring mixing, a usual method can be used. There is no particular limitation on the temperature at which the extraction solvent is added and mixed, but it is preferably 1 to 100 ° C, more preferably 5 to 60 ° C. Addition or mixing of the extraction solvent may be carried out by any apparatus as long as the respective steps can be preferably carried out. For example, the apparatus may be carried out by using a separating lot apparatus.

In the case of ultrafiltration, for example, a method which can be used for desalting / concentration of a silver halide emulsion can be applied. Research Disclosure No. 10208 (1972), No. 13122 (1975) and No. 16351 (1977) are known. An important pressure difference or flow rate as an operating condition can be selected with reference to the characteristic curve described in "Membrane Utilization Handbook" by Haruhiko Oya, published by Seibang Publishing Co. (1978), p. 275. However, It is necessary to find an optimum condition for suppressing the aggregation of the particles. In addition, in the method of replenishing the solvent lost from the membrane permeation, there is a batch system in which the solvent is divided and added intermittently with a static system in which a solvent is continuously added, but a static system having a relatively short desalination time is preferable. As the solvent to be supplemented in this way, pure water obtained by ion exchange or distillation is used, but a poor solvent of a dispersant and a dispersant may be mixed in pure water, or may be directly added to the organic nanoparticle dispersion.

Fig. 10 shows a configuration example of an apparatus for ultrafiltration. As shown in Fig. 10, this apparatus is characterized in that the fatty acid is introduced into the tank 81 by a circulation pump 82 for circulating the dispersion in the tank 81 and a circulation pump 82 And an ultrafiltration module 83 for removing by-produced inorganic salts in the dispersion by permeated water. The dispersion in which the permeated water has been separated is returned to the tank 81 again, and the same operation is repeatedly performed until the predetermined purpose of removal of the by-product inorganic salt is achieved. In addition, this apparatus is provided with a replenishment flow meter 84 used to replenish the solvent lost by permeated water by a certain amount with pure water, and a flow meter 85 for measuring permeation water used for determining the pure replenishment amount ). Further, there is provided a reverse cleaning pump 86 for introducing water to dilute the permeated water.

The ultrafiltration membranes are manufactured by Asahi Kasei Corporation, Daicel Chemical Industries, Ltd., which are already assembled as modules, such as flat plate, helical, cylindrical, hollow tube and homo-fiber types. Toray Industries, Inc., Nitto Denko Corporation, and the like, but from the viewpoint of the total membrane area and the cleaning property, a spiral or hollow tube type is preferable. The fraction molecular weight, which is an index of the threshold value of the component that can permeate the film, needs to be determined from the molecular weight of the dispersant used, but it is preferably 5,000 or more and 50,000 or less, more preferably 5,000 or more and 15,000 or less.

In order to separate the dispersion solvent of the organic nanoparticle dispersion liquid from the concentrated extract, it is preferable to perform filter filtration. As the filter filtration device, for example, a device such as pressure filtration can be used. Preferred filters include nanofilters, ultra filters, and the like. It is preferable that the residual dispersion solvent is removed by filtration of the filter, and the organic nanoparticles in the concentrated extract solution are further concentrated to obtain a concentrated nanoparticle solution.

The method of freeze-drying is not particularly limited, and any method that can be used by those skilled in the art may be employed. For example, a cold magic bulging method, a redundant freezing method, a fruit circulation method, a triple heat exchange method, and an indirect heating freezing method are listed, but preferably a cold magic bulging method, an indirect heating freezing method and more preferably an indirect heating freezing method It is good to do. In either method, it is preferable to perform freeze-drying after preliminary freezing. The conditions of the preliminary freezing are not particularly limited, but it is necessary that all the samples to be freeze-dried are frozen.

Examples of the apparatus for indirect heating and freezing include a small-sized freeze dryer, an FTS freeze dryer, a LYOVAC freeze dryer, a freeze dryer for testing, a freeze dryer for research, a triple-heat exchanger vacuum freeze dryer, a mono cooling type freeze dryer and a HULL freeze dryer It is preferable to use a small size freeze dryer, a freeze dryer for testing, a freeze dryer for research, a mono cooling type freeze dryer, more preferably a small freeze dryer or a mono cooling type freeze dryer.

The temperature for freeze-drying is not particularly limited, but is, for example, -190 to -4 캜, preferably -120 to -20 캜, and more preferably -80 to -60 캜. The freeze-drying pressure is not particularly limited and can be suitably selected by a person skilled in the art, but is preferably 0.1 to 35 Pa, preferably 1 to 15 Pa, more preferably 5 to 10 Pa. The freeze-drying time is, for example, 2 to 48 hours, preferably 6 to 36 hours, more preferably 16 to 26 hours. However, these conditions are suitably selectable by those skilled in the art. The freeze-drying method is described in, for example, the Preparation Machinery and Technology Handbook: Japan Preparation Technology Research Association, Chijin Shokan, p.120 to 129 (September 2000); Vacuum Handbook: Japan Vacuum Technology Co., Ltd., Ohm Publishing Co., Ltd., pp. 328 to 331 (1992); Freezing and Drying Research Meeting: Hiroshi Itou, No.15, p.82 (1965).

The centrifugal separation will be described below.

The centrifugal separator used for concentrating the organic nanoparticles by centrifugation may be any device as far as it can precipitate the organic nanoparticles in the organic nanoparticle dispersion (or concentrated organic nanoparticle extract). Examples of the centrifugal separator include a general centrifugal separator having a skimming function (a function of sucking the supernatant layer during rotation and discharging it out of the system during rotation), and a continuous centrifugal separator continuously discharging solids.

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

Hereinafter, drying will be described.

The apparatus used for concentration of organic nanoparticles by reduced-pressure drying is not particularly limited as long as it can evaporate the solvent of the organic nanoparticle dispersion (or organic nanoparticle concentrated extract). For example, there are enumerated general vacuum driers and rotary pumps, apparatuses capable of drying under reduced pressure while stirring the liquid, and apparatuses capable of continuously drying by passing the liquid through heated and depressed tubes.

The drying temperature under reduced pressure is preferably 30 to 230 ° C, more preferably 35 to 200 ° C, and particularly preferably 40 to 180 ° C. The pressure at the time of the decompression is preferably 100 to 100000 Pa, more preferably 300 to 90000 Pa, and particularly preferably 500 to 80000 Pa.

According to the concentration method as described above, the organic nanoparticles can be efficiently concentrated from the organic nanoparticle dispersion. With regard to the concentration ratio, for example, when the concentration of the nanoparticles in the organic nanoparticle dispersion as the raw material is 1, the concentration in the concentrated organic nanoparticle paste is preferably about 100 to 3,000 times, more preferably 500 to 2,000 times .

In the production of the pigment dispersion composition of the present invention, the organic nanoparticles in the agglomerated state can be redispersed by the above-mentioned concentration (in the present invention, redispersion means that aggregation of the particles in the dispersion is released to increase the degree of dispersion , Also called microdispersion).

The organic particles contained in the organic particle liquid concentrated by the above-mentioned extraction solvent, centrifugal separation, drying and the like are usually agglomerated by the concentration. At this time, in order to enable rapid filter filtration and to obtain a good dispersion state again, it is preferable to obtain a flocculent aggregated to such an extent as to be redispersible.

For this reason, there is a need for a method in which fine particles are insufficiently dispersed at a degree of dispersion using a conventional dispersing method, resulting in a higher fineness efficiency. In such coagulated organic particles (in the present invention, the coagulated organic particles mean aggregated organic particles such as agglomerates gathered by a secondary force, and sometimes referred to as agglomerated nanoparticles when the primary particles have a nanometer size) According to the production method of the organic nanoparticle dispersion of the present invention, the organic particles can be preferably finely dispersed by including a polymer compound having a weight average molecular weight of 1000 or more in the aggregated organic particle solution (in the present invention, Refers to the inclusion of aggregated organic particles in the liquid, and may include aggregated organic particles such as dispersions, concentrates, pastes, slurries, etc.).

Next, the polymer compound preferably used in the method for producing a pigment dispersion composition of the present invention (the "polymer compound" in the present invention means an organic compound having a mass average molecular weight of 1,000 or more and no particular upper limit but a mass average molecular weight of 500,000 or less Practical, preferably 100,000 or less, more preferably 50,000 or less) will be described in detail.

The polymer compound preferably usable in the pigment dispersion composition of the present invention is a polymer compound having a mass average molecular weight of 1,000 or more and represented by the following general formula (1).

In the general formula (1), A ¹ represents an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a saturated oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, And a hydroxyl group, or a monovalent organic group containing an organic pigment structure or a heterocycle which may have a substituent. 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 groups having a carboxylic acid group, a sulfonic acid group, a mono sulfuric acid ester group, a phosphoric acid group, a morpholinic acid ester group, A monovalent organic group is enumerated. Examples of the monovalent organic group having a group having a basic nitrogen atom include a monovalent organic group having an amino group (-NH ₂ ), a monovalent organic group having a substituted imino group (-NHR ⁸ , -NR ⁹ R ¹⁰ ) Each of R ⁸ , R ⁹ and R ¹⁰ independently 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; And a guanidyl group represented by the following general formula (a1), wherein R ^a1 and R ^a2 each independently represent an alkyl group having 1 to 20 carbon atoms, An aralkyl group having 7 or more and 30 or less carbon atoms, an amidinyl group-containing monovalent organic group represented by the following general formula (a2) [in the general formula (a2), R ^a3 and R ^a4 each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryl group having 7 to 30 carbon atoms And the following aralkyl groups.

Examples of the monovalent organic group having a urea group include -NHCONHR ¹⁵ wherein R ¹⁵ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryl group having 7 or more carbon atoms 30 or less aralkyl groups).

Examples of the "monovalent organic group having a urethane group" include -NHCOOR ¹⁶ , -OCONHR ¹⁷ (wherein R ¹⁶ and R ¹⁷ each independently represent an alkyl group having 1 to 20 carbon atoms, an alkyl group having 6 to 20 carbon atoms An aryl group, and an aralkyl group having 7 to 30 carbon atoms), and the like.

Examples of the group having a 'group having a double oxygen atom' include groups having an acetylacetonate group, groups having a crown ether, and the like.

Examples of the "group having 4 or more carbon atoms" include an alkyl group having 4 or more carbon atoms (such as octyl group and dodecyl group), an aryl group having 6 or more carbon atoms (such as phenyl group and naphthyl group), an aralkyl group having 7 or more carbon atoms Benzyl group, etc.), and the like. At this time, although there is no upper limit to the number of carbon atoms, it is preferably 30 or less.
Examples of the "group having an alkoxysilyl group" include groups having a trimethoxysilyl group, a triethoxysilyl group and the like.

Examples of the "group having an epoxy group" include groups having a glycidyl group and the like.

Examples of the "group having an isocyanate group" include 3-isocyanatopropyl group and the like.

Examples of the above "group having a hydroxyl group" include 3-hydroxypropyl group and the like.

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

The organic dye structure or heterocyclic ring is not particularly limited, but more specifically, examples of the organic dye structure include phthalocyanine compounds, insoluble azo compounds, azo lake compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds , Diketopyrrolopyrrole compounds, anthrapyridine compounds, anthanthrone compounds, indanthrone compounds, flavanthrone compounds, perinone compounds, perylene compounds, thioindigo compounds, and the like. Examples of the heterocyclic ring include heterocyclic rings such as thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, Isoindolinone, benzimidazolone, isothiazolone, isothiazolone, isothiazolone, thiadiazole, pyridine, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, Succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, and anthraquinone.

Examples of the substituent include an alkyl group of up to 20 carbon atoms such as a methyl group and an ethyl group, an alkyl group of up to 6 to 16 carbon atoms such as a phenyl group and a naphthyl group Up to 1 to 6 carbon atoms, such as an acyl group, an acyl group, an acyl group having 1 to 6 carbon atoms such as an acyl group, an acyl group, an aryl group, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, A halogen atom such as an alkoxy group, a chlorine atom and a fluorine atom, an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group and a cyclohexyloxycarbonyl group, a cyano group, and a carbonate ester group such as t- do.

It is preferable that A ¹ is a monovalent organic group represented by the following general formula (4).

In the general formula (4), B ¹ represents an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a saturated oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, And an organic pigment structure or a heterocyclic ring which may have a substituent, and R ¹⁸ represents a single bond or an aliphatic organic or inorganic linking group. a1 represents 1 to 5, and a1 B ¹ may be the same or different.

B ¹ are as defined with the A ^1, but also a preferred form, the organic dye structure or a heterocyclic ring include, for example, the phthalocyanine compound in the formula (4), insoluble azo compounds, azo lake compounds, anthraquinone compounds, Organic pigment structures such as quinacridone compounds, dioxazine compounds, diketopyrrolopyrrole compounds, anthrapyridine compounds, anthanthrone compounds, indanthrone compounds, flavanthrone compounds, perinone compounds, perylene compounds, and thioindigo compounds, Thiazole, thiazole, thiadiazole, thiadiazole, thiazole, thiazole, thiazole, thiazole, thiazole, thiazole, thiazole, thiazole, thiazole, Pyridine, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, A heterocyclic ring, such as polyamide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridine money, anthraquinone are exemplified.

Examples of the substituent include an alkyl group of up to 20 carbon atoms such as a methyl group and an ethyl group, an alkyl group of up to 6 to 16 carbon atoms such as a phenyl group and a naphthyl group Up to 1 to 6 carbon atoms, such as an acyl group, an acyl group, an acyl group having 1 to 6 carbon atoms such as an acyl group, an acyl group, an aryl group, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, A halogen atom such as an alkoxy group, a chlorine atom and a bromine atom, an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group and a cyclohexyloxycarbonyl group, a cyano group, and a carbonate ester group such as t-butylcarbonate do.

R ¹⁸ represents a single bond or a linking group of a 1 + 1 valency, and a 1 represents 1 to 5. The linking group R ^{18 may} contain 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 A group consisting of a sulfur atom, 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 these structural units.

When R ¹⁸ has a substituent, examples of the substituent include an alkyl group of up to 20 carbon atoms such as methyl and ethyl, an aryl group of 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, a hydroxyl group, , An acyloxy group having 1 to 6 carbon atoms such as a sulfonamide group, an N-sulfonylamide group and an acetoxy group, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, An alkoxycarbonyl group having 2 to 7 carbon atoms such as a halogen atom, a methoxycarbonyl group, an ethoxycarbonyl group and a cyclohexyloxycarbonyl group, a carbonic ester group such as a cyano group and t-butylcarbonate, and the like.

In the general formula (1), R ¹ represents an (m + n) linking group. and m + n satisfies 3 to 10.

The (m + n) linking group represented by R ¹ may include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 And a group consisting of 0 to 20 sulfur atoms, and may be unsubstituted or may further have a substituent. R ¹ is preferably an organic linking group.

Specific examples of R ¹ include the structural units of the above (t-1) to (t-34) or groups in which the above structural units are combined (may form a ring structure).

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

R ² represents a single bond or a divalent linking group. R ^{2 may} include up to 100 carbon atoms, from 0 to 10 nitrogen atoms, from 0 to 50 oxygen atoms, from 1 to 200 hydrogen atoms, and from 0 to 20 sulfur atoms , And may be unsubstituted or may further have a substituent. R ² is preferably an organic linking group.

Specific examples of R ² include groups in which the structural units of t-3, 4, 7 to 18, 22 to 26, 32, and 34 or the structural units are combined.

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

In the general formula (1), m represents 1 to 8. m is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 to 2.

In addition, n represents 2 to 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 skeleton and can be selected in accordance with the purpose or the like in an ordinary polymer or the like.

Among the polymers, in order to constitute the polymer skeleton, a polymer or copolymer of a vinyl monomer, an ester polymer, an ether polymer, a urethane polymer, an amide polymer, an epoxy polymer, a silicone polymer, a modified product thereof, or a copolymer , A polyether / polyurethane copolymer, a copolymer of a polymer of a polyether / vinyl monomer (any of random copolymers, block copolymers and graft copolymers)] At least one is preferable, and it is more preferable to use at least one polymer selected from the group consisting of polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, and modified products or copolymers thereof, Copolymers are particularly preferred.

The polymer is preferably soluble in an organic solvent. When the affinity with an organic solvent is low, for example, when it is used as a pigment dispersant, the affinity with the dispersion medium is weak, so that it is sometimes impossible to secure a sufficient adsorption layer for dispersion stabilization.

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

In the general formula (2), A ² has the same meaning as A ¹ in the general formula (1) and its specific preferred form is also the same. Specific examples of the organic dye structure include phthalocyanine compounds, azo lake compounds, Quinone compounds, dioxazine compounds, diketopyrrolopyrrole compounds and the like are more preferable. As the heterocyclic rings, imidazole, triazole, pyridine, piperidine, morpholine, triazine, isoindoline, More preferred are imidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, anthraquinone and the like.

Further, good and may have a substituent as with A ^1, for the same substituent as in the case of the A ^1, as a preferred form.

As A ² , a monovalent organic group represented by the general formula (4) is preferable, and details, specific examples, and preferred forms of the organic group are the same.

In the above general formula (2), R ³ represents a linking group of (x + y). The (x + y) linking group represented by R ³ may include 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 And a group consisting of 0 to 20 sulfur atoms, and may be unsubstituted or may further have a substituent.

The (x + y) linking group represented by R ³ has the same meaning as the (m + n) linking group in R ¹ , and its preferable form is also the same. Specific examples thereof include structural units of the above-mentioned methods or groups in which these structural units are combined.

Among them, the linking group represented by R ³ is preferably an organic linking group, and specific examples (specific examples (r-1) to (r-17)) of the organic linking group are shown below. However, the present invention is not limited thereto.

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

When R ³ has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as methyl group and ethyl group, an aryl group having 6 to 16 carbon atoms such as phenyl group and naphthyl group, , An acyloxy group having 1 to 6 carbon atoms such as a carboxyl group, a sulfonamide group, an N-sulfonylamide group and an acetoxy group, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, , Alkoxycarbonyl groups having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group and a cyclohexyloxycarbonyl group, a carbonic ester group such as a cyano group and t-butylcarbonate, and the like.

In the general formula (2), R ⁴ and R ⁵ each independently represent a single bond or a divalent linking group.

The "bivalent linking group" represented by R ⁴ and R ⁵ may have a substituent, and may be a linear, branched or cyclic alkylene group, an arylene group, an aralkylene group, -O-, -S-, -C (= O) -, -N ( R 19) -, -SO-, -SO 2 -, -CO 2 -, -N (R 20) SO 2 -, or a divalent group combining two or more (Wherein R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Among them, an organic linking group is preferable.

R ⁴ is preferably a straight-chain or branched alkylene group, an aralkylene group, or -O-, -C (= O) -, -N (R ¹⁹ ) -, -SO ₂ -, -CO ₂ - ²⁰ ) SO ₂ - (wherein R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), or a divalent group formed by combining two or more of these groups, (O) -, -N (R ¹⁹ ) - (wherein R ¹⁹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), -CO ₂ -, -O-, Or a divalent group formed by combining two or more of these groups is particularly preferable.

The R ^{5 may be a} single bond or a straight chain or branched alkylene group, an aralkylene group, or -O-, -C (= O) -, -N (R ¹⁹ ) -, -SO ₂ -, -CO ₂ - N (R ²⁰ ) SO ₂ - (wherein R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), or a divalent group formed by combining two or more of these groups, -O-, -C (= O) -, -N (R ¹⁹ ) - (wherein R ¹⁹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), -CO ₂ -, or a divalent group formed by combining two or more of these groups is particularly preferable.

When R ⁴ and R ⁵ have a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, An alkoxy group having 1 to 6 carbon atoms such as an acyloxy group having 1 to 6 carbon atoms, such as a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group or an acetoxy group, Halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, cyano groups, and carbonic ester groups such as t-butylcarbonate.

In the general formula (2), y represents 1 to 8, preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 to 2. Further, x represents 2 to 9, preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.

In addition, P ² in the general formula (2) represents a polymer skeleton and can be selected according to the purpose or the like in an ordinary polymer or the like. The preferable form of the polymer is the same as that of P ¹ in the general formula (1), and the preferred form thereof is also the same.

Among the polymer compounds represented by the above general formula (2), particularly those in which R ³ is the same as the above examples (r-1), (r-2), (r- or (r-17), and, R ⁴ is a single bond, a straight-chain, branched alkyl group, an aralkyl group, -O-, -C (= O) -, -N (R l9) - ( wherein R ¹⁹ is hydrogen Or an alkyl group having 1 to 4 carbon atoms), -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, (wherein s is an integer of 1 to 2), P ² is a polymer or copolymer of a vinyl monomer, an ester polymer, an ether polymer, a urethane polymer, or a modification thereof, y is 1 to 2, x A polymer compound having 3 to 6 is particularly preferable. In the following groups, R ²¹ represents a hydrogen atom or a methyl group, and l represents 1 or 2.

The mass average molecular weight of the polymer compound is 1000 or more, but preferably 1,000 to 500,000, more preferably 3,000 to 100,000, still more preferably 5,000 to 80,000, and particularly preferably 7,000 to 60,000. When the mass average molecular weight is within the above range, the effects of a plurality of functional groups introduced at the ends of the polymer are sufficiently exhibited, and the polymer exhibits excellent adsorption on the solid surface, micelle formation ability, and surface activity. Particularly, when the polymer compound related to the present invention is used as a pigment dispersant, 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 or the like. Among the following synthesis methods, synthesis methods such as the following 2, 3, 4, and 5 are more preferable from the viewpoint of ease of synthesis, and the synthesis methods such as the following 3, 4, 5 are particularly preferable.

1. A polymer obtained by introducing a functional group selected from a carboxyl group, a hydroxyl group, an amino group and the like into a terminal and an acid halide having a plurality of functional groups (A ¹ or A ² in the above formula) or a plurality of functional groups ¹ or A ² ), or an isocyanate having a plurality of functional groups (A ¹ or A ² in the above formula).

2. A method in which a polymer having a carbon-carbon double bond introduced at its terminal and a mercaptan having a plurality of functional groups (A ¹ or A ² in the above formula) are subjected to Michael addition reaction.

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

5. A ^process for radical polymerization of a vinyl monomer using a mercaptan compound having a plurality of functional groups (A ¹ or A ² in the above formula) as a chain transfer agent.

The polymer compound (preferably a polymer compound represented by the general formula (2)) used in the production of the pigment dispersion composition of the present invention may be synthesized by any one of the methods 2, 3, 4, and 5 But it is more preferable to synthesize it by the above-mentioned method 5 from the viewpoint of easiness of synthesis.

More specifically, it is preferable to carry out radical polymerization using a compound represented by the following general formula (3) as a chain transfer agent.

In the general formula (3), R ⁶ , R ⁷ , A ³ , g and h are the same as R ³ , R ⁴ , A ² , x and y in the general formula (2) The preferred form is also the same.

Examples of the vinyl monomer include, but are not limited to, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) , Vinyl ethers, esters of vinyl alcohol, styrene, and (meth) acrylonitrile. Examples of such compounds include the following compounds.

Examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl Propyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (Meth) acrylate, octadecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethoxyethyl Diethylene glycol monomethyl ether acrylate, diethylene glycol monoethyl (meth) acrylate, ( (Meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, Dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, nonylphenoxypoly , Perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate, and tribromophenyloxyethyl (meth) acrylate.

Examples of the crotonic acid esters include butyl crotonate, hexyl crotonate, and the like.

Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, and vinyl benzoate.

Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, dibutyl maleate, and the like.

Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, dibutyl itaconate, and the like.

Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N- (Meth) acrylamide, N, N-butyl acryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (Meth) acrylamides such as dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl Amides and the like.

Examples of the styrene include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, Methylstyrene, chloromethylstyrene, hydroxystyrene protected with a group capable of being deprotected by an acidic substance (such as t-Boc), methyl vinylbenzoate and? -Methylstyrene.

Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

(Meth) acrylonitrile, a vinyl group-substituted heterocyclic group (e.g., vinylpyridine, vinylpyrrolidone, vinylcarbazole and the like), N-vinylformamide, N-vinyl acetamide, N-vinyl Imidazole, vinylcaprolactone, and the like can also be used.

In addition to the above compounds, vinyl monomers having functional groups such as urethane groups, urea groups, sulfonamide groups, phenol groups and imide groups can also be used. As the urethane group or urea group-containing monomer, for example, it is possible to synthesize them appropriately by using an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Concretely, an addition reaction of an isocyanate group-containing monomer with a compound containing one hydroxyl group or a compound containing one primary or secondary amino group or an addition reaction of a hydroxyl group-containing monomer or a monomer containing a primary or secondary amino group and a monoisocyanate And can be suitably synthesized by an addition reaction or the like.

These vinyl monomers may be polymerized singly or copolymerized by using two or more kinds of them in combination. These radical polymers are obtained by polymerizing the corresponding vinyl monomers in accordance with the conventional method in the usual manner.

For example, a method of dissolving these vinyl monomers and chain transfer agents in an appropriate solvent, adding a radical polymerization initiator thereto, and polymerizing them in a solution at about 50 to 220 ° C (solution polymerization method).

Examples of a suitable solvent to be used in the solution polymerization method may be arbitrarily selected depending on the solubility of the monomers to be used and the copolymer to be produced. Examples of the solvent include alcohols such as methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy- 2- propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, , Acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, and toluene. These solvents may be used in combination of two or more.

Examples of the radical polymerization initiator include azo compounds such as 2,2'-azobis (isobutyronitrile) (AIBN) and 2,2'-azobis- (2,4'-dimethylvaleronitrile) Peroxides such as seed, and persulfates such as potassium persulfate and ammonium persulfate.

The compound represented by the above general formula (3) can be synthesized by the following method or the like, but the method of the following 7 is more preferable because of the ease of synthesis.

6. A method of converting a halide compound having a plurality of functional groups (A ¹ or A ² in the above formula) into a mercaptan compound (a method of reacting with thiourea to hydrolyze, a method of directly reacting with NaSH, a method of reacting CH ₃ COSNa And a method of hydrolyzing by reacting.)

7. A method in which a compound having 3 to 10 mercapto groups in a molecule and a compound having a functional group (A ¹ or A ² in the above formula) and having a functional group capable of reacting with a mercapto group are subjected to addition reaction

As the " functional group capable of reacting with mercapto group " in the above method 7, an acid halide, an alkyl halide, an isocyanate, a carbon-carbon double bond and the like are preferably exemplified.

It is particularly preferable that the " functional group capable of reacting with the mercapto group " is a carbon-carbon double bond and the addition reaction is synthesized by a radical addition reaction. As the carbon-carbon double bond, a monovalent or divalent vinyl group is more preferable in view of reactivity with a mercapto group.

Specific examples of the compound having 3 to 10 mercapto groups in one molecule include the following compounds.

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

The compound having a functional group (A ¹ or A ² in the above formula) and having a carbon-carbon double bond is not particularly limited, and the following are listed.

For example, the above-mentioned "compound having 3 to 10 mercapto groups in one molecule" and "compound having an acidic group, a basic nitrogen atom, a urea group, a urethane group, The radical addition reaction product of the compound having at least one functional group selected from a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group and a hydroxyl group and having a carbon-carbon double bond is, for example, Group having two or more mercapto groups "and" a group having an acidic group, a basic nitrogen atom, a urea group, a urethane group, a group having a radial oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, A compound having at least one functional group selected from a hydroxyl group and having a carbon-carbon double bond " is dissolved in an appropriate solvent, and a radical generator (Thiol-ene reaction method) which is added at about 50 ° C to 100 ° C.

Examples of preferred solvents to be used in the above-mentioned method include a compound having 3 to 10 mercapto groups in one molecule, a compound having an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, Having a functional group capable of reacting with a mercapto group (for example, a carbon-carbon double bond) having at least one functional group selected from the group consisting of a hydrocarbon group having at least 4 carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group and a hydroxyl group, And the solubility of the resulting radical addition reaction product. Examples of the solvent include alcohols such as methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy- 2- propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, , Acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, and toluene. These solvents may be used in combination of two or more.

Examples of the radical generator include azo compounds such as 2,2'-azobis (isobutyronitrile) (AIBN) and 2,2'-azobis- (2,4'-dimethylvaleronitrile), benzoyl peroxide And persulfates such as potassium persulfate and ammonium persulfate.

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

The polymer compound is preferably a polymer compound having an acidic group, more preferably a polymer compound having a carboxyl group, and more preferably (A) at least one kind of repeating unit derived from a compound having a carboxyl group and (B) A copolymer compound containing at least one repeating unit derived from a compound having an ester group is particularly preferable.

The repeating unit derived from the compound having a carboxyl group (A) is preferably a repeating unit represented by the following formula (I), more preferably a repeating unit derived from acrylic acid or methacrylic acid, The repeating unit derived from the compound having a carboxylic acid ester group is preferably a repeating unit represented by the following formula (I1), more preferably a repeating unit represented by the following formula (IV), and benzyl acrylate, Particularly preferred is a repeating unit derived from benzyl methacrylate, phenethyl acrylate, phenethyl methacrylate, 3-phenylpropyl acrylate, or 3-phenylpropyl methacrylate.

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

(R ₂ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ₃ represents a group represented by the following general formula (III)):

(Wherein R ₄ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxy group, a hydroxyalkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R ₅ and R ₆ each represent a hydrogen atom or a carbon atom Represents an alkyl group of 1 to 5, and i represents a number of 1 to 5.)

(R ₇ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ₈ represents a group represented by the following general formula (V).)

(R ₉ represents an alkyl group of 2 to 5 carbon atoms or an aryl group of 6 to 20 carbon atoms, R ₁₀ and R _{11 each} represent a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, and j represents a number of 1 to 5 .)

In terms of the ratio of the repeating unit derived from the compound having a carboxyl group (A) to the repeating unit derived from the compound having the carboxylic acid ester group (B), the ratio of the repeating unit derived from the compound having a carboxyl group The water percentage ratio is preferably 3 to 40, more preferably 5 to 35.

In the process for producing a pigment dispersion composition of the present invention, the molecular weight of a polymer means a mass average molecular weight unless otherwise specified. As a method for measuring the molecular weight of the polymer, a chromatography method, a viscosity method, a light scattering method, a sedimentation rate method and the like are listed. In the present invention, a mass average molecular weight measured by a chromatographic method is used unless otherwise specified.

The polymer compound may be either water-soluble or usable, and may be water-soluble or usable.

The method of adding the polymer compound may be a solution in an aqueous solvent or an organic solvent, a solid state, or a combination thereof. Examples of the method of adding the solution in a solvent include a method in which the solution is added to a solution of the coagulated organic particles in a solvent such as a solution of the coagulated organic particle solution or a method in which the coagulated organic particles are added Are listed. The concentration of the polymer compound 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 is carried out at the time of forming (or before or after) the organic nanoparticles by the re-precipitation method, at the time of extraction or concentration (or before or after), at the time of dispersing (or before or after) Or may be added to any of them, or a combination thereof. In the method for producing a pigment dispersion composition of the present invention, the polymer compound having a mass average molecular weight of 1,000 or more may be contained in the composition as a binder described later, and may be added, for example, after concentration of the organic particle- .

The amount of the polymer compound to be added is preferably from 0.1 to 1000 parts by mass, more preferably from 5 to 500 parts by mass, and particularly preferably from 10 to 300 parts by mass, based on 100 parts by mass of the organic particles contained in the aggregated organic particles.

Examples of the polymer compound having a molecular weight of 1,000 or more include polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol acetate vinyl copolymer, polyvinyl alcohol- Polyvinyl alcohol-partial butyral, 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, tragacanth gum, and lignin sulfonate may be used.

Examples of the polymer compound having an acidic group include polyvinyl sulfuric acid and condensed naphthalenesulfonic acid.

Examples of the polymer compound having a carboxyl group include polyacrylic acid, polymethacrylic acid, a cellulose derivative having a carboxyl group in the side chain, and the like. (A) at least one kind of repeating unit derived from a compound having a carboxyl group and (B) at least one kind of a repeating unit derived from a compound having a carboxylic acid ester group is disclosed in JP 59-44615 Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Application Laid-open No. 59-53836 and Japanese Patent Laid-Open No. 59-71048 Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers such as those described in the publication. Particularly preferred examples thereof include acrylic acid-acrylic acid ester copolymers, methacrylic acid-acrylic acid ester copolymers, acrylic acid-methacrylic acid ester copolymers, methacrylic acid-methacrylic acid ester copolymers and methacrylic acid-methacrylic acid ester copolymers described in United States Patent No. 4,139,391 , Acrylic acid or methacrylic acid, acrylic acid ester or methacrylic acid ester, and other vinyl compounds.

Examples of the vinyl compound include styrene or substituted styrene (e.g., vinyltoluene, vinyl ethylbenzene), vinylnaphthalene or substituted vinylnaphthalene, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, .

These polymer compounds may be used alone, in combination of two or more, or in combination with a compound having a molecular weight of less than 1,000.

In the present invention, the organic nanoparticle dispersion preferably contains 60 mass% or more of an organic solvent, more preferably 65 mass% or more. The organic solvent is not particularly limited and may be appropriately selected from conventional ones. 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 singly or in combination of two or more.

Examples of the ester compound solvent include 2- (1-methoxy) propyl acetate, ethyl acetate, ethyl lactate and the like. 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, cyclohexane, and the like. Examples of the ketone compound solvent include methyl ethyl ketone, acetone, and cyclohexanone.

[Pigment dispersion composition]

Next, the form of the composition of the present invention or the organic pigment nanoparticles when used in a color filter, an inkjet ink, or the like will be described in detail. In addition to the inkjet ink for the color filter, the inkjet ink may be a normal inkjet ink such as a printing inkjet ink. The organic nanoparticles can be used in a state of being dispersed in, for example, a vehicle. The vehicle refers to a portion of the medium in which the pigment is dispersed when it is in a liquid state and refers to a portion (binder) that coagulates the coating film by binding with the pigment as a liquid phase and a component (organic solvent) . In the present invention, the binder used for forming the nanoparticles and the binder used for redispersion may be the same or different, and they may be referred to separately as the nano-particle-forming binder and the redispersed binder, respectively.

The concentration of the organic nanoparticles in the dispersion composition of the organic nanoparticles after re-dispersion is appropriately determined according to the purpose, but preferably the organic nanoparticles are contained in an amount of 2 to 30 mass%, preferably 4 to 20 mass% %, More preferably from 5 to 15% by mass. The amount of the binder and the dissolving and diluting component is appropriately determined depending on the kind of the organic pigment and the like in the case of dispersing by the above vehicle, but the binder is preferably 1 to 30 mass%, more preferably 3 to 20 mass% By mass, more preferably from 5 to 15% by mass. The content of the dissolved and diluted component is preferably 5 to 80% by mass, more preferably 10 to 70% by mass.

In the concentrated and extracted nanoparticle solution, as described above, it is preferable that the organic nanoparticles are agglomerated by concentration so as to enable rapid filter filtration, and it is preferable to concentrate the agglomerated particles by centrifugation or drying .

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

The ultrasonic wave irradiation apparatus to be used preferably has a function of applying ultrasonic waves of 10 kHz or more, and examples thereof include an ultrasonic homogenizer and an ultrasonic wave cleaner. When the liquid temperature rises during ultrasonic irradiation, thermal agglomeration of nanoparticles occurs (see, for example, " Pigment Dispersion Technique - Method of using surface treatment and dispersant and evaluation of dispersibility " To 100 ° C, and more preferably 5 to 60 ° C. The temperature can be controlled by controlling the temperature of the dispersion liquid, or by controlling the temperature of the temperature control layer for controlling the temperature of the dispersion liquid.

There are no particular restrictions on the dispersing device used for dispersing the concentrated organic nanoparticles by applying physical energy, and examples thereof include dispersing devices such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill. In addition, a high-pressure dispersion method and a dispersion method by use of microparticle beads are also listed as preferable ones.

<1> Distributed method

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

The machine used in the kneading dispersion treatment is two rolls, three rolls, a ball mill, a trommel, a dispenser, a kneader, a coneerator, a homogenizer, a blender, a single shaft and a twin screw extruder and disperses while giving a strong shearing force. Subsequently, a solvent is added and finely dispersed in a bead composed of glass or zirconia having a particle diameter of 0.1 to 1 mm, mainly using a sand or a vertical type sand grinder, a pin mill, a slit mill, an ultrasonic dispersing machine or a high pressure dispersing machine. It is also possible to carry out precision dispersion treatment using fine particle beads of 0.1 mm or less. It is also possible to omit the kneading dispersion treatment. In this case, the pigment, the dispersant or the surface treatment agent are dispersed in the acrylic copolymer and the solvent in the present invention. Alternatively, it is also possible to disperse the main pigment and the security agent, respectively, and then mix the dispersion of the two to further disperse the treatment, or to disperse the main pigment and the security agent together.

Further, details of kneading and dispersing are described in T.C. Patton et al., &Quot; Paint Flow and Pigment Dispersion "(published by John Wiley and Sons in 1964), and the like may be used.

&Lt; 2 >

In order to improve the dispersibility of the organic nanoparticles, a general pigment dispersant or a surfactant may be added to the organic nanoparticle dispersion composition. For example, phthalocyanine derivatives (commercial product EFKA-6745 (product of EFKA)), SOLSPERSE 5000 (product of Zeneca Co., Ltd.); (Manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid type (co) polymer Polyflow No. 75, No. 90, No. 95 (product of Kyoeisha Chemical Co., Ltd.) , W001 (manufactured by Yusho KK); Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol distearate, polyethylene glycol distearate, sorbitan fatty acid Nonionic surfactants such as esters; Anionic surfactants such as W004, W005 and W017 (manufactured by Yusho K.K.); Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 15, EFKA Polymer 401, EFKA Polymer 450 (manufactured by Morishita Sangyo KK), EFKA-47, EFKA-47, EFKA- 9100 (manufactured by San Nopko Limited); Various SOLSPERSE dispersants (manufactured by Zeneca Co., Ltd.) such as SOLSPERSE 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000; (Available from Asahi Denka Kogyo KK) and Isonet S-1, Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, Fl08, L121, 20 (manufactured by Sanyo Chemical Industries, Ltd.). Also, the pigment dispersant described in JP-A-2000-239554, the compound (C) described in JP-A-5-72943, the compound of SYNTHETIC EXAMPLE 1 described in JP-A-2001-31885, have.

It is also preferable to use the compound represented by the item [dispersing agent] again as the dispersing agent for use in forming the organic nanoparticles upon redispersion.

In the organic nanoparticle dispersion composition, the organic nanoparticles (primary particles) after re-dispersion can be made into fine particles, and the particle diameter can be preferably 1 to 200 nm, more preferably 2 to 100 nm, And particularly preferably from 5 to 50 nm. The Mv / Mn of the particles after re-dispersion is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, particularly preferably 1.0 to 1.5.

The pigment dispersion composition of the present invention or the organic pigment nanoparticles contained in the colored photosensitive resin composition to be described later can be dispersed in a concentrated material in spite of the minute particle diameter of nanometer size (for example, 10 to 100 nm). Therefore, when used for a color filter, the optical density is high, the uniformity of the filter surface is excellent, the contrast is high, and the noise of the image can be reduced.

Further, since the pigment dispersion composition and the organic pigment nanoparticles contained in the colored photosensitive composition can be finely and uniformly finely dispersed, a high coloring density can be exhibited with a thin film thickness and a thin layer of a color filter or the like can be formed .

In addition, the pigment dispersion composition and the colored photosensitive resin composition are excellent as an image forming material for producing, for example, color proofing, color filters and the like, by containing a pigment showing a clear color tone and a high coloring power.

Further, with respect to the alkaline developer used for exposure and development at the time of color image formation, the pigment dispersion composition and the colorant photosensitive resin composition which are soluble in an alkaline aqueous solution as a binder (binder) can be used, thereby meeting environmental requirements.

In addition, an organic solvent having a proper drying property can be used as a pigment dispersing composition and a solvent (a dispersion medium of a pigment) usable in the colored photosensitive resin composition, and it is possible to satisfy the requirement even in the case of drying after coating.

[Colored photosensitive resin composition]

The colored photosensitive resin composition of the present invention comprises at least (a) organic pigment nanoparticles, (b) a binder, (c) a polyfunctional monomer having at least two ethylenically unsaturated double bonds, and (d) a photopolymerization initiator or a photopolymerization initiator system do. Each component of the colored photosensitive resin composition of the present invention will be described below.

(a) an organic pigment nanoparticle

The method for producing the organic pigment nanoparticles has already been described in detail. The content of the organic pigment nanoparticles is preferably from 3 to 90% by mass, more preferably from 20 to 80% by mass, based on the total solid content in the colored photosensitive resin composition (in the present invention, the total solid content means the total amount of the composition excluding the organic solvent) , And still more preferably from 25 to 60 mass%. If the amount is too large, the viscosity of the dispersion liquid increases, which may cause problems in manufacturing suitability. If it is too small, the coloring power is not sufficient. The organic pigment nano-particles (pigment particles) functioning as a colorant preferably have a particle diameter of 0.1 占 퐉 or less, particularly 0.08 占 퐉 or less. Further, it may be used in combination with a conventional pigment for coloring. The pigment described above can be used.

(b) a binder

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

(c) a polyfunctional monomer or oligomer having two or more ethylenically unsaturated double bonds

The multifunctional monomer or oligomer having two or more ethylenically unsaturated double bonds contained in the colored photosensitive resin composition of the present invention is a monomer or oligomer which has two or more ethylenically unsaturated double bonds and undergoes addition polymerization by irradiation of light. Such monomers and oligomers include compounds having at least one ethylenically unsaturated group capable of addition polymerization in the molecule and having a boiling point of at least 100 캜 at normal pressure. Examples thereof include monofunctional acrylates such as dipentaerythritol hexa (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) Acrylate; (Meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylol ethane triacrylate, trimethylol propane tri (meth) acrylate, trimethylol propane diacrylate, neopentyl glycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (metha) acrylate, dipentaerythritol penta Acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; Polyfunctional acrylates or polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as trimethylol propane and glycerin, and (meth) acrylate them. Also, as described in general formulas (1) and (2) in Japanese Patent Application Laid-Open No. 10-62986, compounds obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols followed by (meth) Lt; / RTI >

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

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

In addition, "polymerizable compound B" described in Japanese Patent Application Laid-Open No. 11-133600 is also preferable.

These monomers or oligomers (monomers or oligomers preferably have a molecular weight of 200 to 1000) may be used singly or in combination of two or more. The content of the colored photosensitive resin composition to the total solid content is preferably 5 to 50 The mass% is generally in the range of 10 to 40 mass%. If the amount is too large, it becomes difficult to control the developability, which is a problem in manufacturing suitability. If it is too small, the curing force at the time of exposure is insufficient.

(d) a photopolymerization initiator or a photopolymerization initiator system

Examples of the photopolymerization initiator or photopolymerization initiator system contained in the colored photosensitive resin composition of the present invention (in the present invention, the photopolymerization initiator egg refers to a mixture which expresses the function of initiating photopolymerization by combination of a plurality of compounds) is disclosed in United States Patent No. 2367660 , An acyloin ether compound described in the specification of US Patent No. 2448828, an aromatic acyloin compound substituted with? -Hydrocarbon described in U.S. Patent No. 2722512, a compound of the formula A combination of a triarylimidazole dimer and a p-amino ketone described in the specification of US Pat. No. 3,549,367, a combination of a p-amino ketone disclosed in Japanese Patent Publication No. 51-48516 and a polynuclear quinone compound disclosed in Japanese Patent No. 3046127 and Japanese Patent No. 2951758 The benzothiazole compound and the trihalomethyl-s-triazine compound described in U.S. Patent No. 4239850 With a trihalomethyl triazine compound described in methyl, U.S. Patent No. 4,212,976 specification are listed manage the methyl-oxadiazole compound. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole and triarylimidazole dimer are preferred.

In addition, the polymerization initiator C described in JP-A-11-133600, l-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O- Benzoyl-4 '- (benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyloxide, hexafluorophosphorothio-trialkylphenylphosphonium salts and the like are also enumerated can do.

These photopolymerization initiators or photopolymerization initiators can be used singly or in combination of two or more kinds, but two or more types are particularly preferably used. Use of at least two kinds of photopolymerization initiators makes it possible to reduce display characteristics, particularly display unevenness.

The content of the photopolymerization initiator or the photopolymerization initiator system based on the total solid content of the colored photosensitive resin composition is generally from 0.5 to 20% by mass, and preferably from 1 to 15% by mass. If the amount is excessively large, the sensitivity becomes excessively high and control becomes difficult. If it is too small, the exposure sensitivity becomes too low.

(Other additives)

[menstruum]

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

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

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

[Surfactants]

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

From the viewpoint that the color filter of the present invention or the photosensitive resin transferring material of the present invention can be controlled to have a uniform film thickness and effectively prevent uneven application (color unevenness due to film thickness variation) It is preferable to contain an appropriate surfactant.

Examples of the surfactant include surfactants disclosed in JP-A-2003-337424 and JP-A-11-133600. The content of the surfactant is preferably 5% by mass or less based on the total amount of the resin composition.

[Thermal polymerization inhibitor]

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

[Dyes and pigments used as auxiliaries]

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

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

[UV absorber]

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

Specific examples include phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ', 5'-di- 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2'- Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano- 3-diphenyl acrylate, 2,2'-hydroxy-4-methoxybenzophenone, nickel dibutyldithiocarbamate, bis (2,2,6,6-tetramethyl-4- pyridine) , 4-t-butylphenyl salicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinic acid-bis (2,2,6,6- (4-piperidinyl) -ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, (Diethylamino) -5-triazin-2-yl] amino} -3-phenyl coumarin It is listed. The content of the ultraviolet absorber is preferably 5% by mass or less based on the total amount of the resin composition.

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

[Coated film of colored photosensitive resin composition]

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

(Slit-shaped nozzle)

The above-mentioned coating film can be formed by applying the colored photosensitive resin composition by a general coating method and drying, but in the present invention, it is preferable to coat the colored photosensitive resin composition with a slit-shaped nozzle having a slit-shaped hole . Specifically, in Japanese Patent Application Laid-Open Nos. 2004-89851, 2004-17043, 2003-170098, 2003-164787, 2003-10767, and Japanese Patent Slit nozzles and slit coaters described in JP-A-2002-79163 and JP-A-2001-310147 are preferably used.

The method of applying the colored photosensitive resin composition to the substrate is excellent in spin application because it can uniformly and highly precisely apply a thin film of 1 to 3 탆 and can be widely used in the manufacture of color filters. However, in recent years, in order to increase manufacturing efficiency and manufacturing cost in accordance with the enlargement and mass-production of a liquid crystal display device, slit coating suitable for application of a substrate having a wider width and a larger area than that of spin coating has been employed in the production of color filters. In addition, from the viewpoint of liquid deficiency, the slit coating is superior to the spin coating, and a uniform coating film can be obtained with a smaller coating liquid.

The slit coating is carried out by applying an application head having a slit (gap) of several tens of microns wide at the tip end and a length corresponding to the coating width of the rectangular substrate to the substrate while maintaining a clearance (gap) And a coating liquid supplied from the slit at a predetermined discharge amount is applied to the substrate while maintaining a constant relative speed to the head. This slit coating reduces the cleaning process because (1) the liquid loss is smaller than in the spin coating, (2) there is no scattering of the coating liquid, (3) the scattered liquid component does not marry again to the coating film 4) it is possible to shorten the tack time because there is no start stop time of rotation, and (5) it is easy to apply to a large substrate. From these merits, slit coating is preferable for the production of a color filter for a large screen liquid crystal display device and is expected as a coating method which is also advantageous in reducing the amount of coating liquid.

The slit coating needs to maintain a certain relative speed between the coater and the object to be coated when the coating liquid is discharged from the wide slit outlet in order to form a coating film having a much larger area than the spin coating. Therefore, a good fluidity is required for the coating liquid used in the slit coating method. It is particularly required to keep various conditions of the coating liquid supplied to the substrate from the slit of the coating head constant throughout the coating width. If liquid properties such as fluidity and viscoelastic properties of the coating liquid are insufficient, coating unevenness tends to easily occur, and it becomes difficult to keep the coating thickness constant in the coating width direction, which results in a problem that a uniform coating film can not be obtained.

From this, there have been many attempts to improve the fluidity and viscoelastic characteristics of the coating liquid in order to obtain a uniform coating film without unevenness. However, as described above, means for lowering the molecular weight of the polymer or selecting a polymer having excellent solubility in a solvent, selecting various solvents for controlling the rate of evaporation, or using a surfactant have been proposed. It was not enough to improve many problems.

[Photosensitive resin transfer material]

Next, the photosensitive resin transferring 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 Japanese Patent Application Laid-Open No. 5-72724, that is, an integrated film. As an example of the constitutional example of the integral film, there can be enumerated a constitution in which a laminate of a branched resin / a thermoplastic resin layer / an intermediate layer / a photosensitive resin layer / a protective film are laminated in this order. As the photosensitive resin transfer material of the present invention, And a photosensitive resin is formed by using a colored photosensitive resin composition.

(Jerk)

In the photosensitive resin transferring material of the present invention, it is necessary that the branching agent is flexible and does not cause significant deformation, shrinkage or elongation even when it is placed under pressure, pressurization and heating. Examples of such branched materials include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Of these, a biaxially oriented polyethylene terephthalate film is particularly preferable.

(Thermoplastic resin layer)

As the component used in the thermoplastic resin layer, the organic polymer substance described in JP-A-5-72724 is preferable, and the organic polymer substance is preferably a Vicat method (specifically, a method of measuring a polymer softening point according to ASTM D 1235 of the American Society for Testing and Materials) Lt; RTI ID = 0.0 > 80 C < / RTI > or less. Specific examples thereof include polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or their saponified products, chlorinated polymers such as ethylene and acrylic esters or their saponified products, polyvinyl chloride, vinyl chloride and vinyl acetate, Vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or a saponified product thereof, polyvinyltoluene, vinyltoluene and (meth) acrylic acid ester or a saponified product thereof (Meth) acrylic acid ester, (meth) acrylic acid ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer nylon, copolymerized nylon, N-alkoxymethylated nylon, N - organic amides such as polyamide resins such as dimethylaminated nylon It is listed.

(Middle layer)

In the photosensitive resin transferring material of the present invention, it is preferable to form an intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and storage after application. As the intermediate layer, it is preferable to use an oxygen barrier film having an oxygen barrier function described as " separation layer " in Japanese Patent Application Laid-Open No. 5-72724. In this case, sensitivity is increased during exposure, Thereby improving productivity.

The oxygen barrier film preferably exhibits a low oxygen permeability and is dispersed or dissolved in an aqueous solution of water or an alkali, and can be appropriately selected from ordinary ones. Of these, particularly preferred is a combination of polyvinyl alcohol and polyvinylpyrrolidone.

(Protective film)

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

(Method for producing a photosensitive resin transfer material)

The photosensitive resin transferring material of the present invention is obtained by applying a coating liquid (coating liquid for a thermoplastic resin layer) obtained by dissolving an additive of a thermoplastic resin layer on a support and drying the coating liquid to form a thermoplastic resin layer, A solution of an intermediate layer material made of a solvent which does not dissolve the thermoplastic resin layer is applied and dried, and then the photosensitive resin layer is coated with a solvent which does not dissolve the intermediate layer and dried to form the photosensitive resin layer.

It is also possible to prepare a sheet on which a thermoplastic resin layer and an intermediate layer are formed on the branched body and a sheet on which a photosensitive resin layer is formed on a protective film and to adhere them so that the intermediate layer and the photosensitive resin layer are in contact with each other, A sheet having a thermoplastic resin layer formed thereon and a sheet having a photosensitive resin layer and an intermediate layer formed on a protective film, and attaching the thermoplastic resin layer and the intermediate layer so as to be in contact with each other.

In the photosensitive resin transferring material of the present invention, the thickness of the photosensitive resin layer is preferably 1.0 to 5.0 占 퐉, more preferably 1.0 to 4.0 占 퐉, and particularly preferably 1.0 to 3.0 占 퐉. Although not particularly limited, the preferable film thickness of each of the other layers is 15 to 100 탆 in terms of branching, 2 to 30 탆 in the thermoplastic resin layer, 0.5 to 3.0 탆 in the intermediate layer, and 4 to 40 탆 in the protective film Is generally preferred.

In the present invention, the coating can be performed by a coating device (slit coater) using the slit nozzle described in the section of [coating film of colored photosensitive resin composition] . Preferred examples of the slit coater and the like are the same as described above.

[Color Filter]

The color filter of the present invention can use an excellent color filter. The contrast in the present invention indicates the ratio of the amount of transmitted light when the polarization axis is parallel to the polarization axis between two polarizing plates (" 7th Color Optics Conference, 512 color display 10.4 "size TFT- Color filter, Ueki, Kosai, Fukunaga, Yamanaka ").

The high contrast of the color filter means that the discrimination of light and dark when combined with liquid crystal can be made large, and it is a very important performance for the liquid crystal monitor to be replaced with a CRT.

When the color filter of the present invention is used for a television, the chromaticities of all monochromatic colors of red (R), green (G) and blue (B) by the Fl0 light source are values shown in the following table (Hereinafter referred to as " target chromaticity "), preferably within a range of 5, more preferably within 3, and particularly preferably within 2.

In the present invention, the chromaticity is measured by a microscopic spectrophotometer (Olympus Corporation, OSP100 or 200), calculated as a result of the Fl0 light source field 2 degree, and expressed by the xyY value of the xyz color system. The difference from the target chromaticity is represented by the color difference of the La * b * color system.

(Photosensitive resin layer)

The color filter of the present invention can be produced by forming a photosensitive resin layer on a substrate, repeating exposure and development as many as the number of colors. On the other hand, if necessary, it can be said that the boundary is divided into black matrixes.

In the above manufacturing method, the photosensitive resin layer may be formed on the substrate by (a) a method of applying each of the above colored photosensitive resin compositions by a common application device, and (b) a method of applying the above- And a method of joining with a laminator are listed.

(a) Application by application device

In the production of the color filter of the present invention, a conventional coating device can be used for coating the colored photosensitive resin composition. Among them, the description has been given in the section of [the coating film of the colored photosensitive resin composition] Can be used. Preferred examples of the slit coater and the like are the same as described above. When the photosensitive resin layer is formed by coating, the film thickness is preferably 1.0 to 3.0 占 퐉, more preferably 1.0 to 2.5 占 퐉, and particularly preferably 1.5 to 2.5 占 퐉.

(b) Bonding by a laminator

The photosensitive resin transfer material of the present invention can be used to bond the photosensitive resin layer formed in a film form to a substrate to be described later by heating and / or pressing and pressing or hot pressing on a roller or a flat plate. Specifically, the laminator and the lamination method disclosed in Japanese Patent Application Laid-Open Nos. 7-110575, 11-77942, 2000-334836, and 2002-148794 However, it is preferable to use the method described in Japanese Patent Application Laid-Open No. 7-110575 from the viewpoint of low water. On the other hand, when the photosensitive resin layer is formed from the photosensitive resin transfer material of the present invention, its preferable film thickness is equal to the preferable film thickness described in the item [photosensitive resin transfer material].

(Board)

In the present invention, as the substrate on which the color filter is formed, for example, a transparent substrate is used, and a known glass plate such as a soda glass plate, a low expansion glass, a non-alkali glass or a quartz glass plate having a silicon oxide coating on its surface, .

In addition, the substrate is subjected to a coupling treatment in advance, so that the colored photosensitive resin composition or adhesion with the photosensitive resin transfer material can be improved. As the coupling treatment, the method described in JP-A-2000-39033 is preferably used. Although not particularly limited, the film thickness of the substrate is generally 700 to 1200 mu m, particularly preferably 500 to 1100 mu m.

(Oxygen barrier)

In the color filter of the present invention, in the case where a photosensitive resin layer is formed by applying a colored photosensitive resin composition, an oxygen barrier film can be further formed on the photosensitive resin layer, thereby increasing the exposure sensitivity. As the oxygen shielding film, the same ones as described in the section of [intermediate layer of [photosensitive resin transfer material]] are listed. Although not particularly limited, the film thickness of the oxygen shielding film is generally preferably 0.5 to 3.0 占 퐉.

(Exposure and development)

A step of disposing a predetermined mask above the photosensitive resin layer formed on the substrate and thereafter exposing the mask, the thermoplastic resin layer, and the intermediate layer therebetween and above the mask, The color filter of the present invention can be obtained.

Here, as the light source for the exposure, any material capable of irradiating light in a wavelength range (for example, 365 nm, 405 nm, etc.) capable of curing the photosensitive resin layer can be appropriately selected and used. Specific examples thereof include ultra-high pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps. The exposure dose is usually about 5 to 20 mJ / cm ² , and preferably about 10 to 10 mJ / cm ² .

As the developer, there is no particular restriction, and a conventional developer such as those described in JP-A-5-72724 can be used. On the other hand, it is preferable that the developing solution has a developing behavior of the dissolution type of the photosensitive resin layer. For example, it is preferable that the developer contains a compound having pKa = 7 to 13 at a concentration of 0.05 to 5 mol / L, A smaller amount of the organic solvent may be added.

Examples of the organic solvent having water miscibility include methanol, ethanol, 2-propanol-1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n- But are not limited to, alcohols, acetone, methyl ethyl ketone, cyclohexanone,? -Caprolactone,? -Butyrolactone, dimethylformamide, dimethylacetoamide, hexamethylphosphoramide, ethyl lactate, Methyl pyrrolidone and the like. The concentration of the organic solvent is preferably 0.1% by mass to 30% by mass.

Further, a conventional surfactant may be further added to the developer. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.

As the developing method, methods such as paddle development, shower development, shower & spin development, and dip development can be used.

Explaining the shower phenomenon, the uncured portion can be removed by spraying the developer to the exposed photosensitive resin layer by a shower. On the other hand, it is preferable that the thermoplastic resin layer, the intermediate layer and the like are removed by spraying an alkaline liquid having low solubility in the photosensitive resin layer by a shower or the like before development. It is also preferable to remove the developing residue while spraying a cleaning agent or the like after development and rubbing with a brush or the like.

The liquid temperature of the developing solution is preferably 20 to 40 占 폚, and the pH of the developing solution is preferably 8 to 13.

On the other hand, at the time of manufacturing the color filter of the present invention, as described in JP-A-11-248921 and JP-A-3255107, a base is formed by superimposing a colored photosensitive resin composition forming a color filter, It is preferable to form a transparent electrode thereon and to form a spatter by overlapping projections for dividing distribution from the viewpoint of cost reduction.

When the colored photosensitive resin composition is sequentially applied and overlapped, the film is thinned every time it is formed due to the leveling of the coating liquid. For this reason, it is preferable that the four colors of K (black), R, G, and B are superposed to further superpose the dividing orientation projections. On the other hand, when a transfer material having a thermoplastic resin layer is used, it is preferable that the color is three or two colors so that the thickness is kept constant.

The size of the base is preferably 25 占 퐉 or more, and particularly preferably 30 占 퐉 or more, from the viewpoint of preventing deformation of the photosensitive resin layer when the transfer material is laminated and laminated to have a constant thickness.

[Liquid crystal display device]

The liquid crystal display device of the present invention uses the color filter of the present invention having excellent contrast, and has excellent descriptive power such as sharpness of black color. And can also be preferably used as a liquid crystal display of a large screen such as a notebook display or a television monitor.

[CCD device]

The CCD device of the present invention comprises a color filter manufactured using the pigment nanoparticles. Hereinafter, the CCD device of the present invention will be described in detail.

Alkali-soluble resin

The alkali-soluble resin usable for the CCD device is preferably a linear organic polymer, soluble in an organic solvent, and capable of being developed with a weakly alkaline aqueous solution. Examples of such linear organic polymer include polymers having a carboxylic acid in the side chain, for example, JP-A 59-44615, JP-A 54-34327, JP-A 58-12577, Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers such as those described in JP-A-54-25957, JP-A-59-53836 and JP-A-59-71048 Maleic acid copolymer, partially esterified maleic acid copolymer, and the like, and also acidic cellulose derivatives having a carboxylic acid in the side chain. It is also useful to add an acid anhydride to the polymer having a hydroxyl group. Particularly, among these, a poly (methyl methacrylate) / (meth) acrylic acid copolymer and benzyl (meth) acrylate / (meth) acrylic acid / and other monomers are preferable. As the water-soluble polymer, 2-hydroxyethyl methacrylate, polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol and the like are also useful.

Also, there may be mentioned 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in Japanese Patent Application Laid-Open No. 7-140654, 2-hydroxy- Methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, Methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, and the like. The amount of the alkali-soluble resin to be added in the curable composition is preferably 5 to 90% by mass, more preferably 10 to 60% by mass with respect to the total mass of the composition.

Polymerizable monomer

The polymerizable monomer is preferably a compound having at least one addition-polymerizable ethylene group and having an ethylenic unsaturated group with a boiling point of 100 캜 or higher at normal pressure.

(Meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, and the like having at least one addition polymerizable ethylenic unsaturated group and having a boiling point of not lower than 100 deg. Monofunctional acrylate or (meth) acrylate; (Meth) acrylate, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Acryloyloxyethyl) isocyanurate, glycerin, trimetholol ethane, and the like, and the like, such as ethyleneglycol monomethacrylate, erythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols of JP-A-48-41708, JP-A-50-6034, JP-A-51-37193 Urethane acrylates such as those described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, Japanese Patent Publication The No. 52-30490, such as polyester acrylates, epoxy resins with (meth) the reaction product of the epoxy acrylates of the acid as described in each publication can be exemplified a polyfunctional acrylate or methacrylate. Further, those which have been introduced as photo-curable monomers and oligomers in Japan Adhesion Society, Vol. 20, No. 7, pages 300 to 308 can also be used.

Further, a compound represented by the following general formula (B-1) or (B-2) may also be used.

(In the formulas (B-1) and (B-2), B independently represents any one of - (CH ₂ CH ₂ O) - and - (CH ₂ CH (CH ₃ ) O) -; X is independently an acryloyl group, a methacryloyl group or a hydrogen atom, and in the formula (B-1), the sum of the acryloyl group and the methacryloyl group is 5 or 6, B-2) is 3 or 4; n each independently represents an integer of 0 to 6, and the sum of each n is 3 to 24; m each independently represent an integer of 0 to 6, and the sum of m is 2 to 16. < RTI ID = 0.0 >

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

coloring agent

As the coloring agent, conventionally known various dyes, inorganic pigments or organic pigments may be used singly or in combination of two or more.

The dyes are not particularly limited, and dyes known for conventional color filters can be used. For example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, JP-A-2592207, 4808501, US 5667920, US 505950, US 5667920, JP 5-333207, JP 6-35183, and JP 6-51115 And Japanese Unexamined Patent Application Publication No. 6-194828 can be used. Examples of the chemical structure include pyrazole azo compounds, anilino azo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxolin compounds, pyrazolotriazole compounds, pyripyridazo compounds, cyanines, phenothiazines, Methine-based dyes can be used. Particularly, since the curable composition can be cured at a relatively low temperature, problems such as decomposition can be alleviated even when exposed to a high temperature during post-baking for imparting durability to the cured film even if the dye has poor heat resistance as compared with the pigment.

Specific examples of the inorganic pigment include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony, Oxides are listed.

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

These organic pigments may be used alone or in combination of several to enhance color purity. Specific examples are shown below. As the red pigment, an anthraquinone pigment, a perylene pigment alone or a mixture of at least one of them with a disazo yellow pigment or an isoindoline yellow pigment is used. Examples of the anthraquinone pigments include C.I. Pigment Red 177, and perylene pigments such as C.I. Pigment Red 155 can be listed, and in terms of color reproducibility, C.I. Pigment Yellow 83 or C.I. Mixing with Pigment Yellow 139 is good. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. Within this range, light transmittance in the range of 400 nm to 500 nm can be suppressed and the color purity can be increased.

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

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

Also, by using a powdery processed pigment in which the 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, a pigment-containing photosensitive resin having excellent dispersibility and dispersion stability can be obtained.

As the pigment for black matrix, carbon, titanium oxide, iron oxide, carbon and titanium oxide used singly or in combination are preferable. The mass ratio is preferably in the range of 100: 5 to 100: 40. Within this range, the light transmittance at a long wavelength is small and the dispersion stability is good.

solvent

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, butyl butyrate, alkyl esters, , Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, 3-oxypropionic acid alkyl esters such as ethyl propionate; Methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy- , Methyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, 2- Ethyl butanoate; Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; Aromatic hydrocarbons such as toluene, xylene and the like.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, , Ethylcarbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferably used. The amount of the solvent to be added 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.

It is possible to further use a sensitizer. Specific examples thereof include 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2- Anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, benzyl P- (dimethylamino) phenyl-p-methylstyrylketone, benzanthrone, etc., and benzothiazole-based compounds described in Japanese Patent Publication No. 51-48516 .

The above-mentioned main components and other additives which are further used if necessary can be mixed and dispersed by using various mixers and dispersers.

A general method of manufacturing a color filter used in a CCD device is as follows. A step of applying and drying the composition (color resist solution) of the present invention on a substrate, a step of pattern exposure with an i-line stepper or the like, a step of alkali development after exposure, and a step of heat treatment , And the above process is sequentially repeated for each color (three colors or four colors) to produce a cured film to obtain a color filter.

More specifically, the curable composition is coated on a suitable substrate with a spinner or the like so that the film thickness upon drying is generally 0.1 to 5 占 퐉, preferably 0.2 to 2 占 퐉, and left in an oven at 85 占 폚 for 2 minutes A smooth coating film is obtained.

The substrate is not particularly limited, and examples of the substrate include electronic parts such as a glass plate, a plastic plate, an aluminum plate, and a silicon wafer for an imaging device, a transparent resin plate, a resin film, a cathode ray tube display surface, A wafer on which solid state image pickup devices such as CID and BASIS are formed, a contact type image sensor using thin film semiconductor, a liquid crystal monitor surface, a photoconductor for color electrophotography, and a substrate for an electrochromic (EC) display device. Further, it is preferable that the substrate is subjected to a high adhesion treatment in order to improve the adhesion to the color filter layer. Specifically, it is possible to form a pattern of the curable composition after thinly coating a silane coupling agent or the like on the substrate, or to contain a silane coupling agent in advance in the curable composition.

When there is a step on the substrate, the planarizing film for smoothing the coated surface by removing the step can be coated on the substrate, and then the curable composition of the present invention can be applied. For example, an image sensor such as a CCD is composed of a photoelectric conversion portion (photodiode) for generating electrons on the silicon substrate in accordance with the amount of received light and a read gate portion for outputting the generated electrons. However, The correct data can not be outputted. Therefore, a shielding film layer is formed on the top of the readout gate portion, and a step may be formed between the readout gate portion and the photodiode portion having no shielding film layer. When a color resist is coated on such a step and a direct color filter is formed, the length of the optical path becomes long, so that the image is dark and the light-condensing property is deteriorated. In order to improve this, it is preferable to form a transparent planarization film between the CCD and the color filter in order to fill the step difference. Examples of the material of the planarizing film include thermosetting resins such as a photocurable resist solution, acrylic resin, and epoxy resin as in the present invention.

After the photocurable composition is applied, prebaking is usually carried out in order to obtain a dried coating film by evaporating the solvent. Examples of the prebaking method include reduced pressure drying, indirect heating and drying with high temperature air, direct heating and drying (about 80 to 140 ° C for 50 to 200 seconds) with a hot plate, and the like. In addition, the post-baking is performed in order to sufficiently harden the pattern obtained after development to increase the mechanical strength to obtain a permanent film. For example, at the time of manufacturing a color filter of three colors, the pattern formed first is then applied twice, exposure and development are carried out twice. At this time, the post-baking is performed so as to prevent a pattern deficiency due to color mixing with the applied resist solution, exposure, and development. This post-baking is performed in the same manner as pre-baking, but at a temperature higher than the pre-baking condition and for a long time. 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 for the direct heating by a hot plate, about 180 to 250 ° C for about 2 to 10 minutes.

The light source for exposure is not particularly limited, but i-line of mercury lamps can be enumerated as a light source that causes a remarkable effect with respect to the pattern forming property. It is a matter of course that the present invention is particularly advantageous in the production of a color filter for an image sensor in which an i-line, which is one of the line spectra of a mercury lamp, is used.

The developer used for development of the curable composition is not particularly limited, and conventionally known developers can be used. Among them, an organic alkali developer of a quaternary ammonium salt such as tetramethylammonium hydroxide (TMAH) is preferable in view of attaining the object of the present invention.

Polymerization initiator

As the polymerization initiator, a general photopolymerization initiator can be used. Specific examples thereof include biscuit polyketol aldonyl compounds described in U.S. Patent No. 2, 367,660, α-carbonyl compounds described in U.S. Patent Nos. 2, 367,661 and 2, 367,670, and U.S. Patent No. 2,448,828 Hydrocarbyl substituted aromatic acyloin compounds described in US Pat. No. 2,722,512, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, US Pat. 3,549, 367, combinations of triarylimidazole dimers / p-aminophenyl ketones described in the specification, benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-B-51-48516 Can be listed.

The content of the photopolymerization initiator (including the above-mentioned general photopolymerization initiator) in the dye-containing negative curable composition is preferably from 0.01 to 50 mass%, more preferably from 1 to 30 mass%, based on the solids (mass) of the radical polymerizable monomer , And particularly preferably from 1 to 20 mass%. When the content is within the above range, sufficient polymerization and curing are carried out, so that the polymerization is difficult to proceed or the polymerization rate is increased, but the molecular weight is lowered and the film strength is not weakened.

In addition, a sensitizer or a light stabilizer may be used in combination with the 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- Anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10 Anthraquinone, xanthone, 2-methylxanthone, 2-methoxycanthone, 2-ethoxycanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, (Dimethylamino) phenyl styryl ketone, p- (dimethylamino) phenyl-p-methylstyryl ketone, benzophenone, p- (dimethylamino) benzophenone (Diethylamino) benzophenone, benzanthrone and the like, and benzothiazole-based compounds described in JP-B-51-48516, Tinuvin 1130 and Tin 400, and the like.

Example

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

(Example 1)

To 1000 ml of dimethylsulfoxide, 33.3 ml of a 28% methanol solution of sodium methoxide, 20 ml of a pigment C.I. 100 g of Pigment Red 254 (trade name: Irgaphor Red BT-CF, manufactured by Ciba Specialty Chemicals) and 150 g of polyvinyl pyrrolidone were added. Separately, 1000 ml of water containing 16 ml of 1 mol / L hydrochloric acid as a poor solvent was prepared.

Here, the temperature was controlled at 18 占 폚, and the temperature was controlled by Fujisawa Pharmaceutical Co., Ltd. Pigment solution A was dispersed in 1,000 ml of a poor solvent of water stirred at 500 rpm by a GK-0222-10 type Raymond stirrer, using Nihon Seimitsu Kagaku Co., Ltd. 100 ml / min of the product NP-KX-500 large capacity non-pulsating pump was used to form organic pigment particles to prepare Pigment Dispersion A.

The obtained pigment dispersion A was applied to an H-122 type centrifugal filter manufactured by Kokusan Corporation and a Shikishima Canvas Co., Ltd. The product was concentrated using a P89C type spinning column at 4000 rpm for 90 minutes to obtain a dispersion (referred to as dispersion A).

To 16.0 g of the pigment nanoparticle-prepared paste, 50.0 ml of ethyl lactate was added, and the mixture was stirred at 150 ° rpm for 60 minutes in a dissolver, followed by stirring with a SUMITOMO ELECTRIC FINE POLYMER INC. The product was filtered using an FP-010 type filter to obtain a paste-like concentrated pigment solution A (nano pigment concentration 30% by mass).

[Production of pigment dispersion composition]

Using the paste, a pigment dispersion composition A having the following composition was prepared.

21.3 g of the above-mentioned concentrated pigment liquid A

0.6 g of pigment dispersant A (the dispersant, Exemplary Compound 7)

3.2 g of the polymer compound C-16 usable in the present invention

45.3 g of 1-methoxy-2-propyl acetate

The pigment dispersant A was synthesized according to JP-A-2000-239554.

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

The obtained pigment dispersion composition A was measured for particle diameter using a Nano Truck UPA-EX150, a product of NIKKISO Ltd. As a result, the average particle diameter was 31 nm, the particle size distribution was less than 15 nm and the ratio of particles was 5% The ratio of the particles was 7%.

(Example 2)

A pigment-dispersed composition B was prepared in the same manner as in Example 1 except that the pigment dispersion A obtained in Example 1 was concentrated at 500 rpm by using a H-112 type centrifugal filter manufactured by Kokusan Corporation.

(Example 3)

A pigment-dispersed composition C was prepared in the same manner as in Example 1 except that the pigment dispersion A obtained in Example 1 was concentrated by a H-112 type centrifugal filter manufactured by Kokusan Corporation at 500 rpm for 300 minutes.

(Comparative Example 1)

A pigment-dispersed composition D was prepared in the same manner as in Example 1 except that the pigment dispersion A obtained in Example 1 was concentrated by a H-112 type centrifugal filter manufactured by Kokusan Corporation at 340 rpm for 100 minutes.

(Comparative Example 2)

A pigment dispersion composition E having the following composition was produced as follows.

Pigment Red 254 (6.4 g)

64.0 g of sodium chloride

3.2 g of Compound C-16 usable in the present invention

Powder of sodium chloride, pigment (Pigment Red 254) and Compound C-16 which can be used in the present invention were put into a wing-like kneader in a solution of 1-methoxy-2-propyl acetate and kneaded at 80 ° C for 10 hours. After kneading, the mixture was taken out of 500 parts by mass of a 1% hydrochloric acid aqueous solution at 80 ° C and stirred for 1 hour, followed by filtration and washing to remove sodium chloride and solvent. The mixture was dried at 65 ° C for 14 hours and then pulverized. 2.4 g of 2-propyl acetate was added and mixed.

The pigment composition was dispersed for 1 hour at a peripheral speed of 9 m / s using Motor Mill M-50 (manufactured by Eiger, Japan) with zirconia beads having a diameter of 0.65 mm. Pigment dispersion composition E was obtained. The same procedure as in Example 1 was carried out and the measured particle diameters were 53 nm in number average particle diameter, 18% in particle size distribution with a particle size distribution of less than 15 nm, and 24% in particles exceeding 60 nm.

(Comparative Example 3)

A pigment-dispersed composition F was produced in the same manner as in Comparative Example 2 except that the drying conditions after filtration and bathing in Comparative Example 2 were changed to 80 캜 and 48 hours.

[Measurement of contrast]

Each of the obtained Pigment Dispersion Composition A to F was coated on a glass substrate to a thickness of 2 占 퐉 to prepare a sample. As a backlight unit, a three-wavelength cold cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting Corporation) equipped with a diffusion plate was used, and the sample was placed between two polarizing plates (polarizer HLC2-2518 manufactured by SANRITSU Corp.) (The 7th Color Optics Conference in 1990, color filters for 512-color display 10.4 "size TFT-LCD, plant, tentative, recreational, etc.), and the ratio was referred to as contrast The polarizing plate, the sample, and the color luminance meter were installed at positions of 13 mm from the backlight, and 40 mm to 40 mm from the backlight, respectively. A cylinder having a diameter of 1 mm and a length of 20 mm was provided at a position of 60 mm and light transmitted through the sample was irradiated to a measurement sample provided at a position of 65 mm to pass the transmitted light through a polarizing plate provided at a position of 100 mm, Color brightness installed at the location Was measured with a measuring angle of total color luminance was set to 2 °. Light amount of the backlight has set the luminance at the time the two polarizing plates in a state that does not install the sample parallel has set up to Nicol so that 128Ocd / m ^2.

Further, this sample was irradiated with a high-pressure mercury lamp of 90 mW / cm ² for 24 hours, and the color difference before and after irradiation was measured to be an index of light resistance. In the present invention, chromaticity is measured with a brown spectrophotometer (Olympus optical product; OSP 100 or 200), calculated as a result of the Fl0 light source field of view 2 degrees, and represented by the xyY value of the xyz color system. The difference in chromaticity represents the color difference of the La ^* b ^* color system. The smaller the color difference, the better.

Table 1 shows the measurement results of the contrast and the light resistance of the samples obtained from the pigment dispersion compositions A to F.

As shown in Table 1, the pigment dispersion composition of the present invention exhibited remarkably excellent contrast and light resistance as compared with the comparative example.

(Example 4-1)

The pigment dispersion composition A was mixed with other components so as to have the composition shown in Table 2 below to prepare a colored photosensitive resin composition A for a color filter.

The polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate

= 38/25/37 molar ratio, molecular weight: 40,000) 27 parts by mass

Propylene glycol monomethyl ether acetate 73 parts by mass

76 parts by mass of dipentaerythritol hexaacrylate (containing 500 ppm of polymerization inhibitor MEHQ, product of NIPPON KAYAKU Co., Ltd., trade name: KAYARAD DPHA)

Propylene glycol monomethyl ether acetate 24 parts by mass

30 parts by mass of the following compound 1

70 parts by mass of methyl ethyl ketone

Colored photosensitive resin compositions B to F for a color filter were produced in the same manner as above except that Pigment Dispersing Compositions B to F were used in place of Pigment Dispersion Composition A, respectively.

The colored photosensitive composition for fabricating the color filter was coated on a glass substrate using a spin coater and dried at 100 DEG C for 2 minutes to form a film having a thickness of about 2 mu m. Then, it was exposed in an ultra-high pressure mercury lamp under a nitrogen current, and then developed in a 1% aqueous solution of sodium carbonate. The contrast and the light resistance of the obtained R component of each film were measured in the same manner as in [Measurement of contrast], and the results are shown in Table 3 below.

As shown in Table 3, the colored photosensitive resin composition of the present invention exhibited a very excellent contrast and light resistance as compared with the comparative example.

(Example 4-2)

[Production of color filter (production by application using slit-on nozzle)]

(Formation of black (K) image)

The alkali-free glass substrate was cleaned with an UV cleaning device, then cleaned with a brush using a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat treated at 120 ° C for 3 minutes to stabilize the surface state.
The substrate was cooled to obtain a colored photosensitive resin composition K1 having the composition described in the following Table 4 in a coater for a glass substrate (product of F · AS · Asia, product name: MH-1600) having a slit- . Subsequently, a part of the solvent was dried for 30 seconds by a VCD (vacuum drying apparatus; manufactured by TOKYO OHKA KOGYO Co., Ltd.) to remove the fluidity of the coating layer and then prebaked at 120 ° C for 3 minutes to form a photosensitive Whereby a resin layer K1 was obtained.

(A quartz exposure mask having an image pattern) is vertically erected with a substrate of a proximity type exposure apparatus (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, and between the exposure mask surface and the photosensitive resin layer Was set to 200 mu m, and pattern exposure was performed at an exposure amount of 300 mJ / cm < ² >.

Then, pure water was sprayed with a shower nozzle and the surface of the photosensitive resin layer K1 was uniformly wetted. Then, a KOH-based developer (containing KOH, a nonionic surfactant, trade name: CDK-1, manufactured by FUJIFILM Electronic Materials Co., Ltd.) At 23 캜 for 80 seconds and flat nozzle pressure of 0.04 MPa to obtain a patterned image. Subsequently, ultra pure water was jetted at a pressure of 9.8 MPa in an ultra high pressure cleaning nozzle to remove residues to obtain an image K of black (K). Subsequently, heat treatment was performed at 220 캜 for 30 minutes.

(Formation of red (R) pixel)

On the substrate on which the image K was formed, the colored photosensitive resin composition R1 having the composition shown in the following Table 5 was used and the heat-treated pixel R was formed in the same process as the formation of the black (K) image.

The film thickness of the photosensitive resin layer R1 and the application amount of the pigment (C. I. P. R. 254 and C. I. P. R. 177) are shown below.

Photosensitive resin film thickness (占 퐉) 1.60

Pigment application amount (g / m ² ) 1.00

CIPR 254 Application amount (g / m ² ) 0.80

C. l. PR 177 Application amount (g / m ² ) 0.20

(Formation of green (G) pixel)

On the substrate on which the image K and the pixel R were formed, a colored photosensitive resin composition G1 having the composition described in the following Table 6 was used, and a heat-treated pixel G was formed by the same process as the formation of the black (K) image . The film thickness of the photosensitive resin layer G1 and the application amounts of the pigments (C. I. P. G. 36 and C. I. P. Y. 150) are shown below.

Photosensitive resin film thickness (占 퐉) 1.60

Pigment application amount (g / m ² ) 1.92

CIPG 36 Application amount (g / m ² ) 1.34

CIPY 150 Application amount (g / m ² ) 0.58

(Formation of blue (B) pixels)

A color photosensitive resin composition B1 having the composition described in Table 7 below was used for the substrate on which the image K, the pixel R and the pixel G were formed, and the pixel B finished with the heat treatment in the same process as the formation of the black (K) To obtain a desired color filter A.

The film thickness of the photosensitive resin layer B1 and the application amount of the pigment (C. I. P. B. 15: 6 and C. I. P. V. 23) are shown below.

Photosensitive resin film thickness (占 퐉) 1.60

Pigment application amount (g / m ² ) 0.75

CIPB 15: 6 Application amount (g / m ² ) 0.705

C · I · P · V · 23 Application amount (g / m ² ) 0.045

Here, the production of the colored photosensitive resin compositions K1, R1, G1, and B1 described in Tables 4 to 7 will be described in detail.

First, the colored photosensitive resin composition K1 was obtained by weighing K pigment dispersion 1 and propylene glycol monomethyl ether acetate in an amount as shown in Table 4, mixing at a temperature of 24 캜 (占 2 占 폚), stirring at 150 rpm for 10 minutes, The amount of methyl ethyl ketone, binder 2, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 '- (N, N-bisethoxycarbonylmethyl ) Was added in this order at a temperature of 25 占 폚 (占 2 占 폚), and the mixture was stirred at a temperature of 40 占 폚 (占 2 占 폚) at 150 rpm And stirring for 30 minutes.

On the other hand, the compositions of the following components in the compositions shown in Table 4 are shown below.

&Lt; K Pigment Dispersion 1 >

Carbon black (trade name: Nipex 35, manufactured by Degussa Japan Co., Ltd.)

13.1 parts by mass

Dispersant (Compound 2J, below) 0.65 parts by mass

Polymer (benzyl methacrylate / methacrylic acid = 72/28 mole ratio

Random copolymer, molecular weight: 3.7 million) 6.72 parts by mass

Propylene glycol monomethyl ether acetate 79.53 parts by mass

Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio

Random copolymer, molecular weight: 3.8 million) 27 parts by mass

Propylene glycol monomethyl ether acetate 73 parts by mass

The colored photosensitive resin composition R1 was obtained by weighing the R pigment dispersion A, the R pigment dispersion 2 and the propylene glycol monomethyl ether acetate in an amount as shown in Table 5 at a temperature of 24 캜 (占 2 占 폚) And the mixture was stirred for 10 minutes. Then, a solution of methyl ethyl ketone, binder 1, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole, (Trichloromethyl) -6- [4 - (N, N-bisethoxycarbonylmethyl) amino-3'-bromophenyl] -s-triazine and phenothiazine , And the temperature was 24 ° C (± 2 ° C) in this order, and the mixture was stirred at 150 rpm for 30 minutes. Further, the surfactant 1 in the amount shown in Table 5 was further weighed and added at a temperature of 24 ° C (± 2 ° C) Stirred for 5 minutes, and filtered through a nylon mesh # 200.

On the other hand, among the compositions shown in Table 5, the R pigment dispersion A was obtained in the same manner as the pigment dispersion composition A of Example 1, and was produced so that the composition had the following mass parts.

&Lt; R pigment dispersion A >

- 23 parts by mass of the paste-like concentrated pigment solution A (C.I.P.R. 254) of Example 1

Dispersant (Compound 2J) 0.8 parts by mass

Polymer (benzyl methacrylate / methacrylic acid = 72/28 mole ratio

Random copolymer, molecular weight: 30,000) 8 parts by mass

Propylene glycol monomethyl ether acetate 68.2 parts by mass

&Lt; R pigment dispersion 2 >

C. I. P. R. 177 (trade name: Cromophtal Red A2B,

Manufactured by Ciba Specialty Chemicals) 18 parts by mass

Polymer (benzyl methacrylate / methacrylic acid = 72/28 mole ratio

Random copolymer, molecular weight: 30,000) 12 parts by mass

Propylene glycol monomethyl ether acetate 70 parts by mass

The colored photosensitive resin composition G1 was obtained by weighing the G pigment dispersion 1, Y pigment dispersion 1 and propylene glycol monomethyl ether acetate in an amount as shown in Table 6 at a temperature of 24 ° C (± 2 ° C) The mixture was stirred for 10 minutes, and then methyl ethyl ketone, cyclohexanone, binder 2, DPHA solution and 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4- Oxadiazole, 2,4-bis (trichloromethyl) -6- [4 '- (N, N-bisethoxycarbonylmethyl) amino-3'- Azine were weighed out and added in this order at a temperature of 24 DEG C (+/- 2 DEG C), and the mixture was stirred at 150 rpm for 30 minutes. Further, the surfactant 1 in the amount shown in Table 6 was further weighed and taken at a temperature of 24 DEG C (+/- 2 DEG C) , And the mixture was stirred at 30 rpm for 5 minutes and filtered through a nylon mesh # 200.

On the other hand, among the compositions shown in Table 6, the G pigment dispersion 1 was FUJIFILM Electronic Materials Co., Ltd. Product " GT-2 ". The Y pigment dispersion 1 was obtained from MIKUNI COLOR Co. Ltd. &Quot; Product name: CFYellow-EX3393 "

The colored photosensitive resin composition B1 was prepared by first weighing the amounts of B pigment dispersion 1, B pigment dispersion 2 and propylene glycol monomethyl ether acetate as shown in Table 7 at a temperature of 24 占 폚 (占 2 占 폚) The mixture was stirred for 10 minutes, and then methyl ethyl ketone, binder 3, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole The mixture was stirred at 150 rpm for 30 minutes at a temperature of 40 占 폚 (占 2 占 폚) at 25 占 폚 (占 2 占 폚) Activator 1 was further metered in, added at a temperature of 24 ° C (± 2 ° C), stirred at 30 rpm for 5 minutes, and filtered through a nylon mesh # 200.

On the other hand, among the compositions shown in Table 7, the B pigment dispersion 1 was obtained from MIKUNI COLOR Co. Ltd. &Quot; Product name: CF Blue-EX3357 " B pigment dispersion 2 was obtained from MIKUNI COLOR Co. Ltd. Product " CF Blue-EX3383 "

The composition of the binder 3 is as follows.

27 parts by mass of a polymer (random copolymer of benzyl methacrylate / methacrylic acid / methyl methacrylate = 36/22/42 molar ratio, molecular weight: 3.8 million)

Propylene glycol monomethyl ether acetate 73 parts by mass

(Hereinafter referred to as " concentrated pigment liquids B to F ") obtained in Examples 2 and 3 and Comparative Examples 1 to 3 were used instead of the concentrated pigment liquid A used as the R pigment dispersion A to prepare R Pigment dispersions B to F were prepared. Color filters B to F were produced in the same manner as in the above-mentioned production process of the color filter A, except that R pigment dispersions B to F were used instead of R pigment dispersion A, respectively.

Table 8 shows the results of measuring the contrast and the light resistance of each color filter in the same manner as the above [measurement of contrast].

As a result, it can be seen that the color filter of the present invention exhibits a very high contrast and light resistance as compared with the comparative example. If the color difference is different by two or more, it is the degree to which it differs according to the viewer. And the difference is further enlarged by use of a long term (for example, one year or more), resulting in a marked difference on the display screen. All of the color filters of the present invention were high-contrast and good color filters. On the other hand, the color filter of the comparative example had a low contrast and a level that did not satisfy the practical requirement.

(Example 4-3)

[Manufacturing and Evaluation of Liquid Crystal Display Device]

A liquid crystal display was manufactured using the color filters A to F to evaluate the display characteristics.

(Formation of ITO electrode)

A glass substrate on which a color filter was formed was put in a sputtering apparatus, and ITO (indium tin oxide) having a thickness of 1300 ANGSTROM was vacuum deposited on the entire surface at 100 DEG C and then annealed at 240 DEG C for 90 minutes to crystallize ITO to form an ITO transparent electrode .

(Formation of spacer)

A spacer was formed on the ITO transparent electrode prepared in the same manner as the spacer forming method described in [Example 1] of Japanese Patent Application Laid-Open No. 2004-240335.

(Formation of Liquid Crystal Alignment Control Projections)

Using the following coating liquid for a positive-type photosensitive resin layer, a projection for controlling liquid crystal alignment was formed on the ITO transparent electrode on which the spacer was formed.

In the exposure, development and baking processes, the following methods were used.

A Proximity Exposure Machine (manufactured by Hitachi High-Tech Electronic Engineering Co., Ltd.) was disposed so that a prescribed photomask was 100 mu m from the surface of the photosensitive resin layer, and the photomask was interposed therebetween and irradiated And proximity exposure was performed at an energy of 150 mJ / cm ² .

Subsequently, a 2.38% tetramethylammonium hydroxide aqueous solution was sprayed on the substrate at 33 ° C for 30 seconds in a shower type developing apparatus to perform development. Thus, a substrate for a liquid crystal display having a liquid crystal alignment control protrusion made of a photosensitive resin layer patterned in a desired shape on a color filter side substrate was obtained by developing and removing unnecessary portions (exposed portions) of the photosensitive resin layer.

Subsequently, the substrate for a liquid crystal display having the projection for controlling liquid crystal alignment control was baked at 230 캜 for 30 minutes to form a cured liquid crystal alignment control projection on the substrate for a liquid crystal display.

&Lt; Prescription of Coating Liquid for Positive Photosensitive Resin Layer >

A positive resist solution (FUJIFILM electronics

materials Co., Ltd. Product: FH-2413F): 53.3 parts by mass

Methyl ethyl ketone: 46.7 parts by mass

Megafac F-780F (manufactured by Dainippon Ink and Chemicals, Inc.): 0.04 parts by mass

(Preparation of liquid crystal display device)

An alignment film made of polyimide was further provided on the substrate for a liquid crystal display obtained above. Thereafter, an epoxy resin encapsulant is printed at a position corresponding to the black matrix outer frame provided around the pixel group of the color filter, and the liquid crystal for the MVA mode is dropped and bonded to the counter substrate , And the bonded substrate was heat-treated to cure the sealing agent. On both sides of the thus obtained liquid crystal cell, SANRITSU Corp. The polarizing plate HLC2-2518, which is a product, was bonded. Subsequently, a backlight of a 3-wavelength cold cathode fluorescent lamp (FWL18EX-N manufactured by Toshiba Lighting Corporation) was constituted, and was disposed on the back side of the liquid crystal cell on which the polarizing plate was provided.

It was confirmed that the liquid crystal display device using the color filter of the present invention exhibited excellent display characteristics with excellent crispness and red coloring power of black and no display unevenness with respect to the liquid crystal display device using the color filter of the comparative example.

(Example 5-1)

[Production of color filter (Production by lamination of photosensitive transfer material)

(Production of photosensitive resin transfer material)

On the support of a polyethylene terephthalate film having a thickness of 75 탆, a slit-shaped nozzle was used to apply a coating liquid for a thermoplastic resin layer comprising the following formulation H1 and dried. Then, the intermediate layer coating liquid comprising the following formulation P1 was applied and dried. The colored photosensitive resin composition K1 was further coated and dried to form a thermoplastic resin layer having a dry film thickness of 14.6 占 퐉, an intermediate layer having a dry film thickness of 1.6 占 퐉 and a photosensitive resin layer having a dry film thickness of 2.4 占 퐉 And a protective film (a 12 占 퐉 thick polypropylene film) was squeezed.

In this manner, a photosensitive resin transfer material K1 in which the branched structure and the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the photosensitive resin layer of black (K) were integrated was produced.

&Lt; Coating liquid for thermoplastic resin layer: Prescription H1 >

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 占 폚) 5.83 parts by mass

Styrene / acrylic acid copolymer (copolymer composition ratio (molar ratio

= 63/37, molecular weight: 10,000, Tg: about 100 ° C) 13.6 parts by mass

· Addition of pentaethylene glycol monomethacrylate to bisphenol A

2 eq dehydration condensed compound (Shin-nakamura Chemical

Ltd., trade name: 2,2-bis [4- (methacryloxypolyethoxy)

Phenyl] propane) 9.1 parts by mass

0.54 parts by mass of the above-mentioned surfactant 1

· PVA205 (polyvinyl alcohol, Curare product,

Degree of polymerization = 88%, degree of polymerization: 550) 32.2 parts by mass

Polyvinyl pyrrolidone (ISP, Japan, K-30) 14.9 parts by mass

Distilled water 524 parts by mass

Methanol 429 parts by mass

Next, the above-mentioned colored photosensitive resin composition K1 used in the production of the photosensitive resin transfer material K1 was changed to the following colored photosensitive resin compositions R101, G101 and B101 having compositions shown in Tables 9 to 11, Photosensitive resin transfer materials R101, G101 and B101 were prepared. Meanwhile, the production methods of the colored photosensitive resin compositions R101, G101 and B101 are the same as those of the above-mentioned colored photosensitive resin compositions R1, G1 and B1, respectively.

On the other hand, among the compositions shown in Table 9, Phosphoric ester-based special activator (product name: HIPLAAD ED152, product of Kusumoto Chemicals, Ltd.) was used as Additive 1.

(Formation of black (K) image)

The glass cleaner liquid prepared by adjusting the alkali-free glass substrate to 25 ° C was sprayed for 20 seconds by a shower, and the glass cleaner was cleaned with a rotating brush having nylon hairs. After pure shower washing, a silane coupling solution (N- (aminoethyl) (Manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd., 0.3 mass% aqueous solution of trimethoxysilane) was sprayed for 20 seconds by a shower. This substrate was heated at 100 DEG C for 2 minutes by a substrate preheating apparatus and transferred to the next laminator.

After the protective film of the photosensitive resin transfer material K1 was peeled off, a substrate heated at 100 DEG C was heated at 130 DEG C, a linear pressure of 100 N / cm < ² > and a conveying speed And laminated at 2.2 m / min.

The substrate was peeled from the interface with the thermoplastic resin layer, and then the substrate and the mask (quartz exposure mask having an image pattern) were vertically erected with a proximity type exposure device (Hitachi High-Tech Electronic Engineering) having an ultra-high pressure mercury lamp The distance between the exposure mask surface and the thermoplastic resin layer was set to 200 mu m and pattern exposure was performed at an exposure amount of 70 mJ / cm < ² >.

Then, the film was developed with a triethanolamine-based developer (containing 2.5% of triethanolamine, containing a nonionic surfactant and a polypropylene defoamer, trade name: T-PD1, manufactured by FUJI Photo Film Co. Ltd.) Followed by showering at a pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer.

Subsequently, a sodium carbonate-based developer (0.06 mol / L sodium hydrogen carbonate, the same concentration of sodium carbonate, 1% sodium dibutylnaphthalenesulfonate, an anionic surfactant, a defoamer and a stabilizer, trade name: T-CD1, FUJI Photo Film Co. Ltd Ltd.) and subjected to shower development at 29 占 폚 for 30 seconds and a cone nozzle pressure of 0.15 MPa to develop the photosensitive resin layer to obtain a patterned image.

Subsequently, a cleaning solution (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer, trade name T-SD1 (manufactured by FUJI Photo Film Co., Ltd.) or sodium carbonate / phenoxyoxyethylene surfactant, trade name T-SD2 (FUJI Photo Film Co., Ltd.)) at 33 캜 for 20 seconds and at a cone nozzle pressure of 0.02 MPa using a rotary brush having a shower and a nylon horn to obtain an image of black (K). Thereafter, the substrate was further subjected to post-exposure from the side of the resin layer with light of 50 O mJ / cm ^{2 using} ultra-high pressure mercury lamp, and then heat-treated at 220 ° C for 15 minutes.

The substrate on which the image K was formed was again cleaned with a brush as described above. After pure shower cleaning, the silane coupling liquid was sent to the substrate preliminary heating apparatus without using it.

(Formation of red (R) pixel)

Using this photosensitive resin transfer material R101, a pixel R of red (R) subjected to a heat treatment in the same process as that of the photosensitive resin transfer material K1 was obtained. The exposure amount was 40 mJ / cm ² , and the development with the sodium carbonate-based developer was 35 ° C for 35 seconds. The film thickness of the photosensitive resin layer R101 and the application amounts of the pigments (CIPR 254 and CIPR 177) are shown below.

Photosensitive resin film thickness (占 퐉) 2.00

Pigment application amount (g / m ² ) 1.00

C. l. PR 254 Application amount (g / m ² ) 0.80

CIPR 177 Application 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 sent to a substrate preliminary heating apparatus without using a silane coupling liquid after pure shower cleaning.

(Formation of green (G) pixel)

A green (G) pixel G obtained by the above-mentioned photosensitive transfer material G101 and heat-treated in the same manner as the above photosensitive transfer material R101 was obtained. However, the exposure dose was 40 mJ / cm ² , and the development with the sodium carbonate-based developer was performed at 34 ° C for 45 seconds. The film thickness of the photosensitive resin layer G101 and the application amount of the pigment (CIPG 36 and CIPY 150) are shown in the following tables.

Photosensitive resin film thickness (占 퐉) 2.00

Pigment application amount (g / m ² ) 1.92

CIPG 36 Application amount (g / m ² ) 1.34

CIPY 150 Application 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 sent to the substrate preheating apparatus without using a silane coupling liquid after pure shower cleaning.

(Formation of blue (B) pixels)

A pixel B of blue (B) was obtained by heat-treating the photosensitive resin transfer material B101 using the same process as the photosensitive transfer material R101. The exposure amount was 30 mJ / cm ² , and the development with sodium carbonate-based developer was 36 ° C for 40 seconds. The film thickness of the photosensitive resin layer B101 and the application amount of the pigment (CIPB 15: 6 and CIPV 23) are shown below.

Photosensitive resin film thickness (占 퐉) 2.00

Pigment application amount (g / m ² ) 0.75

CIPB 15: 6 Application amount (g / m ² ) 0.705

CIPV 23 Application 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 캜 for 50 minutes to obtain a color filter A1.

With respect to the above-mentioned method of forming the color filter A1, the R pigment dispersion A was changed to the R pigment dispersion B to F, respectively, and the color filters B1 to F1 were produced.

When the contrast and color difference of the obtained color filters A1 to F1 were evaluated in the same manner as in Example 4-2, the effects of the present invention were similarly expressed.

(Example 5-2)

[Manufacturing and Evaluation of Liquid Crystal Display Device]

Using the color filters A1 to F1, liquid crystal displays were manufactured in the same manner as in Example 4-3, and the display characteristics were evaluated. The effects of the present invention were similarly expressed.

(Example 6)

[Production of liquid crystal display device of different display method]

Although the liquid crystal display of the MVA system was fabricated in Examples 4-3 and 5-2, a liquid crystal display was also manufactured by the following method using the same color filter.

Manufacturing of liquid crystal display for PVA mode

A transparent electrode of indium tin oxide (ITO) was further formed on the R pixel, the G pixel, and the B pixel of the color filter substrate obtained above and the black mattress by sputtering. Then, according to Example 1 of Japanese Patent Application Laid-Open No. 2006-64921, a spatter was formed on a portion corresponding to the upper portion of the black mattress on the ITO film formed above.

Separately, a glass substrate was prepared as an opposing substrate, and patterning was performed for the PVA mode on the transparent electrode and the counter substrate of the color filter substrate, and an alignment film of polyimide was further formed thereon.

Thereafter, an encapsulant of an ultraviolet-curing resin is applied by a dispenser method to a position corresponding to the outer frame of the black mattress provided around the pixel group of the color filter, the liquid crystal for the PVA mode is dropped, And the bonded substrate was irradiated with UV light and then heat-treated to cure the sealing agent. On both sides of the thus obtained liquid crystal cell, SANRITSU Corp. The product's polarizer HLC2-2518 is attached. Then, using the DB1112H (Stanley tip LED) as the red LED, the DG1112H (tip LED as Stanley product) as the green (G) LED, and the DB1112H And arranged on the back side of the liquid crystal cell on which the polarizing plate was provided, to form a liquid crystal display device. Evaluation was carried out as in Examples 4-3 and 5-2 using this display device, and the effects of the present invention were similarly expressed.

Manufacturing of liquid crystal display for IPS mode

A transparent electrode of indium tin oxide (ITO) was further formed on the R pixel, G pixel, and B pixel of the color filter substrate obtained above and the black mattress by sputtering. Then, according to Example 1 of Japanese Patent Laid-Open No. 2006-64921, a spatter was formed on the portion corresponding to the upper portion of the black mattress on the ITO film formed above.

Polyimide was coated on the spacer color filter substrate obtained above and rubbed to form an alignment film.

A liquid crystal display element was further manufactured by combining the drive-side substrate and the liquid crystal material with the color filter substrate obtained from the above. That is, an IPS TFT substrate on which a TFT and a comb-shaped pixel electrode (conductive layer) are arranged as a driving-side substrate is prepared, and the surface of the TFT substrate on which the pixel electrode and the like are provided, and the coloring pixel The surface of the layer on which the layer was formed was oriented so as to be inward, and fixed so as to have an interval by the spacers formed thereon. A liquid crystal material was sealed at this interval to provide a liquid crystal layer for image display. On both sides of the thus obtained liquid crystal cell, SANRITSU Corp. Polarizing plate HLC2-2518. Then, a backlight of a cold cathode tube was constituted, and arranged on the side of the back surface of the liquid crystal cell on which the polarizing plate was provided, to obtain a liquid crystal display device. The same evaluation as in Examples 4-3 and 5-2 was carried out by using this display device, and the effect of the present invention on the comparative example in which the degree is smaller is expressed in the same manner as described above.

(Example 7)

[Manufacturing of CCD device]

(Production of pigment dispersion for CCD)

The pigment dispersion (1) was prepared by using the concentrated pigment dispersion A obtained in Comparative Example 1 with the following formulation. Green G, (2) ... Blue B, (3) ... Red R was prepared.

Pigment dispersion (1). I. P. G. 36 90 parts by mass

ㆍ C. I. P. G. 7 25 parts by mass

ㆍ C. I. P. Y. 139 40 parts by mass

PLAAD ED151 20 parts by mass

(Manufactured by Kusumoto Chemicals, Ltd.)

Benzyl methacrylate / methacrylic acid copolymer 25 parts by mass

(Copolymerization molar ratio 70:30, weight average molecular weight 30,000)

Propylene glycol monomethyl ether acetate 625 parts by mass

(2). I. P. B. 15: 6 125 parts by mass

ㆍ C. I. P. V. 23 25 parts by mass

ㆍ PLAAD ED151 40 parts by mass

(Product of Kusumoto Chemicals, Ltd.)

Benzyl methacrylate / methacrylic acid copolymer 25 parts by mass

(Copolymerization molar ratio 70:30, weight average molecular weight 30,000)

Propylene glycol monomethyl ether acetate 785 parts by mass

(3) Pigment dispersion composition A 235 parts by mass

&Lt; - > 40 parts by mass of Compound C-16 usable in the present invention

Benzyl methacrylate / methacrylic acid copolymer 25 parts by mass

(Copolymerization molar ratio 70:30, weight average molecular weight 30,000)

Propylene glycol monomethyl ether acetate 750 parts by mass

(Preparation of colored resin composition)

With respect to each 200 parts by mass of each of the pigment dispersions of the respective colors obtained above, the following compositions were uniformly mixed by a stirrer to prepare colored resin compositions for color filters for respective colors.

Benzyl acrylate / methacrylic acid copolymer 35 parts by mass

(Copolymerization molar ratio = 70/30, weight average molecular weight: 30,000)

38 parts by mass of dipentaerythritol pentaacrylate

Propylene glycol monomethyl ether acetate 120 parts by mass

Ethyl-3-ethoxypropionate 40 parts by weight

4 parts by mass of a halomethyl triazine initiator

(Photopolymerization initiator, product name: TAZ107, manufactured by Midori Chemical Co., Ltd.)

(Fabrication of color filters and CCD devices)

The following composition was mixed with a stirrer to prepare a resist solution for a planarizing film.

[Furtherance]

Benzyl acrylate / methacrylic acid copolymer 165 parts by weight

(Copolymerization molar ratio = 70/30, weight average molecular weight: 30,000)

65 parts by mass of dipentaerythritol pentaacrylate

Propylene glycol monomethyl ether acetate 138 parts by mass

3-ethoxypropionate 123 parts by weight

3 parts by mass of a halomethyl triazine initiator

The obtained resist liquid for planarization was uniformly coated on a 6-inch silicon wafer on which a photodiode was formed by spin-coating. Further, the spinning speed was adjusted so that the film thickness was about 1.5 占 퐉 when the surface temperature of the coated film was heat-treated using a hot plate under the conditions of 100 占 폚 占 120 seconds after application.

Thereafter, the film was placed in an oven at 220 占 폚 for one hour to cure the coated film to form a planarized film so as to cover the photodiode surface formed on the silicon wafer.

Subsequently, 100 parts by mass of the colored resin composition for a color filter was applied onto the planarizing film in the order of G, R, and B for each color, in accordance with the resist solution regulating method for the planarizing film, followed by drying (prebaking) , Alkaline development, rinsing and curing drying (post baking) to form a colored resin film, and a color filter was prepared on a silicon wafer with a photodiode.

The pattern exposure was performed at 500 mJ / cm 2 using a 2-micron mask pattern using an i-line stepper (trade name: FPA-3000i5 +, manufactured by Cannon Co., Ltd.).

For the alkali development, a 40% by mass aqueous solution of an organic alkaline developer (trade name: CD-2000, manufactured by FUJIFILM Electronics Materials Co., Ltd.) was used for paddle development at room temperature for 60 seconds, Rinsing was carried out and water was further washed with pure water. Thereafter, water droplets were blown off with high-temperature air, the substrate was naturally dried to obtain a pattern, and post baking treatment was performed on a hot plate at a surface temperature of 200 占 폚 for 5 minutes.

An image obtained by mounting the CCD device thus obtained on a digital camera and photographing a color chart attached with a gray scale of KODAK product under the same light source was observed on a monitor, and a clear reproduced image was obtained by the present invention.

(Example 8)

[Production of inkjet ink]

With reference to Example 1 of Japanese Patent Laid-Open No. 2002-201387, R ink 1 was prepared by using the pigment dispersion composition A in the following manner, and G ink 1 and B ink 1 were also prepared in the same manner.

As to the method for producing R ink 1, R ink 2 to 6 were produced as follows using Pigment dispersion compositions B to F instead of Pigment dispersion composition A of R ink 1, respectively.

With respect to the mixing of each component in Table 12, the pigment and the polymer dispersant were first put into a part of the solvent, mixed, and stirred using a three-roll mill and a bead mill to obtain a pigment dispersion. On the other hand, another compounding ingredient was added to the remainder of the solvent and stirred to dissolve and disperse to obtain a binder solution. Then, a small amount of the pigment dispersion was added to the binder solution while sufficiently stirring with a dissolver to prepare an ink-jet ink.

delete

[Pixel Formation]

The R ink 1, the G ink 1, and the B ink 1 obtained above were ejected onto a recessed portion surrounded by the light-shielding partition wall by using a piezo head in the following manner. Then, the color filter 1 of the present invention was obtained as follows.

The head had a nozzle density of 150 nozzles in the vicinity of 25.4 mm, and had 318 nozzles. By fixing this nozzle in a direction parallel to the nozzle array by 1/2 of the nozzle interval, .

The head and the ink are controlled such that the vicinity of the discharge portion becomes 50 +/- 0.5 DEG C by circulating hot water in the head.

The ink ejection from the head is controlled by a piezo drive signal applied to the head so that ejection of 6 to 42 pl around one droplet is possible. In this embodiment, the glass substrate is transported from the head at a position of 1 mm below the head . The conveying speed can be set in the range of 50 to 200 mm / s. In addition, the piezo driving frequency can be up to 4.6KHz, and it is possible to control other proper quantity by setting it.

In this embodiment, the conveying speed and the driving frequency are controlled so that the amounts of irregularities of the pigments R, G, and B are 1.1, 1.8, and 0.75 g / m ² , respectively, R, G, and B ink.

The other ink is transported to the exposure part and exposed by an ultraviolet light-emitting diode (UV-LED). In this embodiment, the UV-LED was NCCU033 manufactured by Nichia Corporation. The LED outputs ultraviolet light having a wavelength of 365 nm from one tip, and light of about 100 mW is emitted from the tip by passing a current of about 500 mA. A plurality of these are arranged at intervals of 7 mm, and a power of 0.3 W / cm ² can be obtained from the surface. The time until exposure and the exposure time are different depending on the conveying speed of the medium and the distance between the head and the conveying direction of the LED. In this embodiment, after the deposition, the substrate was dried at 100 degrees for 10 minutes, and then exposed.

The exposure energy on the medium can be adjusted between 0 · 01 and 15 J / cm ^{2 according} to the setting of the distance and the transporting speed. In this embodiment, the exposure energy was adjusted by the conveying speed.

For measurement of these exposure power and exposure energy, USHIO INC. A product of Spectra Radiometer URS-40D was used and a value obtained by integrating the wavelength between 220 nm and 400 nm was used.

The glass substrate after the rubbing was baked in an oven at 230 ° C for 30 minutes to completely cure the light blocking ribs and each pixel hole.

Color filters 2 to 6 were produced in the same manner as the R ink 1 except that R ink 2 to R ink 6 were used instead of R ink 1, respectively.

Table 13 shows the results of measuring the contrast of each color filter in the same manner as the above [measurement of contrast].

[Production of liquid crystal display device]

A liquid crystal display was manufactured using the color filters 1 to 6, and the display characteristics were evaluated.

(Formation of ITO electrode)

(Formation of spider)

A spatter was formed on the ITO transparent electrode prepared above in the same manner as the spattering method described in [Example 1] of JP 2004-240335 A.

(Formation of Liquid Crystal Alignment Control Projections)

A liquid crystal alignment control projection was formed on the ITO transparent electrode on which the spatter was formed by using the following coating liquid for the positive-type photosensitive resin layer.

However, the following methods were used for the exposure, development and baking steps.

A Proximity Exposure Machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) was disposed so that a predetermined photomask was 100 mu m in distance from the surface of the photosensitive resin layer. The photomask was sandwiched therebetween and irradiated with ultraviolet light / cm < ² >.

Subsequently, a 2.38% tetramethylammonium hydroxide aqueous solution was sprayed on the substrate at 33 ° C for 30 seconds in a shower type developing apparatus to perform development. Thus, the unnecessary portion (exposed portion) of the photosensitive resin layer was developed and removed to obtain a substrate for a liquid crystal display having a liquid crystal alignment control projection formed of a photosensitive resin layer patterned in a desired shape on a color filter side substrate .

Then, the substrate for a liquid crystal display having the liquid crystal alignment control protrusion formed thereon was baked at 230 캜 for 30 minutes to form a cured liquid crystal alignment control protrusion on the substrate for a liquid crystal display.

&Lt; Prescription of Coating Liquid for Positive Photosensitive Resin Layer >

A positive resist solution (FUJIFILM Electronics

Materials. Product FH-2413F): 53.3 parts by mass

Methyl ethyl ketone: 46.7 parts by mass

Megafac F-780F (manufactured by Dainippon Ink and Chemicals, Inc.) 0.04 parts by mass

(Preparation of liquid crystal display device)

An alignment film made of polyimide was further provided on the substrate for a liquid crystal display obtained above. Thereafter, an epoxy resin encapsulant is printed at a position corresponding to a black matrix outer frame provided around the pixel group of the color filter, the liquid crystal for the MVA mode is dropped and bonded to the counter substrate, The bonded substrates were heat-treated to cure the sealant. On both sides of the thus obtained liquid crystal cell, SANRITSU Corp. Polarizing plate HLC2-2518. Next, a backlight of a three-wavelength cold cathode tube light source (Toshiba Lighting Corporation FWL18EX-N) was constructed and disposed on the back side of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display device.

It was confirmed that the liquid crystal display device using the filter of the present invention was superior in black sharpness and red color rendering power to the comparative example.

From the above, it can be seen that the effect of the present invention is not only remarkable, but also has a greater effect by relatively simple means such as centrifugal separation conditions in the production process and enhancement of drying.

The pigment dispersing composition of the present invention has a nanometer size and a low water content containing organic pigment nanoparticles with high dispersion stability and can be preferably used as an inkjet ink containing the organic pigment nanoparticles and the photosensitive resin transfer material, It is possible to manufacture a color filter having this excellent high contrast.

Further, the color filter of the present invention is excellent in stability, color purity and high contrast for the purpose and weather resistance. The liquid crystal display device of the present invention using this color filter has an excellent effect that a good sharpness of black color, good display reproducibility, and display irregularity can be improved.

Claims

1. A pigment dispersion composition comprising organic pigment nanoparticles and an organic solvent,

The organic pigment nanoparticles are nanoparticles formed by mixing a solution of an organic pigment dissolved in a good solvent and a poor solvent of the organic pigment compatible with the good solvent,

Wherein the organic pigment nanoparticles have a ratio of particles having a primary particle size of less than 15 nm of less than 10% (number%) and a proportion of particles of more than 60 nm of less than 10% (number%

The water content of the composition is 0.01% by mass to 5% by mass,

Wherein the composition contains a compound represented by the following general formula (I).

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The pigment dispersion composition according to claim 1, wherein the water content is 3 mass% or less.

The pigment dispersion composition according to claim 1, wherein the water content is 1 mass% or less.

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A colored photosensitive resin composition comprising the pigment dispersion composition according to claim 1, a polyfunctional monomer having two or more ethylenically unsaturated double bonds, and a photopolymerization initiator or a photopolymerization initiator system.

A photosensitive resin transfer material characterized by comprising at least a photosensitive resin layer containing the colored photosensitive resin composition according to any one of Claims 6 to 10 on a branched structure.

The pigment dispersion composition according to claim 1, wherein the pigment dispersion composition is an inkjet ink.

A color filter characterized by using the colored photosensitive resin composition according to claim 6 and / or the photosensitive resin transfer material according to claim 7.

A liquid crystal display device comprising the color filter according to claim 9.

The liquid crystal display device according to claim 10, wherein the liquid crystal display device is a VA system.

A CCD device comprising the color filter according to claim 9.