JP2013015828A - Color filter, manufacturing method of pigment, pigment, high-concentration pigment coloring composition, pigment colorant, method for forming color filter, and color display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter (CF) preventing malfunction of a TFT when BM (Black Matrix) and pigments are formed on an active element such as the TFT, and accommodating to methods such as a BOA (Black matrix On Array) method, COA (Color filter On Array) method and IPS (In-Plane Switching) method by improving black or chromatic pigments for forming a component of the color filter.SOLUTION: The CF includes a black matrix (BM), chromatic pigments having trichromatic colors, and columnar spacers provided as needed basis that are formed in contact with, close to or superposed on an electrode. When any of the BM and the chromatic pigments with trichromatic colors, and the columnar spacers provided as needed basis include pigments, each of the columnar spacers is formed by including any one of the black pigment and the chromatic pigment. When the pigment after the composition is washed with water with conductivity of 50 μS/cm or less, the volume resistivity of the pigment itself is 10Ω cm or more and an average particle size thereof is 10 nm to 200 nm.

Description

  The present invention relates to a color filter, a method for forming a color filter, a method for producing a pigment used for forming a color filter, a pigment, a pigment colorant, and a display device equipped with the color filter. More specifically, it is a color filter formed with a chromatic pixel and a black matrix containing an insulating chromatic pigment or black pigment, a method for forming the color filter, and a pigment and a pigment used for the formation. It is a coloring agent and relates to a display device equipped with the color filter.

  With the rapid development of devices that can cope with recent rapid computerization, liquid crystal color displays (hereinafter sometimes abbreviated as “LCD”) are televisions, projectors, personal computers, mobile information devices as information display members. Wide range of information display related devices such as monitor, car navigation, mobile phone, electronic dictionary display screen, information bulletin board, guidance bulletin board, function display board, sign board display, digital camera and video camera shooting screen, etc. Have been used. Accordingly, improvement in LCD display quality and cost reduction have been demanded, and quality of color filters (hereinafter sometimes abbreviated as “CF”) has been improved and costs have been reduced. On the other hand, CFs mounted on LCDs are also required to have superior quality in terms of color characteristics and optical characteristics of image performance such as fineness, color density, light transmission, and contrast.

  In CF, pixels of the three primary colors R (red), G (green), and B (blue) are arranged in stripes, mosaics, and triangles on a glass or other transparent substrate, and illuminated from the back with a backlight. Then, color is generated by additive mixing of the transmitted light of the R, G, and B pixels to form an image. Furthermore, in order to realize a more detailed image, a black matrix (hereinafter abbreviated as “BM”) is formed around each pixel in a grid pattern to shield the backlight light and from adjacent pixels. Color mixture of leaking colored light is prevented, and color is generated by additive color mixing of transmitted light of R, G, and B pixels to form an image.

  While LCD color displays are moving toward larger sizes, they are also becoming increasingly smaller in size such as medium size, mobile size and pocket size. In order to meet these demands, there is a demand for higher image quality and a wider viewing angle, and rationalization of the process for lowering the price is desired. In the CF pixel display method, improvement of ink for pixel formation to improve color sharpness and color reproducibility, and further improvement of color development, sharpness, and contrast of chromatic pigments used for it High performance has been achieved.

  Along with these improvements, the structure of the color filter has also been improved. For example, a black matrix on array method (BOA method) in which a BM is formed on a thin film transistor (TFT) has been proposed. The color filter-on-array method (COA method), in which pixels are stacked on the array substrate side together with the BM, has a high aperture ratio and a large pixel area, which can widen the viewing angle, which was a weak point of conventional LCDs. Also, alignment with the counter substrate is not necessary in the work process, and the bonding process work can be improved and rationalized.

  In order to provide a wider viewing angle, a horizontal electric field drive type in-plane switching method (IPS method) in which a liquid crystal layer is converted by applying an electric field in parallel to the substrate to display a pixel, Vertical alignment method (VA method), which is a vertical alignment method for liquid crystals that enables high contrast, and multi-domain vertical alignment method (MVA method) improved by using distributed light distribution that creates different orientations within the pixel Etc. have been proposed.

  Further, in order to more completely achieve the installation of the IPS electrode, it is necessary to keep the distance (cell gap) between the substrates sandwiching the liquid crystal layer constant and highly accurate. However, it is difficult to uniformly adjust the cell gap with the conventional method of spraying bead-shaped spacers. Therefore, as a method of realizing a uniform cell gap by the fixed columnar spacer, the thickness of the BM itself is increased, or a spacing support member resin such as a colored resin (pixel) layer or a transparent resin layer is stacked on the BM. A method of supporting the cell gap of the substrate, such as increasing it, has been proposed (see Patent Document 1). In this method, since the bead-shaped spacer is not used, the deterioration in display quality due to light scattering and transmission is also improved.

  Furthermore, there has been a demand for improvement of light-shielding black pigments and chromatic pigments for use in these systems. The above-described methods such as the BOA method, the COA method, and the IPS method include a method of forming a BM or pixel film on an active element such as a TFT, or a distance support member resin such as a thickened BM or pixel film. This is a method of forming an active element. Naturally, materials such as BM and pixel film are not high in electrical insulation, and there is a possibility that the TFT malfunctions. For this reason, as a light-shielding black pigment or chromatic color pigment used in these methods, a light-shielding material or chromatic color pigment having high electrical resistance characteristics is desired.

JP 2000-66018 A

  In general, the electrical insulation of pigments used in BM and chromatic pixels is evaluated by measuring the volume resistivity and surface resistance of the coating film containing the pigment. It depends largely on the electrical insulation of the polymer binder material, which is a film forming material for forming a film, and does not correctly show the electrical insulation of the pigment itself. In addition, for example, BM is required to have a sufficient light-shielding property with respect to the backlight. Therefore, the content of the black pigment in the BM coating film is made as high as possible to solve this problem. However, it is not sufficient to rely on the insulation of the binder material to maintain the high electrical insulation with such a high pigment content coating film, and sufficient insulation as the pigment itself. It has been inevitably desired to have

  Therefore, the object of the present invention is to provide a black or organic material used for forming a black matrix, a chromatic pixel, or a columnar spacer provided as necessary, which is a component of CF. To provide a CF that can contribute to the suppression of malfunctions by providing a technology that enables pigments to have sufficient insulating properties and have a fine particle size for pigments themselves. .

The inventors of the present invention have made extensive studies to achieve the development of black pigments and chromatic pigments that can be used with high reliability in the insulating BM and the chromatic color pixels that constitute the CF as described above. also to form a BM or chromatic color pixel on the active element such as, TFT is never cause malfunction due to a short circuit, the pigment itself black or chromatic color, a volume resistivity which is an index of the insulator 10 ⁸ In order to exhibit electrical resistance characteristics of Ω · cm or more, and to satisfy optical properties as pigments and performance requirements as colorants, black pigments and chromatic pigments having an average particle diameter of about 10 nm to 200 nm As a result of the development efforts, the present invention has been completed.

That is, the present invention includes, as its constituent elements, a black matrix formed in a state where it is in contact with or close to an electrode and a chromatic color pixel having at least three primary colors (hereinafter simply referred to as “pixel”). And a columnar spacer provided as necessary (hereinafter, these may be collectively referred to as “CF constituent elements”), the black matrix, the presence of the three primary colors. In the case where at least one of the chromatic pixels and the columnar spacer provided as necessary contains a pigment, each of the columnar spacers is washed with water having a conductivity of 50 μS / cm or less after the pigment synthesis. A black pigment or chromatic color having a volume resistivity of 10 ⁸ Ω · cm or more and an average particle diameter of 10 nm to 200 nm A color filter comprising any one of pigments is provided.

  In the present invention, the chromatic pigment is an anthraquinone pigment, a quinacridone pigment, a diketopyrrolopyrrole pigment, an indigo / thioindigo pigment, a perinone pigment, a perylene pigment, a phthalocyanine pigment, an indoline pigment, an isoline pigment, One chromatic pigment selected from the group consisting of indoline pigments, isoindolinone pigments, dioxazine pigments, quinophthalone pigments, nickel azo pigments, metal complex pigments, insoluble azo pigments and high molecular weight azo pigments, or These are preferably a mixture, a mixed crystal pigment or a stacking (laminated) pigment of two or more chromatic pigments selected from these pigment groups.

  In the present invention, the pigment group includes C.I. I. Pigment Yellow 74, 83, 93, 94, 95, 97, 109, 110, 120, 128, 138, 139, 147, 150, 151, 154, 155, 166, 175, 180, 181, 185, 191; I. Pigment orange 61, 64, 71, 73; C.I. I. Pigment Red 4, 5, 23, 48: 2, 48: 4, 57: 1, 112, 122, 144, 146, 147, 150, 166, 170, 177, 184, 185, 202, 207, 214, 220, 221, 242, 254, 255, 264, 272; I. Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 17: 1, 60, 80, aluminum phthalocyanine blue; C.I. I. Pigment Green 7, 36, 58, poly (13-16) bromocopper phthalocyanine, poly (13-16) bromozinc phthalocyanine; C.I. I. Pigment violet 19, 23, and 37 are preferable.

  In the present invention, the black pigment is one kind of black pigment selected from the group consisting of monoazo black pigments, polyazo black pigments and aniline black black pigments, or two or more kinds selected from these groups The black pigment is preferably a mixture, mixed crystal pigment or stacking pigment.

In another embodiment, the present invention provides a method for producing a black or chromatic pigment having a volume resistivity of 10 ⁸ Ω · cm or more and an average particle diameter of 10 nm to 200 nm. There,
(I) When the particle diameter of the pigment is coarse, a refining step of making the average particle diameter of the pigment 10 nm to 200 nm by any one of the following refining methods (1) or (2) is performed.
(1) Pigment grinder selected from the group consisting of a ball mill, a sand mill, an attritor, a horizontal continuous medium disperser, a kneader, a continuous uniaxial kneader, a continuous biaxial kneader, three rolls, and an open roll continuous kneader. Alternatively, it is refined using a pigment disperser, and if necessary, further refined by filtration and washing (2) In a kneader, kneaded and ground with a water-soluble salt and, if necessary, a water-soluble organic solvent. (II) Cleaning step performed after pigment synthesis or in the cleaning step (I) in the cleaning step Then, following the washing of the salt and the water-soluble solvent by washing with water, a washing step of washing using water having an electric conductivity of 50 μS / cm or less as washing water is performed, and the volume resistivity of the pigment itself is 10 ⁸ Ω · cm. Above To provide a manufacturing method of a pigment, characterized in that.

In another embodiment, the volume resistivity of the pigment itself produced by the above-described pigment production method is 10 ⁸ Ω · cm or more, and the average particle diameter is 10 nm to 200 nm. Provided is a pigment characterized by being a certain black or chromatic pigment.

  As another embodiment, the present invention provides a high-concentration pigment coloring composition characterized by containing a pigment component containing the above black or chromatic pigment in a high concentration in a liquid dispersion medium or a solid dispersion medium. Offer things.

  Further, the present invention, as another embodiment, is a pigment colorant used for forming a component of a color filter, containing the above black or chromatic pigment as a color material, At least one of an organic solvent-based liquid medium, an aqueous liquid medium composed of water or a water-hydrophilic organic solvent mixed solvent, a polymerizable liquid medium composed of a polymerizable oligomer or a polymerizable monomer is used, and It contains at least one film-forming material selected from the group consisting of a non-reactive polymer, a reactive polymer, a reactive oligomer, a polymerizable monomer, and a crosslinking agent, if necessary. A pigment colorant is provided.

Further, as a preferred embodiment of the present invention, the above-mentioned high-concentration pigment coloring composition is used, and the above-mentioned color correction is performed by blending with other chromatic color pigments, other black pigments or extender pigments. Pigment colorant; the above-mentioned pigment colorant in which the blending ratio of the other chromatic color pigment, other black pigment or extender pigment is determined by a method that is optimized using a computer color matching system; For example, the pigment colorant may be a coating film formed to have a volume resistivity of 10 ¹⁰ Ω · cm or more.

  In another embodiment of the present invention, any one of the above-described pigment colorants is used as a black matrix, a chromatic pixel of at least three primary colors, and a columnar spacer provided as necessary. And a method for forming a color filter, which is formed using any one of the forming methods selected from the group consisting of a photolithography method, an ink jet printing method, a printing method, a transfer method, and a pasting method. In the color filter forming method, the forming method is preferably a method of injecting ink into a hole (hole) surrounded by a partition wall.

  In another embodiment, the present invention provides a color display in which any one of the color filters described above is mounted.

In the present invention as described above, the chromatic color or black pigment used for the chromatic color pixel, BM, and the columnar spacer provided as necessary, which is a component of the CF, has a conductivity of about 50 μS / cm or less as washing water. When the chromatic color pigment itself and the black azo pigment itself are measured with powder, the volume resistivity is 10 ^8. Use of an insulating material exhibiting a high electrical resistance characteristic of Ω · cm or more provides a useful CF that can contribute to the suppression of malfunctions. The CF of the present invention is an improved method of various CFs that form BM, chromatic color pixels, or columnar spacers, particularly in contact with or in close proximity to active elements such as TFTs, such as the BOA method, the IPS method, It is preferable to apply to a COA method, a columnar spacer formation method, or the like.

Next, the present invention will be described in more detail with reference to the best mode for carrying out the invention.
The pigment characterizing the present invention is formed in a state where it is in contact with or close to the CF electrode, the chromatic pixel, BM, and the columnar spacer formed as necessary includes the columnar shape. A chromatic pigment and a black pigment used for each of the spacers, and after the pigment synthesis, the volume resistivity of the chromatic pigment and the black pigment itself is obtained by washing with water having an electric conductivity of 50 μS / cm or less. It is about 10 ⁸ Ω · cm or more and the average particle diameter is about 10 nm to 200 nm.

  As the chromatic color pigment, a known chromatic color pigment used for a CF pixel is used. For example, anthraquinone pigment, quinacridone pigment, diketopyrrolopyrrole pigment, indigo / thioindigo pigment, perinone pigment, perylene pigment, phthalocyanine pigment, indoline pigment, isoindoline pigment, isoindolinone pigment , One chromatic pigment selected from the group consisting of dioxazine pigments, quinophthalone pigments, nickel azo pigments, metal complex pigments, insoluble azo pigments, high molecular weight azo pigments, or two or more selected from these groups Of these, a mixture, a mixed crystal pigment, and a stacking (laminated) pigment are preferable.

  More specifically, for yellow pigments, C.I. I. Pigment Yellow (hereinafter abbreviated as “PY”; hereinafter the same) 74, 83, 93, 94, 95, 97, 109, 110, 120, 128, 138, 139, 147, 150, 151, 154 155, 166, 175, 180, 181, 185, 191 and the like; I. Pigment Orange (PO) 61, 64, 71, 73, etc .; I. Pigment Red (PR) 4, 5, 23, 48: 2, 48: 4, 57: 1, 112, 122, 144, 146, 147, 150, 166, 170, 177, 184, 185, 202, 207, 214 220, 221, 242, 254, 255, 264, 272, etc .; and mixed crystal pigments and stacking pigments thereof.

  For blue pigments, C.I. I. Pigment Blue (PB) 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 17: 1, 60, 80, aluminum phthalocyanine blue, etc .; I. Pigment Green (PG) 7, 36, 58, poly (13-16) bromocopper phthalocyanine, poly (13-16) bromozinc phthalocyanine, etc .; I. Pigment violet (PV) 19, 23, 37 and the like, mixed crystal pigments thereof, and one or more chromatic pigments selected from the group consisting of stacking pigments are preferable.

  As the black pigment, a known black pigment used for CF BM is used. For example, one type of black pigment selected from the group consisting of azo black pigments, aniline black black pigments, complex oxide black pigments, or a mixture of two or more black pigments selected from these, Mixed crystal pigments and stacking pigments.

  As a particularly preferred azo-based black pigment used in the present invention, from the viewpoint of exhibiting high insulating properties, at least one of the coupling components includes a 2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide residue. Examples thereof include monoazo black pigments having one azo group in the molecule, black disazo pigments having two or more azo groups, and black trisazo pigments.

  Specific examples of the coupling component having a 2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide residue include 2-hydroxy-11H-benzo [a] -carbazole-3- Anilide, 2-hydroxy-11H-benzo [a] -carbazole-3-carboxy-p-anisidide, 2-hydroxy-11H-benzo [a] -carbazole-3-carboxy- (2-methyl) -p-anisidide, 2-hydroxy-11H-benzo [a] -carbazole-3-carboxy-N-benzimidazolone-5-amide, 2-hydroxy-11H-benzo [a] -carbazole-3-carboxy-naphthylamide, etc .; phenylene- (1,4-) bis (2-hydroxy-11H-benzo [a] -carbazole-3- Rubamide), biphenyl-bis (2-hydroxy-11H-benzo [a] -carbazole-3-carbamide), naphthalene- (1,5-) bis (2-hydroxy-11H-benzo [a] -carbazole-3- Carboamide), benzanilide-4,4′-bis (2-hydroxy-11H-benzo [a] -carbazole-3-carbamide); phenylene (-1)-(2-hydroxy-11H-benzo [a]- Carbazole-3-carboxamide) (-4)-(2-hydroxy-3-naphthoic acid amide) and the like.

  As the diazo component that is diazotized and reacted with the coupling component, a known diazo component is used. Specifically, for example, C.I. I. Azoic diazo component 5, 8, 9, 10, 20, 24, 32, 33, 34, 35, 36, 37, 41, 42, 43, 47, 2-methoxy-5-N-phenylcarbamoyl-aniline, 2 '-Chloro-2-methoxy-5-N-phenylcarbamoyl-aniline, 3'-chloro-2-methoxy-2'methyl-5-N-phenylcarbamoyl-aniline, etc .; 2,5-dichloro-1,4- Phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 3,3′-dimethoxy-4,4′-benzidine, 3,3′-dichloro-4,4′-benzidine; 1,5-diaminonaphthalene 1,2-diaminoanthraquinone, 1,5-diaminoanthraquinone, 4,4′-diaminodiphenylamine, 4,4′-diaminodiphenylate 4,4′-diaminobenzanilide, 4,4′-diamino-2,5-dimethoxy-benzanilide, 4,4′-diamino-2′-chloro-2,5-dimethoxy-benzanilide, 4,5′-diamino-2′-chloro-2,5-dimethoxy-benzanilide, 4- (4-nitrophenyl-azo) -2,5-dimethoxyaniline, and the like.

  Chromatic pigments that are used because R, G, and B pixels are required to have optical characteristics such as high color development, sharpness, and high transparency, in particular, red, green, blue, yellow, and purple pigments. The pigment particles are desirably ultrafine. In addition, in the black pigment for BM, since it is necessary to eliminate the light leakage in order to sufficiently block the light of the backlight, the pigment which is a fine particle solid is filled with high density in the coating film. Therefore, it is necessary to make the pigment finer.

  In addition, the pigment is stably dispersed in the high-concentration pigment coloring composition and the pigment colorant which are pigment dispersions used for the formation of chromatic pixel coating films and BM coating films, and also has high long-term storage stability. When forming BM by this coating method, characteristics such as low viscosity and high fluidity that can form a uniform and flat pixel coating film or BM coating film must be provided.

  Therefore, the chromatic pigment or black pigment particles are desirably fine, and the average particle diameter is required to be about 10 nm to 200 nm. In particular, the color pigment is about 10 nm to 100 nm, preferably about 15 nm to 50 nm, and the black pigment is about 20 nm to 200 nm, preferably about 40 nm to 100 nm. In this case, the particle diameter of the pigment particles is measured by a conventional method. In particular, in order to measure the particle diameter of fine particles, a transmission electron micrograph (60,000 times) is taken, and “image analysis type particle size distribution software” is used. A method of measuring the particle size distribution using “Wear Mac-View” (manufactured by Mountec Co., Ltd.) is preferred. Hereinafter, this method is referred to as “image analysis type particle size distribution measurement method”, but in the present invention, the measurement was performed by the above method.

According to the method for producing a pigment of the present invention, the volume specific resistance of the pigment itself, which is suitable for forming the above-described CF constituent, is 10 ⁸ Ω · cm or more, and its average particle size is 10 nm to 200 nm. Certain black or chromatic pigments can be provided. The method for producing a pigment according to the present invention is characterized in that a pigment refinement step and a specific washing step are performed when the particle size of the pigment is coarse.

When the particle diameter of the pigment is coarse, first, in order to adjust the average particle diameter of the pigment to 10 nm to 200 nm required in the present invention, any one of the following known pigment fine particles of (1) or (2) The refinement | purification pigment is manufactured and a refinement | miniaturization pigment is manufactured.
(1) Pigment grinders or pigment dispersers such as ball mills, sand mills, attritors, horizontal continuous media dispersers, kneaders, continuous uniaxial kneaders, continuous biaxial kneaders, three rolls, open roll continuous kneaders A refinement method that is refined by use, and further filtered and washed as necessary.
(2) A refinement method in which the mixture is refined by a salt milling method in which it is kneaded and ground with a water-soluble salt and, if necessary, a water-soluble organic solvent in a kneader, and then peptized, dispersed, filtered and washed in water.

  A salt milling method that can be suitably used in the present invention will be described. In this method, the water-soluble inorganic salt powder using the pigment as a grinding aid is several times, specifically 2 to 20 times, preferably 3 to 10 times the amount of the pigment to be ground according to the desired particle size of the pigment. Add an amount, add a viscous water-soluble organic solvent such as ethylene glycol, diethylene glycol, polyethylene glycol, and knead and grind. Sodium chloride or sodium sulfate is used as the water-soluble inorganic salt of the grinding aid. After grinding, it is added to dilute sulfuric acid aqueous solution, water, etc. to dissolve the grinding aid, filtered and washed with water to obtain a pigment filter paste (press cake).

Next, a specific cleaning process performed in the method for producing a pigment of the present invention will be described. The chromatic pigment or black pigment obtained by this washing step exhibits a high electrical resistance characteristic in which the volume specific resistance of the pigment itself is 10 ⁸ Ω · cm or more. In the production method of the present invention, following the washing of the salt and the water-soluble solvent by washing in the washing step described in the above-described pigment refinement steps (1) and (2), the influence of contaminant ions and the like is further eliminated. As described above, the washing is performed using water having an electric conductivity of 50 μS / cm or less, preferably 10 μS / cm or less, more specifically, such ion exchange water, reverse osmosis membrane water or distilled water. A process is provided. The highly refined pigment used in the present invention is prepared by sufficiently washing the pigment refined in this process.

When the pigment suspension is filtered with a pressure filter and washed with ion-exchanged water, the evaluation of the degree of washing of the pigment presscake is preferably determined by measuring the conductivity of the filtrate. However, there is a possibility that adhering wastewater is mixed in the drainage path of the filter, which may not always be shown correctly, but according to the study by the present inventors, as a guideline, the filtrate is 500 μS / cm or less, preferably 200 μS. By washing until it shows a value of / cm or less, a value of 10 ⁸ Ω · cm or more is achieved as the volume resistivity of the pigment itself.
The pigment presscake is dried with hot air by a conventional method and then pulverized with a dry pulverizer or redispersed in water, and the pigment dispersion is formed into a powder pigment by spray drying.

Next, a method for examining the electric resistance characteristics of the pigment itself will be described. Specifically, a powder pigment compression-molded tablet was prepared, and the volume resistivity was measured in a state where pigment particles were closely packed and in contact with each other without a polymer binder. The amount used varies depending on the pigment, but about 1 to 1.5 g of powdered pigment is placed in an aluminum ring (inner diameter 3.3 cm, height 5 mm, wall thickness 1 mm), manual compression molding machine (RIKEN SEIKI Co., Ltd.) compressed by Ltd.) to 200 kg / cm ^2, the thickness was molded into 2mm-shaped tablets. The volume resistivity of the obtained pigment tablet was measured using a high resistivity meter “HIRESTA-UP” (measurement range 10 ⁶ to 10 ¹³ Ω · cm, manufactured by Mitsubishi Chemical Analytech Co., Ltd.). It was measured. As a result of measuring the black pigment and chromatic pigment obtained by the above-described production method by the above-described method, the electrical resistance characteristic of the pigment itself was 10 ⁸ Ω · cm or more, indicating that the electrical insulation was very high. Hereinafter, the above measurement method is referred to as “pigment tablet electrical resistance measurement method”. In the present invention, the electrical resistance characteristic of the pigment itself was measured by this method.

  The powder pigment obtained by the production method of the present invention can be dispersed by the above-described various wet dispersers or kneaders to obtain a high concentration pigment coloring composition or pigment colorant. However, as a device to avoid re-aggregation of the pigment due to drying, the press cake is directly processed into a high-concentration pigment coloring composition with a wet disperser, or processed into an organic solvent-based high-concentration pigment coloring composition by a flushing method. It is also preferable to treat the resin in water to make an easily dispersible or processed pigment.

  The pigment colorant of the present invention suitably used for forming “CF constituent elements” such as a BM coating film, a chromatic pixel coating film, or a columnar spacer can be produced by the following method. A method for producing a colorant by sufficiently dispersing a pigment directly with other materials, and a high-concentration pigment coloring composition containing a processed pigment by sufficiently dispersing the pigment in advance at a high concentration as described above, Manufactured by adding a necessary material to make a pigment colorant.

As a pigment component including a black pigment forming BM, in addition to the case where a black pigment is used alone, it is suitable for optical characteristics such as light blocking characteristics by light wavelength, optical density (optical density, OD value), and reflection gloss. In combination, one or more chromatic pigments and extender pigments are selected and used. For example, when the used black pigment has a slight transmission in the low wavelength region of the visible light region, it is corrected by adding a yellow pigment, an orange pigment, etc., and a slight transmission is generated in the long wavelength region. The case is corrected by adding a blue pigment or a green pigment.
It is effective to use a computer color matching system to set the type and amount of pigments. For example, the color adjustment system of “Karacom System” (manufactured by Dainichi Seika Kogyo Co., Ltd.) is used. The Addition of inorganic extender pigments such as silica is desirable in order to remove the gloss of the coating surface and make it matt.

  As a coating agent in the CF BM and pixel formation method, the following liquid “pigment colorant” is used. As the pigment dispersant used for the liquid colorant, a pigment-philic or solvophilic copolymer or oligomer, a low molecular surfactant or the like is used. As the film forming material, an appropriate material is selected and used according to the CF BM or pixel forming method, for example, a heat drying method, a heat curing method, an energy ray curing method, and the like. A mer is selected and used in combination. Since it is a liquid colorant, the pigment dispersant or film-forming material itself is liquid, or contains a liquid medium consisting of an organic solvent system, an aqueous system, or a water-hydrophilic organic solvent mixed solvent system as a dilution medium, If necessary, it further contains additives such as a curing catalyst, a polymerization catalyst, a leveling agent, and an antifoaming agent.

  Furthermore, when preparing the above liquid colorant, a “high concentration pigment coloring composition” in which a pigment to be used in advance is finely dispersed in a dispersion medium is prepared in advance, and this is used to prepare a pigment colorant. Manufacturing can be facilitated. The liquid high-concentration pigment dispersion is called “base color” or “base ink” and is used. Solid or wet type high-concentration pigment coloring compositions are called “master powder”, “masterbatch”, “humidity masterbatch”, etc., and the above liquid material is added and kneaded to make it wet. It is also preferable to make it easily dispersible. In many of these cases, a pigment-philic or amphiphilic copolymer is used as a pigment dispersant. The same applies to the pigment dispersant of the liquid colorant, but in particular, a graft copolymer or a block copolymer in which both functions are separated is preferable.

  Examples of the resin binder that is a film-forming material (film-forming material) include non-reactive, room-temperature drying types that do not have reactive groups or baking type resin binders and energy-ray-curable resin binders that have reactive groups. used. Specific examples of room temperature drying type or baking type resin binders include, for example, acrylic resins, vinyl resins such as styrene (co) polymers, amino resin-modified polyester resins, polyurethane resins, acrylic polyol urethane resins, and soluble resins. Polyamide resin, soluble polyimide resin, soluble polyamideimide resin, soluble polyesterimide resin, alkyd resin, aminoalkyd resin, epoxy resin, chlorinated rubber resin, silicon resin, fluororesin, cellulose acetate resin, nitrocellulose Resin, hydroxyethyl cellulose, water-soluble salt of styrene-maleic acid ester copolymer, water-soluble salt of (meth) acrylic acid ester (co) polymer, water-soluble aminoalkyd resin, water-soluble aminopolyester resin And water soluble Such as polyamide resin and the like, which are used in combination or alone or in combination.

  Examples of the reactive group possessed by the reactive film-forming material include a methylol group, an alkylmethylol group, an isocyanate group, a masked isocyanate group, and an epoxy group. In addition, oligomers and monomers are used depending on applications, and a cross-linking agent such as methylol melamine type, isocyanate type, and epoxy type cross-linking agent is also used in combination.

  Specific examples of energy ray curable coating materials such as light (ultraviolet) curable resin systems and electron beam curable resin systems include, for example, photocurable cyclized rubber resins, photocurable phenolic resins, light Curable polyacrylate resins, photocurable polyamide resins, photocurable polyimide resins, etc., and unsaturated polyester resins, polyester acrylate resins, polyepoxy acrylate resins, polyurethane acrylate resins, polyether acrylate resins And binders such as polyol acrylate resins, or binders to which monomers are further added as reactive diluents.

  Since a high light-shielding property is expected as the BM of CF, the optical density (optical density: sometimes referred to as “OD value”) as a light-shielding standard is 1.6 or more, preferably 2.0 or more. More preferably, it is set to be 3.0 or more. The thickness of the BM that brings about it is usually 0.8 μm to 3 μm. The film thickness of the pixel is usually 0.8 μm to 3 μm. In the case of providing a columnar spacer function, there are a case where the BM itself is thickened, a case where pixels are stacked on the BM, and a case where a colorless resin film is stacked, and 5 μm to 10 μm is preferable.

  Although the OD value per 1 μm thickness is not generally determined by the thickness of the BM, it is set to 1.0 / μm or more, preferably 1.5 / μm or more. When the film thickness is thin, the pigment content in the coating is required to be high, and when it is thick, the pigment content may be low, and the range is about 60 to 20% by mass%, preferably 55 to 30%. In addition, the pigment content of the pigment colorant, for example, a resist ink or an ink-jet ink is about 5 to 15%, preferably about 5% to 10%, and the pigment is stably dispersed. It is preferable that the storage stability is high, the viscosity suitable for coating is maintained, and a uniform colored film is formed.

  In particular, in the formation of a BM or a pixel using inkjet ink (hereinafter sometimes referred to as “IJ ink”), a hole (hole) surrounded by a partition as proposed in JP 2010-66757 A The method using is preferable. The IJ ink used is preferably a low viscosity and high fluid ink. Using such an ink, the RJ, G, and B color inks that can form a predetermined film thickness from the IJ printer head are injected into the holes of the pixels of the substrate, and the corners of the holes surrounded by the partition walls. The ink can be filled uniformly until the medium is dried by post-processing, whereby a uniform and flat coating film is formed, and then necessary film curing is performed to obtain a pixel coating film. According to the method for forming BM and chromatic color pixels by the above method, since the hole is surrounded by the partition wall, the amount of ink liquid can be injected several times the usual amount, so the pigment content and solid content in the ink Therefore, the viscosity of the ink can be lowered. It is also preferable to add an additive such as a surfactant or a leveling agent to prepare a low viscosity, high fluid ink. The ink preferably has a low viscosity of about 10 mPa · sec or less, particularly about 3 to 7 mPa · sec, and preferably a highly fluid pigment dispersion.

A BM formation method and a pixel formation method are performed according to a conventional method. The CF substrate is a known glass CF substrate, plastic CF substrate, and plastic film for transfer or pasting, and is directly or directly transferred or pasted onto the CF substrate using a colorant containing a black azo pigment. The film is formed by one or more forming methods selected from a photolithography method, a laser ablation method, an ink jet printing method, a printing method, a transfer method, a pasting method and the like, with a plastic film for use in between.
Further, chromatic color pixels are formed on the CF substrate on which the BM is formed by a known pixel forming method using a known chromatic color pixel forming colorant. For example, the film is formed by one or two or more forming methods selected from a photolithography method, a laser ablation method, an ink jet printing method, a printing method, a transfer method, a pasting method, and the like.

In the present invention, a BM coating film containing a highly insulating black pigment and a pixel coating film containing a highly insulating chromatic pigment have a volume resistivity of 10 ¹⁰ Ω · cm or more, preferably 10 ^12. Ω · cm or more and high insulation. Accordingly, as a CF structure, a color filter substrate formed in a state in which an electrode such as a TFT and a BM that is substantially highly electrically insulating, a pixel and / or a columnar spacer are in contact or close to each other, and the above-mentioned A color display device equipped with a color filter formed with pixels, BM and / or columnar spacers is provided with high reliability.

  Next, the present invention will be described more specifically with reference to examples. In the text, “part” or “%” is based on mass unless otherwise specified.

[Production Example 1] (Preparation of red fine particle pigment)
(1) Preparation of red pigment-1 by refining treatment Commercially available PR254 (diketopyrrolopyrrole red pigment) is used as a crude pigment (crude, coarse particle pigment) for the color filter through the following refining step and washing step. A red pigment was prepared. 100 parts of PR254, 700 parts of sodium chloride powder, and 50 parts of diethylene glycol were charged into a kneader equipped with a pressure lid. Then, after premixing until a uniformly wet lump was formed in the kneader, the pressure kettle was closed and kneading and grinding were performed while pressing the contents at a pressure of 6 kg / cm ² . At that time, kneading and grinding were performed for 2 hours while controlling the temperature so that the content was 92 to 98 ° C. The obtained ground product was stirred for 1 hour in 3,000 parts of warm water heated to 80 ° C., and then filtered and washed to remove sodium chloride and diethylene glycol. Further, it was washed with ion-exchanged water having a conductivity of 2 μS / cm or less until the conductivity of the washing filtrate was 100 μS / cm or less to obtain a refined PR254 pigment press cake. The pigment press cake was dried and pulverized to obtain a red fine particle pigment. Hereinafter, this is referred to as “red pigment-1”.

(2) Measurement of Particle Size and Volume Specific Resistance of Fine Particle Pigment The particle size of the red pigment-1 obtained above was measured by the “image analysis type particle size distribution measurement method” described above. Specifically, a transmission electron micrograph of the fine particles of red pigment-1 was taken, and the particle size distribution was measured using “image analysis type particle size distribution software”. As a result, the average particle size was approximately 25 nm. Further, the volume resistivity of the red pigment-1 fine particle pigment itself was measured by the “pigment tablet electrical resistance measurement method” described above. Specifically, Red Pigment-1 was placed in an aluminum ring of about 1.5 g and compressed to 200 kg / cm ² with a manual compression molding machine to obtain a tablet having a thickness of about 2 mm. The volume resistivity of the tablet was measured using a high resistivity meter “HIRESTA-UP”. The measurement result showed 10 ¹⁴ Ω · cm or more, and it was confirmed that the red pigment-1 itself has very high electrical resistance characteristics.
In the following production examples, as described above, the particle diameter of the pigment was measured by the “image analysis type particle size distribution measurement method”, and the volume resistivity of the pigment was measured by the “pigment tablet electrical resistance measurement method”. .

[Production Examples 2 to 8] (Preparation of fine color pigments of each color)
Crude pigments used to prepare chromatic pigments for use in pixel formation include PR177 (anthraquinone red pigment), PG36 (copper phthalocyanine green pigment), PB15: 6 (ε-type copper phthalocyanine blue pigment), PY138 ( Yellow pigment) and PV23 (dioxazine violet pigment) were prepared. Further, as a crude pigment used for the preparation of a black pigment for BM, 4-benzoylamino-2,5-dimethoxyaniline is diazotized and then 2-hydroxy-11H-benzo [a] -carbazole-3-carboxy-p. -After diazotization of monoazo black pigment coupled with anisidide (hereinafter referred to as "monoazo black pigment") and 4- (2'-chloro-5'-aminobenzamide) -2,5-dimethoxy-aniline A black disazo pigment (referred to as “black azo pigment-1”) coupled with 2-hydroxy-11H-benzo [a] carbazole-3-carboxy-p-anisidide was prepared.

  According to Production Example 1 (1), the above-mentioned pigments were refined. That is, kneading and grinding were performed in the same manner as described above except that 100 parts of each pigment was charged with the amount of sodium chloride powder shown in Table 1 in a kneader. Subsequently, as a post-treatment, the pigment was poured into warm water in the same manner as in Production Example 1 (1), and the salt and soluble components were dissolved, filtered and washed with water. Further, it was washed with ion-exchanged water having a conductivity of 2 μS / cm or less until the conductivity of the washing filtrate was 100 μS / cm or less, thereby obtaining a pressed cake of chromatic pigments and black pigments for each color. The pigment content in each pigment presscake was 35-45%. These press cakes were dried and pulverized to obtain fine particle pigments. Hereinafter, the obtained pigments were respectively “red pigment-2”, “green pigment-1”, “blue pigment-1”, “yellow pigment-1”, “purple pigment-1”, “black pigment-1”. , “Black Pigment-2”.

The average particle diameter of the obtained fine pigments of each color of chromatic color was about 20 to 25 nm, and the average particle diameter of the black pigment was about 70 to 80 nm. In addition, as shown in Table 1, the volume resistivity of these pigments was 10 ⁸ Ω · cm or more, and it was confirmed that the pigment showed high insulation.

Example 1 (Formation of CF BM)
(1) Preparation of Black Pigment Dispersion Liquid 25 parts of the black pigment-1 prepared above and a benzyl methacrylate-2-hydroxyethyl methacrylate-methacrylic acid copolymer (molar ratio: 60:20:20, mass average molecular weight 3) 25 parts of 40% propylene glycol monomethyl ether acetate (PGMA) solution (hereinafter referred to as “acrylic copolymer solution-1”) and 50 parts of PGMA were sufficiently premixed. Subsequently, the black pigment dispersion liquid was obtained by making it disperse | distribute with a continuous horizontal type medium dispersion machine "Dynomill ECM-pilot 1.5 liters" (made by Shinmaru Enterprises). Hereinafter, this is referred to as “black pigment dispersion-1”.

(2) Preparation of photocurable black resist ink 40 parts of the black pigment dispersion-1 obtained in the above (1), acrylated acrylic polyol photocurable resin 50% PGMA solution (hereinafter referred to as “acrylated acrylic polyol solution”) 6 parts, dipentaerythritol hexaacrylate (DPEHA) 2 parts, ethanone as a photopolymerization initiator, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] 1 part of-, 1- (O-acetyloxime) (trade name: “Irgacure OXE02”, manufactured by BASF) and 51 parts of PGMA were blended and sufficiently stirred with a high-speed stirrer. And it filtered with the filter whose hole diameter is 3 micrometers, and prepared the black resist ink containing black pigment-1. Hereinafter, it is referred to as “photocurable black resist ink-1”.

(3) Evaluation of black coating film Using the photocurable black resist ink-1 obtained above, the ink was applied onto a glass substrate with a spin coater, pre-dried at 60 ° C., pre-baked, Exposure was performed using a high-pressure mercury lamp with a light amount of 400 mJ / cm, and post-baking was performed at 230 ° C. for 30 minutes to obtain a black coating film having a thickness of 3 μm. As shown in Table 2, the optical properties (spectral transmittance) of the black coating film exhibited high absorptivity in the visible light region.

Moreover, the volume resistivity was measured about the black coating film on the glass substrate using the high resistivity meter "Hiresta UP". The measurement result was 10 ¹⁴ Ω · cm or more, and it was confirmed that high insulation was exhibited.

A black pigment dispersion was prepared in the same manner as described above except that the previously prepared “black pigment-2” was used instead of the “black pigment-1” used above. This is referred to as “black pigment dispersion-2”. Furthermore, using this, a black resist ink was prepared in the same manner as described above. This is referred to as “photocurable black resist ink-2”. The obtained photocurable black resist ink-2 was applied onto a glass substrate in the same manner as described above to obtain a black coating film. As a result of evaluating the optical properties of this black coating film, it showed high absorbency in the visible light region as in the case of using black pigment-1, and the measurement result of volume resistivity was 10 ¹⁴ Ω · cm or more. It was confirmed that it exhibits high insulation properties.

[Example 2] (Formation of insulating BM on array substrate)
An insulating BM was formed on a glass substrate as described below using an array substrate provided with a switching active element that activates an array electrode including a source electrode, a drain electrode, and a gate electrode and a pixel electrode. First, the array substrate was set on a spin coater, the photocurable black resist ink-1 obtained in (2) of Example 1 was spin-coated, and prebaked at 80 ° C. for 10 minutes. Next, a photomask having a mosaic pattern in which the width of the BM covering the electric circuit is 20 μm and the opening for the pixel is 280 μm in length and 80 μm in width is arranged on the application surface of the array substrate, and the proximity exposure machine is Using the ultra high pressure mercury lamp, exposure was performed with a light amount of 100 mJ / cm ² . Next, development, washing and drying were performed with a dedicated developer and a dedicated rinse to form a highly insulating BM pattern having a thickness of about 3 μm on the array substrate. Hereinafter, this is referred to as “insulating BM formation array substrate-1”.

  A highly insulating BM pattern was formed on the array substrate in the same manner as described above except that the previously prepared photocurable black resist ink-2 was used instead of the photocurable black resist ink-1. . This was designated as “insulating BM formation array substrate-2”. The obtained insulating BM forming array substrate-2 is used as a pixel pattern forming substrate in the same manner as the insulating BM forming array substrate-1 used in the examples described below. Since almost the same results were obtained when any of the substrates was used, in the following examples, the case where “insulating BM formation array substrate-1” is used will be described as an example.

[Example 3] (Formation of pixel pattern)
(1) Preparation of Pigment Dispersion Liquid Red Pigment-1, Red Pigment-2, Green Pigment-1, Blue Pigment-1 obtained in Production Examples 1-6 in the same manner as in Example 1 (1). Each pigment dispersion containing yellow pigment-1 and purple pigment-1 was prepared. Specifically, 19 parts of each of the above pigments was mixed with 1 part of a pigment derivative having a known tertiary amino group, and 15.2 parts of acryl copolymer solution-1 and 64.8 parts of PGMA were added. Part of the mixed solution. After sufficiently premixing, the mixture was dispersed with a continuous horizontal medium disperser “Dynomill 1.4 liter ECM type” to obtain a pigment dispersion of each color. When the average particle diameter of the pigments of the pigment dispersion liquids of these colors was measured with a particle size measuring instrument N-4, it was about 40 to 45 nm. Hereinafter, these are “PR254 pigment dispersion-1”, “PR177 pigment dispersion-1”, “PG36 pigment dispersion-1”, “PB15: 6 pigment dispersion-1”, “PY138 These are referred to as “Pigment Dispersion-1” and “PV23 Pigment Dispersion-1.”

  Subsequently, each pigment dispersion obtained above was appropriately used to adjust the color of the pixel. For red pixel, PR254 pigment dispersion-1 and PR177 pigment dispersion-1 were blended at 8: 2 to prepare "red pigment dispersion-1". For green pixels, PG36 Pigment Dispersion-1 and PY138 Pigment Dispersion-1 were blended at 5: 5 to prepare “Green Pigment Dispersion-1”. Further, for blue pixels, PB15: 6 pigment dispersion-1 and PV23 pigment dispersion-1 were blended at 8: 2 to prepare "blue pigment dispersion-1".

(3) Preparation of pixel resist ink 33 parts of the toned red pigment dispersion-1 above, 9.2 parts of acrylated acrylic polyol solution, 3 parts of trimethylolpropane triacrylate (TMPTA), light As a polymerization initiator, 0.3 part of 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (“Irgacure OXE01”, manufactured by BASF) and 54 PGMA .5 parts was mixed. This was sufficiently mixed to prepare “red resist ink-1” for red pixels.

  In the same manner as described above, instead of the red pigment dispersion liquid-1, the green pigment dispersion liquid-1 and the blue pigment dispersion liquid-1 are mixed, and the "green resist ink-1" for the green pixel and the blue pixel dispersion liquid-1 are mixed. Of “blue resist ink-1” was prepared.

(4) Formation of CF RGB pixels The insulating BM formation array substrate-1 obtained in Example 2 is set on a spin coater, the red resist ink-1 obtained in (3) above is spin-coated, and 80 Pre-baking was carried out at 10 ° C. for 10 minutes. Next, a mosaic pattern for red pixels having an opening of 280 μm in length and 80 μm in width is formed on the coated surface of the glass substrate with a super high pressure mercury lamp using a photomask and a proximity exposure machine at 100 mJ / cm ² . It was formed by exposing with light. Next, development, washing, and drying were performed with a developer and a rinse to form a red mosaic pattern on the glass substrate. Subsequently, in the same manner as described above, a green mosaic pattern is formed using the green resist ink-1 obtained in (3) above. Further, in the same manner as described above, it is obtained in (3) above. The blue resist ink-1 was used to form a blue mosaic pattern to obtain a CF on which BM, R, G, and B pixels were formed.

[Example 4] (Preparation of color filter with aqueous IJ ink)
(1) Preparation of aqueous pigment resin dispersion (aqueous color base) 20 parts of each of the red, green, blue, yellow, and purple pigment presscakes refined in Production Examples 1 to 6 are used as pure pigment. 16 parts of aqueous “resin pigment dispersant-1” shown below were added. And ion-exchange water was added so that it might become a total of 100 parts. This was stirred with a dissolver for 2 hours, and after confirming that the mass of the pigment had disappeared, dispersion treatment was performed with “Dynomill ECM-Pilot 1.5 liters” to obtain aqueous colors of each color. The average particle size of the water-based color dispersed pigments of each color was measured with a particle size measuring device N-4, which was about 40 to 45 nm. Hereafter, these are “PR254 pigment dispersion-2”, “PR177 pigment dispersion-2”, “PG36 pigment dispersion-2”, “PB15: 6 pigment dispersion-2”, “PY138 This is referred to as “Pigment Dispersion-2” and “PV23 Pigment Dispersion-2”.

  The aqueous “resin pigment dispersant-1” used above is benzyl methacrylate-ethyl methacrylate-2-ethylhexyl methacrylate-2-hydroxyethyl methacrylate-methacrylic acid copolymer (mass ratio; 30:20:20: 20:10) A 50% solids aqueous solution of an ammonium salt. Moreover, the liquid mixture of the ratio of butyl carbitol: isopropanol: water = 35: 35: 30 was used for the medium of this solution.

  Next, the color of the pixel was adjusted using the pigment dispersion obtained above as appropriate. For red pixel, PR254 pigment dispersion-2 and PR177 pigment dispersion-2 were blended at 8: 2 to prepare "Red Pigment Dispersion-2". In addition, for green pixels, PG36 pigment dispersion-2 and PY138 pigment dispersion-2 were blended at a ratio of 5: 5 to prepare “green pigment dispersion-2”, and for blue pixels, PB 15: 6 Pigment Dispersion-2 and PV23 Pigment Dispersion-2 were blended at 8: 2 to prepare "Blue Pigment Dispersion-2".

(2) Preparation of IJ Ink for Pixels 25 parts of the above-mentioned toned red pigment dispersion liquid-2, 10 parts of “acrylic copolymer solution-2” described later, and 50% hexamethoxymethylmelamine methanol solution 3 parts, 10 parts of diethylene glycol monobutyl ether, 1 part of leveling agent, 1 part of defoaming agent (50% solution) and 50 parts of ion-exchanged water are mixed thoroughly and filtered through a membrane filter with a pore size of 3 μm. “Red IJ Ink-1” for red pixels was prepared. The obtained red IJ ink-1 had a viscosity of 5 mPa · sec, and was a low viscosity and high fluidity ink.
In the same manner as described above, “green IJ ink-1” for green pixels was prepared using green pigment dispersion-2 instead of red pigment dispersion-2, and blue pigment dispersion− 2 was used to prepare “Blue IJ Ink-1” for blue pixels.

  The “acrylic polymer solution-2” used above is methyl methacrylate-ethyl methacrylate-2-ethylhexyl methacrylate-styrene-2-hydroxyethyl methacrylate-methacrylic acid (mass ratio; 20: 20: 20: 10: 20: 10) A 40% solids aqueous solution of the ammonium salt of the copolymer. The mass ratio of the medium of the solution is water: n-butanol: isopropyl alcohol = 3: 2: 1.

(3) Preparation of Substrate for Use in IJ Printing Method On the insulating BM formation array substrate-1 obtained in Example 2, holes (holes) for forming pixels with IJ ink were formed. The “positive resist composition” described later was applied to the surface of the substrate with a coater so that the total thickness from the dried glass substrate was 8 μm, and air-dried at 50 ° C. or lower. Next, the positive resist film was exposed to ultraviolet light from the back surface of the substrate. Next, development was performed with a 3% aqueous solution of phosphoric acid and third soda, followed by washing with water. Thereafter, the mixture was neutralized with a 1% aqueous solution of phosphoric acid, washed with water and dried. As a result, a CF substrate was prepared in which an opening surrounded by a partition wall having a height of about 8 μm had holes of 280 μm in length and 80 μm in width.

  The “positive resist composition” used above is composed of 4 parts of ester obtained by reacting 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride with o-chlorophenol-formaldehyde resin, 2 parts of novolak resin, and oil-soluble. This resin composition contains 2 parts of a phenol resin, 2 parts of a water-swellable resin made of an acrylic acid-polystyrene macromonomer (6: 4) copolymer, and 90 parts of ethylene glycol monomethyl ether in a solid content.

(4) Formation of CF RGB pixels by IJ printing method Cartridge filled with red IJ ink-1, green IJ ink-1 and blue IJ ink-1 prepared in (2) above in a piezo method IJ printer, and the above The insulating BM formation array substrate-1 with the pixel formation holes prepared in (3) was loaded. Each color ink of R, G, and B was discharged from the IJ printer head into the hole of each pixel of the substrate. The ejected ink showed a low viscosity and a high fluidity, and uniformly filled the hole surrounded by the partition walls.

  After each color was printed, it was dried and pre-baked. Next, the surface of the substrate was irradiated with ultraviolet rays to photolyze the partition walls made of a positive resist composition, and then immersed in a 4% trisodium phosphate aqueous solution to clean and remove the partition walls. Then, it was neutralized with dilute acid, washed with water and dried. Furthermore, baking was performed at 180 ° C., and the coating film was cured to form red, green, and blue mosaic patterns. As a result, a CF having RGB pixels formed on the insulating BM formation array substrate-1 was obtained. The film thickness of the pixel is about 2 μm, and the pixel film on the formed CF substrate has no independent color mixing, non-uniform color density, smooth surface, and a clear mosaic pattern of three-color pixels. Indicated.

  A liquid crystal display was manufactured according to a conventional method using a substrate on which R, G, and B pixels were formed on the insulating BM formation array substrate-1 obtained in Examples 3 and 4 above. First, an entire overcoat layer was applied on the substrates obtained in Examples 3 and 4, an ITO transparent electrode film was formed by sputtering deposition, an alignment film was then formed, and a CF substrate was manufactured. Next, a counter substrate and a spacer were assembled, and further a liquid crystal was loaded to manufacture a liquid crystal display.

  The CF used above can be manufactured with a manufacturing method that is rational, economical, high-definition, and capable of handling a wide aperture, so it can be used for large-sized liquid crystal displays, medium-sized monitor liquid crystal displays, and compact. Can be provided at low cost.

Claims (15)

As a component thereof, a color having a black matrix, a chromatic pixel having at least three primary colors, and a columnar spacer provided as necessary, formed in a state of overlapping in contact with or close to an electrode In the filter
Each of the black matrix, at least one of the three primary color pixels, and the columnar spacer provided as necessary includes a pigment,
A black pigment or a chromatic pigment whose volume resistivity is 10 ⁸ Ω · cm or more and whose average particle size is 10 nm to 200 nm when the pigment is washed with water having an electric conductivity of 50 μS / cm or less after the pigment synthesis. A color filter comprising any of the above.   The chromatic pigment is anthraquinone pigment, quinacridone pigment, diketopyrrolopyrrole pigment, indigo / thioindigo pigment, perinone pigment, perylene pigment, phthalocyanine pigment, indoline pigment, isoindoline pigment, isoindoline pigment, One kind of chromatic pigment selected from the group consisting of indolinone pigments, dioxazine pigments, quinophthalone pigments, nickel azo pigments, metal complex pigments, insoluble azo pigments and high molecular weight azo pigments, or these pigment groups The color filter according to claim 1, wherein the color filter is a mixture, a mixed crystal pigment, or a stacking (laminated) pigment of two or more chromatic pigments selected from the group consisting of:   The pigment group is C.I. I. Pigment Yellow 74, 83, 93, 94, 95, 97, 109, 110, 120, 128, 138, 139, 147, 150, 151, 154, 155, 166, 175, 180, 181, 185, 191; I. Pigment orange 61, 64, 71, 73; C.I. I. Pigment Red 4, 5, 23, 48: 2, 48: 4, 57: 1, 112, 122, 144, 146, 147, 150, 166, 170, 177, 184, 185, 202, 207, 214, 220, 221, 242, 254, 255, 264, 272; I. Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 17: 1, 60, 80, aluminum phthalocyanine blue; C.I. I. Pigment Green 7, 36, 58, poly (13-16) bromocopper phthalocyanine, poly (13-16) bromozinc phthalocyanine; C.I. I. The color filter according to claim 2, comprising pigment violet 19, 23 and 37.   The black pigment is one kind of black pigment selected from the group consisting of monoazo black pigments, polyazo black pigments and aniline black black pigments, or two or more black pigments selected from these groups, The color filter according to any one of claims 1 to 3, which is a mixture, a mixed crystal pigment, or a stacking pigment.   The color filter according to claim 1, wherein the black pigment is a mixture, mixed crystal pigment, or stacking pigment of the black pigment according to claim 4 and the chromatic pigment according to claim 2 or 3. A method for producing a black or chromatic pigment having a volume resistivity of 10 ⁸ Ω · cm or more and an average particle diameter of 10 to 200 nm,
(I) When the particle diameter of the pigment is coarse, a refining step of making the average particle diameter of the pigment 10 nm to 200 nm by any one of the following refining methods (1) or (2) is performed.
(1) Pigment grinder selected from the group consisting of a ball mill, a sand mill, an attritor, a horizontal continuous medium disperser, a kneader, a continuous uniaxial kneader, a continuous biaxial kneader, three rolls, and an open roll continuous kneader. Alternatively, it is refined using a pigment disperser, and if necessary, further refined by filtration and washing (2) In a kneader, kneaded and ground with a water-soluble salt and, if necessary, a water-soluble organic solvent. (II) Cleaning step performed after pigment synthesis or in the cleaning step (I) in the cleaning step Then, following the washing of the salt and the water-soluble solvent by washing with water, a washing step of washing using water having an electric conductivity of 50 μS / cm or less as washing water is performed, and the volume resistivity of the pigment itself is 10 ⁸ Ω · cm. Above Method for producing a pigment, characterized in that. A black or chromatic pigment having a volume resistivity of 10 ⁸ Ω · cm or more and an average particle diameter of 10 nm to 200 nm produced by the pigment production method according to claim 6. A pigment characterized by being.   A high-concentration pigment coloring composition comprising a pigment component containing the black or chromatic pigment according to claim 7 in a high concentration in a liquid dispersion medium or a solid dispersion medium.   A pigment colorant used for forming a component of the color filter according to claim 1, comprising the black or chromatic pigment according to claim 7 as a coloring material, and an organic solvent as a dilution medium At least one of an aqueous liquid medium composed of water, an aqueous liquid medium composed of water or a water-hydrophilic organic solvent mixed solvent, and a polymerizable liquid medium composed of a polymerizable oligomer or a polymerizable monomer. According to the present invention, it comprises at least one film-forming material selected from the group consisting of a non-reactive polymer, a reactive polymer, a reactive oligomer, a polymerizable monomer, and a crosslinking agent. Pigment colorant.   The pigment coloring of Claim 9 which uses the high concentration pigment coloring composition of Claim 8, and mix | blends this with another chromatic color pigment, another black pigment, or an extender pigment, and correct | amends a color. Agent.   The pigment colorant according to claim 10, wherein a blending ratio of the other chromatic pigment, other black pigment, or extender pigment is determined by a method that is optimized using a computer color matching system. The pigment colorant according to any one of claims 9 to 11, wherein the formed coating film has a volume resistivity of 10 ¹⁰ Ω · cm or more.   A pigment colorant according to any one of claims 9 to 12, wherein a black matrix, a chromatic pixel of at least three primary colors, and a columnar spacer provided as necessary are formed on a color filter substrate, and A method for forming a color filter, characterized in that the color filter is formed using any one of the forming methods selected from the group consisting of a photolithography method, an ink jet printing method, a printing method, a transfer method and a pasting method.   The color filter forming method according to claim 13, wherein the forming method is a method of injecting ink into a hole (hole) surrounded by a partition wall.   A color display comprising the color filter according to any one of claims 1 to 5.