TWI409505B - Color filter, and liquid crystal display device and ccd device each using the color filter - Google Patents

Abstract

A color filter having a layer colored in at least one prescribed hue and formed on a substrate, which comprises: a water-insoluble organic pigment (a), a monomer or oligomer having a polymerizable group (b), and a water-soluble polymer (c), in the form of a pigment dispersion, in which the dispersion is solidified by polymerizing the monomer or oligomer so as to form said colored layer, wherein a content of the water-soluble polymer (c) in the colored layer is at least 0.1 mass % of the total solid content.

Description

Color filter and liquid crystal display device and CCD device using the color filter

The present invention relates to a color filter having a high contrast and an excellent hue, and to a liquid crystal display device and a CCD device using the color filter.

In recent years, with the improvement of the image quality of liquid crystal display devices (LCDs) and the like, LCDs are being used in a wide range of applications to replace CRTs (Braun tubes) belonging to popular displays. Therefore, it has evolved into a product which requires a higher quality image display performance in terms of improving the color reproduction domain and brightness. The key to this requirement is to master the performance improvement of color filters. This is because the color filter plays an important role in imparting coloring to a display image such as an LCD panel, and thus directly affects the color characteristics of the LCD panel.

The required characteristics regarding the color filter include, for example, high light transmittance, color purity, high contrast, low reflection, and the like. In particular, low contrast can cause the display screen to become dark due to the decay of light, and the recognition of light and dark will become inconspicuous. Therefore, the high contrast nature is what I want. Further, it is also required that the color reproduction domains obtained by combining B, G, and R are broad, and the purity of each color obtained thereby is high. However, the improvement of the contrast result of the color filter sometimes results in a decrease in color purity due to a decrease in the color reproduction domain.

In general, in the method of producing a color filter, there has been a technique of forming a coloring layer by using a dispersion stabilizer containing a coloring matter dispersed in an organic solvent (Japanese Patent Laid-Open No. JP-A-10) -130547 ("JP-A" means an uncensored open Japanese invention patent application), Japanese Patent Application Laid-Open No. JP-A-10-148712, and Japanese Invention Patent Special JP-A- 2000-239554). This technique is widely used in all color filter manufacturing methods by coating, printing (transfer), and inkjet. Therefore, materials having high dispersibility in organic systems have been mainly used as polymers of dispersants or binders. In consideration of factors such as the absorption of moisture by a color filter or the like, the reliability thereof is impaired, and therefore, in addition to some rarely used methods such as coloring, etc., there is almost no polymerization with high water-solubility in the colored layer. The literature on the technology of the object.

The technical problem to be solved in the present invention is to provide a color filter having high contrast and excellent chromaticity, and also having continuous manufacturing suitability. Further, another technical problem to be solved in the present invention is to provide a liquid crystal display device and a CCD device which can display excellent image display performance, in which a high quality color filter as described above is used.

The object of the present invention has been achieved by the following methods: (1) a color filter having a layer colored with at least one predetermined hue and formed on a substrate, comprising: a water-insoluble organic pigment (a), The monomer or oligomer (b) having a polymerizable group, and the water-soluble polymer (c) are in the form of a pigment dispersion in which the dispersion is formed by polymerizing a monomer or an oligomer to form a dispersion. A colored layer in which the content of the water-soluble polymer (c) in the colored layer is at least 0.1% by mass based on the total solid content.

(2) The color filter according to Item (1), wherein the pigment dispersion liquid comprises an organic pigment (a) in a particulate form, wherein the fine particles are dissolved in a good solvent by the organic pigment (a) The organic pigment solution and a solvent which is compatible with the good solvent and which acts as a poor solvent for the organic pigment are mixed and precipitated.

(3) The color filter according to Item (2), wherein the number average particle diameter of the pigment particles is in a range from 0.005 μm to 1 μm.

(4) The color filter according to Item (2), wherein the number average particle diameter of the pigment particles is in a range from 0.005 μm to 0.08 μm.

(5) The color filter according to Item (2), wherein the number average particle diameter of the pigment particles is in a range from 0.005 μm to 0.05 μm.

(6) The color filter according to any one of (1) to (5) wherein the water-soluble polymer has a number average molecular weight of 1,000 or more.

(7) A color filter according to any one of (1) to (6).

(8) A CCD device configured by the color filter according to any one of (1) to (6).

(9) A pigment dispersion liquid comprising: a water-insoluble organic pigment (a) and a water-soluble polymer (b), wherein the pigment dispersion has a moisture content of 10% by mass or less, and wherein the water-soluble polymerization The content of the substance (b) is at least 0.1% by mass of the organic pigment (a).

(10) The pigment dispersion according to Item (9), which comprises an organic pigment (a) in a particulate form, wherein the fine particles are an organic pigment solution obtained by dissolving the organic pigment (a) in a good solvent, And a solvent which is compatible with the good solvent and which acts as a poor solvent for the organic pigment is mixed and precipitated.

(11) The pigment dispersion according to Item (10), wherein the number average particle diameter of the pigment fine particles is in the range of from 0.005 μm to 1 μm.

(12) The pigment dispersion according to Item (10), wherein the number average particle diameter of the pigment particles is in a range from 0.005 μm to 0.08 μm.

(13) The pigment dispersion according to Item (10), wherein the number average particle diameter of the pigment fine particles is in the range of from 0.005 μm to 0.05 μm.

(14) The pigment dispersion according to any one of (9) to (13), wherein the water-soluble polymer has a number average molecular weight of 1,000 or more.

Other and further features of the present invention will be more fully described in the following description.

[Best Embodiment of the Invention]

The invention will be described in detail below.

The color filter of the present invention has at least one colored layer formed on a substrate. The substrate is preferably a transparent substrate, and a glass plate made of, for example, a soda lime glass plate having a yttrium oxide film on the surface, a low expansion glass, and a quartz glass plate can be used. Further, a resin film such as polyethylene terephthalate, cellulose triacetate, polystyrene, or polycarbonate may also be used.

The method of forming the coloring layer on the substrate is not particularly limited as long as it is a general method for producing a color filter. As will be described later, the color filter can be coated with a pigment dispersion liquid as described later by using a device such as a spin coater, a slit coater, or a roll coater. The substrate is then exposed and developed to form a colored photosensitive resin layer. Further, the colored layer may be formed by first forming a colored photosensitive resin layer as described above on a temporary support, and then transferring the colored photosensitive resin layer onto the substrate using a laminator, followed by exposure and development; And/or another method is that the colored layer is formed by spraying a pigment dispersion droplet onto a substrate using a so-called "inkjet system". The thickness of the colored layer is not particularly limited, but is preferably in the range of from 0.5 μm to 5 μm, and more preferably in the range of from 1 μm to 3 μm. There is no particular limitation on the area of the colored layer. However, when a fine pixel is formed, the area is preferably in the range from 400 μm ² to 90,000 μm ² , and more preferably in the range from 1,000 μm ² to 15,000 μm ² .

The coloring layer as described above of the color filter of the present invention preferably comprises a water-insoluble organic pigment (a), a monomer or oligomer having a polymerizable group (b), and a water-soluble polymer (c). The pigment dispersion is composed of a polymerized cured product obtained by polymerization. Here, it is preferable to also contain the binder (d) and a polymerization initiator or a polymerization initiator system (e).

(a) Water-insoluble organic pigment There is no particular limitation on the water-insoluble organic pigment as long as the pigment is economically soluble in water. The pigment is preferably dispersed in the dispersion in the form of fine pigment particles. When the pigment is refined, a preferred method can be suitably carried out, for example, from a gas phase method, a grinding pulverization method, a reprecipitation method, and a laser grinding method, depending on the kind and/or purpose of the pigment. Choose the appropriate method. However, from the viewpoint of producing pigment fine particles having a fine particle diameter, a uniform particle size distribution, and excellent dispersion stability, it is preferred to use a fine particle deposition method as described later.

Specifically, examples of the "water-insoluble organic pigment" include, for example, perylene, perynone, quinacridone, quinacridonequinone, anthraquinone, anthraquinone. Anthrone (annhanthrone), benzimidazolone, condensed disazo, disazo, azo, indanthrone, indanthrone, Phthalocyanine, triaryl carbonium, two (dioxazine), aminoanthraquinone, diketopyrrolopyrrole, thioindigo, isoindoline, isoindolinone, pyranthrone Or isoviolanthrone compound pigment, or a mixture thereof.

More specifically, examples of the "water-insoluble organic pigment" include: "anthraquinone compound pigment" such as CI Pigment Red 190 (CI number 71140), CI Pigment Red 224 (CI number 71127), CI Pigment Violet 29 (CI number) 71129), or an analogue thereof; "anthrone compound pigment", for example, CI Pigment Orange 43 (CI number 71105), CI Pigment Red 194 (CI number 71100), or the like; "quinacridone compound pigment", for example CI Pigment Violet 19 (CI number 73900), CI Pigment Violet 42, CI Pigment Red 122 (CI number 73915), CI Pigment Red 192, CI Pigment Red 202 (CI number 73907), CI Pigment Red 207 (CI number 73900, 73906) ), CI Pigment Red 209 (CI number 73905), or an analogue thereof; "quinacridone oxime compound pigment", such as CI Pigment Red 206 (CI number 73900/73920), CI Pigment Orange 48 (CI number 73900/73920) , CI Pigment Orange 49 (CI number 73900/73920), or an analogue thereof; "anthraquinone compound pigment", such as CI Pigment Yellow 147 (CI number 60645), or the like; "anthrone ketone ketone compound pigment" , for example, CI Pigment Red 168 (CI number 59300), or an analogue thereof; "benzimidazolone compound pigment", such as CI Pigment Brown 25 (CI number 12510), CI Pigment Violet 32 (CI number 12517), CI Pigment Yellow 180 (CI number 21290), CI Pigment Yellow 181 (CI number 11777), CI Pigment Orange 62 (CI number 11775), CI Pigment Red 185 (CI number 12516), or the like; "diazo condensed compound pigment", for example, CI Pigment Yellow 93 (CI number 20710), CI Pigment Yellow 94 (CI number 20048), CI Pigment Yellow 95 (CI number 20034) , CI Pigment Yellow 128 (CI number 20047), CI Pigment Yellow 166 (CI number 20035), CI Pigment Orange 34 (CI number 21115), CI Pigment Orange 13 (CI number 21110), CI Pigment Orange 31 (CI number 20050) , CI Pigment Red 144 (CI number 20735), CI Pigment Red 166 (CI number 20730), CI Pigment Red 220 (CI number 20055), CI Pigment Red 221 (CI number 20065), CI Pigment Red 242 (CI number 20067) , CI Pigment Red 248, CI Pigment Red 262, CI Pigment Brown 23 (CI number 20060), or the like; "diazo compound pigment", such as CI Pigment Yellow 13 (CI number 21100), CI Pigment Yellow 83 ( CI number 21108), CI Pigment Yellow 188 (CI number 21094), or the like; "Azo compound pigment", such as CI Pigment Red 187 (CI number 12486), CI Pigment Red 170 (CI number 12475), CI Pigment Yellow 74 (CI Code 11714), CI Pigment Yellow 150 (CI number 48545), CI Pigment Red 48 (CI number 15865), CI Pigment Red 53 (CI number 15585), CI Pigment Orange 64 (CI number 12760), CI Pigment Red 247 (CI No. 15915), or an analogue thereof; "indanthrone (standard reduction blue) compound pigment", such as CI Pigment Blue 60 (CI number 69800), or an analogue thereof; "anthraquinone compound pigment", such as CI Pigment Green 7 (CI number 74260), CI Pigment Green 36 (CI number 74265), Pigment Green 37 (CI number 74255), Pigment Blue 16 (CI number 74100), CI Pigment Blue 75 (CI number 74160: 2), CI Pigment Blue 15:6 (CI number 74160), CI Pigment Blue 15:3 (CI number 74160), or the like; "triarylcarbonium compound pigment", such as CI Pigment Blue 56 (CI number 42800), CI Pigment Blue 61 (CI number 42765: 1), or its analogue; "two "Compound pigment", for example, CI Pigment Violet 23 (CI number 51319), CI Pigment Violet 37 (CI number 51345), or the like; "Amine oxime compound pigment", such as CI Pigment Red 177 (CI number 65300), Or an analogue thereof; "diketopyrrolopyrrole compound pigment", for example, CI Pigment Red 254 (CI number 56110), CI Pigment Red 255 (CI number 561050), CI Pigment Red 264, CI Pigment Red 272 (CI number 561150) , CI Pigment Orange 71, CI Pigment Orange 73, or the like; "thioindigo compound pigment", such as CI Pigment Red 88 (CI number 73312), or an analogue thereof; "isoporphyrin compound pigment", such as CI Pigment Yellow 139 (CI number 56298), CI Pigment Orange 66 (CI number 48210), or the like; "isoindolone compound pigment", such as CI Pigment Yellow 109 (CI number 56284), CI Pigment Yellow 185 ( CI number 56290), CI Pigment Orange 61 (CI number 11295), or the like; "pyridone compound pigment", such as CI Pigment Orange 40 (CI number 59700), CI Pigment Red 216 (CI number 59710), or An analog thereof; "quinacridone compound pigment", such as CI Pigment Yellow 138; or "isopurinone compound pigment", 31 is such as CI Pigment Violet (CI number 60010), or the like.

In the color filter of the present invention, two or more organic pigments or solid solutions thereof may be used in combination. In addition, they can also be used with general dyes.

In the color filter of the present invention, the content of the organic pigment is preferably in the range of from 10% by mass to 70% by mass, and more preferably in the range of from 30% by mass to 60% by mass in the colored layer. The total solids content is based on the benchmark.

(b) a monomer having a polymerizable group or an oligomer having a polymerizable group. The monomer or oligomer having a polymerizable group used in the color filter of the present invention preferably has two or The above-mentioned ethylenically unsaturated double bond is a monomer or oligomer which undergoes addition polymerization by light irradiation. The monomer or oligomer may be a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C or higher at normal pressure. Examples thereof include, for example, "monofunctional acrylates and monofunctional methacrylates", such as dipentaerythritol hexa(meth)acrylate, polyethylene glycol mono(meth)acrylate, poly( Propylene glycol (meth)acrylate, and phenoxyethyl (meth)acrylate; polyethylene glycol di(meth)acrylate, propylene glycol poly(meth)acrylate, trimethylolethane triacrylate , trimethylolpropane tris(meth)acrylate, trimethylolpropane diacrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, three (a) Ethyl pentaerythritol acrylate, ditylar pentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, hexanediol di(meth)acrylate, trimethylol Propane tris(propylene methoxypropyl)ether, tris(propylene methoxyethyl) isocyanate, tris(propylene oxyethyl) cyanurate, glycerol tris(meth)acrylate An ester; a polyfunctional alcohol such as trimethylolpropane or glycerin may be added with ethylene oxide or propylene oxide, and the adduct may be (meth) acrylated, etc. To obtain the "polyfunctional acrylates or polyfunctional methacrylates." Further, another preferred example includes a compound obtained by addition reaction of ethylene oxide or propylene oxide with a polyfunctional alcohol, followed by (meth)acrylation, for example, a Japanese invention patent The general formulae (1) and (2) disclosed in Japanese Laid-Open Patent Publication No. JP-A-10-62986. In the present specification, the term "(meth)acrylate" is used to mean both "acrylate" and "methacrylate".

Examples of the monomer and the oligomer having a polymerizable group include: a urethane acrylate, for example, in Japanese Patent Publication No. JP-B-48-41708 ("JP-B" is intended The disclosed Japanese Patent Application No. 5, the Japanese Patent Application No. JP-B-50-6034, and the Japanese Patent Application Laid-Open No. JP-A-51-37193; Polyester acrylates, for example, Japanese Patent Laid-Open No. JP-A-48-64183, Japanese Invention Patent No. JP-B-49-43191, and Japanese Invention Patent No. JP-B-52 Unexamined in -30490; polyfunctional acrylates or polyfunctional methacrylates, such as epoxy acrylates of the reaction product of an epoxy resin and (meth)acrylic acid.

Among these, trimethylolpropane tris(meth)acrylate, neopentyl tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and penta (A) are preferred. Base) dipentaerythritol acrylate.

In addition, as described above, the "polymerizable compound B" disclosed in Japanese Laid-Open Patent Publication No. JP-A-11-133600 can also be mentioned as a preferred example.

These monomer or oligomer having a polymerizable group preferably have a molecular weight of 200 to 1,000, and they may be used singly or as a mixture of two or more kinds thereof.

In the color filter of the present invention, the content of the monomer or oligomer having a polymerizable group is not particularly limited, but the content thereof is represented by a polymer in the colored layer, usually at a mass of from 5 From 5% to 50% by mass, preferably from 10% by mass to 40% by mass, based on the total solid content in the colored layer. If the content is too large, the control of the developing property becomes difficult to cause a problem of manufacturing suitability. If the content is too small, the hardening force at the time of exposure becomes insufficient.

(c) Water-soluble polymer In the color filter of the present invention, the colored layer contains a water-soluble polymer. The water-soluble polymer preferably has a solubility for pure water (25 ° C) of 10 or more, more preferably 50 or more, and particularly preferably 100 or more. Moreover, it is preferred to be a neutral polymer in the state of an aqueous solution, which means that the polymer hardly affects the color filter. For example, it is preferred that the 50% by mass aqueous solution thereof exhibits a water-soluble compound having a pH of from 5 to 9, and more preferably from 6 to 8. Specifically, a synthesis prepared from, for example, polyvinyl alcohol, polyvinylpyrrolidone, polypropylene decylamine, polyethylene glycol, and polyethylene oxide, and a copolymer of such compounds can be used. Polymer compound. Among these compounds, polyvinylpyrrolidone is particularly preferred. These water-soluble polymers may be used singly or in combination of two or more of them.

The molecular weight of the water-soluble polymer is not particularly limited, but the number average molecular weight (Mn) thereof is preferably from 1,000 to 2,000,000, more preferably from 5,000 to 1,000,000, still more preferably from 10,000 to 500,000, and particularly preferably From 10,000 to 100,000.

In the color filter of the present invention, the content of the water-soluble polymer in the colored layer is 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 1% by mass or more, for coloring. The total solids content in the layer is the basis. The content of the water-soluble polymer in the colored layer is not particularly limited, but in practical use, the content of the water-soluble polymer is 5% by mass or less based on the total solid content in the colored layer.

(d) Adhesive Agent Regarding the binder, a binder having an acidic group is preferred. The binder can be added during the preparation of the ink jet ink or the coloring photosensitive resin composition. Alternatively, it may be added at the time of producing the pigment dispersion as described above, or before preparing it, or at the time of forming pigment particles as described later. The binder may be added to either or both of the organic pigment solution and the poor solvent used in the addition of the organic pigment solution to precipitate the pigment fine particles. Alternatively, the binder solution may be separately added to form the pigment particles.

The binder is preferably an alkali-soluble polymer having a polar group such as a carboxylic acid group or a carboxylate group in its side chain. Examples thereof include: methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, and partially esterified maleic acid. Polymers, for example, Japanese Patent Application Laid-Open No. JP-A-59-44615, Japanese Invention Patent No. JP-B-54-34327, Japanese Invention Patent No. JP-B-58-12577 Japanese Patent No. JP-B-54-25957, Japanese Patent Application Laid-Open No. JP-A-59-53836, and Japanese Patent Laid-Open No. JP-A-59-71048 Descriptor. Further, examples thereof include a cellulose derivative having a carboxylic acid group or a carboxylate group in its side chain. It is also suitable to use a product obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group, in addition to those described above. In addition, a particularly preferred example of the binder is a copolymer of benzyl (meth)acrylate and (meth)acrylic acid as disclosed in the specification of U.S. Patent No. 4,139,391, and (a) a multicomponent copolymer of benzyl acrylate, (meth)acrylic acid, and any other monomer. These polar group-containing binder polymers can be used singly or in combination with a general film-forming polymer.

The "alkali-soluble polymer" herein means an polymerization in which the acid strength is in the pH range of 1 or more but less than 5 when the pH of the aqueous solution in which 50% by mass of the polymer is dissolved is measured. Things. The alkali-soluble polymer is distinguished from the neutral water-soluble polymer as described above based on the acid strength.

Further, for the purpose of improving the crosslinking efficiency, a polymerizable group may be contained in the side chain, and a UV curable resin or a thermosetting resin may be useful. Examples of the polymer containing the polymerizable group are as follows, but are not limited thereto, as long as they contain an alkali-soluble group such as a -COOH group, an OH group, an ammonium group, and the like, and carbon. - When the carbon unsaturated bond is not limited to the ones described below. For example, a compound having an epoxy ring (which is reactive with an -OH group) and a carbon-carbon unsaturated bond group (for example, glycidyl acrylate) can be used, and a compound having an -OH group can be used. a monomer (for example, 2-hydroxyethyl acrylate), a monomer containing a -COOH group (for example, methacrylic acid), and a monomer copolymerizable with the above two types of monomers (for example, an acrylic compound, a vinyl compound, or The compound obtained by reacting the copolymer formed by the analog). As the compound reactive with the -OH group, a compound having an acryloyl group, an acid anhydride, and an isocyanate group may be used instead of the epoxy ring. Further, a reaction product obtained by reacting a compound obtained by reacting a compound having an epoxy ring with an unsaturated carboxylic acid (for example, acrylic acid) with a saturated or unsaturated polybasic acid anhydride, for example, a Japanese invention patent may be used. The above is disclosed in Japanese Laid-Open Patent Publication No. JP-A-6-102669, and Japanese Patent Application Laid-Open No. JP-A-6-1938. Examples of the compound having both an alkali-soluble group (for example, -COOH group) and a carbon-carbon unsaturated group include, for example, DIANAL NR series (trade name, Mitsubishi Rayon Co., Ltd.). ))) PHOTOMER 6173 (Polyurethane acrylic oligomer containing -COOH group, manufactured by Diamond Shamrock Co., Ltd.); VISCOAT R-264 and KS RESIST 106 (both products) Name, manufactured by Osaka Organic Chemical Industry, Ltd.; CYCLOMER P series and PRAXEL CF200 series (all manufactured by Daicel Chemical Industries, Ltd.); EBECRYL 3800 (trade name, manufactured by Daicel-UCB Co., Ltd. (Daicel-UCB Company Ltd.)), and the like.

Further, the binder resin is an organic macromolecular polymer which can be used in a part of the side chain to have a water-soluble atomic group. Preferably, the binder resin is a linear organic macromolecular polymer which is compatible with the monomer and is soluble in an organic solvent and an alkaline solution (preferably a developer which can be developed with a weak alkali solution). Examples of such "alkali-soluble resins" include polymers having a carboxylic acid in a side chain, such as a methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer, and a cis. An adipic acid copolymer, a partially esterified maleic acid copolymer, and the like, for example, Japanese Patent Laid-Open No. JP-A-59-44615, Japanese Patent No. 59-44615 JP-A-54-34327, Japanese Invention Patent No. JP-A-58-12577, Japanese Invention Patent No. JP-A-54-25957, Japanese Invention Patent Special Open JP-J- The above is disclosed in Japanese Laid-Open Patent Publication No. JP-A-59-71048. Similarly to this, an acidic cellulose derivative having a carboxylic acid in a side chain can also be used. In addition to this, a polymer having a hydroxyl group to which an acid anhydride is added or the like can also be used as the alkali-soluble resin. Among these polymers, specifically, a copolymer of benzyl (meth)acrylate/(meth)acrylic acid and benzyl (meth)acrylate/(meth)acrylic acid/others Monomeric multicomponent copolymers. As the alkali-soluble resin, a copolymer composed of at least one of the following components (hereinafter, sometimes referred to as "copolymer A") may be used: (i) at least one acid component single system selection From: maleic anhydride (MAA), acrylic acid (AA), methacrylic acid (MA) and fumaric acid (FA); and (ii) poly(meth)acrylic acid oxyethylene alkyl ester; and Iii) Benzyl (meth)acrylate.

Regarding the combination of the components in the copolymer A as described above, (i) the acid component monomer, (ii) the poly(meth)acrylic acid oxyalkylalkyl ester (Acr(EO) _n :CH ₃ (OC ₂ H ₄ ) _n OCOC(R)=CH ₂ ), and the composition weight of (iii) benzyl (meth)acrylate (Bz(M)A) is preferably 10~25/5~25/50~85, More preferably, it is 15~20/5~20/60~80. Further, in the above-mentioned copolymer, the weight average molecular weight (Mw) in terms of polystyrene is preferably in the range of from 3,000 to 50,000, and more preferably in terms of GPC (gel permeation chromatography). From 5,000 to 30,000.

If the composition weight ratio of the (i) acid component monomer is in the range as described above, the alkali solubility and the solubility property to the solvent hardly decrease. Further, if the weight ratio of (ii) poly(meth)acrylic acid oxyalkylene alkyl ester (Acr(EO) _n :CH ₃ (OC ₂ H ₄ ) _n OCOC(R)=CH ₂ ) is as described above In the range, the solution of the composition can be easily diffused on the substrate, and the dispersibility of the colorant is hardly lowered. Therefore, the effects of the present invention can be effectively achieved. If the composition weight ratio of (iii) benzyl (meth)acrylate (Bz(M)A) is in the range as described above, the dispersion stability of the colorant, the dispersibility of the colorant in the composition, And the alkali developing suitability of the coating film hardly decreases.

(Ii), poly (meth) acrylic acid esters of polyoxyethylene alkyl _{(Acr (EO) n: CH} 3 (OC 2 H 4) n OCOC (R) = CH 2) The weight of the polyethylene oxide (EO) _n of The number n of coating units is preferably in the range of 2 to 15, more preferably in the range of 2 to 10, and particularly preferably in the range of 4 to 10. When the number n of the repeating units is in the range as described above, almost no development residue is generated after development with an alkaline developing solution. In addition to this, when it is in the above range, it is also possible to prevent coating unevenness due to a decrease in fluidity as a composition of the coating liquid. Therefore, this range is a deterioration of both the uniformity of the coating film thickness and the saving of liquid.

These polar group-containing binder polymers can be used singly or in a state in which a binder polymer is combined with a general film-forming polymer and used as a composition. The binder polymer is usually added in an amount of from 10 to 200 parts by mass, preferably from 25 to 100 parts by mass, based on 100 parts by mass of the pigment particles.

If the binder is a polymer compound, the number of acidic groups in the polymer compound is not particularly limited; however, if the number of repeating units in one molecule is set to 100, each has an acidity. The number of the repeating units is preferably from 5 to 100, and more preferably from 10 to 100. In addition, the polymerization ratio between (1) a repeating unit derived from a compound having a carboxyl group and (2) a repeating unit derived from a compound having a carboxylate group is preferably as follows: a repeating unit (1) The ratio is 5 to 40 mol%, the ratio of the repeating unit (2) is 40 to 90 mol%, and the ratio of the repetitive units other than the repetitive units (1) and (2) is 25 m. % or less. In addition to this, the molecular weight of the alkali-soluble binder polymer compound having an acidic group is preferably from 3,000 to 1,000,000, more preferably from 4,000 to 200,000, and particularly preferably from 5,000 to 80,000.

There is no particular limitation on the content of the binder in the color filter of the present invention. However, the content of the binder in the colored layer is usually in the range of from 15 to 50% by mass, preferably from 20 to 45% by mass, based on the total solid content in the colored layer. If the content of the binder is too large, the viscosity of the pigment dispersion used in the production of the color filter becomes too high to cause a problem in manufacturing suitability. On the other hand, if the content of the binder is too small, there is a problem in the formation of the coating film.

(e) Photopolymerization initiator or photopolymerization initiator is an example of a photopolymerization initiator or a photopolymerization initiator (in the specification of the present invention, the term "photopolymerization initiator system" means a combination of several compounds, that is, A polymerization initiating composition capable of exhibiting a photopolymerization initiating function includes: a vicinal polyketaldonyl compound disclosed in U.S. Patent No. 2,367,660, an affinity ether compound disclosed in U.S. Patent No. 2,448,828, and a U.S. invention patent. An aromatic acycing compound substituted with an alpha-hydrocarbon of No. 2,722,512, a polynuclear hydrazine compound disclosed in U.S. Patent No. 3,046,127 and U.S. Patent No. 2,951,758, the disclosure of which is incorporated herein by reference. A combination of a dimer and a p-aminoketone, which is disclosed in Japanese Patent Publication No. JP-B-51-48516, a benzothiazole compound and a trihalomethyl-s-triazo Compound, trihalomethyl-trinitrogen disclosed in U.S. Patent No. 4,239,850 a compound, and a trihalomethyl group disclosed in U.S. Patent No. 4,212,976 Diazole compound. In particular, trihalomethyl-s-trinitrogen is preferred. Trihalomethyl Diazole, and triaryl imidazole dimer.

In addition, as a preferred example, the "polymerization initiator C" and the hydrazines, such as 1-, as disclosed in Japanese Laid-Open Patent Publication No. JP-A-11-133600, Phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)anthracene, O-benzylidene-4'-(benzohydrothio)benzimidino-hexyl-one oxime, 2,4,6-Trimethylphenylcarbonyl-diphenylphosphine oxide, and hexafluorophosphonyl-trialkylphenyl phosphonium salt.

These photopolymerization initiators or photopolymerization initiators can be used individually. It is also possible to use a mixture containing two or more selected from the group consisting of such photopolymerizable initiators and photopolymerization initiators. Specifically, it is preferred to use a mixture containing two or more kinds of photopolymerizable initiators and photopolymerization initiators. When a mixture containing two or more kinds of photopolymerizable initiators and photopolymerization initiators is used, the display characteristics, particularly the uniformity of display thereof, can be improved.

In the color filter of the present invention, the content of the photopolymerization initiator and the photopolymerization initiator to be used is not particularly limited, but in the colored layer, it is usually in the range of from 0.5 to 20% by mass. It is preferably in the range of from 1 to 15% by mass based on the total solid content in the colored layer. If the content of the initiator or initiator series is too large, the exposure sensitivity becomes too high and it is difficult to control. If the content of the initiator or initiator series is too small, the exposure sensitivity becomes too low.

In addition to the components as described above, an organic solvent can be further used. There are no particular restrictions regarding the organic solvent. Examples of the "organic solvent" include: "esters" such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, Isobutyrate, ethyl butyrate, butyl butyrate, alkyl ester compound, methyl lactate, ethyl lactate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl methoxyacetate , methoxyethyl acetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, alkyl 3-hydroxypropionate (eg methyl 3-hydroxypropionate and 3- Ethyl hydroxypropionate), methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate; 2-hydroxyl Methyl propionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate , 2-ethoxypropionic acid methyl ester, 2-ethoxypropionic acid ethyl ester, 2-hydroxy-2-methylpropionic acid methyl ester, 2-hydroxy-2-methylpropionic acid ethyl ester, 2-methyl Methyl oxy-2-methylpropionate Ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoxyacetate, ethyl acetoxyacetate, 2-ketobutyric acid Methyl ester, and ethyl 2-ketobutyrate; "ethers", such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl acetate Sulfate, ethyl sarbutazone acetate, diethylene glycol monomethyl ether, propylene glycol methyl ether acetate; "ketones" such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ring Hexanol, 2-heptanone, and 3-heptanone; and "aromatic hydrocarbons" such as toluene and xylene. Among these solvents, those suitable for use in the present invention as a solvent are preferably methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celecoxib acetate, ethyl lactate, and butyl acetate. Ester, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl hexyl acetate, butyl hexyl acetate, propylene glycol methyl ether acetate, and the like. These solvents may be used singly or in combination of two or more kinds thereof.

Further, a solvent having a boiling point of from 180 ° C to 250 ° C can also be used as needed. Examples of the "high boiling point solvent" include, for example, 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 ester Ether, 2-ethylhexyl acetate, 3-methoxy-3-methylbutyl acetate, γ-butyl lactone, trimethyl propylene glycol methyl ethyl acetate, dipropylene glycol acetate-n-butyl ester, acetic acid Propylene glycol phenyl ether ester, and 1,3-butylene glycol diacetate.

The content of the solvent in the color filter of the present invention is not particularly limited. However, the content of the solvent in the pigment dispersion is preferably from 10 to 95% by mass.

Conventional color filters are intended to achieve high color purity and the color of each pixel has evolved to a deeper level. As a result, the film thickness non-uniformity of the pixels is considered to directly affect the color unevenness. . In view of this, it is required to suppress variations in film thickness that directly affect the film thickness of the pixel.

In the color filter of the present invention, it is preferable to use inkjet ink for color filter from the viewpoint of effectively controlling the uniform film thickness and preventing color unevenness due to film thickness variation. Contains a suitable surfactant.

A preferred example of the surfactant is a surfactant disclosed in Japanese Laid-Open Patent Publication No. JP-A-2003-337424, and Japanese Laid-Open Patent Publication No. JP-A-11-133600. . The content of the surfactant in the color filter of the present invention is not particularly limited. However, the content of the surfactant is preferably 5% by mass or less based on the total solid content in the colored layer.

In the color filter of the present invention, it is preferred to contain a thermal polymerization inhibitor. Examples of the "thermal polymerization inhibitor" include, for example, hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-tertiary-butyl-p-cresol, gallic phenol, tertiary- Butyl catechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary-butylphenol), 2,2'-methylenebis(4-methyl-6- Tertiary-butylphenol), 2-hydrothiobenzimidazole, and thiophene . In the color filter of the present invention, the content of the thermal polymerization inhibitor is not particularly limited. However, it is preferred that the content of the thermal polymerization inhibitor in the colored layer is 1% by mass or less based on the total solid content in the colored layer.

The color filter of the present invention may contain an ultraviolet absorber as needed. Examples of the ultraviolet absorber include, for example, a compound disclosed in JP-A-5-72724, a salicylate-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, and a cyano group. An acrylate-based ultraviolet absorber, a nickel chelate-based ultraviolet absorber, and a hindered amine-based ultraviolet absorber.

Specific examples thereof include: phenyl ruthenate, 4-tris-butyl phenyl salicylate, phenyl-3', 5'-di-tertiary-4'-hydroxybenzoic acid 2,4-di-three Grade-butyl ester, 4-tert-butyl phenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-positive- Octyloxybenzophenone, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tertiary-butyl-5'-A Phenyl)-5-chlorobenzotriazole, ethyl-2-cyano-3,3-diphenylacrylate, 2,2'-hydroxy-4-methoxybenzophenone, dithiamine Dibutyl nickel formate, bis(2,2,6,6-tetramethyl-4-pyridine)-sebacate, 4-tris-butyl phenyl salicylate, phenyl salicylate, 4-hydroxyl -2,2,6,6-tetramethylpiperidine condensate, succinic acid-bis(2,2,6,6-tetramethyl-4-piperidinyl)-ester, 2-[2-hydroxy- 3,5-bis( α , α -dimethylbenzyl)phenyl]-2H-benzotriazole, and 7-{[4-chloro-6-(diethylamino)-5-three nitrogen 2-yl]amino}-3-phenylcoumarin. The content of the ultraviolet absorber in the color filter of the present invention is not particularly limited. However, the content of the ultraviolet absorber is preferably 5% by mass or less based on the total solid content in the colored layer.

In the color filter of the present invention, in the preparation of the colored layer, the pigment dispersion liquid is used in the form of ink jet ink. It is preferred to control the temperature of the ink so that the viscosity of the viscosity is within ±5%. The viscosity at the time of injection is preferably from 5 to 25 mPa. s, more preferably 8 to 22 mPa. s, and particularly good from 10 to 20 mPa. s (viscosity in the present invention, unless otherwise specifically noted, is the value at 25 ° C). In addition to the setting of the injection temperature as described above, the viscosity can also be adjusted by controlling the kind of the component to be contained in the ink and the amount of addition thereof. The viscosity can be measured by a general apparatus such as a conical plate type rotary viscometer or an E type viscometer.

From the viewpoint of improving the smoothness (flatness) of the pixels, it is preferred that the surface tension of the ink at the time of ejection is from 15 to 40 mN/m (the surface tension in the present invention unless otherwise In addition to the special filling, it is the value at 23 ° C). The surface tension is more preferably 20 to 35 mN/m, and most preferably 25 to 30 mN/m. The surface tension can be adjusted by adding a surfactant and selecting the type of solvent to be used. The surface tension is according to a platinum plate method using, for example, a surface tension measuring device (CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.), and a fully automatic balanced electronic surface tension meter ESB. -V (measured by Kyowa Science Co., Ltd.) or the like by a conventional measuring instrument.

A method for spraying a pigment dispersion liquid as described above as an ink jet ink for a color filter, which is a method of continuously jetting a charged ink to be controlled by an electric field; using a piezoelectric element to intermittently print a method of ink; and any of various methods such as a method of intermittently ejecting ink by heating bubbles generated by ink.

Regarding the inkjet method used for forming each pixel (image element), any general method such as a method of thermally hardening the ink, a method of photohardening, and a transparent formation on the substrate may be used. After receiving the image layer, the method of dropping is followed.

Regarding the ink jet head (hereinafter, also simply referred to as "nozzle"), a general head such as a continuous type, instant spot type head can be used. In the instant dot printing type, it is preferable to use a thermal head, for example, a movable valve for discharge which is disclosed in Japanese Laid-Open Patent Publication No. JP-A-9-323420. As for the piezo head, a head which is disclosed, for example, in European Patent No. 277,703A, European Patent No. 278,590A, etc., can be used. The nozzle is preferably provided with a temperature adjustment function, which makes it easy to control the temperature of the ink. Specifically, it is preferred to set the injection temperature so that the viscosity at the time of injection is 5 to 25 mPa. s, and control the ink temperature to make the viscosity change within ± 5%. Further, the driving frequency is preferably operated at 1 to 500 kHz.

After forming each pixel (image element), it is possible to provide a heating step for performing a heat treatment (so-called "baking treatment"). In the heating step, the substrate having the layer photopolymerized by light irradiation is heated in a heater such as an electric furnace or a drying oven, or alternatively, the substrate is irradiated with an infrared lamp. The temperature and time required for heating are determined depending on the composition of the photosensitive coloring composition or the thickness of the layer formed, but from the viewpoint of obtaining sufficient solvent resistance, alkali resistance, and ultraviolet absorbance. It is generally preferred to heat at a temperature of from about 120 ° C to about 250 ° C for a period of from about 10 minutes to about 120 minutes.

The pattern shape of the color filter formed thereby is not particularly limited. In view of this, it may be a stripe shape, a lattice shape, or a triangular arrangement of a general black matrix shape.

It is preferable to use a manufacturing method in which a partition wall is formed in advance and then the ink is supplied to a portion surrounded by the partition wall before the pixel forming step of the ink jet ink using the color filter. There is no special restriction on this partition. However, in the case of manufacturing a color filter, it is preferable to use a partition having a function of a black matrix and a light-shielding property (hereinafter, these partition walls are also simply referred to as "partition walls"). This partition wall can be manufactured by the same method as the same material as the black matrix of a general color filter. Examples of the black matrix include: paragraph numbers [0021] to [0074] in Japanese Patent Application Laid-Open No. JP-A-2005-3861, and Japanese Patent Laid-Open No. JP-A-2004-240039 The paragraphs [0012] to [0021], and the paragraph numbers [0015] to [0020] of Japanese Patent Application Laid-Open No. JP-A-2006-17980, and Japanese Patent Application Laid-Open No. JP A black matrix for inkjet or the like as disclosed in paragraphs [0009] to [0044] of A-2006-10875.

The pigment dispersion liquid as described above is used in a form in which a photosensitive resin composition can be colored to form a coating film. Herein, the "colored photosensitive resin composition" means a composition containing a pigment dispersion. The thickness of the coating film can be appropriately determined. However, the thickness is preferably in the range from 0.5 μm to 5.0 μm, and more preferably in the range from 1.0 μm to 3.0 μm. In the coating film formed using the colored photosensitive resin composition, the polymer film of the colored photosensitive resin composition can be obtained by using a monomer or oligomer having a polymerizable group contained in the composition. Polymerization is carried out to produce a color filter having a polymer film formed thereby (the method for producing a color filter will be described later). The polymerization of a monomer or oligomer having a polymerizable group is carried out by causing a photopolymerization initiator or a photopolymerization initiator to act by light irradiation.

The coating film as described above can be formed by applying a colored photosensitive resin composition by a conventional coating method and then drying it. It is preferable that the colored photosensitive resin composition is applied by using a slit-shaped nozzle having a slit in a portion where the coating liquid is discharged. In particular, it is preferably used in Japanese Patent Laid-Open Publication No. JP-A-2004-89851, Japanese Patent Laid-Open Publication No. JP-A-2004-17043, and Japanese Patent Laid-Open No. JP-A. Japanese Laid-Open Patent Publication No. JP-A-2003-164787, Japanese Patent Laid-Open Publication No. JP-A-2003-10767, Japanese Patent Application Laid-Open No. JP-A-2002 A slit nozzle and a slit coater disclosed in Japanese Laid-Open Patent Publication No. JP-A-2001-310147, and the like.

The method of applying the colored photosensitive resin composition on the substrate is particularly preferably a spin coating from the viewpoint of uniformly coating a film of 1 μm to 3 μm with high precision. Therefore, the spin coating is widely and generally used for the manufacture of color filters. However, in recent years, with the increase in size and mass production of liquid crystal display devices, it has been demanded to further improve manufacturing efficiency and reduce manufacturing costs. A slit coating which is more suitable for coating of a wide-width and large-area substrate than rotary coating has been employed in the manufacture of color filters. In addition, from the viewpoint of liquid-saving, slit coating is superior to rotary coating; and slit coating can produce uniform coating with a small amount of coating liquid. membrane.

"Slit coating" is a coating nozzle having a slit (gap) having a width of several tens of micrometers at the front end and a length corresponding to a coating width of a rectangular substrate, and the substrate is made And/or the coating nozzle moves at a relative speed while maintaining a clearance (gap) between the substrate and the coating nozzle of a distance of tens of microns to hundreds of microns, and will be from the slit A coating method of a coating method in which a coating liquid having a predetermined discharge amount is applied to a substrate or the like. The advantages of the slit coating are: (1) the liquid loss is less than that of the rotary coating; (2) the amount of the workload at the time of the cleaning treatment can be reduced because there is no scattering of the coating liquid; There is no contamination caused by the scattered liquid components mixed into the coating film; (4) the production interval can be shortened because no start and stop time of rotation is required, and (5) large substrates can be easily applied. Based on these advantages, slit coating is a color filter suitable for manufacturing a large-screen liquid crystal display device, and slit coating has been expected to be used for reducing the amount of coating liquid.

By slit coating, it is possible to form a coating film having a much larger area than that of a spin coater. Therefore, when the coating liquid is discharged from the wide slit outlet, it is required to maintain a certain relative speed between the coater and the object to be coated. For this reason, the coating liquid for a slit coating method is required to have excellent fluidity. Further, in the slit coating, it is particularly required that the conditions of the coating liquid supplied from the slit of the coating head to the substrate be kept constant for the entire coating width. When the liquid properties of the coating liquid such as fluidity and viscoelastic properties are not sufficient, coating unevenness is likely to occur, so that the coating thickness in the coating width direction is not easily maintained constant. As a result of coating unevenness, the problem of a uniform coating film could not be obtained.

In view of this, many attempts have been made to improve the fluidity or viscoelastic properties of the coating liquid in order to obtain a uniform coating film having no unevenness. However, as described above, proposals have been made, for example, to reduce the molecular weight of the polymer, to select a polymer having excellent solubility in a solvent, to select various solvents to control the evaporation rate, and to use a surfactant. However, these methods still fail to satisfactorily improve the problems as described above.

The photosensitive resin transfer material can be produced by providing a coloring photosensitive resin composition as described above. The photosensitive resin transfer material is preferably formed by using a composite film similar to the photosensitive resin transfer material disclosed in Japanese Laid-Open Patent Publication No. JP-A-5-72724. An example of the constitution of the composite film is a structure including a laminate in which the temporary support, the thermoplastic resin layer, the intermediate layer, the photosensitive resin layer, and the protective film are arranged in this order.

The temporary support must be flexible and does not significantly deform, shrink or elongate even under pressure, or under pressure and heat. Examples of such temporary supports include: polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and polycarbonate film. Among these, a polyethylene terephthalate film which is biaxially stretched is particularly preferred.

The component to be used in the thermoplastic resin layer is preferably an organic polymer material as disclosed in Japanese Laid-Open Patent Publication No. JP-A-5-72724. The substance is particularly preferably selected from the group consisting of organic polymers having a softening point of about 80 ° C or less according to the Vicat method (specifically, the polymer softening point measurement according to American Material Testing Method ASTM D 1235). substance. Specifically, the substance may be an organic polymer, and examples thereof include: a polyolefin such as polyethylene or polypropylene; an ethylene copolymer, such as an ethylene copolymer of ethylene and vinyl acetate or a saponified product thereof; a copolymer of ethylene and acrylate or a saponified product thereof; polyvinyl chloride; a vinyl chloride copolymer, such as a copolymer of vinyl chloride and vinyl acetate, and a saponified product thereof; polyvinylidene chloride; Ethylene copolymer; polystyrene; styrene copolymer, such as a copolymer of styrene and (meth) acrylate or a saponified product thereof; polyvinyl toluene; vinyl toluene copolymer, such as vinyl a copolymer of toluene and (meth) acrylate or a saponified product thereof; a poly(meth) acrylate; a (meth) acrylate copolymer such as butyl (meth) acrylate and vinyl acetate; Polyamine resin, such as vinyl acetate copolymer nylon, copolymerized nylon, N-alkoxymethylated nylon, and N-dimethyl aminated nylon.

In the photosensitive resin transfer material, it is preferable to provide an intermediate layer for the purpose of preventing mixing of components such as coating of a plurality of layers and storage after coating. The intermediate layer is preferably an oxygen barrier film having an oxygen barrier function as a "separation layer" as disclosed in Japanese Laid-Open Patent Publication No. JP-A-5-72724. By using such oxygen to block the film, the sensitivity at the time of exposure can be improved, and the time load of the exposure machine can be reduced to improve productivity.

The oxygen barrier film is preferably a film having low oxygen permeability and dispersible or soluble in water or an aqueous alkali solution. These films are suitably selected from conventional oxygen barrier films. Among these, a combination of polyvinyl alcohol and polyvinylpyrrolidone is particularly preferred.

A thin protective film is preferably provided on the photosensitive resin layer to protect the photosensitive resin layer from contamination or damage during storage. The protective film may be the same or similar material as the temporary support, but must be easily detachable from the photosensitive resin layer. The protective film material is preferably, for example, an anthrone paper, a polyolefin sheet or a polytetrafluoroethylene sheet.

The photosensitive resin transfer material is formed by coating a temporary support with a coating liquid (coating liquid for a thermoplastic resin layer) which is an additive for dissolving the thermoplastic resin layer, and drying the coating liquid to form a thermoplastic resin layer. Then, the thermoplastic resin layer is coated with the coating liquid for the intermediate layer containing the solvent which does not dissolve the thermoplastic resin layer, and the intermediate layer is dried with the coating liquid; then, the photosensitive layer containing the solvent which does not dissolve the intermediate layer is used. The intermediate layer is applied to the coating liquid for a resin layer, and the photosensitive resin layer is dried by a coating liquid.

Another possible method is that the photosensitive resin transfer material can be obtained by preparing a sheet having a thermoplastic resin layer and an intermediate layer disposed on a temporary support as described above, and having a photosensitive resin layer disposed on the protective film. The sheet is produced by bonding the sheets to each other such that the intermediate layer and the photosensitive resin layer are in contact with each other. The photosensitive resin transfer material can also be obtained by preparing a sheet having a thermoplastic resin layer disposed on the temporary support as described above, and having a sheet on which a photosensitive resin layer and an intermediate layer are disposed on the protective film, and the sheet The mutual bonding is performed such that the thermoplastic resin layer and the intermediate layer are in contact with each other.

In the photosensitive resin transfer material, the thickness of the photosensitive resin layer is preferably from 1.0 to 5.0 μm, more preferably from 1.0 to 4.0 μm, and particularly preferably from 1.0 to 3.0 μm. In general, the thickness of the temporary support is preferably 15 to 100 μm, the thickness of the thermoplastic resin layer is preferably 2 to 30 μm, the thickness of the intermediate layer is preferably 0.5 to 3.0 μm, and the thickness of the protective film is preferably 4 to 40 μm. However, the thickness of the relevant layers is not limited to the range as described above.

The coating operation in the method as described above can be performed by a conventional coating apparatus. In the present invention, it is preferably carried out by a coating apparatus (slit coater) using a slit nozzle. A preferred example of the slit coater is as described above.

The color filter of the present invention is four different hue which may have only a single hue, or have three different hue such as red, blue, and green, or another may further include black depending on the end use. The pattern of the coloring layer on the substrate and the method of forming the pattern are not particularly limited.

The color filter of the present invention can be used as a superior contrast. The term "comparison" as used in the specification of the present invention means the amount of transmitted light when the color filter is placed between two polarizing plates, when the polarization axis is parallel, and the amount of transmitted light when the polarization axis is perpendicular. Ratio (see, for example, "7th Color Optics Conference in 1990; color filter for TFT-LCD showing 512 colors, 10.4" size, Ueki, Koseki, Fuyong (Fukunaga), Yamanaka, etc.).

The color filter with high contrast means that when the color filter is combined with the liquid crystal, the recognition of light and dark can be improved. Therefore, high contrast is a very important performance that needs to be replaced by a liquid crystal display device. The comparison of the color filters according to the present invention is preferably 3,000 or more, more preferably 5,000 or more, and particularly preferably 7,000 or more in the case of a monochromatic type. Regarding a color filter having R pixels, G pixels, and B pixels, and further setting a black matrix as needed, the contrast is preferably 3,000 or more, more preferably 5,000 or more, and particularly preferably 6,000 or the above. The invention is characterized in that this high contrast can be achieved thereby.

When the color filter of the present invention is used as a color filter for a television monitor, the chromaticity of the red (R) photosensitive resin layer measured using the F10 light source is as shown in the following table. The difference between the red target chromaticity (ΔE), the green (G) photosensitive resin layer and the green target chromaticity shown in the following table (ΔE), and blue (B) sensitivity The difference (ΔE) between the chromaticity of the resin layer and the blue target chromaticity shown in the following table is preferably 5 or less, more preferably 3 or less, and still more preferably 2 or less.

Here, the chromaticity in the present invention is measured by a microspectrophotometer (OSP100 or 200, manufactured by Olympus Optics Co., Ltd.), and is obtained by calculating the result under the F10-light source at a viewing angle of 2 degrees. The xyY value of the xyz color system is expressed. In addition, the difference from the "target chromaticity" is expressed by the "color difference" of the La ^* b ^* color system.

The color filter of the present invention can be produced by, for example, repeating: forming a photosensitive resin layer on a substrate and exposing and developing the photosensitive resin layer until each relevant color layer is provided. A black matrix may be introduced as needed to distinguish the boundaries of the photosensitive resin layer.

In the manufacturing method as described above, the method of forming the photosensitive resin layer on the substrate includes, for example, a method of coating each of the related colored photosensitive resin compositions by using (a) a conventional coating device, or This is carried out by (b) a method of attaching the photosensitive resin transfer material as described above to a laminator or the like.

In the manufacture of the color filter of the present invention, any conventional coating device can be used to coat the colored photosensitive resin composition. Among these, it is particularly preferable to use a slit coater. A preferred example of the slit coater is as described above. When the photosensitive resin layer is formed by coating, the film thickness thereof is preferably from 1.0 to 3.0 μm, more preferably from 1.0 to 2.5 μm, and still more preferably from 1.5 to 2.5 μm.

Using a photosensitive resin transfer material, the photosensitive resin layer formed into a film shape is pressed or heated by using a heated or/or pressurized roller or plate as described above, thereby being attached to the substrate. on. In particular, the laminating machine and the laminating method disclosed in the following documents can be used: Japanese Laid-Open Patent Publication No. JP-A-7-110575, Japanese Laid-Open Patent Publication No. JP-A-11-77942 Japanese Laid-Open Patent Publication No. JP-A-2000-334836, and Japanese Laid-Open Patent Publication No. JP-A-2002-148794. From the viewpoint of suppressing the contamination of the foreign matter, the method disclosed in Japanese Laid-Open Patent Publication No. JP-A-7-110575 is preferably used.

In the color filter of the present invention, when a photosensitive resin layer is formed by applying a colored photosensitive resin composition, an oxygen blocking film can be further provided on the photosensitive resin layer, whereby the color filter can be improved. Exposure sensitivity. Regarding the oxygen shutoff film, the same as described above can be used. The thickness of the oxygen barrier film is not particularly limited, and in general, the thickness is preferably from 0.5 to 3.0 μm.

The color filter of the present invention can be carried out, for example, by repeating: a specific mask is disposed over the photosensitive resin layer formed on the substrate; thereafter, the mask, the thermoplastic resin layer, and the intermediate layer are interposed therebetween On the other hand, the photosensitive resin layer is exposed from above the mask, and then the photosensitive resin layer is developed with a developing solution until the respective color layers are provided.

The light source for exposure is suitably selected from a light source capable of emitting light in a wavelength range (for example, 365 nm, 405 nm, etc.) which can harden the photosensitive resin layer. Specific examples thereof include, for example, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and the like. The exposure amount is usually from about 5 to 200 mJ/cm ² , and preferably from about 10 to 100 mJ/cm ² .

The developer is not particularly limited, and a known developer such as the developer described in Japanese Laid-Open Patent Publication No. JP-A-5-72724 can be used. The developer is preferably a developer of a type which dissolves the unhardened photosensitive resin layer at the time of development; for example, it preferably contains a pKa value of 7 to 13 at a concentration of 0.05 to 5 m/liter. Developer solution of the compound. The developer may also contain a small amount of an organic solvent which is miscible with water.

Examples of the "organic solvent having water-miscibility with water" include, for example, methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, and ethylene glycol. Ethyl ether, ethylene glycol mono-n-butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε -caprolactone, γ -butyrolactone, dimethylformamide, dimethyl Ethyl amide, hexamethylphosphoniumamine, ethyl lactate, methyl lactate, ε -caprolactam, and N-methylpyrrolidone. The concentration of the organic solvent is preferably from 0.1% by mass to 30% by mass.

A developer can be further added with a conventional surfactant. The concentration of the surfactant is preferably from 0.01% by mass to 10% by mass.

The developing method may be a conventional method such as immersion development, spray development, spray and rotary development, or immersion development.

Hereinafter, the shower development will be explained. In the shower development, the developer is sprayed on the exposed photosensitive resin layer by a shower to remove the unhardened portion. It is preferable to remove the thermoplastic resin layer, the intermediate layer, and the like by spraying a basic liquid having low solubility to the photosensitive resin layer by using a shower or the like before the development. Further, after development, it is preferred to spray the detergent or the like by using a shower while wiping the surface with a brush or the like to remove the development residue.

The liquid temperature of the developer is preferably from 20 ° C to 40 ° C, and the pH of the developer is preferably from 8 to 13.

In a specific example of the present invention, in manufacturing the color filter of the present invention, the colored photosensitive resin composition for forming a color filter is stacked to form a substrate, and a transparent electrode is formed thereon, and further A protrusion for dividing and aligning is stacked thereon to form a spacer, as disclosed in Japanese Laid-Open Patent Publication No. JP-A-11-248921, and Japanese Patent No. 3255107. This specific example is a preferred method from the viewpoint of cost reduction.

When the colored photosensitive resin composition is stacked by the sequential coating operation, the film thickness is thinned by each lamination due to the leveling of the coating liquid. For this reason, it is preferable to stack four colors of K (black), R, G, and B, and to provide protrusions for division and alignment thereon. On the other hand, when a transfer material having a thermoplastic resin layer is used, since the thickness is kept constant, it is preferably two or three colors stacked.

From the viewpoint of preventing deformation of the photosensitive resin layer when laminating by laminating the transfer material and maintaining a certain thickness, the size of the substrate is preferably 25 μm × 25 μm or more, and Preferably 30 μm × 30 μm or more.

The liquid crystal display device of the present invention uses the color filter of the present invention having superior contrast, and therefore has an excellent resolution of black density or the like. Therefore, it is also suitable for use as a large-screen liquid crystal display device such as a notebook computer display or a television monitor.

As described above, the pigment dispersion liquid used in the color filter of the present invention preferably contains pigment particles. The pigment fine particles are preferably an organic pigment solution in which a green pigment is dissolved in a good solvent, together with a solvent which is compatible with the good solvent but acts as a poor solvent for the organic pigment (hereinafter, the solvent has It is also called "poor solvent for organic pigments" or simply referred to as "poor solvent" to form (precipitate). (In the following, this method is sometimes referred to as "particle precipitation method"). Related to this is that the good solvent and the poor solvent selected for combination are required to exhibit sufficient difference in solubility for the organic pigment; and it is necessary to select an appropriate solvent depending on the pigment used. However, any combination of solvents may be selected as long as they are capable of achieving the steps described above.

The "poor solvent" of the organic pigment is not particularly limited as long as it is compatible with or can be uniformly mixed with a good solvent for dissolving the organic pigment. Regarding the poor solvent of the organic pigment, the solubility of the organic pigment in the poor solvent is preferably 0.02% by mass or less, and more preferably 0.01% by mass or less. There is no particular lower limit on the solubility of the organic pigment in a poor solvent. However, in consideration of the conventional organic pigment, the solubility is 0.000001% by mass or more in practical use. The solubility can also be the solubility of the organic material when dissolved in the presence of an acid or a base. Further, the compatibility or uniform mixing property between the good solvent and the poor solvent is such that the amount of the good solvent dissolved in the poor solvent is preferably 30% by mass or more, and more preferably 50% by mass or more. Although there is no particular upper limit for the amount of good solvent to be dissolved in a poor solvent, in practical applications, the solvent can be mixed with each other at any ratio.

Examples of the "poor solvent" include aqueous solvents (for example, water, hydric alcohol, hydrochloric acid, and aqueous sodium hydroxide), alcohol compound solvents, ketone compound solvents, ether compound solvents, and aromatics. A compound solvent, a carbon disulfide solvent, an aliphatic compound solvent, a nitrile compound solvent, a halogen-containing compound solvent, an ester compound solvent, an ionic solvent, and a mixed solvent thereof. Examples of preferred poor solvents include: aqueous solvents, alcohol compound solvents, ketone compound solvents, ether compound solvents, ester compound solvents, or mixed solvents thereof; and examples of more preferable poor solvents are Including: aqueous solvents, alcohol compound solvents, and ester compound solvents.

Examples of the "alcohol compound solvent" include, for example, methanol, ethanol, isopropanol, n-propanol, 1-methoxy-2-propanol and the like. Examples of the "ketone compound solvent" include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like. Examples of the "ether compound solvent" include, for example, dimethyl ether, diethyl ether, tetrahydrofuran, and the like. Examples of the "aromatic solvent" include, for example, benzene, toluene, and the like. Examples of the "aliphatic compound solvent" include, for example, hexane or the like. Examples of the "nitrile compound solvent" include, for example, acetonitrile or the like. Examples of the "halogen-containing compound solvent" include, for example, dichloromethane, trichloroethylene, and the like. Examples of the "ester compound solvent" include, for example, ethyl acetate, ethyl lactate, 2-(1-methoxy)propyl acetate, and the like. Examples of the "ionic solvent" include, for example, a salt of 1-butyl-3-methylimidazolium and PF ₆ ^{- and} the like.

The "good solvent" is not particularly limited as long as it is capable of dissolving the organic pigment used and is compatible with the poor solvent as described above, or can be uniformly mixed. Regarding the solubility of the organic pigment in a good solvent, the solubility of the organic pigment is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. There is no particular upper limit for the solubility of the organic pigment in a good solvent. However, in consideration of a conventional organic material, the solubility is 50% by mass or less in practical use. The solubility can also be the solubility of the organic material when dissolved in the presence of an acid or a base. A preferred range of compatibility or uniform mixing between the poor solvent and the good solvent is as described above.

Examples of the "good solvent" include, for example, an alcohol compound solvent, a guanamine compound solvent, a ketone compound solvent, an ether compound solvent, an aromatic solvent, a carbon disulfide solvent, an aliphatic solvent, and a nitrile solvent. Examples, an anthraquinone compound solvent, a halogen-containing compound solvent, an ester compound solvent, an ionic liquid, or a mixed solvent thereof. Among these, preferred are alcohol compound solvents, ketone compound solvents, ether compound solvents, hydrazine compound solvents, ester compound solvents, guanamine compound solvents, and mixed solvents thereof; more preferably alcohols The compound solvent, the ester compound solvent, the hydrazine compound solvent, and the guanamine compound solvent; and particularly preferably an ytterbium compound solvent and a guanamine compound solvent.

Examples of the "indium sulfonium compound solvent" include, for example, dimethyl hydrazine, diethyl hydrazine, hexamethylene fluorene, and cyclobutyl hydrazine. Examples of the "melamine compound solvent" include, for example, N,N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl- 2-imidazolidinone, 2-pyrrolidone, ε-caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N,N-dimethyl Acetamide, N-methylpropane decylamine, and hexamethylphosphoric acid triamide.

In addition, the concentration of the organic pigment solution prepared by dissolving the organic pigment in a good solvent is preferably a saturated concentration of the organic pigment to the good solvent at the time of dissolution to about 1/100 of the saturated concentration. The scope.

The preparation conditions of the organic pigment solution are not particularly limited, and may be selected from the range of normal pressure to subcritical and supercritical conditions. If the solution is prepared under normal pressure, the temperature thereof is preferably from -10 to 150 ° C, more preferably from -5 to 130 ° C, and particularly preferably from 0 to 100 ° C.

The example good solvent as described above is common to the poor solvents, but the exact same solvent is not selected at the same time as a combination of a good solvent and a poor solvent. Any solvent may be used in combination with any of the organic materials used as long as the solubility in the good solvent is sufficiently higher than in the poor solvent. Specifically, the difference in solubility between the good solvent and the poor solvent is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. There is no special upper limit for the difference in solubility between them. However, when considering the organic materials generally used, the upper limit of practical application is 50% by mass or less.

In the fine particle deposition method as described above, it is preferred that the organic pigment is uniformly dissolved in the good solvent, and it is further preferred that the organic pigment is dissolved when the solvent is acidic or alkaline. In general, if the organic pigment has a group which can be dissociated under basic conditions in its molecule, an alkaline solvent can be used; if the organic pigment does not have a group which can be dissociated under alkaline conditions in its molecule In the case, when there are many nitrogen atoms in the molecule which are easy to bond protons, an acidic solvent is used. For example, quinacridone, diketopyrrolopyrrole, and a diazo condensed compound pigment are dissolved under alkaline conditions; however, the anthraquinone compound pigment is dissolved under acidic conditions.

When the organic pigment is dissolved in an alkaline solvent, examples of the "base" which can be used include, for example, "inorganic bases" such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and hydrogen. Cerium oxide; and "organic bases" such as trialkylamine, diazabicycloundecene (DBU), and metal alkoxides. Preferred are inorganic bases.

The amount of the base to be used is not particularly limited as long as the base can uniformly dissolve the pigment. In the case of an inorganic base, the amount thereof is preferably from 1.0 to 30 mol equivalents, more preferably from 1.0 to 25 mol equivalents, and still more preferably from 1 to 20 mol equivalents, relative to the organic pigment. In the case of an organic base, the amount thereof is preferably from 1.0 to 100 mol equivalents, more preferably from 5.0 to 100 mol equivalents, and still more preferably from 20 to 100 mol equivalents, relative to the organic pigment.

If the organic pigment is dissolved in an acidic solvent, examples of the acid to be used include, for example, "inorganic acids" such as sulfuric acid, hydrochloric acid, and phosphoric acid; and "organic acids" such as acetic acid, trifluoroacetic acid, oxalic acid, and methane. Sulfonic acid and trifluoromethanesulfonic acid. Among these, inorganic acids are preferred, and sulfuric acid is particularly preferred.

The amount of the acid to be used is not particularly limited as long as the amount of the acid is such that the organic pigment can be uniformly dissolved. In many cases, the amount of acid used is greater than or greater than the amount of base. Regardless of the type of the acid being an inorganic acid or an organic acid, the amount of the acid to be used is preferably from 3 to 500 mol equivalents, more preferably from 10 to 500 mol equivalents, and still more preferably from 30 to 30 mol equivalents. 200 mole equivalents.

If a base or an acid is mixed with an organic solvent and a mixture is used as a good solvent for the organic pigment, a small amount of a solvent having a high solubility to a base or an acid such as water or a lower alcohol may be added to the organic solvent to cause a base or The acid can be completely dissolved. The amount of the water or the lower alcohol is preferably 50% by mass or less, or more preferably 30% by mass or less, based on the total amount of the organic pigment solution. Specific examples thereof which can be used include water, methanol, ethanol, n-propanol, isopropanol, butanol and the like.

The conditions of the poor solvent in the formation of the organic pigment are not particularly limited, and may be selected from the range of atmospheric conditions to subcritical or supercritical conditions. The temperature at which the organic fine particles are precipitated under normal pressure is preferably from -30 to 100 ° C, more preferably from -10 to 60 ° C, and particularly preferably from 0 to 30 ° C. The viscosity of the pigment microparticles is preferably from 0.5 to 80.0 mPa. The range of s, and more preferably from 1.0 to 50.0 mPa. The range of s.

When the organic pigment solution is mixed with the poor solvent, it may be added by mixing either of them, but it is preferred to add the organic pigment solution to the poor solvent for mixing; and it is also preferable to mix the poor solvent. Must be in a state of being stirred. The stirring rate is preferably from 100 to 10,000 rpm, more preferably from 150 to 8,000 rpm, and particularly preferably from 200 to 6,000 rpm. When adding, a pump or the like may or may not be used. Regarding the addition method, one method is liquid addition, and the other method is liquid addition; a preferred method is liquid addition. In the present invention, it is preferred that one of the liquids is continuously supplied to the liquid via the supply pipe using a pump. The inner diameter of the supply tube is preferably from 0.1 mm to 200 mm, and more preferably from 0.2 mm to 100 mm. The rate of supply of the other liquid from the supply tube is preferably from 1 to 10,000 ml/min, and more preferably from 5 to 5,000 ml/min.

The mixing ratio of the organic pigment solution to the poor solvent (the good solvent/poor solvent ratio in the pigment particle precipitation liquid) is preferably from 1/50 to 2/3, more preferably from 1/40 to 2,000 by volume. 1/2, and particularly preferably in the range from 1/20 to 3/8.

The concentration of the pigment in the pigment microparticles is not particularly limited as long as it can prepare organic fine particles, but the amount of the organic fine particles is preferably from 10 to 40,000 mg per 1,000 ml of the dispersion solvent, more preferably 20 to 30,000 mg, and particularly preferably 50 to 25,000 mg.

The modulation ratio in the preparation of the pigment fine particles is not particularly limited. However, the modulation ratio is preferably such that the mixing amount of the poor solvent is from 10 to 2,000 liters, and more preferably from 50 to 1,000 liters.

Regarding the particle size of the organic fine particles, although the method of numerically calculating the average size of the group by the measurement method has been used, the most commonly used method includes the "most frequent value path" indicating the maximum value of the distribution, and corresponds to The "median diameter" of the central value of the integral distribution curve, various "average diameters" (quantity average, length average, area average, weight average diameter, volume average diameter, etc.), etc., but in the present invention, unless otherwise specified In addition to the designation, the so-called "particle size" is the number average diameter. The particle diameter of the pigment particles (primary particle) is preferably from 1 nm to 1 μm, more preferably from 1 nm to 100 nm, further preferably from 5 to 80 nm, and particularly preferably from 5 to 50 nm. The organic fine particles may be in the form of a crystalline plasmid or an amorphous plasmid, or a mixture of such fine particles, or in a solid solution. Further, it is preferred that a mixture or a solid solution is formed by the simultaneous presence of two or more organic fine particles; and the organic fine particles have a so-called "core-shell structure" in which the surface of the fine particles is uniform. The ground forms a layer composed of another substance.

Further, in the present invention, the ratio of the volume average diameter (Mv) to the number average diameter (Mn) (Mv/Mn) is used as an index of the monodispersity of the particles (the uniformity of the particle size) unless otherwise specifically added. Note. The monodispersity (Mv/Mn ratio) of the pigment fine particles (primary particles) is preferably from 1.0 to 2.0, more preferably from 1.0 to 1.8, and particularly preferably from 1.0 to 1.5.

Examples of the method of measuring the particle diameter of the organic fine particles include, for example, microscopic method, gravimetric method, light scattering method, light shielding method, electric resistance method, acoustic method, and dynamic light scattering method. Among these, it is particularly preferred to be a microscopic method and a dynamic light scattering method. Examples of the microscope used in the microscopy include, for example, a scanning electron microscope and a transmission electron microscope. Examples of the particle measuring device according to the dynamic light scattering method include, for example, Nanotrac UPA-EX150 (trade name) manufactured by NIKKISO Co., Ltd., and OTSUKA ELECTRONICS CO. ., LTD.) Dynamic light scattering meter manufactured by DLS-7000 series (trade name).

In the preparation of the dispersion of the pigment particles, it is preferred to use a dispersant therein. The step of using the dispersing agent is not particularly limited, but it is preferred to add the dispersing agent to either or both of the organic pigment solution and the poor solvent. Further, it is preferred to add the dispersant solution in a manner separate from the two solutions as described above when preparing the pigment particles. In addition to this, it is also preferred to use pigment fine particles which have been surface-treated in advance with a dispersing agent; and the pigment fine particles are surface-treated which can promote adsorption of the dispersing agent on the pigment fine particles. The dispersing agent has a function of (1) a dispersing agent can be rapidly adsorbed on the surface of the precipitated pigment to form fine nano-fine particles, and (2) a dispersing agent can prevent the particles from re-aggregating.

As the dispersant, those produced by anionic, cationic, diionic, nonionic, or pigment derivative type low molecular or polymeric dispersants can be used. The molecular weight of the polymer dispersant used may be any value as long as the dispersant can be uniformly dissolved in the solution, but the polymer dispersant preferably has a molecular weight of 1,000 to 2,000,000, more preferably 5,000 to 1,000,000, further More preferably, it is 10,000 to 500,000, and particularly preferably 10,000 to 100,000. Specific examples of the "polymer dispersant" include, for example, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, polypropylene decylamine. , vinyl alcohol-vinyl acetate copolymer, polyvinyl alcohol - partial formaldehyde, polyvinyl alcohol - partial butyral, vinyl pyrrolidone - vinyl acetate copolymer, polyethylene oxide / Propylene oxide block copolymer, polyacrylate, polyvinyl sulfate, poly(4-vinylpyridine) salt, polyamine, polyallylamine salt, condensed naphthalene sulfonate Classes, cellulose derivatives, and starch derivatives. Further, natural polymers may be used, and examples thereof include: alginate, gelatin, albumin, casein, gum arabic, tragacanth gum, and ligninsulfonic acid salts. ). Among these, it is preferred to use any of the water-soluble polymers as described above, and it is more preferred to use polyvinylpyrrolidone. These polymers may be used singly or in combination of two or more kinds thereof. These pigment dispersants may be used singly or in combination of two or more kinds thereof. The pigment dispersant for dispersing pigments has been on pages 29 to 46 of "Pigment Dispersion Stabilization and Surface Treatment Technology. Evaluation" (Japan Association for International Chemical Information, published in December 2001). There are detailed instructions.

Examples of the "anionic dispersant (anionic surfactant)" include, for example, N-fluorenyl-N-alkyl taurates, fatty acid salts, alkyl sulfate salts, alkylbenzenesulfonates Acid salts, alkylnaphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate salts, naphthalenesulfonic acid/formaldehyde condensates, and polyoxyethylene alkyl sulfates. Particularly preferred are N-fluorenyl-N-alkyl taurates. The N-fluorenyl-N-alkyl taurate is preferably those disclosed in Japanese Laid-Open Patent Publication No. JP-A-3-273067. These anionic dispersing agents may be used singly or in combination of two or more kinds thereof.

Examples of the "cationic dispersant (cationic surfactant)" include, for example, quaternary ammonium salts, alkoxylated polyamines, aliphatic amine polyglycol ethers, aliphatic amines, derived from Diamines and polyamines of aliphatic amines and aliphatic alcohols; imidazolines derived from fatty acids; and salts containing such cationic substances. These cationic dispersants may be used singly or in combination of two or more kinds thereof.

The "two-ionic dispersing agent" is an anionic group having both an anionic group portion in a molecule of an anionic dispersing agent and a cationic group portion in a molecule of a cationic dispersing agent in its molecule. Dispersant.

Examples of the "nonionic dispersing agent (nonionic surfactant)" include, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene fatty acid esters, sorbitan Alcohol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, and glycerin fatty acid esters. Among these, polyoxyethylene alkyl aryl ethers are preferred. These nonionic dispersing agents may be used singly or in combination of two or more kinds thereof.

"Pigment derivative-type dispersant" is defined as a dispersant derived from an organic pigment as a parent substance, and is produced by chemically modifying a parent structure, or by chemically modified pigment precursor The pigment is formed by a reaction. Examples of the "pigment derivative type dispersant" include, for example, a sugar-containing pigment derivative type dispersant, a piperidinyl group-containing pigment derivative type dispersant, a naphthalene or anthracene-derived pigment derivative type dispersant, and a pigment derivative type dispersant which is bonded to a functional group of a pigment precursor structure by a methylene group, a pigment derivative type dispersant which is chemically modified by a polymer (parent structure), and a pigment derivative type dispersion having a sulfonic acid group Agent, pigment derivative type dispersant having sulfonamide group, pigment derivative type dispersant having ether group, and pigment derivative type dispersant having carboxylic acid group, carboxylate group or carboxamide group .

In the case of preparing an organic pigment solution dissolved in a good solvent, it is preferred that the amine-containing pigment dispersant be present together with the organic pigment. The term "amine group" as used herein includes: a primary amine group, a secondary amine group, and a tertiary amine group, and the number of the amine groups may be one or several. The amine group-containing pigment dispersant may be a polymer derivative compound which introduces a substituent having an amine group into a pigment skeleton, or may be a polymer compound which is polymerized using a monomer having an amine group as a polymerization component. Examples of such compounds include: Japanese Patent Laid-Open Publication No. JP-A-2000-239554, Japanese Patent Laid-Open Publication No. JP-A-2003-96329, and Japanese Patent Laid-Open No. JP-A a compound disclosed in Japanese Laid-Open Patent Publication No. JP-A-10-339949, and Japanese Patent Laid-Open Publication No. JP-B-5-72943, but the present invention is Not limited to these compounds.

As the dispersant as described above, at least one selected from the group consisting of compounds represented by the following formulae (D1), (D3), and (D4) is preferably used.

<1. Compound represented by the general formula (D1)>

General formula (D1) A-N=N-X-Y

In the formula (D1), A represents a component capable of forming an azo dye with X-Y. The component A can be arbitrarily selected as long as the component can form a compound of an azo dye after coupling with a diazonium compound. Specific examples of the component A are as follows, but the present invention is not limited to such compounds.

In the formula (D1), X is a group representing a single bond or a divalent linking group selected from the structural formulae of the general formulae (i) to (v) described below.

In the formula (D1), Y represents a group represented by the formula (D2) shown below.

In the formula (D2), Z represents a lower alkyl group. In other words, Z is representable as -(CH ₂ ) _b -, wherein b is an integer from 1 to 5, and preferably represents 2 or 3. In the formula (D2), -NR ₂₁ represents a lower alkylamino group or a nitrogen-containing 5 or 6 membered saturated heterocyclic group. If the -NR ₂₁ is a lower alkylamine group, the lower alkylamino group can be represented by -N(C _r H _2r+1 ) ₂ , wherein the r is an integer from 1 to 4, and preferably To represent 1 or 2. In the case where the -NR ₂₁ is a 5- or 6-membered saturated heterocyclic group which contains nitrogen, the heterocyclic group is preferably any heterocyclic group represented by the structural formula shown below.

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

Specific examples of the compound represented by the formula (D1) are as follows, but the invention is not limited to the examples.

The compound represented by the formula (D1) can be synthesized by a method disclosed in, for example, Japanese Laid-Open Patent Publication No. JP-A-2000-239554.

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

In the formula (D3), Q represents a compound selected from the group consisting of: an anthraquinone compound dye, an azo compound dye, an indocyanin compound dye, a quinophthalone compound dye, and two Compound dyes, pyrimidine compound dyes, anthrone compound dyes, indanthrone compound dyes, flavanthrone compound dyes, pyridone compound dyes, anthrone dyes, anthraquinone compound dyes, and thioindigo compound dyes Etc. organic dye residues. Among these organic dyes, preferred are azo compound dyes and two A compound dye, and more preferably an azo compound dye.

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

Y ₂ represents an alkylene group or an extended aryl group which may be substituted each. Among these groups, a phenyl group, a tolyl group and a hexyl group are preferred, and a phenyl group is more preferred.

R ₁₁ and R ₁₂ each independently represent a substituted or unsubstituted alkyl group, and another possibility is that R ₁₁ and R ₁₂ may be bonded together to form a heterocyclic group containing at least a nitrogen atom. Among these groups, a methyl group, an ethyl group, a propyl group, and a pyrrolidinyl group having a nitrogen atom are preferred, and an ethyl group is more preferred.

Y ₁ represents -NH- or -O-.

Z ₁ represents a hydroxyl group or a group represented by the formula (D3a), and the limitation is that if the n1 is 1, the Z ₁ may be -NH-X ₁ -Q. M1 is an integer representing 1 to 6, and is preferably 2 or 3. N1 is an integer representing 1 to 4, and is preferably 1 or 2.

In the formula (D3a), Y ₃ represents -NH-, or -O-, and ml, R ₁₁ and R ₁₂ have the same meanings as those in the formula (D3).

Specific examples of the compound represented by the formula (D3) are represented by the formula shown below.

Further, in the general formulae (D3-1) to (D3-6), Q, m1, n1, R ₁₁ and R ₁₂ have the same meanings as those in the general formula (D3). Specific examples of the compound represented by the formula (D3) are exemplified below, but the invention is not intended to be limited thereto. Hereinafter, Cu-Pc is a representative of copper anthraquinone.

Compound of the formula (D3) is represented by the three nitrogen by a dye for example by having a compound with an amine compound of R ₁₁ and R ₁₂ and R ₁₁ and R having the alcohol compound with a halogenating ₁₂ The intermediate product obtained by the reaction of the compound is obtained by a reaction. Further, the synthesis of the compound can also be referred to in the specification of Japanese Patent Application Laid-Open No. JP-B-5-72943.

<3. Pigment Dispersant Containing Graft Copolymer>

When the pigment fine particles as described above are prepared by a deposition method, it is also preferred to use a dispersing agent containing a graft copolymer having an amine group and an ether group, and optionally containing other components which are appropriately selected.

The graft copolymer as described above has at least an amine group and an ether group, and may also contain other monomers or the like as a copolymer unit.

The weight average molecular weight of the graft copolymer is preferably in the range of from 3,000 to 100,000, and more preferably in the range of from 5,000 to 50,000. If the weight average molecular weight is too small, it is difficult to prevent the pigment particles from aggregating, and sometimes the viscosity is increased. If the weight average molecular weight is too large, the solubility in an organic solvent becomes insufficient, and sometimes the viscosity may increase.

The graft copolymer as described above preferably contains at least (i) a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal, (ii) a single having an amine group and an ethylenically unsaturated double bond. And (iii) a polymerizable monomer having an ether group, and optionally (iv) another monomer as a copolymerization unit.

The content of each of the copolymer units in the graft copolymer is as follows: the content of the polymerizable oligomer is preferably in the range of 15 to 98% by mass, and more preferably in the range of from 25 to 90% by mass; (ii) the content of the amino group-containing monomer is preferably in the range of from 1 to 40% by mass, and more preferably in the range of from 5 to 30% by mass; and (iii) the polymerizable monomer having an ether group The content is preferably in the range of from 1 to 70% by mass, and more preferably in the range of from 5 to 60% by mass.

If the content of the polymerizable oligomer is too small, there is a possibility that the steric repulsion effect which should be achieved by the dispersing agent is hardly obtained, and as a result, it is difficult to prevent aggregation of the pigment particles. If the content of the polymerizable oligomer is too large, there is a possibility that the ratio of the monomer having an amine group is relatively decreased, and as a result, the adsorption ability to the organic fine particles is lowered, and the dispersibility sometimes becomes insufficient. Happening. If the content of the amino group-containing monomer is too small, there is a possibility that the dispersibility sometimes becomes insufficient due to a decrease in the adsorption ability to the organic fine particles. If the content of the monomer having an amine group is too large, there is a possibility that the ratio of the polymerizable oligomer is relatively decreased, and as a result, the steric repulsion effect which should be achieved by the dispersing agent is hardly obtained, making it difficult to obtain. The situation in which the pigment particles are agglomerated is sufficiently prevented. When the content of the polymerizable monomer having an ether group is too small, the development suitability at the time of producing a color filter or the like may sometimes become insufficient. When the content of the polymerizable monomer having an ether group is too large, there is a possibility that the ability to be used as a dispersing agent sometimes decreases.

(i) Polymerizable oligomer The polymerizable oligomer (herein sometimes referred to as "macromonomer") is a group having an ethylenically unsaturated double bond at one or both ends (ends thereof). Among the polymerizable oligomers as described above, in the present invention, it is preferred that the oligomer is a group having an ethylenically unsaturated double bond at one end only at the end of the oligomer.

With regard to the oligomer as described above, mention may be made of including, for example, alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, styrene, acrylonitrile, vinyl acetate. a homopolymer or a copolymer formed by at least one of a monomer such as an ester or butadiene. Among these oligomers, a homopolymer or a copolymer of alkyl (meth)acrylates and polystyrene are preferred. In the present invention, such oligomers may be further substituted. The substituent is not particularly limited; a halogen atom is an example which may be mentioned as a substituent.

Examples of the group having an ethylenically unsaturated double bond include: a (meth) acrylonitrile group and a vinyl group. Among these groups, a (meth)acryl fluorenyl group is particularly preferred.

Among these polymerizable oligomers used in the present invention, an oligomer represented by the following formula (E6) is preferred.

In the above formula (E6), R ⁶¹ and R ⁶³ each represent a hydroxyl group or a methyl group. R ⁶² is an alkylene group having 1 to 8 carbon atoms which may be substituted with an alcoholic hydroxyl group, and R ⁶² preferably represents an alkylene group having 2 to 4 carbon atoms. Y ⁶ is a phenyl group representing a phenyl group, an alkyl group having 1 to 4 carbon atoms, or -COOR ⁶⁴ (wherein R ⁶⁴ is a group having 1 to 6 carbon atoms and the group may be an alcoholic hydroxyl group or a halogen atom) a substituted alkyl group; a phenyl group, an aralkyl group having 7 to 10 carbon atoms; and Y ⁶ preferably represents a phenyl group, or -COOR ⁶⁴ (wherein R ⁶⁴ represents a group having 1 to 4 carbon atoms) It is an alkyl group which may be substituted with an alcoholic hydroxyl group). q is a number representing from 20 to 200.

Specific examples of the "polymerizable oligomer" include, for example, poly(methyl) methacrylate, polystyrene, poly(methyl) methacrylate, poly(meth)acrylic acid n-butyl Ester, poly(butyl) methacrylate, and copolymers of such monomers. Among these polymers, a polymer having a (meth)acryl fluorenyl group bonded to one end of the molecule is preferred.

The "polymerizable oligomer" may be a commercially available commercial grade product or may be suitably synthesized. Examples of commercially available commercial grade products include, for example, single-end methacryl oxime-based polystyrene oligomers (Mn = 6,000, trade name: AS-6, TOAGOSEI CO.). , LTD.)); single-end methacryl-methylated polymethyl methacrylate oligomer (Mn = 6,000, trade name: AA-6, manufactured by Toagosei Chemical Co., Ltd.); single-end methyl group Acryl thiolated poly-n-butyl acrylate oligomer (Mn = 6,000, trade name: AB-6, manufactured by East Asia Synthetic Chemical Co., Ltd.); single-end methacryl oxime-based polymethyl methacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7,000, trade name: AA-714, manufactured by Toagosei Chemical Co., Ltd.); single-end methacryl oxime polybutyl methacrylate / methyl 2-hydroxyethyl acrylate oligomer (Mn = 7,000, trade name: 707 S, manufactured by East Asia Synthetic Chemical Co., Ltd.); and single-end methacryl thiolated polyethyl methacrylate 2-ethylhexyl ester / 2-hydroxyethyl methacrylate oligomer (Mn = 7,000, Name: AY-707 S, AY-714 S, manufactured by Toagosei Chemical Industry Co., Ltd.) and the like.

In the present invention, a preferred specific example of the polymerizable oligomer is a polymer selected from the group consisting of alkyl (meth)acrylates, and a copolymer of alkyl (meth)acrylate and polystyrene. At least one oligomer, and having an oligomer having a number average molecular weight of 1,000 to 20,000, and an oligomer having a (meth) acrylonitrile group at the terminal.

(ii) Amino group-containing monomer With respect to the amine group-containing monomer, a preferred example is any compound represented by the following formula (E2).

In the above formula (E2), R ²¹ represents a hydroxyl group or a methyl group. R ²² is an alkylene group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, and particularly preferably 2 to 3 carbon atoms.

X ² represents -N(R ²³ )(R ²⁴ ), or -R ²⁵ N(R ²⁶ )(R ²⁷ ), wherein each of R ²³ and R ²⁴ represents a hydrogen atom, an alkane having 1 to 6 carbon atoms Or a phenyl group, and R ²⁵ is an alkylene group having 1 to 6 carbon atoms, and each of R ²⁶ and R ²⁷ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

R ²³ and R ^{24 in} -N(R ²³ )(R ²⁴ ) are preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and -R ²⁵ N(R ²⁶ ) (R ^{27 )} 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 are each representing 1 or 0. Preferably, if m2=1 and n2=1, and if m2=1 and n2=0. (The monomers obtained are corresponding to the monomers represented by the general formulae (E3) and (E4) as described below.)

In the present invention, among the monomers represented by the formula (E2), at least one monomer selected from the monomers represented by the formula (E3) or (E4) described below is preferably selected. .

In the above 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 above formula (E4), R ⁴¹ has the same meaning as R ²¹ . X ⁴ has the same meaning as X ² , and X ^{4 is} preferably -N(R ⁴³ )(R ⁴⁴ ) (wherein R ⁴³ and R ⁴⁴ have the same meaning as R ²³ and R ²⁴ ), or R ⁴⁵ N(R ⁴⁶ )(R ⁴⁷ ) (wherein R ⁴⁵ , R ⁴⁶ and R ⁴⁷ have the same meanings as R ²⁵ , R ²⁶ and R ²⁷ ).

Preferred specific examples of the monomer represented by the above formula (E2) include: "(meth)acrylamide" such as dimethyl(meth)acrylamide, diethyl (Meth) acrylamide, diisopropyl (meth) acrylamide, di-n-butyl (meth) acrylamide, di-iso-butyl (meth) acrylamide, morpholine (meth) acrylamide, piperidinyl (meth) acrylamide, N-methyl-2-pyrrolidinyl (meth) acrylamide, and N, N-methyl phenyl (methyl Ethyl amide; and "aminoalkyl (meth) acrylamide", such as 2-(N,N-dimethylamino)ethyl(meth) acrylamide, 2-(N, N-diethylamino)ethyl(meth)acrylamide, 3-(N,N-diethylamino)propyl(meth)acrylamide, 3-(N,N-dimethyl Amino) propyl (meth) acrylamide, 1-(N,N-dimethylamino)-1,1-dimethylmethyl(meth) acrylamide, and 6-(N , N-Diethylamino)hexyl (meth) acrylamide.

(iii) Polymerizable monomer having an ether group The polymerizable monomer having an ether group is preferably at least one selected from the group consisting of monomers represented by the following formula (E1).

In the above formula (E1), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² is an alkylene group representing an alkylene group having 1 to 8 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 2 to 3 carbon atoms. X ¹ represents -OR ¹³ or -OCOR ¹⁴ . Wherein R ¹³ is a phenyl group representing a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, or an alkyl group having 1 to 18 carbon atoms. The R ¹⁴ is an alkyl group having 1 to 18 carbon atoms. Moreover, m3 represents a number of 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 the monomer is polymerizable and has an ether group, and the monomer is appropriately selected from conventionally known monomers. Examples thereof include, for example, poly(ethylene) methacrylate, poly(meth)acrylic acid propylene glycol, poly(meth)acrylic acid ethylene glycol-propylene glycol ester, and poly-methacrylic acid tetra Methylene glycol ester and the like. Such materials may be commercially available product grade products, or may be suitably synthesized. Examples of such commercially available graded products include, for example, polymethoxyethylene glycol methacrylate [trade names: NK ESTER M-40G, M-90G, and M-230G (East Asian Synthetic Chemical Industry) Co., Ltd.); trade name: BLENMER-PME-100, PME-200, PME-400, PME-1000, PME-2000 and PME-4000 (Nippon Oil & Fats Co., Ltd. ))); polyethylene monomethacrylate (trade name: BLENMER-PE-90, PE-200, and PE-350 (manufactured by Nippon Oil & Fats Co., Ltd.)); poly(propylene glycol methacrylate) (commodity) Name: BLENMER-PP-500, PP-800 and PP-1000 (manufactured by Nippon Oil & Fat Co., Ltd.)); Polyethylene glycol methacrylate-propylene glycol (trade name: BLENMER-70PEP-370B) Manufactured by the company); poly(ethylene glycol methacrylate-tetramethylene glycol ester (trade name: BLENMER-55PET-800 (manufactured by Nippon Oil & Fats Co., Ltd.)); and poly(methacrylic acid propylene glycol-tetrazol) Methyl glycol ester (trade name: BLENMER-NHK-5050 (Japan Oils and Fats has Inc.)) and so on.

(iv) Other monomers The graft copolymer system as described above may further contain other monomers as described above as the copolymer unit, and the other monomers are not particularly limited, and they may be The purpose is chosen appropriately. Examples of other monomers include, for example, aromatic vinyl compounds (for example, styrene, α-methylstyrene, vinyltoluene); alkyl (meth)acrylates (for example, (meth)acrylic acid) Esters, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl methacrylate); alkyl aryl (meth) acrylates (eg, benzyl (meth) acrylate) Methyl ester); glycidyl (meth)acrylate; vinyl carboxylate (eg, vinyl acetate, vinyl propionate); vinyl cyanide (eg, (meth)acrylonitrile, alpha-chloroacrylonitrile) And aliphatic conjugated dienes (for example, 1,3-butadiene, isoprene); and (meth)acrylic acid. Among these monomers, unsaturated carboxylic acids, alkyl (meth)acrylates, alkyl aryl (meth)acrylates, and vinyl carboxylates are preferred.

The content of the other monomer in the graft copolymer as described above is preferably, for example, in the range of from 5 to 70% by mass. If the content is too small, it sometimes becomes difficult to control the physical properties of the coating film. If the content is too large, sometimes the grafted copolymer becomes difficult to fully exhibit its ability as a dispersing agent.

Preferred specific examples of the graft copolymer include, for example, (11) 3-(N,N-dimethylamino)propyl acrylamide/poly(ethylene) acrylate/ a copolymer of methyl methacrylate-methylated methyl (meth) acrylate; (12) 3-(N,N-dimethylamino)propyl acrylamide/poly(meth)acrylic acid a copolymer of ethylene glycol ester/terminal methacryl oxime polystyrene; (13) 3-(N,N-dimethylamino)propyl acrylamide/poly(meth)acrylic acid Ethylene glycol ester / methyl (meth) acrylate / terminal methacryl oxime polystyrene copolymer; (14) 3-(N, N-dimethylamino) propyl decylamine Copolymer of a copolymer of methyl (meth) acrylate / terminal methacryl thiolated methyl (meth) acrylate and 2-hydroxyethyl methacrylate; (17) 3 -(N,N-Dimethylamino)propyl acrylamide/poly(meth)acrylic acid propylene glycol/terminal methacryl fluorenated poly(methyl) acrylate copolymer; 18) 3-(N,N-Dimethylamino)propyl acrylamide/poly(meth)acrylic acid ethylene glycol-propylene glycol a copolymer of methyl methacrylate-methylated methyl (meth) acrylate; (19) 3-(N,N-dimethylamino)propyl acrylamide/poly(methyl) a copolymer of ethylene glycol acrylate-tetramethylene glycol ester/terminal methacryl fluorenated poly(methyl) acrylate; (20) 3-(N,N-dimethylamino) A copolymer of propyl acrylamide/poly(meth)acrylic acid propylene glycol-tetramethylene glycol ester/terminal methacryl oxime-based poly(methyl) acrylate.

Among these copolymers, (11), (14) and (18) are preferred. More preferably, it is a compound represented by the following formula (D4). In the formula (D4), Me represents a methyl group.

The graft copolymer as described above can be obtained by radical polymerization of a component constituting a unit of the copolymer as described above, for example, in a solvent. When the radical polymerization is carried out, a radical polymerization initiator can be used. Further, a chain transfer agent (for example, 2-hydrogenthioethanol, and dodecyl mercaptan) can also be further used. The pigment dispersant containing a graft copolymer is also produced by the method disclosed in Japanese Laid-Open Patent Publication No. JP-A-2001-31885.

In order to further improve the uniform dispersibility and storage stability of the pigment fine particles, the content of the dispersant is preferably in the range of from 0.1 to 1,000 parts by mass, more preferably in the range of from 1 to 500 parts by mass, and further preferably. It is based on 100 parts by mass of the pigment in the range of from 5 to 20 parts by mass. If the content is too small, there is a possibility that the dispersion stability of the pigment fine particles is not improved. The dispersing agent may be used alone or in combination of several kinds of dispersing agents.

In order to further improve the uniform dispersibility and storage stability of the organic fine particles, the content of the dispersant is preferably in the range of from 0.1 to 1,000 parts by mass, more preferably in the range of from 1 to 500 parts by mass, and further preferably. It is based on 100 parts by mass of the organic fine particles in the range of from 5 to 20 parts by mass. If the content is too small, there is a possibility that the dispersion stability of the organic fine particles is not improved. The dispersing agent may be used alone or in combination of several kinds of dispersing agents.

(concentrate)

The concentrate of the color filter coating liquid or the ink jet type ink can be produced on an industrial scale by desalting and concentrating the pigment fine particle dispersion.

There is no particular limitation on the concentration method as long as the pigment fine liquid can be concentrated by this method. An example of a preferred concentration method includes, for example, adding a mixed extraction solvent to the pigment microparticle dispersion, concentrating the pigment microparticles into the extraction solvent phase, and filtering the concentrated extract by a filter or the like to prepare a concentrated solution. a method of nanoparticle liquid; a method of concentrating pigment particles by centrifugation; a method of desalting and concentration by ultrafiltration; a method of sublimating a solvent by vacuum freeze drying; and heating or subtracting The method of drying the solvent and concentrating it is pressed. Another possible and excellent method is to use a combination of two or more of these methods.

The concentration of the pigment fine particles after concentration is preferably from 1 to 100% by mass, more preferably from 5 to 100% by mass, and particularly preferably from 10 to 100% by mass.

The extraction solvent used in the steps of concentration and extraction is not particularly limited, and is preferably a solvent which is substantially incompatible (immiscible) with a dispersion solvent (for example, an aqueous solvent) of the pigment microparticle dispersion. In the specification of the present invention, the term "substantially incompatible" means that the compatibility thereof is low, and the amount of the extraction solvent soluble in the dispersion solvent is preferably 50% by mass or less, and more preferably 30% by mass or less. Although the extraction solvent is not soluble in the amount of the dispersion solvent, there is no particular lower limit, but in practice, if the solubility in a general solvent is considered, the amount is 1% by mass or more, and in the extraction The solvent is mixed with the dispersion solvent and allowed to stand to form a solvent at the interface. In addition to this, the extraction solvent is preferably a solvent which causes weak agglomeration so that the pigment particles can be redispersed in the extraction solvent. As used herein, the term "weak redispersibility agglomeration" means a floc that is redispersible without the application of high shear forces, such as by grinding or high speed agitation. It is preferable in such a state because it can prevent strong agglomeration which may cause a change in particle size, and can swell the desired pigment particles with an extraction solvent, in addition to dispersing a solvent such as water. It can also be removed easily and quickly by filter filtration. The extraction solvent is preferably an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, or an aliphatic compound solvent; more preferably an ester compound solvent, an aromatic compound solvent, or an aliphatic compound solvent; Particularly preferred are ester compound solvents.

Examples of the "ester compound solvent" include, for example, 2-(1-methoxy)propyl acetate, ethyl acetate, ethyl lactate, and the like. Examples of the "alcohol compound solvent" include, for example, n-butanol, isobutanol, and the like. Examples of the "aromatic solvent" include, for example, benzene, toluene, xylene, and the like. Examples of the "aliphatic compound solvent" include, for example, n-hexane, cyclohexane, and the like. Further, the extraction solvent may be one of the preferred solvents as described above, and it may also be a mixed solvent of several solvents.

The amount of the extraction solvent is not particularly limited as long as the solvent is an extractable pigment fine particle, but if it is considered that concentrated extraction is required, the amount of the extraction solvent is preferably less than the amount of the pigment fine particle dispersion. If it is expressed by volume ratio and it is assumed that the pigment fine particle dispersion is 100, the addition amount of the extraction solvent 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. The scope. If it is too much, it will cause the enrichment time to be prolonged. However, if it is too small, the extraction may be insufficient to allow the nanoparticles to remain in the dispersion solvent.

After the extraction solvent is added, it is preferably thoroughly stirred and mixed so that it can sufficiently contact the dispersion. Stirring mixing can be carried out using any conventionally used method. The temperature at the time of addition and mixing of the extraction solvent is not particularly limited, but is preferably from 1 to 100 ° C, and more preferably from 5 to 60 ° C. Any apparatus may be used as long as it can appropriately carry out the steps of addition and mixing of the extraction solvent, and for example, it can be carried out using a separatory funnel type apparatus.

Regarding the method of ultrafiltration, a method used for desalting/concentrating of a silver halide emulsifier is suitably used. Examples of such methods are disclosed in Research Disclosure, No. 10, page 208 (1972), No. 13, page 122 (1975), and No. 16, page 351 (1977). Regarding the important pressure difference or flow rate in the operating conditions, it can be referred to the "Membrane Utilization Technique Handbook" by Haruhiko Oya, published by Saiwai Shobo, (1978). The characteristic curve disclosed on page 275 is selected, but in terms of processing the target pigment particle dispersion composition, it is necessary to find the optimum conditions to inhibit the aggregation of the particles. Further, regarding the method for replenishing the solvent lost due to the permeation of the membrane, there are a fixed volume type in which a solvent is continuously added, and a batch type in which the addition is intermittently added. In the present invention, it is preferred that the desalination treatment time is a relatively short fixed volume type. The solvent supplemented as described above is usually pure water obtained by ion exchange or distillation. The dispersant or dispersant may be mixed with the poor solvent in pure water. It is also possible to add the dispersant or dispersant directly to the pigment particle dispersion with a poor solvent.

About "Ultrafiltration Membrane", a separator that has been used in combination with a flat type, a spiral type, a cylindrical type, a hollow fiber type, a hollow fiber type, etc. is commercially available as a commercial grade available from Asahi Chemical Industry Co., Ltd. (Asahi Chemical Industry Co., Ltd.) Co., Ltd.), Daicel Chemical Industry Co., Ltd., Toray Industries, Inc., NITTO DENKO CORP., and the like. From the viewpoint of total membrane area or detergency, these are preferably hollow fiber type and spiral type. Further, the fractional molecular weight which can be used as an index of the threshold of the substance permeable to the separator must be determined depending on the molecular weight of the dispersant to be used. In the present invention, it is preferred to use those having a classification molecular weight of 5,000 to 50,000, and more preferably 5,000 to 15,000.

In order to separate the dispersion solvent of the pigment fine particle dispersion from the concentrated extract, it is preferred to filter by using a filter. As the means for filtering the filter, for example, a device for pressure filtration can be used. Preferred filters include, for example, nano filters, ultrafilters, and the like. It is preferred to filter by a filter to remove the residual dispersion solvent, and further to further concentrate the pigment fine particles in the concentrated extract to obtain a concentrated nanoparticle liquid.

The method of freeze-drying is not particularly limited, and any method can be employed as long as it is familiar to those skilled in the art. Examples of the "freeze drying method" include, for example, a direct refrigerant expansion method, a multiple freezing method, a heat medium circulation method, a triple heat exchange method, and an indirect heating freezing method. Among these, it is preferred to employ a direct refrigerant expansion method, an indirect heating freezing method, and more preferably an indirect heating freezing method. In each method, it is preferred to carry out pre-freezing before performing freeze-drying. Although the conditions of the pre-freezing are not particularly limited, it is necessary to uniformly freeze the sample to be freeze-dried.

The apparatus for "indirect heating and freezing method" includes, for example, a small freeze dryer, an FTS freeze dryer, a LYOVAC freeze dryer, an experimental freeze dryer, a research freeze dryer, a triple heat exchange vacuum freeze dryer, and a single cooling. Freeze dryer, HULL freeze dryer, etc. Among these, a small freeze dryer, an experimental freeze dryer, a research freeze dryer, and a single-cooling freeze dryer are preferable; and a small freeze dryer or a single-cooling freeze dryer is more preferably used.

Although the temperature of the freeze-drying is not particularly limited, it is, for example, -190 to -4 ° C, preferably about -120 to -20 ° C, and more preferably about -80 to -60 ° C. The pressure of freeze-drying is also not particularly limited, and may be appropriately selected by those skilled in the art, but it is recommended that the freeze-drying is, for example, about 0.1 to 35 Pa, preferably 1 to 15 Pa, and more preferably about It is carried out under a pressure of 5 to 10 Pa. The freeze-drying time is, for example, about 2 to 48 hours, preferably about 6 to 36 hours, or more preferably about 16 to 26 hours. However, it should be noted that such conditions are suitably selected by those skilled in the art. For the freeze drying method, for example, the "Pharmaceutical Machinery and Engineering Handbook": JAPAN SOCIETY OF PHARMACEUTICAL MACHINERY AND ENGINEERING, edited by Chijinshokan Co., Ltd., Pages 120 to 129 (September 2000); Vacuum Handbook: Edited by ULVAC, Inc., published by Ohmsha, Ltd., pp. 328-331 (1992) Year); or Freezing and Drying workshop paper: published by Koji Ito et al., 15th, 82nd (1965), etc.

The centrifugal separator used for concentrating the pigment fine particles by the centrifugal separation method may be any device as long as the pigment fine particles in the pigment fine particle dispersion liquid (or the pigment fine particle concentrated extract liquid) can be sedimented. Examples of the centrifugal separator include, for example, a general-purpose device, a system having a function of removing scum (that is, a function of pumping a liquid layer to the outside of the system when the system is rotated), and continuously A continuous centrifugal separator that discharges solids, and the like.

With respect to the conditions of the centrifugal separation, the centrifugal force (i.e., the ratio of the applied centrifugal acceleration to the gravitational acceleration) is preferably from 50 to 10,000, more preferably from 100 to 8,000, and particularly preferably from 150 to 6,000. The temperature at the time of centrifugation depends on the kind of the solvent of the dispersion, but is preferably -10 to 80 ° C, more preferably -5 to 70 ° C, and particularly preferably 0 to 60 ° C.

The apparatus used for concentrating the pigment fine particles by the vacuum drying method is not particularly limited as long as the solvent in the pigment fine particle dispersion (or the pigment fine particle concentrated extract) can be evaporated. Examples of devices that can be used include, for example, a general-purpose vacuum dryer and a general-purpose rotary pump; a device capable of heating and decompressing a liquid while stirring a liquid; and a device capable of reducing the liquid by internal heating A device that continuously performs drying by pressing a tube.

The temperature for heating under reduced pressure is preferably from 30 to 230 ° C, more preferably from 35 to 200 ° C, and particularly preferably from 40 to 180 ° C. The pressure for the pressure reduction is preferably from 100 to 100,000 Pa, more preferably from 300 to 90,000 Pa, and particularly preferably from 500 to 80,000 Pa.

According to the concentration method as described above, the pigment fine particles can be efficiently concentrated from the pigment fine particle dispersion. With respect to the concentration ratio, for example, when the concentration of the nanoparticles in the pigment microparticle dispersion as a raw material is 1, the concentration in the concentrated pigment microparticle paste is preferably about 100 to 3,000 times, and more preferably about 500 to 2,000 times.

[fine dispersion]

When the pigment fine particles are in agglomerated state due to concentration or the like as described above, it is preferred to finely disperse the aggregate. (In the specification of the present invention, the term "finely dispersed" means a step for releasing the particles in the dispersion from the agglomerated state, thereby enhancing the degree of dispersion thereof.

The organic fine particles contained in the organic fine particle liquid concentrated by the extraction solvent, centrifugation, and drying as described above are usually in a state of aggregation due to concentration of the organic fine particles. In order to enable rapid filtration and to obtain a superior dispersion state, it is preferred to obtain pigment particles as described above for flocs. The so-called "flock" is an aggregate in which fine particles are weakly condensed and redispersible (soft agglomerated). By forming the pigment fine particles into flocs, it is possible to rapidly separate the organic pigment fine particles precipitated in the aqueous mixed solution by, for example, filtration from the medium. Moreover, it is effective to form a color filter which is dispersed in an organic solvent (non-aqueous dispersion composition) by redispersing the separated floc (soft aggregate) in an organic solvent. Pigment dispersion composition. In other words, when the mixed solvent of the good solvent and the poor solvent is an aqueous solvent, the dispersion medium (continuous phase) can be changed by efficiently replacing the aqueous solvent with a third solvent composed of an organic solvent. The average particle diameter of the floc is not particularly limited, but is preferably from 0.5 to 500 μm, and more preferably from 5 to 100 μm, in consideration of the filtration efficiency as described above. Further, in the specification of the present invention, a solvent different from both the good solvent (first solvent) and the poor solvent (second solvent) is collectively referred to as "third solvent".

Further, in the case where some of the fine particles are insufficient to sufficiently disperse the fine particles by a general dispersion method, it is necessary to carry out a method having a higher finening efficiency. Even if the organic fine particles are in a strongly agglomerated state, by introducing a polymer compound having a number average molecular weight of 1,000 or more into the agglomerated organic fine particle liquid, it is also possible to make the organic fine particles appropriately finely and dispersed. Dispersing solution. (In the specification of the present invention, the term "aggregated organic fine particles" means an aggregate of organic particles collected by a secondary force, such as an aggregate; if it is a primary particle of a nanometer size, then The term "aggregated nanoparticle" is also referred to as "aggregated nanoparticle". (In the present specification, the term "aggregated organic microparticle" means a liquid containing agglomerated organic microparticles, and the liquid may be, for example, a dispersion, a concentrate, or a paste. Or a slurry, as long as the liquid contains agglomerated organic fine particles.) More specifically, when a mixed solution containing a good solvent and a poor solvent is precipitated, by adding a polymer compound, excellent fine dispersion can be obtained. Properties (that is, properties that achieve uniform and fine particle size) and excellent dispersion stability (that is, properties that maintain uniformity and fine particle size over a long period of time), even when the medium is changed to be suitable for color filters. After the organic solvent is dispersed, the fine particles can be re-dispersed in the medium to maintain uniformity, thereby realizing a high-performance color filter. In addition, the polymer compound can further improve the color filter by interacting with the coloring property of the organic pigment particles without deteriorating the optical characteristics and other characteristics of the color filter. Characteristics of liquid crystal display devices.

The polymer compound as described above is preferably a polymer compound represented by the following formula (1).

In the formula (1), A ¹ represents a group having a carbon atom selected from the group consisting of an acidic group, a nitrogen-containing basic group, a urea group, a urethane group, and a coordinating oxygen atom. a "monovalent organic group" of a group consisting of a hydrocarbon group of 4 or more, an alkoxyalkyl group, an epoxy group, an isocyanate group, and a hydroxyl group; or an organic dye structure or a hetero group each of which may be substituted The "one-price organic base" of the ring. If n is 2 or more, then several A ¹ 's may be the same or different.

Specifically, there is no particular limitation on A ¹ . Examples of the "acid group-valent organic group" include an organic group having an acidic group such as a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate group, and a boric acid group. In addition, examples of the "monovalent organic group having a nitrogen-containing basic group" include: a monovalent organic group having an amine group (-NH ₂ ), and a substituted imido group (-NHR ⁸ , —NR ⁹ R ¹⁰ ) a monovalent organic group (wherein R ⁸ , R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or An aralkyl group having 7 to 30 carbon atoms, which is a "monovalent organic group having a fluorenyl group" represented by the following formula (a1) (wherein, in the formula (a1), R ^a1 and R ^a2 are Each 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 represented by the following formula (a2) "having a fluorenyl group-valent organic group" (wherein, in the formula (a2), R ^a3 and R ^a4 each independently represent an alkyl group having 1 to 20 carbon atoms, and have 6 to 20 carbon atoms An aryl group, or an aralkyl group having 7 to 30 carbon atoms).

Examples of the "monovalent organic group having a urea group" include, for example, -NHCONHR ¹⁵ (wherein R ¹⁵ is a hydrogen atom or an alkyl group having from 1 to 20 carbon atoms, and has a carbon number of from An aryl group of 6 to 20 or an aralkyl group having from 7 to 30 carbon atoms or the like.

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

Examples of the "valent organic group having a "coordinating oxygen atom-containing group" include, for example, a group having an ethyl acetoacetone group, a group having a crown ether, and the like.

Examples of the "monovalent organic group having a hydrocarbon group having 4 or more carbon atoms" include: an alkyl group having 4 or more carbon atoms (for example, an octyl group, a dodecyl group, etc.) having a carbon number An aryl group of 6 or more (e.g., phenyl, naphthyl, etc.), an aralkyl group having 7 or more carbon atoms (e.g., benzyl group, etc.), and the like. Although there is no upper limit on the number of carbon atoms of these groups; however, the number of carbon atoms is preferably 30 or less.

Examples of the "monovalent organic group having an alkoxyalkyl group" include, for example, a group having a trimethoxyalkyl group, a triethoxyalkyl group or the like.

Examples of the "monovalent organic group having an epoxy group" include, for example, a group having a glycidyl group or the like.

Examples of the "monovalent organic group having an isocyanate group" include, for example, 3-isocyanatopropyl group and the like.

Examples of the "one-valent organic group having a hydroxyl group" include, for example, 3-hydroxypropyl group and the like.

In the group represented by A ¹ as described above, it is preferred to have a value of any one of an acidic group, a nitrogen-containing basic group, a urea group, and a hydrocarbon group having 4 or more carbon atoms. Organic base.

The "organic dye structure or heterocyclic ring" as described above is not particularly limited. More specifically, however, examples of the "organic dye structure" include, for example, an anthraquinone compound, an insoluble azo compound, an azo lake compound, an anthraquinone compound, a quinophthalone compound, and two. A compound, a diketopyrrolopyrrole compound, an anthrapyridine compound, an anthrone compound, an indanthrone compound, a yellow ketone compound, an anthrone compound, an anthraquinone compound, and a thioindigo compound. Further, examples of the "heterocycle" include, for example, thiophene, furan, (xanthene), pyrrole, pyrroline, pyrrolidine, two Dioxolane, pyrazole, pyrazoline, pyrazole, imidazole, Oxazole, thiazole, Diazole, triazole, thiadiazole, piperazine, pyridine, piperidine, two Alkane, morpholine, anthracene Pyrimidine, piperazine Trinitrogen , trithiane, isoporphyrin, isoindolinone, benzimidazolone, amber imine, phthalimide, naphthyl imine, carbendazim, hydrazine, quin Porphyrin, carbazole, acridine, acridone, and hydrazine.

The "organic dye structure or heterocyclic ring" as described above may also have a substituent T, and examples of the "substituent T" include, for example, an alkyl group having 1 to 20 carbon atoms (for example, a methyl group or an ethyl group). An aryl group having 6 to 16 carbon atoms (for example, a phenyl group, a naphthyl group), a decyloxy group having 1 to 6 carbon atoms (for example, an ethoxy group), and an alkane having 1 to 6 carbon atoms An oxy group (for example, a methoxy group, an ethoxy group), a halogen atom (for example, chlorine, bromine), an alkoxycarbonyl group having 2 to 7 carbon atoms (for example, a methoxycarbonyl group, an ethoxycarbonyl group, Cyclohexylhydroxycarbonyl), cyano, carbonate (for example, tertiary butyl carbonate), hydroxyl, amine, carboxyl, sulfonylamino, and N-sulfonylguanamine.

Further, A ¹ as described above may be represented by the following general formula (4).

In the formula (4), B ¹ represents a group selected from an acidic group, a nitrogen-containing basic group, a urea group, a urethane group, a ligand-containing oxygen atom, having a carbon number of 4 or A group of a group consisting of a hydrocarbon group, an alkoxyalkyl group, an epoxy group, an isocyanate group, and a hydroxyl group; or an "organic dye structure" or a heterocyclic ring each of which may be further substituted. R ¹⁸ is an organic or inorganic linking group representing a single bond or (a1+1)-valent. A1 is representative of 1 to 5. Here, when a1 is 2 or more, the number of B ¹ s may be the same or different.

A preferred specific example of the group represented by the formula (4) is the same as A ¹ as described above.

R ¹⁸ is a linking group representing a single bond or (a1+1)-valent. A1 is representative of 1 to 5. Examples of the linking group represented by R ¹⁸ include: from 1 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. A group consisting of an atom or the like, wherein the group may be unsubstituted or substituted with a substituent. R ¹⁸ is preferably an organic linking group.

Specific examples of R ¹⁸ include, for example, structural units as described below, or a group composed of a combination of the structural units. In addition to this, the linking group R ¹⁸ may have a "substituent T" as described above.

In the above formula (1), R ¹ is a linking group representing a (m+n)-valent group. m+n is in the range of 3 to 10.

Examples of the (m+n)-valent linking group represented by R ¹ include: from 1 to 100 carbon atoms, from 0 to 10 nitrogen atoms, from 0 to 50 oxygen atoms, from 1 to 200 hydrogen atoms, And a group consisting of atoms of 0 to 20 sulfur atoms or the like, wherein the group may be unsubstituted or substituted with a substituent. R ¹ is preferably an organic linking group.

Examples of R ¹ include a group of (t-1) to (t-34) as described above, or a group composed of a combination of a plurality of such groups (which may have a ring structure). If the linking group R ¹ as described above is a substituent, an example of the substituent includes the substituent T as described above.

R ² represents a single bond or a divalent linking group. Examples of R ² include: consisting of atoms having from 1 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 the like. a group wherein the group is unsubstituted or substituted with a substituent. Specific examples of R ² include: t-3 to t-5, t-7 to t-18, t-22 to t-26, t-32, and t-34 as described above, or a plurality of The basis of the basis. Preferably, R ² is a position having a sulfur atom bonded to R ¹ at the R ² . If R ² is a case having a substituent, examples of the substituent include the substituent T as described above.

In the above formula (1), m is represented by 1 to 8, and m is preferably from 1 to 5, more preferably from 1 to 3, and particularly preferably from 1 to 2.

n represents 2 to 9, and n is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.

In the above formula (1), P ¹ represents a polymer skeleton. This polymer skeleton is suitably selected from a general polymer.

If it is desired to form a polymer backbone, it is preferred to use a polymer or copolymer derived from a vinyl monomer, an ester compound polymer, an ether compound polymer, a urethane compound polymer, a guanamine. a compound polymer, an epoxy compound polymer, a polyoxymethylene polymer, and the like, or a copolymer (including, for example, a polyether/polyurethane copolymer, and a polyether) a copolymer of a polymer derived from a vinyl monomer, etc.; such a copolymer may be a group consisting of a random copolymer, a block copolymer, and a graft copolymer At least one of; and more preferably selected from the group consisting of polymers or copolymers derived from vinyl monomers, ester compound polymers, ether compound polymers, urethane compound polymers, and the like. Or at least one of the groups consisting of a copolymer; and particularly preferably a homopolymer or a copolymer derived from a vinyl monomer.

Besides, it is preferred that the polymer is soluble in an organic solvent. When the affinity between the polymer and the organic solvent is low, if the polymer is used as, for example, a pigment dispersant, the affinity between the polymer and the dispersion medium may be weak. Therefore, it sometimes happens that it is difficult to secure a sufficient adsorption layer for dispersion stabilization.

It is preferred that P ¹ has a sulfur atom at a position where the P ^{1 is} bonded to R ¹ .

Among the polymer compounds represented by the above formula (1), those polymer compounds represented by the formula (2) are more preferred.

In the above formula (2), A ² has the same meaning as A ¹ in the above formula (1). Specific and preferred specific examples of A ² and A ¹ are the same person. A ² may also have a substituent, and an example thereof includes the substituent T as described above.

In the above formula (2), R ³ is a linking group representing a (x + y)-valent group. R ³ has the same meaning as R ¹ . The preferred range of R ³ to R ¹ is the same person. If R ³ is a group representing a (x + y)-valent linking group, the value of x and its preferred range are the same as those in the general formula (1). Similarly, the value of y and its preferred range are the same as those of m; the value of x+y and its preferred range are the same as those of m+n.

The linking group represented by R ³ is preferably an organic linking group. Preferred specific examples of the organic linking group are as described below. However, the invention is not limited thereto.

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

If R ³ is a substituent, an example of the substituent includes the substituent T as described above.

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

With respect to the "divalent linking group" represented by R ⁴ and R ⁵ as described above, it is preferably a linear, branched or cyclic alkyl group or an extended aryl group which may be substituted as needed. Or an aralkyl group, -O-, -S-, -C(=O)-, -N(R ¹⁹ )-, -SO-, -SO ₂ -, -CO ₂ -, or -N (R ²⁰ ) SO ₂ -, or a divalent group of (wherein, R ¹⁹ and R by the combination of two or more of these groups are formed by ²⁰ each independently represent a hydrogen atom or a carbon atoms, alkoxy of 1 to 4 base). The divalent linking group as described above is preferably an organic linking group.

With respect to R ⁴ , a linear or branched alkyl or aralkyl group, or -O-, -C(=O)-, -N(R ¹⁹ )-, -SO ₂ -, - is preferred. CO ₂ -, or -N(R ²⁰ )SO ₂ -, or a divalent group formed by combining two or more of these groups. Particularly preferred are linear or branched alkyl or aralkyl groups, or -O-, -C(=O)-, -N(R ¹⁹ )-, or -CO ₂ -, or by combination A divalent group formed by two or more such groups.

With respect to R ⁵ , a single bond, a straight or branched alkyl or aralkyl group, or -O-, -C(=O)-, -N(R ¹⁹ )-, -SO ₂ is preferred. -, -CO ₂ -, or -N(R ²⁰ )SO ₂ -, or a divalent group formed by combining two or more of these groups. Particularly preferred are linear or branched alkyl or aralkyl groups, or -O-, -C(=O)-, -N(R ¹⁹ )-, or -CO ₂ -, or by combination A divalent group formed by two or more such groups.

If R ⁴ or R ⁵ is a case having a substituent, examples of the substituent include the substituent T as described above.

P ² in the formula (2) represents a polymer compound residue (polymer skeleton) and may be appropriately selected from a general polymer. A preferred specific example of the polymer is the same as P ¹ in the above formula (1), and a preferred specific example thereof is also the same as P ¹ .

Among the polymer compounds represented by the above formula (2), it is particularly preferred that in the polymer compound, R ³ is as described above (r-1), (r-2), ( a specific group such as r-10), (r-11), (r-16), or (r-17); R ⁴ is a single bond, a straight or branched alkyl or an aralkyl group, or -O-, -C(=O)-, -N(R ¹⁹ )-, or -CO ₂ -, or a divalent organic group formed by combining two or more of these groups; R ⁵ is a single bond, an ethyl group, a propyl group, or a linker represented by the formula (s-a) or (s-b) as described below; P ² is a polymer derived from a vinyl monomer or a total of a polymer, an ester compound polymer, an ether compound polymer, a urethane compound polymer, or a modified compound of such polymers; y is 1 to 2; and x is 3 to 6. In the following groups, R ²¹ represents a hydrogen atom or a methyl group; and 1 represents a 1 or 2.

The polymer compound as described above has a weight average molecular weight of at least 1,000, preferably from 3,000 to 100,000, more preferably from 5,000 to 80,000, and particularly preferably from 7,000 to 60,000. If the weight average molecular weight is within the range as described above, a plurality of functional groups at the end of the introduced polymer can sufficiently exert their effects, and thus can be adsorbed on a solid surface, and the micelle (micelle) Excellent performance in terms of formability, interface activation, and the like. Thereby, excellent dispersibility and dispersion stability can be achieved.

Specific examples of the compound represented by the formula (1) are as described below. However, the present invention is not limited to such specific examples.

As the polymer compound having a weight average molecular weight of at least 1,000 as described above, any of the following polymer compounds having an acidic group (hereinafter, this compound is also simply referred to as "acid group-containing polymer compound") can be used. As the polymer compound, a polymer compound having a carboxyl group is preferred. More preferred are copolymerized compounds containing (A) at least one repeating unit derived from a compound having a carboxyl group and (B) at least one repeating unit derived from a compound having a carboxylate group.

The repeating unit (A) derived from the compound having a carboxyl group is preferably a repeating unit represented by the following general formula (I), and more preferably a repeating unit derived from acrylic acid or methacrylic acid; The repeating unit (B) of the compound of the carboxylate group is preferably a repeating unit represented by the following formula (II), more preferably a repeating unit represented by the following formula (IV), and particularly preferred Repetitive unit derived from benzyl acrylate, benzyl methacrylate, phenylethyl acrylate, phenylethyl methacrylate, 3-phenylpropyl acrylate or 3-phenylpropyl methacrylate .

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

(R ₂ is an alkyl group representing a hydrogen atom or having 1 to 5 carbon atoms. R ₃ is a group represented by the following formula (III).)

(R ₄ is an alkyl group having 1 to 5 carbon atoms, or a hydroxyl 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 is an alkyl group each representing a hydrogen atom or having 1 to 5 carbon atoms; and i is a number representing 1 to 5.)

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

(R ₉ is an alkyl group having 2 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms. R ₁₀ and R ₁₁ each represent a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms. j is the number representing 1 to 5.)

Regarding the polymerization ratio between the repeating unit (A) derived from the compound having a carboxyl group and the repeating unit (B) derived from the compound having a carboxylate group, the repeating unit (A) relative to the total repeating unit The number ratio (%) of the number is preferably from 3 to 40, and more preferably from 5 to 35.

In the specification of the present invention, the "molecular weight" of the polymer means "number average molecular weight" unless otherwise stated. Examples of the method for measuring the molecular weight of the polymer include chromatography, viscosity, light scattering, sedimentation speed, and the like. In the specification of the present invention, the number average molecular weight measured by gel permeation chromatography (GPC) (carrier: tetrahydrofuran) in terms of polystyrene is used unless otherwise specified.

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

The polymer compound may be added in a state of being dissolved in an aqueous solvent or an organic solvent, or may be added in a solid state. In addition to this, it is also possible to combine and use these addition methods. An example of the method of adding the polymer compound in a state of being dissolved in a solvent includes, for example, a method of adding a polymer compound to the agglomerated organic fine particle liquid in a state of being dissolved in the same solvent as the agglomerated organic fine particle liquid; And a method of adding the polymer compound to the agglomerated organic fine particle liquid in a state of being dissolved in a different solvent compatible with the solvent of the agglomerated organic fine particle liquid. When the polymer compound is added in a state of being dissolved in a solvent, the concentration of the polymer compound is not particularly limited, but the concentration thereof is preferably from 1 to 70% by mass, more preferably from 2 to 65% by mass. And particularly preferably from 3 to 60% by mass.

The polymer compound may be added at or after the precipitation and formation of the pigment particles, may be added before or after concentration, may be added before or after the concentrated agglomerated organic particles are concentrated, or may be added after the steps are completed. . Another possibility is that the polymer compound can be added in several portions in several portions. In the present invention, a polymer compound having a weight average molecular weight of 1,000 or more as described above may be used in combination as a binder as described above. For example, it is preferred that the polymer compound is added when the aggregated organic fine particles obtained after the concentration of the pigment fine particles-precipitating solution are finely dispersed.

The amount of the polymer compound to be added is preferably from 0.1 to 1,000 parts by mass, more preferably from 5 to 500 parts by mass, even more preferably from 10 to 300 parts by mass, per 100 parts by mass of the pigment fine particles.

Examples of the polymer compound, in addition to the compounds as described above, include, for example, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, poly Propylene glycol, polypropylene decylamine, vinyl alcohol-vinyl acetate copolymer, polyvinyl alcohol-particulate formaldehyde, polyvinyl alcohol-partial butyralate, vinyl pyrrolidone-vinyl acetate copolymer, Polyethylene oxide/propylene oxide block copolymers, polyamines, cellulose derivatives, and starch derivatives. Further, natural polymer compounds can also be used, and examples thereof include: alginate, gelatin, albumin, casein, gum arabic, tragacanth, and lignosulfonates.

Examples of the "polymer compound having an acidic group" include polyvinyl sulfate, condensed naphthalenesulfonic acid and the like.

Examples of the "polymer compound having a carboxyl group" include, for example, polyacrylic acid, polymethacrylic acid, and a cellulose derivative having a carboxyl group on either side thereof. Examples of the copolymer comprising at least one repeating unit (A) derived from a compound having a carboxyl group and at least one repeating unit (B) derived from a compound having a carboxylate group include: for example, a Japanese invention patent JP-A-59-44615, Japanese Invention Patent No. JP-B-54-34327, Japanese Invention Patent No. JP-B-58-12577, Japanese Invention Patent No. JP-A JP -M-acrylic acid as disclosed in Japanese Laid-Open Patent Publication No. JP-A-59-53836, and Japanese Laid-Open Patent Publication No. JP-A-59-71048 Copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, and partially esterified maleic acid copolymer. In addition, particularly preferred examples of the co-polymer include: acrylic acid/acrylate copolymers, methacrylic acid/acrylate copolymers, acrylic acid as disclosed in the specification of U.S. Patent No. 4,139,391. / methacrylate copolymer, methacrylic acid / methacrylate copolymer, and a multicomponent copolymer comprising acrylic acid or methacrylic acid, and acrylate or methacrylate, and any other vinyl compound.

Examples of the "vinyl compound" include, for example, styrene or substituted styrene (e.g., vinyl toluene, vinyl ethylbenzene), vinyl naphthalene or substituted vinyl naphthalene, acrylamide, methyl Acrylamide, acrylonitrile, and methacrylonitrile. Among these, styrene is preferred.

The polymer compound having a weight average molecular weight of 1,000 or more may be used singly or in combination of two or more kinds thereof, or may be used in combination with a compound having a molecular weight of less than 1,000.

The dispersion of the pigment fine particles is preferably an organic solvent containing 60% by mass or more, and more preferably 65% by mass or more. The organic solvent is not particularly limited and may be appropriately selected from general solvents. Examples of preferred solvents include ester compound solvents, alcohol compound solvents, aromatic solvent materials, aliphatic compound solvents, and ketone compound solvents. Among these, ester compounds and ketone compound solvents are particularly preferred. These solvents may be used singly or in combination of two or more kinds thereof.

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

The pigment fine particles as described above can be used, for example, in a state of being dispersed in a vehicle. In the case of a paint as an example, "vehicle" means a portion of a medium for dispersing a pigment when the paint is in a liquid state. The vehicle liquid is in a liquid state and contains a portion (adhesive) for bonding with the pigment as described above to cure the coating film and a component (organic solvent) for dissolving and diluting the portion. In the present invention, the binder used in forming the nanoparticles and the binder used in the redispersion may be identical or different from each other, and sometimes they are separately referred to as "nano". "Particle forming binder" and "re-dispersion binder".

After the redispersion, the concentration of the pigment fine particles in the dispersed composition of the pigment fine particles can be appropriately determined depending on the purpose of their use. However, the pigment fine particle concentration is preferably in the range of from 2 to 30% by mass, more preferably in the range of from 4 to 20% by mass, and particularly preferably in the range of from 5 to 15% by mass, to disperse the composition. The total amount is the benchmark. When the pigment fine particles are dispersed in the above-described vehicle liquid, the amount of the binder and the dissolved diluent component can be appropriately determined depending on, for example, the type of the organic pigment. However, the amount of the binder is preferably in the range of from 1 to 30% by mass, more preferably in the range of from 3 to 20% by mass, and particularly preferably in the range of from 5 to 15% by mass, to disperse the composition. The total amount is based on the benchmark. The amount of the dissolved diluent component is preferably in the range of from 5 to 80% by mass, and more preferably in the range of from 10 to 70% by mass based on the total amount of the dispersed composition.

For the concentrated extracted nanoparticulate liquid as described above, as described above, in order to allow rapid filter filtration, it is preferred to concentrate the pigment particles by concentration. It is preferably concentrated by centrifugation or drying to agglomerate it.

Examples of the method for finely dispersing the aggregated nanoparticles include, for example, a method of dispersing ultrasonic waves, and a method of applying physical energy.

The ultrasonic illuminating device which can be used is preferably a device having a function of applying an ultrasonic wave of 10 kHz or more, and examples thereof include, for example, an ultrasonic homogenizer, an ultrasonic cleaner, and the like. The liquid temperature at the time of ultrasonic irradiation is preferably maintained at 1 to 100 ° C, and more preferably 5 to 60 ° C, because if the liquid temperature is increased, thermal agglomeration of the nanoparticles is caused (refer to "Current Pigment" (Current Pigment) Dispersion Technology)", Technical Information Institute Co., Ltd., 1995, p. 166). The temperature can be controlled by, for example, adjusting the temperature of the dispersion or adjusting the temperature of the temperature adjustment layer for controlling the temperature of the dispersion.

The dispersing machine that can be used is not particularly limited by applying physical energy to disperse the concentrated pigment particles, and examples of the dispersing machine include: a kneader, a roll mill, a vertical agitating ball mill, Ultrafine powder grinding and pulverizing machine, dissolving and dispersing machine, homomixing machine, and sanding machine. Further, a high pressure dispersion method or a dispersion method using microbeads can also be exemplified as a preferred method.

By the above-described production method, for example, the pigment fine particles contained in each of the pigment fine particle dispersion composition and the colored photosensitive resin composition can be concentrated and redispersed, although their fine particle diameters are small. The extent to the nanometer size (for example, 10 to 100 nm). Therefore, when any one of the compositions is used for a color filter, a color filter which exhibits high optical density, excellent uniformity of the surface of the filter, high contrast, and reduced image noise can be obtained.

Further, the pigment fine particles contained in the pigment fine particle-dispersed composition or the colored photosensitive composition can be finely and uniformly finely dispersed into fine particles. In view of this, the film formed of each of the compositions can exhibit a high coloring density even with a thin film thickness, whereby thinning of the color filter can be achieved, for example.

In addition, when a pigment having a vivid color tone and a high coloring power is used in each of the pigment fine particle dispersion composition and the colored photosensitive resin composition, each composition system can be advantageously used as a manufacturing color correction or An image forming material such as a color filter.

Further, each of the pigment microparticle-dispersed composition and the colored photosensitive resin composition is a binder which is soluble in an alkaline aqueous solution, and is compatible with an alkaline developer used for exposure and development to form a colored image. Therefore, each composition is in compliance with the requirements of environmental protection.

In addition, an organic solvent having a moderate drying property can be used as a solvent (dispersion medium for a pigment) in each of the pigment fine particle dispersion composition and the colored photosensitive resin composition, and the obtained composition can satisfy the coating. The required performance after drying of the cloth composition.

The color filter of the present invention has a high contrast and a superior hue, and is also suitable for continuous mass production on an industrial scale. When applied to a liquid crystal display device or a CCD device, the color filter of the present invention can display superior display characteristics.

The invention will be explained in more detail based on the following examples, but the invention is not limited to the examples.

"Embodiment" [Example 1-1]

In 1,000 ml of dimethyl hydrazine (manufactured by Wako Pure Chemical Industries, Ltd.), 10 ml of sodium methoxide in 28% methanol solution (Wako Pure Chemicals) was added. Manufactured by Industrial Co., Ltd., 10,000 mg of CI Pigment Red 254 (Irgaphor Red BT-CF, manufactured by Ciba Specialty Chemicals Inc.), 10,000 mg of polyvinylpyrrolidone K25 ( Wako Pure Chemical Industries Co., Ltd.) to prepare a pigment solution. Separately from the pigment solution, 9,000 ml of ion-exchanged water containing 100 ml of 1 N hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared as a poor solvent.

The entire amount of the pigment solution was injected into the poor solvent as described above at a temperature controlled at 18 ° C using a pulseless flow pump at a flow rate of 100 ml/min, and stirred at 500 rpm with a four blade propeller type agitator. A pigment fine particle dispersion having a pigment concentration of 0.1% by mass was prepared. The pigment dispersion thus prepared was filtered under reduced pressure using a PTFE membrane filter, and then washed, followed by concentration to a pigment concentration of 20% by mass. The average particle diameter of the pigment particles measured by an electron microscope was 22 nm.

Using the pigment concentrate thus prepared, R pigment dispersion 1-1 was prepared as a composition as shown in Table 1.

In Table 1, polymer dispersant 1 was prepared by random copolymerization of benzyl methacrylate with methacrylic acid at a molar ratio of 60/40. The number average molecular weight (Mn) thereof measured by gel permeation chromatography was 32,000. Further, the compound J1 described below was used as the dispersant A.

Using the R-pigment dispersion 1-1 as described above, the colored photosensitive resin composition R1-1 was produced according to the composition as disclosed in Table 2.

<Binder>. Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate random copolymer (Morby: 38 / 25 / 37); Mn: 40,000): 25 parts by mass. Propylene glycol monomethyl ether acetate: 75 parts by mass

<Dipentaerythritol hexaacrylate solution (DPHA solution)>. Dipentaerythritol hexaacrylate (containing 500 ppm of polymerization inhibitor MEHQ; manufactured by Nippon Kayaku Co., Ltd.; trade name: KAYARAD DPHA): 70 parts by mass. Propylene glycol monomethyl ether acetate: 30 parts by mass

<Polymerization initiator A>. 2,4-bis(trichloromethyl)-6-[4'-(N,N-diethoxycarbonylmethyl)amino-3'-bromophenyl]-s-triazole

<Surfactant>. The structural formula 1: 24 mass parts as described below. Methyl ethyl ketone: 76 parts by mass

The color filter 1-1 in which the black matrix, the R pixel, the G pixel, and the B pixel are disposed is manufactured according to the method described below.

[Production of Color Filter (Manufacturing by Using Slit Nozzle Coating)] <Formation of Black (K) Image> Washing the alkali-free glass substrate with a UV cleaning device, and then using a detergent Wash with a brush and then perform ultrasonic cleaning with ultrapure water. The substrate was subjected to heat treatment at 120 ° C for 3 minutes to stabilize the surface state thereof.

The substrate was cooled and the temperature was controlled at 23 °C. The colored photosensitive resin composition K having the composition shown in the following Table 3 was applied using a coating machine for a glass substrate (manufactured by FAS Japan Corp., trade name: MH-1600) equipped with a slit nozzle. Coated on the substrate. Then, a part of the solvent was dried using a VCD (Vacuum Drying Apparatus, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds, thereby eliminating the fluidity of the coating layer. . Then, the unnecessary coating liquid around the substrate was removed by EBR (Optical Industry Repellent Edge Wash: Edge Bead Remover). The prebaking was carried out at 120 ° C for 3 minutes, whereby a photosensitive resin layer K having a film thickness of 2.4 μm was obtained.

A proximity exposure machine equipped with an ultra-high pressure mercury lamp (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.), a substrate and a mask (a quartz exposure image with an image pattern) In a state where the cover was erected in a vertical state, the distance between the exposure mask surface and the photosensitive resin layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ/cm ² .

Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the photosensitive resin layer K1, and then a KOH-based developing solution (developer containing KOH and a nonionic surfactant; brand name: CDK-1; Fujifilm Photoelectric Electronic Materials Co., Ltd. manufactured by FUJIFILM Electronic Materials Co., Ltd.) spray-developed at a temperature of 23 ° C for 80 seconds and a flat nozzle pressure of 0.04 MPa. Image. Next, ultrapure water was sprayed at a pressure of 9.8 MPa using an ultra-high pressure washing nozzle to remove the residue, whereby a black (K) image K was obtained. Next, heat treatment was performed at 220 ° C for 30 minutes.

The colored photosensitive resin composition K as described above is prepared according to the following method: First, carbon black and propylene glycol monomethyl ether acetate are weighed, and then they are at a temperature of 24 ° C (± 2 ° C). Mix underneath and stir at 150 rpm for 10 minutes. Then, weigh out methyl ethyl ketone, binder, hydroquinone monomethyl ether, DPHA solution, polymerization initiator A, and surfactant, and then they are at a temperature of 25 ° C (± 2 ° C) This was added sequentially, and the obtained mixture was stirred at 150 rpm, 40 ° C (± 2 ° C) for 30 minutes.

<Formation of Red (R) Element> On the substrate on which the image K as described above is formed, a heat-treated pixel R is obtained by using the colored photosensitive resin composition R1 as described above. -1, and formed in the same steps as the formation of the black (K) image. The film thickness of the photosensitive resin layer R obtained by this and the coating amount of the pigment are as follows. The colored photosensitive resin composition R1-1 is obtained in the same manner as the coloring photosensitive resin composition K described above.

<Formation of Green (G) Pixels> On a substrate on which the image K and the pixel R as described above are formed, a heat-treated pixel G is used as shown in Table 4 below. The colored photosensitive resin composition G composed of the composition is formed in the same step as the formation of the black (K) image. The film thickness of the photosensitive resin layer G obtained by this and the coating amount of the pigment are as follows. The colored photosensitive resin composition G is obtained in the same manner as the coloring photosensitive resin composition K described above.

<G-Pigment Dispersion>

<Y-Pigment Dispersion>. CF Yellow EX3393 (trade name) manufactured by Mikuni Color Ltd.

<Formation of Blue (B) Pixel> On a substrate having the image K, the pixel R, and the pixel G formed thereon as described above, a heat-treated pixel B is used by using the following The colored photosensitive resin composition B1 composed of the composition shown in Table 5 was formed in the same procedure as the formation of a black (K) image. In this way, the desired color filter A can be obtained. The film thickness of the photosensitive resin layer B1 obtained by this and the coating amount of the pigment are as follows. The colored photosensitive resin composition B1 is obtained in the same manner as the coloring photosensitive resin composition K described above.

<B-Pigment Dispersion>. CF Blue EX3357 (trade name) manufactured by Yuki Co., Ltd.

<V-Pigment Dispersion>. CF Blue EX3383 (trade name) manufactured by Yuki Co., Ltd.

[Example 1-2]

R-pigment dispersion 1-2, colored photosensitive resin composition R1-2, and a color filter 1-2 using the colored photosensitive resin composition R1-2 are in the same manner as in Example 1-1. The manufacture was carried out in the same manner except that the amount of the polyvinylpyrrolidone used in the preparation of the R-pigment dispersion 1-1 was changed to 20,000 mg. The average particle diameter of the pigment particles measured by an electron microscope was 23 nm.

[Example 1-3]

R-pigment dispersion 1-3, colored photosensitive resin composition R1-3, and a color filter 1-3 using the colored photosensitive resin composition R1-3 are in the same manner as in Example 1-1. The manufacture was carried out in the same manner except that the amount of the polyvinylpyrrolidone used in the preparation of the R-pigment dispersion 1-1 was changed to 50,000 mg. The average particle diameter of the pigment particles measured by an electron microscope was 21 nm.

[Examples 1-4]

R-pigment dispersion 1-4, colored photosensitive resin composition R1-4, and a color filter 1-4 using the colored photosensitive resin composition R1-4 are in the same manner as in Example 1-1. The manufacture was carried out in the same manner except that the amount of the polyvinylpyrrolidone used in the preparation of the R-pigment dispersion 1-1 was changed to 100,000 mg. The average particle diameter of the pigment particles measured by an electron microscope was 20 nm.

[Example 2]

R-Pigment Dispersion Liquid 2, Colored Photosensitive Resin Composition R2, and Color Filter 2 Using the Colored Photosensitive Resin Composition R2 were manufactured in the same manner as in Example 1-1, with the exception of In the case of preparing the R-pigment dispersion 1-1, 50,000 mg of polyvinylpyrrolidone K90 (manufactured by Wako Pure Chemical Industries, Ltd.) was added in place of polyvinylpyrrolidone K25. As a result of measurement by an electron microscope, it was found that the average particle diameter of the pigment particles was 20 nm.

[Example 3]

A pigment dispersion liquid and a pigment concentrate were produced in the same manner as in Example 1-4, except that the temperature of the poor solvent was changed to 45 °C. The average particle diameter of the pigment particles measured by an electron microscope was 53 nm.

By using the pigment concentrate thus obtained, the R-pigment dispersion 3, the colored photosensitive resin composition R3, and the color filter 3 using the colored photosensitive resin composition R3 are in the embodiment. 1-1 is manufactured in the same manner.

[Comparative Example 1]

The R-pigment dispersion A, the colored photosensitive resin composition RA, and the color filter A using the colored photosensitive resin composition RA were produced in the same manner as in Example 1-1, with the exception of When the R-pigment dispersion 1-1 was prepared, it was prepared by preparing a pigment stock solution which was not added to the polyvinylpyrrolidone. The average particle diameter of the pigment particles measured by an electron microscope was 21 nm.

[Comparative Example 2]

First, 20,000 mg of methacrylic acid/benzyl methacrylate copolymer (mol ratio 30/70, Mw 30,000, 40% by mass of propylene glycol monomethyl ether acetate solution), 80,000 mg of sodium chloride And 80,000 mg of CI Pigment Red 254 were mixed. Then, the obtained mixture was placed in a double arm type kneader (manufactured by Moriyama Company Ltd.), and kneaded at 80 ° C for 10 hours. After kneading, the mixture was taken out and transferred to 500 parts by mass of a 1% by mass aqueous hydrochloric acid solution, followed by stirring for 1 hour, followed by filtration, washing with hot water, drying and grinding. Then, 2.4 g of propylene glycol monomethyl ether acetate was added per 1 g of the ground pulverized product and mixed. The obtained pigment composition was dispersed by using a motor mill M-50 (manufactured by Eigar Japan Co., Ltd.) and a zirconium bead having a diameter of 0.5 mm at a peripheral speed of 10 m/s for 1 hour. The pigment dispersion thus obtained is labeled as R-pigment dispersion B. The average particle diameter of the pigment particles measured by an electron microscope was 48 nm.

By using the R-pigment dispersion B, a colored photosensitive resin composition RB, and a color filter B using the colored photosensitive resin composition RB are in the same manner as in Example 1-1. To manufacture.

The amount of polyvinylpyrrolidone in each of the pigment dispersions 1-1 to 1-4, 2, 3, A, and B thus prepared is determined according to the method described below: 1. Pigment The dispersion was evaporated to dryness at 100 ° C and atmospheric pressure. The solids thus obtained were ground and pulverized.

2. Each of the ground pulverized materials was pelleted according to the KBr method to prepare a sample.

The amount of polyvinylpyrrolidone in each sample was measured using a Fourier Transform Infrared Spectrophotometer FTIR-8400S (trade name) manufactured by Shimadzu Corporation.

Further, the moisture content in each of the pigment dispersions 1-1 to 1-4, 2, 3, A, and B is a card type manufactured by Kyoto Electronics Manufacturing Co., Ltd. Determination by Karl Fisher moisture meter MKA-3.

For the purpose of evaluating the properties of the pigment dispersions 1-1 to 1-4, 2, 3, A, and B thus prepared, the comparison of the coated products was measured according to the following method.

A three-wavelength cold cathode tube light source (FWL18EX-N (trade name), manufactured by Toshiba Lighting & Technology Corporation) equipped with a diffusion plate is used as a backlight unit. Each color filter was placed between two polarizing plates (HLC2-2518 (trade name), manufactured by Sanritz Corporation), and then measured when the polarizing axes of the two polarizing plates were parallel, and when the polarizing axis was vertical The amount of transmitted light. The ratio of the amount of transmitted light is defined as "contrast" (see, "Mumu, Xiaoguan, Fuyong, Shanzhong" published "512-color display size 10.4" TFT-LCD color filter ("Color Filter For 512 color display 10.4"-size TFT-LCD")", the 7th Color Optics Symposium (1990), etc.). The chromaticity was measured using a color luminance meter (BM-5 (trade name), manufactured by Topcon Techno House Corporation). The two polarizing plates, the color filters, and the color luminance meter as described above are placed in the following positions: the polarizing plate is disposed at a position of 13 mm from the backlight. A cylinder with a diameter of 11 mm and a length of 20 mm is placed at a distance of 40 mm to 60 mm from the backlight. The light transmitted through the cylinder is a color filter that is irradiated to a position set at a distance of 65 mm from the backlight. The transmitted light was passed through another polarizing plate disposed at a position of 100 mm from the backlight, and the measurement was performed with a color luminance meter set at a distance of 400 mm from the backlight. The measurement angle of the color luminance meter is set to 2°. The amount of light of the backlight is set such that when the two polarizing plates are arranged in a parallel Nichol and the color filter is not provided, the luminance (luminance) can be 1,280 cd/m ² .

Next, the number of the polyvinylpyrrolidone contained in the colored layer of each of the color filters 1-1 to 1-4, 2, 3, A, and B thus obtained is based on the following The method described is as follows: 1. A portion of the color layer of each color filter is scraped with a spatula under a stereo micrometer to prepare a sample for analysis.

2. A suitable number of each sample was collected and analyzed according to pyrolysis gas chromatography mass spectrometry. The thermal cracking is a model of Curie Point Pyrolyzer manufactured by JAI Corporation: JHP-5 thermal cracking apparatus (trade name). Gas chromatography mass spectrometry was carried out using a Model 5973 device (trade name) manufactured by Agilent Technologies Corporation.

3. Analysis of polyvinylpyrrolidone was carried out according to the SIM method. The quantitative value is calculated according to the absolute calibration curve method or the standard addition method.

The comparison of the case of the coated pigment dispersion and the content of the polymer in the color filter (polyvinylpyrrolidone) are shown in Table 7.

According to the results as described above, it is possible to understand the comparison of the respective color filters 1-1 to 1-4, 2, and 3, which contains 0.1% by mass or more of polyvinylpyrrolidone in the colored layer. (Water-soluble polymer) is higher than those contained in the color filters A and B. It is expected that the liquid crystal display device and the CCD device equipped with the color filters 1-1 to 1-4, 2, and 3 will exhibit improved performance.

Color filter 3 showed a relatively low contrast, although it contained a water soluble polymer. It can be assumed that the result may be due to the fact that the pigment particles contained in the color filter 3 have a diameter of up to about 50 nm. Associated with this is that the color filter 3 exhibits a contrast superior to the color filter B, and although they contain pigment particles having almost the same particle diameter, they are shown to contain the effect of a water-soluble polymer.

[Example 4 and Comparative Example 3]

Next, the liquid crystal display device obtained by separately arranging the color filters as described above is as follows, and the image quality evaluation thereof is evaluated.

[Manufacture of liquid crystal display device]

(Formation of ITO electrode) The glass substrate on which the color filter was formed was placed in a sputtering apparatus, and the glass substrate was subjected to full vacuum evaporation at 100 ° C to form a thickness of 1,300. ITO (indium tin oxide). Then, annealing was carried out at 240 ° C for 90 minutes to crystallize the ITO. Thereby, an ITO transparent electrode can be formed.

The spacer (formation of the spacer) is produced in the same manner as the spacer formation method disclosed in the first embodiment of the Japanese Patent Laid-Open Publication No. JP-A-2004-240335. It is formed on the ITO transparent electrode.

(Formation of Protrusion for Control of Liquid Crystal Alignment) A liquid crystal alignment control projection is formed on an ITO transparent electrode on which a spacer as described above is formed by using a coating liquid for a positive photosensitive resin layer as described below.

Here, the exposure, development, and baking steps are carried out according to the following methods.

The proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Co., Ltd.) is disposed such that a specific photomask is located at a distance of 100 μm from the surface of the photosensitive resin layer. The proximity exposure was carried out by using an ultrahigh pressure mercury lamp through the reticle at an exposure of 150 mJ/cm ² .

Next, development was carried out by spraying a 2.38% aqueous solution of tetramethylammonium hydroxide on the substrate at 33 ° C for 30 seconds using a shower-type developing device. In this way, an unnecessary portion (exposed portion) of the photosensitive resin layer is removed by development. By this, a substrate for a liquid crystal display device in which a liquid crystal alignment control protrusion having a photosensitive resin layer having a desired shape is formed can be obtained on the color filter side substrate.

Then, the substrate for a liquid crystal display device having the liquid crystal alignment control projections formed thereon was baked at 230 ° C for 30 minutes. Thereby, the cured liquid crystal alignment control protrusion can be formed on the substrate for a liquid crystal display device.

<Formation of Coating Liquid for Positive Photosensitive Resin Layer>

(Production of Liquid Crystal Display Device) On the substrate for a liquid crystal display device obtained thereby, an alignment film made of polyimide is further provided. Then, the sealant made of the epoxy resin is printed at a position corresponding to the outer frame of the black matrix provided in such a manner as to surround the pixel group surrounding the color filter. After the liquid crystal for MVA (Multi-domain division vertical alignment) mode was dropped, the substrate as described above and the counter substrate were bonded together. The bonded substrate is subjected to heat treatment to harden the sealant. A polarizing plate HLC2-2518 manufactured by Sanritz Corporation was attached to both sides of the liquid crystal cell obtained thereby. Next, a backlight having a three-wavelength cold cathode tube light source (FWL18EX-N (trade name), manufactured by Toshiba Lighting Technology Co., Ltd.) was constructed, and the backlight was disposed on the back side of the liquid crystal cell on which the polarizing plate was disposed. Thereby, a liquid crystal display device can be obtained.

With respect to the liquid crystal display device thus obtained, the liquid crystal display device in which the color filter 1-1 is disposed is referred to as a liquid crystal display device 1-1. The liquid crystal display devices 1-2 to 1-4, 2, 3, A, and B were respectively produced in the same manner as described above.

The image quality of each liquid crystal display device was evaluated according to the following method: 1. The eight groups of liquid crystal display devices as described above were randomly arranged without being marked and displayed to the examiner for observation. The image quality (black density and modulation) of the device is based on the level of the tester from 8 o'clock to 1 o'clock. The 8 o'clock level is the best and the 1 point is the worst.

2. Ten examiners performed the same assessment. The sum of the scores obtained thereby is used to evaluate the image quality of the produced liquid crystal display device.

A liquid crystal display device which can exhibit a total score of 25 or more is sufficient in practical applications.

The results obtained are shown in Table 8.

As shown in Table 8, it is understood that a liquid crystal display device having a color filter having a polyvinylpyrrolidone content of 0.1% by mass or more in the colored layer can be realized, and an excellent image can be realized. quality. In addition, as in the case of the results shown in Table 7, it should be understood that in the sample containing the pigment particles used as the color filter and whose particle diameters are almost identical, then Image quality tends to increase as the content of polypyrrolidone increases.

[Industrial use possibility]

The color filter of the present invention has a high contrast and a superior hue, and is suitable for continuous mass production on an industrial scale. When applied to a liquid crystal display device or a CCD device, the color filter of the present invention can achieve superior display characteristics.

The above is a specific example of the present invention, but the present invention is not limited to the details of the description, unless otherwise specifically mentioned, but is widely constructed within the meaning and scope of the appended claims.

Claims (12)

A color filter having a layer colored with at least one hue and formed on a substrate, comprising: a water-insoluble organic pigment (a), a monomer having a polymerizable group or an oligomer (b), and a water-soluble solution The polymer (c) is in the form of a pigment dispersion, wherein the dispersion is cured by polymerizing a monomer or an oligomer to form a colored layer, wherein the water-soluble polymer (c) is in the colored layer. The content is at least 0.1% by mass of the total solid content, wherein the pigment dispersion comprises an organic pigment (a) in the form of fine particles, wherein the fine particles are an organic pigment solution by dissolving the organic pigment (a) in a good solvent, and The solvent which is compatible with the good solvent and which acts as a poor solvent for the organic pigment is mixed and precipitated; and the water-soluble polymer (c) is added to either or both of the organic pigment solution and the poor solvent. A color filter according to claim 1, wherein the number average particle diameter of the pigment fine particles is in the range of from 0.005 μm to 1 μm. The color filter of claim 1, wherein the number average particle diameter of the pigment particles is in the range of from 0.005 μm to 0.08 μm. The color filter of claim 1, wherein the number average particle diameter of the pigment particles is in the range of from 0.005 μm to 0.05 μm. A color filter according to any one of claims 1 to 4, wherein the water-soluble polymer has a number average molecular weight of 1,000 or more. A liquid crystal display device is provided with a color filter according to any one of claims 1 to 5. A CCD device configured by a color filter according to any one of claims 1 to 5. A pigment dispersion comprising: a water-insoluble organic pigment (a) and a water-soluble polymer (b) as a dispersing agent, wherein the pigment dispersion has a moisture content of 10% by mass or less, and wherein the water-soluble polymerization The content of the substance (b) is at least 0.1% by mass of the organic pigment (a); wherein the pigment dispersion liquid contains the organic pigment (a) in the form of fine particles, wherein the fine particles are dissolved in the good by dissolving the organic pigment (a) a solvent of an organic pigment solution, and a solvent which is compatible with the good solvent and which acts as a poor solvent for the organic pigment, and is precipitated together; and the water-soluble polymer (b) is added to the organic pigment solution and the poor solvent. Or any one. A pigment dispersion according to claim 8 wherein the number average particle diameter of the pigment fine particles is in the range of from 0.005 μm to 1 μm. The pigment dispersion according to claim 8, wherein the number average particle diameter of the pigment fine particles is in the range of from 0.005 μm to 0.08 μm. A pigment dispersion according to claim 8 wherein the number average particle diameter of the pigment fine particles is in the range of from 0.005 μm to 0.05 μm. The pigment dispersion according to any one of claims 8 to 11, wherein the water-soluble polymer has a number average molecular weight of 1,000 or more.