KR101381194B1 - Color filter and liquid crystal display using the same - Google Patents

Abstract

(Problem) Provide a color filter having a high display quality and a liquid crystal display device using the same, which have a high contrast and can suppress the occurrence of display defects due to burn-in during image display, and can suppress the generation of pigment precipitates. do.

(Solution means) A color filter having a colored layer, wherein the colored layer exhibits a diffraction peak having a half width of 0.6 ° or more at a Bragg angle of 28 ± 1 ° in an X-ray diffraction spectrum with respect to Cu—K α rays.

Color filter, liquid crystal display device

Description

COLOR FILTER AND LIQUID CRYSTAL DISPLAY USING THE SAME}

The present invention relates to a color filter and a liquid crystal display device using the same. The present invention also relates to a high contrast, high quality color filter, and a liquid crystal display device using the same.

In recent years, the image quality of liquid crystal display (LCD) has been improved, and the use of CRT (Brown Tube), which is a popular display, has been widely used. In addition, the required quality such as the color reproduction range and the luminance is further increased, and the performance improvement of the color filter is the key to this. This is because the color filter plays a role of coloring the display image of the LCD panel or the like and directly influences the color characteristics of the LCD panel.

As the required characteristics of the color filter, high light transmittance, color purity, high contrast, low reflection, and the like are listed. In particular, when the contrast is low, the light is attenuated and the display screen becomes dark or the contrast becomes unclear. For this reason, high contrast is desired. Further, it is also expected that the reproduction region of the color obtained by combining RGB is wide, and that each color purity is high. However, if the contrast of the color filter is improved, the color purity may decrease, and the color reproduction area may decrease.

In addition, there is a demand for a highly reliable color filter which does not cause display defects, and for example, a solution for display defects due to burn-in during image display is required. On the other hand, there exists an example using the photosensitive composition containing the pigment whose voltage retention is 80% or more as a coating composition for RGB pixel formation (patent document 1). However, no color filter has yet been provided which has high contrast and can sufficiently suppress the occurrence of display defects due to burn-in during image display.

Moreover, the solution of the precipitation of diketopyrrolopyrrole (DPP) pigment crystal | crystallization to the color filter surface in the ITO sputtering process at the time of transparent conductive film manufacture is calculated | required. In this regard, a DPP pigment having a peak half width of 0.600 ° or more and 0.800 ° or less in the range of 2θ = 28 to 29 ° in the X-ray diffraction spectrum has been proposed (Patent Document 2). However, since the pigment uses concentrated sulfuric acid at the time of manufacture, the display quality of the image and its durability are unclear.

(Patent Document 1) Japanese Unexamined Patent Publication No. 2000-329929

(Patent Document 2) Japanese Unexamined Patent Publication No. 2002-265840

Disclosure of Invention The present invention provides a color filter having a high contrast and a display quality having a high display quality capable of suppressing generation of display defects due to burn-in during image display and suppressing generation of pigment precipitates, and a liquid crystal display device using the same. The purpose.

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

(1) A color filter having a colored layer, wherein the colored layer exhibits at least one diffraction peak having a half width of 0.6 ° or more at a Bragg angle of 28 ± 1 ° in an X-ray diffraction spectrum with respect to Cu—K α rays. Color filter.

(2) The color filter as described in (1) containing C.I. pigment red 254 in the said colored layer.

(3) C.I. (1) A pigment solution in which Pigment Red 254 is dissolved, and organic pigment fine particles produced by mixing a solvent which is compatible with the good solvent and becomes a poor solvent for the organic pigment. ) Or (2) the color filter.

(4) The said colored layer contains organic pigment microparticles | fine-particles, The number of particle | grains of 20 nm-30 nm of particle diameters in the said pigment microparticles | fine-particles are 30% or more of all the organic pigment microparticles, in any one of (1)-(3) characterized by the above-mentioned. The described color filter.

(5) The said colored layer contains organic pigment microparticles | fine-particles, and the number average primary particle diameter (Dp) of the said pigment microparticles is 30 nm or less, The color filter in any one of (1)-(4) characterized by the above-mentioned.

(6) The color filter according to any one of (1) to (5), wherein the number average particle diameter (Df) of the dispersed particles in the pigment dispersion used when forming the colored layer is 50 nm or less.

(7) The color filter according to any one of (1) to (6), wherein the half width of the diffraction peak is 0.70 ° or more.

(8) The color filter according to any one of (1) to (7), wherein the half width of the diffraction peak is 0.80 ° or more.

(9) A liquid crystal display device comprising the color filter according to any one of (1) to (8).

The color filter of the present invention has a high contrast and good color, and exhibits an excellent effect of suppressing occurrence of display defects due to burn-in during image display. In addition, by using the high quality color filter, it is possible to provide a liquid crystal display device which is excellent in black vividness and can exhibit high display performance without color unevenness.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly researched about the high contrast of a color filter, and by adjusting the half value width of the X-ray-diffraction spectrum of the colored layer of a color filter, it is compatible with the high contrast of a color filter and suppression of the display defect by burn-in, I found something that could be realized. In addition, it has been found that display defects due to burn-in can be more effectively suppressed by appropriately selecting a good solvent during pigment particle formation. The present invention has been completed on the basis of these findings.

Hereinafter, the present invention will be described in detail.

The color filter of this invention has a colored layer. This colored layer exhibits a diffraction peak having a peak half width of 0.6 ° or more at a Bragg angle of 28 ± 1 ° in an X-ray diffraction spectrum with respect to Cu—K α rays, and preferably has a half width of 0.7 ° or more and 0.8 ° or more. More preferred.

Here, it is preferable that the said colored layer contains an organic pigment, and it is more preferable to contain microparticles | fine-particles of an organic pigment. The method for producing the organic pigment fine particles can be appropriately selected from the methods such as the vapor phase method, the grinding method, the reprecipitation method, the laser ablation method and the like according to the pigment species and the target performance. It is preferable by the fine particle precipitation method mentioned later from the point which obtains the pigment fine particle which is fine, the particle size distribution is uniform, and is excellent in dispersion stability.

In the color filter of this invention, it is preferable to use a diketopyrrolopyrrole compound pigment among organic pigments. C.I. Pyrrolopyrrole compound pigments represented by Pigment Red 254, 255, and 264 have an absorption area suitable for increasing the color purity of the red pixels constituting the color filter, and are suitable for use as a color filter because the color reproduction area can be widened. Do.

In the diketopyrrolopyrrole compound pigments, the C.I. Pigment Red 254 (compound represented by the following formula (Z)), 255 (compound represented by the following formula (W)), 264 (compound represented by the following formula (V)) are preferable, and C.I. Pigment Red 254 is more preferred in terms of absorption spectrum.

Also, C.I. As Pigment Red 254, Irgaphor Red B-CF (manufactured by Ciba Specialty Chemicals), Cromophtal DPP Red BO, Irgazin DPP Red BO, Microlen DPP Red BP, etc. may be used, and C.I. As Pigment Red 255, Cromophtal Coral Red C, Irgazin DPP Red 5G, etc. can be used, and C.I. As Pigment Red 264, Hostapeperm Rubin D3B LP2615, Irgazin DPP Rubin TR, etc. can be used (all are brand names).

 Specific examples of the organic pigments that can be used together include, for example, perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone , Phthalocyanine, triarylcarbonium, dioxadine, aminoanthraquinone, thioindigo, isoindolin, isoindolinone, pyrantrone or isoviolantron compound pigments, mixtures thereof, and the like.

 More specifically, C.I. Pigment Red 190 (C.I. No. 71140), C.I. Pigment Red 224 (C.I. No. 71127), C.I. Pigments of perylene compounds such as pigment violet 29 (C.I. No. 71129), C.I. Pigment Orange 43 (C.I. No. 71105), or C.I. Pigments of perinone compounds such as Pigment Red 194 (C.I. No. 71100), C.I. Pigment Violet 19 (C.I. No. 73900), C.I. Pigment Violet 42, C.I. Pigment Red 122 (C.I. No. 73715), C.I. Pigment Red 192, C.I. Pigment Red 202 (C.I. No. 73907), C.I. Pigment Red 207 (C.I. Nos. 73900, 73906), or C.I. Quinacridone compound pigment of Pigment Red 209 (C.I. No. 73905), C.I. Pigment Red 206 (C.I. No. 73900/73920), C.I. Pigment Orange 48 (C.I. No. 73900/73920), or C.I. Quinacridone quinone compound pigments such as Pigment Orange 49 (C.I. No. 73900/73920), C.I. Pigments of anthraquinone compounds such as Pigment Yellow 147 (C.I. No. 60645), and C.I. Pigments of anthanthrone compounds such as Pigment Red 168 (C.I. No. 59300), C.I. Pigment Brown 25 (C.I. No. 12510), C.I. Pigment Violet 32 (C.I. No. 12517), C.I. Pigment Yellow 180 (C.I. No. 21290), C.I. Pigment Yellow 181 (C.I. No. 11777), C.I. Pigment Orange 62 (C.I. No. 111775), or C.I. Pigments of benzimidazolone compounds such as Pigment Red 185 (C.I. No. 12516), C.I. Pigment Yellow 93 (C.I. No. 20710), C.I. Pigment Yellow 94 (C.I. No. 20038), C.I. Pigment Yellow 95 (C.I. No. 20034), C.I. Pigment Yellow 128 (C.I. No. 20037), C.I. Pigment Yellow 166 (C.I. No. 20035), C.I. Pigment Orange 34 (C.I. No. 21115), C.I. Pigment Orange 13 (C.I. No. 21110), C.I. Pigment Orange 31 (C.I. No. 20050), C.I. Pigment Red 144 (C.I. No. 20735), C.I. Pigment Red 166 (C.I. No. 20730), C.I. Pigment Red 220 (C.I. No. 20055), C.I. Pigment Red 221 (C.I. No. 20065), C.I. Pigment Red 242 (C.I. No. 20067), C.I. Pigment Red 248, C.I. Pigment Red 262, or C.I. Disazo condensation compound pigments such as Pigment Brown 23 (C.I. No. 20060), C.I. Pigment Yellow 13 (C.I. No. 21100), C.I. Pigment Yellow 83 (C.I. No. 21108), or C.I. Disazo compound pigments such as Pigment Yellow 188 (C.I. No. 21094), and C.I. Pigment Red 187 (C.I. No. 12486), C.I. Pigment Red 170 (C.I. No. 12475), C.I. Pigment Yellow 74 (C.I. No. 1714), C.I. Pigment Yellow 150 (C.I. No.48545), C.I. Pigment Red 48 (C.I. No. 15865), C.I. Pigment Red 53 (C.I. No. 15585), C.I. Pigment Orange 64 (C.I. No. 12760), or C.I. Azo compound pigments such as Pigment Red 247 (C.I. No. 15915), and C.I. Pigments of indanthrone compounds such as Pigment Blue 60 (C.I. No. 69800), C.I. Pigment Green 7 (C.I. No.74260), C.I. Pigment Green 36 (C.I. No. 74265), C.I. Pigment Green 37 (C.I. No.74255), C.I. Pigment Blue 16 (C.I. No. 74100), C.I. Pigment Blue 75 (C.I. No. 74160: 2), C.I. Pigment Blue 15: 6 (C.I. No. 74160), or C.I. Phthalocyanine compound pigments such as pigment blue 15: 3 (C.I. No. 74160), C.I. Pigment Blue 56 (C.I. No. 42800), or C.I. Pigments of triarylcarbonium compounds such as Pigment Blue 61 (C.I. No. 42765: 1), C.I. Pigment Violet 23 (C.I. No. 551319), or C.I. Pigments of dioxadine compounds such as pigment violet 37 (C.I. No. 51345), and C.I. Pigments of aminoanthraquinone compounds such as Pigment Red 177 (C.I. No. 65300), and C.I. Thioindigo compound pigments such as Pigment Red 88 (C.I. No. 73312), and C.I. Pigment Yellow 139 (C.I. No. 56298), C.I. Pigments of isoindolin compounds such as pigment orange 66 (C.I. No. 4482), C.I. Pigment Yellow 109 (C.I. No.56284), C.I. Pigment Yellow 185 (C.I. No.56290), or C.I. Pigments of isoindolinone compounds such as Pigment Orange 61 (C.I. No. 11295), C.I. Pigment Orange 40 (C.I. No. 59700), or C.I. Pigments of pyrantrone compounds such as Pigment Red 216 (C.I. No. 59710), C.I. Pigments such as Pigment Yellow 138, or C.I. Isovioletrone compound pigments, such as pigment violet 31 (60010), are mentioned.

In the color filter of this invention, two or more types of organic pigments or solid solutions of organic pigments may be used in combination, and also it may be used in combination with general dye.

In the color filter of this invention, it is preferable that it is 10-70 mass% with respect to whole solid content in a colored layer, and, as for content of an organic pigment, it is more preferable that it is 30-60 mass%.

In the pigment dispersion containing the organic layer (a), the monomer or oligomer (b) having a polymerizable group, and the water-soluble polymer (c), the colored layer of the color filter of the present invention comprises the polymerizable monomer or oligomer ( It is preferable that it consists of superposition | polymerization solidified polymerized b). At this time, it is also preferable to contain a binder (d), a polymerization initiator, or a polymerization initiator system (e) in a pigment dispersion. Although the thickness of a colored layer does not specifically limit, It is preferable that it is 0.5-5.0 micrometers, and it is more preferable that it is 1.0-3.0 micrometers. The area of the colored layer and are not particularly limited, for example, if a fine pixels, it is preferable that the desirable, and 1000 ~ 15000㎛ ² of 400 ~ 90000㎛ ^2. Moreover, it is preferable that the colored layer of the color filter of this invention was shape | molded without using strong acid, and what was formed without using concentrated sulfuric acid etc. is preferable.

The monomer or oligomer having the polymerizable group preferably has two or more ethylenically unsaturated double bonds, and is preferably polymerized by light irradiation. These may include compounds having at least one addition polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at atmospheric pressure. Examples thereof include monofunctional acrylates such as dipentaerythritol hexa (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) Acrylate; Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimetholethane triacrylate, trimetholpropane tri (meth) acrylate, trimetholpropane diacrylate, neopentyl glycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) Acrylate, trimetholpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; Polyfunctional acrylates and polyfunctional methacrylates, such as those obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as trimetholpropane and glycerin and then (meth) acrylated, may be listed. Furthermore, as described in General Formulas (1) and (2) in Japanese Patent Application Laid-Open No. 10-62986, a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated is also suitable. Listed as.

Urethane acrylates described in Japanese Patent Application Laid-Open No. 48-41708, Japanese Patent Application Laid-open No. 50-6034, and Japanese Patent Application Laid-open No. 51-37193; Polyester acrylates described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191 and Japanese Patent Publication No. 52-30490; Polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid can be exemplified.

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

In addition, "polymerizable compound B" described in Unexamined-Japanese-Patent No. 11-133600 can also be enumerated as a preferable thing.

These polymerizable monomers or oligomers preferably have a molecular weight of 200 to 1000, and may be used alone or in combination of two or more thereof.

Although content of the polymerizable monomer or oligomer in the color filter of this invention is not specifically limited, It is common that it is 5-50 mass% with respect to the total solid content in a colored layer, and it is preferable that it is 10-40 mass%. When this amount is too large, developability control becomes difficult and becomes a problem in manufacture aptitude. If it is too small, the curing force at the time of exposure is insufficient.

It is preferable that the water solubility polymer is 100 mass% or more in the solubility with respect to the pure water of 25 degreeC. Moreover, it is hard to affect a color filter, and it is preferable that it is neutral in the state of aqueous solution. Specifically, synthetic polymer compounds such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyethylene glycol, polyethylene oxide, and copolymers thereof can be used. Among these polymer compounds, polyvinylpyrrolidone is particularly preferable. One type of these water-soluble polymers may be used, and 2 or more types may be combined.

Although the molecular weight of a water-soluble polymer is not specifically limited, Preferably number average molecular weight Mn is 1,000-2,000,000, 5,000-1,000,000 is more preferable, 10,000-500,000 are more preferable, 10,000-100,000 are especially preferable.

In the color filter of this invention, it is preferable that content of a water-soluble polymer is 0.1 mass% or more with respect to the total solid content in a colored layer, It is preferable that it is 1 mass% or more, It is more preferable that it is 3 mass% or more, It is 5 mass% or more Is particularly preferred.

As a binder, the binder which has an acidic group is preferable, and you may add at the time of preparation of an inkjet ink or a coloring photosensitive resin composition. It is also preferable to add at the time of manufacturing the said pigment dispersion, or at the time of pigment fine particle formation mentioned later. The binder may be added to both or one side of the poor solvent for adding the organic pigment solution and the organic pigment solution to produce the pigment fine particles. Or it is also preferable to add a binder solution at the time of pigment fine particle formation separately.

As a binder, alkali-soluble polymer which has polar groups, such as a carboxylic acid group and a carboxylate group, in a side chain is preferable. Examples include Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Publication No. 59-53836 Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer as described in Japanese Patent Application Laid-Open No. 59-71048 And the like. Moreover, the cellulose derivative which has a carboxylic acid group, a carboxylic acid salt, etc. in a side chain can also be enumerated, In addition, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. Further preferred examples include copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391 and polyunsaturated copolymers of benzyl (meth) acrylate with (meth) acrylic acid and other monomers. can do. These binder polymers having polar groups may be used alone or in a state of a composition used in combination with a conventional film-forming polymer.

Moreover, in order to improve crosslinking efficiency, you may have a polymeric group in a side chain, and UV curable resin, a thermosetting resin, etc. are also useful. Although the example of the polymer containing these polymerizable groups is shown below, if alkali-soluble groups, such as a COOH group, an OH group, and an ammonium group, are included, a carbon-carbon unsaturated bond is not limited to the following. Epoxy ring and carbon-carbon unsaturated having a OH group in a copolymer of a monomer such as 2-hydroxyethyl acrylate having an OH group, a methacrylic acid containing a COOH group, and an acrylic or vinyl compound copolymerizable with these, and the like. Compounds having a linking group such as compounds obtained by reacting a compound such as glycidyl acrylate may be used. In the reaction with OH, in addition to the epoxy ring, a compound having an acid anhydride and an isocyanate group and having an acryloyl group can also be used. Furthermore, a saturated or unsaturated polybasic acid anhydride is reacted with a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring disclosed in JP-A-6-102669 and JP-A-6-1938. The reactants obtained can also be used. Examples of the compound having a carbon-carbon unsaturated group and an alkali solubilizer such as COOH include, for example, the DIANAL NR series (manufactured by MITSUBISHI RAYON CO., LTD.), Photomer 6173 (COOH group-containing polyurethane polyurethane oligomer, Diamond Shamrock Co. Ltd., Products), Biscot R-264, KS Resist 106 (all from Osaka Organic Chemical Industry Co. Ltd.), CYCLOMER P Series, PLACSELL CF 200 Series (all from Daicel Chemical Industry Co. Ltd.), Ebecryl 3800 (Daicel UCB) Co. Ltd.).

As the binder resin, an organic polymer having a water-soluble atomic group in a part of the side chain can be used. It is preferable that the said binder resin is a linear organic high polymer which is compatible with a monomer, and is also an organic solvent and alkali solubility (preferably what can develop with weak alkaline aqueous solution). Examples of the alkali-soluble resin include polymers having a carboxylic acid in the side chain, such as Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, and Japanese Patent Publication No. 54-25957 Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer as described in Japanese Patent Application Laid-Open No. 59-53836 and Japanese Patent Laid-Open No. 59-71048 , Partially esterified maleic acid copolymers, and the like, and acidic cellulose derivatives having carboxylic acid in the side chain are likewise listed. As said alkali-soluble resin, what added the acid anhydride to the polymer which has a hydroxyl group, etc. are useful. Among these, specifically, a benzyl (meth) acrylate / (meth) acrylic acid copolymer, a benzyl (meth) acrylate / (meth) acrylic acid /, and a multi-component copolymer with another monomer are preferable. The alkali-soluble resin includes at least one acid component monomer selected from at least (i) maleic anhydride (MAA), acrylic acid (AA), methacrylic acid (MA) and fumaric acid (FA), and (ii) alkylpolyoxyethylene Copolymers consisting of (meth) acrylate and (iii) benzyl (meth) acrylate (hereinafter may be referred to as "copolymer A") can be used.

Examples of the copolymer A include (i) an acid component monomer and (ii) an alkyl polyoxyethylene (meth) acrylate (Acr (EO) _n : CH ₃ (OC ₂ H ₄ ) _n OCOC (R) = CH ₂ ) And (iii) the composition mass ratio of benzyl (meth) acrylate (Bz (M) A) is preferably 10-25 / 5-25 / 50-85, more preferably 15-20 / 5-20 / 60 80 is preferable. Moreover, as polystyrene conversion mass mean molecular weight (Mw) by GPC of the said copolymer, Preferably it is 3,000-50,000, More preferably, it is 5,000-30,000.

When the composition mass ratio of the (i) acid component monomer is in the above range, alkali solubility and solubility in a solvent are less likely to decrease. Further, (ii) alkyl of polyoxyethylene (meth) acrylate _{(Acr (EO) n: CH} 3 (OC 2 H 4) n OCOC (R) = CH 2) If there is a composition mass ratio of the above range, the substrate of the composition of the Since the spread of the liquid to the phase is easy and the dispersibility of the colorant is hard to be lowered, the effect of the present invention can be effectively achieved. (iii) When the composition mass ratio of benzyl (meth) acrylate (Bz (M) A) is in the said range, dispersion stability of a coloring agent, solubility in a composition, and alkali developing ability of a coating film will not fall easily.

(ii) repeating number n of polyoxyethylene (EO) _n of alkyl polyoxyethylene (meth) acrylate (Acr (EO) _n : CH ₃ (OC ₂ H ₄ ) _n OCOC (R) = CH ₂ ) -15 is preferable, 2-10 are more preferable, and 4-10 are especially preferable. When the number n of repetitions is in the above range, development residues are less likely to occur after development with an alkaline developer, fluidity as a coating liquid of the composition is lowered, and coating nonuniformity can be prevented. Deterioration of liquid properties can be prevented.

The binder polymers having these polar groups may be used alone or in a state of a composition used in combination with an ordinary film-forming polymer, and the amount of addition to 100 parts by mass of the pigment fine particles is generally 10 to 200 parts by mass, and 25 to 100 mass parts is preferable.

When the binder is a high molecular compound, the number of acidic groups in the high molecular compound is not particularly limited, but when the number of repeating units contained in one molecule is set to 100, the repeating unit having an acidic group is preferably 5 to 100, It is more preferable that it is 10-100. In addition, when it is referred as polymerization ratio of the repeating unit derived from the compound which has (1) carboxyl group, and the repeating unit derived from the compound which has said (2) carboxylic acid ester group, mole% of repeating unit (1) is 5-40. It is preferable that it is preferable that it is preferable that the repeating unit (2) is 40-90, and it is preferable that repeating units other than the repeating unit (1) or (2) are 25 or less. Moreover, 3000-1 million are preferable, as for the molecular weight of the high molecular compound of the alkali-soluble binder which has an acidic group, 4000-200000 are more preferable, 5000-80000 are especially preferable.

Although content of a binder is not specifically limited in the color filter of this invention, It is common that it is 15-50 mass% with respect to the total solid amount in a colored layer, and it is preferable that it is 20-45 mass%. When this amount is too large, the viscosity of the composition becomes too high, which is a problem in production aptitude. If it is too small, there is a problem in formation of a coating film.

As a photoinitiator or a photoinitiator type | system | group (in this invention, a photoinitiator type | system | group refers to the polymerization start composition which expresses the function of photoinitiation in the combination of a some compound.) Bisinal polyketal disclosed in the specification of US2367660. Donyl Compound, Acyloinether Compounds Described in US Patent No. 2448828, Aromatic Hydroxylo Substituted Compounds Replaced with α-Hydrocarbons, US Patent No. 3046127 and US Pat. No. 2951758 Polynuclear quinone compound described in the specification, a combination of triarylimidazole dimer and p-amino ketone described in US Pat. No. 3549367, benzothiazole compound and trihalo described in Japanese Patent Publication No. 51-48516 Methyl-s-triazine compound, trihalomethyl-triazine compound described in US Pat. No. 4239850, US Specific Trihaloalkyl as set forth in claim specification No. 4212976 can be exemplified such as methyl oxadiazole compound. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole and triarylimidazole dimers are preferred.

In addition, "Polymerization initiator C" described in Unexamined-Japanese-Patent No. 11-133600, 1-phenyl- 1, 2- propanedione 2- (o-ethoxycarbonyl) oxime, O- as an oxime system Benzoyl-4 '-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyl oxide, hexafluorophosphoro-trialkylphenylphosphonium salt, etc. are also listed as suitable. can do.

Although these photoinitiators or photoinitiator system may be used individually or in mixture of 2 or more types, it is preferable to use 2 or more types especially. By using at least two photopolymerization initiators, display characteristics, in particular, display unevenness can be reduced.

Although the content of a photoinitiator or a photoinitiator system is not specifically limited in the color filter of this invention, 0.5-20 mass% is common with respect to the total solid content in a colored layer, and 1-15 mass% is preferable. If this amount is too large, the sensitivity becomes too high and control becomes difficult. If it is too small, the exposure sensitivity becomes too low.

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

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

Although content of a solvent is not specifically limited, It is preferable that it is 10-95 mass% in a pigment dispersion.

In the color filter used conventionally, in order to realize high color purity, the color of each pixel became dark and the film thickness nonuniformity of a pixel was recognized as color nonuniformity as it is. Therefore, the improvement of the film thickness variation which directly affects the film thickness of a pixel has been calculated | required.

In the color filter of this invention, it is preferable to contain a suitable surfactant in the inkjet ink for color filters from a viewpoint of being able to control to a uniform film thickness and to effectively prevent the color nonuniformity by the film thickness variation.

Examples of the surfactant include surfactants disclosed in JP-A-2003-337424 and JP-A-11-133600. Although content of surfactant is not specifically limited, It is preferable that it is 5 mass% or less with respect to the total solid amount in a colored layer.

It is preferable that the color filter of this invention contains a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thio Bis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like. Although content of a thermal-polymerization inhibitor is not specifically limited, It is preferable that it is 1 mass% or less with respect to the total solid amount in a colored layer.

The color filter of this invention can contain a ultraviolet absorber as needed. As a ultraviolet absorber, besides the compound of Unexamined-Japanese-Patent No. 5-72724, a salicylate type, a benzophenone type, a benzotriazole type, a cyanoacrylate type, a nickel chelate type, a hindered amine type, etc. are mentioned.

Specifically, phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butyl phenyl-3 ', 5'-di-t-4'-hydroxybenzoate, 4-t -Butylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2'-hydroxy Hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3 -Diphenylacrylate, 2,2'-hydroxy-4-methoxybenzophenone, nickel dibutyldithiocarbamate, bis (2,2,6,6-tetramethyl-4-pyridine) -sebacate , 4-t-butylphenyl salicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinic acid-bis (2,2,6,6-tetramethyl- 4-piperidenyl) -ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- ( Diethylamino) -5-triazin-2-yl] amino} -3-phenylcoumarin, etc. This is listed. Although content of a ultraviolet absorber is not specifically limited, It is preferable that it is 5 mass% or less with respect to the total solid amount in a colored layer.

In forming the color filter of this invention, when using the said pigment dispersion as inkjet ink, it is preferable to control ink temperature so that the fluctuation range of the viscosity may be within +/- 5%. It is preferable that the viscosity at the time of injection is 5-25 mPa * s, It is more preferable that it is 8-22 mPa * s, It is especially preferable that it is 10-20 mPa * s (The viscosity is 25 degreeC in this invention unless it is specifically determined in this invention. Value when). In addition to the setting of the injection temperature, the viscosity can be adjusted by adjusting the type and the amount of the component to be contained in the ink. The said viscosity can be measured by general apparatuses, such as a conical flat rotational viscometer and an E-type viscometer, for example.

The surface tension of the ink during injection is preferably 15 to 40 mN / m from the viewpoint of improving the flatness of the pixel (in the present invention, the surface tension is a value at 23 ° C unless otherwise specified). More preferably, it is 20-35 mN / m, Most preferably, it is 25-30 mN / m. The adjustment of surface tension can be adjusted by addition of surfactant and the kind of solvent. The surface tension is, for example, a known surface tension measuring device (Cyowa Interface Science Co., Ltd. product, CBVP-Z), a fully automatic balanced type electro surface tension meter ESB-V (product of Kyowa Scientific Co., Ltd.) and the like. It can be measured by the platinum plate method using the measuring device of.

As a method of spraying the pigment dispersion as inkjet ink for color filters, a method of spraying charged ink continuously and controlling it by electric field, a method of spraying ink intermittently using a piezoelectric element, and heating the ink Various methods, such as the method of spraying intermittently using foaming, can be employ | adopted.

In addition, as for the inkjet method used for forming each pixel, conventional methods such as a method of thermosetting ink, a photocuring method, and a method of forming a transparent aqueous phase layer on a substrate in advance and then performing it can be used. have.

A conventional one can be applied to the inkjet head (hereinafter, also referred to simply as head), and a continuous type and a dot-on-demand type can be used. Among the dot-on-demand types, the type provided with a movable valve as described in Japanese Patent Application Laid-open No. Hei 9-323420 is preferable because of the discharge in the thermal head. In the piezo head, for example, heads described in European Patent A277,703, European Patent A278,590 and the like can be used. The head preferably has a temperature control function so that the temperature of the ink can be managed. It is preferable to set the injection temperature so that the viscosity at the time of injection may be 5-25 mPa * s, and to control ink temperature so that the fluctuation range of a viscosity may be within +/- 5%. Moreover, it is preferable to operate at 1-500 kHz as a drive frequency.

Furthermore, after forming each pixel, the heating process of heat processing (so-called baking process) can be provided. That is, the board | substrate which has a layer photopolymerized by light irradiation is heated in an electric furnace, a dryer, etc., or an infrared lamp is irradiated. The heating temperature and time depend on the composition of the photosensitive deep color composition or the thickness of the formed layer, but generally from about 120 ° C. to about 250 ° C. for about 10 minutes to about 120 minutes in terms of obtaining sufficient solvent resistance, alkali resistance and ultraviolet absorbance. It is preferable to heat.

The pattern shape of the color filter thus formed is not particularly limited, and may be a stripe shape, a lattice shape, or a delta array shape, which is a general black matrix shape.

Before the pixel formation process using the inkjet ink for color filters, the manufacturing method which manufactures a partition beforehand and gives ink to the part enclosed by the said partition is preferable. The barrier rib may be any type, but in the case of manufacturing a color filter, the barrier rib is preferably a barrier rib having a light blocking function having a black matrix function (hereinafter also referred to simply as a barrier rib). The partition wall can be manufactured by a material and a method such as a black matrix for a conventional color filter. For example, paragraphs [0021] to [0074] of Japanese Patent Laid-Open Publication No. 2005-3861, black matrix described in paragraphs [0012] to [0021] of Publication No. 2004-240039, and Japanese Patent Laid-Open Publication 2006 Paragraph Nos. [0015] to [0020] of -17980, and Paragraph Nos. [0009] to [0044] of Japanese Patent Application Laid-Open No. 2006-10875 are listed.

It can be set as a coating film using the said pigment dispersion as a coloring photosensitive resin composition, The thickness can be suitably determined, It is preferable that it is 0.5-5.0 micrometers, and it is more preferable that it is 1.0-3.0 micrometers. In the coating film using this coloring photosensitive resin composition, the color filter which has this can be manufactured by superposing | polymerizing the polymerizable monomer or oligomer contained in this, and making it as a polymerization film of a coloring photosensitive resin composition. It will be described later). The polymerization of the polymerizable monomer or the polymerizable oligomer can be performed by acting a photopolymerization initiator or a photopolymerization initiator system by light irradiation.

In addition, although the said coating film can be formed by apply | coating and drying a coloring photosensitive resin composition by a general coating method, it is preferable to apply | coat with a slit-shaped nozzle which has a slit-shaped hole in the part which liquid discharges. Specifically, Japanese Patent Application Laid-Open No. 2004-89851, Japanese Patent Application Laid-Open No. 2004-17043, Japanese Patent Publication No. 2003-170098, Japanese Patent Publication No. 2003-164787, Japanese Patent Publication No. 2003-10767, Japan The slit-shaped nozzles and slit coaters described in JP 2002-79163 A, JP 2001-310147 A, etc. are suitably used.

The coating method of a colored photosensitive resin composition to a board | substrate is excellent in spin coating in that it can apply | coat a thin film of 1-3 micrometers uniformly with high precision, and can be widely used for manufacture of a color filter. However, in recent years, in order to further increase manufacturing efficiency and manufacturing cost, as the size and mass production of liquid crystal display devices are increased, slit coating suitable for coating a substrate having a wider area and larger than spin coating has been adopted to manufacture color filters. . Also, from the viewpoint of bioliquidity, slit coating is superior to spin coating, and a uniform coating film can be obtained with a smaller amount of coating liquid. Here, it is preferable that a board | substrate is a transparent board | substrate, and glass plates, such as a soda glass plate, a low expansion glass, and a quartz glass plate which have a silicon oxide film on the surface, can be used. Moreover, you may use resin films, such as polyethylene terephthalate, cellulose triacetate, polystyrene, and a polycarbonate.

The slit coating has a slit of several tens of microns in width at the tip and is fixed to the substrate and the coating head while maintaining a clearance (gap) with the substrate of several 10 to several hundred microns in length for the application head having a length corresponding to the application width of the rectangular substrate. It is a coating method which apply | coats the coating liquid supplied from a slit to a board | substrate by maintaining a relative speed. This slit coating has (1) less liquid loss compared to spin coating, (2) cleaning process is reduced because there is no scattering of the coating liquid, and (3) no remixing of the scattered liquid component into the coating film ( 4) Since there is no starting stop time of rotation, the tack time can be shortened, and (5) it is easy to apply to a large substrate. From these advantages, slit coating is suitable for the production of color filters for large screen liquid crystal display devices, and is expected as an advantageous coating method even in reducing the amount of coating liquid.

Since slit coating forms a coating film with a much larger area than spin coating, it is necessary to maintain a certain relative speed between the coater and the coated object when discharging the coating liquid from the wide slit outlet. Therefore, a good fluidity is required for the coating liquid used in the slit coating method. It is particularly required to keep various conditions of the coating liquid supplied to the substrate from the slit of the coating head constant throughout the coating width. Insufficient liquid properties such as fluidity and viscoelastic properties of the coating liquid tend to cause coating unevenness, and it becomes difficult to keep the coating thickness constant in the coating width direction, resulting in a problem that a uniform coating film cannot be obtained.

From these, many attempts have been made to improve the fluidity and viscoelastic properties of the coating liquid in order to obtain a uniform coating film without any nonuniformity. As described above, however, there have been proposed means for lowering the molecular weight of the polymer, selecting a polymer having excellent solubility in the solvent, selecting various solvents for controlling the evaporation rate, or using a surfactant. It was not enough to remedy these various problems.

The photosensitive resin transfer material can be produced by forming a photosensitive resin using the above-described colored photosensitive resin composition, and is formed by using the photosensitive resin transfer material described in Japanese Patent Laid-Open No. 5-72724, that is, an integral film. It is desirable to. As a structural example of the said integral film, the structure which laminated | stacked a support body / thermoplastic resin layer / intermediate | middle layer / photosensitive resin layer / protective film in this order is mentioned.

It is necessary for the branch member to be flexible and to not generate significant deformation, shrinkage or extension even under pressure or under pressure and heating. Examples of such branched materials include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Of these, a biaxially oriented polyethylene terephthalate film is particularly preferable.

As a component used for a thermoplastic resin layer, the organic high molecular material of Unexamined-Japanese-Patent No. 5-72724 is preferable, and it uses the Vicat method (specifically, the method of measuring the softening point of a polymer by the American material test method ASTMD1235). Particular preference is given to selecting from organic polymer materials having a softening point of about 80 ° C. or less. Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products, ethylene and acrylic acid esters or saponified products thereof, and chlorides such as polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof. Vinyl copolymers, polyvinylidene chloride, vinylidene chloride copolymers, polystyrene, styrene copolymers such as styrene and (meth) acrylic acid esters or saponified salts thereof, polyvinyltoluene, vinyltoluene and (meth) acrylic acid esters or saponified salts thereof Vinyltoluene copolymers, poly (meth) acrylic acid esters, (meth) acrylic acid ester copolymers such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer nylon, copolymer nylon, N-alkoxymethylated nylon, N-dimethyl Organic polymers such as polyamide resins such as aminated nylon Who are listed.

In photosensitive resin transfer material, it is preferable to form an intermediate | middle layer in order to prevent mixing of the components at the time of application | coating of several application layer, and the storage after application | coating. As the intermediate layer, it is preferable to use an oxygen barrier film having an oxygen barrier function described as " separation layer " in Japanese Patent Application Laid-Open No. 5-72724. In this case, sensitivity is increased during exposure, Thereby improving productivity.

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

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

The photosensitive resin transfer material is coated with a coating liquid (a coating liquid for thermoplastic resin layer) in which an additive of a thermoplastic resin layer is dissolved on a support and dried to form a thermoplastic resin layer, and then a thermoplastic resin layer on the thermoplastic resin layer. It can manufacture by apply | coating and drying the solution of the intermediate | middle layer material which consists of a solvent which does not melt | dissolve, and apply | coating and drying the photosensitive resin layer with the solvent which does not dissolve an intermediate layer after that.

Further, by preparing a sheet having a thermoplastic resin layer and an intermediate layer formed on the support and a sheet having a photosensitive resin layer formed on a protective film, and adhering the intermediate layer and the photosensitive resin layer to contact each other, It is also possible to prepare a sheet having a thermoplastic resin layer formed thereon, and a sheet having a photosensitive resin layer and an intermediate layer formed thereon on a protective film, and attaching each other so that the thermoplastic resin layer and the intermediate layer are in contact with each other.

In the photosensitive resin transfer material, 1.0-5.0 micrometers is preferable, as for the film thickness of the photosensitive resin layer, 1.0-4.0 micrometers is more preferable, 1.0-3.0 micrometers is especially preferable. In addition, although it is not specifically limited, As a preferable film thickness of each other layer, a support body is 15-100 micrometers, a thermoplastic resin layer is 2-30 micrometers, an intermediate layer is 0.5-3.0 micrometers, and a protective film is 4-40 micrometers Is generally preferred.

In addition, although the application | coating in the said manufacturing method can be performed by a general coating apparatus etc., it is preferable to carry out by the coating apparatus (slit coater) using a slit-shaped nozzle. Preferred examples of the slit coater and the like are the same as described above.

The color filter of the present invention may have only a single color or may have three different colors, such as red, blue, and green, depending on the application. And the pattern of the colored layer on a board | substrate and its formation method are not specifically limited.

The color filter of this invention can be used because it is excellent in contrast. In the present invention, the contrast refers to the ratio of the amount of transmitted light when the polarization axes are parallel and perpendicular between the two polarizing plates ("The 7th Color Optical Conference of 1990, 512 Color Display for 10.4" Size TFT-LCD Color filters, Ueki, Kosei, Fukunaga, Yamanaka, etc.).

The high contrast of the color filter means that the contrast of the contrast when combined with the liquid crystal can be large, which is a very important performance for the liquid crystal display to replace the CRT. It is preferable that the contrast of the color filter of this invention is 3000 or more in monochromatic color, It is more preferable that it is 5000 or more, It is especially preferable that it is 7000 or more. In the color filter having an R pixel, a G pixel, a B pixel, and a black matrix, it is preferable that it is 3000 or more, It is more preferable that it is 5000 or more, It is especially preferable that it is 6000 or more. The present invention has a feature capable of realizing such high contrast.

When the color filter of the present invention is used for televisions, the chromaticity of all of the monochromatic colors of red (R), green (G), and blue (B) by the F10 light source are shown in the table below. It is preferable to be within a range of 5 or less, more preferably 3 or less, and particularly preferably 2 or less in the difference ΔE).

In the present invention, the chromaticity is measured by a microspectral photometer (Olympus Corporation; OSP100 or 200), calculated as a result of the F10 light source field of view 2 degrees, and represented by the xyY value of the xyz colorimeter. The difference from the target chromaticity is represented by the color difference of the La * b * color system.

The color filter of this invention can be manufactured by methods, such as the method of forming a photosensitive resin layer on a board | substrate, and repeating exposure and image development by the number of colors. Further, if necessary, the boundary may be divided into a black matrix.

In the above production method, as the method of forming the photosensitive resin layer on the substrate, (a) a method of applying the respective colored photosensitive resin compositions by a general coating device or the like, and (b) the photosensitive resin transfer material described above is used. For example, the method of sticking by a laminator, etc. are mentioned.

When manufacturing the color filter of this invention, although the general coating apparatus can be used for application | coating of the coloring photosensitive resin composition, the slit coater demonstrated above especially can be used suitably. Preferred examples of the slit coater and the like are the same as described above. When forming the photosensitive resin layer by application | coating, 0.5-5.0 micrometers is preferable and, as for the film thickness, 1.0-3.0 micrometers is especially preferable.

Using the photosensitive resin transfer material, the photosensitive resin layer formed in the film shape can be adhere | attached by crimping or heat-compressing with the roller or flat plate heated and / or pressed on the board | substrate mentioned later. Specifically, laminators and lamination methods described in Japanese Patent Laid-Open No. 7-110575, Japanese Patent Laid-Open No. 11-77942, Japanese Patent Laid-Open No. 2000-334836, and Japanese Patent Laid-Open No. 2002-148794 are listed. It is preferable to use the method of Unexamined-Japanese-Patent No. 7-110575 from a low foreign material viewpoint.

When the color filter of this invention forms a photosensitive resin layer by application of a coloring photosensitive resin composition, an oxygen barrier film can be further formed on the said photosensitive resin layer, and it can raise exposure sensitivity by this. As said oxygen blocking film, the same thing as what was already demonstrated is mentioned. In addition, it is although it does not specifically limit, As a film thickness of an oxygen barrier film, 0.5-3.0 micrometers is generally preferable.

A predetermined mask is disposed above the photosensitive resin layer formed on the substrate, and then exposed through the mask, the thermoplastic resin layer, and the intermediate layer from above the mask, and then developed using a developing solution. By repeating as many times as possible, a color filter can be obtained.

Here, as the light source of the exposure, any light can be irradiated (for example, 365 nm, 405 nm, etc.) in a wavelength region capable of curing the photosensitive resin layer, and can be used as appropriate. Specifically, ultra high pressure mercury lamps, high pressure mercury lamps, metal halide lamps and the like are listed. As an exposure amount, it is about 5-200mJ / cm <2> normally, Preferably it is about 10-100mJ / cm <2>.

In addition, there is no restriction | limiting in particular as said developing solution, General developing solutions, such as those of Unexamined-Japanese-Patent No. 5-72724, can be used. In addition, it is preferable that the developing solution has a photosensitive resin layer having a dissolution-type developing behavior, for example, containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L. You may add a little further solvent.

Organic solvents that are miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzyl Alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetoamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N- Methylpyrrolidone and the like. As for the density | concentration of the said organic solvent, 0.1 mass%-30 mass% are preferable.

Further, a conventional surfactant may be further added to the developer. As for the density | concentration of surfactant, 0.01 mass%-10 mass% are preferable.

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

Here, when the shower phenomenon is explained, the uncured portion can be removed by spraying the developing solution with a shower on the photosensitive resin layer after exposure. Moreover, it is preferable to spray a alkaline liquid with low solubility of the photosensitive resin layer by shower etc. before image development, and to remove a thermoplastic resin layer, an intermediate | middle layer, etc. Moreover, after image development, it is preferable to remove a image development residue, spraying a detergent etc. with a shower, and rubbing with a brush etc.

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

Further, when producing the color filter of the present invention, as described in Japanese Patent Application Laid-Open No. 11-248921 and Japanese Patent No. 3255107, a colored photosensitive resin composition for forming a color filter is stacked to form a foundation thereon. It is preferable from the viewpoint of cost reduction that a transparent electrode is formed, and the division alignment projections are further stacked to form a spacer.

In the case where the colored photosensitive resin composition is sequentially applied and superimposed, the film thickness becomes thinner every time due to the leveling of the coating liquid. For this reason, it is preferable to overlap four colors of K (black), R, G, and B, and to further overlap the projection for divisional orientation. On the other hand, in the case of using a transfer material having a thermoplastic resin layer, the thickness is preferably set to three or two colors in order to keep the thickness constant.

The size of the base is preferably 25 µm or more, particularly preferably 30 µm or more, from the viewpoint of preventing deformation of the photosensitive resin layer when laminating and transferring the transfer material to maintain a constant thickness.

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

In the color filter of this invention, it is preferable that a colored layer contains organic pigment microparticles | fine-particles, The microparticles | fine-particles are compatible with the organic pigment solution which melt | dissolved the organic pigment in the alkaline good solvent, and are compatible with the said good solvent, It is preferable that they are fine particles produced by mixing a solvent that becomes a poor solvent (hereinafter, this solvent may be referred to as [poor solvent of organic pigment] or simply [poor solvent], etc.). It may be called "precipitation method."). In addition, the combination of the poor solvent and the good solvent needs to have a sufficient difference in the solubility of the organic material, and it is necessary to select a preferable one according to the pigment, but any combination can be selected as long as it is a combination that enables this process.

The poor solvent of the organic pigment is not particularly limited as long as it is compatible with or uniformly mixed with a good solvent in which the organic pigment is dissolved. It is preferable that the solubility of an organic pigment is 0.02 mass% or less, and, as a poor solvent of an organic pigment, it is more preferable that it is 0.01 mass% or less. There is no particular lower limit to the solubility of the organic pigment in the poor solvent, but considering the organic pigments that are usually used, 0.000001 mass% or more is practical. The solubility may be the solubility in the presence of an acid or an alkali. The compatibility or homogeneous mixing of the good solvent with the poor solvent is preferably 30% by mass or more, more preferably 50% by mass or more, of the good solvent in the poor solvent. There is no particular upper limit to the amount of solubility of the good solvent in the poor solvent, but it is practical to mix each other in any ratio.

As a poor solvent, for example, an aqueous solvent (eg, water or hydrochloric acid, aqueous sodium hydroxide), an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, an aromatic compound solvent, a carbon disulfide solvent, an aliphatic compound solvent, a nitrile compound solvent, Halogen compound solvents, ester compound solvents, ionic liquids, mixed solvents thereof, and the like, and an aqueous solvent, an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, an ester compound solvent, or a mixture thereof is preferable, and an aqueous solvent. , Alcohol compound solvent or ester compound solvent is more preferable.

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

A good solvent can melt | dissolve the organic pigment to be used, and if it is compatible with the said poor solvent or mixed uniformly, it will not specifically limit. It is preferable that the solubility of an organic pigment is 0.2 mass% or more, and, as for the solubility to the good solvent of an organic pigment, it is more preferable that it is 0.5 mass% or more. Although there is no particular upper limit to the solubility of an organic pigment in the alkaline good solvent, it is practical that it is 50 mass% or less considering the organic pigment normally used. This solubility may be solubility when dissolved in the presence of an acid or a base. The preferred range of compatibility or homogeneous mixing of the poor solvent and the good solvent is as described above.

As a good solvent, for example, water, hydrochloric acid, dilute sulfuric acid, concentrated sulfuric acid, aqueous sodium hydroxide solution, alcohol compound solvent, amide compound solvent, ketone compound solvent, ether compound solvent, aromatic compound solvent, carbon disulfide solvent, aliphatic compound solvent, nitrile Compound solvents, sulfoxide compound solvents, halogen compound solvents, ester compound solvents, ionic liquids, mixed solvents thereof, and the like, include aqueous solvents, alcohol compound solvents, ketone compound solvents, ether compound solvents, sulfoxide compound solvents, esters It is preferable to contain a compound solvent, an amide compound solvent, or a mixture thereof. Especially, it is preferable to contain an aqueous solvent, an alcohol compound solvent, an ester compound solvent, a sulfoxide compound solvent, or an amide compound solvent, It is more preferable to contain an aqueous solvent, a sulfoxide compound solvent, or an amide compound solvent, and sulfoxide It is particularly preferable to contain a compound solvent or an amide compound solvent.

Examples of the sulfoxide compound solvent include dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, sulfolane, and the like. As the amide compound solvent, for example, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone ε-caprolactam, formamide, N-methylformamide, acetoamide, N-methylacetoamide, N, N-dimethylacetoamide, N-methylpropanamide, hexamethylphosphoric triamide and the like.

Moreover, as a density | concentration of the organic pigment solution which melt | dissolved the organic pigment in a good solvent, the range of the saturated concentration with respect to the good solvent of the organic pigment in the conditions at the time of melt | dissolution, about 1/100 of this is preferable.

There is no restriction | limiting in particular in the conditions of organic pigment solution preparation, The range of subcritical and supercritical conditions can be selected from normal pressure. The temperature at normal pressure is preferably -10 to 150 占 폚, more preferably -5 to 130 占 폚, particularly preferably 0 to 100 占 폚.

Although it is common in what is listed here as an example of a good solvent, and what is listed as a poor solvent, it is not combining the same thing as a good solvent and a poor solvent, but the solubility with respect to a good solvent in relationship with each organic pigment employ | adopted. It may be higher than the solubility in the poor solvent, for example, the solubility difference is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. There is no particular upper limit to the difference in solubility between the good solvent and the poor solvent, but it is practical that it is 50 mass% or less in consideration of the organic material used normally.

In the fine particle deposition method, in order to dissolve the organic pigment uniformly in a good solvent, it is preferable to dissolve in the presence of a base. Generally, in the case of pigments having an alkaline dissociable group in the molecule, a solvent containing a base is used. For example, quinacridone, diketopyrrolopyrrole, and disazo condensation compound pigments are preferably dissolved in the presence of a base.

As the base, inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide or barium hydroxide, or organic bases such as trialkylamine, diazabicyclo undecene (DBU) and metal alkoxide can be used. Is an inorganic base.

The amount of the base to be used is an amount which can dissolve the pigment uniformly and is not particularly limited, but in the case of the inorganic base, it is preferably 1.0 to 30 molar equivalents, more preferably 1.0 to 25 molar equivalents, more preferably relative to the organic pigment. Preferably it is 1.0-20 molar equivalent. In the case of an organic base, Preferably it is 1.0-100 molar equivalent with respect to an organic pigment, More preferably, it is 50-100 molar equivalent, More preferably, it is 20-100 molar equivalent.

In order to improve the solubility of an organic pigment, a good solvent can add the solvent which has high solubility with respect to bases, such as some water and a lower alcohol, to an organic solvent. 50 mass% or less is preferable with respect to the organic pigment solution whole quantity, and, as for the quantity of water and a lower alcohol, 30 mass% or less is more preferable. Specifically, water, methanol, ethanol, n-propanol, isopropanol, butyl alcohol, etc. can be used.

There is no restriction | limiting in particular in the conditions of the poor solvent at the time of precipitate-generating pigment microparticles | fine-particles, The range of subcritical and supercritical conditions can be selected from normal pressure. The temperature at normal pressure is preferably -30 to 100 占 폚, more preferably -10 to 60 占 폚, and particularly preferably 0 to 30 占 폚. 0.5-80.0 mPa * s is preferable and, as for the viscosity of a pigment fine particle precipitation liquid, 1.0-50.0 mPa * s is more preferable.

When mixing an organic pigment solution and a poor solvent, you may add and mix both, but it is preferable to add and mix an organic pigment solution to a poor solvent, and it is preferable that the poor solvent is stirred at that time. As for stirring speed, 100-10000 rpm is preferable, 150-8000 rpm is more preferable, 200-6000 rpm is especially preferable. A pump or the like may or may not be used for the addition. In addition, it may be added to the liquid, or may be added outside the liquid. In the present invention, it is preferable to continuously supply from the pump to the liquid through the supply pipe. 0.1-200 mm is preferable and, as for the internal diameter of a supply pipe, 0.2-100 mm is more preferable. As a speed | rate supplied from a supply pipe to a liquid, 1-10000 ml / min is preferable and 5-5000 ml / min is more preferable.

As for the mixing ratio (good solvent / poor solvent ratio in pigment fine particle precipitation liquid) of an organic pigment solution and a poor solvent, 1/50-2/3 are preferable by volume ratio, 1/40-1/2 are more preferable, 1/20 ˜3 / 8 is particularly preferred.

The concentration of the pigment fine particle precipitate is not particularly limited as long as it can produce organic particles, but the organic particles are preferably in the range of 10 to 40000 mg, more preferably in the range of 20 to 30000 mg, with respect to 1000 ml of the dispersion solvent. Preferably it is the range of 50-25000 mg.

Moreover, although the preparation scale at the time of producing | generating pigment microparticles | fine-particles is not specifically limited, It is preferable that it is a preparation scale whose mixing amount of a poor solvent is 10-2000L, and it is more preferable that it is a preparation scale which is 50-1000L.

The particle size of the organic particles can be quantified by a measurement method to express the average size of the population. However, the particle size of the organic particles is well used. The mode diameter representing the maximum value of the distribution, the median diameter corresponding to the median of the integral distribution curve, and the average diameter are various. (Number average, length average, area average, mass average, volume average, etc.), etc. In the present invention, the average particle diameter refers to the number average diameter unless otherwise specified. It is preferable that it is 1-30 nm, and, as for the average primary particle diameter Dp of the pigment fine particle (primary particle) contained in the colored layer of a color filter, it is more preferable that it is 1-20 nm. The pigment fine particles may be crystalline particles, amorphous particles, or a mixture thereof.

In addition, in this invention, the ratio (Mv / Mn) of volume average particle diameter (Mv) and number average particle diameter (Mn) is used as an index which means monodispersity of particle | grains, unless it is specifically determined. It is preferable that monodispersity, ie Mv / Mn, of a pigment fine particle (primary particle) is 1.0-2.0, It is more preferable that it is 1.0-1.8, It is especially preferable that it is 1.0-1.5.

As a measuring method of the particle diameter of organic particle | grains, a microscopic method, a mass method, the light scattering method, the light blocking method, the electrical resistance method, the acoustic method, the dynamic light scattering method are mentioned, A microscope method and the dynamic light scattering method are especially preferable. Examples of the microscope used in the microscopic method include a scanning electron microscope and a transmission electron microscope. Particle measuring apparatus by dynamic light scattering method, for example, Nikkiso Co., Ltd. Product details of NAN0RACK UPA-EX150, Otsuka Electronics Co. Ltd. Dynamic light scattering photometer DLS-7000 series.

In preparing the dispersion liquid of the said pigment microparticles | fine-particles, it is preferable to contain a dispersing agent. Although the process of containing a dispersing agent is not specifically limited, It is preferable to add a dispersing agent to both or one side of an organic pigment solution and a poor solvent, and to contain it. Moreover, it is also preferable to add a dispersing agent solution at the time of pigment fine particle formation in a system separate from the said both liquids. It is also preferable to use the pigment particle which surface-treated with the dispersing agent previously, and surface treatment may be given to the pigment particle so that adsorption of a dispersing agent may be promoted. A dispersing agent has the effect of (1) adsorb | sucking quickly to the precipitated pigment surface, forming fine nanoparticles, and (2) preventing these particles from aggregating again.

As dispersants which can be used, for example, low molecular or polymeric dispersants of anionic, cationic, zwitterionic, nonionic or pigment derivatives can be used. Moreover, you may use the water-soluble polymer mentioned above. The molecular weight of the polymer dispersant is not particularly limited as long as it can be uniformly dissolved in a solution. The molecular weight is preferably 1,000 to 2,000,000, more preferably 5,000 to 1,000,000, still more preferably 10,000 to 500,000, Is particularly preferable. Specifically as the polymer dispersant, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, polyvinyl alcohol- Partial Formalate, Polyvinyl Alcohol-Partial Butyralate, Vinyl Pyrrolidone-Vinyl Acetate Copolymer, Polyethylene Oxide / Propylene Oxide Block Copolymer, Polyacrylate, Polyvinyl Sulfate, Poly (4-Vinylpyridine) Salt , Polyamides, polyarylamine salts, condensed naphthalene sulfonates, cellulose derivatives, starch derivatives and the like. In addition, natural polymers such as alginate, gelatin, albumin, casein, arabian rubber, tragacanth rubber and lignin sulfonate can also be used. Especially, it is preferable to use the water-soluble polymer demonstrated above, and polyvinylpyrrolidone is more preferable. These polymers may be used singly or in combination of two or more. These dispersants may be used alone or in combination. Dispersants used to disperse pigments are described in detail on pages 29 to 46 of "Pigment Dispersion Stabilization and Surface Treatment Technology and Evaluation" (Chemical Information Association, December 2001).

Anionic dispersants (anionic surfactants) include N-acyl-N-alkyltaurine salts, fatty acid salts, alkylsulfuric acid ester salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkylsulfosuccinic acid salts, alkylphosphate ester salts, naphthalene Sulfonic acid formalin condensates, polyoxyethylene alkyl sulfate ester salts, and the like. Among them, N-acyl-N-alkyltaurine salts are preferable. As the N-acyl-N-alkyltaurine salt, those described in Japanese Patent Application Laid-Open No. 3-273067 are preferable. These anionic dispersants may be used alone or in combination of two or more.

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

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

 Nonionic dispersants (nonionic surfactants) include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, glycerin fatty acids Esters and the like. Among them, polyoxyethylene alkyl aryl ethers are preferred. These nonionic dispersants may be used alone or in combination of two or more.

The pigment derivative-type dispersant is defined as a pigment derivative-type dispersant derived from an organic pigment as a parent material and produced by chemical modification of its friend, or a pigment derivative-type dispersant obtained by a pigmentation reaction of a chemically modified pigment precursor. For example, a sugar-containing pigment derivative dispersant, a piperidyl-containing pigment derivative dispersant, a naphthalene or perylene-derived pigment derivative dispersant, a pigment derivative dispersant having a functional group linked to a pigment friend via a methylene group, a pigment friend chemically modified with a polymer Crude pigment derivative dispersants having sulfonic acid groups, pigment derivative dispersants having sulfonamido groups, pigment derivative dispersants having ether groups, or pigment derivative dispersants having carboxylic acid groups, carboxylic acid ester groups or carboxyamide groups. .

When preparing the organic pigment solution which melt | dissolved in the good solvent, it is preferable to coexist the pigment dispersant containing an amino group. Here, an amino group contains a primary amino group, a secondary amino group, and a tertiary amino group, and the number of amino groups may be one, or multiple may be sufficient as it. The pigment derivative compound which introduce | transduced the substituent which has an amino group in a pigment skeleton, or the polymer compound which made the monomer which has an amino group the polymerization component may be sufficient. As examples thereof, for example, the compounds described in Japanese Patent Application Laid-Open No. 2000-239554, 2003-96329, 2001-31885, Japanese Patent Application Laid-Open No. 10-339949, Japanese Patent Application Laid-Open No. 5-72943, and the like. Are enumerated, but not limited to these.

As said dispersing agent, it is preferable to use at least 1 sort (s) chosen from the compound represented by the following general formula (D1), (D3), and a formula (D4).

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

In the general formula (D1), A represents a component capable of forming an azo dye together with X-Y. The A may be arbitrarily selected as long as it is a compound capable of forming an azo dye by coupling with a diazonium compound. Specific examples of the above-mentioned A are shown below, but the present invention is not limited thereto at all.

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

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

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

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

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

The compound represented by the general formula (D1) can be synthesized by the method described in, for example, JP-A-2000-239554.

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

In general formula (D3),

Q is an anthraquinone compound pigment, an azo compound pigment, a phthalocyanine compound pigment, a quinacridone compound pigment, a dioxazine compound pigment, an anthrapyrimidine compound pigment, an anthrone compound pigment, an indanthrone compound pigment, a flavantron compound pigment, a pyrantrone The organic pigment | dye residue chosen from a compound pigment | dye, a perinone compound pigment | dye, a perylene compound pigment | dye, and a thioindigo compound pigment | dye is shown, Especially, it is preferable that it is an azo compound pigment | dye or a dioxazine compound pigment | dye, and it is more preferable that it is an azo compound pigment | dye. .

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

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

R ₁₁ and R ₁₂ may each independently form a substituted or unsubstituted alkyl group or a heterocyclic group containing at least a nitrogen atom with R ₁₁ and R ₁₂ . Especially, it is preferable that it is a pyrrolidinyl group containing a methyl group, an ethyl group, a propyl group, or a nitrogen atom, and it is more preferable that it is an ethyl group.

Y ₁ represents -NH- or -O-.

Z ₁ represents a hydroxyl group or a group represented by formula (D3a), or -NH-X ₁ -Q when n1 is 1. m1 represents an integer of 1 to 6, preferably 2 to 3; n1 represents an integer of 1 to 4, preferably 1 to 2;

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

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

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

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

<3. Pigment Dispersant Containing Graft Copolymer>

In the precipitation generation of the pigment fine particles, it is also preferable to use a dispersant containing a graft copolymer having an amino group and an ether group and containing other components suitably selected as necessary.

The graft copolymer has at least an amino group and an ether group, and other monomers and the like may be contained as a copolymer unit.

As a weight average molecular weight (Mw) of the said graft copolymer, 3000-100000 are preferable and 5000-50000 are more preferable. When the said weight average molecular weight (Mw) is less than 3000, aggregation of pigment microparticles | fine-particles cannot be suppressed and a viscosity may rise, and when it exceeds 100000, the solubility with respect to an organic solvent may be insufficient and a viscosity may rise. .

The graft copolymer comprises (i) a polymerizable oligomer having an ethylenically unsaturated double bond at its end, (ii) a monomer having an amino group and an ethylenically unsaturated double bond, and (iii) a polymerizable monomer having an ether group as a copolymer unit. It is preferable to include at least and to contain (iv) another monomer as a copolymerization unit as needed.

As content in the said graft copolymer of these copolymer units, it is preferable that (i) the said polymerizable oligomer is 15-98 mass%, It is more preferable that it is 25-90 mass%, (ii) Amino group containing It is preferable that a monomer is 1-40 mass%, It is more preferable that it is 5-30 mass%, (iii) It is preferable that the polymerizable monomer which has the said ether group is 1-70 mass%, It is 5-60 mass% It is more preferable.

When the content of the polymerizable oligomer is less than 15% by mass, the steric repulsion effect as a dispersant may not be obtained and aggregation of the pigment fine particles may not be prevented. When the content of the polymerizable oligomer exceeds 98% by mass, the proportion of the nitrogen-containing monomer is reduced. As a result, the adsorption capacity to the pigment fine particles may be lowered and the dispersibility may not be sufficient. When the content of the nitrogen-containing monomer is less than 1% by mass, the adsorption capacity to organic particles may be lowered and the dispersibility may not be sufficient. When the content of the nitrogen-containing monomer exceeds 40% by mass, the ratio of the polymerizable oligomer decreases, so as a dispersant. The steric repulsion effect may not be obtained and aggregation of organic particles may not be sufficiently prevented. When content of the polymerizable monomer which has the said ether group is less than 1 mass%, development suitability at the time of manufacture of color filters etc. may not be enough, and when it exceeds 70 mass%, the capability as a dispersing agent may fall.

(i) a polymerizable oligomer

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

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

As a group which has the said ethylenically unsaturated double bond, a (meth) acryloyl group, a vinyl group, etc. are mentioned suitably, among these, A (meth) acryloyl group is especially preferable among these.

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

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

Specific examples of the polymerizable oligomer include poly-2-hydroxyethyl (meth) acrylate, polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and poly-i-butyl (meth). In acrylate and these copolymers, the polymer in which the (meth) acryloyl group couple | bonded with one of the molecular terminals is preferable.

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

Preferable specific examples of the polymerizable oligomer in the present invention are at least one oligomer selected from polymers of alkyl (meth) acrylates and copolymers of alkyl (meth) acrylates and polystyrenes, and the number average molecular weight is 1000. 20000 and the thing which has a (meth) acryloyl group at the terminal is mentioned.

(ii) an amino group-containing monomer

As said amino-group containing monomer, at least 1 sort (s) chosen from the compound represented, for example by following General formula (E2) is mentioned preferably.

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

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

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

In this invention, at least 1 sort (s) chosen from the monomer represented by either of the following general formula (E3) and (E4) among the monomer represented by the said general formula (E2) is preferable.

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

In the general formula (E4), R ⁴¹ has the same meaning as R ²¹ . X ⁴ is the same as X ² and is -N (R ⁴³ ) (R ⁴⁴ ) (wherein R ⁴³ and R ⁴⁴ are the same as R ²³ and R ²⁴ ), or -R ⁴⁵ -N ⁴⁶ ) (R ⁴⁷ ) (wherein R ⁴⁵ , R ⁴⁶ and R ⁴⁷ are the same as R ²⁵ , R ²⁶ and R ²⁷ , respectively).

Specific examples of the monomer represented by the general formula (E2) include dimethyl (meth) acrylamide, diethyl (meth) acrylamide, diisopropyl (meth) acrylamide, di- (Meth) acrylamide, N-methylpyrrolidyl (meth) acrylamide, N, N-methylphenyl (meth) acrylamide, Metha) acrylamide (above, (meth) acrylamides); 2- (N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, N-diethylamino) ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth ) Acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylamide, 6- (N, N -Diethylamino) hexyl (meth) acrylamide (above, aminoalkyl (meth) acrylamides) etc. are mentioned as a preferable thing.

(iii) a polymerizable monomer having an ether group

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

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

The polymerizable monomer having an ether group is not particularly limited as long as it has an ether group and is polymerizable, and can be appropriately selected from conventional ones. For example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Acrylate, polyethyleneglycol polypropylene glycol mono (meth) acrylate, polytetramethylene glycol monomethacrylate, etc. are mentioned, These may be a commercial item, and what synthesize | combined suitably may be sufficient. As commercial products, methoxypolyethylene glycol methacrylate (trade name: NK ESTER M-40G, M-90G, M-230G (manufactured by Toagosei Chemical Industry Co., Ltd.), BLENMER PME- (Trade name: BLENMER PE-90, PE-200, PE-200, PME-400, PME-1000, PME-2000 and PME-4000 manufactured by Nippon Yushi Co., Ltd.), polyethylene glycol monomethacrylate 350, manufactured by Nippon Yushi Co., Ltd.), polypropylene glycol monomethacrylate (trade name: BLENMER PP-500, PP-800, PP-1000, manufactured by Nippon Yushi Co., Ltd.), polyethylene glycol polypropylene glycol (Manufactured by Nippon Yushi Co., Ltd.), polyethylene glycol polytetramethylene glycol monomethacrylate (trade name: BLENMER 55PET-800, manufactured by Nippon Yushi Co., Ltd.), and polypropylene glycol monomethacrylate (trade name: BLENMER 70PEP- Polypropylene glycol polytetramethylene glycol monomethacrylate (trade name: BLENMER NHK-5050, manufactured by Nippon Yushi Co., Ltd.) ) Are listed.

(iv) other monomers

The graft copolymer may further contain the other monomer as a copolymer unit, and the graft copolymer may be appropriately selected depending on the purpose without being particularly limited to the other monomer, but for example, an aromatic vinyl compound (eg, styrene, α- Methylstyrene and vinyltoluene), (meth) acrylic acid alkyl esters (e.g., methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate and i-butyl (meth) acrylate), (Meth) acrylic acid alkylaryl esters (e.g. benzyl (meth) acrylate), glycidyl (meth) acrylates, carboxylic acid vinyl esters (e.g. vinyl acetate and vinyl propionate), vinyl cyanide (e.g. (meth) Acrylonitrile and α-chloroacrylonitrile) and aliphatic conjugated dienes (eg, 1, 3-butadiene and isoprene), (meth) acrylic acid and the like. Of these, unsaturated carboxylic acids, alkyl (meth) acrylates, alkylaryl (meth) acrylate esters and carboxylic acid vinyl esters are preferred.

As content of the said other monomer in the said graft copolymer, 5-70 mass% is preferable, for example. If the said content rate is less than 5 mass%, the physical property control of a coating film may become impossible, and when it exceeds 70 weight%, the capability as a dispersing agent may not fully be exhibited.

As specific preferred examples of the graft copolymer,

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

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

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

(14) copolymers of 3- (N, N-dimethylamino) propylacrylamide / polyethyleneglycol mono (meth) acrylate / terminal methacryloylated methyl (meth) acrylate and 2-hydroxyethylmethacrylate Copolymer,

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

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

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

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

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

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

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

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

It is preferable that it is the range of 0.1-1000 mass parts with respect to 100 mass parts of pigments, and, as for content of a dispersing agent further improves the uniform dispersibility and storage stability of a pigment particle, More preferably, it is the range of 1-500 mass parts, Preferably it is the range of 5-20 mass parts. If it is less than 0.1 mass part, the improvement of the dispersion stability of a pigment fine particle may not be seen. In addition, a dispersing agent may be used independently or may be used in combination of several things.

In order to further improve the uniform dispersibility and storage stability of organic particle | grains, it is preferable that it is the range of 0.1-1000 mass parts with respect to 100 mass parts of organic pigments, More preferably, it is the range of 1-500 mass parts, More preferably, it is the range of 5-20 mass parts. If it is less than 0.1 mass part, the improvement of the dispersion stability of a pigment fine particle may not be seen.

[concentration]

By desalting and concentrating the pigment fine particle dispersion, it is possible to produce a concentrate suitable for a color filter coating liquid or an inkjet ink on an industrial scale.

The concentration method is not particularly limited as long as the pigment fine particle liquid can be concentrated. For example, an extraction solvent is added and mixed to the pigment fine particle dispersion, the pigment fine particles are concentrated and extracted on the extraction solvent, and the concentrated extract liquid is filtered by a filter or the like. To concentrate the fine particles by centrifugation, to concentrate the pigment fine particles by centrifugation, to perform desalination concentration by ultrafiltration, to sublimate the solvent by vacuum lyophilization, and to concentrate by heating or reduced pressure. The method of drying and concentrating a solvent is preferable. Combinations of these and the like are also very preferably used.

About the pigment fine particle concentration after concentration, 1-100 mass% is preferable, 5-100 mass% is more preferable, 10-100 mass% is especially preferable.

Although the extraction solvent used for this concentrated extraction is not specifically limited, The thing which is not substantially mixed with the dispersion solvent (for example, aqueous solvent) of a pigment fine particle dispersion (it does not mix substantially in this invention means a low compatibility) ), 50 mass% or less of melt | dissolution is preferable, and 30 mass% or less is more preferable. There is no particular lower limit to this amount of dissolution, but considering the solubility of a general solvent, it is practically 1 mass% or more. In addition, it is preferable that the extractant is a solvent that produces a weak agglomeration (a floc capable of redispersing without applying a high shear force such as milling or high speed stirring) that the pigment fine particles can be redispersed in the extractant. Such a state is preferable in that it is possible to wet the desired pigment fine particles in the extraction solvent without causing strong agglomeration which changes the particle size, and can easily remove the dispersion solvent such as water by filter filtration or the like. As the extraction solvent, an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, an aliphatic compound solvent is preferable, an ester compound solvent, an aromatic compound solvent or an aliphatic compound solvent is more preferable, and an ester compound solvent is particularly preferable.

Examples of the ester compound solvent include 2- (1-methoxy) propyl acetate, ethyl acetate, ethyl lactate, and the like. Examples of the alcohol compound solvent include n-butanol and isobutanol. Examples of the aromatic compound solvent include benzene, toluene, xylene, and the like. Examples of the aliphatic compound solvent include n-hexane, cyclohexane, and the like. Further, the extraction solvent may be a pure solvent by the above-mentioned preferable solvent or a mixed solvent by a plurality of solvents.

The amount of the extraction solvent is not particularly limited as long as it can extract the pigment fine particles, but is preferably smaller than the pigment fine particle dispersion in consideration of concentration and extraction. When this is represented by volume ratio, when the pigment fine particle dispersion is 100, it is preferable that the extraction solvent added is the range of 1-100, More preferably, it is the range of 10-90, and the range of 20-80 is especially preferable. If it is too much, enormous time is required for the concentration, and if it is too small, the extraction is insufficient and the nanoparticles remain in the dispersion solvent.

After the extraction solvent is added, it is preferable to stir and mix so as to be in sufficient contact with the dispersion. For stirring mixing, a usual method can be used. Although there is no restriction | limiting in particular in the temperature at the time of adding and mixing an extraction solvent, It is preferable that it is 1-100 degreeC, and it is more preferable that it is 5-60 degreeC. Addition and mixing of the extraction solvent may be used as long as the respective steps can be preferably performed, but may be carried out using, for example, a separation lot type device.

In case of ultrafiltration, for example, the method used for desalting / concentrating the silver halide emulsion may be applied. Research Disclosure No. 10208 (1972), No. 13122 (1975) and No. 16351 (1977) are known. Although the pressure difference and the flow rate which are important as the operating conditions can be selected by referring to the characteristic curve described in Harajiko Oya, `` Measurement of Handbook for Membrane '' (1978), p. 275, in terms of treating the target pigment fine particle dispersion, In order to suppress aggregation of particles, it is necessary to find out the optimum conditions. In addition, in the method for replenishing the solvent lost from the membrane permeation, there is a fixed-volume formula for continuously adding the solvent and a batch formula for intermittently adding the solvent. As the solvent to be replenished in this way, pure water obtained by ion exchange or distillation is used, but a poor solvent of a dispersant and a dispersant may be mixed in the pure water, or may be added directly to the pigment fine particle dispersion.

The ultrafiltration membranes are manufactured by Asahi Kasei Corporation, Daicel Chemical Industries, Ltd., which are already assembled as modules, such as flat plate, helical, cylindrical, hollow tube and homo-fiber types. Although it is commercially available from Toray Industries, Inc., Nitto Denko Corporation, etc., a spiral or hollow fiber type is preferable from the viewpoint of total film area and cleanability. In addition, although the fractional molecular weight used as an index of the threshold value of the component which can permeate a membrane needs to be determined from the molecular weight of the dispersing agent used, 5,000 or more and 50,000 or less are preferable, and 5,000 or more and 15,000 or less are more preferable.

In order to separate the dispersion solvent of a pigment fine particle dispersion and a concentrated extract liquid, it is preferable to filter. As the filter filtration device, for example, a device such as pressure filtration can be used. Preferred filters include nanofilters, ultra filters, and the like. It is preferable to remove residual dispersion solvent by filter filtration, and to further concentrate the pigment fine particles in the concentrated extract liquid to obtain the concentrated nanoparticle liquid.

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

The apparatus of the indirect heating freeze method includes 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, a monocooled freeze dryer, a HULL freeze dryer, It is preferable to use a small freeze dryer, an experimental freeze dryer, a research freeze dryer, a monocooled freeze dryer, more preferably a small freeze dryer, a monocooled freeze dryer.

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

The centrifugal separator used for the concentration of the pigment fine particles by centrifugation may be any device as long as the fine particles can be precipitated in the pigment fine particle dispersion (or pigment fine particle concentrated extract liquid). Examples of the centrifugal separator include a skimming function (a function of sucking the supernatant layer during rotation and discharging it out of the system) in addition to the general-purpose apparatus, and a continuous centrifuge for continuously discharging solids.

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

The apparatus used for concentrating the pigment fine particles by drying under reduced pressure is not particularly limited as long as the solvent of the pigment fine particle dispersion (or pigment fine particle concentrate extract) can be evaporated. For example, a general-purpose vacuum dryer and a rotary pump, the apparatus which can dry under reduced pressure while stirring a liquid, the apparatus which can continuously dry by passing a liquid through the heat-decompressed tube, etc. are mentioned.

30-230 degreeC is preferable, 35-200 degreeC is more preferable, and 40-180 degreeC of the heating and decompression drying temperature is especially preferable. The pressure at the time of the decompression is preferably 100 to 100000 Pa, more preferably 300 to 90000 Pa, and particularly preferably 500 to 80000 Pa.

According to the concentration method as described above, the pigment fine particles can be efficiently concentrated from the pigment fine particle dispersion. Regarding the concentrated magnification, for example, when the concentration of the nanoparticles in the pigment fine particle dispersion serving as the raw material is 1, the concentration in the concentrated pigment fine particle paste is preferably about 100 to 3000 times, more preferably about 500 to 2000 times. Can be concentrated.

[Microdispersion]

It is preferable to fine-disperse when pigment microparticles are in the aggregation state by the said concentration etc. (In this invention, microdispersion means loosening agglomeration of the particle | grains in a dispersion liquid, and increasing a dispersion degree).

Pigment microparticles contained in the organic particle liquid concentrated by the above-mentioned extraction solvent, centrifugation, drying, etc. usually cause aggregation by the concentration. At this time, in order to enable rapid filter filtration and to obtain a good dispersion state again, it is preferable to obtain the pigment fine particles as flocs. Herein, floc refers to an aggregate of finely aggregated finely aggregated particles. Thus, by making a pigment fine particle into a floc, organic pigment microparticles | fine-particles precipitated in the aqueous liquid mixture can be promptly separated from a medium by filtration etc., for example. Therefore, the separated floc (soft aggregate) can be redispersed in the organic solvent suitable for manufacture of a color filter, and can be made into the pigment dispersion composition (non-aqueous dispersion composition) of an organic solvent efficiently. That is, when the mixed solvent of a good solvent and a poor solvent is an aqueous solvent, this can be efficiently substituted by the 3rd solvent which consists of organic solvents, and can convert a dispersion medium (continuous phase). Although the average particle diameter of a floc is not specifically limited, In view of the filterability mentioned above, it is preferable that it is 0.5-500 micrometers, and it is more preferable that it is 5-100 micrometers. In addition, in this invention, the solvent different from any of the said good solvent (1st solvent) and the said poor solvent (2nd solvent) is collectively called "third solvent."

Moreover, the dispersion | distribution using the normal dispersing method is inadequate for microparticles | fine-particles, and the method with high refinement efficiency may be needed further. Even in such strong aggregated organic particles (in the present invention, the aggregated organic particles are those in which organic particles such as aggregates are aggregated with a secondary force. When the primary particles are nanometer size, they are aggregated nanoparticles. In addition, by incorporating the polymer compound having a mass average molecular weight of 1000 or more into the aggregated organic particle liquid, it is possible to obtain a dispersion in which the organic particles are finely dispersed in the present invention. It indicates that the organic particles are contained in the liquid, and aggregated organic particles may be contained even in a dispersion liquid, a concentrated liquid, a paste, a slurry, and the like.). In more detail, by using the polymer compound, good fine dispersibility (a characteristic in which uniform and small particle sizes are realized) and dispersion stability (uniform and fine particle diameters for a long time when precipitated in a mixed solution of a good solvent and a poor solvent) Retained characteristics) are maintained even after the medium is changed to an organic solvent suitable for the color filter and redispersed, thereby achieving high performance in the color filter. Furthermore, the high molecular compound can realize high performance in color filters and liquid crystal display devices by interacting with the coloring properties of the organic pigment fine particles without disturbing the optical properties of the color filters.

It is preferable that it is a high molecular compound represented by following General formula (1) as said high molecular compound.

In Formula (1), A ¹ represents an acidic group, a basic group having a nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, and an isocyanate group. And a monovalent organic group having a group selected from hydroxyl groups, or a monovalent organic group including an organic pigment structure or a heterocycle which may have a substituent. n A ^{1 s} may be the same or different.

The Specifically, A ¹ is not particularly limited, and the as the "monovalent organic group having an acidic group", for example a carboxylic acid group, a sulfonic acid group, a mono sulfuric acid ester group, phosphoric acid group, morpholine acid ester group, boric acid group, etc. The monovalent organic group which has is listed. Further, as the "monovalent organic group having a basic group having a nitrogen atom", for example, monovalent having a monovalent organic group, a substituted imino group ^{(-NHR 8, -NR 9 R 10} ) having an amino group (-NH ₂₎ Organic group (R ⁸ , R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms.) Monovalent organic group having a guanidyl group represented by the following general formula (a1) [In general formula (a1), R ^a1 and R ^a2 each independently represent an alkyl group having 1 to 20 carbon atoms, and 6 or more carbon atoms. 20 or less aryl groups, or a C7-C30 aralkyl group.] The monovalent organic group which has the amidinyl group represented by the following general formula (a2) [R in general formula (a2) ^a3 and R ^a4 each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbons, and carbon. Several or more and thirty or less aralkyl groups are represented.] And the like are listed.

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 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 carbon atoms And 30 or less aralkyl groups are mentioned above.

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

As said "monovalent organic group which has a group which has a coordinating oxygen atom", the group which has an acetylacetonate group, the group which has a crown ether, etc. are mentioned, for example.

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 (e.g., an octyl group, a dodecyl group, etc.), an aryl group having 6 or more carbon atoms (e.g., a phenyl group, a naphthyl group, etc.), and 7 or more carbon atoms. Aralkyl groups (eg, benzyl groups, etc.). Although there is no upper limit in carbon number at this time, it is preferable that it is 30 or less.

As said "monovalent organic group which has an alkoxy silyl group", group which has a trimethoxy silyl group, a triethoxy silyl group, etc. is mentioned, for example.

As said "monovalent organic group which has an epoxy group", the group which has glycidyl group etc. is mentioned, for example.

As said "monovalent organic group which has an isocyanate group", 3-isocyanatopropyl group etc. are mentioned, for example.

As said "monovalent organic group which has a hydroxyl group", 3-hydroxypropyl group etc. are mentioned, for example.

It is preferable that it is a monovalent organic group which has an acidic group, a basic group which has a nitrogen atom, a urea group, and a C4 or more hydrocarbon group as said A <^1> .

The organic pigment structure or heterocycle is not particularly limited. More specifically, the organic pigment structure includes, for example, a phthalocyanine compound, an insoluble azo compound, an azolake compound, an anthraquinone compound, a quinacridone compound, and a dioxazine compound. And diketopyrrolopyrrole compounds, anthrapyridine compounds, ananthrone compounds, indanthrone compounds, flavantron compounds, perinone compounds, perylene compounds, thioindigo compounds, and the like. Moreover, as a heterocyclic ring, for example, thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole , Triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindolin, isoindolinone, benzimidazolone , Succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridon, anthraquinone and the like.

Moreover, the said organic pigment | dye structure or heterocyclic ring may have substituent T, As said substituent T, C6-C16 aryl groups, such as C1-C20 alkyl groups, such as a methyl group and an ethyl group, a phenyl group, a naphthyl group, etc. C1-C6 alkoxy groups, such as an oxy group, C1-C6 alkoxy groups, such as a methoxy group and an ethoxy group, Halogen atoms, such as chlorine and a fluorine, A methoxycarbonyl group, an ethoxycarbonyl group, a cyclohexyloxycarbonyl group, etc. Carbonic ester groups, such as a C2-C7 alkoxycarbonyl group, a cyano group, t-butyl carbonate, a hydroxyl group, an amino group, a carboxyl group, sulfonamide group, and N-sulfonylamide group, etc. are mentioned.

In addition, A ¹ may be represented by the following general formula (4).

In the general formula (4), B ¹ is an acid group, a basic group having a nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group and a group selected from a hydroxyl group, or an import also a good organic dye structure or a heterocyclic substituent, R ¹⁸ represents a single bond or a divalent connecting group a1 of an organic or inorganic. a1 represents 1 to 5, and a1 B ¹ may be the same or different.

The preferable aspect in group represented by General formula (4) is the same as that of said A <^1> .

R <^18> represents a single bond or a1 + monovalent coupling group, and a1 represents 1-5. The linking group R ¹⁸ includes a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. You may be. R ¹⁸ is preferably an organic linking group.

To Examples of the structural unit R ¹⁸ or can be exemplified the groups being formed by a combination of the structural units. The linking group R ¹⁸ may have the substituent T.

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

The (m + n) -valent linking group represented by R ¹ includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. A group is contained and may be unsubstituted or may have a substituent further. R ¹ is preferably an organic linking group.

As a specific example of R <^1> , group (the ring structure may be formed) formed by combining the group of said (t-1)-(t-34) or its plurality can be mentioned. When the linking group R ¹ has a substituent, the substituent T is listed as the substituent.

R ² represents a single bond or a divalent linking group. R ² includes a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms, and even if unsubstituted, may further have a substituent good. As a specific example of R <^2> , the group comprised by combining the said t-3-5, 7-18, 22-26, 32, 34 or its plurality can be enumerated. R ² preferably has a sulfur atom at a linking position with R ¹ . When said R <^2> has a substituent, the said substituent T is mentioned as said substituent.

In the general formula (1), m represents 1 to 8. As m, 1-5 are preferable, 1-3 are more preferable, and 1-2 are especially preferable.

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

In said general formula (1), P <^1> represents a high molecular compound residue (polymer skeleton), and can select suitably from a normal polymer etc.

Among the polymers, polymers or copolymers of vinyl monomers, ester compound polymers, ether compound polymers, urethane compound polymers, amide compound polymers, epoxy compound polymers, silicone compound polymers, and modified substances thereof, or air may be used to construct a polymer skeleton. A group consisting of a copolymer (e.g., a copolymer of a polyether / polyurethane copolymer, a polymer of a polyether / vinyl monomer) and the like (random copolymer, block copolymer, graft copolymer may be any). At least 1 sort (s) selected from is preferable, At least 1 sort (s) chosen from the group which consists of a polymer or copolymer of a vinyl monomer, an ester compound polymer, an ether compound polymer, a urethane compound polymer, and these modified or copolymers is more preferable, and vinyl Polymers or copolymers of monomers are particularly It is preferred.

In addition, the polymer is preferably soluble in an organic solvent. When affinity with an organic solvent is low, when used as a pigment dispersant, for example, affinity with a dispersion medium may be weak and it may become impossible to ensure the adsorption layer sufficient for dispersion stabilization.

In addition, P ¹ preferably has a sulfur atom at a linking position with R ¹ .

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

In the said General formula (2), A <^2> is the same as A <^1> in the said General formula (1), and its specific preferable aspect is also the same. In addition, A <^2> may have a substituent and the said substituent T is enumerated.

In the above general formula (2), R ³ represents a linking group of (x + y). R <^3> is synonymous with R <^1>, and its preferable range is also the same. In this case, R ³ is an x + y-valent linking group, but the value of x and its preferred range have the same meaning as n in General Formula (1), and the value of y and its preferred range have the same meaning as m, and x + The value of y and its preferred range have the same meaning as the value of m + n.

It is preferable that the coupling group represented by R <^3> is an organic coupling group, and the preferable specific example of this organic coupling group is shown below. However, the present invention is not limited thereto.

Among the above, from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents, (r-1), (r-2), (r-10), (r-11), (r-16), The group of (r-17) is preferable.

Moreover, when said R <^3> has a substituent, the said substituent T is mentioned as said substituent.

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

As a "bivalent coupling group" represented by said R <^4> , R <^5> , you may have a substituent, and it is a linear, branched or cyclic alkylene group, arylene group, aralkylene group, -O-, -S-, -C (= O )-, -N (R ¹⁹ )-, -SO-, -SO _2- , -CO _2- , or -N (R ²⁰ ) SO _2- , or a divalent group in which two or more of these groups are combined is preferable. R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.). Among them, an organic linking group is preferable.

R ^{4 may be a} linear or branched alkylene or aralkylene group, —O—, —C (═O) —, —N (R ¹⁹ ) —, —SO ₂ —, —CO ₂ —, or —N (R ²⁰ ) SO ₂ -or a divalent group obtained by combining two or more of these groups is more preferable, and a linear or branched alkylene group or aralkylene group, -O-, -C (= O)-, -N (R ¹⁹ )- Or -CO ₂ -or a divalent group in which two or more of these groups are combined is particularly preferable.

R ^{5 may be a} single bond, a linear or branched alkylene group, an aralkylene group, —O—, —C (═O) —, —N (R ¹⁹ ) —, —SO ₂ —, —CO ₂ — or —N (R ²⁰ ) SO ₂ -or a divalent group obtained by combining two or more of these groups is more preferable, and a linear or branched alkylene group, aralkylene group, -O-, -C (= 0)-, and -N (R ¹⁹ )-or -CO ₂ -or divalent groups in which two or more groups thereof are combined are particularly preferred.

In addition, when said R <^4> , R <^5> has a substituent, the said substituent T is mentioned as said substituent.

In addition, P <^2> in General formula (2) represents a polymer skeleton, and can be selected suitably from a normal polymer. The preferable form of the polymer is the same as that of P ¹ in the general formula (1), and the preferred form thereof is also the same.

Of the polymer compounds represented by the general formula (2), in particular, R ³ is the specific examples (r-1), (r-2), (r-10), (r-11), (r-16), Or (r-17), R ⁴ is a single bond, a straight chain or a branched alkylene or aralkylene group, -O-, -C (= 0)-, -N (R ^l9 ) ^-or -CO _2- , Or a divalent organic group in which two or more of these groups are combined, R ⁵ is a single bond, an ethylene group, a propylene group, or a linking group represented by the following general formula (sa) or (sb), and P ² is a polymer of a vinyl monomer. Or a polymer compound having a copolymer, an ester polymer, an ether polymer, a urethane polymer, or a modified product thereof, y of 1 to 2 and x of 3 to 6 is particularly preferable. In addition, in the following group, R <^21> represents a hydrogen atom or a methyl group, and ℓ represents 1 or 2.

Although the mass mean molecular weight of the said high molecular compound is 1000 or more, 3000-100000 are preferable at a mass mean molecular weight, 5000-80000 are more preferable, 7000-60000 are especially preferable. When the mass average molecular weight is in the above range, the effect of the plurality of functional groups introduced at the terminal of the polymer is sufficiently exerted, and exhibits excellent performance of adsorption to the solid surface, micelle formation ability, and surfactant activity, and achieves good dispersibility and dispersion stability. can do.

The specific example of the compound represented by General formula (1) is shown below. However, this invention is not limited to these specific examples at all.

As the polymer compound having a molecular weight of 1000 or more, a polymer compound having the following acidic group (hereinafter, the compound may be simply referred to as an "acid group-containing polymer compound") may be used, and a polymer having a carboxyl group as the polymer compound. It is preferable that it is a compound, and the copolymer compound containing at least 1 sort (s) of the repeating unit derived from the compound which has (A) carboxyl group, and at least 1 sort (s) of the repeating unit derived from the compound which has (B) carboxylic acid ester group is more preferable. Do.

As a repeating unit derived from the compound which has the said (A) carboxyl group, it is preferable that it is a repeating unit represented with the following general formula (I), It is more preferable that it is a repeating unit derived from acrylic acid or methacrylic acid, The said (B As a repeating unit derived from the compound which has a carboxylic ester group, it is preferable that it is a repeating unit represented with the following general formula (II), It is more preferable that it is a repeating unit represented with the following general formula (IV), and benzyl Particular preference is given to repeating units derived from acrylate, benzyl methacrylate, phenethyl acrylate, phenethyl methacrylate, 3-phenylpropylacrylate or 3-phenylpropylmethacrylate.

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

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

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

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

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

In addition, when referring to the polymerization ratio of the repeating unit derived from the compound which has the (A) carboxyl group, and the repeating unit derived from the said compound which has the said (B) carboxylic acid ester group, with respect to the total number of repeating units of the repeating unit (A) It is preferable that the yield ratio% is 3-40, and it is more preferable that it is 5-35.

In the present invention, the molecular weight of the polymer refers to the mass average molecular weight unless otherwise specified. As a method for measuring the molecular weight of a polymer, a chromatographic method, a viscosity method, a light scattering method, a sedimentation rate method and the like are enumerated, but in the present invention, unless otherwise specified, polystyrene measured by gel permeation chromatography method (carrier tetrahydrofuran) A mass average molecular weight in terms of weight is used.

The high molecular compound may be either water-soluble or oil-soluble, or may be water-soluble and oil-soluble.

The method of adding the polymer compound may be a solution dissolved in an aqueous solvent or an organic solvent, may be in a solid state, or a combination thereof. As a method of adding to a solution dissolved in a solvent, for example, a method of adding to a solution of agglomerated organic particles in a state in which it is dissolved in the same solvent as a solvent of a solution of agglomerated organic particles, or a solution of dissolved in another solvent compatible with a solvent of agglomerated organic particles. How to do is listed. Although the density | concentration of a high molecular compound in the case of adding to the solution melt | dissolved in the solvent is not specifically limited, 1-70 mass% is preferable, 2-65 mass% is more preferable, 3-60 mass% is especially preferable.

The addition of the high molecular compound may be added at any time during or after the precipitation of the pigment fine particles, during or before the concentration, during or after the dispersion of the aggregated organic particles after the concentration, and after these steps are completed. You may add separately. In the production method of the present invention, the polymer compound having a mass average molecular weight of 1000 or more may be contained in the composition as a binder to be described later. For example, after the pigment fine particle precipitate is concentrated, it is preferably added during fine dispersion of the aggregated organic particles.

When the amount of the polymer compound added is 100 parts by mass of the pigment fine particles, preferably 0.1 to 1000 parts by mass, more preferably 5 to 500 parts by mass, and particularly preferably 10 to 300 parts by mass.

As the polymer compound having a molecular weight of 1000 or more, in addition to the above compounds, for example, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, Polyvinyl alcohol-part formales, polyvinyl alcohol-part butyral compounds, vinylpyrrolidone-vinyl acetate copolymers, polyethylene oxide / propylene oxide block copolymers, polyamides, cellulose derivatives, starch derivatives, and the like. do. In addition, natural high molecular compounds, such as alginate, gelatin, albumin, casein, arabian rubber, tragacanth rubber, and lignin sulfonate, can also be used. Examples of the high molecular compound having an acidic group include polyvinyl sulfate, condensed naphthalene sulfonic acid, and the like.

Examples of the polymer compound having a carboxyl group include polyacrylic acid, polymethacrylic acid, a cellulose derivative having a carboxyl group in the side chain, and the like. Copolymer compounds comprising at least one of repeating units derived from a compound having (A) a carboxyl group and at least one of repeating units derived from a compound having a (B) carboxylic acid ester group are disclosed in Japanese Patent Application Laid-Open No. 59-44615 Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Publication No. 59-53836 and Japanese Patent Publication No. 59-71048 Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and the like as described in the publication can be cited. Further preferred examples include acrylic acid-acrylic acid ester copolymers, methacrylic acid-acrylic acid ester copolymers, acrylic acid-methacrylic acid ester copolymers, methacrylic acid-methacrylic acid ester copolymers described in US Pat. (B) polycyclic copolymers of acrylic acid or methacrylic acid, acrylic acid esters or methacrylic acid esters, and other vinyl compounds;

Examples of vinyl compounds include styrene or substituted styrenes (eg, vinyltoluene, vinylethylbenzene), vinylnaphthalene or substituted vinylnaphthalene, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, and the like. This is preferred.

Only 1 type may be used for a high molecular compound of 1000 or more molecular weight, may be used for it in combination of 2 or more type, and may be used together with the compound of molecular weight less than 1000.

It is preferable that the dispersion liquid of the said pigment fine particle contains 60 mass% or more of organic solvents, and it is more preferable that it is 65 mass% or more. The organic solvent is not particularly limited and may be appropriately selected from conventional ones. For example, an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, an aliphatic compound solvent and a ketone compound solvent are preferable, and an ester compound solvent and a ketone compound solvent are particularly preferable. These may be used singly or in combination of two or more.

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

The pigment fine particles can be used, for example, in a state of being dispersed in a vehicle. The vehicle refers to a portion of a medium in which a pigment is dispersed when in a liquid state, and refers to a portion (binder) that binds to the pigment as a liquid and solidifies the coating film, and a component (organic solvent) that dissolves and dilutes the coating film. It contains. In addition, in this invention, the binder used at the time of nanoparticle formation and the binder used for re-dispersion may be same or different, and may be distinguished as a nanoparticle formation binder and a re-dispersion binder, respectively.

Although the pigment fine particle density | concentration of the dispersion composition of the pigment fine particle after redispersion is suitably determined according to the objective, Preferably it is preferable that it is 2-30 mass% with respect to the whole amount of a dispersion composition, and it is 4-20 mass% More preferably, it is especially preferable that it is 5-15 mass%. In the case of being dispersed by the above-mentioned vehicle, the amounts of the binder and the dissolved dilution component are appropriately determined according to the type of the organic pigment, etc., but it is preferable that the binder is 1 to 30% by mass based on the total amount of the dispersion composition, and 3 to 20 It is more preferable that it is mass%, and it is especially preferable that it is 5-15 mass%. The content of the dissolved and diluted component is preferably 5 to 80% by mass, more preferably 10 to 70% by mass.

In the concentrated-extracted nanoparticle liquid described above, in order to enable rapid filter filtration as described above, it is preferable to aggregate the pigment fine particles by concentration, and to concentrate and aggregate by centrifugation or drying. .

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

The ultrasonic irradiation apparatus used preferably has a function capable of applying ultrasonic waves of 10 kHz or more, and examples thereof include ultrasonic homogenizers and ultrasonic cleaners. When liquid temperature rises during ultrasonic irradiation, since thermal aggregation of nanoparticles arises (refer nonpatent literature 1), it is preferable to make liquid temperature 1-100 degreeC, and 5-60 degreeC is more preferable. The temperature can be controlled by controlling the temperature of the dispersion liquid, or by controlling the temperature of the temperature control layer for controlling the temperature of the dispersion liquid.

There is no restriction | limiting in particular as a disperser used when disperse | distributing the concentrated pigment microparticles | fine-particles by applying physical energy, For example, dispersers, such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill, are mentioned. In addition, a high-pressure dispersion method and a dispersion method by use of microparticle beads are also listed as preferable ones.

When finely dispersed into a pigment dispersion redispersed in an organic solvent suitable for the production of color filters by the production method, the primary particles are usually dispersed in the form of dispersed particles consisting of a plurality of aggregated secondary particles, the polymer compound or The size of the dispersed particles varies depending on the progress of the dispersed state. From such a viewpoint, the number average particle diameter (Df) of the dispersed particles contained in the dispersion used for producing the colored layer of the color filter is preferably 50 nm or less, more preferably 30 nm or less. The particle diameter of the dispersed particles in the dispersion is an important factor influencing the contrast of the color filter, and the closer the particle diameter of the dispersed particles to the primary particle diameter is, the better the contrast becomes when the colored layer of the color filter is used. In addition, although the lower limit of the average particle diameter of the dispersed particle in the dispersion used for manufacture of the colored layer of a color filter is not specifically limited, it is realistic to become the range of the number average particle diameter Dp of the primary particle in the colored layer mentioned above. to be.

As a measuring method of the average particle diameter of this dispersed particle, light scattering method and dynamic light scattering method are enumerated.

According to the above production method, for example, the pigment particles contained in the pigment fine particle dispersion composition and the colored photosensitive resin composition described later can be concentrated and redispersed in spite of their small particle size such as nanometer size (for example, 10 to 100 nm). For this reason, when used for a color filter, optical density is high, the filter surface uniformity is excellent, contrast is high, and image noise can be reduced.

In addition, since the pigment fine particles contained in the pigment fine particle dispersion composition and the colored photosensitive composition can be finely dispersed in a highly and uniform manner, a high color density can be exerted at a thin film thickness to enable thinning of a color filter or the like. .

In addition, in the pigment fine particle dispersion composition and the coloring photosensitive resin composition, it is excellent as an image forming material for producing a color proof, a color filter, etc. by containing the pigment which shows vivid color tone and high coloring power.

Moreover, about the alkaline developing solution used for the exposure and development at the time of colored image formation, what is soluble in alkaline aqueous solution can be used as a binder (binder) to pigment fine particle dispersion composition and colored photosensitive resin composition, and it can respond to environmental requirements. .

Moreover, as a solvent (dispersion medium of a pigment) used for a pigment fine particle dispersion composition and a coloring photosensitive resin composition, the organic solvent which has moderate dryness can be used, and the demand can also be satisfy | filled also in the point of drying after application | coating.

Example

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in more detail based on an Example, this invention is not limited to this.

(Example 1)

<Production of color filter A1 (production by application using slit nozzle)>

[Preparation of Concentrated Pigment Liquid A]

To 1000 ml of dimethyl sulfoxide (from Wako Pure Chemical Industries), 31.5 ml of 30% methanol solution of sodium methoxide, pigment C.I. Pigment Solution A to which 30 g of Pigment Red 254 (Irgaphor Red BT-CF, trade name, manufactured by Ciba Specialty Chemicals) was added was prepared. Separately from this, 1000 ml of water containing 30 ml of an aqueous solution of 1 mol / 1 hydrochloric acid (manufactured by Wako Pure Chemical Industries) was prepared as a poor solvent.

Here, the pigment solution A was added to 1200 ml of water of the poor solvent which temperature-controlled at 18 degreeC and stirred at 400 rpm by GK-0222-10 type Raymond stirrer (brand name, the product made by Fujisawa Pharmaceutical Co., Ltd.). An organic pigment particle was formed by injecting 100 ml at a flow rate of 150 ml / min using a KX-500 type large-capacity no-flow pump (trade name, manufactured by Nihon Seimitsu Kagaku Co., Ltd.) to prepare Pigment Dispersion 1. The particle dispersion and monodispersity of this pigment dispersion were measured using a nanotrack UPA-EX150 (trade name, manufactured by Nikkiso Co., Ltd.), and the number average particle diameter was 30 nm and Mv / Mn 1.30.

The pigment nanoparticle dispersion prepared by the above method was centrifuged at a high speed centrifugal cooler HIMAC SCR20B (trade name, manufactured by Hitachi Co. Ltd.) at 3100 rpm (2000G) for 1 hour, and the supernatant was discarded to precipitate the pigment nanoparticle concentrate paste. Recovered. It was 21.1 mass% when the pigment content of the paste was measured using the 8453-type spectrophotometer (brand name: Agilent Technologies).

Paste concentration was added by adding 50.0 ml of ethyl lactate to 13.0 g of the pigment nanoparticle preparation paste, followed by stirring using a dissolver at 1500 rpm for 60 minutes, followed by filtration using a FP-010 filter (manufactured by SUMITOMO ELECTRIC FINE POLYMER INC.). Pigment liquid A (nano pigment concentration 28 mass%) was obtained.

[Preparation of R Pigment Dispersion A]

R paste dispersion A of the following composition was prepared using this paste.

12.8 g of the concentrated pigment liquid A of the paste

Pigment Dispersant A 1.0g

(Example compound 7 of the compound represented by the said general formula (D1))

6.2 g of methacrylic acid / methacrylic acid benzyl copolymer

(Molar ratio 28/72, mass average molecular weight: 30,000, 40% 1-methoxy-2-propyl acetate solution)

19.8 g of 1-methoxy-2-propyl acetate (from Wako Pure Chemical Industries)

Pigment dispersant A was synthesized according to Japanese Patent Application Laid-Open No. 2000-239554.

R pigment dispersion A of the above composition was dispersed with motor mill M-50 (trade name, manufactured by Eiger Japan) at circumferential speed of 7 m / s for 1 hour using zirconia beads having a diameter of 0.65 mm.

[Formation of Black (K) Image]

The alkali-free glass substrate was washed with a UV cleaner, and then brush-washed with a cleaning agent, followed by further ultrasonic cleaning with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.

After cooling the said board | substrate and adjusting temperature to 23 degreeC, the coloring photosensitive resin composition K1 which consists of a composition shown in following Table 1a is apply | coated with the coater for glass substrates (FASASIA make, brand name: MH-1600) which has a slit-shaped nozzle. It was. Subsequently, a part of the solvent was dried for 30 seconds with VCD (vacuum drying device; manufactured by Tokyo Ohka Kogyo Co Ltd.) to remove fluidity of the coating layer, and then prebaked at 120 ° C. for 3 minutes to form a photosensitive resin layer having a thickness of 2.4 μm. K1 was obtained.

Table 1a
K pigment dispersion 1 (carbon black) 25 parts by mass
8.0 parts by mass of propylene glycol monomethyl ether acetate
53 parts by mass of methyl ethyl ketone
Binder 2 9.1 parts by mass
0.002 parts by mass of hydroquinone monomethyl ether
4.2 parts by mass of DPHA liquid
0.16 parts by mass of polymerization initiator A
0.044 parts by mass of surfactant 1

Between the exposure mask surface and the photosensitive resin layer in a state where the substrate and the mask (a quartz exposure mask having an image pattern) are upright with a proximal exposure machine (manufactured by Hitachi Electronic Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp. The distance was set to 200 µm, and the pattern was exposed at an exposure dose of 300 mJ / cm 2.

Next, pure water was sprayed with a shower nozzle, and the surface of the photosensitive resin layer K1 was uniformly wetted, and then KOH-based developer (KOH, containing a nonionic surfactant, trade name: CDK-1, Fuji Film Electronics Materials Co., Ltd) The product was showered at 80 ° C. at 23 ° C. with 0.04 MPa of flat nozzle pressure for 100 seconds to obtain a patterned image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultra-high pressure washing nozzle to remove residue, thereby obtaining a black (K) image K. Then, it heat-processed at 220 degreeC for 30 minutes.

The colored photosensitive resin composition K1 first weighed K pigment dispersion 1, propylene glycol monomethyl ether acetate, mixed at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 rpm for 10 minutes, and then methyl ethyl ketone, binder 2, hydro Quinone monomethyl ether, DPHA solution, polymerization initiator A (2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) amino-3'-bromophenyl] -s-triazine) and Surfactant 1 were weighed and added in this order at the temperature of 25 degreeC (± 2 degreeC), and it obtained by stirring for 30 minutes at 150 rpm at the temperature of 40 degreeC (± 2 degreeC).

<K Pigment Dispersion 1>

Carbon black (trade name: Nipex 35, manufactured by Degussa) 13.1 parts by mass

0.65 parts by mass of dispersant (following compound J1)

6.72 parts by mass of polymer (random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, molecular weight of 3.7 million)

79.53 parts by mass of propylene glycol monomethyl ether acetate

 <Binder 2>

27 parts by mass of polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 3.8 million)

73 parts by mass of propylene glycol monomethyl ether acetate

<Surfactant 1>

Megafac F-780-F from Dainippon Ink and Chemicals, Incorporated.

40 parts by mass of C ₆ F ₁₃ CH ₂ CH ₂ 0COCH = CH ₂ ,

55 mass parts of H (OCH (CH ₃ ) CH ₂ ) ₇ OCOCH = CH ₂ , and

_{H (OCH 2 CH 2) 7} OCOCH = CH 2 5 parts by weight of a copolymer (molecular weight 30,000), 30 parts by weight

70 parts by mass of methyl ethyl ketone

[Formation of red (R) pixels]

The heat treatment finishing pixel R was formed on the board | substrate which formed the said image K using the coloring photosensitive resin composition R1 which consists of a composition of following Table 1b by the same process as formation of the said black (K) image. The film thickness of the said photosensitive resin layer R1 and the application amount of a pigment are shown below. In addition, the preparation procedure of a coloring photosensitive resin composition was made the same as the said coloring photosensitive resin composition K1.

Photosensitive resin film thickness (μm) 1.60

Pigment Coating Amount (g / ㎡) 1.00

C.I.P.R. 254 Coating amount (g / ㎡) 0.80

C.I.P.R. 177 Coating amount (g / ㎡) 0.20

Table 1b
R pigment dispersion A 40 parts by mass
4.5 parts by weight of pigment dispersion 2 (CIPR177)
Propylene glycol monomethyl ether acetate 7.6 parts by mass
37 parts by mass of methyl ethyl ketone
0.7 parts by mass of binder 1
3.8 parts by mass of DPHA liquid
0.12 parts by mass of 2-trichloromethyl- (p-styrylstyryl) -1,3,4-oxadiazole
0.05 parts by mass of polymerization initiator A
0.01 part by mass of phenothiazine
0.06 parts by mass of surfactant 1

<R Pigment Dispersion 2>

C.I.P.R. 177 (brand name: Cromophtal Red A2B, product of Ciba Specialty Chemicals)

18 parts by mass

Polymer (benzyl methacrylate / methacrylic acid = random copolymer of 72/28 molar ratio, molecular weight 30,000)

12 parts by mass

70 parts by mass of propylene glycol monomethyl ether acetate

<Binder 1>

Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 40,000)

27 parts by mass

73 parts by mass of propylene glycol monomethyl ether acetate

[Formation of Green (G) Pixels]

The heat treatment finishing pixel G was formed on the board | substrate which formed the said image K and the pixel R using the coloring photosensitive resin composition G1 which consists of a composition shown in following Table 1c in the same process as formation of the said black (K) image. The film thickness of the said photosensitive resin layer G1 and the application amount of a pigment are shown below. In addition, the preparation procedure of a coloring photosensitive resin composition was made the same as the said coloring photosensitive resin composition K1.

Photosensitive resin film thickness (μm) 1.60

Pigment application amount (g / ㎡) 1.92

C.I.P.G. 36 Coating amount (g / ㎡) 1.34

C.I.P.Y. 150 Coating amount (g / ㎡) 0.58

Table 1c
G pigment dispersion 1 (CIPG36) 28 parts by mass
15 parts by mass of pigment Y dispersion 1 (CIPY150)
Propylene glycol monomethyl ether acetate 29 parts by mass
Methyl ethyl ketone 26 parts by mass
1.3 parts by mass of cyclohexanone
Binder 2 2.5 parts by mass
3.5 parts by mass of DPHA liquid
0.12 parts by mass of 2-trichloromethyl- (p-styrylstyryl) -1,3,4-oxadiazole
0.05 parts by mass of polymerization initiator A
0.01 part by mass of phenothiazine
0.07 parts by mass of surfactant 1

<G Pigment Dispersion 1>

Fuji Film Electronics Materials Co., Ltd. Product `` brand name: GT-2 ''

<Y Pigment Dispersion 1>

Mikuni Color Co., Ltd. Product `` brand name: CF yellow EX3393 ''

[Formation of Blue (B) Pixels]

On the substrate in which the said image K, the pixel R, and the pixel G were formed, using the coloring photosensitive resin composition B1 which consists of a composition of following Table 1d, the heat processing finishing pixel B is formed in the same process as formation of the said black (K) image. It was. The film thickness of the said photosensitive resin layer B1 and the application amount of a pigment are shown below. In addition, the preparation procedure of a coloring photosensitive resin composition was made the same as the said coloring photosensitive resin composition K1.

Photosensitive resin film thickness (μm) 1.60

Pigment Coating Amount (g / ㎡) 0.75

C.I.P.B. 15: 6 Coating amount (g / ㎡) 0.705

C.I.P.V. 23 Coating amount (g / ㎡) 0.045

Table 1d
B pigment dispersion 1 (CIPB15: 6) 8.6 parts by mass
V pigment dispersion 2 (CIPB15: 6 + CIPV23) 15 parts by mass
28 parts by mass of propylene glycol monomethyl ether acetate
Methyl ethyl ketone 26 parts by mass
Binder 3 17 parts by mass
DPHA liquid 4.0 parts by mass
0.17 parts by mass of 2-trichloromethyl- (p-styrylstyryl) -1,3,4-oxadiazole
Phenothiazine 0.02 parts by mass
0.06 parts by mass of surfactant

B Pigment Dispersion 1

Mikuni Color Co., Ltd. Product `` brand name: CF BLUE-EX3357 ''

B Pigment Dispersion 2

Mikuni Color Co., Ltd. Product `` brand name: CF BLUE-EX3383 ''

<Binder 3>

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

73 parts by mass of propylene glycol monomethyl ether acetate

[Production of ITO Electrodes]

A glass substrate on which each pixel was formed was placed in a sputtering apparatus, and ITO (Indium Tin Oxide) having a thickness of 1300 에서 at 100 ° C. was vacuum-deposited, followed by annealing at 240 ° C. for 90 minutes to crystallize ITO to form an ITO transparent electrode. It was completed as A1.

[Measurement of Number Average Particle Size (Df) of Dispersed Particles]

R pigment dispersion A was diluted to 0.005 mass% of pigment concentration with 1-methoxy-2-propyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.), sonicated for 5 minutes in an ultrasonic cleaner to prepare a measurement sample. It measured using the particle size distribution measuring apparatus LB-550 (brand name, HORIBA, LTD.). The obtained number average particle diameter Df is shown in Table 2A below.

[Measurement of X-ray Diffraction Spectrum]

The color filter A1 was immersed in a 16% HCl aqueous solution at 50 ° C. for 30 minutes to remove ITO, and only the ITO was rubbed off and washed with a soft brush so as not to damage the resin of the partition or pixel. After immersion in 10% hydrogen fluoride solution for 1 minute to remove the glass substrate, X-ray diffraction spectrum of 100 randomly selected R pixels was measured under the following conditions, and the peak half width at 2θ = 28 ° ± 1 ° was measured. Δx. The results are shown in Table 2b below.

Device: Bruker AXS, D8-discover with GADDS

Province: Cu

Tube voltage: 50kV

Goniometer: D8-discover (brand name)

Collimeter diameter: 20 ㎛

Irradiation area: about 50㎛

[Definition of peak half width Δx]

The half value width of the peak of 2θ = 28 ° ± 1 ° in the measured X-ray diffraction spectrum is defined as follows. For the peak at 2θ = 28 ° ± 1 °, the point starting from the baseline level including noise is called starting points a and b. The intersection point of the line connecting this starting point a and b and the waterline lowered from the peak vertex c is called the intersection d. The length of the line segment ef which intersects the midpoint of the line segment cd starting from this intersection d, and is fitted to the ridge of the peak in the line parallel to the X axis (diffraction angle) is called half width.

[Measurement of particle size distribution of pigment fine particles and number average primary particle size (Df)]

The color filter A1 was immersed in a 16% HCl aqueous solution at 50 ° C. for 30 minutes to remove ITO, and only the ITO was rubbed off and washed with a soft brush so as not to damage the resin of the partition or pixel. Further, after immersing in a 10% hydrogen fluoride solution for 1 minute to remove the glass substrate, the particle diameter distribution of the pigment particles contained in the R pixel was measured under the following conditions, and the ratio P and the number of particles having a particle diameter of 20 nm or more and 30 nm or less were measured. The average primary particle diameter Dp was calculated. The results are shown in Table 2b below.

 <TEM shooting>

Device: Hitachi Co. Ltd. Product, H-7650 electron microscope

Acceleration voltage: 110 kV

(The graphography observation was performed, and the projection area of the particles was obtained by taking the surface with little overlap between the particles from the 3D reconstruction data.)

 <Image measurement>

Device: Carl Zeiss Inc. Product, KS-400 (brand name)

(The TEM images of 5000 pigment particles selected randomly were measured to calculate the original equivalent diameter from the projected area to calculate the ratios P and Dp.)

(Example 2)

<Production of Color Filter B1>

In Example 1, in 1000 ml of dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries), 31.5 ml of sodium methoxide 30% methanol solution and pigment C.I. Pigment Red 254 (Irgaphor Red BT-CF, trade name, manufactured by Ciba Specialty Chemicals) 30 g and polyvinylpyrrolidone (K-30, trade name, manufactured by Wako Pure Chemical Industries) were added to prepare pigment solution A '. In the same manner as in Example 1 to prepare a R pigment dispersion B to prepare a color filter B1. Df of R pigment dispersion B was measured in the same manner as in Example 1. The results are shown in Table 2a below. Δx, P, and Dp of the color filter B1 were measured in the same manner as in Example 1. The results are shown in Table 2b below.

(Example 3)

<Production of Color Filter C1>

The same procedure as in Example 2 was repeated except that 1000 ml of dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries) and 31.5 ml of 30% methanol solution of sodium methoxide were changed to 1000 ml of methanesulfonic acid (manufactured by Wako Pure Chemical Industries). R pigment dispersion C was prepared to obtain color filter C1. Df of R pigment dispersion C was measured in the same manner as in Example 1. The results are shown in Table 2a below. Δx, P, and Dp of the color filter C1 were measured in the same manner as in Example 1. The results are shown in Table 2b below.

(Example 4)

<Production of Color Filter D1>

 In Example 2, 1000 ml of dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries) and 31.5 ml of 30% methanol solution of sodium methoxide were changed to 1000 ml of concentrated sulfuric acid (95% sulfuric acid) (manufactured by Wako Pure Chemical Industries). In the same manner as in Example 2, R pigment dispersion D was prepared to prepare color filter D1. Df of R pigment dispersion D was measured in the same manner as in Example 1. The results are shown in Table 2a below. Δx, P, and Dp of the color filter D1 were measured in the same manner as in Example 1. The results are shown in Table 2b below.

(Example 5)

<Production of Color Filter E1>

R pigment dispersion E was prepared in the same manner as in Example 2 except that 100 g of polyvinylpyrrolidone (K-30, trade name, manufactured by Wako Pure Chemical Industries, Ltd.) was changed to 200 g in Example 2. Was prepared. Df of R pigment dispersion E was measured in the same manner as in Example 1. The results are shown in Table 2a below. Δx, P, and Dp of the color filter E1 were measured in the same manner as in Example 1. The results are shown in Table 2b below.

(Example 6)

<Production of Color Filter F1>

In Example 1, except that the pigment solution A was injected to 100 ml at a flow rate of 200 ml / min using a NP-KX-500 large-capacity no-flow pump (trade name, manufactured by Nihon Seimitsu Kagaku Co., Ltd.). In the same manner as in Example 1, R pigment dispersion F was prepared, thereby preparing Color Filter F1. Df of R pigment dispersion F was measured in the same manner as in Example 1. The results are shown in Table 2a below. Δx, P, and Dp of the color filter F1 were measured in the same manner as in Example 1. The results are shown in Table 2b below.

(Example 7)

<Production of Color Filter G1>

In Example 6, 1000 ml of dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries), 31.5 ml of a 30% methanol solution of sodium methoxide, and pigment C.I. A pigment solution A "was prepared by adding 30 g of Pigment Red 254 (Irgaphor Red BT-CF, trade name, manufactured by Ciba Specialty Chemicals), and 90 g of polyvinylpyrrolidone (K-30, trade name, manufactured by Wako Pure Chemical Industries). A color filter G1 was prepared by preparing R pigment dispersion G in the same manner as in Example 6. Df of R pigment dispersion G was measured in the same manner as in Example 1. The results are shown in Table 2A below. Δx, P, and Dp of the color filter G1 were measured in the same manner as in Example 1. The results are shown in Table 2b below.

(Example 8)

<Production of Color Filter H1>

A pigment dispersion H was prepared in the same manner as in Example 7, except that 90 g of polyvinylpyrrolidone (K-30, trade name, manufactured by Wako Pure Chemical Industries, Ltd.) was changed to 230 g in Example 7. Was prepared. Df of R pigment dispersion H was measured in the same manner as in Example 1. The results are shown in Table 2a below. Δx, P, and Dp of the color filter H1 were measured in the same manner as in Example 1. The results are shown in Table 2b below. In addition, the X-ray chart of the color filter H1 is shown in FIG.

(Example 9)

<Production of Color Filter I1>

In Example 8, R pigment dispersion I was prepared in the same manner as in Example 8 except that the water temperature of the poor solvent was adjusted to 5 ° C., and dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries) was set to 650 ml. Color filter I1 was prepared. Df of R pigment dispersion I was measured in the same manner as in Example 1. The results are shown in Table 2a below. Δx, P and D _f of the color filter I1 were measured in the same manner as in Example 1. The results are shown in Table 2b below. In addition, the X-ray chart of the color filter I1 is shown in FIG.

(Comparative Example 1)

<Production of Color Filter J1>

The dispersion J of the following composition was prepared using the bead disperser as follows.

Pigment (C.I. Pigment Red 254) 6.4 g

(Irgaphor Red BT-CF, trade name, product of Ciba Specialty Chemicals)

Pigment Dispersant A 0.9g

(Example compound 7 of the compound represented by the said general formula (D1))

5.0 g of polyvinylpyrrolidone

(K-30, trade name, product of Wako Pure Chemical Industries, molecular weight 40,000)

Methacrylic Acid / Methacrylic Acid Benzyl Copolymer 10.4g

(Molar ratio 28/72, mass average molecular weight: 30,000, 40% 1-methoxy-2-propyl acetate solution)

35.9 g of 1-methoxy-2-propyl acetate (from Wako Pure Chemical Industries)

In a 1-methoxy-2-propyl acetate solution, a powder of pigment (Pigment Red 254), pigment dispersant A, polyvinylpyrrolidone, and methacrylic acid / benzyl methacrylic acid copolymer were charged and stirred to obtain a mixed liquid. Next, this mixed solution was dispersed for 9 hours at a circumferential speed of 9 m / s using zirconia beads having a diameter of 0.65 mm with a motor mill M-50 (trade name, manufactured by Eiger Japan), to obtain R pigment dispersion J. The particle size and monodispersity measured and treated in the same manner as in Example 1 were 68 nm in number average particle diameter and 1.5 in Mv / Mn.

Color filter J1 was prepared in the same manner as in Example 1 using the prepared R pigment dispersion J. Df of R pigment dispersion J was measured in the same manner as in Example 1. The results are shown in Table 2a below. Δx, P, and Dp of the color filter J1 were measured in the same manner as in Example 1. The results are shown in Table 2b below. In addition, the X-ray chart of the color filter J1 is shown in FIG.

(Comparative Example 2)

<Production of Color Filter K1>

R pigment dispersion K and color filter K1 were produced like Example 1 except having adjusted the temperature of the poor solvent water to 45 degreeC in Example 1. Df of R pigment dispersion K was measured similarly to Example 1. The results are shown in Table 2a below. Δx, P, and Dp of the prepared color filter K1 were measured in the same manner as in Example 1. The results are shown in Table 2b below.

(Comparative Example 3)

<Production of Color Filter L1>

R pigment dispersion L and color filter L1 were produced in the same manner as in Comparative Example 1 except that the dispersion time of Motor Mill M-50 (trade name, manufactured by Eiger Japan) was 5 hours in Comparative Example 1. Df of R pigment dispersion L was measured similarly to Example 1. The results are shown in Table 2a below. Δx, P, and Dp of the prepared color filter L1 were measured in the same manner as in Example 1. The results are shown in Table 2b below.

Table 2a
R Number Dispersion Dispersion Particles Average Particle Size Df A 48 nm
B 43nm
C 33 nm
D 68 nm
E 38nm
F 46nm
G 36nm
H 41 nm
I 25 nm
J 73 nm
K 66nm
L 93nm

Table 2b
Color Filter Δx P Dp A1 0.64 ° 28% 25nm
B1 0.73 ° 27% 22nm
C1 0.76 ° 25% 25nm
D1 0.75 ° 29% 40nm
E1 0.84 ° 23% 27nm
F1 0.66 ° 33% 28nm
G1 0.77 ° 38% 24nm
H1 0.89 ° 31% 27nm
I1 0.87 ° 32% 18nm
J1 0.59 ° 31% 32nm
K1 0.56 ° 37% 35nm
L1 0.51 ° 25% 55nm

As shown in Table 2b, the R pixels of the color filters A1 to I1 obtained in Examples exhibited at least one diffraction peak having a half width of 0.6 ° or more at a Bragg angle of 28 ± 1 ° in the X-ray diffraction spectrum.

(Example 9, Comparative Example 3)

[Measure Contrast of Color Filters A1 to L1]

As a backlight unit, two polarizers (HLC2-2518, trade name, SANRITSU Co. ., Ltd.), and the amount of transmitted light when the polarization axis is parallel and perpendicular to each other was measured, and the ratio was made to be contrast (Ueki, Kosei, Fukunaga, Yamanaka, "512 color display"). 10.4 "Color Filter for TFT-LCD", 7th Color Optical Conference (1990), etc.) A chromatic luminance meter (TOPCON CORPORATION, BM-5) was used to measure chromaticity. Two polarizers and color filters In the color filter where the color luminance meter is installed, the polarizer is placed at the position of 13mm from the backlight, and the cylinder with the diameter of 11mm and the length of 20mm is installed at the position of 40mm to 60mm, and the light transmitted through the center is installed at the position of 65mm. Irradiated and transmitted light at a position of 100 nm The measurement was performed with a color luminance meter installed at a position of 400 mm after passing through the installed polarizing plate, and the measurement angle of the color luminance meter was set to 2 ° The light quantity of the backlight was determined by parallel nicol with two polarizing plates without a color filter installed. The luminance at the time of installation was set to be 1280 cd / m ² .

Table 5 shows the measurement results of the contrast of the color filters A1 to L1.

[Evaluation of burn-in]

(Production of spacer)

On the ITO film of the color filter substrate in which the ITO film prepared above was sputtered, the transfer material was manufactured by the same process as the formation of the said black (K) image using the following spacer prescription A which consists of a composition shown in Table 3 below. It exposed, developed, and formed the spacer pattern. The obtained spacer pattern was columnar shape of diameter 16micrometer and average height 3.7micrometer.

Next, the color filter substrate on which the spacer pattern was formed was heat-processed at 230 degreeC for 30 minutes (heat processing process), and the spacer was manufactured.

Table 3
Spacer Prescription A
Pigment 1 120 parts by mass
456 parts by mass of 1-methoxy-2-propyl acetate
Methyl ethyl ketone 243 parts by mass
17 parts by mass of methanol
Binder 4 80 parts by mass
79 parts by mass of DPHA liquid
2.2 parts by mass of polymerization initiator A
0.100 parts by mass of hydroquinone monomethyl ether
0.86 parts by mass of surfactant 1
17 parts by mass of colored dyes

Pigment 1

30% methyl isobutyl ketone dispersion of silicasol

(Brand name: MIBK-ST, product of Nissan Chemical Industries)

<Binder 4>

Methacrylic acid / allyl methacrylate copolymer

(= 20/80 [molar ratio], mass average molecular weight 36,000; polymer material)

<Coloring dye>

Victoria Pure Blue BOH-M (product of Hodogaya Kagaku Co., Ltd.)

In addition, DPHA liquid, surfactant 1, and polymerization initiator A are the same as that mentioned above.

(Manufacture of projection for liquid crystal alignment control)

On the side (on the color filter) in which the ITO film | membrane of the color filter board | substrate with the spacer obtained above was formed (on a color filter), the same process as the formation of the said black (K) image using the following liquid crystal orientation control projection prescription B which consists of a composition shown in following Table 4 By the process, the transfer material was produced, transferred, and exposed. The exposure amount was 50 mJ / cm 2.

Table 4
Projection prescription B for LCD alignment control
Positive resist liquid FH-2413F 53.3 parts by mass
(Product of Fuji Film Electronics Materials Co., Ltd.)
Methyl ethyl ketone 46.7 parts by mass
0.04 parts by mass of surfactant 1

Then, it developed similarly to Example 1 except having used the following developing solution instead of the sodium carbonate type developing solution.

(developer)

An aqueous solution containing 0.085 mol / L sodium carbonate, 0.085 mol / L sodium hydrogen carbonate, and 1% sodium dibutylnaphthalenesulfonate.

As a result, a liquid crystal alignment control protrusion was formed on the color filter (RGB pixel) including the photosensitive resin layer for the liquid crystal alignment control protrusion patterned in a desired shape.

Subsequently, the color filter substrate on which the liquid crystal alignment control projections were formed was baked at 240 ° C. for 50 minutes, thereby forming a liquid crystal alignment control projection having a semicircular longitudinal cross section with a height of 1.5 μm on the color filter (RGB pixel).

Apart from the above, a TFT substrate was prepared as a counter substrate. One surface of this TFT substrate is formed with an indium tin oxide (ITO) film by sputtering.

Subsequently, an alignment film made of polyimide was formed on the ITO film on the TFT substrate and on the ITO film on the side where the spacer of the color filter substrate was formed.

Thereafter, a sealant of an epoxy resin was printed at a position corresponding to a frame of a black matrix formed around the pixel group of the color filter, and the color filter substrate was bonded to the TFT substrate.

Subsequently, the two bonded substrates were heat treated to cure the sealant, thereby obtaining two substrate laminates. After degassing this laminated body under vacuum, it returned to atmospheric pressure and the liquid crystal was inject | poured into the clearance gap of two glass substrates. After the completion of the injection, the liquid crystal cell was obtained by applying an adhesive to the injection hole and sealing by irradiating with ultraviolet rays.

The polarizing plate (HLC2-2518, SANRITSU Co., Ltd. product) was attached to both surfaces of the liquid crystal cell obtained in this way. Subsequently, although not shown, a side light method using FR1112H as a red (R) LED, DG1112H as a green (G) LED, and DB1112H (all chip type LEDs manufactured by Stanley Electric Co., Ltd.) as a blue (B) LED is used. The backlight of the liquid crystal display panel was arranged on the side of the liquid crystal cell on which the polarizing plate was formed, thereby manufacturing an MVA mode liquid crystal display device.

About the manufactured liquid crystal display device, the residual DC voltage which generate | occur | produced in the liquid crystal cell was measured by the method of obtaining the optimum common voltage which minimizes the flicker of FIG. 4B of Unexamined-Japanese-Patent No. 2000-275645. Burn-in failure of a liquid crystal display device is considered to be less likely to occur as the residual DC voltage is smaller. In addition, in the present Example, when the residual DC voltage is less than 55 mV, it is called "5", and when it is 55 mV or more and less than 70 mV, it is called "4", and when it is 70 m or more and less than 85 mV is "3", 85 mV or more is 100 mV. The case where it was less than was called "2", the case where it was 100 mV or more and less than 115 mV was called "1", and the case where the residual DC voltage was 115 mV or more was evaluated as "0". If this evaluation value is "1" or more, it can satisfy substantially practical needs, and when a high quality image is calculated | required, it is preferable that it is "2" or more.

Table 5 shows the evaluation results of the burn-in prevention properties of the color filters A1 to L1.

(Table 5)
Color filter contrast burn-in prevention A1 8030 2
B1 7800 3
C1 8000 2
D1 6500 1
E1 8200 4
F1 8500 3
G1 8700 4
H1 8300 5
I1 9300 5
J1 5900 0
K1 5700 0
L1 1500 3

As apparent from the results of Table 5, the color filters J1 to L1 have excessively low burn-in prevention or contrast. On the other hand, it turns out that the color filters A1-I1 of this invention can fully suppress the display defect by burn-in practically. Further, it can be seen that the color filters A1 to I1 of the present invention exhibit very high contrast and exhibit good display characteristics as compared with the color filters J1 to L1. Furthermore, by using a specific thing as a pigment dispersion which forms the colored layer of a color filter, the display defect by burn-in could be further suppressed more effectively.

(Example 10, Comparative Example 4)

<Production of Color Filters A2 to L2 (Production by Lamination of Photosensitive Resin Transfer Material)>

[Production of Photosensitive Resin Transfer Material]

On the 75-micrometer-thick polyethylene terephthalate film support body, the coating liquid for thermoplastic resin layers which consists of following formula H1 was apply | coated and dried using the slit-shaped nozzle. Next, the coating liquid for intermediate | middle layers which consists of following prescription P1 was apply | coated and dried. Furthermore, the following colored photosensitive resin composition K1 is apply | coated and dried, the thermoplastic resin layer whose dry film thickness is 14.6 micrometers, the intermediate | middle layer whose dry film thickness is 1.6 micrometers, and the photosensitive resin layer whose dry film thickness are 2.4 micrometers on the said support body. Was formed and the protective film (thickness 12 micrometers, polypropylene film) was crimped | bonded.

In this way, the photosensitive resin transfer material K1 which integrated the support body, the thermoplastic resin layer, the intermediate | middle layer (oxygen barrier film), and the black (K) photosensitive resin layer was produced.

<Coating solution for thermoplastic resin layer: Prescription H1>

Methanol 11.1 parts by mass

Propylene glycol monomethyl ether acetate 6.36 parts by mass

52.4 parts by mass of methyl ethyl ketone

Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 90,000, Tg: about 70 ° C.)

                               5.83 parts by mass

13.6 parts by mass of styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 63/37, molecular weight = 10,000, Tg: about 100 ° C.)

Dehydrated-condensed compound having 2 equivalents of pentaethylene glycol monomethacrylate in bisphenol A (manufactured by Shin-nakamura Chemical Corporation, trade name: 2,2-bis [4- (methacryloxy polyethoxy) phenyl] propane) 9.1 mass part

0.54 parts by mass of surfactant 1

<Coating solution for intermediate layer: prescription P1>

PVA205 (polyvinyl alcohol, product of Kuraray Co., Ltd., saponification ratio = 88%, degree of polymerization 550)

32.2 parts by mass

14.9 parts by mass of polyvinylpyrrolidone (ISP Japan Ltd., K-30)

524 parts by mass of distilled water

Methanol 429 parts by mass

Next, the said colored photosensitive resin composition K1 used in manufacture of the said photosensitive resin transfer material K1 was changed to the following colored photosensitive resin composition R101, G101, and B101 which consist of the composition shown in following Tables 6a-6c, and the same except that Photosensitive resin transfer materials R101, G101 and B101 were prepared by the method. In addition, the preparation method of colored photosensitive resin composition R101, G101, and B101 is based on the preparation method of the said colored photosensitive resin composition R1, G1, and B1, respectively.

Table 6a
R101
R pigment dispersion A 40 parts by mass
4.5 parts by weight of pigment dispersion 2 (CIPR177)
Propylene glycol monomethyl ether acetate 7.6 parts by mass
37 parts by mass of methyl ethyl ketone
Binder 1 0.8 parts by mass
4.4 parts by mass of DPHA liquid
0.14 parts by mass of 2-trichloromethyl- (p-styrylstyryl) -1,3,4-oxadiazole
0.06 parts by mass of polymerization initiator A
0.01 part by mass of phenothiazine
0.52 parts by mass of additive 1
0.06 parts by mass of surfactant 1

Table 6b
G101
G pigment dispersion 1 (CIPG36) 28 parts by mass
15 parts by mass of pigment Y dispersion 1 (CIPY150)
Propylene glycol monomethyl ether acetate 29 parts by mass
Methyl ethyl ketone 26 parts by mass
1.3 parts by mass of cyclohexanone
Binder 2 3.0 parts by mass
4.3 parts by mass of DPHA liquid
0.15 parts by mass of 2-trichloromethyl- (p-styrylstyryl) -1,3,4-oxadiazole
0.06 parts by mass of polymerization initiator A
0.01 part by mass of phenothiazine
0.07 parts by mass of surfactant 1

Table 6c
B101
B pigment dispersion 1 (CIPB15: 6) 8.6 parts by mass
B pigment dispersion 2 (CIPB15: 6 + CIPV23) 15 parts by mass
28 parts by mass of propylene glycol monomethyl ether acetate
Methyl ethyl ketone 26 parts by mass
Binder 3 18.5 parts by mass
4.3 parts by mass of DPHA liquid
0.17 parts by mass of 2-trichloromethyl- (p-styrylstyryl) -1,3,4-oxadiazole
Phenothiazine 0.02 parts by mass
0.06 parts by mass of surfactant 1

In addition, in the composition described in Table 6a, additive 1 used a phosphate ester-based special activator (Kusumoto Chemicals, Ltd., trade name: HIPLAAD ED152).

[Formation of Black (K) Image]

The glass-free liquid solution which adjusted the alkali free glass substrate to 25 degreeC was sprayed for 20 second by the shower, and it wash | cleans with a rotary brush with a nylon hair, and after washing with pure water, a silane coupling liquid (N-((amino ethyl) (gamma) -aminopropyl tree) A methoxysilane 0.3 mass% aqueous solution, brand name: KBM603, the product of Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds by shower, and the pure water shower wash | cleaned. This board | substrate was heated at 100 degreeC for 2 minutes by the board | substrate preheater, and was sent to the next laminator.

After peeling off the protective film of the said photosensitive resin transfer material K1, the board | substrate heated at 100 degreeC using the laminator (made by Hitachi Industries Co., Ltd. (Lamic II type)), the rubber roller temperature 130 degreeC, 100N of linear pressures / cm and a conveyance speed of 2.2 m / min.

After the branch is peeled off at the interface with the thermoplastic resin layer, a substrate and a mask (a quartz exposure mask having an image pattern) are perpendicular to each other by a proximity type exposure machine (manufactured by Hitachi Electronic Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp. In this state, the distance between the exposure mask surface and the thermoplastic resin layer was set to 200 µm, and the pattern exposure was performed at an exposure dose of 70 mJ / cm 2.

Next, a triethanolamine developer (containing 2.5% of triethanolamine, trade name: T-PD2, Fuji Photo Film Co., Ltd.) was diluted 12 times with pure water (1 part of T-PD2 and 11 parts of pure water). Mixed)), and the thermoplastic resin layer and the intermediate layer were removed by shower development at 30 DEG C, 50 seconds, and a flat nozzle pressure of 0.04 MPa.

Then, sodium carbonate developer (0.38 mol / L sodium hydrogen carbonate, 0.47 mol / L sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoamer, stabilizer containing, brand name: T-CD1, Fuji Photo Using a film obtained by diluting the product of Film Co., Ltd. five times with pure water), shower development was carried out at 29 ° C for 30 seconds at a cone nozzle pressure of 0.15 MPa to develop a photosensitive resin layer, thereby obtaining a patterned image.

Subsequently, using a liquid diluted 10 times with pure water, a detergent (trade name "T-SD1 (manufactured by Fuji Photo Film Co., Ltd.)" was used at 33 DEG C for 20 seconds at a cone nozzle pressure of 0.02 MPa for shower and nylon wool. The residue was removed with a rotating brush to obtain an image of black (K) Thereafter, the substrate was post-exposured with light of 500 mJ / cm 2 with ultra-high pressure mercury lamp from the side of the resin layer, followed by 15 minutes at 220 ° C. Heat treatment.

The board | substrate which formed this image K was wash | cleaned again with a brush as mentioned above, and after pure water shower cleaning, it sent to the board | substrate preheater without using a silane coupling liquid.

[Formation of red (R) pixels]

The heat treatment finish red (R) pixel R was obtained by the same process as the said photosensitive resin transfer material K1 using the said photosensitive resin transfer material R101. However, the exposure amount was 40 mJ / cm <2> and the image development by the sodium carbonate type developing solution was 35 degreeC, and 35 second. The film thickness of the photosensitive resin layer R101 and the coating amount of the pigments (C.I.P.R.254 and C.I.P.R.177) are shown below.

Photosensitive resin film thickness (μm) 2.00

Pigment Coating Amount (g / ㎡) 1.00

C.I.P.R. 254 Coating amount (g / ㎡) 0.80

C.I.P.R. 177 Coating amount (g / ㎡) 0.20

The board | substrate which formed this image K and the pixel R was again wash | cleaned with a brush as mentioned above, and after pure water shower washing, it sent to the board | substrate preheater without using a silane coupling liquid.

[Formation of Green (G) Pixels]

Using the photosensitive resin transfer material G101, a heat treatment finish green (G) pixel G was obtained in the same process as the photosensitive resin transfer material R101. However, the exposure amount was 40 mJ / cm 2, and the development by the sodium carbonate developer was 34 ° C. and 45 seconds. The film thickness of the photosensitive resin layer G101 and the coating amount of the pigments (C.I.P.G.36 and C.I.P.Y.150) are shown below.

Photosensitive resin film thickness (μm) 2.00

Pigment application amount (g / ㎡) 1.92

C.I.P.G. 36 Coating amount (g / ㎡) 1.34

C.I.P.Y. 150 Coating amount (g / ㎡) 0.58

The board | substrate which formed this image K, the pixel R, and the pixel G was again wash | cleaned with a brush as mentioned above, and it sent to the board | substrate preheater, without using a silane coupling liquid after pure water shower washing.

[Formation of Blue (B) Pixels]

Using the photosensitive resin transfer material B101, a heat treatment finish blue (B) pixel B was obtained in the same process as the photosensitive resin transfer material R101. However, the exposure amount was 30 mJ / cm 2 and the development by the sodium carbonate developer was 36 ° C. and 40 seconds. The film thickness of the said photosensitive resin layer B101 and the application amount of a pigment (C.I.P.B. 15: 6 and C.I.P.V. 23) are shown below.

Photosensitive resin film thickness (μm) 2.00

Pigment Coating Amount (g / ㎡) 0.75

C.I.P.B. 15: 6 Coating amount (g / ㎡) 0.705

C.I.P.V. 23 Coating amount (g / ㎡) 0.045

After baking the board | substrate which formed this pixel R, the pixel G, the pixel B, and the image K for 50 minutes at 240 degreeC, it carried out similarly to Example 1, and formed the ITO transparent electrode and obtained the color filter A2.

About the manufacturing method of the said color filter A2, R pigment dispersion A was changed into R pigment dispersions B-L, respectively, and the color filters B2-L2 were manufactured.

Δx, P, and Dp of the obtained color filters A2 to L2 were measured in the same manner as in Example 1. The results are shown in Table 7 below.

Table 7
Color Filter Δx P Dp A2 0.66 ° 21% 24nm
B2 0.75 ° 25% 22nm
C2 0.77 ° 24% 27nm
D2 0.75 ° 22% 38nm
E2 0.82 ° 27% 28nm
F2 0.69 ° 38% 29nm
G2 0.76 ° 35% 23nm
H2 0.85 ° 36% 27nm
I2 0.87 ° 33% 19nm
J2 0.56 ° 32% 34nm
K2 0.53 ° 34% 37nm
L2 0.51 ° 26% 52nm

As shown in Table 7, the R pixels of the color filters A2 to I2 obtained in the examples exhibited at least one diffraction peak having a half width of 0.6 ° or more at a Bragg angle of 28 ± 1 ° in the X-ray diffraction spectrum.

The contrast and burn-in prevention of the obtained color filters A2 to L2 were evaluated in the same manner as in Example 9 and Comparative Example 3. The results are shown in Table 8.

(Table 8)
Color filter contrast burn-in prevention A2 7000 2
B2 6700 3
C2 6400 2
D2 5900 1
E2 7200 4
F2 7400 3
G2 7800 4
H2 7200 5
I2 8100 5
J2 5500 0
K2 5700 0 L2 2300 3

According to the result of Table 8, according to this invention, also in the color filter in which the colored layer was formed by the lamination system, it can be seen that the display defect by burn-in is fully suppressed, the contrast is very high, and favorable display characteristics are shown.

(Example 11, Comparative Example 5)

<Production of Color Filters A3 to L3 (Production by Inkjet)>

The photosensitive resin transfer material K2 was manufactured in the same manner as in the manufacturing procedure of the photosensitive resin transfer material K1 in Example 10 and Comparative Example 4, except that carbon black was replaced with Degussa product "Special Black 250 (trade name)." .

[Formation of partition wall having light shielding property]

The glass-free liquid solution which adjusted the alkali free glass substrate to 25 degreeC was sprayed for 20 second by the shower, and it wash | cleans with a rotary brush with a nylon hair, and after washing with pure water, a silane coupling liquid (N-((amino ethyl) (gamma) -aminopropyl tree) A methoxysilane 0.3 mass% aqueous solution, brand name: KBM603, the product of Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds by shower, and the pure water shower wash | cleaned. The substrate was heated at 100 ° C. for 2 minutes in a substrate preheater.

After peeling off the protective film of the said photosensitive resin transfer material K2, the board | substrate heated at 100 degreeC for 2 minutes using the laminator (Hitachi Industries Co., Ltd. product (Lamic II type)), the rubber roller temperature 130 degreeC, Lamination was carried out at a linear pressure of 100 N / cm and a conveyance speed of 2.2 m / min.

After peeling off the supporting member, the exposure mask was placed vertically with a substrate and a mask (a quartz exposure mask having an image pattern) by a proximity exposure machine (manufactured by Hitachi Electronic Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp. The distance between a surface and the said thermoplastic resin layer was set to 200 micrometers, and pattern exposure was carried out with exposure amount 100mJ / cm <2>. The mask shape was lattice-shaped, and the radius of curvature of the convex angle was 0.6 µm on the side of the partition having the light shielding at the portion corresponding to the critical line between the pixel and the partition having the light shielding property.

Next, 30 DEG C, 50 seconds, using a triethanolamine developer (containing 2.5% of triethanolamine, containing a nonionic surfactant, containing a polypropylene antifoaming agent, trade name: T-PD1, manufactured by Fuji Photo Film Co., Ltd.) Shower development was carried out at a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer (oxygen barrier layer).

Then, sodium carbonate developer (0.06 mol / L sodium hydrogen carbonate, sodium carbonate at the same concentration, 1% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer containing, trade name: T-CD1, Fuji Photo Film Co , Ltd.) was shower-developed at a cone nozzle pressure of 0.15 MPa at 29 ° C. for 30 seconds to develop a resin layer having light shielding properties, thereby obtaining a patterned separation partition wall (partition pattern having light shielding properties).

Subsequently, using a cleaning agent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer, trade name "T-SDl" (Fuji Photo Film Co., Ltd.)), the cone nozzle pressure was 33 ° C for 20 seconds. The residue was removed by a rotating brush having a shower and nylon wool at 0.02 MPa to obtain a partition having a light shielding property. Thereafter, the substrate was heat-treated at 240 ° C. for 50 minutes after post-exposure with light of 500 mJ / cm 2 using ultra-high pressure mercury lamp from the side of the resin layer.

[Plasma water repellent treatment]

Thereafter, plasma water repellent treatment was performed by the following method.

Plasma water repelling treatment was performed on the substrate having the light shielding partition on the following conditions using a cathode coupling type parallel plate type plasma processing apparatus.

Gas Used: CF ₄

Gas flow rate: 80sccm

Pressure: 40Pa

RF power: 50 W

Processing time: 30 sec

[Preparation of Inkjet Ink for Color Filter]

The ink was prepared with the following prescription with reference to Example 1 of Unexamined-Japanese-Patent No. 2002-201387.

(Table 9)
Ingredient Content
(Parts by mass) Ink R 1 G ink 1 Ink B 1 R Pigment Dispersion A
(CIPR 254) 14 G pigment
(CIPR 36) 5.0 B pigment
(CIPR 15: 6) 5.0 Polymer Dispersant (SOLSPERSE 24000 from AVECIA LTD.) 2.0 2.0 2.0 Binder (benzyl methacrylate-methacrylic acid copolymer) 3.0 3.0 3.0 Dipentaerythritol pentaacrylate 2.0 2.0 2.0 Tripropylene glycol diacrylate 5.0 5.0 5.0 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 2.0 2.0 2.0 Diethylene glycol monobutyl ether acetate 29.9dyn / cm 72 81 81 Ink Viscosity at Injection
(mPa · s) 15 10 10 Ink Surface Tension at Injection
(mN / m) 26 21 21

<Viscosity>

The viscosity of the ink was measured by an E-type viscometer (TOKI SANGYO CO., LTD., RE80L (brand name)) under the conditions of 25 degreeC, the rotor 1 degree 34'xR24, and measurement time 2 minutes.

<Surface tension>

The surface tension of the ink was measured using a surface tension meter FACE SURFACE TENSIOMETER CBVB-A3 (manufactured by Kyowa Interface Science Co., LTD.) At a measurement temperature of 23 ° C.

About mixing of each component of the said Table 9, the pigment and the polymeric dispersing agent were first thrown in and mixed with a part of solvent, and it stirred using three rolls and a bead mill, and obtained the pigment dispersion liquid. On the other hand, another compounding component was thrown into the remainder of the solvent, stirred and dissolved to obtain a binder solution. And the pigment dispersion liquid was fully stirred by the dissolver, adding a small amount in the binder solution, and the inkjet ink for color filters was prepared.

[Pixel formation]

Using ink of R ink 1, G ink 1, and B ink 1 obtained above, a piezo-type head was first used to inject ink into recesses surrounded by light-shielding partitions as follows. And the color filter of this invention was obtained as follows.

The head has 318 nozzles at a nozzle density of 150 per 25.4 mm, and by fixing this by shifting 1/2 of the nozzle interval in the two nozzle row directions, 300 drops per 25.4 mm in the nozzle array direction are hit on the substrate.

The head and the ink are controlled to circulate the hot water in the head so that the discharge portion is near 50 ± 0.5 ° C.

The ink ejection from the head is controlled by the piezoelectric drive signal applied to the head to enable ejection of 6 to 42 pl per drop. In this embodiment, the glass substrate is transferred from the head while being conveyed at a position of 1 mm below the head. The conveying speed can be set in the range of 50 to 200 mm / s. In addition, the piezoelectric driving frequency can be up to 4.6KHz, and the strike amount can be controlled by these settings.

In the present embodiment, the conveyance speed and the driving frequency are controlled so that the coating amounts of the pigments are 1.1, 1.8, and 0.75 g / m 2, respectively, and R, G, and B are R, G, and B, respectively. Inks of G and B were punched out.

Targeted ink is conveyed to an exposure part and exposed by an ultraviolet light emitting diode (UV-LED). UV-LED used NCCU033 from Nichia Corporation. This LED outputs ultraviolet light having a wavelength of 365 nm from one chip, and light of about 100 mW is emitted from the chip by energizing a current of about 500 mA. A plurality of these are arranged at intervals of 7 mm to obtain a power of 0.3 W / cm 2 at the surface. The time from exposure to exposure and the exposure time can be changed depending on the conveyance speed of the medium and the distance in the conveyance direction of the head and the LED. In the present Example, after impacting, it dried for 10 minutes at 100 degreeC, and exposed after that.

According to the setting of the distance and the conveyance speed, the exposure energy on the medium can be adjusted between 0.01 to 15 J / cm 2. In this example, exposure energy was adjusted by the conveyance speed.

Measurement of these exposure powers and exposure energies is carried out by Ushio, Inc. Using the spectroradiometer URS-40D of the product, the value which integrated between wavelength 220nm and 400nm was used.

After baking the glass substrate in an oven at 230 ° C. for 30 minutes, the light shielding partition and all the pixels were completely cured, and in the same manner as in Example 1, an ITO transparent electrode was formed to produce color filter A3.

Regarding the manufacturing procedure of the color filter A3, R pigment dispersion A was changed to R pigment dispersions B to L, respectively, to prepare color filters B3 to L3.

Δx, P, and Dp of the obtained color filters A3 to L3 were measured in the same manner as in Example 1. The results are shown in Table 10 below.

(Table 10)
Color Filter Δx P Dp A3 0.67 ° 25% 23nm
B3 0.74 ° 24% 21nm
C3 0.72 ° 27% 25nm
D3 0.77 ° 23% 35nm
E3 0.81 ° 25% 25nm
F3 0.65 ° 37% 26nm
G3 0.79 ° 33% 21nm
H3 0.83 ° 37% 24nm
I3 0.82 ° 31% 16nm
J3 0.58 ° 37% 32nm
K3 0.59 ° 33% 36nm
L3 0.55 ° 23% 57nm

As shown in Table 10, the R pixels of the color filters A3 to I3 obtained in the examples exhibited at least one diffraction peak having a half width of 0.6 ° or more at a Bragg angle of 28 ± 1 ° in the X-ray diffraction spectrum.

The contrast and burn-in of the obtained color filters A3 to L3 were evaluated in the same manner as in Example 9 and Comparative Example 3. The results are shown in Table 11.

(Table 11)
Color filter contrast burn-in prevention A3 10000 2
B3 11000 3
C3 9900 2
D3 7800 1
E3 10200 4
F3 11400 3
G3 12000 4
H3 11800 5
I3 13200 5
J3 7700 0
K3 7500 0
L3 5400 3

As is apparent from the results in Table 11, it was found that even in a color filter having a colored layer formed by the inkjet method, display defects due to burn-in were sufficiently suppressed, and very high contrast was exhibited, showing good display characteristics. Can be.

1 is a diagram illustrating an X-ray chart of color filter H1.

2 is a diagram illustrating an X-ray chart of color filter J1.

Claims (13)

A color filter having a colored layer, the colored layer exhibiting at least one diffraction peak having a half width of 0.6 ° or more at a Bragg angle of 28 ± 1 ° in an X-ray diffraction spectrum with respect to Cu—K α rays, The colored layer contains organic pigment fine particles having an average particle diameter of 10 to 100nm consisting of a diketopyrrolopyrrole compound, C.I. wherein said organic pigment fine particles are organic pigments in a good solvent in the presence of a base. It is produced by mixing an organic pigment solution in which Pigment Red 254 is dissolved with a solvent which is compatible with the above good solvent and becomes a poor solvent for the organic pigment, The good solvent is an amide compound solvent or a sulfoxide compound solvent, The color filter, characterized in that the poor solvent is an aqueous solvent. delete delete The particle number of the organic pigment fine particles according to claim 1, wherein the number of particles having a particle diameter of 20 nm or more and 30 nm or less is 30% or more of the total organic pigment fine particles, The number average primary particle diameter (Dp) of the said organic pigment microparticles | fine-particles is 30 nm or less, A color filter, wherein the number average particle diameter (Df) of the dispersed particles consisting of secondary particles in which a plurality of primary particles are aggregated is 50 nm or less. delete delete The color filter according to claim 1 or 4, wherein the half width of the diffraction peak is 0.70 ° or more. The color filter according to claim 1 or 4, wherein the half width of the diffraction peak is 0.80 ° or more. A liquid crystal display device comprising the color filter according to claim 1. The color filter according to claim 1 or 4, wherein the dispersion liquid of the organic pigment fine particles produced by mixing the organic pigment solution and the poor solvent is concentrated and flocculated, and redispersed in a vehicle. The color filter according to claim 1 or 4, wherein the organic pigment fine particles and a polymer compound having a mass average molecular weight of 1,000 or more coexist. The color filter of Claim 1 or 4 which coexisted the said organic pigment microparticle and the pigment dispersant containing an amino group. The color filter of Claim 1 or 4 whose thickness of the said colored layer is 0.5-5.0 micrometers.

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