JP2007163689A - Method for manufacturing color filter, color filter and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a color filter at a low cost in high efficiency, by which the generation of a mixture of colors, a void or the like is restrained, a pixel is formed with high positional precision, and an uneven display is restrained when the color filter is loaded in a liquid crystal display device, and also to provide the color filter obtained by this producing method and the liquid crystal display device equipped with the color filter. <P>SOLUTION: The method for manufacturing the color filter comprises the steps of: forming light shielding partition walls on a substrate; and applying ink of each color of R, G and B to a concave part partitioned by the partition walls to form a colored layer. The partition wall is formed by exposing a photo-polymerizable light shielding layer to an oxygen-poor condition. The ink contains a coloring agent, a polymerizable compound and a polymerization initiator and the amount of a solvent in the ink is ≤50 mass%. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a color filter manufacturing method, a color filter, and a liquid crystal display device.

  In the color filter for display device, red (R), green (G), and blue (B) dot images are arranged in a matrix on a substrate such as glass, and the boundaries are divided by partitions such as a black matrix. Structure. As a method for producing such a color filter, conventionally, a substrate such as glass is used as a support, 1) a dyeing method, 2) a printing method, 3) application of a colored photosensitive resin solution, and repeated exposure and development. Colored photosensitive resin liquid method (colored resist method, see, for example, Patent Document 1), 4) A method of transferring images formed on a temporary support sequentially onto a final or temporary support (for example, Patent Document 2) Refer to.) 5) Form a colored layer by applying a pre-colored photosensitive resin solution on a temporary support, transfer the photosensitive colored layer directly onto the substrate, and expose and develop. There is known a method (transfer method) for forming a multicolor image by a method of repeating the same number of colors (for example, see Patent Document 3). A method using an ink jet method is also known (see, for example, Patent Document 4).

  Among these methods, although the color resist method can produce a color filter with high positional accuracy, it is not advantageous in terms of cost due to a large loss in application of the photosensitive layer resin solution. On the other hand, the ink-jet method has a problem that the positional accuracy of the pixels is poor, although the loss of the resin liquid is small and advantageous in terms of cost.

In order to overcome these problems, a color filter manufacturing method has been proposed in which a black matrix is formed by a colored resist method and RGB pixels are formed by an ink jet method. However, when the cross-sectional shape of the formed black matrix is observed, Since the edges are rounded and each of the color inks that are subsequently ejected easily passes over the black matrix, there is a possibility that bleeding, bleeding, color mixing with adjacent pixels, white spots, etc. may occur. In order to prevent this, a method has been disclosed in which the black matrix and the ink are repelled from each other and the ink wettability of the black matrix gap is increased (for example, Patent Documents 5 and 6). And 7).
However, these methods require special materials for the black matrix coloring resist and ink, and require a step of increasing the surface energy of the black matrix gap (surface modification treatment), which is a cost problem. It is still left.

  In addition, a method for improving productivity using a monofunctional monomer and a polyfunctional monomer and using an ink that is cured with an active energy ray immediately after adhesion is disclosed (for example, see Patent Document 8), but the characteristics are not sufficient. However, when mounted on a display device, display unevenness and the like are seen, and a problem remains.

JP-A-63-298304 JP-A-61-99103 JP-A-61-99102 JP-A-8-227010 JP-A-6-347637 JP-A-7-35915 JP-A-10-142418 JP 2002-371216 A

  As described above, the color filter manufacturing method in which the black matrix is formed by the color resist method and the RGB pixels are formed by the ink jet method has the advantage that the pixels can be formed with high positional accuracy, and that the cost is low and the efficiency is high. However, the present situation is that it has not been possible to sufficiently suppress the occurrence of mixed colors, white spots, display unevenness, and the like.

  The present invention has been made in view of the above, and can suppress the occurrence of mixed colors and white spots, can form pixels with high positional accuracy, and suppress display unevenness when mounted on a liquid crystal display device. It is an object of the present invention to provide a low-cost and high-efficiency color filter manufacturing method, a color filter obtained by this method, and a liquid crystal display device including this color filter, and to achieve the object And

  As a result of diligent research, the present inventors have found that the upper end of the light-shielding partition (black matrix) formed under anoxic conditions and the cross-sectional shape of the edge thereof are less likely to be round and are close to a rectangular shape. Then, it was found that the ink of each color that was subsequently ejected was difficult to pass over the black matrix. As a result, it has been found that bleeding, protrusion, color mixing with adjacent pixels, and white spots can be prevented. Furthermore, as the ink of each color of R (red), G (green), and B (blue), the volume shrinkage after curing of the colored layer of each color is reduced by using an ink having a solvent amount of 50% by mass or less. As a result, it was found that the smoothness at the center of the pixel is good and the color uniformity is improved, and as a result, the occurrence of display unevenness can be suppressed when mounted on a liquid crystal display device.

Based on these findings, the above problems are solved by the following means. That is, the present invention
<1> Manufacture of a color filter that forms a light-blocking partition on a substrate and forms colored layers by applying inks of R, G, and B colors to the recesses partitioned by the partition by an ink jet method In the method, the partition is formed by exposing the photopolymerizable light-shielding layer under anoxic conditions, the ink contains a colorant, a polymerizable compound, and a polymerization initiator, and the amount of solvent in the ink Is a method for producing a color filter, wherein the content is 50% by mass or less.

<2> The color filter according to <1>, wherein the poor oxygen condition is a condition in which an oxygen partial pressure is reduced from an oxygen partial pressure in an atmospheric pressure of 1 atmosphere by decompression or filling with an inert gas. It is a manufacturing method.

<3> The method for producing a color filter according to <1>, wherein the poor oxygen condition is a condition in which an oxygen blocking layer is formed on a photopolymerizable light blocking layer.

<4> The above-mentioned poor oxygen condition is a condition in which the partial pressure of oxygen is reduced from the partial pressure of oxygen at 1 atmosphere by reducing the pressure or filling with an inert gas, and the oxygen blocking layer is formed on the photopolymerizable light blocking layer. <1> The method for producing a color filter according to <1>.

<5> The production of a color filter according to any one of <1> to <4>, wherein the photopolymerizable light-shielding layer contains at least a light-shielding agent, a polymerizable compound, and a polymerization initiator. Is the method.

<6> The method for producing a color filter according to any one of <1> to <5>, wherein a height of the light-shielding partition wall is 1 to 20 μm.

<7> The method for producing a color filter according to any one of <1> to <6>, wherein the ink includes a radical polymerizable composition.

<8> A color filter manufactured by the manufacturing method according to any one of <1> to <7>.

<9> A liquid crystal display device comprising the color filter according to <8>.

  According to the present invention, it is possible to suppress the occurrence of mixed colors and white spots, to form pixels with high positional accuracy, and to suppress display unevenness when mounted on a display device. A highly efficient color filter manufacturing method, a color filter obtained by this method, and a liquid crystal display device including this color filter can be provided.

The present invention will be described in detail below.
The present invention provides a color filter for forming a colored layer by forming a light-blocking partition on a substrate and applying inks of R, G, and B colors to the recesses partitioned by the partition by an ink jet method. In the production method, the partition is formed by exposing the photopolymerizable light-shielding layer under poor oxygen conditions, the ink contains a colorant, a polymerizable compound, and a polymerization initiator, and the solvent in the ink The amount is 50% by mass or less.

≪Anoxia condition≫
In the present invention, the poor oxygen condition refers to a condition in which the oxygen present on the surface of the photopolymerizable light-shielding layer is less in the exposure of the photopolymerizable light-shielding layer than in the case where exposure is performed in the air.
The hypoxic condition is, for example, a condition in which the partial pressure of oxygen is reduced from the partial pressure of oxygen at 1 atmosphere of atmospheric pressure (hereinafter sometimes referred to as “anoxic atmosphere”) and / or photopolymerization. A condition in which an oxygen blocking layer is formed on the light shielding layer is preferable.

<Anoxic atmosphere>
In the present invention, the oxygen-poor atmosphere is preferably an atmosphere in which the partial pressure of oxygen is 0.15 atm or less, and these are as follows in detail.
Usually, the partial pressure of oxygen is 0.21 atm under the atmosphere (1 atm). Therefore, in order to lower the oxygen partial pressure to 0.15 atm or less, (a) the atmosphere at the time of exposure is reduced to 0 Or (b) a gas other than air and oxygen (for example, an inert gas such as nitrogen or argon) mixed at 40 vol% or more with respect to air.
The poor oxygen atmosphere in the present invention is not particularly limited, and any of the above methods can be used.
When using the method in which the oxygen partial pressure is 0.15 atm or less, 0.10 atm or less is preferable, 0.08 atm or less is more preferable, and 0.05 atm or less is particularly preferable. When the oxygen partial pressure is higher than 0.15 atm, the polymerization on the partition wall surface is inhibited by oxygen, and the surface roughness may increase.
There is no restriction | limiting in particular in the minimum of oxygen partial pressure. By substituting the vacuum or atmosphere with a gas other than air (eg, nitrogen), the oxygen partial pressure can be reduced to virtually zero, which is also a preferred method. The oxygen partial pressure can be measured using an oximeter.

The inert gas refers to general gases such as N ₂ , H ₂ , CO ₂ , and rare gases such as He, Ne, Ar. Among these, N ₂ is preferably used because of safety, availability, and cost.

  The term “under reduced pressure” refers to a state of 500 hPa or less, preferably 100 hPa or less.

<Oxygen barrier layer>
Examples of the oxygen barrier layer used in the present invention include polyvinyl ether / maleic anhydride polymer, water-soluble salt of carboxyalkyl cellulose described in JP-A Nos. 46-2121 and 56-40824. Water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polyvinyl alcohol, polyvinylpyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, various starches And a group of water-soluble salts thereof, styrene / maleic acid copolymers, maleate resins, and combinations of two or more thereof.

  Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable. The polyvinyl alcohol preferably has a saponification rate of 80% or more, and the content of polyvinyl pyrrolidone is preferably 1 to 75% by mass, more preferably 1 to 50% by mass, and still more preferably the alkali-soluble resin layer solid content. It is 10-40 mass%.

The oxygen permeability coefficient of the oxygen barrier layer capable of blocking oxygen formed in this way is preferably 75 cm ³ / m ² · day · 1000 hPa or less, more preferably 50 cm ³ / m ² · day · 1000 hPa or less, and 25 cm ³ / Most preferred is m ² · day · 1000 hPa or less. When the oxygen permeability coefficient is 75 cm ³ / m ² · day · 1000 hPa or less, oxygen can be blocked efficiently, and the partition wall can have a cross-sectional shape close to a desired rectangular shape.

≪Ink≫
The R, G, and B inks used in the present invention are characterized in that the amount of solvent in the ink is 50% by mass or less. That the amount of solvent in the ink is 50% by mass or less is a condition for clearly defining an ink that does not substantially contain a solvent.
By using the ink, the volume shrinkage after curing of the colored layers of the respective colors can be reduced, the smoothness at the center of the pixel becomes good, and the color uniformity is improved. As a result, occurrence of display unevenness when mounted on a liquid crystal display device can be suppressed.
The solvent referred to in the present invention refers to a solvent described in "New Edition Solvent Pocket Book (edited by Organic Synthetic Science Association, published by Ohm)" such as water, alcohols and ketones.
Further, the R, G, and B inks used in the present invention include a colorant, a polymerizable compound, and a polymerization initiator. The ink is preferably composed of a polymerizable coloring composition that is cured by a polymerization reaction with actinic rays.

<Colorant>
Known colorants (dyes and pigments) can be used as the colorant. In the case of using a pigment among the known colorants, it is desirable that the pigment is uniformly dispersed in the ink. Therefore, the particle diameter is preferably 0.1 μm or less, particularly 0.08 μm or less.
Specific examples of the known dyes or pigments include the color materials described in JP-A-2005-17716 [0038] to [0040] and JP-A-2005-361447 [0068] to [0072]. The pigment described in JP-A-2005-17521 and the colorants described in [0080] to [0088] can be preferably used.

  As the colorant in the present invention, among the above colorants, (i) R (red) ink is C.I. I. Pigment Red 254 is C.I. for (ii) G (green) ink. I. Pigment Green 36 is C.I. for (iii) B (blue) ink. I. Pigment Blue 15: 6 is a preferable example. Furthermore, the above pigments may be used in combination.

In the present invention, the combination of the above-described pigments preferably used in combination is C.I. I. In pigment red 254, C.I. I. Pigment red 177, C.I. I. Pigment red 224, C.I. I. Pigment yellow 139 or C.I. I. A combination with Pigment Violet 23; I. In Pigment Green 36, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 138 or C.I. I. A combination with CI Pigment Yellow 180, and C.I. I. In Pigment Blue 15: 6, C.I. I. Pigment violet 23 or C.I. I. A combination with Pigment Blue 60 is mentioned.
C. in the pigment when used together in this way. I. Pigment red 254, C.I. I. Pigment green 36, C.I. I. The content of Pigment Blue 15: 6 is C.I. I. Pigment Red 254 is preferably 80% by weight or more, particularly preferably 90% by weight or more. C. I. The pigment green 36 is preferably 50% by weight or more, particularly preferably 60% by weight or more. C. I. Pigment Blue 15: 6 is preferably 80% by weight or more, particularly preferably 90% by weight or more.

  The pigment is desirably used as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the pigment and the pigment dispersant to a polymerizable compound described later. The disperser used for dispersing the pigment is not particularly limited. For example, the kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, first edition, Asakura Shoten, 2000, 438, Known dispersing machines such as a roll mill, an atrider, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, fine grinding may be performed using frictional force by mechanical grinding described in Item 310 of the document.

  The colorant (pigment) used in the present invention preferably has a number average particle diameter of 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm. When the number average particle diameter of the pigment is less than 0.001 μm, the particle surface energy is increased and the particles are easily aggregated, so that it is difficult to disperse the pigment and it is difficult to keep the dispersion state stable. On the other hand, if the number average particle diameter of the pigment exceeds 0.1 μm, the polarization is canceled by the pigment, and the contrast is lowered. The “particle diameter” here means the diameter when the electron micrograph image of the particle is a circle of the same area, and the “number average particle diameter” is the above-mentioned particle diameter for many particles, This 100 average value is said.

  The contrast of the colored pixels can be improved by reducing the particle size of the dispersed pigment. Reduction of the particle size can be achieved by adjusting the dispersion time of the pigment dispersion. For dispersion, the known disperser described above can be used. The dispersion time is preferably 10 to 30 hours, more preferably 18 to 30 hours, and most preferably 24 to 30 hours. When the dispersion time is less than 10 hours, the pigment particle size is large, the polarization due to the pigment is canceled, and the contrast may be lowered. On the other hand, if it exceeds 30 hours, the viscosity of the dispersion increases, and it may be difficult to discharge from the inkjet head.

  The contrast of each colored pixel of the color filter produced using the colorant is preferably 2000 or more, more preferably 2800 or more, still more preferably 3000 or more, and most preferably 3400 or more. When the contrast of each colored pixel constituting the color filter is 2000 or less, when an image of a liquid crystal display device having the color pixel is observed, an overall whitish impression is obtained, which is not preferable. Further, the difference in contrast between the colored pixels is preferably within 600, more preferably within 410, still more preferably within 350, and most preferably within 200. It is preferable that the difference in contrast between the colored pixels is within 600 because the amount of light leakage from each colored pixel portion during black display does not differ greatly, and the color balance of black display is good.

  In the present specification, “contrast of colored pixels” means a contrast that is individually evaluated for each color of R, G, and B constituting the color filter. The contrast measurement method is as follows. In the state where the polarizing plates are overlapped on both sides of the object to be measured and the polarizing directions of the polarizing plates are parallel to each other, the backlight Y is applied from the side of one polarizing plate, and the luminance Y1 of the light passing through the other polarizing plate is obtained. taking measurement. Next, in a state where the polarizing plates are orthogonal to each other, a backlight is applied from the side of one polarizing plate, and the luminance Y2 of the light passing through the other polarizing plate is measured. The contrast is calculated by Y1 / Y2 using the obtained measurement value. The polarizing plate used for the contrast measurement is the same as the polarizing plate used for the liquid crystal display device using the color filter.

<Polymerizable compound>
As the polymerizable compound in the present invention, a radical polymerizable compound that is cured by a polymerization reaction by a radical active species and a cationic polymerizable compound that is cured by a cationic polymerization reaction by a cationic active species can be used.

(Radically polymerizable compound)
Specific examples of the radical polymerizable compound include compounds shown below, but are not limited thereto.
Monofunctional monomers having one ethylenically unsaturated double bond include butanediol monoacrylate, N, N-dimethylaminoethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, 2-methoxyethyl Acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, acryloylmorpholine, N-vinylformamide, cyclohexyl acrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, glycidyl acrylate, isobornyl acrylate, isodecyl acrylate, phenoxy methacrylate, stearyl acrylate, Tetrahydrofurfuryl acrylate, 2-phenoxyethyl acrylate, 2-hydroxypro Acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, isobornyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, benzyl Examples include acrylate, ethoxyethoxyethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxydipropylene glycol acrylate, methylphenoxyethyl acrylate, and dipropylene glycol acrylate.

As a bifunctional or higher monomer, the oligomer includes ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethoxylated 1,6 -Hexanediol diacrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol diacrylate 1,4-butanediol di (meth) acrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, 2-n-butyl-2-ester 1,3-propanediol diacrylate, dimethylol-tricyclodecane diacrylate, neopentyl glycol diacrylate hydroxypivalate, 1,3-butylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate , Propoxylated bisphenol A di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, dimethylol dicyclopentane diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, Pentaerythritol triacrylate, tetramethylolpropane triacrylate, tetramethylol methane triacrylate, pentae Thritol tetraacrylate, caprolactone-modified trimethylolpropane triacrylate, ethoxylated isocyanuric acid triacrylate, tri (2-hydroxyethyl isocyanurate) triacrylate, propoxylate glyceryl triacrylate, tetramethylol methane tetraacrylate, pentaerythritol tetraacrylate, ditril Methylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, neopentyl glycol oligoacrylate, 1,4-butanediol oligoacrylate, 1,6-hexanediol oligoacrylate, trimethylolpropane oligoacrylate, pentaerythritol Oligoacrylate, U Examples thereof include letane acrylate, epoxy acrylate, and polyester acrylate.
These compounds may be used alone or in combination of two or more as required.

(Cationically polymerizable compound)
As a cationically polymerizable compound, a cationically polymerizable compound can be used as a compound that causes a polymerization reaction by a cationically active species generated from a photopolymerization initiator and cures.
As the cationically polymerizable compound, various known cationically polymerizable monomers known as photocationically polymerizable monomers can be used. Examples of the cationic polymerizable monomer include various publications such as JP-A-6-9714, JP-A-2001-31892, JP-A-2001-40068, JP-A-2001-55507, JP-A-2001-310938, JP-A-2001-310937, and JP-A-2001-220526. And vinyl ether compounds, oxetane compounds, and oxirane compounds described in 1).

Specific examples of the cationically polymerizable compound having vinyl ether as a functional group include urethane vinyl ether (vinyl ether urethane), ester vinyl ether, and the like. These oligomers can be used alone or in combination.
Specific examples of aromatic epoxy resins include polyphenols having at least one aromatic ring, or polyglycidyl ethers of alkylene oxide adducts thereof such as bisphenol A, bisphenol F, and further alkylene oxide added thereto. And glycidyl ether, epoxy novolac resin, bisphenol A novolac diglycidyl ether, and bisphenol F novolac diglycidyl ether.
Specific examples of the alicyclic epoxy resin include cyclohexene oxide obtained by epoxidizing a polyglycidyl ether of polyhydric alcohol having at least one alicyclic ring or a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. Examples thereof include a structure-containing compound, a cyclopentene oxide structure-containing compound, or a vinylcyclohexane oxide structure-containing compound obtained by epoxidizing a compound having a vinylcyclohexane structure with an oxidizing agent. For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylcyclohexanecarboxylate 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane Meta Oxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methyl Cyclohexyl carboxylate, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), epoxy hexahydro Examples include dioctyl phthalate and di-2-ethylhexyl epoxyhexahydrophthalate.

  Specific examples of aliphatic epoxy resins include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, and aliphatic long-chain unsaturated hydrocarbons oxidized with an oxidizing agent. Examples thereof include epoxy-containing compounds, glycidyl acrylate or glycidyl methacrylate homopolymers, glycidyl acrylate or glycidyl methacrylate copolymers, and the like. Representative compounds include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol tetra 1 in glycidyl ether of polyhydric alcohols such as glycidyl ether, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, and aliphatic polyhydric alcohols such as propylene glycol and glycerin Polyglycidyl ethers of polyether polyols obtained by adding seeds or two or more alkylene oxides, aliphatic long-chain dibases Like diglycidyl ester of. Furthermore, monoglycidyl ethers of higher aliphatic alcohols, phenols, cresols, butylphenols, polyether alcohol monoglycidyl ethers obtained by adding alkylene oxides to these, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxy stearin Examples include octyl acid, epoxy butyl stearate, and epoxidized linseed oil.

  When the component having curability by irradiation with these active energy rays falls to 50% by mass or less of the total ink amount, curability becomes insufficient with the intensity of general active energy rays. Therefore, it is necessary to take measures such as extending the irradiation time. From the above, it is desirable that the amount of the curable component is 50% by mass or more, more preferably 60% by mass or more of the total ink.

<Polymerization initiator>
As the polymerization initiator used in the present invention, radical active species are generated by irradiation with actinic rays, and radical polymerization initiators that start polymerization of radical polymerizable compounds and cationic active species are generated, and are cationically polymerizable. Any of the cationic polymerization initiators that initiate the polymerization of the compound can be used in accordance with the polymerizable compound.

(Radical polymerization initiator)
Examples of the photopolymerization initiator that can be used in the present invention include the following. As benzophenone series, benzophenone, benzoylbenzoic acid, 4-phenylbenzophenone, 4,4-diethylaminobenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, etc. Thioxanthone, 2-chlorooxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, isopropylxanthone and the like are 2-methyl-1- (4-methylthio) phenyl-2-morpholine as acetophenone series. Linopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxy Cyclohexyl Phenyl ketone, 2,2-dimethyl-2-hydroxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 4-phenoxydichloroacetophenone, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone and the like are Benzoin methyl ether, benzoin isobutyl ether, benzyl methyl ketal, etc. are acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) acylphosphine oxide, etc. Is mentioned.

(Cationic polymerization initiator)
As the cationic polymerization initiator, diazonium salts, iodonium salts, sulfonium salts, iron arene complexes, and organic polyhalogen compounds can be preferably used. Examples of the diazonium salt, iodonium salt, and sulfonium salt include Japanese Patent Publication No. 54-14277, Japanese Patent Publication No. 54-14278, Japanese Patent Publication No. 51-56885, U.S. Pat. Nos. 3,708,296, and 3,853. And compounds described in No. 002 and the like.
Examples of the photocationic polymerization initiator include aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metallocene compounds, silicon compounds / aluminum complexes, and the like.

≪Bulk wall≫
The partition wall according to the present invention separates two or more pixel groups and has a light shielding property. The partition wall in the present invention is preferably formed by exposing the photopolymerizable light-shielding layer under the above-mentioned poor oxygen condition and then developing it.

<Photopolymerizable light shielding layer>
The composition forming the photopolymerizable light-shielding layer in the present invention is hereinafter simply referred to as a dark color composition.
Here, the dark color composition is a composition having a high optical density, and the value thereof is 2.0 to 10.0. The optical density of the dark color composition is preferably 2.5 to 6.0, particularly preferably 3.0 to 5.0. Further, since this dark color composition is preferably cured by a photoinitiating system as described later, the optical density with respect to the exposure wavelength (generally the ultraviolet region) is also important. That is, the value is 2.0 to 10.0, preferably 2.5 to 6.0, and most preferably 3.0 to 5.0. If it is less than 2.0, the shape of the partition may not be as desired, and if it exceeds 10.0, polymerization cannot be started and it is difficult to produce the partition itself. As long as it has such properties, the light-shielding agent in the composition may be an organic substance (various dyes such as dyes and pigments), carbon in various forms, metals or alloys thereof and oxides. It may also be a combination of these. Such a light shielding agent is not particularly limited, but a black body is most often used. Examples of black bodies include carbon black, titanium carbon, iron oxide, titanium oxide, graphite, silver and tin, and alloys thereof, among which carbon black, silver, tin, and alloys thereof are preferable.

  The dark color composition preferably comprises at least a polymerizable compound and a polymerization initiator in addition to the light-shielding agent. Further, if necessary, a known additive such as a plasticizer, a filler, a stabilizer, a polymerization inhibitor, a surfactant, a solvent, an adhesion promoter, and the like can be further contained. Furthermore, the dark color composition is preferably softened or tacky at a temperature of at least 150 ° C., and is preferably thermoplastic. From such a viewpoint, it can be modified by adding a compatible plasticizer.

(Polymerization initiator)
As a method for curing the dark color composition, a thermal initiation system using a thermal polymerization initiator and a photoinitiation system using a photopolymerization initiator are common, but it is preferable to use a photoinitiation system.
The photopolymerization initiator used here generates an active species that initiates polymerization of a polyfunctional monomer, which will be described later, upon irradiation with radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray (also referred to as exposure). It is a compound to be obtained and can be appropriately selected from known photopolymerization initiators or photopolymerization initiator systems.
For example, trihalomethyl group-containing compounds, acridine compounds, acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds Compound, etc. can be mentioned.

Specifically, a trihalomethyl group-substituted trihalomethyloxazole derivative or s-triazine derivative described in JP-A No. 2001-117230, a trihalomethyl-s-triazine compound described in US Pat. No. 4,239,850, A trihalomethyl group-containing compound such as the trihalomethyloxadiazole compound described in Japanese Patent No. 4221976;
9-phenylacridine, 9-pyridylacridine, 9-pyrazinylacridine, 1,2-bis (9-acridinyl) ethane, 1,3-bis (9-acridinyl) propane, 1,4-bis (9-acridinyl) ) Butane, 1,5-bis (9acridinyl) pentane, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, 1,8-bis (9-acridinyl) octane, Bis such as 1,9-bis (9-acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, 1,12-bis (9-acridinyl) dodecane Acridine compounds such as (9-acridinyl) alkanes;
6- (p-methoxyphenyl) -2,4-bis (trichloromethyl) -s-triazine, 6- [p- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl] -2,4-bis ( Triazine compounds such as trichloromethyl) -s-triazine; 9,10-dimethylbenzphenazine, Michler's ketone, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, benzyldimethyl ketal, thioxanthone / amine, 2,2 ′ -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like.

Among the above, at least one selected from a trihalomethyl group-containing compound, an acridine compound, an acetophenone compound, a biimidazole compound, and a triazine compound is preferable, and particularly selected from a trihalomethyl group-containing compound and an acridine compound. It is preferable to contain at least one kind. Trihalomethyl group-containing compounds and acridine compounds are also useful in that they are versatile and inexpensive.
Particularly preferred as the trihalomethyl group-containing compound is 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole, and as the acridine compound, 9-phenylacridine is preferred. Further, 6- [p- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl] -2,4-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6 -[4 '-(N, N-bisethoxycarbonylmethyl) amino-3'-bromophenyl] -s-triazine, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadi Trihalomethyl group-containing compounds such as azoles, and Michler's ketone, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetrafe Le 1,2' is a bi-imidazole.

  The said photoinitiator may be used independently and may use 2 or more types together. The total amount of the photopolymerization initiator in the dark color composition is preferably from 0.1 to 20% by weight, particularly preferably from 0.5 to 10% by weight, based on the total solid content (mass) of the dark color composition. When the total amount is less than 0.1% by mass, the photocuring efficiency of the composition is low and exposure may take a long time. When it exceeds 20% by mass, an image pattern formed during development is formed. May be lost or the pattern surface may be rough.

The photopolymerization initiator may be configured using a hydrogen donor in combination. The hydrogen donor is preferably a mercaptan compound or an amine compound as defined below from the viewpoint that sensitivity can be further improved. The “hydrogen donor” herein refers to a compound that can donate a hydrogen atom to a radical generated from the photopolymerization initiator by exposure.
The mercaptan-based compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “ A mercaptan-based hydrogen donor). The amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, and more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as “the amine compound”). , Referred to as “amine-based hydrogen donor”). These hydrogen donors may have a mercapto group and an amino group at the same time.

Specific examples of the mercaptan-based hydrogen donor include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-2. , 5-dimethylaminopyridine, and the like. Of these, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.
Specific examples of the amine-based hydrogen donor include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl. Examples include -4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like. Of these, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferable, and 4,4′-bis (diethylamino) benzophenone is particularly preferable.

  The hydrogen donor can be used alone or in admixture of two or more, and the formed image is difficult to drop off from the permanent support during development, and can be improved in strength and sensitivity. It is preferable to use a combination of one or more mercaptan hydrogen donors and one or more amine hydrogen donors.

  Specific examples of the combination of the mercaptan hydrogen donor and the amine hydrogen donor include 2-mercaptobenzothiazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / 4,4′-. Examples thereof include bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone. More preferred combinations are 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylaminobenzophenone, and a particularly preferred combination is 2-mercaptobenzothiazole. / 4,4'-bis (diethylamino) benzophenone.

  When the mercaptan hydrogen donor and the amine hydrogen donor are combined, the mass ratio (M: A) of the mercaptan hydrogen donor (M) to the amine hydrogen donor (A) is usually 1: 1-1: 4 is preferable, and 1: 1-1: 3 is more preferable. The total amount of the hydrogen donor in the dark color composition is preferably from 0.1 to 20% by weight, particularly preferably from 0.5 to 10% by weight, based on the total solid content (mass) of the dark color composition.

(Polymerizable compound)
A polyfunctional monomer can be used as the polymerizable compound of the present invention.
As the polyfunctional monomer, the following compounds can be used alone or in combination with other monomers. Specifically, t-butyl (meth) acrylate, ethylene glycol di (meth) acrylate, 2-hydroxypropyl (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 2- Ethyl-2-butyl-propanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, polyoxy Ethylated trimethylolpropane tri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, 1,4-diisopropenylbenzene, 1,4-dihydroxy Nzenji (meth) acrylate, decamethylene glycol di (meth) acrylate, styrene, diallyl fumarate, triallyl trimellitate, lauryl (meth) acrylate, (meth) acrylamide, xylylenebis (meth) acrylamide, and the like.
Reaction of compounds having hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and polyethylene glycol mono (meth) acrylate with diisocyanates such as hexamethylene diisocyanate, toluene diisocyanate and xylene diisocyanate Things can also be used.
Of these, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and tris (2-acryloyloxyethyl) isocyanurate are particularly preferable.

  The content of the polyfunctional monomer in the dark color composition is preferably 5 to 80% by weight, particularly preferably 10 to 70% by weight, based on the total solid content (mass) of the dark color composition. When the content is less than 5% by mass, the resistance to an alkaline developer at the exposed portion of the composition may be inferior. When the content exceeds 80% by mass, the tackiness of a dark color composition increases. Therefore, the handleability may be inferior.

(binder)
The dark color composition for forming a dark color separation image wall can be constituted using at least one kind of binder.
As the binder, a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain is preferable. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-59-53836. As disclosed in JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc. Can be mentioned.

Moreover, the cellulose derivative which has a carboxylic acid group in a side chain is also mentioned. Furthermore, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably.
As particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate, (meth) acrylic acid, and other monomers can be used. Mention may be made of multi-component copolymers. These binders having a polar group may be used singly or may be used in the state of a composition used in combination with a normal film-forming polymer.

  As content in the dark color composition of a binder, 20-50 mass% is preferable with respect to the total solid (mass) of a layer or a composition, and 24-45 mass% is more preferable.

(solvent)
In general, the dark color composition used for producing the separation wall in the present invention can be constituted using an organic solvent in addition to the above components. Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam and the like.

(Other ingredients)
In the dark color composition layer in the present invention, the following components, for example, surfactants, ultraviolet absorbers, and known additives such as plasticizers, fillers, stabilizers, thermal polymerization inhibitors, solvents, adhesion An accelerator or the like can be contained. Furthermore, the photosensitive resin composition is preferably softened or tacky at a temperature of at least 150 ° C., and is preferably thermoplastic. From such a viewpoint, it can be modified by adding a compatible plasticizer.

-Surfactant-
When the dark color composition is applied on a substrate or a temporary support of a photosensitive transfer material described later, a uniform film thickness can be controlled by including a surfactant in the dark color composition. Unevenness can be effectively prevented. Preferred examples of the surfactant include surfactants described in JP-A Nos. 2003-337424 and 11-133600. In addition, as content in the deep color composition of surfactant, 0.001-1% is common with respect to the total solid (mass) of this composition, 0.01-0.5 % Is preferable, and 0.03 to 0.3% is particularly preferable.

-UV absorber-
The dark color composition may contain an ultraviolet absorber as necessary.
Examples of the ultraviolet absorber include compounds described in JP-A-5-72724, and compounds such as salicylates, benzophenones, benzotriazoles, cyanoacrylates, nickel chelates, and hindered amines.

For example, phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-4′-hydroxybenzoate, 4-t-butylphenyl salicylate, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy -3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3-di-phenyl acrylate, 2,2'-hydroxy-4-methoxybenzophenone, nickel dibutyl Dithiocarbamate, 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-piperenyl) Ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- (diethylamino) -5-triazine-2 -Yl] amino} -3-phenylcoumarin and the like.
In the case of using the ultraviolet absorber, the content of the ultraviolet absorber with respect to the total solid content of the dark color composition is generally 0.5 to 15%, preferably 1 to 12%, preferably 1.2 to 10%. Is particularly preferred.

-Thermal polymerization inhibitor-
The dark composition preferably contains a thermal polymerization inhibitor. Examples of thermal polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl- 6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like.
When the thermal polymerization inhibitor is used, the content with respect to the total solid content of the dark color composition is generally 0.01 to 1%, preferably 0.02 to 0.7%, preferably 0.05 to 0%. .5% is particularly preferred.

  Further, in addition to the above components, the dark color composition may contain “adhesion aid” described in JP-A-11-133600, other additives, and the like.

<Surface roughness of partition walls>
In the present invention, since the photopolymerizable light-shielding layer is exposed under poor oxygen conditions when forming the partition walls, it is difficult to be affected by oxygen, and the surface roughness of the partition walls can be reduced. The surface roughness Ra value of the partition walls can be 5 nm or less, preferably 4.0 nm or less, more preferably 3.6 nm or less. When the surface roughness Ra value of the partition wall is 5 nm or less, the movement of the colored liquid composition such as ink on the surface of the partition wall can be suppressed. As a result, color mixture due to the movement of the colored liquid composition between adjacent pixels is prevented. Can be prevented.

<Height of partition wall>
In the present invention, the height of the partition wall is preferably 1 μm to 20 μm, and more preferably 1.5 μm to 5 μm. By setting the thickness to 1 μm to 20 μm, it is possible to prevent color mixing more effectively.

<Cross sectional shape of partition wall>
The cross-sectional shape of the partition wall in the present invention is preferably close to a rectangular shape from the viewpoint of preventing bleeding, protrusion, color mixture with adjacent pixels, and white spots.

<< Board >>
As the substrate (permanent support) constituting the color filter of the present invention, a metal support, a metal bonded support, glass, ceramic, a synthetic resin film, or the like can be used. Particularly preferred are transparent glass and synthetic resin film having good dimensional stability.

≪Photosensitive transfer material≫
In order to realize such a partition shape easily and at low cost, there is a method of using a photosensitive transfer material having at least a photopolymerizable light shielding layer and an oxygen blocking layer on a temporary support. When such a material is used, the photopolymerizable light-shielding layer is protected by the oxygen barrier layer, so that it is automatically in an anoxic condition. Therefore, there is no need to carry out the exposure process under an inert gas or under reduced pressure, so that there is an advantage that the current process can be used as it is.

  The photosensitive transfer material may have a thermoplastic resin layer as necessary. Such a thermoplastic resin layer is alkali-soluble and includes at least a resin component, and the resin component preferably has a substantial softening point of 80 ° C. or less. By providing such a thermoplastic resin layer, good adhesion to the permanent support can be exhibited in the partition wall forming method described later.

  Examples of alkali-soluble thermoplastic resins having a softening point of 80 ° C. or lower include saponified products of ethylene and acrylate copolymers, saponified products of styrene and (meth) acrylate copolymers, vinyltoluene and (meth) acrylic. Examples thereof include saponification products of acid ester copolymers, saponification products such as poly (meth) acrylic acid esters, and (meth) acrylic acid ester copolymers such as butyl (meth) acrylate and vinyl acetate.

  For the thermoplastic resin layer, at least one of the above-mentioned thermoplastic resins can be appropriately selected and used. Further, “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, published by the Industrial Research Council, Among those organic polymers having a softening point of about 80 ° C. or lower, issued on October 25, 1968), those soluble in an alkaline aqueous solution can be used.

  In addition, for an organic polymer substance having a softening point of 80 ° C. or higher, by adding various plasticizers compatible with the polymer substance to the organic polymer substance, the substantial softening point is 80 ° C. or lower. It can also be used by lowering. In addition, these organic polymer substances include various polymers, supercooling substances, adhesion improvers or interfaces within the range where the substantial softening point does not exceed 80 ° C. for the purpose of adjusting the adhesive force with the temporary support. Activators, mold release agents, etc. can also be added.

  Specific examples of preferable plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate biphenyl, and diphenyl phosphate.

  The temporary support in the above photosensitive transfer material can be appropriately selected from those that are chemically and thermally stable and composed of a flexible substance. Specifically, a thin sheet such as Teflon (registered trademark), polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, or a laminate thereof is preferable. As thickness of the said temporary support body, 5-300 micrometers is suitable, Preferably it is 20-150 micrometers.

≪Color filter manufacturing method≫
Hereinafter, the manufacturing method of the color filter of this invention is demonstrated.
<Formation of partition walls>
The method for forming the partition wall in the present invention is as follows.
(1) A method in which a coating solution containing a dark color composition is applied onto a substrate to form a photopolymerizable light-shielding layer, and an oxygen-blocking film is applied thereon as needed (2) on a temporary support In addition, a method of transferring a photosensitive transfer material having at least a photopolymerizable light-shielding layer composed of a dark color composition and, if necessary, an oxygen-blocking film onto a substrate is preferable. Hereinafter, the method (1) is simply referred to as a coating method, and the method (2) is also referred to as a transfer method.
Hereinafter, these will be described in detail.

(Partition formation by coating method)
First, after cleaning the substrate, the substrate is heat-treated to stabilize the surface state. After the temperature of the substrate is adjusted, the dark color composition is applied. Subsequently, after part of the solvent is dried to eliminate the fluidity of the coating layer, pre-baking is performed to obtain a photopolymerizable light-shielding layer. At this time, unnecessary coating liquid around the substrate may be removed by EBR (edge bead remover) or the like.
The coating is not particularly limited, and is a glass substrate coater having a known slit nozzle (for example, product name: MH-1600 manufactured by FAS Asia) or glass having a slit nozzle. A substrate coater (manufactured by Hirata Kiko Co., Ltd.) can be used.
The drying can be performed using a known drying apparatus (for example, VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.)).
Although it does not specifically limit as prebaking, For example, it can achieve by making 120 degreeC 3 minutes.

Subsequently, in a state where the substrate and a mask having an image pattern (for example, a quartz exposure mask) are vertically set, the distance between the exposure mask surface and the photopolymerizable light-shielding layer is appropriately set (for example, 200 μm), Exposure is performed in the above-mentioned poor oxygen atmosphere.
The exposure is performed, for example, with a proximity type exposure machine (for example, manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp, and the exposure amount may be appropriately selected (for example, 300 mJ / cm ² ). it can.

  Here, an oxygen blocking layer may be formed on the photopolymerizable light blocking layer and exposed. In this case, the exposure may be performed in the poor oxygen atmosphere or in the air. The oxygen blocking layer can be formed by the same method as the photopolymerizable light blocking layer.

Next, it develops with a developing solution and a patterning image is obtained, and if necessary, it wash-processes and obtains a partition.
Prior to the development, it is preferable to spray pure water with a shower nozzle or the like to uniformly wet the surface of the dark color photosensitive resin layer. As the developer used in the development process, a dilute aqueous solution of an alkaline substance is used, but it may be further added with a small amount of an organic solvent miscible with water.
Examples of the light source used for the light irradiation include medium to ultrahigh pressure mercury lamps, xenon lamps, metal halide lamps, and the like.

(Partition formation by transfer method)
Next, the case where a partition is formed using the above-described photosensitive transfer material will be described.
First, after cleaning the substrate, the substrate is heat-treated to stabilize the surface state. Next, a photosensitive transfer material in which an oxygen blocking layer, a photopolymerizable light-shielding layer, and a cover sheet is provided on the photopolymerizable light-shielding layer is prepared on a temporary support. Here, a thermoplastic resin layer may be provided between the temporary support and the oxygen barrier layer.
First, after removing and removing the cover sheet, the exposed surface of the photopolymerizable light-shielding layer is bonded onto a permanent support (substrate) and laminated by heating and pressing through a laminator or the like (laminate). As the laminator, those appropriately selected from conventionally known laminators, vacuum laminators and the like can be used, and an auto-cut laminator can also be used in order to increase productivity.

Subsequently, it peels between a temporary support body and an oxygen barrier layer (a thermoplastic resin layer, when there is a thermoplastic resin layer), and a temporary support body is removed. Subsequently, with the substrate and a mask having an image pattern (for example, a quartz exposure mask) standing vertically, the exposure mask surface and the oxygen blocking layer (a thermoplastic resin layer if a thermoplastic resin layer is provided) The distance between them is set appropriately (for example, 200 μm), and exposure is performed in the atmosphere. In addition, you may perform exposure in the said poor oxygen atmosphere.
The exposure is performed, for example, with a proximity type exposure machine (for example, manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp, and the exposure amount may be appropriately selected (for example, 300 mJ / cm ² ). it can.
After the exposure, development processing is performed using a predetermined processing solution. As the developer used in the development process, a dilute aqueous solution of an alkaline substance is used, but it may be further added with a small amount of an organic solvent miscible with water. Examples of the light source used for the light irradiation include medium to ultrahigh pressure mercury lamps, xenon lamps, metal halide lamps, and the like.

  Suitable alkaline substances include alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg, sodium carbonate, potassium carbonate), alkali metal bicarbonates (eg, sodium bicarbonate). , Potassium bicarbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali metal metasilicates (eg, sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, Examples include morpholine, tetraalkylammonium hydroxides (for example, tetramethylammonium hydroxide), trisodium phosphate, and the like. The concentration of the alkaline substance is preferably 0.01 to 30% by mass, and the pH is preferably 8 to 14.

  Examples of the “water-miscible organic solvent” include, for example, 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, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like are preferable. . The concentration of the organic solvent miscible with water is preferably 0.1 to 30% by mass. Furthermore, a known surfactant can be added, and the concentration of the surfactant is preferably 0.01 to 10% by mass.

  The developer can be used as a bath solution or a spray solution. When removing the uncured portion of the photosensitive resin layer, methods such as rubbing with a rotating brush or wet sponge in the developer can be combined. The liquid temperature of the developer is usually preferably from about room temperature to 40 ° C. The development time is usually about 10 seconds to 2 minutes, depending on the composition of the photosensitive resin layer, the alkalinity and temperature of the developer, and the type and concentration when an organic solvent is added. If it is too short, the development of the non-exposed area may be insufficient, and the absorbance of ultraviolet rays may be insufficient, and if it is too long, the exposed area may be etched. In any case, it is difficult to make the partition shape suitable. It is also possible to put a water washing step after the development processing. In this development step, the partition wall shape is formed as described above.

  Next, the ink for forming the RGB pixels is made to enter the gaps in the gaps formed in the development step. However, the shape of the partition may be fixed before forming the pixels. The means is not particularly limited, and examples include the following. That is, 1) re-exposure after development (sometimes referred to as post-exposure), and 2) heat treatment at a relatively low temperature after development. The heat treatment here refers to heating a substrate having a partition wall in an electric furnace, a dryer or the like, or irradiating an infrared lamp.

Here, the exposure amount when performing the above 1) is 500 to 3000 mJ / cm ² , preferably 1000 to 2000 mJ / cm ² in the atmosphere, and lower exposure in the poor oxygen atmosphere. It is also possible to expose in quantity. Moreover, the heating temperature in the case of performing 2) is 50 to 250 ° C., preferably about 70 to 200 ° C., and the heating time is about 10 to 40 minutes. When the temperature is lower than 50 ° C., there is a concern that the curing of the partition walls does not proceed, and when the temperature is higher than 250 ° C., there is a concern that the shape of the partition walls may collapse.

<Formation of each pixel>
A known method can be used for the ink jet method used for forming each pixel.
Preferably, after each pixel is formed, a heating step of performing a heat treatment (so-called baking treatment) is provided. That is, a substrate having a layer photopolymerized by light irradiation is heated in an electric furnace, a dryer or the like, or an infrared lamp is irradiated. The temperature and time of heating depend on the composition of the photosensitive dark color composition and the thickness of the formed layer, but generally from about 120 ° C. to the point of obtaining sufficient solvent resistance, alkali resistance, and ultraviolet absorbance. Heating at about 250 ° C. for about 10 minutes to about 120 minutes is preferred.
The pattern shape of the color filter thus formed is not particularly limited, and may be a general black matrix stripe shape, a lattice shape, or a delta arrangement. May be.

≪Display device≫
The color filter of the present invention can be suitably used for a display device. The display device refers to a display device such as a liquid crystal display device, a plasma display display device, an EL display device, or a CRT display device. For the definition of display devices and explanation of each display device, refer to “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (written by Junaki Ibuki, Sangyo Tosho Co., Ltd.) Issue)).
Among the display devices of the present invention, a liquid crystal display device is particularly preferable. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to various types of liquid crystal display devices described in, for example, the “next generation liquid crystal display technology”. Among these, the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention can be applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS and a pixel division method such as MVA. These methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends-(issued in 2001 by Toray Research Center Research Division)".

  In addition to the color filter, the liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The black matrix of the present invention can be applied to a liquid crystal display device composed of these known members. For example, “'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Kentaro Shima, CMC 1994)” and “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” (Table Yoshiyoshi) Fuji Chimera Research Institute, published in 2003) ”.

≪Target use≫
The color filter of the present invention can be applied to applications such as televisions, personal computers, liquid crystal projectors, game machines, mobile phones and other portable terminals, digital cameras, car navigation systems and the like.

  The present invention will be described more specifically with reference to the following examples. The materials, reagents, ratios, equipment, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the following examples, “%” and “parts” represent “mass%” and “parts by mass” unless otherwise specified, and the molecular weight indicates the weight average molecular weight.

・ポリマー（ベンジルメタクリレート／メタクリル酸＝７２／２８モル比のランダム共重合物、分子量３．７万） ・・・ ６．７２％
・プロピレングリコールモノメチルエーテルアセテート ・・・７９．５３％
＜バインダー２＞
・ポリマー（ベンジルメタクリレート／メタクリル酸＝７８／２２モル比のランダム共重合物、分子量３．８万） ・・・ ２７％
・プロピレングリコールモノメチルエーテルアセテート ・・・ ７３％
＜ＤＰＨＡ液＞
・ジペンタエリスリトールヘキサアクリレート（重合禁止剤ＭＥＨＱ ５００ｐｐｍ含有、日本化薬(株)製、商品名：ＫＡＹＡＲＡＤ ＤＰＨＡ） ・・・ ７６％
・プロピレングリコールモノメチルエーテルアセテート ・・・ ２４％
＜界面活性剤１＞
・下記構造物１ ・・・ ３０％

・メチルエチルケトン ７０％ [Example 1]
<Preparation of partition wall forming dark color composition K1>
The dark color composition K1 is first weighed in the amounts of K pigment dispersion 1 and propylene glycol monomethyl ether acetate listed in Table 1, mixed at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 RPM for 10 minutes, and then Methyl ethyl ketone, binder 2, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 '-(N, N-diethoxycarbonylmethyl) amino-3' in the amounts shown in Table 1 -Bromophenyl] -s-triazine and surfactant 1 were weighed out, added in this order at a temperature of 25 ° C. (± 2 ° C.), and stirred at a temperature of 40 ° C. (± 2 ° C.) for 150 RPM for 30 minutes. . In addition, the quantity of Table 1 is a mass part, and has the following composition in detail.
<K pigment dispersion 1>
・ Carbon black (Nexex 35 manufactured by Degussa) ... 13.1%
・ Dispersant: 0.65%

-Polymer (Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, molecular weight 37,000) ... 6.72%
・ Propylene glycol monomethyl ether acetate: 79.53%
<Binder 2>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 38,000) 27%
・ Propylene glycol monomethyl ether acetate 73%
<DPHA solution>
・ Dipentaerythritol hexaacrylate (containing polymerization inhibitor MEHQ 500ppm, Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76%
・ Propylene glycol monomethyl ether acetate 24%
<Surfactant 1>
・ The following structure 1 ・ ・ ・ 30%

・ Methyl ethyl ketone 70%

<Formation of partition walls>
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle has the composition described in the above table. Dark color composition K1 was applied. Subsequently, a part of the solvent was dried with a VCD (vacuum drying apparatus, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to form a photopolymerizable light-shielding layer K1. Got.

Exposure mask surface and photopolymerization in a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) with an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask with image pattern) standing vertically The distance between the light shielding layers K1 was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² in an environment where the pressure was reduced to 0.2 atm.

Next, after spraying pure water with a shower nozzle to uniformly wet the surface of the photopolymerizable light-shielding layer K1, a KOH developer (KOH, containing nonionic surfactant, trade name: CDK-1, (Fujifilm Electronics Materials Co., Ltd.) was subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultra-high pressure cleaning nozzle to remove the residue, and post exposure was performed in the atmosphere with an exposure amount of 2000 mJ / cm ² to obtain an optical density of 3.9. A black partition was obtained.

<Preparation of radical polymerizable ink>
-Preparation of pigment dispersion The compositions shown in Table 2 below were mixed and stirred with a stirrer for 1 hour. The mixture after stirring was dispersed with an Eiger mill to obtain R, G, and B pigment dispersions. Dispersion conditions were as follows: zirconia beads having a diameter of 0.65 mm were filled at a filling rate of 70%, the peripheral speed was 9 m / s, and the dispersion time was 1 hour.

-Preparation of ink liquid R, G, B pigment dispersions were mixed in the composition shown in Table 3 and stirred with a stirrer for 1 hour to obtain R1, G1, B1 inks.

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

In this example, the transfer speed and drive frequency are controlled so that the coating amount of the pigment is 1.1, 1.8, and 0.75 g / m ^{2 for} each of R, G, and B. R, G, and B inks were ejected onto the recesses corresponding to G and B.

The ejected ink is conveyed to an exposure unit and exposed by an ultraviolet light emitting diode (UV-LED). In this embodiment, NCC A03C manufactured by Nichia Chemical was used as the UV-LED. This LED outputs ultraviolet light having a wavelength of 365 nm from one chip. When a current of about 500 mA is applied, light of about 100 mW is emitted from the chip. A plurality of these are arranged at intervals of 7 mm, and a power of 0.3 W / cm ² can be obtained on the surface. The exposure time after the droplet ejection and the exposure time can be changed according to the medium transport speed and the distance between the head and the LED transport direction. In this embodiment, the exposure is performed about 0.5 seconds after landing.

Depending on the setting of the distance and the conveyance speed, the exposure energy on the medium can be adjusted between 0.01 and 15 J / cm ² . In this embodiment, the exposure energy is adjusted according to the conveyance speed.

For the measurement of the exposure power and exposure energy, a spectroradiometer URS-40D manufactured by USHIO INC. Was used, and a value obtained by integrating the wavelength between 220 nm and 400 nm was used.
The glass substrate after droplet ejection was baked in an oven at 230 ° C. for 30 minutes, so that both the light-shielding partition and each pixel were completely cured.

  In the color filter thus obtained, the ink constituting each pixel fits exactly in the gap between the black partition walls, and no defects such as bleeding, protrusion, color mixture with adjacent pixels and white spots were found.

<Formation of ITO electrode>
The glass substrate on which the color filter is formed is put into a sputtering apparatus, and ITO (indium tin oxide) with a thickness of 130 nm is vacuum-deposited at 100 ° C., and then annealed at 240 ° C. for 90 minutes to crystallize the ITO. An ITO transparent electrode was formed.

[Example 2]
<Formation of partition walls>
A light-shielding partition was formed in the same manner as in Example 1 except that the exposure process was changed to an exposure process under an environment reduced to 0.5 atm.
<Preparation of cationic polymerizable ink>
-Preparation of Pigment Dispersion First, the pigment, monomer and dispersant shown in Table 4 below were placed in a ball mill and dispersed for 16 hours using zircon beads having a diameter of 0.6 mm to obtain a pigment dispersion.

-Preparation of ink liquid The components shown in Table 5 were mixed with stirring and filtered through a 5.0 µm membrane filter to obtain RGB ink.

<Recording RGB pixels with cationically polymerizable ink>
A color filter was produced in the same manner as in Example 1 except that the radical polymerizable ink in Example 1 was replaced with the above cationic polymerizable ink, and an ITO transparent electrode was formed.

  In the color filter thus obtained, the ink constituting each pixel fits exactly in the gap between the black partition walls, and no defects such as bleeding, protrusion, color mixture with adjacent pixels and white spots were found. Further, the ITO resistance of the color filter was measured (“Loresta” manufactured by Mitsubishi Chemical Corporation; sheet resistance was measured by a four-probe method), and a very low value of 11Ω / □ was shown. This is probably because the flatness of the color filter surface was unexpectedly increased by using the present invention.

[Example 3]
A color filter was produced in the same manner as in Example 1 except that the step of exposing the partition walls was changed to a step of exposing in a state of 90% nitrogen and 10% oxygen.

[Example 4]
A color filter was produced in the same manner as in Example 1 except that the step of exposing the partition walls was changed to a step of exposing in a state of 96% nitrogen and 4% oxygen.

[Example 5]
A color filter was produced in the same manner as in Example 1 except that the step of exposing the partition walls was changed to a step of exposing under the condition of 100% nitrogen.

[Example 6]
A color filter was produced in the same manner as in Example 1 except that the step of exposing the partition walls was changed to a step of exposing in a state of 100% helium gas.

[Example 7]
A color filter was produced in the same manner as in Example 1 except that the step of exposing the partition walls was changed to a step of exposing under the condition of 100% argon gas.

[Example 8]
On the photopolymerizable light-shielding layer K1, the following oxygen-blocking layer coating liquid formulation P1 is applied, and an exposure process is performed in the state where an oxygen-blocking layer having a dry film thickness of 1.6 μm is provided. A color filter was produced in the same manner as in Example 1 except that the exposure step was changed under an oxygen partial pressure of 0.21 atm)).

<Coating liquid for oxygen barrier layer: prescription P1>
-PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd., degree of saponification = 88%, degree of polymerization 550) ... 32.2 parts-Polyvinylpyrrolidone (manufactured by ASP Japan, K-30)
・ ・ ・ 14.9 parts ・ Distilled water ・ ・ ・ 524 parts ・ Methanol ・ ・ ・ 429 parts

[Example 9]
<Production of photosensitive transfer material>
On a 75 μm thick polyethylene terephthalate film temporary support, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle. Next, an oxygen barrier layer coating solution having the following formulation P1 was applied and dried. Further, the dark color composition K2 in Table 6 was applied and dried. In this way, a thermoplastic resin layer having a dry film thickness of 14.6 μm, an oxygen blocking layer having a dry film thickness of 1.6 μm, and a photopolymerizable light-shielding layer are provided on the temporary support, and finally a protective film ( A 12 μm-thick polypropylene film) was pressure-bonded.
In this way, a black photosensitive transfer material was produced in which the temporary support, the thermoplastic resin layer, the oxygen blocking layer, and the black (K) photopolymerizable light-shielding layer were integrated.

<Coating liquid for thermoplastic resin layer: Formulation H1>
Methanol: 11.1 parts Propylene glycol monomethyl ether acetate: 6.36 parts Methyl ethyl ketone: 52.4 parts Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (co-polymer) Polymerization composition ratio (molar ratio) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg≈70 ° C.)
... 5.83 parts styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 63/37, molecular weight = 10,000, Tg≈100 ° C.)
... 13.6 parts 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd.)
9.1 parts ・ Surfactant 1 ・ ・ ・ 0.54 parts

<Coating liquid for oxygen barrier layer: prescription P1>
-PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd., degree of saponification = 88%, degree of polymerization 550) ... 32.2 parts-Polyvinylpyrrolidone (manufactured by ASP Japan, K-30)
・ ・ ・ 14.9 parts ・ Distilled water ・ ・ ・ 524 parts ・ Methanol ・ ・ ・ 429 parts

  The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM603, Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.

On the obtained silane coupling treated glass substrate, the cover film is removed from the photosensitive transfer material produced by the above production method, and the surface of the photopolymerizable light-shielding layer exposed after the removal and the silane coupling treated glass substrate The substrates are heated so as to be in contact with each other, and a laminator (manufactured by Hitachi Industries (Lamic II type)) is used to heat the substrate at 100 ° C. for 2 minutes. The rubber roller temperature is 130 ° C., the linear pressure is 100 N / cm, Lamination was performed at a conveyance speed of 2.2 m / min. Subsequently, the polyethylene terephthalate temporary support was peeled off at the interface with the thermoplastic resin layer to remove the temporary support. After peeling off the temporary support, exposure is performed with a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp with the substrate and mask (quartz exposure mask with image pattern) standing vertically. The distance between the mask surface and the thermoplastic resin layer was set to 200 μm, and pattern exposure was performed with an exposure amount of 70 mJ / cm ² .

  Next, 30 ° C. in a triethanolamine developer (containing 2.5% triethanolamine, nonionic surfactant, polypropylene antifoam, trade name: T-PD1, manufactured by Fuji Photo Film Co., Ltd.) The thermoplastic resin layer and the oxygen barrier layer were removed by shower development for 50 seconds with a flat nozzle pressure of 0.04 MPa.

  Subsequently, a sodium carbonate-based developer (0.06 mol / liter sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer, trade name: T-CD1, manufactured by Fuji Photo Film Co., Ltd.) was used for shower development at 29 ° C. for 30 seconds and a cone type nozzle pressure of 0.15 MPa to develop the dark photosensitive resin composition layer to obtain a patterned pixel.

Subsequently, using a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer, trade name “T-SD1 (manufactured by Fuji Photo Film)” at 33 ° C. for 20 seconds, cone type nozzle pressure of 0. Residue removal was performed with a rotating brush having a shower and nylon hair at 02 MPa to obtain a black (K) image.
Thereafter, the substrate was further post-exposed with 500 mJ / cm ² of light from an ultrahigh pressure mercury lamp from the dark color photosensitive resin composition layer side, and then heat-treated at 220 ° C. for 15 minutes to obtain partition walls.

<Method for producing radically polymerizable ink>
A radical polymerizable ink was prepared in the same manner as in Example 1 except that the compositions of the pigment dispersion and the ink were changed to those shown in Tables 7 and 8.

In the same manner as in Example 1, the RGB ink obtained above was ejected into a recess surrounded by a light-shielding partition using a piezo-type head to produce a color filter, and an ITO transparent electrode was formed.
In the color filter thus obtained, the ink constituting each pixel fits exactly in the gap between the black partition walls, and no defects such as bleeding, protrusion, color mixture with adjacent pixels and white spots were found.

[Example 10]
A color filter was produced in the same manner as in Example 8 except that the step of exposing the partition walls was changed to a step of exposing under the condition of 100% nitrogen.

[Example 11]
A color filter was produced in the same manner as in Example 9 except that the step of exposing the partition walls was changed to a step of exposing under the condition of 100% nitrogen.

[Example 12]
A color filter was produced in the same manner as in Example 9 except that the height of the partition walls was changed to 2.5 μm.

[Comparative Example 1]
An ink having the composition shown in Table 9 was prepared, and the amount of pigment applied to the concave portion of the glass substrate having the light-shielding partition wall of Example 1 was changed according to Example 1 to the ink corresponding to the R, G, and B patterns by the inkjet method. The droplets were shot in the same way.

After droplet ejection, it was naturally dried for 30 minutes and further dried at 150 ° C. Thereafter, baking was performed in the same manner as in Example 1 to obtain a color filter.
When the obtained color filter was observed, each of the R, G, and B pixels was mixed with pigments of inks of other colors that passed over the light-shielding partition walls, and color mixing was observed, and the desired hue could not be obtained. It was.

<Production of substrate for liquid crystal display device>
Using the color filters obtained in Examples 1 to 11 and Comparative Example 1, substrates for liquid crystal display devices were produced as follows.

(Spacer formation)
A spacer was formed on the ITO transparent electrode produced above by the same method as the spacer forming method described in [Example 1] of JP-A-2004-240335.

(Formation of liquid crystal alignment control protrusions)
A liquid crystal alignment control protrusion was formed on the ITO transparent electrode on which the spacer was formed, using the following positive photosensitive resin layer coating solution.
However, the following methods were used for exposure, development, and baking.

A proximity exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) is arranged so that the predetermined photomask is at a distance of 100 μm from the surface of the photosensitive resin layer, and the irradiation energy is 150 mJ / cm with an ultrahigh pressure mercury lamp through the photomask. Proximity exposure was performed at ² .
Subsequently, a 2.38% tetramethylammonium hydroxide aqueous solution was developed by spraying it on a substrate at 33 ° C. for 30 seconds in a shower type developing device. Thus, unnecessary portions (exposed portions) of the photosensitive resin layer were developed and removed, thereby forming liquid crystal alignment control protrusions made of the photosensitive resin layer patterned in a desired shape on the color filter side substrate.

  Next, the substrate on which the liquid crystal alignment control protrusions were formed was baked at 230 ° C. for 30 minutes to obtain a liquid crystal display device substrate having a cured liquid crystal alignment control protrusion.

-Coating formulation for positive photosensitive resin layer-
・ Positive type resist solution (FH-2413F manufactured by FUJIFILM Electronics Materials Co., Ltd.) ・ ・ ・ 53.3 parts ・ Methyl ethyl ketone ・ ・ ・ 46.7 parts ・ Megafac F-780F (Dainippon Ink Chemical Co., Ltd.) Made) ... 0.04 part

<Production of liquid crystal display device>
An alignment film made of polyimide was further provided on the liquid crystal display substrate obtained above.
After that, an epoxy resin sealant is printed at a position corresponding to a black matrix outer frame provided around the pixel group of the color filter, and MVA mode liquid crystal is dropped and bonded to the counter substrate. The bonded substrate was heat treated to cure the sealant. A polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached to both surfaces of the liquid crystal cell thus obtained. Next, a backlight of a three-wavelength cold-cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) was constructed and placed on the side of the liquid crystal cell on which the polarizing plate was provided to obtain a liquid crystal display device.

<Evaluation>
-Display unevenness-
When the obtained liquid crystal display devices 1 to 4 were inputted with a gray test signal, they were observed visually and with a magnifying glass to check for the occurrence of unevenness, and judged according to the following criteria.
A: Unevenness is not seen at all (very good)
B: Slight unevenness is observed on the edge of the glass substrate, but there is no problem in the display (good)
C: Slight unevenness on the display, but practical level (normal)
D: Display is uneven (somewhat bad)
E: Strong unevenness in display (very bad)

-White-
Observation from the substrate and the pixel forming side in the thickness direction was performed with an optical microscope, and white spots were evaluated. As for white spots, it was observed whether there was a portion of the pixel where no ink was adhered, and whether ink remained on the upper surface of the partition wall was observed.
The white spots were observed at arbitrary 100 points in the pixel with convex corners toward the partition wall, and the number of pixels where white spots could be confirmed was counted. If it is 5 or less, it is a practical level.

Table 10 shows the evaluation results.
As can be seen from Table 10, the color filters of the present invention (Examples 1 to 12) have no white spots or are at a practical level, and a liquid crystal display device manufactured using the color filters has a display function. Even if there was no unevenness, it was at a practical level.
On the other hand, with respect to the color filter (Comparative Example 1) in which the oxygen-blocking layer is not provided on the photopolymerizable light-shielding layer and the partition wall is formed by exposing the photopolymerizable light-shielding layer in the atmosphere, white spots occur. In the liquid crystal display device manufactured using the color filter, strong display unevenness occurred.

Claims (9)

  This is a method for producing a color filter, in which a partition having light-shielding properties is formed on a substrate, and a colored layer is formed by applying inks of R, G, and B colors to the recesses partitioned by the partition by an inkjet method. The partition is formed by exposing the photopolymerizable light-shielding layer under poor oxygen conditions, the ink contains a colorant, a polymerizable compound, and a polymerization initiator, and the amount of solvent in the ink is 50% by mass. % Or less, a method for producing a color filter.   2. The method for producing a color filter according to claim 1, wherein the poor oxygen condition is a condition in which an oxygen partial pressure is lowered from an oxygen partial pressure in an atmospheric pressure of 1 atmosphere by reducing pressure or filling with an inert gas.   The method for producing a color filter according to claim 1, wherein the poor oxygen condition is a condition in which an oxygen blocking layer is formed on a photopolymerizable light blocking layer.   The poor oxygen condition is a condition in which the partial pressure of oxygen is reduced from the partial pressure of oxygen at atmospheric pressure by reducing the pressure or filling with an inert gas, and an oxygen blocking layer is formed on the photopolymerizable light shielding layer. The method for producing a color filter according to claim 1.   The method for producing a color filter according to claim 1, wherein the photopolymerizable light-shielding layer contains at least a light-shielding agent, a polymerizable compound, and a polymerization initiator.   The method for producing a color filter according to claim 1, wherein a height of the partition wall is 1 to 20 μm.   The method for producing a color filter according to claim 1, wherein the ink is a radically polymerizable composition.   A color filter manufactured by the manufacturing method according to claim 1.   A liquid crystal display device comprising the color filter according to claim 8.