JP2007323064A - Method for manufacturing color filter, color filter and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a high-quality color filter which achieves high contrast and proper partial-discoloration suppression effect, when incorporated into a display device, because flat pixels free of color mixing and void generation can be formed by the method. <P>SOLUTION: The method for manufacturing the color filter, having a plurality of pixels and partitions between the adjacent pixels on a substrate includes (a) a step of forming partitions comprising a resin composition on a substrate; (b) subjecting the substrate on which the partitions have been formed to plasma treatment; and (c) a step of forming pixels by providing an ink for ink jet comprising C.I. Pigment Red 254, a solvent, a surfactant and a monomer having two or more polymerizable groups by an ink jet method, to gaps between the partitions formed on the substrate. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a color filter in which pixels are formed by an inkjet method between ink-repellent partition walls, a color filter obtained by the manufacturing method, and a display device such as a liquid crystal display and a liquid crystal color television.

In recent years, demand for color displays such as liquid crystal displays for personal computers and liquid crystal color televisions has been increasing, and there has been an increasing demand for improvement in characteristics and cost reduction of color filters indispensable for such displays.
Conventionally, as a method for producing a color filter, a dyeing method, a pigment dispersion method, an electrodeposition method, a printing method, and the like have been performed.

For example, in the dyeing method, a water-soluble polymer material layer, which is a dyeing material, is formed on a transparent substrate, patterned into a desired shape by a photolithography process, and then the obtained pattern is immersed in a dyeing bath. To obtain a colored pattern. By repeating this step three times, a colored layer comprising three colored portions of R (red), G (green), and B (blue) is formed.
In addition, the pigment dispersion method has been actively performed in recent years, and a monochromatic pattern can be obtained by forming a photosensitive resin layer in which a pigment is dispersed on a transparent substrate and patterning the photosensitive resin layer. This is a method of forming a colored layer comprising three colored portions of R, G, and B by repeating three times.
In the electrodeposition method, a transparent electrode is patterned on a transparent substrate and immersed in an electrodeposition coating solution containing a pigment, a resin, an electrolytic solution, etc., and the first color is electrodeposited. This process is repeated three times to form a colored layer composed of colored portions of R, G, and B, and finally fired.
The printing method is a method of forming a colored layer by dispersing a pigment in a thermosetting resin and repeating the printing three times to separate R, G, and B, and then thermosetting the resin. .
In any of these production methods, a protective layer is generally formed on the obtained colored layer.

  The point common to these methods is that it is necessary to repeat the same process three times in order to form red, green, and blue three-color pixels, resulting in high costs. In addition, since the number of processes is large, there is a problem that the yield is likely to decrease.

  In order to overcome these problems, in recent years, a method for producing a color filter in which a black matrix is formed by a pigment dispersion method and RGB pixels are produced by an ink jet method has been studied. In this inkjet method, pixels of R, G, and B colors are sequentially applied to the gaps (concave portions) of the black matrix to form pixels. The method using the ink jet method has an advantage that the manufacturing process is simple and the cost is low.

  As described above, the method of applying droplets by the ink jet method has been applied to the manufacture of a color filter because the manufacturing process can be simplified and the cost can be reduced. Specific problems in the manufacture of filters include the problems of “mixed colors” and “white spots”.

Color mixing means forming a black matrix and applying ink to the gaps (openings) of the black matrix to form pixel portions between the adjacent pixel portions where ink overflows beyond the black matrix serving as a partition wall. It is a phenomenon that mixes.
White spots are phenomena in which the wettability between the glass surface of the gap or the side face of the partition wall and the ink is poor, the ink does not spread sufficiently over the entire gap, or a gap is formed between the partition wall and the applied ink. It is.
These mixed colors and white spots cause display defects such as color unevenness and a decrease in contrast.

As a technique for preventing color mixture and white spots, ink repellent treatment of partition walls by fluorine plasma treatment has been tried (see, for example, Patent Document 1), and high-quality color that does not cause color mixture or white spots by fluorine plasma treatment. A filter can be formed.
However, Patent Document 1 described above is a dye-based study, and a detailed study has not been made on a pigment-based material that has been actively used in recent years.

In contrast, pigments have vivid color tone, high coloring power, light resistance, etc., and are widely used in many fields. Especially in color filters used in liquid crystal color televisions, they are very preferable in terms of light resistance. It is used.
However, in such a pigment system, the viscosity is likely to increase due to the cohesive strength of the pigment, the presence of the dispersion resin, and the like, and there has been a problem in the deterioration of ejection properties in the ink jet apparatus. In addition, when the viscosity is high, the ink applied to the gaps between the partitions does not have a good shape, and convex pixels are formed, which may cause color unevenness.

Accordingly, monomers are preferably used as the polymerizable compound contained in the ink in that the viscosity is difficult to increase and is preferable from the viewpoint of dischargeability. Of these, monofunctional monomers are often used because the viscosity is particularly difficult to increase.
However, when monofunctional monomers are used as the polymerizable compound, the ink applied to the gaps of the partition walls by the ink jet method may not be sufficiently cured, and in the case of insufficiently cured pixels, when forming a display device It was inferior in ITO sputter suitability, resulting in the occurrence of color unevenness.

Among the pigments, red pixels in the production of color filters include C.I. I. It is known that the use of CI Pigment Red (CIPR) 254 is very suitable for increasing color purity.
However, C.I. I. P. R. When 254 is used, there is a problem that the contrast of the red pixel is greatly lowered when the color filter is made into a display device.
JP 2003-344640 A

An object of the present invention is to solve the above-mentioned conventional drawbacks.
That is, an object of the present invention is to provide a method for producing a high-quality color filter that can form flat pixels without color mixing or white spots, and a color filter by the production method. Another object of the present invention is to provide a high-quality display device that has high contrast and suppresses occurrence of color unevenness.

In view of the above circumstances, the present inventors have conducted intensive research and found that C.I. I. P. R. Even when 254 is used, by using at least one monomer having two or more polymerizable groups as a polymerizable compound used in the ink jet ink, it is possible to prevent a decrease in contrast of the red pixel and to obtain a good ITO. It was found that suitability was obtained and color unevenness could be suppressed. However, when a pigment is used as a colorant and a monomer having two or more polymerizable groups is used, the viscosity becomes high, and convex pixels are formed, causing color unevenness.
On the other hand, the present inventors conducted further research and found that by adding a surfactant, a flat and well-shaped pixel could be formed, and the present invention was achieved.

That is, the present invention
<1> A method for producing a color filter having a plurality of pixels and a partition wall between adjacent pixels on a substrate, comprising at least the following steps a), b) and c) in this order: It is a manufacturing method of a filter.
a) Step of forming partition walls made of a resin composition on the substrate b) Step of performing plasma treatment on the substrate on which the partition walls have been formed c) At least C. is formed in the gap between the partition walls formed on the substrate. I. Step of forming a pixel by applying an inkjet ink containing Pigment Red 254, a solvent, a surfactant, and a monomer having two or more polymerizable groups by an inkjet method <2> The plasma treatment Is a method for producing a color filter as described in <1> above, which is an atmospheric pressure plasma treatment.
<3> The method for producing a color filter according to <1> or <2>, wherein the monomer is a monomer having three or more polymerizable groups.
<4> The method for producing a color filter according to any one of <1> to <3>, wherein the polymerizable group is a group having an ethylenic double bond.
<5> The method for producing a color filter according to any one of <1> to <4>, wherein the polymerizable group is an epoxy group.
<6> The method for producing a color filter according to any one of <1> to <4>, wherein the polymerizable group is at least one selected from an acryloyl group and a methacryloyl group. .
<7> The color filter according to any one of <1> to <6>, wherein the inkjet ink contains at least one selected from a photopolymerization initiator and a thermal polymerization initiator. It is a manufacturing method.
<8> The method for producing a color filter according to any one of <1> to <7>, wherein the surfactant contains fluorine.
<9> The surfactant is at least one of a structural unit a derived from a monomer represented by the following general formula (a) and at least a structural unit b derived from a monomer represented by the following general formula (b) <1>, wherein at least one copolymer having a mass ratio (a / b) between the structural unit a and the structural unit b of 20/80 to 80/20 is contained. It is a manufacturing method of the color filter given in any 1 paragraph of <8>.

In the general formula (a), R ¹ represents a hydrogen atom or a methyl group. Further, _-C m _{F 2m + 1} in the general formula (a) is a straight or branched chain. m represents an integer of 2 to 14. n represents an integer of 1 to 18.
In General Formula (b), R ² and R ³ each independently represent a hydrogen atom or a methyl group, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p and q each independently represent an integer of 0 to 18, and p and q do not represent 0 (zero) at the same time.
<10> After the step c), the ink composition is polymerized to form pixels through at least one step selected from the following d) and e): <1> to <9> The method for producing a color filter according to any one of the above.
d) Step of irradiating active energy rays after the solvent in the ink is removed e) Step of heating

<11> A color filter produced by the production method according to any one of <1> to <10>.
<12> A display device comprising the color filter according to <11>.

  According to the present invention, it is possible to provide a high-quality color filter manufacturing method capable of forming flat pixels without color mixing or white spots, and a color filter by the manufacturing method. In addition, it is possible to provide a high-quality display device with high contrast and suppressed occurrence of color unevenness.

The method for producing a color filter of the present invention is a method for producing a color filter having a plurality of pixels and a partition wall between adjacent pixels on a substrate, wherein at least the following steps a), b) and c) are performed in this order. It is characterized by having.
a) Step of forming a partition made of a resin composition on a substrate (partition formation step)
b) A step of performing plasma treatment on the substrate on which the partition walls are formed (plasma treatment step).
c) At least C.I. in the gap between the partition walls formed on the substrate. I. P. R. A step of forming a pixel by applying an inkjet ink containing 254, a solvent, a surfactant, and a monomer having two or more polymerizable groups by an inkjet method (pixel formation step)

  Hereinafter, in describing the present invention in detail, the ink-jet ink is first described in detail, and then a color filter manufacturing method, a display device, and a manufacturing method thereof are described.

<Inkjet ink>
The ink-jet ink of the present invention has at least C.I. I. P. R. 254 (colorant), a solvent, a surfactant, and a monomer having two or more polymerizable groups. In addition, other colorants, dispersants, binders, photopolymerization initiators, thermal polymerization initiators, or other additives may be appropriately contained.
However, from the viewpoint of ensuring dischargeability from the inkjet head, the viscosity of the inkjet ink is preferably 3 mPa · s to 50 mPa · s, and more preferably 5 mPa · s to 30 mPa · s. Thus, it is not preferable that the viscosity of the inkjet ink is too high.
Moreover, as surface tension, 10-50 dyne / cm is preferable and 20-40 dyne / cm is more preferable.

(Polymerizable monomer)
The polymerizable monomer used in the ink jet ink of the present invention (hereinafter sometimes simply referred to as “ink”) includes a radical polymerizable compound that is cured by a polymerization reaction with a radical active species, and a cationic polymerization reaction with a cationic active species. A cationically polymerizable compound that can be cured can be used, and it is an essential requirement to contain at least one monomer having two or more polymerizable groups (hereinafter sometimes referred to as “bifunctional or higher monomer”).
The ink composition of the present invention can be constituted as a radical polymerizable composition when the radical polymerizable compound is used, or as a cationic polymerizable composition when a cationic polymerizable compound is used. Is preferred.

As mentioned above, C.I. I. P. R. When a color filter is formed using 254 to form a display device, the contrast of red pixels is reduced. However, the use of the above-mentioned bifunctional or higher monomer can effectively prevent the reduction of the contrast. From the viewpoint of obtaining a more remarkable effect, it is more preferable to use a monomer having 3 or more polymerizable groups, and a monomer having 5 or more polymerizable groups is particularly preferable.
Further, by using a bifunctional or higher monomer, good ITO suitability can be obtained, and color unevenness that occurs when a display device is formed can be efficiently suppressed. From the viewpoint of imparting ITO suitability, it is more preferable to use a monomer having three or more polymerizable groups, and a monomer having five or more polymerizable groups is particularly preferable.

10 mass% or more is preferable and, as for the ratio of the monomer more than bifunctional to the whole polymerizable monomer, 30 mass% or more is more preferable. The bifunctional or higher monomer preferably has a viscosity at 25 ° C. of 7000 mPa · s or less, more preferably 1000 mPa · s or less, and particularly preferably 500 mPa · s or less.
Further, the number of functional groups (polymerizable groups) in the monomer is preferably 15 or less and more preferably 6 or less so that the viscosity of the inkjet ink does not become too high. There is no restriction | limiting in particular as a kind of polymeric group, It can select in the range by which the viscosity of an ink does not become high too much.

  A small amount of high-viscosity polyfunctional monomer having a viscosity at 25 ° C. of 7000 mPa · s or higher, highly polar monomer such as urethane acrylate, oligomer, etc. is used to supplement the strength of the film or to provide adhesion to the substrate. You may use together. There are no particular restrictions on the polyfunctional monomer, the highly polar monomer, and the oligomer that are preferred for use in combination, and general-purpose monomers can be used. For example, isocyanuric acid EO (ethylene oxide) -modified diacrylate, isocyanuric acid EO-modified triacrylate , Ε-caprolactone-modified tris (acryloxyethyl) isocyanurate, urethane acrylate (for example, Allonics M-1000, M-1200, M-1210, M-1600 manufactured by Toa Gosei Co., Ltd.), polyester acrylate (for example, Toa Gosei) Allonics M-6100, M-6200, M-6250, M-6500, M-7100, M-7300K, M-8030, M-8060, M-8100, M-8530, M-8560, M -9050) and the like.

-Radically polymerizable compounds-
Specific examples of the radical polymerizable compound include, but are not limited to, the following compounds. The radically polymerizable compound includes monomers and oligomers having two or more functional groups, and among them, a group having an ethylenic double bond (more preferably, an acryloyloxy group, a methacryloyloxy group) or an epoxy group as a polymerizable group. What is contained is particularly preferable.

  Examples of the bifunctional or higher monomer and oligomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 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 di Acrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, 2-n-butyl-2- Til-1,3-propanediol diacrylate, dimethylol-tricyclodecane diacrylate, hydroxypivalic acid neopentyl glycol diacrylate, 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, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated tri Methylolpropane triacrylate,

Pentaerythritol triacrylate, tetramethylolpropane triacrylate, tetramethylolmethane triacrylate, pentaerythritol tetraacrylate, caprolactone-modified trimethylolpropane triacrylate, ethoxylated isocyanuric acid triacrylate, tri (2-hydroxyethyl isocyanurate) triacreate, propoxy Rate glyceryl triacrylate, tetramethylol methane tetraacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, neopentyl glycol oligoacrylate, 1,4-butanediol oligoacrylate 1,6-hexanediol oligoacrylate, trimethylolpropane oligoacrylate, pentaerythritol oligoacrylate, urethane acrylate, epoxy acrylate, polyester acrylate.

  In addition, as specific examples of the trifunctional or higher functional polymerizable monomer, a trifunctional epoxy group-containing monomer described in paragraphs [0061] to [0063] of JP-A-2001-350012, and JP-A-2002-371216 are disclosed. Examples thereof include trifunctional or higher acrylate monomers and methacrylate monomers described in paragraph [0016] of the publication, and trifunctional or higher functional monomers described in “Market Prospects of Reactive Monomers” published by CMMC.

Among the above specific examples, trimethylolpropane triacrylate, trimethylolpropane PO (propylene oxide) modified triacrylate, trimethylolpropane EO (ethylene oxide) modified triacrylate, pentaerythritol tetraacrylate, trimethylolpropane are particularly preferable. Examples include trimethacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like.
These compounds may be used alone or in combination of two or more as required.

-Cationically polymerizable compound-
The cationic polymerizable compound is a compound that causes a polymerization reaction by a cationic active species generated from a polymerization initiator and cures.
Examples of the cationic polymerizable compound include various known cationic polymerizable monomers known as photo cationic polymerizable monomers. For example, JP-A-6-9714, JP-A-2001-31892, JP-A-2001-40068, Examples thereof include vinyl ether compounds, oxetane compounds, and oxirane compounds described in JP-A Nos. 2001-55507, 2001-310938, 2001-310937, and 2001-220526.

  Examples of the cationic polymerizable compound having vinyl ether as a functional group include urethane vinyl ether (vinyl ether urethane) and ester vinyl ether. These oligomers can be used alone or in combination.

  In addition, an epoxy compound can also be used as the polymerizable monomer. As the epoxy compound, various epoxy compounds such as an aromatic epoxy resin can be used.

  As specific examples of the aromatic epoxy resin, polyhydric phenol having at least one aromatic ring, or polyglycidyl ether of an alkylene oxide adduct thereof such as bisphenol A, bisphenol F, or further alkylene oxide is added thereto. Examples thereof include glycidyl ether, epoxy novolac resin, bisphenol A novolac diglycidyl ether, and bisphenol F novolac diglycidyl ether.

In addition, as a specific example of an aromatic epoxy resin, it contains a polyhexidyl ether of a polyhydric alcohol having at least one alicyclic ring or cyclohexene oxide structure obtained by epoxidizing a cyclopentene ring-containing compound with an oxidizing agent. Examples thereof include a 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.

As specific examples of aliphatic epoxy resins, 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 are oxidized with an oxidizing agent. And an epoxy-containing compound, a homopolymer of glycidyl acrylate or glycidyl methacrylate, a copolymer of glycidyl acrylate or glycidyl methacrylate, 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 And the like of the diglycidyl ester. 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.

  Other various bifunctional or higher epoxy compounds can also be used. For example, it is widely disclosed in “Epoxy resin handbook” edited by Masaki Shinbo, published by Nikkan Kogyo Shimbun (1987), and the like can be used. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin , Fluorene type epoxy resin, phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional type epoxy resin, tetraphenylolethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, water Bisphenol A type epoxy resin, bisphenol A nucleated polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy Shi resin, glycidyl amine type epoxy resins, glyoxal type epoxy resins, alicyclic epoxy resins, and the like heterocyclic epoxy resin.

In the case of using an epoxy compound, a curing agent is usually combined in combination from the viewpoint of preventing color unevenness.
As the curing agent, for example, a polyvalent carboxylic acid anhydride, a polyvalent carboxylic acid, or a blocked polyvalent carboxylic acid is used. From the viewpoint of setting the viscosity of the ink within the preferable range described, the carboxylic acid is preferably acid anhydride or blocked, and particularly preferably blocked. As the compound that blocks carboxylic acid, alkyl vinyl ether is preferable, and primary alkyl vinyl ether is particularly preferable.

  Specific examples of polyhydric carboxylic acid anhydrides include phthalic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, hexahydrophthalic anhydride, dimethyltetrahydro anhydride Aliphatic or alicyclic dicarboxylic anhydrides such as phthalic acid, hymic anhydride, and nadic anhydride; fats such as 1,2,3,4-butanetetracarboxylic dianhydride and cyclopentanetetracarboxylic dianhydride Aromatic polycarboxylic dianhydrides; aromatic polycarboxylic anhydrides such as pyromellitic anhydride, trimellitic anhydride, and benzophenone tetracarboxylic anhydride; ester groups such as ethylene glycol bistrimellitate and glycerin tristrimitate Containing acid anhydrides, particularly preferably aromatic poly It may be mentioned carboxylic acid anhydrides. Moreover, the epoxy resin hardening | curing agent which consists of a commercially available carboxylic acid anhydride can also be used suitably.

Specific examples of the polyvalent carboxylic acid used in the present invention include aliphatic polyvalent carboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid, and itaconic acid; hexahydrophthalic acid, Aliphatic polycarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, and phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, Aromatic polyvalent carboxylic acids such as 1,4,5,8-naphthalenetetracarboxylic acid and benzophenonetetracarboxylic acid can be mentioned, and aromatic polyvalent carboxylic acids can be mentioned preferably.
Moreover, the blocking compound of these polyhydric carboxylic acid can be mentioned.

Among them, a blocked aromatic polyvalent carboxylic acid is preferable, and a blocked trimellitic acid and a blocked pyromellitic acid are particularly preferable.
These curing agents can be used singly or in combination of two or more. The compounding quantity of the hardening | curing agent used for this invention is the range of 1-100 mass parts normally per 100 mass parts of components (binder epoxy compound and polyfunctional epoxy compound) containing an epoxy group, Preferably it is 5-5. 50 parts by mass.
These monomers may be used alone or in combination of two or more as required.

  In addition, a monofunctional monomer may be used in combination with the polymerizable monomer composition as appropriate for the purpose of reducing the viscosity of the ink. Examples of these monofunctional monomers include monofunctional epoxy group-containing monomers described in paragraph No. [0065] of JP-A No. 2001-350012 and paragraph numbers [0015] to [0016] of JP-A No. 2002-371216. And monofunctional monomers described in “Market Prospects of Reactive Monomers” published by CMC Publishing Co., Ltd.

In the present invention, the amount of the polymerizable monomer used in the inkjet ink is preferably 10% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more in the ink solid content.
By making the usage-amount of the whole polymerizable monomer into said range, C.I. I. P. R. Therefore, it is possible to prevent a decrease in contrast of the red pixel of the color filter after being made into a display device using H.254, and to obtain good ITO suitability.

(Surfactant)
As mentioned above, C.I. I. P. R. In the present invention, a bifunctional or higher monomer is used in the present invention from the viewpoint of preventing a decrease in contrast of the red pixel of the color filter when it is made into a display device using 254, and good ITO suitability. These monomers also have the property of increasing the viscosity of the ink. For this reason, when an ink containing a bifunctional or higher monomer is used, the formed pixels are not flat but convex. Note that the convex shape refers to a shape in which the central portion of the pixel is raised compared to the ridge (portion close to the boundary with the partition wall) of the pixel, and when this shape is formed, density unevenness in the pixel occurs. It becomes a color filter with uneven color. As a result of intensive studies, the present inventors have found that the color unevenness can be prevented by adding a surfactant. The action mechanism is presumed as follows.

When a surfactant is added, it is generally presumed that the paintability of the ink to the pixel surface (substrate surface) is improved and pixels with a good shape (flat) are obtained, but the above effect is obtained by improving wettability. Turned out not to be. Specifically, when the surfactant is not added to the ink and when it is added, the contact angle with the substrate does not change, but the pixel shape is convex when the surfactant is not added to the ink. In addition, a phenomenon of flattening was observed when added.
This phenomenon can be understood as follows.
Since the ink contains a solvent and other additives, the paintability to the substrate is not bad in the first place. Even if a surfactant is added in this state, there is not much improvement effect of wettability in a macro sense considered from surface tension. For this reason, it is considered that the contact angle does not change much as described above. On the other hand, when the ink deposited on the pixels is observed closely, the convex shape of the ink that is raised and deposited in the concave portion of the partition wall is fixed as if it was filmed in the middle of drying when the surfactant is not added. . On the other hand, when the surfactant is added, the convex shape is not fixed, and it is slowly dried to finally form a flat pixel.
In general, the amount of ink ejected by an ink jet apparatus is on the order of pL (picoliter), which is very small (for example, the contact angle measurement is on the order of μL), and since the surface area per unit volume is large, drying tends to be very fast. For this reason, when the surfactant is not added, it is considered that drying occurs rapidly on the surface of the ink and the film is stretched.
On the other hand, when the surfactant is added, it is considered that the rapid drying of the ink is suppressed by the action of the surfactant, and the ink is dried without filming, so that a pixel having a flat and good shape can be obtained. It is done. With regard to the action of the surfactant, it is conceivable that the surfactant is localized at the air interface of the ink and covers the ink surface, or that the surfactant and solvent molecules interact. Therefore, the planarization effect of a fluorine-containing surfactant having a very large surface orientation and a surfactant having a large site capable of interacting with solvent molecules such as polyethylene oxide and polypropylene oxide is generally large. Among these, a fluorine-containing surfactant that effectively covers the ink surface is more effective, and a fluorine-containing surfactant containing polyethylene oxide or polypropylene oxide is particularly effective.

  In addition, the shape of the pixel can be measured using a contact type surface roughness meter P-10 (manufactured by Tencor). Specifically, when the color filter itself is available, the pixel of the color filter is measured, and when the color filter is not available, the color filter is carefully taken out from the display device and the pixel is measured. If necessary, ITO can be removed by treating the color filter with hydrochloric acid or sulfuric acid.

The surfactant used in the inkjet ink of the present invention is not particularly limited. For example, paragraph number [0021] of JP-A-7-216276, JP-A-2003-337424, and JP-A-11-133600 are disclosed. The surfactants disclosed in (1) may be mentioned as suitable.
Among these, it is preferable that the surfactant contains fluorine in terms of preventing color unevenness with a smaller amount of addition, and it is also preferable from the same viewpoint that polyethylene oxide or polypropylene oxide is included, and the surfactant is a polymer. Is preferable from the same viewpoint. In particular, a fluorine-containing polymer surfactant and a polymer surfactant containing polyethylene oxide or polypropylene oxide are preferred, and a fluorine-containing polymer surfactant containing polyethylene oxide or polypropylene oxide is most preferred. As fluorine, a perfluoroalkyl group having 1 to 14 carbon atoms is preferable, and a perfluoroalkyl group having 4 to 8 carbon atoms is particularly preferable.
The weight average molecular weight of the polymer surfactant is preferably from 1,000 to 100,000, more preferably from 5,000 to 40,000. In addition, the weight average molecular weight in this invention is calculated | required by polystyrene conversion in GPC measurement.

Of these, the following fluorosurfactants are particularly preferred.
-Fluorosurfactant-
The inkjet ink composition in the present invention is derived from at least one of structural units a derived from a monomer represented by the following general formula (a) and a monomer represented by the following general formula (b) as a surfactant. At least one of the structural units b, and the mass ratio (a / b) of the structural unit a to the structural unit b is 20/80 to 80/20 (hereinafter referred to as “specific”). It is preferable to contain a “fluorine-based surfactant”. This fluorosurfactant is a fluorine-containing polymer, and is particularly preferable from the viewpoint of forming flat and well-shaped pixels.

The monomer represented by general formula (a) (hereinafter also referred to as monomer a) will be described.
In the general formula (a), R ¹ represents a hydrogen atom or a methyl group. Further, _-C m _{F 2m + 1} in the formula (a) may be straight or branched. m represents an integer of 2 to 14, preferably an integer of 4 to 8. n represents an integer of 1 to 18, preferably 2 to 10.

As the _-C m _{F 2m + 1,} for _{example, -C 2 F 5, C 4} F 9, C 6 F 13, such as _{C 8 F 17, C 12 F} 25 and the like.

Ratio of the _-C m _{F 2m + 1} is with respect to the total mass of the monomers a, preferably 20 to 80 mass%, particularly preferably 40 to 60 wt%.

Among the monomers a, a compound in which R ¹ is a hydrogen atom, -C _m F _{2m + 1} is C ₆ F ₁₃ and n is 2 is particularly preferable.

The monomer represented by general formula (b) (hereinafter also referred to as monomer b) will be described.
In General Formula (b), R ² and R ³ each independently represent a hydrogen atom or a methyl group, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p and q each independently represent an integer of 0 to 18, and p and q do not represent 0 (zero) at the same time. p and q are preferably 2 to 8.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^4, a methyl group, an ethyl group are preferable.

Among the monomers b, a R ² is a hydrogen atom, R ³ is a methyl group, an R ⁴ is a hydrogen atom, a p is 7, the compound and q is 0, R ² A compound in which is a hydrogen atom, R ³ is a hydrogen atom, R ⁴ is a hydrogen atom, p is 0, and q is 7 is particularly preferable.

  As the monomer a contained in one molecule of the specific fluorosurfactant, only one kind having the same structure may be used, or plural kinds having different structures may be used. The same applies to the monomer b.

  1000-100000 are preferable and, as for the weight average molecular weight Mw of a specific fluorine-type surfactant, 5000-40000 are more preferable.

  The specific fluorosurfactant is a copolymer obtained by copolymerizing at least the monomer a and the monomer b as described above, and the monomer a / monomer b ratio (mass ratio) in the copolymer. Is 20/80 to 80/20. When the copolymerization ratio is within the above range, the top surface of the ink, i.e., coloring, is applied to the concave portion finely divided by the partition wall and dried by applying an ink jet so as to rise above the wall height of the partition wall. The surface of the colored region that becomes the pixel can be flattened.

  As the specific fluorosurfactant, a copolymer obtained by copolymerizing other optional monomers together with the above-mentioned monomers a and b is also suitable. In this case, examples of other copolymerizable monomers other than the monomers a and b include, for example, styrene, vinyl toluene, α-methyl styrene, 2-methyl styrene, chlorostyrene, vinyl benzoic acid, vinyl benzene sulfonate, Styrene such as aminostyrene and derivatives thereof, substituted products, dienes such as butadiene and isoprene, acrylonitrile, vinyl ethers, methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid, partially esterified maleic acid, styrenesulfonic anhydride Examples thereof include vinyl monomers such as maleic acid, cinnamic acid, vinyl chloride, and vinyl acetate.

For example, when the specific fluorosurfactant is 100 parts by mass, a binary or ternary or higher copolymer consisting of 20 to 80 parts by mass of monomer a and 80 to 20 parts by mass of monomer b, 20 to 80 parts by mass of monomer a And a ternary or higher copolymer consisting of 80 to 20 parts by mass of the monomer b and other optional monomers (remaining mass).
Furthermore, a binary or ternary or higher copolymer comprising 25 to 60 parts by mass of monomer a and 60 to 40 parts by mass of monomer b, 25 to 60 parts by mass of monomer a, 60 to 40 parts by mass of monomer b, and other optional monomers A ternary or higher copolymer consisting of (the remaining mass) is preferred.

  The specific fluorine-based surfactant is a copolymer obtained by copolymerizing at least monomer a and monomer b, and there is no particular limitation on the monomer sequence, and even random copolymerization, such as regular block copolymerization, grafting, etc. Any of copolymerization may be used.

  Two or more specific fluorosurfactants having different molecular structures and / or monomer compositions can be used as a mixture.

  Hereinafter, specific examples of the specific fluorine-based surfactant will be shown. However, the present invention is not limited to these.

  As content of the said specific fluorine-type surfactant in all the surfactants used for the inkjet ink which concerns on this invention, 1-100 mass% is preferable, 50-100 mass% is more preferable, 90-100 Mass% is particularly preferred.

  In addition, the content of the total surfactant in the ink jet ink according to the present invention is preferably 10% by mass or less, more preferably 0.01 to 8% by mass with respect to the total amount of the ink composition, and 0.05 to 5% by mass is particularly preferred. 30 mass% or less is preferable with respect to ink solid content, 0.01-15 mass% is more preferable, 0.1-10 mass% is especially preferable. When the content of all the surfactants in the ink is within the above range, pixels having a good shape can be formed more remarkably, and as a result, display unevenness in the image when the image is displayed is effectively generated. Can be prevented.

(Coloring agent)
In the present invention, the colorant used in the ink composition for forming the red pixel is C.I. I. Pigment Red (C.I.P.R.) 254 is an essential requirement, and the ink composition may be composed of other known pigments. C. I. P. R. By using H.254, high color purity required for color displays such as liquid crystal displays for personal computers and liquid crystal color televisions can be realized.
However, C.I. I. P. R. It is desirable that all the pigments including 254 are uniformly dispersed in the colored liquid composition, and therefore, the number average particle diameter is preferably 0.01 to 0.12 μm, particularly 0.02 to 0.08 μm. It is preferable.
The particle diameter here means the diameter of a circle having the same area as the pigment image obtained by taking an electron micrograph of the pigment. The number average particle diameter means an arithmetic average of particle diameters for 100 particles.

  C. I. P. R. As a method for confirming the presence of 254, known analysis methods such as infrared spectroscopy, Raman spectroscopy, chromatography, mass spectrum, and various elemental analysis can be used. In terms of simplicity, infrared spectroscopy and Raman spectroscopy are preferred. TOF-SIMS is preferable in terms of high sensitivity. One analysis method can be used, or a plurality of analysis methods can be used for confirmation. In order to increase the accuracy of analysis, it is preferable to confirm using a plurality of analyzes, and it is particularly preferable to confirm using Raman spectroscopy and TOF-SIMS.

  Examples of the known dyes or pigments used in combination include the pigments and dyes described in JP-A-2005-17716 [0038] to [0054], and JP-A-2004-361447 [0068] to [0072]. And the colorants described in JP-A-2005-17521 [0080] to [0088] can be suitably used. Among these, pigments are particularly preferable from the viewpoint of storage stability of pixels.

  The other color ink composition used in the method for producing a color filter of the present invention includes C.I. I. Pigment Green 36 is C.I. in the ink composition of B (blue). I. Pigment Blue 15: 6 is a preferable example.

Here, the combination of pigments that are preferably used in combination will be described. 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 is preferred.
The C.I. 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. Pigment Yellow 180 is a combination of C.I. I. In Pigment Blue 15: 6, C.I. I. Pigment violet 23, or C.I. I. A combination with CI Pigment Blue 60 is preferred.

C. in the pigment when used in combination. I. The content of Pigment Red 254 is preferably 80% by mass or more, and particularly preferably 90% by mass or more.
In addition, C.I. I. Pigment green 36, or C.I. I. As each content of Pigment Blue 15: 6, C.I. I. In the pigment green 36, the content is preferably 50% by mass or more, particularly preferably 60% by mass or more. I. In pigment blue 15: 6, 80 mass% or more is preferable, and especially 90 mass% or more is preferable.

  The pigment is preferably 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 (or vehicle or solvent) described later. The disperser used for dispersing the pigment is not particularly limited. For example, a kneader or a roll mill described in “Encyclopedia of Pigments” (written by Asakura Kunizo, 1st edition, Asakura Shoten, 2000, item 438). And known dispersers such as an atrider, a super mill, a dissolver, a homomixer, and a sand mill. Further, it may be finely pulverized by frictional force by mechanical grinding described in item 310 of “Pigment Encyclopedia”.

The particle diameter of the colorant (pigment) is preferably 0.001 to 0.1 [mu] m, more preferably 0.01 to 0.08 [mu] m in terms of number average particle diameter. By setting this range, high contrast can be achieved.
The term “particle size” refers to the diameter when the particles of an electron micrograph image are represented by a circle having the same area as this, and the “number average particle size” refers to 100 particles obtained by determining the particle size of the particles. The average value obtained by averaging.

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 the dispersion, the known disperser 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. If the dispersion time is less than 10 hours, the pigment particle size is large, and the polarization may be canceled by the pigment and the contrast may be lowered. If the dispersion time exceeds 30 hours, the viscosity of the dispersion increases, and Discharging may be difficult.
Further, the difference in contrast between two or more colored regions is preferably within 600, but in order to adjust within 600, it is desirable to adjust the pigment particle size.

  The contrast of each colored pixel constituting the color filter 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 is less than 2000, when an image of a liquid crystal display device provided with this color filter is observed, the whole image may become whitish and difficult to see. The difference in contrast between the colored pixels is preferably 600 or less, more preferably 410 or less, still more preferably 350 or less, and most preferably 200 or less. If the difference in contrast is within 600, the amount of light leakage from each colored pixel portion at the time of black display does not differ greatly, so that the color balance of black display is good.

  The “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 can be measured for each pixel by setting the measurement angle small. Contrast measurement is the light that passes through the other polarizing plate with the backlight applied from the side of one polarizing plate with the polarizing plates overlapped on both sides of the object to be measured and the polarizing directions of the polarizing plates are parallel to each other. The brightness Y1 was measured, and the backlight Y was applied from the side of one polarizing plate in a state where the polarizing plates were orthogonal to each other, and the luminance Y2 of the light that passed through the other polarizing plate was measured. Y1 / Y2 can be calculated using the value. As a polarizing plate used for measurement, it is preferable to determine a predetermined polarizing plate. When a predetermined polarizing plate cannot be obtained, contrast measurement can be performed with a polarizing plate used in a display device.

  The amount of the pigment in the ink composition can be appropriately selected in order to obtain a desired hue and density, but is preferably 3.0% by mass or more, more preferably based on the total mass of the ink composition. 5.0% by mass or more.

  The contrast of the color filter after the display device is made is measured as described above by carefully disassembling the completed display device, taking out the color filter portion.

(Polymerization initiator)
As the polymerization initiator used in the present invention, either a photopolymerization initiator or a thermal polymerization initiator can be used, and radical active species are generated by irradiation with active energy rays, thereby polymerizing a radical polymerizable compound. Any of a radical polymerization initiator that initiates polymerization and a cationic polymerization initiator that generates cationically active species and initiates polymerization of the cationic polymerizable compound can be used in accordance with the polymerizable compound.

-Radical polymerization initiator-
Examples of the radical polymerization initiator include the following. For example, benzophenone, benzophenone, benzoylbenzoic acid, 4-phenylbenzophenone, 4,4-diethylaminobenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, and the like are thioxanthone. As the system, thioxanthone, 2-chlorooxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, isopropylxanthone, and the like are 2-methyl-1- (4-methylthio) phenyl-2 as the acetophenone system. -Morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-hydroxy-2-methyl-1-phenylpropan-1-one, -Hydroxysic Hexyl 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 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) acylphosphine oxide, etc. as acylphosphine oxides. Can be mentioned.

-Cationic polymerization initiator-
As the cationic polymerization initiator, for example, diazonium salts, iodonium salts, sulfonium salts, iron arene complexes, and organic polyhalogen compounds are preferable. 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, US Pat. No. 3,708,296, And compounds described in the specification of US Pat. No. 3,853,002.
Examples of the cationic photopolymerization initiator include aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metallocene compounds, silicon compounds / aluminum complexes, and the like.

  The amount of the polymerization initiator in the ink composition is preferably 5 to 60% by mass, more preferably 10 to 50% by mass with respect to the polymerizable compound (mass). When the polymerization initiator is within the above range, curability can be satisfied with the intensity of general active energy rays, and there is no need to increase the irradiation time.

(solvent)
In addition to the above components, the ink composition of the present invention uses a solvent as an essential requirement. When a solvent is contained, moderate fluidity can be imparted for droplet ejection by the ink jet method, and it is effective for the formation of flatness by the surfactant according to the present invention described above. The amount of the solvent can be appropriately selected within a range not impairing the effects of the present invention.

  The solvent in the present invention assists the dissolution or dispersion of functional materials such as colorants, polymerizable monomers, additives, and polymers contained in the ink composition of the present invention, and the fluidity of the ink composition of the present invention. In addition to making it easier to perform droplet ejection, etc., after ink droplets have been deposited and subjected to prescribed drying or heat treatment, most (approximately 90% or more) of the ink composition is removed by evaporation, etc. belongs to. For example, the polymerizable monomer is also in a liquid state, but when the solvent is added thereto, the fluidity is further increased and droplet ejection is facilitated. Usually, a solvent having a boiling point of 100 ° C. or higher is used. For the purpose of preventing the ink from drying and preventing clogging of the head, a high boiling point solvent having a boiling point of 200 ° C. or lower, and sometimes higher, is used.

  Examples of the solvent include those described in “New Edition Solvent Pocket Book” (edited by Organic Synthetic Science Association, published by Ohm Co., Ltd.) and “Solvent Handbook” (Shozo Asahara et al., Kodansha, 1976). As ion-exchange water, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; diethylene glycol monoalkyl such as diethylene glycol mono-n-butyl ether acetate Ether acetates; propylene glycol monoalkyls such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate Ether acetates; Butylene glycol diacetates such as 1,3-butylene glycol diacetate; Other ethers such as diethylene glycol dimethyl ether; Ketones such as cyclohexanone, 2-heptanone, 3-heptanone, methyl ethyl ketone, methyl isobutyl ketone, and acetone Alkyl lactates such as ethyl 2-hydroxypropionate; 3-methyl-3-methoxybutylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-acetate Other esters such as butyl, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate; high such as γ-butyrolactone Boiling solvents can be used.

  The inkjet ink composition of the present invention preferably has a solid content of 5 to 99 mass%, more preferably 10 to 50 mass%, and more preferably 10 to 30 mass% from the viewpoint of imparting flatness. Is most preferred. Here, solid content means components other than a solvent, and a solvent is as above-mentioned.

<Color filter and manufacturing method thereof>
The color filter according to the present invention includes a pixel group of two or more colors having different hues and a light-shielding partition wall that separates the pixels constituting the pixel group on the substrate, and is surrounded by the partition wall. A pixel pattern is formed by providing a colored region (colored layer) in the gap (concave portion) by an ink jet method.

The method for producing the color filter of the present invention includes:
a) Step of forming a partition made of a resin composition on a substrate (partition formation step)
b) A step of performing plasma treatment on the substrate on which the partition walls are formed (plasma treatment step).
c) At least C.I. in the gap between the partition walls formed on the substrate. I. P. R. A step of forming a pixel by applying an inkjet ink containing 254, a solvent, a surfactant, and a monomer having two or more polymerizable groups by an inkjet method (pixel formation step)
At least three steps, and after the step c),
d) A step of irradiating active energy rays after the solvent in the ink is removed. e) It is preferable to provide a curing step such as a heating step.

-Partition formation process-
In the method for producing a color filter of the present invention, a partition forming step for forming a partition is first provided. In this partition forming step, the partition is formed using a dark color composition.

  The dark color composition is preferably a composition having a high optical density, and the preferred optical density is an optical density which becomes 2.0 to 10.0 when a photosensitive resin composition layer having a partition wall-corresponding thickness is formed. is there. A more preferable optical density is 2.5 to 6.0, and particularly preferably 3.0 to 5.0. Further, the photosensitive resin layer and the dark color composition preferably have an optical density with respect to the exposure wavelength (generally in the ultraviolet region) when cured by a photoinitiating system as described later, and the value is 2.0 to 10.0 is preferable, more preferably 2.5 to 6.0, and most preferably 3.0 to 5.0. When it is within the above range, polymerization and curing are improved, and a partition having a desired shape can be formed. The dark color property can be imparted by using various color materials such as dyes and pigments described later, or materials of various forms of carbon or combinations thereof, and black is most preferable. The optical density of the partition wall is the absorbance of light at 555 nm of the partition wall.

  The dark color composition can be composed of at least a colorant, a polymerization initiation system, and a polymerizable compound, and the polymerization initiation system includes a thermal initiation system using a thermal initiator and a photoinitiation using a photoinitiator. Although systems are generally mentioned, it is preferred that they are composed of photoinitiated systems.

In the case of using the photoinitiating system, the formation of the partition walls constituting the color filter in the present invention is performed, for example, by using a dark color composition on at least one of the substrates before performing the pixel forming process and the curing process described later. Can be suitably carried out by exposing the developed photosensitive resin layer to a pattern (preferably under poor oxygen conditions) and developing it. As described above, the partition wall is a partition pattern that separates colored regions (pixels) formed by ejecting droplets of the curable ink (inkjet ink composition) of the present invention by the inkjet method. Further, after forming and exposing at least the photosensitive resin layer in the partition wall forming step, plasma treatment as an ink repellent treatment is performed, and other steps such as a baking treatment can be provided as necessary.
Hereinafter, the case where it is configured using a photoinitiation system as a polymerization initiation system will be mainly described.

[Formation of photosensitive resin layer]
The photosensitive resin layer can be constituted by using a dark color composition containing a coloring material, a polymerizable compound, and a photoinitiating system, and if necessary, further a binder, a known additive such as a plasticizer, filling Other components such as an agent, a stabilizer, a polymerization inhibitor, a surfactant, a solvent, and an adhesion promoter can be used.
Specifically, the photosensitive resin layer is a method of applying a dark color composition (for example, a polymerizable monomer, a photopolymerization initiator, a binder, and a coloring material) on a substrate (preferably, a dark color composition. And a method of transferring a photosensitive resin layer onto a substrate (transfer method) using a photosensitive transfer material having a photosensitive resin layer using a dark color composition. Details of the dark color composition and the photosensitive transfer material will be described later.

In the case of applying the photosensitive resin layer by coating (coating method), the coating is preferably performed using a slit nozzle or a slit coater having a slit-like hole at the portion where the liquid is discharged.
Specifically, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002-79163. Slit nozzles and slit coaters described in Japanese Patent Laid-Open No. 2001-310147 and the like can be suitably used. As other examples, a coating machine such as a spinner, a winder, a roller coater, a curtain coater, a knife coater, a wire bar coater, or an extruder may be used.

In the case of the coating method, a step of coating and forming a photosensitive resin layer using a dark color composition on a substrate is provided. As will be described later, the coated and formed photosensitive resin layer [preferably under poor oxygen conditions ( For example, an oxygen barrier layer is further formed on the photosensitive resin layer and the barrier ribs are formed by patterning through exposure, development and patterning via the oxygen barrier layer or in an inert gas atmosphere or reduced pressure condition). . The oxygen blocking layer can be configured in the same manner as the oxygen blocking layer of the photosensitive transfer material described later.
Details of exposure and development will be described later.

In the case of the transfer method, a photosensitive transfer material described later is used, and the photosensitive resin layer formed in a film form on the temporary support is pressure-bonded or heat-pressed with a roller or flat plate heated and / or pressed on the substrate surface. The photosensitive resin layer is transferred (laminated), leaving the temporary support (under anoxic conditions) or transferring the photosensitive resin layer by peeling off the temporary support further and transferring the photosensitive resin layer. The partition walls are formed by exposing the photosensitive resin layer [preferably under an oxygen-poor condition (for example, through an oxygen blocking layer provided on the photosensitive resin layer)], developing and patterning. Details of exposure and development will be described later.
Specifically, the laminating can be performed by a laminator and a laminating method described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. Details of the photosensitive transfer material and transfer by a transfer method will be described later.

  The layer thickness of the photosensitive resin layer is not particularly limited depending on the solid content of the dark color composition and the height of the partition wall to be formed, but is generally preferably 1.5 to 10 μm, and 1.8 -7.0 micrometers is more preferable, and 2.2-5.0 micrometers is still more preferable.

-Deep color composition, photosensitive resin layer-
Hereinafter, the dark color composition for forming a partition and the structural component of the photosensitive resin layer using the same are explained in full detail.

-Polymerizable compound-
It is preferable that the photosensitive resin layer or the dark color composition for forming the partition wall contains at least one polymerizable compound. It can be cured by the action of active species from the photoinitiating system described later to form a pattern.

  Examples of the polymerizable compound include monofunctional or polyfunctional monomers, and polyfunctional monomers are preferable. The polyfunctional monomer is a polymerizable monomer having two or more polymerizable groups, and can be used alone or in combination with other monomers.

Specific examples of the monofunctional or polyfunctional monomers include t-butyl (meth) acrylate, ethylene glycol di (meth) acrylate, 2-hydroxypropyl (meth) acrylate, triethylene glycol di (meth) acrylate, Methylolpropane tri (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di Pentaerythritol penta (meth) acrylate, polyoxyethylated trimethylolpropane tri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, 1,4-diiso Lopenylbenzene, 1,4-dihydroxybenzene di (meth) acrylate, decamethylene glycol di (meth) acrylate, styrene, diallyl fumarate, triallyl trimellitic acid, lauryl (meth) acrylate, (meth) acrylamide, xylylene bis (meth) ) Acrylamide and the like.
Moreover, the compound which has hydroxyl groups, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and polyethyleneglycol mono (meth) acrylate, and diisocyanates, such as hexamethylene diisocyanate, toluene diisocyanate, and xylene diisocyanate. A reactant may also be mentioned.

  Of the above, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and tris (2-acryloyloxyethyl) isocyanurate are particularly preferable.

  The content of the polymerizable compound in the photosensitive resin layer or dark color composition is preferably 5 to 80% by mass, particularly 10 to 70% by mass, based on the total solid content (mass) of the layer or composition. preferable. When the content is within the above range, it is effective to ensure resistance to the alkali developer after photocuring.

-Photoinitiation system-
The photosensitive resin layer or dark color composition for forming the partition preferably contains at least one photoinitiating system. The photoinitiating system is a compound that generates an active species that initiates polymerization of the polymerizable compound upon irradiation with radiation (also referred to as exposure) such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It can select suitably from a compound.

  For example, trihalomethyl group-containing compounds, acridine compounds, acetophenone compounds, bisimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds Compound, etc. can be mentioned.

  Specifically, a trihalomethyloxazole derivative or an s-triazine derivative substituted with a trihalomethyl group, a trihalomethyl-s-triazine compound described in US Pat. No. 4,239,850 described in JP-A-2001-117230, 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 (9-acridinyl) pentane, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, 1,8-bis (9-acridinyl) octane 1,9-bis (9-acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, 1,12-bis (9-acridinyl) dodecane, etc. Acridine compounds such as bis (9-acridinyl) alkane;

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, hexaarylbisimidazole / mercaptobenzimidazole, benzyldimethyl ketal, thioxanthone / amine, 2,2 ′ -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-bisimidazole, and the like.

  Among the above, at least one selected from a trihalomethyl group-containing compound, an acridine compound, an acetophenone compound, a bisimidazole compound, and a triazine compound is preferable, and at least one selected from a trihalomethyl group-containing compound and an acridine compound Is particularly preferred. Trihalomethyl group-containing compounds and acridine compounds are also useful in that they are versatile and inexpensive.

  Particularly preferable examples of the trihalomethyl group-containing compound include 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole, 2- (p-butoxystyryl) -5-trichloro. Methyl-1,3,4-oxadiazole, 9-phenylacridine as the acridine compound, and 6- [p- (N, N-bis (ethoxycarbonylmethyl)] as the triazine compound. Amino) phenyl] -2,4-bis (trichloromethyl) -s-triazine, the benzophenone compound is Michler's ketone, and the biimidazole compound is 2,2′-bis (2,4 -Dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-bisimidazole.

The polymerization initiation system (particularly the photoinitiation system) may be used in combination of two or more, in addition to being used alone.
The total amount in the photosensitive resin layer or dark color composition of the polymerization initiation system (particularly the photoinitiation system) is preferably 0.1 to 20% by mass relative to the total solid content (mass) of the layer or composition. 0.5-10 mass% is especially preferable. When the total amount is within the above range, the curing efficiency is high and curing can be performed in a short time, and the image pattern formed during development is not lost or the pattern surface is not roughened.

  The photoinitiating system may be configured with a hydrogen donor. The hydrogen donor is preferably a mercaptan compound or an amine compound as defined below from the viewpoint that sensitivity can be further improved. Here, the “hydrogen donor” 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 “ 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, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as “the amine compound”). , "Amine hydrogen donor").
The hydrogen donor may have a mercapto group and an amino group at the same time.

  Specific examples of the mercaptan hydrogen donor include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 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 singly or in combination of two or more, and the formed image is difficult to drop off from the substrate during development, and the strength and sensitivity can be improved. 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 and 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and a particularly preferred combination is 2-mercaptobenzobenzone. Thiazole / 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 photosensitive resin layer or dark color composition is preferably 0.1 to 20% by mass, and preferably 0.5 to 10%, based on the total solid content (mass) of the layer or composition. Mass% is particularly preferred.

-Color material-
The photosensitive resin layer or dark color composition for forming the partition preferably contains at least one kind of coloring material. By containing a color material, a visible image having a desired color can be formed.

  Examples of the color material include pigments and dyes described in paragraphs [0038] to [0054] of JP-A-2005-17716, and paragraphs [0068] to [0072] of JP-A-2004-361447. Pigments and colorants described in paragraph numbers [0080] to [0088] of JP-A No. 2005-17521 can be suitably used.

Of these, organic pigments, inorganic pigments, dyes, and the like are suitable, and when a light-shielding property is required for the photosensitive resin layer or the dark color composition, a metal oxide such as carbon black, titanium carbon, titanium oxide, or iron oxide is used. A mixture of pigments such as red, blue, and green, as well as light-shielding agents such as powder, metal sulfide powder, and metal powder can be used. Known colorants (dyes and pigments) can be used. Examples of the black color material include carbon black, titanium carbon, iron oxide, titanium oxide, graphite and the like, and carbon black is particularly preferable.
Moreover, when selecting a pigment as a color material, it is preferable to disperse | distribute uniformly in the photosensitive resin layer or a deep color composition.

  The content of the color material in the photosensitive resin layer or the dark color composition is preferably 30 to 70% by mass with respect to the solid content (mass) of the layer or the composition in terms of shortening the development time. -60 mass% is more preferable, and 50-55 mass% is still more preferable.

  The pigment is preferably 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 in an organic solvent (or vehicle) described later. The vehicle refers to a portion of the medium in which the pigment is dispersed when the paint is in a liquid state, and is a liquid portion that binds to the pigment and hardens the coating film (binder), which is dissolved and diluted. Component (organic solvent). The disperser used for dispersing the pigment is not particularly limited. For example, a kneader described in “Encyclopedia of Pigments” [Asakura Kunizo, 1st edition, 438, Asakura Shoten (2000)], 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, it may be finely pulverized by using frictional force by mechanical grinding described in Item 310 of “Pigment Encyclopedia”.

  The particle diameter of the coloring material (particularly pigment) is preferably 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm in terms of number average particle diameter from the viewpoint of dispersion stability. The “particle diameter” refers to the diameter when the particle is represented by a circle having the same area as the area of the particle in an electron micrograph, and the “number average particle diameter” refers to the particle diameter of 100 This means the average value.

-Binder-
The photosensitive resin layer or the dark color composition for forming the partition 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.

  The content of the binder in the photosensitive resin layer or the dark color composition is preferably 20 to 50% by mass, and more preferably 25 to 45% by mass with respect to the total solid content (mass) of the layer or composition.

-Solvent-
In general, the dark color composition used for producing the partition wall in the present invention can be constituted using a solvent in addition to the above components. Examples of the 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.

  In the dark color composition or photosensitive resin layer in the present invention, the following components, for example, surfactants, ultraviolet absorbers, and known additives such as plasticizers, fillers, stabilizers, thermal polymerization are further included. An inhibitor, a solvent, an adhesion promoter and the like can be 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.

-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 adding 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. The content of the surfactant in the dark color composition is generally 0.001 to 1% by mass with respect to the total solid content (mass) of the composition. 5 mass% is preferable and 0.03-0.3 mass% is especially 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.
When the ultraviolet absorber is used, the content of the ultraviolet absorber relative to the total solid content of the dark color composition is generally 0.5 to 15% by mass, preferably 1 to 12% by mass, and 1.2 to 10% by mass 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% by mass, preferably 0.02 to 0.7% by mass, 0.05 -0.5 mass% is especially preferable.

  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.

-Photosensitive transfer material-
Next, the photosensitive transfer material used for the transfer method will be described in detail.
The photosensitive transfer material is formed by providing a photosensitive resin layer composed of at least the dark color composition on a temporary support, preferably an oxygen blocking layer and a photosensitive resin layer from the temporary support side. What was provided and can be used. When using a material in which an oxygen blocking layer is provided on the photosensitive resin layer, the photosensitive resin layer made of the dark-colored composition is automatically protected against oxygen in the atmosphere by the oxygen blocking layer. It becomes the condition. Therefore, it is not necessary to perform the exposure process under an inert gas or under reduced pressure, and there is an advantage that the current process can be used as it is. It is also effective in that the partition walls can be formed easily and at low cost.

  The photosensitive transfer material can be configured by further providing a thermoplastic resin layer, a protective film, or the like as necessary.

-Temporary support-
The temporary support can be appropriately selected from those that are chemically and thermally stable and made of a flexible material. Specifically, a thin sheet or film such as Teflon (registered trademark), polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, polyester, or a laminate thereof is preferable. Among these, a biaxially stretched polyethylene terephthalate film is particularly preferable.

  As thickness of a temporary support body, 5-300 micrometers is suitable, Preferably it is 20-150 micrometers. When the thickness is within the above range, it is possible to avoid tearing when the temporary support is peeled off, and to avoid a decrease in resolution when exposed through the temporary support.

-Photosensitive resin layer-
The photosensitive resin layer is formed using the above-described dark color composition, and the characteristics such as the shape and the forming method are the same as those of the layer formed by the above-described coating method, and the preferred embodiments are also the same. .

-Oxygen barrier layer-
It is preferable to further provide an oxygen blocking layer between the temporary support and the photosensitive resin layer, or between the thermoplastic resin layer and the photosensitive resin layer. The oxygen blocking layer is a layer having an oxygen transmission rate of 2000 cm ³ / (m ² · day · atm) or less, and the oxygen transmission rate is preferably 100 cm ³ / (m ² · day · atm) or less, More preferably, it is 50 cm ³ / (m ² · day · atm) or less. When the oxygen permeability is higher than 2000 cm ³ / (m ² · day · atm), oxygen may not be effectively blocked and a partition having a desired shape may not be obtained.

  Specific examples include polyvinyl ether / maleic anhydride polymer, water-soluble salt of carboxyalkyl cellulose, water-soluble cellulose ethers described in JP-A Nos. 46-2121 and 56-40824. Water-soluble salt of carboxyalkyl starch, polyvinyl alcohol, polyvinylpyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salt of polyacrylic acid, gelatin, ethylene oxide polymer, various starches and the like Group of water-soluble salts, styrene / maleic acid copolymers, maleate resins, and combinations of two or more thereof.

A layer containing polyethylene, polyvinylidene chloride, polyvinyl alcohol (PVA) or the like as a main component (particularly PVA as a main component) is preferable, and a polymer such as polyvinyl pyrrolidone or polyacrylamide may be added if necessary. A combination with polyvinylpyrrolidone is particularly preferred. As the PVA, those having a saponification rate of 80% or more are preferable, and the content of polyvinylpyrrolidone is preferably 1 to 75% by mass, more preferably 1 to 50% by mass, and still more preferably the total solid content of the oxygen barrier layer. It is 10-40 mass%.
As content of PVA in an oxygen interruption layer, 25-99 mass% is preferable, 50-90 mass% is more preferable, 50-80 mass% is especially preferable. The addition amount of these polymers is 1-40 mass% of the whole layer, More preferably, it is 10-35 mass%. In addition, when there is too much addition amount of polyvinylpyrrolidone, oxygen barrier property may become inadequate.

-Thermoplastic resin layer-
A thermoplastic resin layer can be provided between the temporary support and the photosensitive resin layer as necessary. Providing the thermoplastic resin layer is effective for improving the adhesion to the substrate on which the partition walls are formed.

The thermoplastic resin layer preferably includes at least a resin component and is configured to be alkali-soluble. The resin component is preferably a thermoplastic resin that is alkali-soluble and has a substantial softening point of 80 ° C. or lower.
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 Saponification products with (meth) acrylic acid ester copolymers, poly (meth) acrylic acid esters, saponification products with (meth) acrylic acid ester copolymers such as butyl (meth) acrylate and vinyl acetate, etc. Can be mentioned.

  In addition to the above, an organic polymer having a softening point of about 80 ° C. or less in “Plastic Performance Handbook” (edited by the Japan Plastic Industry Federation, edited by the All Japan Plastics Molding Industry Association, published by the Industrial Research Council, published on October 25, 1968) Among them, those soluble in an alkaline aqueous solution can be used.

In addition, an organic polymer substance having a softening point of 80 ° C. or higher can be made to have a substantial softening point of 80 ° C. or less by adding various plasticizers compatible with the polymer substance to the organic polymer substance. It can also be lowered.
These organic polymer substances include various polymers, supercooling substances, adhesion improvers or surfactants 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. , Mold release agents, and the like 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, and biphenyl diphenyl phosphate.

-Protective film-
A protective film is preferably provided on the surface of the photosensitive resin layer formed on the temporary support to protect it from contamination and damage during storage. The protective film may be made of the same or similar material as the temporary support, and it is important that the protective film can be easily separated from the photosensitive resin layer in terms of good transfer.
As a material constituting the protective film, for example, silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable. The thickness of the protective film is generally 4 to 40 μm, preferably 5 to 30 μm, and particularly preferably 10 to 25 μm.

The photosensitive transfer material is, for example, provided with a thermoplastic resin layer by applying a coating liquid (thermoplastic resin layer coating liquid) in which a constituent component of the thermoplastic resin layer is dissolved on a temporary support, and drying the coating liquid. Apply a solution that uses a solvent that does not dissolve the thermoplastic resin layer on the thermoplastic resin layer, dry it to stack an oxygen barrier layer, and then use a solvent that does not dissolve the oxygen barrier layer on the oxygen barrier layer. Then, it can be produced by applying the dark color composition prepared as described above, and drying and laminating the photosensitive resin layer.
The application can be performed by the known application method described above, but it is preferable to use an application apparatus (slit coater) using a slit-like nozzle.

  In addition to the above, the photosensitive transfer material is prepared by preparing a sheet provided with a thermoplastic resin layer and an oxygen blocking layer on a temporary support, and a sheet provided with a photosensitive resin layer on a protective film, and blocking oxygen. A sheet having a thermoplastic resin layer on a temporary support and a sheet having a photosensitive resin layer and an oxygen barrier layer on a protective film are prepared by bonding so that the layer and the photosensitive resin layer are in contact with each other. And it can also carry out by bonding together so that a thermoplastic resin layer and an oxygen interruption | blocking layer may contact | connect.

-Board-
Examples of the substrate (permanent support) include a metal base, a base on which a metal is bonded, glass, ceramic, a synthetic resin film, and the like. Preferred are those that are transparent and have good dimensional stability, particularly glass and synthetic resin films.

[Exposure, development]
The photosensitive resin layer formed as described above can be exposed by using a mask provided with a desired pattern and irradiating the photosensitive resin layer with light through the mask. At this time, the exposure is preferably performed under an oxygen-poor condition. The poor oxygen condition is, for example, that a layer capable of blocking oxygen (for example, a temporary support remaining without being removed during exposure when an oxygen blocking layer or a photosensitive transfer material is used) is provided on the photosensitive resin layer. Or by using an inert gas atmosphere or a reduced-pressure atmosphere. In particular, it is preferable to perform exposure under an anoxic condition formed by adjusting to an inert gas atmosphere or a reduced pressure atmosphere.

An anoxic condition refers to an inert gas atmosphere, a reduced pressure, or a layer capable of blocking oxygen.
The inert gas refers to a general gas such as N ₂ , H ₂ or CO ₂ or a rare gas such as He, Ne or Ar. Among these, N ₂ is preferable from the viewpoints of safety, availability, and cost.
The term “under reduced pressure” refers to a state of 500 hPa or less, preferably 100 hPa or less.
In addition, as the layer capable of blocking oxygen, the oxygen blocking layer in the photosensitive transfer material described above and various films can be applied, for example, polyesters including polyethylene terephthalate (PET), nylon, and the like. Also suitable are polyamides and ethylene-vinyl acetate copolymers (EVAs). These films may be stretched as necessary, and the thickness is suitably 5 to 300 μm, preferably 20 to 150 μm. In the case where the partition walls are produced using the photosensitive transfer material, the hypoxic condition is formed by providing the temporary support and / or the oxygen blocking layer on the photosensitive resin layer.

  For the exposure, for example, a proximity type exposure machine (for example, manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultrahigh pressure mercury lamp can be used. Examples of the light source include medium to ultra high pressure mercury lamps, xenon lamps, metal halide lamps, and the like.

The illuminance, preferably at 25 mW / cm ² or more, and particularly preferably 80 mW / cm ² or more. From the viewpoint of obtaining the effects of the present invention, there is no particular upper limit value of the illuminance, and the illuminance can be increased to a desired illuminance if there is no problem with the apparatus and equipment. The illuminance can be adjusted to the above range by a method such as increasing the output of the light source, increasing the number of light sources, or reducing the distance between the light source and the object to be exposed.

  After the exposure, development processing is performed using a developer to form a pattern image on the photosensitive resin layer. Thereafter, a water washing process is performed as necessary.

  Prior to development, it is preferable that pure water is sprayed on the photosensitive resin layer with a shower nozzle or the like to uniformly wet the surface of the photosensitive resin layer. A dilute aqueous solution of an alkaline substance is preferably used as the developer used for the development process, but a solution containing a small amount of a water miscible solvent may be added.

  Examples of the alkaline substance include alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide), alkali metal carbonates (for example, sodium carbonate, potassium carbonate), alkali metal bicarbonates (for example, sodium bicarbonate, Potassium hydrogen carbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali metal metasilicates (eg, sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, 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 solvent” include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, Preferable examples include benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, and N-methylpyrrolidone. The concentration of the water-miscible solvent is preferably 0.1 to 30% by mass.
Further, a known surfactant may 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 a wet sponge in the developer can be combined. The 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 a solvent is added. Within this range, a partition having a suitable shape can be obtained. In other words, if the development time is too short, the development of the area to be developed and removed may be insufficient, and at the same time, the absorbance of the ultraviolet rays may be insufficient. is there. It is also possible to put a water washing step after the development processing.

  The height of the partition wall in the present invention is preferably 1.0 to 6.0 μm, and more preferably 1.5 to 5.0 μm, in terms of the height in the substrate normal direction. When the height is within the above range, when the colored region (pixel) is formed by ink jetting as described above, it is difficult for the ink to get over the partition wall, the ink oozes or protrudes, and between adjacent pixel patterns. Is effective in forming a color filter having a good hue and a high display quality.

  The width of the partition wall in the present invention is preferably 5.0 μm or more and 50 μm or less in the direction orthogonal to the normal direction of the substrate. And the variation width of the thickness in the substrate normal direction of the colored region (R pixel, G pixel, B pixel, etc.) within 10 μm in the direction parallel to the substrate surface from the end of the partition wall (for example, the end surface) is 0.5 μm or less. It is preferable that When the fluctuation range is within the above range, it is possible to effectively prevent display unevenness such as color unevenness in an image when the image is displayed by being incorporated in a display device such as a liquid crystal display device. This fluctuation range is preferably 0.4 μm or less, and can be adjusted by adding a surfactant to the ink forming the colored pixels.

Hereinafter, the example which forms a partition is demonstrated concretely.
1) Formation of partition walls by coating with dark color composition After cleaning the substrate, the substrate is heat treated to stabilize the surface state. Thereafter, the temperature of the substrate is adjusted, and the dark color composition is applied onto the temperature-controlled substrate. After coating, part of the solvent in the coating layer is dried to eliminate the fluidity of the layer, and then the unnecessary coating solution around the substrate is removed with EBR (edge bead remover), etc., and pre-baked for photosensitivity. A functional resin layer is obtained. The coating can be performed using a known glass substrate coater (for example, MH-1600 manufactured by FAS Asia) provided with a slit-like nozzle. Moreover, drying can be performed by a known drying apparatus (for example, VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.)), and prebaking can be performed by heating at 120 ° C. for 3 minutes, for example. The layer thickness of the photosensitive resin layer is as described above.
Subsequently, in a state where the substrate on which the photosensitive resin layer is formed and a mask having a pattern (for example, a quartz exposure mask) are vertically set, a distance between the mask surface and the photosensitive resin layer is appropriately set (for example, 200 μm). Exposure is performed under a nitrogen atmosphere by setting, purging with nitrogen, and controlling the oxygen partial pressure. The exposure can be performed by, for example, a proximity type exposure machine (for example, manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultrahigh pressure mercury lamp, and the exposure amount can be appropriately selected (for example, 300 mJ / cm ² ). The oxygen partial pressure at this time can be measured using an oxygen meter (for example, G-102 type manufactured by Iijima Electronics Co., Ltd.). After exposure, development processing is performed with a developing solution to obtain a pattern image, and washing is performed as necessary to obtain partition walls.

2) Formation of partition wall by transfer method using photosensitive transfer material First, the protective film of the photosensitive transfer material is peeled and removed, and the surface of the exposed photosensitive resin layer is superimposed on the substrate surface and passed through a laminator or the like. Heat and / or press to form a laminate. The laminator can be appropriately selected from conventionally known laminators, vacuum laminators, and the like, and an auto-cut laminator can also be used from the viewpoint of increasing productivity. Next, the temporary support is peeled off from the laminate. Subsequently, a desired photomask (for example, a quartz exposure mask) is disposed above the exposed surface (oxygen barrier layer surface) exposed by removing the temporary support, and a pattern is formed through the mask under reduced oxygen conditions under reduced pressure. Are irradiated with ultraviolet rays, and after the irradiation, development processing is performed using a predetermined processing solution to obtain partition walls. At this time, a water washing process is performed as needed. The developer used for the development process and the light source used for the exposure are the same as the developer and the light source used in the coating method.

-Plasma treatment process-
In the method for producing a color filter of the present invention, plasma treatment is performed for the purpose of imparting ink repellency to the substrate on which the partition walls are formed as described above. By providing ink repellency to the upper surface of the partition wall, it is possible to effectively prevent the occurrence of “color mixing”. Examples of the plasma treatment include a batch-type treatment with reduced pressure (decompression plasma treatment) and a continuous-type treatment without pressure reduction (atmospheric pressure plasma treatment). In particular, atmospheric pressure plasma treatment is preferred.

(1) Low-pressure plasma treatment As a gas containing at least fluorine atoms introduced in this step, halogen selected from CF ₄ , CHF ₃ , C ₂ F ₆ , SF ₆ , C ₃ F ₈ , and C ₅ F ₈ It is preferable to use one or more gases. In particular, C ₅ F ₈ (octafluorocyclopentene) has an ozone depletion ability of 0, and at the same time, has an atmospheric life (CF ₄ : 50,000 years, C ₄ F ₈ : 3200 years) as compared with conventional gases. It is very short with 98 years. Therefore, the global warming potential is 90 (100-year integrated value assuming CO ₂ = 2), which is very small (CF ₄ : 6500, C ₄ F ₈ : 8700) compared to conventional gases, and the ozone layer and the global environment It is extremely effective for protection and is desirable for use in the present invention.

Further, as the introduced gas, a gas such as oxygen, argon, or helium may be used in combination as necessary. In this step, when a mixed gas of at least one halogen gas selected from CF ₄ , CHF ₃ , C ₂ F ₆ , SF ₆ , C ₃ F ₈ , and C ₅ F ₈ and O ₂ is used, It becomes possible to control the degree of ink repellency on the surface of the partition treated in this step. However, in the mixed gas, the oxidation reaction mixture ratio by O ₂ exceeds 30% of O ₂ is dominant, because the ink repellency enhancing effect is prevented, also, O ₂ mixing ratio is more than 30% When the mixed gas is used, it is necessary to use O ₂ in a range where the mixing ratio of O ₂ is 30% or less.

  As a method for generating plasma, methods such as low frequency discharge, high frequency discharge, and microwave discharge can be used. Conditions such as a pressure, a gas flow rate, an output, and a processing time during plasma processing can be arbitrarily set, but in order to achieve the effects of the present invention, the following conditions are more preferable.

  The pressure during the plasma treatment is preferably 10 to 100 Pa, more preferably 20 to 80 Pa, and further preferably 30 to 50 Pa. The gas flow rate is preferably 40 to 300 sccm, more preferably 50 to 200 sccm, and still more preferably 60 to 100 sccm. The output is preferably 10 to 100 W, more preferably 20 to 90 W, and even more preferably 30 to 80 W. The treatment time depends on the pressure and output, is preferably 20 to 200 sec, more preferably 20 to 100 sec, and further preferably 20 to 50 sec.

(2) Atmospheric pressure plasma treatment The atmospheric pressure plasma treatment is a process in which a reactive gas such as a hydrocarbon gas which is a gas at normal temperature is mixed with an inert gas such as helium, and plasma excitation is performed under atmospheric pressure. In the case of using a reactive gas of a gaseous compound at room temperature such as ethylene or CF _{4, the} surface treatment can be performed by a very stable glow discharge plasma at atmospheric pressure. is there.

In the atmospheric pressure plasma treatment, as the diluting gas (inert gas), any known inert gas can be used, and examples thereof include helium, neon nitrogen, argon, and lower aliphatic hydrocarbons. It is preferable to use argon and a lower aliphatic hydrocarbon in combination.
The lower aliphatic hydrocarbon used in combination with argon is preferably a methane-based hydrocarbon having 1 to 6 carbon atoms such as methane, ethane, propane, n-butane, iso-butane, pentane, Examples thereof include isopentane and neopentane, hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, among which methane, propane, n-butane and n-pentane are preferred. Used. Two or more of the above aliphatic hydrocarbons used together with argon may be used in combination.

  The reactive gas used in the atmospheric pressure plasma treatment is a gas that forms a polymer thin film on the surface of the object to be processed in a plasma-excited state, or a chemical compound that reacts with the surface of the object to be processed in a plasma-excited state. A gas or the like that reacts to form a thin film of a reaction product on the surface.

  Examples of reactive gases that form a polymer thin film on the surface of an object to be processed include α, β-unsaturated hydrocarbons such as ethylene, propylene, and styrene, and benzene, toluene, and the like that can cause plasma-excited radical polymerization. Aromatic hydrocarbons and the like can be exemplified.

Examples of the gas that forms a thin film of the reaction product on the surface of the object to be processed include halogenated hydrocarbons such as CF ₄ , C ₃ F ₆ , and CHF ₃ , silicon compounds such as monosilane, disilane, and trimethylchlorosilane. It can be illustrated.
Two or more kinds of the reactive gases may be mixed and used as necessary.

  The atmospheric pressure plasma treatment is performed by exciting a reactive gas by glow discharge to form high energy plasma. This plasma is formed by applying a high voltage, and the value of the voltage to be applied is appropriately determined according to the surface property of the object to be processed, the time of the surface treatment, etc., and is generally 1,000 to 8,000 V, for example. Is more preferable, and a voltage of 1,000 to 5,000 V is more preferable.

  The frequency of the power source is appropriately selected according to the type of material of the object to be processed, such as plastic, cotton, paper, metal, glass, ceramic, etc., but for example, 1 for a plastic object to be processed. 3,000 Hz to 10 GHz, 3,000 Hz to 10 GHz for metal objects such as silicon, and 1,000 Hz to 10 GHz are suitable for natural material objects such as cotton.

  The above atmospheric pressure plasma treatment does not require expensive helium, can use a relatively inexpensive inert gas composition mainly composed of argon, and performs highly stable glow discharge on the surface of the object to be treated. An excellent effect that treatment for imparting hydrophobicity can be performed is achieved.

  Further, the atmospheric pressure plasma treatment has an advantage that a hydrophobic polymer film or a hydrophobic reaction product film can be easily formed without much influence of oxygen.

  The atmospheric pressure plasma treatment is described in detail in paragraphs [0010] to [0024] of JP-A-6-41755.

-Pixel formation process-
In the pixel forming step, droplets of the ink composition for ink jet according to the present invention described above are applied to the gap (concave portion) between the partition walls by the ink jet method to form a colored region. This colored region is a color pixel of red (R), green (G), blue (B), etc. that constitutes the color filter.

  As described above, the colored region is formed as a colored liquid composition for forming colored pixels (for example, RGB three-color pixel pattern) in the recesses surrounded by the partition formed on the substrate as described above. The ink composition can be penetrated to form a plurality of pixels of two or more colors.

  As the ink jet method, known methods such as a method of thermally curing ink, a method of photocuring, and a method of ejecting droplets after forming a transparent image receiving layer on a substrate in advance can be used.

  In this step, the discharge amount to be discharged into the recess surrounded by the partition can be appropriately selected in order to obtain a desired hue and density, but preferably the size of one droplet is 0.1 to 100 pl. (Picoliter) is preferable, and 1 to 50 pl is more preferable.

  The shape of the color filter pattern is not particularly limited, and may be a general stripe shape as a partition (black matrix) shape, a lattice shape, or a delta array shape.

  As an ink jet method, a method in which charged ink is continuously ejected and controlled by an electric field, a method in which ink is ejected intermittently using a piezoelectric element, and a method in which ink is heated and ejected intermittently using its foaming Various methods can be employed.

  As the ink ejection conditions, it is preferable from the viewpoint of ejection stability that the ink is kept at 25 to 70 ° C. and ejected with a constant ink viscosity. Ink jet ink compositions generally have higher viscosities than aqueous inks, and therefore have a large viscosity fluctuation range due to temperature fluctuations. It is important to keep the ink temperature as constant as possible, since the viscosity variation directly affects the droplet size and the droplet ejection speed and easily causes image quality degradation.

  As the ink jet head (hereinafter also simply referred to as a head), a known one can be applied, and a continuous type or a dot on demand type can be used. Among the dot-on-demand types, the thermal head is preferably a type having an operation valve as described in JP-A-9-323420 for discharging. As the piezo head, for example, the 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 controlled. It is preferable to set the injection temperature so that the viscosity at the time of ejection is 5 to 25 mPa · s, and to control the ink temperature so that the fluctuation range of the viscosity is within ± 5%. Moreover, as a drive frequency, it is preferable to operate | move at 1-500 kHz.

  The color filter of the present invention is preferably in the form of a group composed of three colored regions (colored layers) by spraying at least RGB three colors of ink. In addition to the above RGB, pixels such as V (purple), W (transparent), C (cyan), Y (yellow), and M (magenta) can be appropriately formed.

-Curing process-
Next, processes that can be provided after the pixel formation process are described below. A description will be given of a case where three colored regions of RGB are formed.
<< First curing step >>
A step (first curing step) of irradiating and curing at least one colored region formed in the pixel forming step with active energy rays can be provided. In the first curing step, cured color regions (pixels) can be formed by curing curable inks of each color including red (R), green (G), and blue (B). Curing may be performed every time a colored region of one color is formed, or may be performed after forming colored regions of a plurality of colors.

  Curing of the curable ink according to the present invention such as R, G, B, etc. can be carried out by performing an exposure process that promotes polymerization using an energy source that emits active energy rays in a wavelength region corresponding to the photosensitive wavelength of the ink. The

  Examples of energy sources include 450-200 nm ultraviolet light, far ultraviolet light, g-line, h-line, i-line, KrF excimer laser light, ArF excimer laser light, electron beam, X-ray, molecular beam, or ion beam. Those to which the above-mentioned polymerization initiator is sensitive can be appropriately selected and used. Specifically, a light source that emits actinic rays belonging to a wavelength region of 250 to 450 nm, preferably 365 ± 20 nm, for example, LD, LED (light emitting diode), fluorescent lamp, low pressure mercury lamp, high pressure mercury lamp, metal halide lamp, carbon arc lamp. , Xenon lamps, chemical lamps and the like. Preferred light sources include LEDs, high pressure mercury lamps, and metal halide lamps.

The irradiation time of the active energy ray can be appropriately set according to the combination of the polymerizable compound and the polymerization initiator. For example, when exposure is performed at an illuminance of 20 mW / cm ² , the irradiation time is 1 to 750 seconds. Can do.
Irradiation of the active energy ray can be performed from either side of the substrate, but irradiation from the surface of the substrate (the surface of the substrate to which ink has been applied) can efficiently apply energy to the ink. This is preferable.

<< Second curing step >>
In the method for producing a color filter of the present invention, a step (second curing step) of curing all the colored regions of a desired hue including red (R), green (G), and blue (B) with heat. Can be provided. By providing the first curing step and the second curing step, it is possible to achieve both the production efficiency of the color filter and the display characteristics.

  In this step, a colored region and partition walls having a desired hue are formed, and after the first curing step, a heat treatment (so-called baking treatment) is further performed to cure by heat. That is, a substrate on which colored regions and partition walls photopolymerized by light irradiation are formed is put into an electric furnace, a dryer, or the like, or heated or irradiated with an infrared lamp.

  As the size of the colored region (pixel) formed by the method for producing a color filter of the present invention, the length of one side of the pixel is preferably 50 to 300 μm, more preferably 70 to 300 μm, and particularly preferably 100 to 300 μm. Alternatively, a stripe shape in which pixels of the same color are arranged in a vertical shape may be used.

  The heating temperature and heating time at this time depend on the composition of the ink composition for inkjet and the thickness of the colored region, but are generally 120 ° C. to 250 ° C. from the viewpoint of ensuring sufficient solvent resistance, alkali resistance, and ultraviolet absorbance. It is preferable to heat at 10 ° C. for 10 minutes to 120 minutes.

  The surface roughness (Ra value) of the colored region (colored layer) formed by inkjet application of the inkjet ink composition of the present invention is preferably 5 nm or less, more preferably 4 nm or less. This Ra value is measured by a contact film thickness meter (a stylus type surface roughness meter P10 manufactured by Tencor).

-Other processes-
The method for producing a color filter of the present invention includes a baking step (heat treatment and post-exposure described below) in which the formed partition walls and colored regions are further heated (baked) and cured, and an OC for forming an overcoat (OC) layer. Other steps such as a step may be provided.

~Heat treatment~
By performing heat treatment (also referred to as post-baking), it is possible to ensure the hardness of the partition walls by reacting the monomer or the crosslinking agent contained in the dark color composition or the photosensitive resin layer.
The temperature of the heat treatment is preferably in the range of 150 to 250 ° C. If the temperature is less than 150 ° C, the hardness may be insufficient, and if it exceeds 250 ° C, the resin may be colored and the color purity may be deteriorated. The heat treatment time is preferably 10 to 150 minutes. If the time is less than 10 minutes, the hardness may be insufficient, and if it exceeds 150 minutes, the resin may be colored and the color purity may deteriorate. The heat treatment may be changed depending on the color. Further, after all colors are formed by the above-described ink jet method, the final heat treatment may be further performed to stabilize the hardness. In that case, it is preferable from the point of hardness to implement at higher temperature (for example, 240 degreeC).

~ Post exposure ~
In the partition formation, post-exposure (also referred to as re-exposure) can be performed between development and heat treatment.
Post-exposure is preferable from the viewpoints of controlling the cross-sectional shape of the partition walls, controlling the hardness of the partition walls, controlling the surface roughness of the partition walls, and controlling the film thickness reduction of the partition walls. Examples of the light source used for the post-exposure include an ultra-high pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp described in paragraph No. [0074] of JP-A-2005-3861. In the post-exposure, it is preferable from the viewpoint of simplification of equipment and power saving that the substrate is directly irradiated with light from a light source such as an ultra-high pressure mercury lamp or a metal halide without using an exposure mask. If necessary, can be carried out from both sides of the substrate, in this case, the exposure amount, 100~5000mJ / cm ² on the upper side, in the range of 100~5000mJ / cm ² on the lower surface side, depending on the control object Can be adjusted accordingly.

  After forming the color filter by forming the colored region (colored pixel) and the partition as described above, an overcoat layer is formed so as to cover the entire surface of the colored region and the dark partition for the purpose of improving the durability. Can do.

The overcoat layer can protect the colored regions such as R, G, and B and the dark partition walls and can flatten the surface. However, it is preferably not provided from the point of increasing the number of steps.
An overcoat layer can be comprised using resin (OC agent), and acrylic resin composition, an epoxy resin composition, a polyimide resin composition etc. are mentioned as resin (OC agent). Among them, the acrylic resin composition is desirable because it is excellent in transparency in the visible light region, and the resin component of the photocurable composition for color filters is usually mainly composed of an acrylic resin, and has excellent adhesion. . Examples of the overcoat layer include those described in paragraphs [0018] to [0028] of JP-A No. 2003-287618, and commercially available overcoat agents such as Optomer SS6699G manufactured by JSR.

  The color filter of the present invention is produced by the method for producing the color filter of the present invention described above. For example, a television, a personal computer, a liquid crystal projector, a game machine, a mobile terminal such as a mobile phone, a digital camera, a car navigation system It can be suitably applied to applications such as without particular limitation.

<Display device>
As described above, the display device (liquid crystal display device or the like) of the present invention is formed using the color filter of the present invention, and the color filter of the present invention has good ITO sputtering suitability. Therefore, it is possible to obtain a high-quality display device with high contrast and suppressed color unevenness.
The display device of the present invention is not particularly limited except that it has the color filter, and components used in known display devices can be used.

  In addition to the color filter, it is configured by using various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film. Regarding these materials, for example, “'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Kentaro Shima, CMC Co., Ltd., published in 1994)”, “Current Status and Future Prospects of the 2003 Liquid Crystal Related Market (Volume 2) (Table Yoshiyoshi, Fuji Chimera Research Institute, Inc., published in 2003) ”.

  The display device of the present invention includes ECB (Electrically Controlled Birefringence), TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), OCB (OpticBandNitRic). Various display modes such as (Vertical Aligned), HAN (Hybrid Aligned Nematic), and GH (Guest Host) can be adopted.

  As a display device according to the present invention, for example, a liquid crystal display device includes a liquid crystal layer sandwiched between two substrates having conductive layers on opposite surfaces, and a liquid crystal alignment control protrusion and a spacer on the substrate. The liquid crystal layer can be provided so as to protrude from the conductive layer to the liquid crystal layer side. An alignment film can be formed on the conductive layer so as to cover them.

As a basic configuration aspect of the display device of the present invention, for example, (1) a driving side in which driving elements such as thin film transistors (hereinafter sometimes referred to as “TFTs”) and pixel electrodes (conductive layers) are arrayed is formed. A substrate and a color filter layer-side substrate including a color filter and a counter electrode (conductive layer), which are arranged to face each other with a spacer and a laminated portion interposed therebetween, and a liquid crystal material is sealed in the gap portion; (2 ) A color filter integrated drive substrate in which a color filter is directly formed on the drive side substrate and a counter substrate having a counter electrode (conductive layer) are arranged to face each other with a spacer and a laminated portion interposed therebetween, and a liquid crystal is provided in the gap portion. The thing etc. which enclose a material are mentioned.
Examples of the conductive layer include an ITO film; a metal film such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; a metal oxide film such as SiO _2. A membrane is particularly preferred.
The substrate can be used as the base material for the driving side substrate, the color filter layer side substrate, and the counter substrate.
As a driving side substrate in which driving elements such as TFTs and pixel electrodes are arranged, for example, TFTs and TFTs connected to data bus lines and gate bus lines arranged in a matrix so as to cross each other vertically are arranged. For example, a conductive layer connected to the data bus line may be provided.
In any of the above embodiments, a conductive layer is formed on both of the substrates constituting the liquid crystal display element, a voltage is applied between the two conductive layers, and the liquid crystal material sandwiched therebetween changes the alignment state according to the voltage. Display. Therefore, the liquid crystal alignment control protrusion described above can be formed on any conductive layer in a desired shape and form.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these. Unless otherwise specified, in the following examples, “part” represents “part by mass”, “%” represents “mass%”, and “molecular weight” represents “weight average molecular weight”.

[Example 1]
-Formation of partition walls-
(Preparation of dark color composition for barrier rib formation)
In the dark color composition K1, first, K pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 2 below are weighed, mixed at a temperature of 24 ° C. (± 2 ° C.), and stirred at 150 rpm for 10 minutes. Next, methyl ethyl ketone, cyclohexanone, binder 2, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) amino-3'- in the amounts shown in Table 2 Bromophenyl] -s-triazine, phenothiazine, surfactant 1 are weighed out and added in this order at a temperature of 25 ° C. (± 2 ° C.) and stirred at a temperature of 40 ° C. (± 2 ° C.) at 150 rpm for 30 minutes. can get.

In addition, the composition of Table 2 has the following composition in detail.
<K pigment dispersion 1>
・ Carbon black (Nippex 35 manufactured by Degussa) 13.1%
-Dispersant 1 (the following compound 1) 0.65%
・ Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio
Random copolymer, 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 500 ppm of polymerization inhibitor MEHQ, manufactured by Nippon Kayaku Co., Ltd.,
Product name: KAYARAD DPHA) 76%
・ Propylene glycol monomethyl ether acetate 24%

<Surfactant 1>
・ The following structure 1 30%
(N = 6, x = 55, y = 5, Mw = 33940, Mw / Mn = 2.55,
(PO: propylene oxide, EO: ethylene oxide)
・ 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 dark color prepared as described above with a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. Composition K1 was applied. Subsequently, a part of the solvent was dried with a VCD (vacuum dryer, 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 obtain a thick film with a thickness of 2.3 μm. The photosensitive resin layer K1 was obtained.
Subsequently, pattern exposure was performed with a mirror projection type exposure machine (MPA-8800CF, manufactured by Canon Inc.) at an exposure amount of 200 mJ / cm ² .
Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the dark photosensitive resin layer K1, and then a KOH developer (containing nonionic surfactant, trade name: CDK-1, Fuji). Film Electronics Materials Co., Ltd. 100-fold diluted) 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 from the upper surface with an exposure amount of 2500 mJ / cm ^{2 in the} atmosphere. Furthermore, it baked for 30 minutes in 230 degreeC oven, and obtained the partition (black matrix) with a film thickness of 2.0 micrometers and optical density 4.0.

(Ink-repellent plasma treatment)
The substrate on which the barrier ribs were formed was subjected to ink repellent plasma treatment under the following conditions using a cathode coupling parallel plate type plasma treatment apparatus.
Gas used: CF ₄
Gas flow rate: 80sccm
Pressure: 40Pa
RF power: 50W
Processing time: 30 sec

-Preparation of inkjet ink-
(Preparation of pigment dispersion)
First, the pigment dispersion for G (G1) was obtained by the following method.
Formulated in Brominated Phthalocyanine Green (CI Pigment Green 36) with Dispersant 1 (Compound 1) and 1,3-butanediol diacetate (1,3-BGDA) as a solvent as shown in Table 3 below. Then, after premixing, with a motor mill M-50 (manufactured by Eiger Japan), dispersed for 9 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm, and a pigment dispersion for G (G1) Was prepared.

Next, another dispersion was obtained by the following method.
In the preparation of the pigment dispersion for G (G1), the pigment dispersion for G (G2) was prepared in the same manner as in the preparation of the pigment dispersion for G (G1), except that the pigment and other components were blended as shown in Table 3. ), R pigment dispersions (R1) and (R2), and B pigment dispersions (B1) and (B2).

(Preparation of inkjet ink)
First, an inkjet ink for G was obtained by the following method.
As shown in the following Table 4, 1,3-butanediol diacetate (boiling point 232 ° C.), propylene glycol monomethyl ether acetate (PGMEA; boiling point 146 ° C.), 1,6-hexanediol diacrylate, the surfactant 1 , Heat polymerization initiator (V-40: azobis (cyclohexane-1-carbonitrile), manufactured by Wako Pure Chemical Industries, Ltd.) components were mixed and stirred at 25 ° C. for 30 minutes, and then it was confirmed that there was no insoluble matter A monomer solution was prepared.
Next, while stirring the pigment dispersion liquid for G (G1) and the pigment dispersion liquid for G (G2), the monomer liquid is slowly added and stirred at 25 ° C. for 30 minutes, and the inkjet ink for G (ink G- 1) was prepared.

  Next, an inkjet ink for R (ink R-1) and an inkjet ink for B (ink B-1) were prepared in the same manner as the preparation of ink G-1, except that the formulation was changed as shown in Table 4. The “1,3-BGDA” used for preparing the ink is “1,3-butanediol diacetate (boiling point 232 ° C.)”.

-Formation of pixel part by inkjet method-
Next, using the inks R-1, G-1, and B-1 described above, Dimatix Co., Ltd. is placed in the region (the concave portion surrounded by the convex portion) divided by the partition wall of the color filter substrate obtained above. Ink was discharged with a manufactured inkjet head (SE-128, head temperature 28 ° C.) until the desired concentration was reached, and dried on a 100 ° C. hot plate for 5 minutes. Further, the partition walls and the pixels were completely cured by baking in an oven at 230 ° C. for 30 minutes, and a color filter composed of R, G, and B patterns was produced.

[Color filter / Red pixel contrast measurement]
Here, the contrast of the red pixel of the color filter obtained above was measured by the following method (contrast 1).
A backlight unit using a three-wavelength cold-cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) and a diffuser plate between two polarizing plates (G1220DUN manufactured by Nitto Denko Corporation) A sample was placed and the amount of transmitted light was measured when the polarization axis was parallel and when the polarization axis was vertical, and the ratio was taken as contrast (“1990 7th Color Optical Conference, 512-color display 10.4” size TFT- LCD color filter, planting, Koseki, Fukunaga, Yamanaka ") For measuring the luminance, a color luminance meter (BM-7A manufactured by Topcon Corporation, with an attachment lens AL-11) was used. Two polarizing plates, a sample, and a color luminance meter are installed at a position 20 mm from the backlight, a polarizing plate is placed at a position 40 mm to 60 mm, and a cylinder 11 mm in diameter and 20 mm in length. Was measured with a color luminance meter placed in the center of the red pixel at a position of 88 mm through a polarizing plate set at a position of 67 mm. . The measurement angle of the color luminance meter was set to 0.1 °. The light quantity of the backlight was set so that the luminance when the two polarizing plates were installed in parallel Nicol was 36000 cd / m ² with no sample installed. The color filter substrate was placed with the glass side facing the backlight.

[Color filters / color mixing, evaluation of white spots]
In addition, the above color filter was observed using an optical microscope to observe whether any 3000 pixels had white spots and mixed colors, and evaluated according to the following criteria. Allowable is A rank, B rank or C rank for all items.
A rank: Nothing B rank: 1-2 places C rank: 3-4 places D rank: 5-10 places E rank: 11 places or more

[Evaluation of color filter / pixel level difference]
Next, the pixel shape (convex or flat) was evaluated.
The surface shape of an arbitrary red pixel was measured with a surface roughness meter P-10 manufactured by Tencor, and the difference in height between the most raised portion at the center of the pixel and the lowest portion of the pixel wrinkles was determined. The allowable step is 0.1 μm or less.

-Manufacture of liquid crystal displays-
A transparent electrode made of ITO (Indium Tin Oxide) was further formed by sputtering on the R pixel, G pixel, B pixel and partition wall (black matrix) of the color filter substrate obtained above.
Next, according to Example 1 of Japanese Patent Application Laid-Open No. 2006-64921, a spacer was formed in a portion corresponding to the upper part of the partition wall (black matrix) on the ITO film formed as described above.
Separately, a glass substrate was prepared as a counter substrate, patterned on the transparent electrode of the color filter substrate and the counter substrate for the PVA mode, and an alignment film made of polyimide was further provided thereon.
After that, a UV curable resin sealant is applied by a dispenser method at a position corresponding to the outer wall of the partition wall (black matrix) provided so as to surround the pixel group of the color filter. After bonding to the substrate, the bonded substrate was irradiated with UV and 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, FR1112H (chip type LED manufactured by Stanley Co., Ltd.) as a red (R) LED, DG1112H (chip type LED manufactured by Stanley Co., Ltd.) as a green (G) LED, and DB1112H (Stanley (as a blue (B) LED) A side-light type backlight was constructed using a chip type LED manufactured by Co., Ltd., and was placed on the back side of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display device.

[Display device / visual evaluation]
Here, whether or not the liquid crystal display device obtained as described above can normally display various images was visually evaluated according to the following criteria.
Excellent: Various images are displayed normally and the image feels particularly powerful.
Good: Various images are displayed normally.
Difficulties: There are difficulties such as visually seeing color irregularities and images appearing whitish.

[Display device / Red pixel contrast measurement]
Thereafter, the sample was carefully disassembled, the color filter was taken out, and the contrast of the red pixel was measured by the same method as above (contrast 2).

〔Comprehensive judgment〕
From the above evaluation, comprehensive evaluation was determined according to the following criteria.
A: No color mixing or white spots, pixels are flat, color filter and display device have very good contrast, and display quality is very high. ○: No color mixing or white spots, pixels are flat. Display device with good color filter and display device contrast and high display quality ○ ': No problem of mixed colors and white spots, flat pixels, good color filter and display device contrast, high display quality Display device x: Display device with low color display quality due to difficulty in color mixing, white spots, flatness, contrast, or contrast of display device

  The above evaluation results are shown in Table 9 and Table 10 below.

[Examples 2-7, Comparative Examples 1-3]
In Example 1, a color filter and a liquid crystal display device were produced and evaluated in the same manner as in Example 1 except that the monomers and surfactants in the ink were changed to those shown in Table 9 and Table 10 below.

[Example 8]
In the preparation of the inkjet ink (inks B-1, R-1 and G-1) of Example 5, the addition amount of the surfactant 1 (amount described in Table 4) was changed to 0.3 part. Produced and evaluated a color filter and a liquid crystal display device in the same manner as in Example 5.

[Example 9]
In the preparation of the inkjet inks (inks B-1, R-1 and G-1) of Example 5, the addition amount of the surfactant 1 (amount described in Table 4) was changed to 3.2 parts. Produced and evaluated a color filter and a liquid crystal display device in the same manner as in Example 5.

[Example 10]
A color filter and a liquid crystal display device were produced and evaluated in the same manner as in Example 5 except that the ink repellent treatment method was changed to the method described below.

(Ink-repellent plasma treatment)
Ink repellency treatment of the partition walls was performed using an apparatus in which the atmospheric pressure plasma apparatus shown in FIG. 1 of JP-A-7-111195 was enlarged to a volume of 1200 L. As conditions, the introduced gas was mixed with argon gas as an inert gas, and further propane gas was mixed in order to stabilize glow discharge. The mixing rate is 2.4 L / min of propane gas with respect to 600 L / min of argon gas. After the air was completely replaced with this mixed gas, CF ₄ gas (tetrafluoromethane) was introduced at a rate of 18 L / min, and a high frequency voltage of 5000 V was applied between the upper and lower electrodes. The frequency was 13.5 MHz and the irradiation time was 20 seconds. An orange glow discharge occurred and was extremely stable.

[Example 11]
A color filter and a liquid crystal display device were produced and evaluated in the same manner as in Example 5 except that the method for forming the partition walls was changed as follows.

-Formation of partition walls-
(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 C 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 K1 described in Table 2 was applied and dried. Thus, on the temporary support, a thermoplastic resin layer having a dry film thickness of 14.6 μm, an oxygen barrier layer having a dry film thickness of 1.6 μm, and a photosensitive resin layer having a dry film thickness of 2.3 μm. Finally, a protective film (12 μm thick polypropylene film) was pressure-bonded.
Thus, a photosensitive transfer material K1 in which the temporary support, the thermoplastic resin layer, the oxygen blocking layer, and the black (K) photosensitive resin layer were integrated was produced.

<Coating liquid for thermoplastic resin layer: Formulation C>
・ Methanol 11.1 parts ・ Propylene glycol monomethyl ether 6.36 parts ・ Methyl ethyl ketone 52.4 parts ・ Methyl methacrylate / 2-ethylhexyl acrylate /
Benzyl methacrylate / methacrylic acid copolymer (copolymerization 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. Compound obtained by dehydration condensation of 2 equivalents of pentaethylene glycol monomethacrylate with bisphenol A (BPE-500, Shin-Nakamura Chemical Co., Ltd.) 9.1 parts. Activator 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 BASF, K-30) 14.9 parts, distilled water 524 parts, methanol 429 parts

(Formation of partition walls)
A glass cleaner liquid adjusted to 25 ° C. is sprayed onto an alkali-free glass substrate with a shower for 20 seconds while being washed with a rotating brush having nylon bristles. After washing with pure water, silane coupling liquid (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.
After peeling off the protective film of the photosensitive transfer material K1, a substrate heated at 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)), rubber roller temperature 130 ° C., linear pressure 100N / Cm, laminating at a conveyance speed of 2.2 m / min.
Subsequently, the PET temporary support was peeled off at the interface with the thermoplastic resin layer, and the temporary support was removed. After peeling off the temporary support, pattern exposure was performed with an exposure amount of 90 mJ / cm ^{2 using} a mirror projection type exposure machine (MPA-8800CF, manufactured by Canon Inc.).
Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the photosensitive resin layer K1, and then a KOH developer (KOH, containing nonionic surfactant, trade name: CDK-1 ( (Fujifilm Arch) diluted 100 times with pure water) 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 ultrahigh pressure washing nozzle to remove residues, and an image of matrix-like black (K) was obtained. Thereafter, the substrate is further post-exposed with 1000 mJ / cm ² light from the side of the resin layer with an ultrahigh pressure mercury lamp, and further 1000 mJ / cm with an ultrahigh pressure mercury lamp from the side opposite to the resin layer. Post-exposure was performed with the light of No. ² , and then heat treatment was performed at 220 ° C. for 30 minutes to form partition walls.

[Example 12]
In the preparation of the inkjet ink (inks B-1, R-1 and G-1) of Example 5, the thermal polymerization initiator (V-40) was changed to 2,4-bis (trichloromethyl) -6- [4 ′. -(N, N-bisethoxycarbonylmethyl) amino-3'-bromophenyl] -s-triazine, and the curing method of the pixel was changed from "30 minutes baking in 230 ° C oven" to the following method. A color filter and a liquid crystal display device were produced and evaluated in the same manner as in Example 5 except for the change.

-Pixel curing method (exposure)-
The ink-jet ink (inks B-1, R-1, and G-1) is desired in the region (the concave portion surrounded by the convex portion) divided by the partition wall of the color filter substrate in the same manner as in Example 5. After being discharged to a density of 1, after drying in the same manner as in Example 5, the entire surface was exposed from the substrate surface (the surface on which the ink was applied to the substrate) with an ultrahigh pressure mercury lamp at an exposure amount of 110 mJ / cm ^2. Was cured. Next, the color filter was baked in an oven at 230 ° C. for 30 minutes to completely cure both the partition walls and the pixels.

[Example 13]
Evaluation was performed in the same manner as in Example 11 except that the manufacturing method of the liquid crystal display device was changed as follows.

-Manufacture of liquid crystal displays-
An ITO (Indium Tin Oxide) transparent electrode was further formed by sputtering on the R pixel, G pixel, and B pixel of the color filter substrate and the partition wall. Separately, a glass substrate was prepared as a counter substrate, and an ITO transparent electrode was similarly formed by sputtering. Then, a photo spacer was provided in a portion corresponding to the upper part of the partition on the ITO transparent electrode, and an alignment film made of polyimide was further provided thereon.

(Formation of liquid crystal alignment split projections)
A projection photosensitive resin layer coating solution having the following formulation A was applied onto the ITO transparent electrode on the color filter by the same slit coater as described above, and dried to form a projection photosensitive resin layer.
Next, a protective layer having a dry film thickness of 1.6 μm was provided on the protrusion photosensitive resin layer by using the oxygen barrier layer coating solution having the formulation P1.

<Coating liquid for photosensitive resin layer for protrusions: Formulation A>
-Positive resist solution 53.3 parts (FH-2413F, manufactured by FUJIFILM Electronics Materials Co., Ltd.)
-Methyl ethyl ketone-46.7 parts-Surfactant 1-0.04 parts

Pattern exposure was performed with an exposure amount of 150 mJ / cm ^{2 using a} mirror projection type exposure machine (MPA-8800CF, manufactured by Canon Inc.).
Thereafter, a 2.38% tetramethylammonium hydroxide aqueous solution was developed by spraying on the photosensitive resin layer for protrusions at 33 ° C. for 30 seconds in a shower type developing device, and an unnecessary portion (exposure) of the photosensitive resin layer for protrusions was exposed. Part) was developed and removed. Then, protrusions patterned in a desired shape were formed on portions above the R, G, and B pixels on the ITO transparent electrode of the color filter. Next, the color filter substrate on which the protrusions are formed is baked at 240 ° C. for 50 minutes, so that the height of the color filter substrate is 1.5 μm and the vertical cross-sectional shape (surface parallel to the normal direction of the glass substrate surface). Can be formed.

  After that, a UV curable resin sealant is applied to the position corresponding to the outer wall of the partition wall that surrounds the pixel group of the color filter by a dispenser method, and the MVA mode liquid crystal is dropped and bonded to the counter substrate. The bonded substrate was irradiated with UV and then heat-treated to cure the sealant. A liquid crystal cell was thus obtained. A polarizing plate HLC2-2518 (manufactured by Sanritz Co., Ltd.) was pasted on both sides of this liquid crystal cell, and then arranged on the back surface side of the liquid crystal cell provided with the polarizing plate by constituting a backlight of a cold cathode tube, A liquid crystal display device was obtained.

[Example 14]
The production was evaluated in the same manner as in Example 5 except that the surfactant was changed to a silicon-based surfactant Paintad 32 (manufactured by Toray Dow Corning) containing an alkylene oxide structure. Specifically, the surfactant 1 in Table 4 was changed to Paintad 32, and the addition amount was changed from 1.0 part by mass to 0.3 part by mass (the surfactant solid content is the same as that of Example 5).

[Example 15]
The production was evaluated in the same manner as in Example 5 except that the ink was changed as follows.

(Production Example A: Synthesis of Polymer (A-1))
In a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, 41.0% of the solvent diethylene glycol monobutyl ether acetate (also called butyl carbitol acetate, BCA) containing no hydroxyl group was added according to the blending ratio shown in Table 5. A mass part was charged and heated with stirring to 140 ° C. Next, 54.7 parts by mass of a monomer having a composition described in Table 5 and a polymerization initiator mixture (dropping component) at a temperature of 140 ° C. was dropped at a constant rate from a dropping funnel over 2 hours. After completion of the dropwise addition, the temperature was lowered to 110 ° C., 5.0 parts by mass of a mixture of polymerization initiator and solvent-free diethylene glycol monobutyl ether acetate (BCA) containing no hydroxyl group (additional catalyst component) was added, and the temperature at 110 ° C. was maintained for 2 hours. By the way, the main polymer (A-1) was obtained by terminating the reaction. The weight average molecular weight was 4200.

The abbreviations in the table are as follows.
GMA: glycidyl methacrylate MMA: methyl methacrylate MEA: methoxyethyl acrylate perbutyl O: t-butylperoxy-2-ethylhexanoate (manufactured by NOF Corporation)
Moreover, a weight average molecular weight is the value of polystyrene conversion by gel permeation chromatography.

(Production Example B: Synthesis of Blocked Carboxylic Acid Compound (B-1))
A four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel is charged with a solvent, a raw material (polybasic carboxylic acid), and a blocking agent (vinyl ether) according to the mixing ratio shown in Table 6, while stirring. It heated and heated up at 70 degreeC. Next, stirring was continued while maintaining a temperature of 70 ° C., and the reaction was terminated when the acid value of the mixture became 5 or less. A blocked carboxylic acid compound (B-1) was obtained. The acid value was 1.3 and the blocking rate was 99.5%.

The acid value of the solution was calculated by titration with a 0.1 N · KOH ethanol solution.
The blocking rate was calculated in terms of solid content from the acid value of the solution.
The block acid solid content was measured by gas chromatography (GC).

(Preparation of pigment dispersion)
A pigment dispersion (G3, G4, R3, R4, B3, B4) was prepared in the same manner as in Example 1 except that the formulation was changed as shown in Table 7 below.

(Preparation of inkjet ink)
According to the blending ratio shown in Table 8, the polymer (A-1) described in Preparation Example A, the blocked carboxylic acid (B-1) described in Preparation Example B, a polyfunctional epoxy resin (Ep # 157), and halogen-free The acidic catalyst (LC-1) was added and sufficiently stirred and dissolved at room temperature to obtain an ink.

Abbreviations in the table are as follows.
Ep # 157: tetrafunctional epoxy resin (trade name Epicoat 157S70, manufactured by Japan Epoxy Resin Co., Ltd.)
LC-1: Product name Novucure LC-1 (Nippon Yushi Co., Ltd.)

  The red pixel of the color filter after measuring contrast 2 was peeled off from the substrate with a 12% hydrofluoric acid aqueous solution, washed with water, dried, embedded in resin, and an ultrathin slice having a thickness of 20 nm was obtained. Cut out. This sample was photographed by TEM (100,000 times) and the number average particle diameter of the pigment (CIPR 254) was measured to be 37 nm.

[Example 16]
It was produced and evaluated in the same manner as in Example 5 except that the surfactant was changed to a fluorosurfactant surfactant 251 (manufactured by Neos) containing an ethylene oxide structure. Specifically, the surfactant 1 in Table 4 was changed to the detergent 251 and the addition amount was changed from 1.0 part by mass to 0.3 part by mass (the surfactant solid content is the same as in Example 5). .

[Example 17]
The production was evaluated in the same manner as in Example 5 except that the surfactant was changed to a fluorosurfactant polyfox 652 (OMNOVA, PF652) containing an ethylene oxide structure. Specifically, the surfactant 1 in Table 4 was changed to Polyfox 652, and the addition amount was changed from 1.0 part by mass to 0.6 parts by mass (the surfactant solid content was the same as in Example 5). .

The abbreviations in Table 9 and Table 10 are as follows.
EF802: Fluorosurfactant containing a C8 perfluoroalkyl group and polyethylene oxide / polypropylene oxide structure Neugen EA80: Non-fluorine surfactant containing polyethylene oxide / polypropylene oxide structure

Claims (12)

A method for producing a color filter having a plurality of pixels and a partition wall between adjacent pixels on a substrate, wherein the method comprises at least the following steps a), b) and c) in this order: Method.
a) Step of forming partition walls made of a resin composition on the substrate b) Step of performing plasma treatment on the substrate on which the partition walls have been formed c) At least C. is formed in the gap between the partition walls formed on the substrate. I. A step of forming a pixel by applying an inkjet ink containing Pigment Red 254, a solvent, a surfactant, and a monomer having two or more polymerizable groups by an inkjet method   The method for producing a color filter according to claim 1, wherein the plasma treatment is an atmospheric pressure plasma treatment.   The method for producing a color filter according to claim 1 or 2, wherein the monomer is a monomer having three or more polymerizable groups.   The method for producing a color filter according to claim 1, wherein the polymerizable group is a group having an ethylenic double bond.   The method for producing a color filter according to claim 1, wherein the polymerizable group is an epoxy group.   The method for producing a color filter according to claim 1, wherein the polymerizable group is at least one selected from an acryloyl group and a methacryloyl group.   The method for producing a color filter according to claim 1, wherein the inkjet ink contains at least one selected from a photopolymerization initiator and a thermal polymerization initiator.   The method for producing a color filter according to claim 1, wherein the surfactant contains fluorine. The surfactant comprises at least one of a structural unit a derived from a monomer represented by the following general formula (a) and at least one of a structural unit b derived from a monomer represented by the following general formula (b). It contains and contains at least 1 type of the copolymer whose mass ratio (a / b) of the structural unit a and the structural unit b is 20 / 80-80 / 20, Any one of Claims 1-8 characterized by the above-mentioned. The manufacturing method of the color filter of Claim 1.

In the general formula (a), R ¹ represents a hydrogen atom or a methyl group. Further, _-C m _{F 2m + 1} in the general formula (a) is a straight or branched chain. m represents an integer of 2 to 14. n represents an integer of 1 to 18.
In General Formula (b), R ² and R ³ each independently represent a hydrogen atom or a methyl group, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p and q each independently represent an integer of 0 to 18, and p and q do not represent 0 (zero) at the same time. 10. The pixel according to claim 1, wherein after the step c), the ink composition is polymerized through at least one step selected from the following d) and e) to form a pixel. The manufacturing method of the color filter of description.
d) Step of irradiating active energy rays after the solvent in the ink is removed e) Step of heating   A color filter produced by the production method according to claim 1.   A display device comprising the color filter according to claim 11.