JPWO2018062105A1 - Photosensitive colored resin composition for color filter, color filter, and display device - Google Patents

Abstract

（一般式（１）の各符号は、明細書に記載のとおりである。）Provided is a photosensitive colored resin composition for a color filter which can form a colored layer having improved brightness and has a good sensitivity. A color, comprising a color material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, wherein the photoinitiator contains an oxime ester compound represented by the following general formula (1) Photosensitive colored resin composition for filters.

(Each symbol of General Formula (1) is as described in the specification.)

Description

  The present invention relates to a photosensitive colored resin composition for color filters, a color filter, and a display device.

In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of mobile displays (mobile phones, smartphones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding. Further, recently, an organic light emitting display device such as an organic EL display having high visibility due to self light emission is also attracting attention as a next generation image display device. In the performance of these image display devices, further improvement in image quality and reduction in power consumption are strongly desired.
Color filters are used for these liquid crystal display devices and organic light emitting display devices. For example, in the formation of a color image of a liquid crystal display device, light passing through a color filter is colored as it is to the color of each pixel constituting the color filter, and light of those colors is combined to form a color image. As a light source at that time, in addition to a conventional cold cathode tube, an organic light emitting element emitting white light or an inorganic light emitting element emitting white light may be used. In addition, in the organic light emitting display device, a color filter is used for color adjustment and the like.

  As a trend in recent years, power saving of the image display apparatus is required, and in order to improve the utilization efficiency of the backlight, the luminance enhancement of the color filter is particularly required. This is particularly a big issue for mobile displays (mobile phones, smart phones, tablet PCs).

Here, a color filter is generally formed on a substrate, a colored layer formed on the substrate and made of colored patterns of three primary colors of red, green and blue, and a substrate so as to separate each colored pattern. And a light shielding portion.
As a method of forming a colored layer in a color filter, for example, a colored resin composition obtained by adding a binder resin, a photopolymerizable compound and a photoinitiator to a coloring material dispersion obtained by dispersing a coloring material with a dispersing agent etc. After coating and drying on a glass substrate, exposure is performed using a photomask, and development is performed to form a colored pattern, and the pattern is fixed by heating to form a colored layer. These steps are repeated for each color to form a color filter.

  Even in color filters, while the demand for higher luminance is increasing, the concentration of coloring material in the colored layer of the color filter is higher than in the prior art, so the components required for photopolymerization relatively decrease, making patterning difficult. It has become to. Furthermore, in order to improve the productivity of color filters, it is required to reduce the integrated exposure amount required for patterning, and how to secure the curability necessary for patterning becomes a major issue.

  As a method of obtaining a colored resin composition capable of achieving high sensitivity, it has been proposed to use an oxime ester photoinitiator. For example, Patent Document 1 proposes an oxime ester compound having a specific structure containing a carbazole skeleton. Patent Document 2 proposes an oxime ester fluorene compound having a specific structure in which an oxime ester group is bonded to a fluorene skeleton without a carbonyl group. Patent Document 3 proposes an oxime ester compound having a specific substituent including a diphenyl sulfide skeleton or a carbazole skeleton and containing a cycloalkyl group in an oxime ester group.

Patent No. 3992725 gazette Japanese Patent Application Publication No. 2015-523318 Chinese Patent Application Publication No. 103293855

  However, conventional colored resin compositions using oxime ester photoinitiators tend to have insufficient brightness. In particular, the conventional oxime ester type photoinitiator having high sensitivity tends to lower the luminance. On the other hand, oxime ester type photoinitiators whose brightness tends to be relatively good are low in sensitivity, and the influence of oxime ester type photoinitiators on sensitivity and brightness has a trade-off relationship. Therefore, there is a need for a colored resin composition that can achieve high sensitivity and can form a colored layer with even higher brightness.

  The present invention has been made in view of the above situation, and it is possible to form a colored layer with improved brightness, and a photosensitive colored resin composition for color filter having good sensitivity, and a photosensitive colored resin composition for the color filter It is an object of the present invention to provide a color filter having a colored layer formed using an object, and a display device using the color filter.

The photosensitive colored resin composition for color filters according to the present invention contains a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent.
The said photoinitiator contains the oxime ester compound represented by following General formula (1).

（一般式（１）において、Ｒ^ａ及びＲ^ｂはそれぞれ独立に、水素原子又はアルキル基であり、Ｒ^ｃは、チオエーテル結合（−Ｓ−）、エーテル結合（−Ｏ−）及びカルボニル結合（−ＣＯ−）から選択される少なくとも１種の２価の連結基を含んでいてもよい炭化水素基であり、Ｚは、水素原子又は−（Ｃ＝Ｏ）Ｒ^ｄであり、Ｒ^ｄは酸素原子及び硫黄原子から選択される少なくとも１種を含んでいてもよい炭化水素基、又は、窒素原子を含まず、酸素原子及び硫黄原子から選択される少なくとも１種を含む複素環基であり、Ｒ^ｅは、炭素数１〜１０の炭化水素基である。）

(In the general formula (1), R ^a and R ^b are each independently a hydrogen atom or an alkyl group, R ^c is a thioether bond (-S-), an ether bond (-O-) and a carbonyl bond (- A hydrocarbon group which may contain at least one kind of divalent linking group selected from CO-), Z is a hydrogen atom or-(C = O) R ^d , and R ^d is an oxygen atom And a hydrocarbon group which may contain at least one selected from sulfur, or a heterocyclic group containing no nitrogen, at least one selected from oxygen and sulfur, R ^e Is a hydrocarbon group having 1 to 10 carbon atoms.)

The color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a photosensitive colored resin composition for a color filter according to the present invention. It is a colored layer which consists of a cured product of the product.
The present invention also provides a display device having the color filter according to the present invention.

  According to the present invention, it is possible to form a colored layer having improved brightness, and a photosensitive colored resin composition for color filters having good sensitivity, and a color formed using the photosensitive colored resin composition for color filters A color filter having a layer and a display device using the color filter can be provided.

FIG. 1 is a schematic view showing an example of the color filter of the present invention. FIG. 2 is a schematic view showing an example of the liquid crystal display device of the present invention. FIG. 3 is a schematic view showing an example of the organic light emitting display device of the present invention.

Hereinafter, the photosensitive colored resin composition for color filters, the color filter, and the display device according to the present invention will be described in detail in order.
In the present invention, light includes electromagnetic waves of wavelengths in the visible and non-visible regions, and radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.
In the present invention, (meth) acrylic represents each of acrylic and methacrylic, and (meth) acrylate represents each of acrylate and methacrylate.
In the present specification, unless otherwise noted, the chromaticity coordinates x and y are in the XYZ color system of JIS Z8701 measured using a C light source.

I. Photosensitive Colored Resin Composition for Color Filter The photosensitive colored resin composition for color filter according to the present invention contains a coloring material, an alkali soluble resin, a photopolymerizable compound, a photoinitiator and a solvent,
The said photoinitiator contains the oxime ester compound represented by following General formula (1).

（一般式（１）において、Ｒ^ａ及びＲ^ｂはそれぞれ独立に、水素原子又はアルキル基であり、Ｒ^ｃは、チオエーテル結合（−Ｓ−）、エーテル結合（−Ｏ−）及びカルボニル結合（−ＣＯ−）から選択される少なくとも１種の２価の連結基を含んでいてもよい炭化水素基であり、Ｚは、水素原子又は−（Ｃ＝Ｏ）Ｒ^ｄであり、Ｒ^ｄは酸素原子及び硫黄原子から選択される少なくとも１種を含んでいてもよい炭化水素基、又は、窒素原子を含まず、酸素原子及び硫黄原子から選択される少なくとも１種を含む複素環基であり、Ｒ^ｅは、炭素数１〜１０の炭化水素基である。）

(In the general formula (1), R ^a and R ^b are each independently a hydrogen atom or an alkyl group, R ^c is a thioether bond (-S-), an ether bond (-O-) and a carbonyl bond (- A hydrocarbon group which may contain at least one kind of divalent linking group selected from CO-), Z is a hydrogen atom or-(C = O) R ^d , and R ^d is an oxygen atom And a hydrocarbon group which may contain at least one selected from sulfur, or a heterocyclic group containing no nitrogen, at least one selected from oxygen and sulfur, R ^e Is a hydrocarbon group having 1 to 10 carbon atoms.)

  The photosensitive colored resin composition for a color filter according to the present invention can form a colored layer with improved luminance by using the oxime ester compound represented by the above general formula (1) as a photoinitiator, which is favorable. Sensitivity. In addition, the photosensitive colored resin composition for color filters according to the present invention suppresses generation of development residues, and it is easy to simultaneously form desired micropores in the colored layer when patterning the colored layer. There is a merit.

The photosensitive colored resin composition for a color filter according to the present invention has no effect as described above by using the oxime ester compound represented by the above general formula (1) as a photoinitiator. It is elucidation, but it is presumed as follows.
The decrease in the brightness of the colored layer may be attributed to the coloration of the photoinitiator due to the reactive residue. In the past, oxime ester initiators with high sensitivity but insufficient brightness of the colored layer are presumed to have a structure in which the reaction residue of the photoinitiator is easily colored, such as having a carbazole skeleton, for example. Ru. On the other hand, since the oxime ester compound represented by the said General formula (1) used for this invention has a structure with the high transmittance | permeability whose reaction residue does not become a cause of coloration easily, coloring of the colored layer by reaction residue is carried out As a result, it is considered that a colored layer with improved brightness can be formed.
Further, since the oxime ester compound represented by the above general formula (1) used in the present invention has a fluorene skeleton and has an oxime ester group via a carbonyl group, the conjugated system of the structure has a brightness of It is estimated that the sensitivity is improved by the structure that improves the absorption intensity at the time of exposure without adversely affecting the Furthermore, the oxime ester compound represented by the above general formula (1) used in the present invention is a photopolymerization initiator that generates a methyl radical, and a photopolymerization initiator that generates an alkyl radical or an aryl radical having a large number of carbon atoms It is considered to have good sensitivity because radical migration occurs more rapidly than in the case of
Further, in the photosensitive colored resin composition for color filter of the present invention, the oxime ester compound represented by the above general formula (1) or the reactive residue thereof has high affinity to the aqueous alkali solution during alkali development. Since it is easy, it is estimated that the development residue is easy to be suppressed.
Moreover, the photosensitive coloring resin composition for color filters of this invention tends to form a desired fine hole in a colored layer simultaneously at the time of patterning a colored layer. When a more sensitive photoinitiator is used to form a colored layer, radicals are moved to the unexposed area after radicals are generated, and while maintaining the shape of the unexposed area inside the exposed area It is difficult to form the periphery of the exposed portion without flicker. Therefore, in the conventional photosensitive resin composition, it is difficult to form micropores, even if the linearity of the fine line pattern is good, if a high sensitivity photoinitiator capable of forming the fine line pattern is used. . In addition, as shown in Comparative Example 2 described later, when a relatively low-sensitivity photoinitiator is used, there is a problem that the residual film rate is lowered even though micropores can be formed. On the other hand, in the photosensitive colored resin composition for color filters of the present invention, micropores are easily formed by using the oxime ester compound represented by the general formula (1). In particular, by adjusting the content of the photoinitiator and the content of the antioxidant to be used in combination, it is possible to form micropores of a good shape more easily. The photosensitive colored resin composition for color filters of the present invention can easily form desired fine holes in the colored layer, so for example, in order to form a reflective color filter, the colored layer is formed on the TFT substrate, At the same time, it is also suitable for use in forming through holes in the colored layer for conduction.
Furthermore, the oxime ester compound represented by the general formula (1) used in the present invention has an oxime ester group in the fluorene skeleton without the carbonyl group in the fluorene skeleton by having the oxime ester group in the fluorene skeleton via the carbonyl group. As compared with the oxime ester compound having a bonded structure, the crystallinity is reduced, so that the solvent solubility and the solvent resolubility are improved, and the compatibility with other components is improved. By using a photoinitiator having improved solvent solubility, solvent resolubility, and compatibility with other components, the linearity of the fine line pattern can be improved, and the flicker of the micropores can be easily suppressed.
Moreover, since the oxime ester compound represented by the said General formula (1) has high thermal decomposition temperature, generation | occurrence | production of the outgas at the time of coating film heating can be suppressed. Therefore, the reliability of the resist is high, and, for example, when another layer such as a conductive film is further stacked on a coating film, damage due to outgassing of the stacked layer can be suppressed.

The photosensitive colored resin composition for color filter according to the present invention contains a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator and a solvent, and the effect of the present invention is impaired. Within the range, other components may be further contained.
Hereinafter, each component of the colored resin composition of the present invention will be described in detail in order from the above-mentioned photo-initiator characteristic of the present invention.

[Photo initiator]
<Oxime ester compound represented by the general formula (1)>
The photoinitiator used in the present invention contains the oxime ester compound represented by the general formula (1).

In the general formula (1), R ^a and R ^b are each independently a hydrogen atom or an alkyl group. From the viewpoint of solvent solubility and compatibility with other components, R ^a and R ^b are preferably each independently an alkyl group. The alkyl group may be any of linear, branched, cyclic, or a combination of these. As the alkyl group, for example, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, n-hexyl group, cyclopentyl group, methylcyclopentyl Group, cyclopentyl methyl group, cyclohexyl group and the like, and among them, an alkyl group having 2 to 6 carbon atoms is preferable, an alkyl group having 2 to 4 carbon atoms is more preferable, and still more preferably 2 carbon atoms. It is a -4 linear alkyl group.

In the above general formula (1), R ^c contains at least one divalent linking group selected from a thioether bond (-S-), an ether bond (-O-) and a carbonyl bond (-CO-) It is a hydrocarbon group which may be
Examples of the hydrocarbon group for R ^c, for example, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, and the like. The alkyl group may be linear, branched or cyclic, or may be a combination of linear and cyclic. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl and n-dodecyl. Groups, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclohexylmethyl, cyclopentylethyl, cyclohexylethyl, bornyl, isobornyl, dicyclopentanyl, adamantyl, lower alkyl substituted adamantyl, etc. it can. The alkenyl group may be linear, branched or cyclic, and examples thereof include a vinyl group, an allyl group and a propenyl group. Examples of the aryl group include phenyl group, biphenyl group, naphthyl group, tolyl group and xylyl group. Examples of the aralkyl group include benzyl group, phenethyl group, naphthylmethyl group and naphthylethyl group. The hydrocarbon group for R ^c is preferably a hydrocarbon group having 1 to 14 carbon atoms, and is preferably an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, and 6 to 10 carbon atoms. An aryl group is more preferable, and an alkyl group having 1 to 10 carbon atoms is even more preferable. Further, the hydrocarbon group in R ^c preferably has a carbon number of 2 or more from the viewpoint of improving the shape of the micropores when the micropores are formed in the colored layer. The hydrocarbon group in R ^c is preferably a structure containing a cyclic and linear alkyl group such as a cyclopentylmethyl group and a cyclohexylmethyl group from the viewpoint of solvent solubility and compatibility.
In the case of R ^c , when the hydrocarbon group contains the divalent linking group, solvent solubility and compatibility can be improved. Among the above, the divalent linking group is preferably a thioether bond (-S-) or an ether bond (-O-) from the viewpoint of improving solvent solubility. In R ^c , when the hydrocarbon group contains the divalent linking group, the hydrocarbon group may be bonded to a carbon atom of an oxime ester group through the divalent linking group, The carbon atom of the hydrocarbon group may be directly bonded to the carbon atom of the oxime ester group. In the case of R ^c , in the case where the hydrocarbon group contains the divalent linking group and the carbon atom of the hydrocarbon group is directly bonded to the carbon atom of the oxime ester group, for example, the R ^c is carbonized The case where it is the group which couple | bonded hydrogen groups by the said bivalent coupling group is mentioned. Examples of the group in which hydrocarbon groups are linked by a divalent linking group include an alkylthio alkyl group such as a methylthiomethyl group, and a thioether bond (—S—) such as an aryl thioalkyl group; a methoxymethyl group, Structure containing an ether bond (-O-) such as methoxycyclohexyl group, alkoxyalkyl group, aryloxyalkyl group etc .; structure containing a carbonyl bond (-CO-) such as acetylmethyl group, benzoylmethyl group, acylalkyl group And the like.

In the above general formula (1), Z is a hydrogen atom or — (COO) R ^d , and R ^d is a hydrocarbon group which may contain at least one selected from an oxygen atom and a sulfur atom, Or a heterocyclic group which does not contain a nitrogen atom and which contains at least one selected from an oxygen atom and a sulfur atom.
The at least one kind of which may contain a hydrocarbon group selected from an oxygen atom and a sulfur atom in the R ^d, for example, a hydrocarbon group described for R ^c, a hydrocarbon group described for R ^c And at least one type of linking group selected from linking groups containing an oxygen atom such as an ether bond (-O-), a carbonyl bond (-CO-) and the like, and a linking group containing a sulfur atom such as a thioether bond (-S-) And the like. Among them, hydrocarbon groups having 1 to 14 carbon atoms are preferable, and alkyl groups having 1 to 10 carbon atoms, aralkyl groups having 7 to 8 carbon atoms, and 6 to 10 carbon atoms are particularly preferable. The aryl group is more preferable, and the aryl group having 6 to 10 carbon atoms is even more preferable.
In addition, as the heterocyclic ring in a heterocyclic group which does not contain a nitrogen atom and contains at least one selected from an oxygen atom and a sulfur atom, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a thienothiophene ring, There may be mentioned furofuran ring, thienofuran ring and the like. The hydrocarbon group or the heterocyclic group for R ^d preferably has 1 to 10 carbon atoms from the viewpoint of developability.
Above all, Z is preferably a hydrogen atom from the viewpoint of developability and luminance. On the other hand, when Z is-(C = O) R ^d , solvent solubility and compatibility can be improved.

In the general formula (1), R ^e is a hydrocarbon group having 1 to 10 carbon atoms. Examples of the hydrocarbon group having 1 to 10 carbon atoms, for example, of the hydrocarbon group described for R ^c, include those having 1 to 10 carbon atoms. Among them, from the viewpoint of improving the sensitivity, R ^e is preferably an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and 1 to 4 carbon atoms. The alkyl group of is more preferred, and the methyl group is particularly preferred.

  The molecular weight of the oxime ester compound represented by the general formula (1) is not particularly limited, but is preferably 1,000 or less, and more preferably 800 or less from the viewpoint of reducing the content of the photoinitiator. Is preferred.

As the oxime ester compound represented by the general formula (1), for example, both R ^a and R ^b are alkyl groups having 1 to 4 carbon atoms, and R ^c is an alkyl group having 1 to 4 carbon atoms, Compounds in which Z is a hydrogen atom and R ^e is an alkyl group having 1 to 4 carbon atoms; R ^a and R ^b are both alkyl groups having 1 to 6 carbon atoms, and R ^c is a linear alkyl group and a cyclic group A compound having 4 to 10 carbon atoms in combination with an alkyl group, Z being a hydrogen atom, and R ^e being an alkyl group having 1 to 4 carbon atoms; R ^a and R ^b are both a hydrogen atom or carbon And R ^c is an alkyl group having 1 to 4 carbon atoms, Z is-(C = O) R ^d , and R ^d is an aryl group having 6 to 10 carbon atoms. , R ^e compound is an alkyl group having 1 to 4 carbon atoms; mentioned as preferred are such It is, but not limited thereto.

  As an oxime ester compound represented by the said General formula (1), at least 1 type chosen from following compound (1-1)-(1-4) is mentioned as a thing more preferable.

  For the oxime ester compound represented by the general formula (1), for example, referring to JP-A-2012-526185, fluorene or a derivative thereof is used in place of diphenyl sulfide or a derivative thereof, and it depends on the material used The synthesis can be performed by appropriately selecting the solvent, reaction temperature, reaction time, purification method and the like.

  The colored resin composition of the present invention is capable of forming a colored layer with improved luminance and having a good sensitivity, since the photo-initiator contains two or more kinds of oxime ester compounds not having a carbazole skeleton. It is preferable from the point which adjustment of the line width in the case of is easy. The oxime ester compound which does not have a carbazole skeleton can suppress the decrease in luminance of the colored layer because the reaction residue is less likely to cause coloring. Further, by appropriately selecting and combining two or more kinds of oxime ester compounds having different sensitivities, including the oxime ester compound represented by the general formula (1), it is possible to form a pattern while maintaining good sensitivity. The line width can be adjusted. When the colored resin composition of the present invention contains two or more types of oxime ester compounds having no carbazole skeleton, it is sufficient to include at least one type of oxime ester compound represented by the general formula (1). Two or more types of oxime ester compounds represented by 1) may be contained, and a carbazole different from the oxime ester compound represented by the general formula (1) and the oxime ester compound represented by the general formula (1) You may include in combination the oxime ester compound which does not have frame | skeleton.

Among them, using an oxime ester compound represented by the general formula (1) in combination with an oxime ester compound having a diphenyl sulfide skeleton does not significantly reduce the luminance, the developability, and the sensitivity. It is preferable from the point which is easy to improve a shape.
As the oxime ester compound having a diphenyl sulfide skeleton, for example, an oxime ester compound represented by the following general formula (2) can be suitably used.

（一般式（２）において、Ｒ^ｃ’及びＲ^ｆは、それぞれ独立に、チオエーテル結合（−Ｓ−）、エーテル結合（−Ｏ−）及びカルボニル結合（−ＣＯ−）から選択される少なくとも１種の２価の連結基を含んでいてもよい炭素数１〜１４の炭化水素基であり、Ｚ^１は、水素原子、ニトロ基又は−（Ｃ＝Ｏ）Ｒ^ｄ’であり、Ｒ^ｄ’は酸素原子及び硫黄原子から選択される少なくとも１種を含んでいてもよい炭化水素基、又は、窒素原子を含まず、酸素原子及び硫黄原子から選択される少なくとも１種を含む複素環基である。）

(In the general formula (2), R ^{c ′} and R ^f are each independently at least one selected from a thioether bond (—S—), an ether bond (—O—) and a carbonyl bond (—CO—) R ¹ is a hydrocarbon group having 1 to 14 carbon atoms which may contain a divalent linking group, Z ¹ is a hydrogen atom, a nitro group or — (C = O) R ^{d ′} and R ^{d ′} is It is a hydrocarbon group which may contain at least one selected from an oxygen atom and a sulfur atom, or a heterocyclic group which does not contain a nitrogen atom and contains at least one selected from an oxygen atom and a sulfur atom. )

At least one divalent linking group selected from a thioether bond (-S-), an ether bond (-O-) and a carbonyl bond (-CO-) of R ^{c '} and R ^f in the general formula (2) As the hydrocarbon group having 1 to 14 carbon atoms which may contain, for example, a thioether bond (—S—), an ether bond (—O—) and a carbonyl bond (—O) in R ^c of the general formula (1) can be mentioned. Among the hydrocarbon groups which may contain at least one divalent linking group selected from CO—), those similar to those having 1 to 14 carbon atoms can be mentioned. As R ^{c ′} in the general formula (2), those preferably used as R ^{c in the} general formula (1) can be preferably used in the same manner. As R ^f in the general formula (2), an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms are preferable from the viewpoint of improving sensitivity among them, and an alkyl group having 1 to 6 carbon atoms is more preferable. The alkyl group having 1 to 4 carbon atoms is more preferable, and the methyl group is particularly preferable.
Z ¹ in the general formula (2) is a hydrogen atom, a nitro group or-(C = O) R ^{d '} , and R ^d' contains at least one selected from an oxygen atom and a sulfur atom A good hydrocarbon group or a heterocyclic group containing at least one member selected from an oxygen atom and a sulfur atom without containing a nitrogen atom, and the R ^{d ′} is, for example, R in the general formula (1) ^{The same as d} . Wherein Z ¹ is, inter alia, from the viewpoints of developability and brightness, hydrogen atom or - preferably (C = O) a R d ^', it is more preferable in terms of the luminance is a hydrogen atom.

  The molecular weight of the oxime ester compound represented by the general formula (2) is not particularly limited, but is preferably 1,000 or less, and more preferably 800 or less from the viewpoint of reducing the content of the photoinitiator. Is preferred.

As the oxime ester compound represented by the general formula (2), for example, R ^{c ′} is an alkyl group having 6 to 10 carbon atoms in which a linear alkyl group and a cyclic alkyl group are combined, and Z ¹ is hydrogen A compound which is an atom and R ^f is an alkyl group having 1 to 4 carbon atoms; R ^{c ′} is an alkyl group having 6 to 10 carbon atoms in which a linear alkyl group and a cyclic alkyl group are combined, Z ¹ is -(C = O) R ^{d '} , wherein R ^d' is a heterocyclic group containing no sulfur atom and containing a sulfur atom, and R ^f is an alkyl group having 1 to 4 carbon atoms; Is mentioned as a suitable thing, It is not limited to these.

  As an oxime ester compound represented by the said General formula (2), at least 1 type chosen from following compound (2-1)-(2-2) is mentioned as a thing suitable more.

  The oxime ester compound represented by the general formula (2) can be synthesized, for example, with reference to JP-A-2012-526185.

  The photosensitive colored resin composition for color filters of the present invention may further be used in combination with other photoinitiator different from the above-mentioned oxime ester compound as a photoinitiator. The photoinitiator used in the colored resin composition of the present invention includes a chain transfer agent in addition to the photopolymerization initiator.

<Other photoinitiators>
As another photoinitiator, for example, an oxime ester photoinitiator different from an oxime ester compound having no carbazole skeleton including the oxime ester compound represented by the general formula (1), an α-amino ketone photoinitiator Agents, biimidazole photoinitiators, thioxanthone photoinitiators, acyl phosphine oxide photoinitiators, and mercapto chain transfer agents.
Above all, when forming a fine line pattern while further improving the luminance, the linearity is further improved, the ability to form the fine line pattern as designed for the mask line width is improved, and the shape of the micropores is improved. From the point of view, to the oxime ester compound represented by the general formula (1), an .alpha.-amino ketone photoinitiator, a biimidazole photoinitiator, a thioxanthone photoinitiator, an acylphosphine oxide photoinitiator, and It is preferable to use in combination at least one selected from mercapto chain transfer agents. Among them, it is preferable to further combine and use an acyl phosphine oxide-based photoinitiator from the viewpoint of easily forming micropores with good dimensional accuracy because the formation of micropores is prevented from flickering at the end of the pores. . Since the acyl phosphine oxide type photoinitiator has a thermal decomposition temperature higher than that of other initiators, it is considered that the side effect due to heating at the time of pre-baking is less likely to occur, so that the flicker is suppressed.
“Improvement in linearity” means that the end of the colored layer formed in the developing step after the application of the coloring composition is less uneven, and is formed in a linear or substantially linear shape. Further, "billing" refers to a defect in which the straight line or the curve at the end portion of the pattern becomes uneven to deteriorate the dimensional accuracy.

  In addition, from the viewpoint of improving the shape of the micropores and suppressing the flicker, the oxime ester compound represented by the above general formula (1) includes an α-amino ketone based photoinitiator, a biimidazole based photoinitiator, and a thioxanthone based compound. It is preferable to use a combination of at least one selected from a photo initiator, an acyl phosphine oxide photo initiator, and a mercapto chain transfer agent with the oxime ester compound having the diphenyl sulfide skeleton, and further, the oxidation described later. It is more preferable to use an inhibitor in combination.

The α-amino ketone photoinitiator has the property of curing the middle from the coating film surface, and since it is easy to suppress the curing property in the deep part of the coating film, it is combined with the oxime ester compound represented by the general formula (1) It is preferable from the point which the tendency to improve the coating film deep part hardenability is high.
As the α-amino ketone photoinitiator, for example, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (for example, Irgacure 907, manufactured by BASF), 2-benzyl-2-phenol (Dimethylamino) -1- (4-morpholinophenyl) -1-butanone (eg IRGACURE 369, manufactured by BASF Corp.), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [ 4- (4-morpholinyl) phenyl] -1-butanone (IRGACURE 379 EG, manufactured by BASF) and the like.
As the α-amino ketone photoinitiator, one may be used alone or in combination of two or more. Among them, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone is preferable from the viewpoint of improving the residual film rate, and 2-methyl-1- (4-methylthiophenyl) -2 -Morpholino propan 1-one is more preferable from the point of suppressing the flicker of micropores.

The biimidazole-based photoinitiator has the property of curing the coating film deep portion, which easily suppresses the surface curing property of the coating film, and when combined with the oxime ester compound represented by the general formula (1), the coating film surface curing It is preferable from the viewpoint of high tendency to improve the properties.
As a biimidazole photoinitiator, for example, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) ) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl- 1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 ′ -Bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenyl-1 2′-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 And 4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole etc. can be mentioned.
As a biimidazole photoinitiator, you may use individually or in combination of 2 or more types, Especially, it is preferable to use in combination with a mercapto type | system | group chain transfer agent from the point of improving coating-film hardenability.

As a thioxanthone type photoinitiator, a 2, 4- isopropyl thioxanthone, a 2, 4- diethyl thioxanthone, 1-chloro- 4-propoxy thioxanthone, a 2, 4- dichloro thioxanthone etc. are mentioned, for example.
As a thioxanthone type photoinitiator, you may use individually or in combination of 2 or more types, Among them, using 2,4-isopropyl thioxanthone and 2,4-diethyl thioxanthone is from the point of improving the transition of radical generation. preferable.

Since the acyl phosphine oxide photoinitiator has a property that yellowing due to heat is small, it is suitable for improving the brightness, but generally the sensitivity is low and sufficient curability may not be obtained. However, when combined with the oxime ester compound represented by the general formula (1), the overall coating film curability is improved, and when forming the micropores, the flickering of the end of the pores is suppressed and the dimensional accuracy is improved. It is preferable from the point which is easy to form a favorable micropore.
Examples of the acyl phosphine oxide photoinitiator include benzoyl-diphenyl phosphine oxide, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, 2,3,5,6- tetramethyl benzoyl diphenyl phosphine oxide, 3, 4-Dimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylethoxyphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2 , 4, 4-trimethyl-pentyl phosphine oxide, bis (2, 6-dimethyl benzoyl)-ethyl phosphine oxide and the like.
As an acyl phosphine oxide type photoinitiator, you may use individually or in combination of 2 or more types, and using bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide especially is coating film hardenability. Is preferable because the

Mercapto-based chain transfer agents have the property of receiving radicals from slow-reacting radicals to accelerate the reaction, and are particularly preferable in combination with a biimidazole-based photoinitiator because they tend to improve the reaction rate.
Examples of mercapto chain transfer agents include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3- Mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-) Mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyl) Rate), pen Erythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate) and the like.
As a mercapto type | system | group chain transfer agent, you may use individually or in combination of 2 or more types, It is preferable to use 2-mercaptobenzothiazole especially from the point which reaction speed improves.

Although the total content of the photoinitiator used in the photosensitive colored resin composition for color filters of the present invention is not particularly limited as long as the effects of the present invention are not impaired, the solid content of the photosensitive colored resin composition for color filters is Preferably it is 0.1 mass% or more and 12.0 mass% or less, More preferably, it is in the range of 1.0 mass% or more and 8.0 mass% or less with respect to the whole part. When the content is at least the above lower limit, light curing proceeds sufficiently to suppress elution of the exposed portion during development, while when the content is at the above upper limit, yellowing of the obtained colored layer is intensified and the luminance is increased. Can be suppressed.
In addition, solid content is all things other than a solvent, and a liquid polyfunctional monomer etc. are also contained.

  Content of the oxime ester compound represented by the said General formula (1) used in the photosensitive coloring resin composition for color filters of this invention is with respect to solid content whole quantity of the photosensitive coloring resin composition for color filters. The content is preferably in the range of 0.1% by mass to 8.0% by mass, and more preferably in the range of 0.5% by mass to 6.0% by mass. When the content is at least the above lower limit, light curing proceeds sufficiently to suppress elution of the exposed portion during development, while when the content is at the above upper limit, yellowing of the obtained colored layer is intensified and the luminance is increased. Can be suppressed.

  The photosensitive colored resin composition for color filters of the present invention includes the oxime ester compound represented by the general formula (1) when the photoinitiator contains two or more oxime ester compounds having no carbazole skeleton. The total content of two or more of the oxime ester compounds having no carbazole skeleton is preferably 0.1% by mass or more and 12.0% by mass or less, more preferably the total solid content of the photosensitive colored resin composition for color filter Is preferably in the range of 1.0% by mass or more and 8.0% by mass or less from the viewpoint of sufficiently exhibiting the combined effect with these photoinitiators.

  When the oxime ester compound represented by the general formula (1) is combined with the oxime ester compound having the diphenyl sulfide skeleton as a photoinitiator used in the present invention, the oxime ester compound having the diphenyl sulfide skeleton is The content is preferably 0.1% by mass to 4.0% by mass, and more preferably 0.3% by mass to 3.0% by mass, with respect to the total solid content of the photosensitive colored resin composition for color filter It is preferable that it is in the following range from the point of fully exhibiting the combined effect of the oxime ester compound represented by the said General formula (1), and the oxime ester compound which has the said diphenyl sulfide structure.

  When the oxime ester compound represented by the general formula (1) is combined with the oxime ester compound having a diphenyl sulfide skeleton as a photoinitiator used in the present invention, the oxime ester represented by the general formula (1) The ratio of the compound to the oxime ester compound having a diphenyl sulfide skeleton is 10 parts by mass of the oxime ester compound having a diphenyl sulfide skeleton relative to 100 parts by mass of the oxime ester compound represented by the general formula (1) The content is preferably 150 parts by mass or less, and more preferably 15 parts by mass or more and 120 parts by mass or less in terms of luminance and sensitivity. From the point of facilitating formation of micropores, 10 parts by mass to 70 parts by mass of the oxime ester compound having a diphenyl sulfide skeleton is based on 100 parts by mass of the oxime ester compound represented by the general formula (1) The content is preferably 15 parts by mass or more and 50 parts by mass or less.

In the photosensitive colored resin composition for color filter of the present invention, when the photoinitiator further contains the other photoinitiator, the oxime ester compound represented by the general formula (1) and the diphenyl sulfide skeleton It is preferable that it is 30 mass parts or more in total 100 mass parts of photoinitiators used for this invention, and, as for total content of the oxime ester compound which has these, it is more preferable that it is 40 mass parts or more, and 50 mass More preferably it is part or more.
On the other hand, the total content of the oxime ester compound represented by the general formula (1) and the oxime ester compound having the diphenyl sulfide skeleton is, from the viewpoint of sufficiently exerting the combined effect with the other photoinitiators, It is preferable that it is 95 mass parts or less in 100 mass parts of photoinitiators used for this invention, and it is more preferable that it is 85 mass parts or less.

  Further, the photoinitiator to be used in the present invention is selected from α-amino ketone photoinitiators, biimidazole photoinitiators, thioxanthone photoinitiators, acylphosphine oxide photoinitiators, and mercapto chain transfer agents. When containing at least one of the above, the total content of these is 0.1% by mass or more and 4.0% by mass or less with respect to the total solid content of the photosensitive colored resin composition for color filter, and further 0.5 It is preferable from the point of fully exhibiting the combined effect with these photoinitiators that it exists in the range of mass% or more and 2.0 mass% or less.

[Color material]
In the present invention, the coloring material is not particularly limited as long as it can form a desired color upon forming the colored layer of the color filter, and is not particularly limited, and various organic pigments, inorganic pigments, dispersible dyes, and dyes These can be used alone or in combination of two or more. Among them, organic pigments are preferably used because they have high color developability and high heat resistance. As the organic pigment, for example, compounds classified into Pigment in Color Index (CI; published by The Society of Dyers and Colourists), specifically, Color Index (C. I as shown below) .) Can be mentioned.
When the color index name is described in the following, when the color index names that list only different numbers are listed, only the numbers may be listed.

C. I. Pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 155, 155, 155, 155, 155 156, 166, 168, 175, 185;
C. I. Pigment orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73;
C. I. Pigment violet 1, 19, 23, 29, 32, 36, 38;
C. I. Pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 23, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 4, 49: 4, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 06,207,208,209,215,216,220,224,226,242,243,245,254,255,264,265;
C. I. Pigment blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Pigment green 7, 36, 58, 59;
C. I. Pigment brown 23, 25;
C. I. Pigment blacks 1 and 7.

  Further, specific examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, oxidized Examples thereof include chromium green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like.

  For example, when forming a pattern of a light shielding layer on a substrate of a color filter using the photosensitive colored resin composition for a color filter according to the present invention, a black pigment having a high light shielding property is blended in the ink. As the black pigment having high light shielding property, for example, an inorganic pigment such as carbon black or iron trioxide or an organic pigment such as cyanine black can be used.

As the above-mentioned dispersible dye, a dye which can be dispersed by imparting various substituents to the dye to be insoluble in the solvent, a dye which can be dispersed by using it in combination with a solvent having low solubility, or a solvent And a dye which is insoluble in water and salted with a counter ion to be insolubilized (laked). By using such a dispersible dye in combination with a dispersing agent, the dispersibility and the dispersion stability of the dye can be improved.
As a standard, if the amount of the dye dissolved in 10 g of solvent (or mixed solvent) is 100 mg or less, it can be determined that the dye can be dispersed in the solvent (or mixed solvent).

The dye can be appropriately selected from conventionally known dyes. Examples of such dyes include azo dyes, metal complex azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes and the like. Specifically, for example, C.I. I. Solvent Yellow 4, 14, 15, 24, 82, 88, 94, 98, 162, 179;
C. I. Solvent Red 45, 49;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56;
C. I. Solvent Blue 35, 37, 59, 67;
C. I. Acid Red 50, 52, 289;
C. I. Acid Violet 9, 30;
C. I. Acid Blue 19; and the like.

When forming a blue colored layer, at least one of a triarylmethane dye, a xanthene dye and a cyanine dye is preferable among them from the viewpoint of increasing brightness, and from the viewpoint of high heat resistance, tria among others At least one selected from reel methane dyes and xanthene dyes is preferred.
In the present invention, it is preferable to include a lake color material having a triarylmethane dye from the viewpoint of being able to improve the brightness of the color filter, and in particular, to include a triarylmethane basic dye and a polyacid anion. preferable.

  In the present invention, the lake color material is excellent in heat resistance and light resistance, and is a color material represented by the following general formula (i), among others, from the viewpoint of achieving high luminance of the color filter. It is preferable in that it is in a state of association and exhibits better heat resistance.

（一般式（ｉ）中、Ａは、Ｎと直接結合する炭素原子がπ結合を有しないａ価の有機基であって、当該有機基は、少なくともＮと直接結合する末端に飽和脂肪族炭化水素基を有する脂肪族炭化水素基、又は当該脂肪族炭化水素基を有する芳香族基を表し、炭素鎖中にＯ、Ｓ、Ｎが含まれていてもよい。Ｂ^ｃ−はｃ価のポリ酸アニオンを表す。Ｒ^ｉ〜Ｒ^ｖは各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、Ｒ^ｉｉとＲ^ｉｉｉ、Ｒ^ｉｖとＲ^ｖが結合して環構造を形成してもよい。Ａｒ^１は置換基を有していてもよい２価の芳香族基を表す。複数あるＲ^ｉ〜Ｒ^ｖ及びＡｒ^１はそれぞれ同一であっても異なっていてもよい。
ａ及びｃは２以上の整数、ｂ及びｄは１以上の整数を表す。ｅは０又は１であり、ｅが０のとき結合は存在しない。複数あるｅは同一であっても異なっていてもよい。）

(In general formula (i), A is an a-valent organic group in which a carbon atom directly bonded to N does not have a π bond, and the organic group is a saturated aliphatic carbon group at the end directly linked to N It represents an aliphatic hydrocarbon group having a hydrogen group or an aromatic group having the aliphatic hydrocarbon group, and O, S, N may be contained in the carbon chain B ^c- is a c-valent poly R ^{i to} R ^v each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ⁱⁱ and R ⁱⁱⁱ , R good .Ar ¹ be ^iv and ^{R v} are bonded to form a ring structure represents a divalent aromatic group which may have a substituent. plural ^R i to R ^v and Ar ¹ each It may be the same or different.
a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. The plurality of e may be the same or different. )

The cation part of the coloring material represented by the general formula (i) may be the same as the cation part of the coloring material represented by the general formula (i) described in WO 2012/144521.
A in the general formula (i) is an a-valent organic group in which a carbon atom directly bonded to N (nitrogen atom) does not have a π bond, and the organic group is saturated at least at a terminal directly bonded to N Represents an aliphatic hydrocarbon group having an aliphatic hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group, and O (oxygen atom), S (sulfur atom), N (nitrogen atom) in the carbon chain It may be included. Since the carbon atom directly bonded to N does not have a π bond, the color characteristics such as color tone and transmittance of the cationic color forming site are not affected by the linking group A and other color forming sites, and the monomer Similar colors can be maintained.
In A, an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the end directly bonded to N has a linear, branched or cyclic structure if the terminal carbon atom directly bonded to N has no π bond. And any carbon atom other than the terminal may have an unsaturated bond, may have a substituent, and O, S, N are contained in the carbon chain It is also good. For example, a carbonyl group, a carboxy group, an oxycarbonyl group, an amido group or the like may be contained, and a hydrogen atom may be further substituted by a halogen atom or the like.
The aromatic group having the above aliphatic hydrocarbon group in A is a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the end directly bonded to N at least And may have a substituent, and may be a heterocyclic ring containing O, S and N.
Among them, A preferably contains a cyclic aliphatic hydrocarbon group or an aromatic group from the viewpoint of backbone fastness.
Among them, a bridged alicyclic hydrocarbon group is preferable as the cyclic aliphatic hydrocarbon group from the viewpoint of the fastness of the skeleton. The bridged alicyclic hydrocarbon group is a polycyclic aliphatic hydrocarbon group having a crosslinked structure in an aliphatic ring and having a polycyclic structure, and examples thereof include norbornane and bicyclo [2,2,2]. Examples include octane, dicyclopentadiene, adamantane and the like. Among the bridged alicyclic hydrocarbon groups, norbornane is preferred. Moreover, as an aromatic group, the group containing a benzene ring and a naphthalene ring is mentioned, for example, Especially, the group containing a benzene ring is preferable.
From the viewpoint of the availability of raw materials, A is preferably divalent or tetravalent, is preferably divalent or trivalent, and is more preferably divalent. For example, when A is a divalent organic group, a straight chain, branched or cyclic alkylene group having 1 to 20 carbon atoms, or an aromatic group having two alkylene groups of 1 to 20 carbon atoms such as xylylene group substituted Group groups and the like.

The alkyl group in R ^{i to} R ^v is not particularly limited. Examples thereof include linear or branched alkyl groups having 1 to 20 carbon atoms, and the like, among which linear or branched alkyl groups having 1 to 8 carbon atoms are preferable, and 1 to 5 carbon atoms. The following linear or branched alkyl groups are more preferable in terms of easiness of production and raw material procurement. Among them, the alkyl group in R ^{i to} R ^v is particularly preferably an ethyl group or a methyl group. The substituent which the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group and the like, and examples of the substituted alkyl group include a benzyl group and the like.
The aryl group in R ^{i to} R ^v is not particularly limited. For example, a phenyl group, a naphthyl group etc. are mentioned. As a substituent which an aryl group may have, an alkyl group, a halogen atom, etc. are mentioned, for example.

The fact that R ⁱⁱ and R ⁱⁱⁱ and R ^iv and R ^v are combined to form a ring structure means that R ⁱⁱ and R ⁱⁱⁱ and R ^iv and R ^v are forming a ring structure via a nitrogen atom. Say The ring structure is not particularly limited, and examples include pyrrolidine ring, piperidine ring, morpholine ring and the like.

Among them, from the viewpoint of chemical stability, R ^{i to} R ^v each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v Are preferably combined to form a pyrrolidine ring, piperidine ring or morpholine ring.

R ⁱ to R ^v may take the structure are each independently but, among them, it is preferable that in terms of color purity R ⁱ is a hydrogen atom, further R ⁱⁱ ~ in terms of manufacturing and ease of procurement of raw materials More preferably, all R ^v are identical.

The divalent aromatic group in Ar ¹ is not particularly limited. The aromatic group may be a heterocyclic group in addition to an aromatic hydrocarbon group consisting of carbon rings. As the aromatic hydrocarbon in the aromatic hydrocarbon group, fused polycyclic aromatic hydrocarbons such as naphthalene ring, tetralin ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring and the like other than benzene ring; biphenyl, terphenyl, And chain polycyclic hydrocarbons such as diphenylmethane, triphenylmethane and stilbene. The chained polycyclic hydrocarbon may have O, S, and N in the chain skeleton as in diphenyl ether and the like. On the other hand, as the heterocyclic ring in the heterocyclic group, 5-membered heterocyclic rings such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole and pyrazole; 6-membered heterocyclic rings such as pyrane, pyrone, pyridine, pyrone, pyridazine, pyrimidine and pyrazine And fused polycyclic heterocyclic rings such as benzofuran, thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, quinoxaline and the like. These aromatic groups may have a substituent.

  As a substituent which an aromatic group may have, a C1-C5 alkyl group, a halogen atom, etc. are mentioned.

Ar ¹ is preferably an aromatic group having 6 to 20 carbon atoms, and more preferably an aromatic group composed of a fused polycyclic carbon ring having 10 to 14 carbon atoms. Among them, a phenylene group or a naphthylene group is more preferable in view of the simple structure and the inexpensive raw materials.

Plural R ^{i to} R ^v and Ar ¹ in one molecule may be the same or different. When a plurality of R ^{i to} R ^v and Ar ¹ are identical to each other, the color forming site exhibits the same color, so that the same color as a single color forming site can be reproduced, which is preferable in terms of color purity. On the other hand, when at least one of R ^{i to} R ^v and Ar ¹ is a different substituent, a color obtained by mixing a plurality of monomers can be reproduced, and adjustment to a desired color can be performed. it can.

The anion (B ^c− ) of the coloring material represented by the general formula (i) is a polyacid anion having two or more valences.
Among them, polyacid anions are preferably polyacid anions containing at least one of tungsten (W) and molybdenum (Mo) from the viewpoint of high luminance and excellent heat resistance and light resistance, and at least tungsten is contained, And it is more preferable from a heat resistant point that it is a polyacid anion which may contain molybdenum.

In the polyacid anion containing at least tungsten (W), the content ratio of tungsten to molybdenum is not particularly limited, but the molar ratio of tungsten to molybdenum is in the range of 100: 0 to 85:15 from the viewpoint of particularly excellent heat resistance. It is preferably inside, more preferably in the range of 100: 0 to 90:10.
The polyacid anion (B ^c- ) can be used singly or in combination of two or more of the above-mentioned polyacid anions, and when used in combination of two or more, tungsten and molybdenum in the whole polyacid anion It is preferable that the molar ratio thereof is within the above range.

The coloring material represented by the general formula (i) may be in the form of a double salt further containing other cations or anions as long as the effects of the present invention are not impaired. Specific examples of such a cation include, in addition to other basic dyes, an organic compound containing a functional group capable of forming a salt with an anion such as amino group, pyridine group, imidazole group, sodium ion, potassium ion, magnesium ion And metal ions such as calcium ion, copper ion and iron ion. In addition to acid dyes, specific examples of the anion include halide ions such as fluoride ion, chloride ion and bromide ion, and anions of inorganic acids. Examples of the anion of the inorganic acid include anions of oxo acids such as phosphate ion, sulfate ion, chromate ion, tungstate ion (WO ₄ ^2- ), molybdate ion (MoO ₄ ^2- ) and the like.
The coloring material represented by the general formula (i) can be prepared, for example, with reference to WO 2012/144520.

  In the case of forming a green colored layer, C.I. I. Pigment green 59 (PG 59) and C.I. I. Pigment green 58 (PG 58) can be preferably used a green color material in which a yellow color material is further combined.

  As yellow colorants used in combination with zinc phthalocyanine pigments such as PG59 and PG58, C.I. I. Pigment Yellow 150 derivative pigments are preferred. C. I. Specifically, as a derivative pigment of CI Pigment Yellow 150, mono-, di-, tri-, and azo compounds according to the following general formula (ii) or one of the tautomeric structures thereof serving as a host of at least one guest compound: Tetraanions and metals corresponding to Li, Cs, Mg, Cd, Co, Al, Cr, Sn, Pb, particularly preferably Na, K, Ca, Sr, Ba, Zn, Fe, Ni, Cu, Mn and La Mention may be made of metal complexes. Such C.I. I. It is preferable to use a derivative pigment of pigment yellow 150 from the viewpoint of improving the luminance.

（上記一般式（ｉｉ）中、Ｒ^３１はそれぞれ独立して、ＯＨ、ＮＨ_２、ＮＨ−ＣＮ、アシルアミノ、アルキルアミノ、またはアリールアミノであり、Ｒ^３２はそれぞれ独立して、−ＯＨまたは−ＮＨ_２である）

(In the above general formula (ii), each R ³¹ is independently OH, NH ₂ , NH—CN, acylamino, alkylamino or arylamino, and each R ³² is independently —OH or —NH ₂ )

Among them, at least one anion selected from the group consisting of mono-, di-, tri- and tetra-anions of the azo compound represented by the above general formula (ii) and the azo compound of the tautomeric structure thereof And containing at least two kinds of metal ions selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn improve the brightness and contrast. It is preferable from the point of improving.
By containing two or more types of metal ions, crystal growth of the coloring material is suppressed and it becomes possible to atomize, and further, since it is used in combination with a dispersing agent described later, it is atomized in the coloring material dispersion and contrast is It is presumed that an improved colored layer can be formed.

The acyl group in the acylamino group in the general formula (ii) is, for example, an alkylcarbonyl group, a phenylcarbonyl group, an alkylsulfonyl group, a phenylsulfonyl group, a carbamoyl group optionally substituted by alkyl, phenyl or naphthyl, an alkyl And a sulfamoyl group which may be substituted with phenyl or naphthyl, a guanyl group which may be substituted with alkyl, phenyl or naphthyl, and the like. It is preferable that the said alkyl group is C1-C6. Also the alkyl group, for example F, Cl, halogen such as Br, -OH, -CN, -NH _2, and / or may be substituted with an alkoxy group having 1 to 6 carbon atoms. Further, the phenyl group and the naphthyl group are, for example, halogen such as F, Cl and Br, -OH, -CN, -NH ₂ , -NO ₂ , an alkyl group having 1 to 6 carbon atoms, and / or 1 to 6 carbon atoms It may be substituted by 6 alkoxy groups.
The alkyl group in the alkylamino group in the general formula (ii) preferably has 1 to 6 carbon atoms. The alkyl group, for example F, Cl, halogen such as Br, -OH, -CN, -NH _2, and / or may be substituted with an alkoxy group having 1 to 6 carbon atoms.
Examples of the aryl group in the arylamino group in the general formula (ii) include a phenyl group and a naphthyl group, and these aryl groups include, for example, halogen such as F, Cl and Br, -OH, having 1 to 6 carbon atoms alkyl group, an alkoxy group having 1 to 6 carbon _atoms, -NH 2, may be substituted with such -NO ₂ and -CN.

In the azo compound represented by the above general formula (ii) and the azo compound of the tautomeric structure thereof, R ³¹ is independently -OH, -NH ₂ , -NH-CN, or alkylamino. Is preferable from the viewpoint of hue, and two R ³¹ may be the same or different.
In the above general formula (ii), two R ^{31 's} are, in terms of hue, particularly when both are —OH, when both are —NH—CN, or one is —OH and one is —NH— More preferred is CN, and even more preferred is both -OH.

Further, in the azo compound represented by the general formula (ii) and the azo compound of the tautomeric structure thereof, it is more preferable as R ³² that both are —OH in terms of hue.

In the case of containing ions of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, the at least two metals are, among others, It is preferable to include at least one metal that becomes a divalent or trivalent cation, and to include at least one selected from the group consisting of Ni, Cu, and Zn, and further to include at least Ni. Is preferred.
Furthermore, it is preferable to further include Ni and at least one metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu and Mn, and further more preferably Ni and Ni. Furthermore, it is preferable to contain at least one metal selected from the group consisting of Zn, Cu, Al and Fe. Among them, the at least two metals are particularly preferably Ni and Zn, or Ni and Cu, and particularly preferably Ni and Zn from the viewpoint of the affinity to the zinc phthalocyanine pigment. .

When containing ions of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, the content ratio of at least two metals is appropriately selected It should be adjusted.
Among them, the content ratio of Ni and at least one metal further selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu and Mn is Ni: other said at least It is preferable to include the 1 type metal in a molar ratio of 97: 3 to 10:90, and further preferably in a molar ratio of 90:10 to 10:90.
Among them, Ni and Zn are preferably contained in a molar ratio of 90:10 to 10:90, and more preferably 70:30 to 10:90. Among them, it is preferable that Zn is contained more than Ni in the ratio of Ni and Zn in that the coloring power is increased and the development residue in the micropores is easily suppressed when combined with the zinc phthalocyanine pigment, and Ni and Zn It is further preferable that the molar ratio of Ni: Zn is 40:60 to 10:90.
Alternatively, Ni and Cu are preferably contained in a molar ratio of 97: 3 to 10:90, and more preferably in a molar ratio of 96: 4 to 20:80.

  In the case of containing ions of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, C.I. I. The pigment of the pigment yellow 150 may further contain a metal ion different from the ion of the specific metal. For example, it may contain at least one metal ion selected from the group consisting of Li, Cs, Mg, Na, K, Ca, Sr, Ba, and La.

  C. I. In the pigment yellow 150 derivative pigment, as an embodiment containing ions of at least two metals, ions of at least two metals are contained in a common crystal lattice, and one in each of another crystal lattices. The case where the crystal | crystallization which contains the metal ion of is aggregated is mentioned. Among them, the case where ions of at least two metals are contained in a common crystal lattice is preferable from the viewpoint of further improving the contrast. It should be noted that whether it is an embodiment in which ions of at least two metals are contained in a common crystal lattice or an embodiment in which crystals in which one metal ion is contained in another crystal lattice are aggregated, For example, it can judge suitably using an X-ray-diffraction method with reference to Unexamined-Japanese-Patent No. 2014-12838.

  The average primary particle diameter of the coloring material used in the present invention is not particularly limited as long as it can form a desired color when it is a colored layer of a color filter, and is not particularly limited, and varies depending on the type of coloring material used Is preferably in the range of 10 nm to 100 nm, and more preferably 15 nm to 60 nm. When the average primary particle diameter of the coloring material is in the above range, a display device provided with a color filter manufactured using the coloring material dispersion liquid according to the present invention can have high contrast and high quality. it can.

  The colorant used in the present invention can be produced by a known method such as a recrystallization method or a solvent salt milling method. In addition, commercially available coloring materials may be used after being finely processed.

  The total content of the color material may be blended in a proportion of 3% by mass to 65% by mass, more preferably 4% by mass to 60% by mass, with respect to the total solid content of the photosensitive colored resin composition for color filter preferable. If it is more than the said lower limit, the colored layer at the time of apply | coating the photosensitive colored resin composition for color filters to a predetermined | prescribed film thickness (usually 1.0 micrometer-5.0 micrometers) has sufficient color density. Moreover, if it is below the said upper limit, while it is excellent in storage stability, the colored layer which has sufficient hardness and adhesiveness with a board | substrate can be obtained. In particular, when forming a colored layer having a high coloring material concentration, the total content of the coloring material is preferably 15% by mass to 65% by mass, more preferably the total solid content of the photosensitive colored resin composition for color filter It is preferable to mix | blend in the ratio of 25 mass%-60 mass%.

[Alkali-soluble resin]
The alkali-soluble resin in the present invention has an acidic group, can be appropriately selected and used from among those which act as a binder resin and are soluble in an alkali developing solution used when forming a pattern.
In the present invention, the alkali-soluble resin can have an acid value of 40 mg KOH / g or more as a standard.
The preferred alkali-soluble resin in the present invention is a resin having an acidic group, usually a carboxy group, and specifically, an acrylic such as an acrylic copolymer having a carboxy group and a styrene-acrylic copolymer having a carboxy group. Examples thereof include epoxy resin and epoxy (meth) acrylate resin having a carboxy group. Among these, particularly preferred are those having a carboxy group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. It is because the film strength of the cured film formed by containing a photopolymerizable functional group is improved. Moreover, acrylic resins such as these acrylic copolymers and styrene-acrylic copolymers, and epoxy acrylate resins may be used as a mixture of two or more.

Acrylic resins such as an acrylic copolymer having a structural unit having a carboxy group and a styrene-acrylic copolymer having a carboxy group are, for example, a carboxy group-containing ethylenically unsaturated monomer, and optionally a co-polymer. It is a (co) polymer obtained by (co) polymerizing other polymerizable monomers by a known method.
Examples of carboxy group-containing ethylenic unsaturated monomers include (meth) acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl esters of maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, etc. Be Also, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate with a cyclic anhydride such as maleic anhydride, phthalic anhydride or cyclohexanedicarboxylic acid anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylate and the like can also be used. In addition, as a precursor of the carboxy group, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride, citraconic anhydride and the like may be used. Among them, (meth) acrylic acid is particularly preferable in view of copolymerizability, cost, solubility, glass transition temperature and the like.

The alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer. It was found that the alkali-soluble resin has a hydrocarbon ring which is a bulky group, whereby the solvent resistance of the obtained colored layer, in particular, the swelling of the colored layer is suppressed. Although the effect is unknown, the inclusion of a bulky hydrocarbon ring in the colored layer suppresses the movement of molecules in the colored layer, resulting in an increase in the strength of the coating and suppression of swelling by the solvent. It is estimated that
As such a hydrocarbon ring, a cyclic aliphatic hydrocarbon ring which may have a substituent, an aromatic ring which may have a substituent, and a combination of these may be mentioned. May have a substituent such as a carbonyl group, a carboxy group, an oxycarbonyl group or an amido group. Among them, when an aliphatic ring is contained, the heat resistance and adhesion of the colored layer are improved, and the luminance of the obtained colored layer is improved.
Specific examples of the hydrocarbon ring include aliphatic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, tricyclo [5.2.1.0 (2, 6)] decane (dicyclopentane), adamantane and the like Rings; aromatic rings such as benzene, naphthalene, anthracene, phenanthrene and fluorene; chain polycyclic rings such as biphenyl, terphenyl, diphenylmethane, triphenylmethane and stilbene; cardo structures shown in the following chemical formula (A) etc. Be

  The alkali-soluble resin also preferably has a maleimide structure represented by the following general formula (B).

（一般式（Ｂ）において、Ｒ^Ｍは、置換されていてもよい炭化水素環である。）

(In the general formula (B), R ^M is a hydrocarbon ring which may be substituted.)

When the alkali-soluble resin has a maleimide structure represented by the general formula (B), the polymer has a structural unit represented by the general formula (I) described later because it has a nitrogen atom in the hydrocarbon ring. The compatibility with the basic dispersant is very good, and the effect of suppressing development residues is improved.
Specific examples of the optionally substituted hydrocarbon ring in R ^M in the general formula (B) include the same as the specific examples of the above-mentioned hydrocarbon ring.

When an aliphatic ring is contained as a hydrocarbon ring, while the heat resistance and adhesiveness of a colored layer improve, it is preferable from the point which the brightness | luminance of the obtained colored layer improves.
Moreover, when the cardo structure shown by said Chemical formula (A) is included, the hardenability of a colored layer improves and it is especially preferable from the point which solvent resistance (NMP swelling suppression) improves.

In the alkali-soluble resin used in the present invention, it is easy to adjust the amount of each constituent unit by using the acrylic copolymer having the constituent unit having the above-mentioned hydrocarbon ring separately from the constituent unit having a carboxy group. It is preferable from the point of being easy to improve the function which the said structural unit has by increasing the amount of structural units which have a hydrocarbon ring.
An acrylic copolymer having a structural unit having a carboxy group and the above-mentioned hydrocarbon ring is prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned "copolymerizable other monomer". be able to.
Examples of the ethylenically unsaturated monomer having a hydrocarbon ring combined with the oxime ester compound represented by the general formula (1) include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate and adamantyl (meth) acrylate And isobornyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, styrene and the like, and from the viewpoint that the cross-sectional shape of the colored layer after development is maintained in heat treatment, the cyclohexyl ( Meta) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate, styrene are preferred, and styrene is particularly preferred.
Further, from the viewpoint of the effect of suppressing development residues, as the ethylenically unsaturated monomer having a hydrocarbon ring, the monomer having a maleimide structure and styrene are preferable, and styrene is particularly preferable.

The alkali-soluble resin used in the present invention preferably also has an ethylenic double bond in the side chain. In the case of having an ethylenic double bond, the alkali-soluble resins, or the alkali-soluble resin, the photopolymerizable compound and the like may form a crosslink in the curing step of the resin composition at the time of producing a color filter. By combining with the oxime ester compound represented by the general formula (1) used in the present invention, the film strength of the cured film is further improved to improve the development resistance, and the heat shrinkage of the cured film is suppressed. The adhesion to the substrate is excellent.
The method of introducing the ethylenic double bond into the alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a method in which a compound having both an epoxy group and an ethylenic double bond in the molecule, such as glycidyl (meth) acrylate, is added to a carboxy group possessed by an alkali-soluble resin to introduce an ethylenic double bond in the side chain. Or introducing a structural unit having a hydroxyl group into a copolymer, adding a compound having an isocyanate group and an ethylenic double bond in the molecule, and introducing an ethylenic double bond in the side chain Etc.

  The alkali-soluble resin of the present invention may further contain other structural units such as methyl (meth) acrylate, ethyl (meth) acrylate, and structural units having an ester group. The structural unit having an ester group not only functions as a component that suppresses the alkali solubility of the photosensitive colored resin composition for color filter, but also functions as a component that improves the solubility in a solvent and the solvent resolubility. .

  The alkali-soluble resin in the present invention is preferably an acrylic resin such as an acrylic copolymer and a styrene-acrylic copolymer, which have a structural unit having a carboxy group and a structural unit having a hydrocarbon ring, It is an acrylic resin such as an acrylic copolymer and a styrene-acrylic copolymer having a constitutional unit having a carboxy group, a constitutional unit having a hydrocarbon ring, and a constitutional unit having an ethylenic double bond Is more preferred.

  The alkali-soluble resin can be made an alkali-soluble resin having desired performance by appropriately adjusting the amount of each structural unit charged.

The amount of the carboxy group-containing ethylenically unsaturated monomer to be added is preferably 5% by mass or more, and more preferably 10% by mass or more based on the total amount of monomers, from the viewpoint of obtaining a good pattern. On the other hand, it is preferable that the preparation amount of the carboxy group-containing ethylenic unsaturated monomer is 50% by mass or less, and 40% by mass or less based on the total amount of monomers, from the viewpoint of suppressing film roughness and the like on the pattern surface after development. It is more preferable that
The solubility of the coating film to be obtained when the proportion of the carboxy group-containing ethylenically unsaturated monomer is at least the above lower limit is sufficient for the alkali developing solution, and the proportion of the carboxy group-containing ethylenically unsaturated monomer is the above upper limit Below, it tends to be hard to occur drop-off from a substrate of a formed pattern and film roughening of the surface of a pattern at the time of development with alkaline developing solution.

  In addition, acrylic resins such as acrylic copolymers having a structural unit having an ethylenic double bond and acrylic resins such as styrene-acrylic copolymers, which are more preferably used as alkali-soluble resins, include an epoxy group and an ethylenic double The compound having a combination with the bond is preferably 10% by mass to 95% by mass, and more preferably 15% by mass to 90% by mass, with respect to the charged amount of the carboxy group-containing ethylenically unsaturated monomer.

The preferred weight average molecular weight (Mw) of the carboxy group-containing copolymer is preferably in the range of 1,000 to 50,000, and more preferably 3,000 to 20,000. If it is less than 1,000, the binder function after curing may be significantly reduced, and if it is more than 50,000, pattern formation may be difficult at the time of development with an alkali developer.
The weight average molecular weight (Mw) of the carboxy group-containing copolymer can be measured using Shodex GPC System-21 H (Shodex GPC System-21 H) using polystyrene as a standard substance and THF as an eluent.

The epoxy (meth) acrylate resin having a carboxy group is not particularly limited, but an epoxy (meth) obtained by reacting a reaction product of an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride. Acrylate compounds are suitable.
The epoxy compound, the unsaturated group-containing monocarboxylic acid, and the acid anhydride can be appropriately selected from known ones and used. The epoxy (meth) acrylate resins having a carboxy group may be used alone or in combination of two or more.

The alkali-soluble resin is preferably selected from those having an acid value of 50 mg KOH / g or more from the viewpoint of developability (solubility) in an aqueous alkali solution used for the developer. The alkali-soluble resin preferably has an acid value of 70 mgKOH / g or more and 300 mgKOH / g or less from the viewpoint of developability (solubility) to an aqueous alkali solution used for a developer and adhesion to a substrate, and in particular, It is preferable that it is 70 mgKOH / g or more and 280 mgKOH / g or less.
In the present invention, the acid value can be measured in accordance with JIS K 0070.

The ethylenically unsaturated bond equivalent in the case of having an ethylenically unsaturated group in the side chain of the alkali-soluble resin is a cured film by combining it with the oxime ester compound represented by the general formula (1) used in the present invention. The film strength is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 to 1500, from the viewpoint of improving the development resistance and improving the development resistance and achieving excellent adhesion with the substrate. When the ethylenically unsaturated bond equivalent is 2000 or less, the development resistance and the adhesion are excellent. In addition, if it is 100 or more, the proportion of other structural units such as the structural unit having a carboxy group or the structural unit having a hydrocarbon ring can be relatively increased, so that the developing property and heat resistance are excellent. There is. It is preferable to use the oxime ester compound represented by the said General formula (1) used by this invention in combination with content mentioned above.
Here, the ethylenically unsaturated bond equivalent is the weight average molecular weight per mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (1).

Formula (1)
Ethylenically unsaturated bond equivalent (g / mol) = W (g) / M (mol)
(In the formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of ethylenic double bonds contained in the alkali-soluble resin W (g).)

  The above ethylenically unsaturated bond equivalent can be obtained, for example, by measuring the number of ethylenic double bonds contained in 1 g of the alkali-soluble resin in accordance with the test method for iodine value described in JIS K 0070: 1992. It may be calculated.

  The alkali-soluble resin used in the photosensitive colored resin composition for color filter may be used singly or in combination of two or more, and the content thereof is not particularly limited, but color The alkali-soluble resin is preferably in the range of 5% by mass to 60% by mass, more preferably 10% by mass to 40% by mass, with respect to the total solid content of the photosensitive colored resin composition for a filter. When the content of the alkali-soluble resin is not less than the above lower limit, sufficient developability of the alkali resin is obtained, and when the content of the alkali-soluble resin is not more than the above upper limit, the film is roughened or a pattern is chipped during development. It can be suppressed.

[Photopolymerizable compound]
The photopolymerizable compound used in the photosensitive colored resin composition for color filter is not particularly limited as long as it can be polymerized by the photoinitiator, and usually, two or more ethylenic unsaturated double bonds are used. The compound which it has is used suitably, It is preferable that it is especially polyfunctional (meth) acrylate which has 2 or more of acryloyl group or methacryloyl groups.
As such a polyfunctional (meth) acrylate, it may select suitably from conventionally well-known things, and may be used. As a specific example, the thing of Unexamined-Japanese-Patent No. 2013-029832, etc. are mentioned, for example.

  One of these polyfunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination. In addition, when excellent photocurability (high sensitivity) is required for the photosensitive colored resin composition for color filters of the present invention, the multifunctional (meth) acrylate has three polymerizable double bonds ( Those having three or more functional groups are preferable, and poly (meth) acrylates of polyhydric alcohols having three or more valences or their dicarboxylic acid modified products are preferable. Specifically, trimethylolpropane tri (meth) acrylate, Pentaerythritol tri (meth) acrylate, succinic acid modified product of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Succinic acid modification of penta (meth) acrylate Things, dipentaerythritol hexa (meth) acrylate are preferable.

The content of the photopolymerizable compound used in the photosensitive colored resin composition for color filter is not particularly limited, but the photopolymerizable compound is preferably used relative to the total solid content of the photosensitive colored resin composition for color filter Is preferably in the range of 5% by mass to 60% by mass, more preferably 10% by mass to 40% by mass. When the content of the photopolymerizable compound is at least the above lower limit, photocuring proceeds sufficiently, and the exposed portion can suppress elution at the time of development, and the content of the photopolymerizable compound is at most the above upper limit Alkali developability is sufficient.
The content ratio of the photopolymerizable compound used in the photosensitive colored resin composition for color filter and the content ratio of the photo initiator are excellent in the curability, the residual film rate, and further, the electric reliability is improved. It is preferable that the total content ratio of the said photoinitiator is 5 mass parts or more with respect to 100 mass parts of said photopolymerizable compounds from the point to be carried out, Furthermore, it is preferable that it is 10 mass parts or more, 40 mass parts or less It is preferable that it is 30 mass parts or less.

[solvent]
The solvent used in the present invention is not particularly limited as long as it is an organic solvent which does not react with each component in the photosensitive colored resin composition for color filter and which can dissolve or disperse these components. The solvents can be used alone or in combination of two or more.
Specific examples of the solvent include, for example, alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; Ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, Ester solvents such as ethyl lactate and cyclohexanol acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and the like Ton solvents; glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate and ethoxyethyl acetate; methoxyethoxyethyl acetate, ethoxy Carbitol acetate solvents such as ethoxyethyl acetate and butyl carbitol acetate (BCA); diacetates such as propylene glycol diacetate and 1,3-butylene glycol diacetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene Glycol ether solvents such as glycol diethyl ether, propylene glycol monomethyl ether and dipropylene glycol dimethyl ether; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like; γ-butyrolactone and the like Lactone solvents; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane and N-octane; toluene, Organic solvents such as aromatic hydrocarbons such as xylene can be mentioned. Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents and ester solvents are preferably used in view of the solubility of the other components. Among them, as the solvent used in the present invention, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, And it is preferable from the point of the solubility of another component, and the applicability | paintability that it is 1 or more types selected from the group which consists of 3-methoxy butyl acetate.

  In the photosensitive colored resin composition for a color filter according to the present invention, the content of the solvent may be appropriately set within the range in which the colored layer can be formed with high accuracy. Based on the total amount of the photosensitive colored resin composition for color filters containing the solvent, it is usually preferably in the range of 55% by mass to 95% by mass, and more preferably in the range of 65% by mass to 88% by mass It is more preferable that When the content of the solvent is in the above range, the coating property can be excellent.

[Dispersing agent]
In the photosensitive colored resin composition for color filters of the present invention, the colorant is preferably dispersed in a solvent by a dispersant and used. In the present invention, the dispersant can be appropriately selected and used from conventionally known dispersants. As the dispersant, for example, surfactants of cationic type, anionic type, nonionic type, amphoteric type, silicone type and fluorine type can be used. Among the surfactants, polymer dispersants are preferable in that they can be dispersed uniformly and finely.

  As the polymer dispersant, for example, (co) polymers of unsaturated carboxylic acid ester such as polyacrylic acid ester; (partial) amine salt of (co) polymer of unsaturated carboxylic acid such as polyacrylic acid (Partially) ammonium salts and (partially) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylic acid esters and modified products thereof; polyurethanes; unsaturated polyamides; Long-chain polyamino amide phosphates; Polyethylenimine derivatives (amides obtained by reaction of poly (lower alkylenimines) with free carboxy group-containing polyesters and their bases); Polyallylamine derivatives (polyallylamine and free carboxy Co-condensates of polyesters, polyamides or esters with Li esteramide) reaction products obtained by reacting one or more compound selected from among the three compounds of the), and the like.

Among these, as the polymer dispersant, from the viewpoint of being able to suitably disperse the coloring material and having good dispersion stability, a polymer dispersant containing a nitrogen atom in the main chain or side chain and having an amine value is preferable, Among them, a polymer dispersant composed of a polymer containing a repeating unit having a tertiary amine is preferable from the viewpoint of improving the brightness and the contrast by preventing the deposition of foreign matter at the time of forming a coating film.
The repeating unit having a tertiary amine is a site having affinity with the color material. A polymer dispersant consisting of a polymer containing a repeating unit having a tertiary amine usually contains a repeating unit serving as a site having affinity with a solvent. The polymer containing a repeating unit having a tertiary amine is, among others, a block copolymer having a block part consisting of a repeating unit having a tertiary amine and a block part having solvent affinity, It is preferable from the point which becomes possible to form the coating film which becomes excellent in brightness and high.

The repeating unit having a tertiary amine may have a tertiary amine, and the tertiary amine may be contained in the side chain of the block polymer or may constitute the main chain.
Among them, a repeating unit having a tertiary amine in a side chain is preferable, and among them, the main chain skeleton is a structure represented by the following general formula (I) from the viewpoint of being difficult to thermally decompose and having high heat resistance. Is more preferred.

（一般式（Ｉ）中、Ｒ^１は、水素原子又はメチル基、Ｑは、２価の連結基、Ｒ^２は、炭素数１〜８のアルキレン基、−［ＣＨ（Ｒ^５）−ＣＨ（Ｒ^６）−Ｏ］_ｘ−ＣＨ（Ｒ^５）−ＣＨ（Ｒ^６）−又は−［（ＣＨ_２）_ｙ−Ｏ］_ｚ−（ＣＨ_２）_ｙ−で示される２価の有機基、Ｒ^３及びＲ^４は、それぞれ独立に、置換されていてもよい鎖状又は環状の炭化水素基を表すか、Ｒ^３及びＲ^４が互いに結合して環状構造を形成する。Ｒ^５及びＲ^６は、それぞれ独立に水素原子又はメチル基である。
ｘは１〜１８の整数、ｙは１〜５の整数、ｚは１〜１８の整数を示す。）

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, Q is a divalent linking group, R ² is an alkylene group having 1 to 8 carbon atoms,-[CH (R ⁵ ) -CH ( R ⁶ ) —O] _x —CH (R ⁵ ) —CH (R ⁶ ) — or — [(CH ₂ ) _y —O] _z — (CH ₂ ) _{y— a} divalent organic group, R ³ And R ⁴ each independently represent a chain-like or cyclic hydrocarbon group which may be substituted, or R ³ and R ⁴ bond to each other to form a cyclic structure, and R ⁵ and R ^{6 each} represent Each of them is independently a hydrogen atom or a methyl group.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

  Examples of the divalent linking group Q in the above general formula (I) include an alkylene group having 1 to 10 carbon atoms, an arylene group, a -CONH- group, a -COO- group, and an ether group having 1 to 10 carbon atoms (- R'-OR "-: R 'and R" each independently represent an alkylene group), a combination thereof, and the like. Among them, Q is a -COO- group or -CONH- from the viewpoints of the heat resistance of the obtained polymer, the solubility in propylene glycol monomethyl ether acetate (PGMEA) suitably used as a solvent, and a relatively inexpensive material. It is preferably a group.

The divalent organic group R ² of the above general formula (I) is an alkylene group having 1 to 8 carbon atoms,-[CH (R ⁵ ) -CH (R ⁶ ) -O] _x -CH (R ⁵ ) -CH (R ⁶ )-or-[(CH ₂ ) _y -O] _z- (CH ₂ ) _y- . The alkylene group having 1 to 8 carbon atoms may be linear or branched, and examples thereof include methylene, ethylene, trimethylene, propylene, various butylenes, various pentylenes, and various hexylenes. And various octylene groups.
R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group.
As R ² above, from the viewpoint of dispersibility, an alkylene group having 1 to 8 carbon atoms is preferable, and in particular, R ² is more preferably a methylene group, ethylene group, propylene group or butylene group, methylene group and ethylene group Groups are more preferred.

Examples of the cyclic structure formed by bonding R ³ and R ^{4 in the} above general formula (I) to each other include a 5- to 7-membered nitrogen-containing heterocyclic single ring or a fused ring formed by condensing two of these. Be The nitrogen-containing heterocyclic ring is preferably one having no aromaticity, and more preferably a saturated ring.

  As the repeating unit represented by the above general formula (I), alkyl group-substituted amino such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate and the like Examples thereof include group-containing (meth) acrylates, and alkyl group-substituted amino group-containing (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide. Among them, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylamide can be preferably used in terms of improvement in dispersibility and dispersion stability.

  It is preferable that 3 or more of the structural units represented by general formula (I) are contained in the block part which consists of a repeating unit which has the said tertiary amine. Among them, from the viewpoint of improving dispersibility and dispersion stability, 3 to 100 are preferably contained, 3 to 50 are more preferably contained, and 3 to 30 are further preferably contained.

A block co-having a block part (hereinafter sometimes referred to as A block) composed of a repeating unit having a tertiary amine and a block part (hereinafter sometimes referred to as B block) having solvent affinity. The block portion having solvent affinity in the polymer does not have a structural unit represented by the above general formula (I) from the viewpoint of improving the solvent affinity and improving the dispersibility, and the above general formula It has a solvent affinity block having a structural unit copolymerizable with I). In the present invention, the arrangement of each block of the block copolymer is not particularly limited. For example, an AB block copolymer, an ABA block copolymer, a BAB block copolymer and the like can be used. Among them, an AB block copolymer or an ABA block copolymer is preferable in terms of excellent dispersibility.
The B block may be similar to the B block of WO 2016/104493.

  The number of structural units constituting the solvent compatible block may be appropriately adjusted within the range in which the colorant dispersibility is improved. Among them, the number of structural units constituting the block portion of solvent affinity is 10 to 200, since the solvent affinity portion and the colorant affinity portion effectively act to improve the dispersibility of the colorant. Is preferably 10 to 100, and more preferably 10 to 70.

The solvent compatible block may be selected to function as a solvent compatible site, and the repeating unit constituting the solvent compatible block may consist of one type, or two or more types. The repeating unit of may be included.
In the block copolymer used as the dispersant of the present invention, the number m of units of the constituent unit represented by the general formula (I) and the number n of units of the other constituent units constituting the block unit having solvent affinity The ratio m / n is preferably in the range of 0.01 to 1, and more preferably in the range of 0.05 to 0.7 from the viewpoint of the dispersibility of the colorant and the dispersion stability. .

Among them, in the present invention, the dispersant has a structure represented by the general formula (I), and a polymer having an amine value of 40 mgKOH / g or more and 120 mgKOH / g or less is excellent in dispersibility and at the time of coating film formation It is preferable from the point which does not precipitate a foreign material and improves a brightness | luminance and contrast.
When the amine value is in the above range, the viscosity stability with time and heat resistance are excellent, and the alkali developability and solvent resolubility are also excellent. When the amine value of the dispersant is high, the dispersibility and the dispersion stability are improved, and the solvent solubility and the solvent resolubility are improved, the compatibility with other components becomes good, and the fine line pattern of the colored layer The linearity of the micropores is improved, and the flicker of the micropores is easily suppressed. In the present invention, among the amine values of the dispersant, the amine value is preferably 80 mg KOH / g or more, and more preferably 90 mg KOH / g or more. On the other hand, the amine value of the dispersant is preferably 110 mg KOH / g or less, more preferably 105 mg KOH / g or less, from the viewpoint of solvent resolubility.
The amine value refers to the number of mg of potassium hydroxide equivalent to perchloric acid required to neutralize the amine component contained in 1 g of the sample, and can be measured by the method defined in JIS-K7237. In the case of the amino group which forms a salt with the organic acid compound in the dispersant as measured by the method, the organic acid compound usually dissociates, so the block copolymer itself used as the dispersant Can be measured.

The acid value of the dispersant used in the present invention is preferably 1 mg KOH / g or more as the lower limit from the viewpoint of the effect of suppressing development residues. Among them, the acid value of the dispersant is more preferably 2 mg KOH / g or more from the viewpoint that the effect of suppressing development residues is more excellent. In addition, the acid value of the dispersant used in the present invention can prevent the deterioration of the development adhesion and the solvent resolubility, the linearity of the fine line pattern of the colored layer is improved, and the flicker of the micropores is suppressed. From the viewpoint of easiness, the upper limit of the acid value of the dispersant is preferably 18 mg KOH / g or less. Among them, the acid value of the dispersant is more preferably 16 mg KOH / g or less, and still more preferably 14 mg KOH / g or less, from the viewpoint of improving the development adhesion and solvent resolubility.
In the dispersant used in the present invention, the acid value of the block copolymer before salt formation is preferably 1 mg KOH / g or more, and more preferably 2 mg KOH / g or more. This is because the effect of suppressing development residues is improved. The upper limit of the acid value of the block copolymer before salt formation is preferably 18 mg KOH / g or less, more preferably 16 mg KOH / g or less, and still more preferably 14 mg KOH / g or less . It is because development adhesion and solvent resolubility become good.

Further, in the present invention, the glass transition temperature of the dispersant is preferably 30 ° C. or more from the viewpoint of improving the development adhesion. That is, it is preferable that the glass transition temperature of a dispersing agent is 30 degreeC or more whether it is a block formation block before salt formation or it is a salt type block copolymer. When the glass transition temperature of the dispersant is low, it is particularly close to the developer temperature (usually about 23 ° C.), and there is a possibility that the development adhesion may be lowered. This is presumably because, when the glass transition temperature is close to the developer temperature, the movement of the dispersant increases during development, and as a result, the development adhesion deteriorates. When the glass transition temperature is 30 ° C. or higher, the molecular motion of the dispersant during development is suppressed, and therefore, it is presumed that the decrease in development adhesion is suppressed.
The glass transition temperature of the dispersant is preferably 32 ° C. or more, more preferably 35 ° C. or more, from the viewpoint of development adhesion. On the other hand, it is preferable that the temperature is 200 ° C. or less from the viewpoint of operability at the time of use, such as easy precise measurement.
The glass transition temperature of the dispersant in the present invention can be determined by differential scanning calorimetry (DSC) according to JIS K7121.
Moreover, the glass transition temperature (Tg) of a block part and a block copolymer can be calculated by the following formula.
1 / Tg = Σ (Xi / Tgi)
Here, in the block portion, n monomer components from i = 1 to n are copolymerized. Xi is the weight fraction of the ith monomer (ΣXi = 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the ith monomer. Is the sum of i = 1 to n. As the value (Tgi) of homopolymer glass transition temperature of each monomer, the value of Polymer Handbook (3rd Edition) (J. Brandrup, EHImmergut (Wiley-Interscience, 1989)) can be adopted.

  When the colorant concentration is increased and the dispersant content is increased, the amount of binder is relatively decreased, and thus the colored resin layer is easily peeled off from the base substrate at the time of development. When the dispersant contains a B block including a structural unit derived from a carboxy group-containing monomer, and has the above-mentioned specific acid value and glass transition temperature, the development adhesion is improved. When the acid value is too high, although it is excellent in developability, it is presumed that the polarity is too high and peeling tends to occur at the time of development instead.

  From the above, in the present invention, the dispersing agent is a polymer having a structure represented by the general formula (I) and having an amine value of 40 mgKOH / g or more and 120 mgKOH / g or less, and an acid value of It is excellent in coloring material dispersion stability that a glass transition temperature is 30 degreeC or more by 1 mgKOH / g or more and 18 mgKOH / g or less, a contrast is improved, and the oxime ester compound represented by said General formula (1) is included. When a colored resin composition is formed, it is easy to form micropores excellent in solvent resolubility, further having high development adhesion, and further excellent in shape while generation of development residues is suppressed; It is preferable from the point of being easy to suppress the flicker of a hole and the development residue.

  As the carboxy group-containing monomer, a monomer copolymerizable with the monomer having a constitutional unit represented by the general formula (I) and containing an unsaturated double bond and a carboxy group can be used. Examples of such a monomer include (meth) acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl ester of maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer and the like. Also, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate with a cyclic anhydride such as maleic anhydride, phthalic anhydride or cyclohexanedicarboxylic acid anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylate and the like can also be used. In addition, as a precursor of the carboxy group, an acid anhydride group-containing monomer such as maleic anhydride, itaconic anhydride, citraconic anhydride and the like may be used. Among them, (meth) acrylic acid is particularly preferable in view of copolymerizability, cost, solubility, glass transition temperature and the like.

In the block copolymer before salt formation, the content ratio of the structural unit derived from the carboxy group-containing monomer may be appropriately set so that the acid value of the block copolymer falls within the range of the specific acid value, and in particular It is preferable that it is 0.05 mass%-4.5 mass% with respect to the total mass of all the structural units of a block copolymer, although it is not limited, It is 0.07 mass%-3.7 mass% Is more preferred.
When the content ratio of the structural unit derived from the carboxy group-containing monomer is not less than the lower limit value, the effect of suppressing development residues is expressed, and when it is not more than the upper limit value, the development adhesion is deteriorated or the solvent resolubility It can prevent the deterioration.
In addition, the structural unit derived from a carboxy-group containing monomer should just become said specific acid value, may consist of 1 type, and may contain 2 or more types of structural units.

  Further, a monomer having a glass transition temperature value (Tgi) of 10 ° C. or higher, from the viewpoint of improving the development adhesion by setting the glass transition temperature of the dispersant used in the present invention to a specific value or higher. The total amount of B in the B block is preferably 75% by mass or more, and more preferably 85% by mass or more.

  In the block copolymer, the ratio m / n of the unit number m of the constituent units of the A block and the unit number n of the constituent units of the B block is in the range of 0.05 to 1.5. Is preferable, and in the range of 0.1 to 1.0 is more preferable in terms of the dispersibility of the colorant and the dispersion stability.

The weight average molecular weight Mw of the block copolymer is not particularly limited, but it is preferably 1000 to 20, 000, and preferably 2000 to 15000 from the viewpoint of making the colorant dispersibility and the dispersion stability favorable. More preferably, it is more preferably 3000 to 12000.
Here, the weight average molecular weight (Mw) is determined as a standard polystyrene equivalent value by gel permeation chromatography (GPC). In addition, it carries out on said conditions also about the macromonomer used as the raw material of a block copolymer, a salt type block copolymer, and a graft copolymer.

  As a specific example of the block copolymer which has a block part which consists of a repeating unit which has such a tertiary amine, and a block part which has solvent affinity, the block copolymer of patent 4911253 is mentioned, for example. It can mention as a suitable thing.

  When the coloring material is dispersed using a polymer containing a repeating unit having a tertiary amine as a dispersant, a polymer containing a repeating unit having the tertiary amine per 100 parts by mass of the coloring material The content of is preferably 15 parts by mass to 300 parts by mass, and more preferably 20 parts by mass to 250 parts by mass. Within the above range, the dispersibility and the dispersion stability are excellent, and the effect of improving the contrast becomes high.

In the present invention, from the viewpoint of the dispersibility and dispersion stability of the coloring material, at least a part of the amino groups in the polymer containing the repeating unit having a tertiary amine, an organic acid compound and a halogenated hydrocarbon It is preferable to use, as a dispersant, one in which a salt has been formed (hereinafter such a polymer may be referred to as a salt-type polymer).
Among them, the polymer having a tertiary amine-containing repeating unit is a block copolymer, and the organic acid compound is an acidic organic phosphorus compound such as phenylphosphonic acid and phenylphosphinic acid, and the like, and the dispersibility of the coloring material And the dispersion stability is preferable. As a specific example of the organic acid compound used for such a dispersing agent, the organic acid compound as described in Unexamined-Japanese-Patent No. 2012-236882 etc. is mentioned as a suitable thing, for example.
The halogenated hydrocarbon is preferably at least one of allyl halides such as allyl bromide and benzyl chloride and aralkyl halides from the viewpoint of excellent dispersibility of the colorant and dispersion stability.

  The content in the case of using the dispersing agent is not particularly limited as long as the coloring material can be uniformly dispersed, but, for example, to the total solid content of the photosensitive colored resin composition for color filter It can be used at 1% by mass to 40% by mass. Furthermore, it is preferable to mix | blend by 2 mass%-30 mass% with respect to solid content whole quantity of the photosensitive colored resin composition for color filters, and it is preferable to mix | blend in the ratio of 3 mass%-25 mass% especially. If it is more than the said lower limit, it is excellent in the dispersibility and dispersion stability of a color material, and is excellent by the storage stability of the photosensitive coloring resin composition for color filters. Further, if it is not more than the above upper limit value, developability becomes good. In particular, when forming a colored layer having a high coloring material concentration, the content of the dispersing agent is preferably 2% by mass to 25% by mass, more preferably the total solid content of the photosensitive colored resin composition for color filter. It is preferable to mix | blend in the ratio of 3 mass%-20 mass%.

[Antioxidant]
The photosensitive colored resin composition for color filters according to the present invention may further contain an antioxidant. The photosensitive colored resin composition for a color filter according to the present invention can improve heat resistance by containing an antioxidant in combination with the oxime ester compound represented by the general formula (1), and can be exposed and Since the decrease in luminance after post-baking can be suppressed, the luminance can be improved, and when forming micropores in the cured film, excessive radical chain reaction in the micropores can be controlled without impairing the curability. The desired shape of the micropores can be more easily formed.
The antioxidant used in the present invention is not particularly limited, and may be appropriately selected from conventionally known ones. Specific examples of the antioxidant include, for example, hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, etc. From the viewpoint of improving the point and the shape of the micropores, it is preferable to use a hindered phenolic antioxidant.

A hindered phenolic antioxidant contains at least one phenol structure, and a structure in which at least one of the 2- and 6-positions of hydroxyl groups of the phenol structure is substituted with a substituent having 4 or more carbon atoms It means the antioxidant which it has.
Specific examples of the hindered phenol-based antioxidant include, for example, dibutyl hydroxytoluene (BHT) and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1010, manufactured by BASF), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2, 4, 6 -Tris (4-hydroxy-3,5-di-tert-butylbenzyl) mesitylene (trade name: Irganox 1330, manufactured by BASF), 6- (4-hydroxy-3,5-di-tert-butylanilino) -2 , 4-Bis (octylthio) -1,3,5-triazine (trade name: Irganox 565) BASF), 2,2'-thiodiethylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1035, BASF), 1,2-bis [3- (4-hydroxy-3,5-di-tert-butylphenyl) propionyl] hydrazine (trade name: Irganox MD 1024, manufactured by BASF), 3- (4-hydroxy-3,5-diisopropylphenyl) propionic acid Octyl (trade name: Irganox 1135, manufactured by BASF), 4,6-bis (octylthiomethyl) -o-cresol (trade name: Irganox 1520 L, manufactured by BASF), N, N'-hexamethylene bis [3- (3,5-Di-tert-butyl-4-hydroxyphenyl) propanamide] (trade name: Irganox 1098 (manufactured by BASF), 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 259, manufactured by BASF), 1-dimethyl- 2-[(3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5.5] undecane (trade name: ADK STAB AO-80) (Made by Adeka), bis (3-tert-butyl-4-hydroxy-5-methylbenzenepropionic acid) ethylenebis (oxyethylene) (trade name: Irganox 245, manufactured by BASF), 1,3,5-tris [ [4- (1,1-Dimethylethyl) -3-hydroxy-2,6-dimethylphenyl] methyl] -1,3,5-triazine- , 4, 6 (1H, 3H, 5H) -trione (trade name: Irganox 1790, manufactured by BASF), 2,2'-methylenebis (6-tert-butyl-4-methylphenol) (trade name: Sumilyzer MDP- S, manufactured by Sumitomo Chemical Co., Ltd., 6,6'-thiobis (2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), 3,5-di-tert-butyl-4-hydroxyl Diethyl benzyl phosphonate (trade name: Irgamod 195, manufactured by BASF), acrylic acid 2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl (trade name: Sumilyzer GM, manufactured by Sumitomo Chemical Co., Ltd., 4,4'-thiobis (6-tert-butyl-m-cresol) (trade name: Sumilyzer WX) R, manufactured by Sumitomo Chemical Co., Ltd.), 6,6'-di -tert- butyl-4,4'-Buchiridenji -m- cresol (trade name: ADK STAB AO-40, manufactured by ADEKA), and the like. In addition, oligomer type and polymer type compounds having a hindered phenol structure can also be used.

In the present invention, a latent antioxidant may be used as the antioxidant. In the present invention, the latent antioxidant is a compound having a protecting group that can be removed by heating, and is a compound that exhibits an antioxidant function by removing the protecting group. Among them, those which are easy to remove the protective group by heating at 150 ° C. or higher are preferable. Since the latent antioxidant does not have an antioxidant function at the time of exposure, it does not deactivate the radicals generated from the photoinitiator, suppresses the decrease in sensitivity, suppresses the narrowing of the line width, and the residual film rate It is easy to improve. On the other hand, in the heating step performed after the exposure, the protective group is desorbed to exhibit an antioxidant effect, so that the color fading of the coloring material and the like is suppressed, and a colored layer with high brightness can be obtained.
As the latent antioxidant preferably used in the present invention, the phenolic hydroxyl group of the hindered phenolic antioxidant can be protected by heating from the viewpoint of improving the heat resistance and the shape of the micropores. The latent hindered phenol type antioxidant protected by group is mentioned, Although although following Chemical formula (a)-(c) etc. are mentioned as a specific example, it is not limited to these.

The method for producing the latent antioxidant is not particularly limited, but, for example, JP-A-57-111375, JP-A-3-173843, JP-A-6-128195, JP-A-7-206771, JP-A-7-252191, It is obtained by reacting a phenolic compound produced by the method described in each publication of 2004-501128 with an acid anhydride, an acid chloride, a Boc forming reagent, an alkyl halide compound, a silyl chloride compound, an allyl ether compound, etc. Can. Alternatively, commercially available products may be used.
Examples of the heat-removable protecting group include reaction residues of acid anhydrides, acid chlorides, Boc-forming reagents, alkyl halide compounds, silyl chloride compounds, or allyl ether compounds, and typically And t-butoxycarbonyl group.

  Although it does not specifically limit as content in the case of using antioxidant, For example, 0.1 mass%-20 mass% are used with respect to the solid content whole quantity of the photosensitive coloring resin composition for color filters be able to. Furthermore, it is preferable to mix | blend by 0.2 mass%-10 mass% with respect to solid content whole quantity of the photosensitive colored resin composition for color filters, and the ratio of 0.3 mass%-5 mass% is especially preferable. It is preferable from the point of sufficiently exhibiting the combined effect with the photo initiator.

In addition, when the photosensitive colored resin composition for color filter of the present invention further contains an antioxidant, the photoinitiator used in the present invention from the viewpoint of sufficiently exhibiting the combined effect with the photo initiator. The total amount is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more with respect to 100 parts by mass in total.
On the other hand, the amount is preferably 300 parts by mass or less, and more preferably 200 parts by mass or less, based on 100 parts by mass of the total of the photoinitiator used in the present invention, from the viewpoint of maintaining appropriate sensitivity.

[Optional Additives]
The photosensitive colored resin composition for color filter may contain various additives as required. As an additive, a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, surfactant, an antifoamer, a silane coupling agent, an ultraviolet absorber, an adhesion promoter, etc. are mentioned, for example.
As a specific example of surfactant and a plasticizer, the thing of Unexamined-Japanese-Patent No. 2013-029832 is mentioned, for example.

  The ratio of the mass (P) of the color material used in the present invention to the mass (V) of solid content other than the color material (hereinafter sometimes referred to as “P / V ratio”) is the color layer of the color filter In the above case, the color development is not limited as long as desired color development is possible, but is preferably in the range of 0.05 or more and 1.00 or less, and is in the range of 0.10 or more and 0.80 or less. More preferably, it is more preferably in the range of 0.15 or more and 0.75 or less, and particularly preferably in the range of 0.20 or more and 0.70 or less. When the P / V ratio is in the above range, a photosensitive colored resin composition for a color filter capable of forming a colored layer capable of desired color formation can be formed, and further, the photosensitive colored resin composition for the above color filter It can be uniformly dispersed in a substance.

In the case of using a red colored resin composition, the P / V ratio is preferably 0.50 or more, more preferably 0.60 or more, and still more preferably 0.74 or more from the viewpoint of desired color development. Is preferred. Moreover, it is preferable that it is 1.0 or less.
In the case of using a green colored resin composition, the P / V ratio is preferably 0.46 or more, more preferably 0.56 or more, and still more preferably 0.68 or more from the viewpoint of desired color development. Is preferred. Moreover, it is preferable that it is 1.0 or less.
In the case of using a blue colored resin composition, the P / V ratio is preferably 0.24 or more, more preferably 0.34 or more, and still more preferably 0.41 or more from the viewpoint of desired color development. Is preferred. Moreover, it is preferable that it is 1.0 or less. If it is respectively above the above lower limit value, the color density of the photosensitive colored resin composition for color filter can be increased, and the color filter pixel can be made to have a higher color rendering and a smaller film thickness. Moreover, if it is each upper limit or less, while it is excellent in storage stability, the colored layer which has sufficient hardness and adhesiveness with a board | substrate can be obtained.

<Method of producing photosensitive colored resin composition for color filter>
The process for producing a photosensitive colored resin composition for a color filter according to the present invention comprises a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, preferably a dispersant, and an antioxidant. It is preferable from the viewpoint of improving the contrast that it is a method in which the coloring material can be uniformly dispersed in the solvent by the dispersing agent, containing various additive components optionally used, and mixing using known mixing means. It can be prepared by
As a method for preparing the resin composition, for example, (1) First, a coloring material and a dispersing agent are added to a solvent to prepare a coloring material dispersion, and to the dispersion, an alkali-soluble resin, light and the like are added. A method of mixing a polymerizable compound, a photoinitiator, and various additive components optionally used; (2) in a solvent, a coloring material, a dispersant, an alkali soluble resin, a photopolymerizable compound, and photoinitiation Method of simultaneously charging and mixing the agent and various additive components optionally used; (3) in the solvent, the dispersant, the alkali-soluble resin, the photopolymerizable compound, the photoinitiator and optionally used A method of adding and mixing various additive components and then mixing and dispersing a coloring material; (4) adding a coloring material, a dispersing agent and an alkali soluble resin to a solvent to prepare a coloring material dispersion To the dispersion, an alkali-soluble resin, a solvent, and light And the like; and polymerizable compound, a photoinitiator, by adding various additive components optionally used, mixing method.
Among these methods, the methods (1) and (4) are preferable from the viewpoint of effectively preventing aggregation of the coloring material and enabling uniform dispersion.

  The method for preparing the colorant dispersion can be appropriately selected and used from conventionally known dispersion methods. For example, (1) The dispersant is mixed in a solvent and stirred beforehand to prepare a dispersant solution, and then, if necessary, an organic acid compound is mixed to form a salt of the amino group of the dispersant and the organic acid compound Let Method of mixing the colorant and other components as needed, and dispersing it using a known stirrer or disperser; (2) mixing the dispersant with a solvent and stirring to prepare a dispersant solution; A method of mixing the coloring material and, if necessary, the organic acid compound and, if necessary, other components, and dispersing them using a known stirrer or disperser; (3) mixing the dispersant with the solvent and stirring , Prepare a dispersant solution, then mix the colorant and other components as needed, and use a known stirrer or disperser to make a dispersion, and then add an organic acid compound as required Methods etc.

  Examples of the disperser for performing the dispersion treatment include roll mills such as 2 rolls and 3 rolls, ball mills such as ball mill and vibration ball mill, paint conditioners, bead mills such as continuous disc type bead mill and continuous annular type bead mill. As a preferable dispersion condition of a bead mill, the bead diameter to be used is preferably 0.03 mm to 2.00 mm, more preferably 0.10 mm to 1.0 mm.

II. Color filter The color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is the photosensitivity for the color filter according to the present invention. It has a colored layer which consists of a hardened material of a colored resin composition.

  Such a color filter according to the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention includes a substrate 1, a light shielding portion 2, and a colored layer 3.

(Colored layer)
At least one of the colored layers used in the color filter of the present invention is a colored layer comprising a cured product of the photosensitive colored resin composition for color filters according to the present invention.
The colored layer is usually formed at an opening of a light shielding portion on a substrate described later, and is usually composed of a colored pattern of three or more colors.
Moreover, it does not specifically limit as arrangement | sequence of the said colored layer, For example, it can be set as general arrangement, such as stripe type, mosaic type, triangle type, 4 pixel arrangement | positioning type | mold. In addition, the width, area, and the like of the colored layer can be set arbitrarily.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration and viscosity of the photosensitive colored resin composition for color filter, etc., but usually, it is preferably in the range of 1 μm to 5 μm. .

The colored layer can be formed, for example, by the following method.
First, the photosensitive colored resin composition for a color filter of the present invention described above will be described later using a coating method such as a spray coating method, dip coating method, bar coating method, roll coating method, spin coating method or die coating method. Apply on top to form a wet coating. Among them, spin coating and die coating can be preferably used.
Next, the wet coating film is dried using a hot plate, an oven or the like, and then exposed to light through a mask of a predetermined pattern to photopolymerize an alkali-soluble resin, a photopolymerizable compound, etc. It is a cured coating film. As a light source used for exposure, ultraviolet rays, such as a low pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp, an electron beam etc. are mentioned, for example. The exposure amount is appropriately adjusted depending on the light source to be used, the thickness of the coating film, and the like.
Further, heat treatment may be performed to promote the polymerization reaction after exposure. The heating conditions are appropriately selected depending on the blending ratio of each component in the photosensitive colored resin composition for color filter to be used, the thickness of the coating film, and the like.

Next, development processing is performed using a developer, and the unexposed area is dissolved and removed to form a coating film in a desired pattern. As a developing solution, usually, a solution in which an alkali is dissolved in water or a water-soluble solvent is used. An appropriate amount of surfactant or the like may be added to the alkaline solution.
Moreover, the developing method can employ | adopt a general method.
After the development processing, washing of the developing solution and drying of the cured coating film of the photosensitive colored resin composition for color filter are usually performed to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after image development processing. There is no limitation in particular as heating conditions, According to the use of a coating film, it selects suitably.

Further, when the color filter according to the present invention has a color filter on array structure or the like, micro holes may be formed in the colored layer during the development process. In the present invention, since the photosensitive colored resin composition for color filters described above is used, desired micropores can be easily formed in the colored layer. The shape of the micropores is appropriately selected depending on the application and is not particularly limited. In the present invention, for example, micropores having a size of about 10 μm × 10 μm to 30 μm × 30 μm can be formed. Further, the shape of the micropores is not particularly limited, and examples thereof include a circle, an ellipse, and a polygon.
As a method of forming the micropores in the colored layer, for example, as a photomask used when forming the colored layer, a micropore for forming the micropores in an opening pattern of a pattern photomask capable of forming a fine line pattern There is a method of using a pattern photomask in which a mask is arranged.

(Light blocking part)
The light shielding portion in the color filter of the present invention is formed in a pattern on a substrate to be described later, and can be similar to that used as a light shielding portion in a general color filter.
It does not specifically limit as a pattern shape of the said light-shielding part, For example, shapes, such as stripe form and a matrix form, are mentioned. The light shielding portion may be a metal thin film such as chromium by sputtering method, vacuum evaporation method or the like. Alternatively, the light shielding portion may be a resin layer in which light shielding particles such as carbon fine particles, metal oxides, inorganic pigments and organic pigments are contained in a resin binder. In the case of a resin layer containing light shielding particles, a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light shielding particles, a method of thermally transferring a photosensitive resist, etc. is there.

  The film thickness of the light shielding portion is set to about 0.2 μm to 0.4 μm in the case of a metal thin film, and set to about 0.5 μm to 2 μm in the case where a black pigment is dispersed or dissolved in a binder resin. Be done.

(substrate)
As the substrate, a transparent substrate to be described later, a silicon substrate, and a transparent substrate or a silicon substrate on which an aluminum, silver, silver / copper / palladium alloy thin film or the like is formed are used. On these substrates, another color filter layer, a resin layer, a transistor such as a TFT, a circuit, or the like may be formed.

The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a substrate transparent to visible light, and a transparent substrate used for general color filters can be used. Specifically, transparent non-flexible rigid material such as quartz glass, non-alkali glass, synthetic quartz plate or the like, or transparent transparent flexible film such as transparent resin film, resin plate for optics, flexible glass etc. Materials are included.
Although the thickness of the said transparent substrate is not specifically limited, According to the use of the color filter of this invention, a thing about 100 micrometers-about 1 mm can be used, for example.
In the color filter of the present invention, in addition to the substrate, the light shielding portion and the colored layer, for example, an overcoat layer, a transparent electrode layer, an alignment film, alignment protrusions, columnar spacers and the like are formed. It is also good.

III. Display Device The display device according to the present invention is characterized by having the color filter according to the present invention. In the present invention, the configuration of the display device is not particularly limited, and can be appropriately selected from conventionally known display devices, and examples thereof include a liquid crystal display device and an organic light emitting display device.

[Liquid crystal display device]
The liquid crystal display device is characterized by including the above-described color filter according to the present invention, an opposing substrate, and a liquid crystal layer formed between the color filter and the opposing substrate.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic view showing an example of the liquid crystal display device of the present invention. As exemplified in FIG. 2, the liquid crystal display device 40 of the present invention comprises a color filter 10, an opposing substrate 20 having a TFT array substrate, etc., and a liquid crystal layer formed between the color filter 10 and the opposing substrate 20. And 30.
The liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2 and can be generally known as a liquid crystal display device using a color filter.

The drive method of the liquid crystal display device of the present invention is not particularly limited, and a drive method generally used for a liquid crystal display device can be adopted. As such a driving method, for example, a TN method, an IPS method, an OCB method, an MVA method and the like can be mentioned. In the present invention, any of these systems can be suitably used.
In addition, the opposite substrate can be appropriately selected and used in accordance with the driving method and the like of the liquid crystal display device of the present invention.
Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy, and a mixture thereof can be used according to the driving method and the like of the liquid crystal display device of the present invention.

  As a method of forming a liquid crystal layer, a method generally used as a method of manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method. After forming the liquid crystal layer by the above method, the liquid crystal cell can be gradually cooled to room temperature to orient the enclosed liquid crystal.

[Organic light emitting display]
The organic light emitting display device is characterized by including the above-described color filter according to the present invention and an organic light emitter.
Such an organic light emitting display according to the present invention will be described with reference to the drawings. FIG. 3 is a schematic view showing an example of the organic light emitting display device of the present invention. As illustrated in FIG. 3, the organic light emitting display device 100 of the present invention has a color filter 10 and an organic light emitting body 80. An organic protective layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitting body 80.

As a method of laminating the organic light emitting body 80, for example, the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 are sequentially formed on the upper surface of the color filter. The method, the method of bonding the organic light-emitting body 80 formed on another substrate on the inorganic oxide film 60, etc. are mentioned. The transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 in the organic light emitting body 80 can be appropriately selected from other known constitutions. The organic light emitting display device 100 manufactured in this manner is applicable to, for example, a passive drive type organic EL display and an active drive type organic EL display.
The organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and can be generally known as an organic light emitting display device using a color filter.

Hereinafter, the present invention will be specifically described by way of examples. These descriptions do not limit the present invention.
The structures of the obtained compounds are 1 H- and 13 C-NMR spectra measured using a nuclear magnetic resonance apparatus (Bruker Biospin AG, AVANCE III HD 500 MHz), and a liquid chromatograph mass spectrometer (Shimadzu Corporation, LC- 30A, confirmed by mass spectrometry using Bruker Daltonics Inc. (micrOTO FQ 2).

Synthesis Example 1: Synthesis of Compound A
(1) Synthesis of Intermediate A1 0.60 mol of fluorene, 2.4 mol of potassium hydroxide and 0.06 mol of potassium iodide are dissolved in 500 ml of anhydrous dimethyl sulfoxide under a nitrogen atmosphere and maintained at 15 ° C., 1.33 mol of bromobutane The reaction was stirred at 15 ° C. for 1 hour with slow addition over 2 hours. After that, 2 L of distilled water was added to the reaction product, and after stirring for about 30 minutes, the product was extracted with 2 L of dichloromethane, and the extracted organic layer was washed twice with 2 L of distilled water. Then, the collected organic layer is dried over anhydrous MgSO ₄ , and the solvent is distilled under reduced pressure, and the product obtained is purified by silica gel column chromatography (developing solvent: ethyl acetate: n-hexane = 1: 20), The following intermediate A1 was obtained.

(2) Synthesis of Intermediate A2 The intermediate A1 (0.11 mol) is dissolved in 500 ml of dichloromethane and cooled to −5 ° C., 0.13 mol of AlCl ₃ is gradually added, and the temperature of the reaction product is not raised Thus, a solution consisting of 15 ml of dichloromethane and 0.13 mol of cyclohexylpropionyl chloride was slowly added dropwise over 1 hour and stirred at -5 ° C for 1 hour. Thereafter, the reaction product was gradually poured into 500 ml of ice water and stirred for 30 minutes, and then the organic layer was washed with 200 mL of distilled water. Subsequently, the product obtained by distilling under reduced pressure the recovered organic layer was purified by silica gel column chromatography (developing solvent; ethyl acetate: n-hexane = 1: 4) to obtain the following Intermediate A2.

(3) Synthesis of Intermediate A3 The above Intermediate A2 (0.042 mol) is dissolved in 200 ml of tetrahydrofuran (THF), and 25 ml of 4 N HCl dissolved in 1,4-dioxane and 0.063 mol of isobutyl nitrite are added in order to cause a reaction. The mixture was stirred at 25 ° C. for 6 hours. Thereafter, 200 ml of ethyl acetate was added to the reaction solution, and the mixture was stirred for 30 minutes to separate the organic layer, and then washed with 200 ml of distilled water. Then, the collected organic layer is dried over anhydrous MgSO ₄ , and the solvent is distilled under reduced pressure, and the product obtained is purified by silica gel column chromatography (developing solvent; ethyl acetate: n-hexane = 1: 4), The following intermediate A3 was obtained.

(4) Synthesis of Compound A The intermediate A3 (0.056 mol) is dissolved in 200 ml of N-methyl-2-pyrrolidinone (NMP) in a nitrogen atmosphere and maintained at -5 ° C, and 0.068 mol of triethylamine is added thereto. The reaction solution was stirred for 30 minutes. Thereafter, a solution consisting of 0.068 mol of acetyl chloride and 10 ml of N-methyl-2-pyrrolidinone was gradually added over 30 minutes, and the mixture was stirred for 30 minutes so that the reaction was not heated. Thereafter, 200 ml of distilled water was gradually added to the reaction product, and the mixture was stirred for 30 minutes to separate the organic layer. Then, the collected organic layer was dried over anhydrous MgSO ₄ , and the solvent was distilled under reduced pressure, and the product obtained was recrystallized using 1 L of ethanol and then dried to obtain the following compound A.

Synthesis Example 2: Synthesis of Compound B
(1) Synthesis of Intermediate B1 In the same manner as in (1) of Synthesis Example 1 except that purification by silica gel column chromatography was not performed using the same mole of bromoethane instead of bromobutane in (1) of Synthesis Example 1. The following Intermediate B1 was obtained.

(2) Synthesis of Intermediate B2 Except that the same molar intermediate B1 was used in place of intermediate A1 and the same molar propionyl chloride was used in place of cyclohexyl propionyl chloride in the synthesis example 1 (2), The following Intermediate B2 was obtained in the same manner as in Synthesis Example 1 (2).

(3) Synthesis of Intermediate B3 In (3) of Synthesis Example 1, ethyl acetate: n-hexane (1: 6) was used in place of intermediate A2 and using the same molar amount of the intermediate B2 instead of silica gel column chromatography. The following Intermediate B3 was obtained in the same manner as (3) of Synthesis Example 1 except that purification was performed by drying after recrystallization using the mixed solvent of).

(4) Synthesis of Compound B The following compound B was prepared in the same manner as (4) in Synthesis Example 1 except that the same molar intermediate B3 was used instead of Intermediate A3 in Synthesis Example 1 (4). I got

Synthesis Example 3: Synthesis of Compound C
The following compound C was obtained in the same manner as in Synthesis Example 2 except that the same molar amount of butyryl chloride was used instead of propionyl chloride in Synthesis Example 2 (2).

Synthesis Example 4 Synthesis of Compound D
(1) Synthesis of Intermediate D1 0.030 mol of 9H-fluoren-2-yl- (phenyl) methanone was dissolved in 45 ml of dichloromethane, cooled to -5 ° C, 0.033 mol of anhydrous AlCl ₃ was added, and then 9 ml of dichloromethane A solution consisting of and 0.033 mol of propionyl chloride was gradually added over 1 hour so that the temperature of the reaction product was not raised, and stirred at -5 ° C for 1 hour. Thereafter, the reaction product was gradually poured into 250 g of ice water and stirred for 30 minutes, and then the organic layer was separated and washed with 100 ml of distilled water. Next, the product obtained by distilling the collected organic layer under reduced pressure was recrystallized with 20 ml of a mixed solution of toluene: ethyl acetate (5: 1) to obtain the following intermediate D1.

(2) Synthesis of Intermediate D2 The intermediate D1 (0.010 mol) is dissolved in 30 ml of tetrahydrofuran (THF), and 4.5 ml of 4 N HCl dissolved in 1,4-dioxane and 0.015 mol of isopentyl nitrite are sequentially added The reaction was stirred at 25 ° C. for 24 hours. Thereafter, 20 ml of ethyl acetate and 50 ml of distilled water were added to the reaction solution to extract the organic layer. The extracted organic layer is dried over anhydrous MgSO ₄ , and the product obtained by distilling the solvent under reduced pressure is recrystallized using 30 ml of a mixed solvent of ethanol: ethyl acetate (5: 1) and then dried. The following intermediate D2 was obtained.

(3) Synthesis of Compound D The above intermediate D2 (0.006 mol) is dissolved in 25 ml of ethyl acetate under nitrogen atmosphere, the reaction product is maintained at -5 ° C, 0.007 mmol of triethylamine is added, and the reaction solution is kept for 30 minutes. After stirring, a solution consisting of 0.007 mol of acetyl chloride and 5 ml of ethyl acetate was gradually added over 30 minutes so that the reaction was not heated, and stirred for 30 minutes. Thereafter, 100 ml of distilled water was gradually added to the reaction product, and the mixture was stirred for about 30 minutes to separate the organic layer. Then, the collected organic layer was dried over anhydrous MgSO ₄ , and the solvent was distilled under reduced pressure to obtain the following compound D.

Synthesis Example 5 Synthesis of Compound E
(1) Synthesis of Intermediate E1 In a 500 ml four-necked flask, 0.2 mol of diphenylthioether, 0.22 mol of crushed AlCl ₃ and 150 ml of dichloroethane are charged and stirred, and argon gas is flowed in an ice bath When cooled to a temperature of 0 ° C., a solution consisting of 0.22 mol of cyclohexylpropionyl chloride and 42 g of dichloroethane was added dropwise, and added over about 1.5 hours while adjusting the temperature to 10 ° C. or less. The temperature was raised to 15 ° C. and stirring was continued for 2 hours, and then the reaction solution was drained.
The reaction solution is gradually added under stirring into dilute hydrochloric acid containing 400 g of ice and 65 ml of concentrated hydrochloric acid, and the lower layer is separated by a separatory funnel, and the upper layer is extracted with 50 ml of dichloroethane, and then the extract and the lower layer The solution was combined. After that, it was washed with a NaHCO ₃ solution containing 10 g of NaHCO ₃ and 200 g of water, and further washed three times with 200 ml of water until the pH value became neutral, and dried with 60 g of anhydrous MgSO ₄ to remove water. After that, dichloroethane was evaporated by rotary evaporation. The solid powder remaining in the rotary evaporation bottle was placed in 200 ml of petroleum ether, subjected to suction filtration, further poured into 150 ml of absolute ethanol and heated to reflux. Thereafter, the mixture was cooled to room temperature, further cooled with ice for 2 hours, suction-filtered, and then dried in an oven at 50 ° C. for 2 hours to obtain the following Intermediate E1.

(2) Synthesis of Intermediate E2 In a 500 ml four-necked flask, 42 g of the intermediate E1, 400 g of tetrahydrofuran, 200 g of concentrated hydrochloric acid and 24.2 g of isoamyl nitrite were added and stirred at room temperature for 5 hours After that, the reaction solution was drained.
The reaction solution was placed in a large beaker, and 1000 ml of water was added and stirred, and then allowed to stand overnight to separate layers, to obtain a yellow viscous liquid. The viscous稠状liquid extraction with dichloroethane, after is dried over anhydrous MgSO ₄ for 50 g, subjected to suction filtration, the filtrate rotary evaporated to remove the solvent to give a viscous oil稠物. Subsequently, the viscous material was poured into 150 ml of petroleum ether, stirred, precipitated, and suction filtered to obtain a white powdery solid. Thereafter, the resultant was dried at 60 ° C. for 5 hours to obtain the following Intermediate E2.

(3) Synthesis of Compound E In a 1000 ml four-necked flask, 34 g of the intermediate E2, 350 ml of dichloroethane and 12.7 g of triethylamine were added and stirred, and cooled in an ice bath to a temperature of 0 ° C. When dropping, a solution consisting of 15.7 g of acetic acid chloride and 15 g of dichloroethane was added dropwise and added over about 1.5 hours. After stirring for 1 hour, 500 ml of cold water was added dropwise, and the layers were separated with a separatory funnel. Wash once with 200 ml of 5% NaHCO ₃ solution and twice with 200 ml of water until the pH value becomes neutral, then wash once with dilute hydrochloric acid containing 20 g of concentrated hydrochloric acid and 400 ml of water, then 200 ml of water After washing with 3 times, it was dried over 100 g of anhydrous MgSO ₄ and the solvent was removed by rotary evaporation to obtain a viscous liquid. An appropriate amount of methanol was added to the viscous liquid, and the precipitated white solid was filtered and dried to obtain the following compound E.

Synthesis Example 6: Synthesis of Compound F
The following compound F was synthesized in the same manner as in Synthesis Example 5 except that the same molar amount of [4- (phenylthio) phenyl] -2-thienyl-methanone was used in place of diphenylthioether in (1) of Synthesis Example 5 did.

Synthesis Example 7 Preparation of Dispersant (Block Copolymer A)
250 parts by mass of THF and 0.6 parts by mass of lithium chloride are added to a 500 mL round-bottom four-neck separable flask equipped with a condenser, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer The After cooling the reaction flask to -60 ° C, 4.9 parts by mass of butyllithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine and 1.0 parts by mass of methyl isobutyrate were injected using a syringe. B-block monomers: 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA), 18.7 parts by mass of 2-hydroxyethyl methacrylate (HEMA), 12.8 parts by mass of 2-ethylhexyl methacrylate (EHMA), methacrylic 13.7 parts by mass of n-butyl acid (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA) and 17.5 parts by mass of methyl methacrylate (MMA) were dropped over 60 minutes using an addition funnel . After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, and diluted with PGMEA to obtain a solid solution of 30% by mass. 32.5 parts by mass of water was added, the temperature was raised to 100 ° C., and reaction was carried out for 7 hours to deprotect the structural unit derived from EEMA to obtain a structural unit derived from methacrylic acid (MAA). The block copolymer PGMEA solution obtained is reprecipitated in hexane, purified by filtration and vacuum drying, and a structural unit derived from an A block containing a structural unit represented by the general formula (I) and a carboxyl group-containing monomer Block copolymer A (acid value: 8 mg KOH / g, Tg 38 ° C.) containing B block having a solvent resistance. The block copolymer A thus obtained was confirmed by GPC (gel permeation chromatography), and the weight average molecular weight Mw was 7730. Moreover, the amine titer was 95 mg KOH / g.

Synthesis Example 8 Synthesis of Alkali-Soluble Resin A Solution
A mixed solution of 40 parts by mass of styrene, 15 parts by mass of MMA, 25 parts by mass of MAA, and 3 parts by mass of AIBN is dropped into a polymerization tank containing 150 parts by mass of PGMEA at 100 ° C. for 3 hours under a nitrogen stream. did. After completion of the dropwise addition, the solution was further heated at 100 ° C. for 3 hours to obtain a polymer solution. The weight average molecular weight of this polymer solution was 7,000.
Next, 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol are added to the obtained polymer solution, and heated at 110 ° C. for 10 hours to react Air was bubbled into the solution. The obtained alkali-soluble resin A is a resin in which a side chain having an ethylenic double bond is introduced to the main chain formed by the copolymerization of styrene, MMA and MAA using GMA, and the solid content is 42.6 mass. %, Acid value 74 mg KOH / g, and weight average molecular weight 12000. The weight average molecular weight was measured by Shodex GPC system-21 H (Shodex GPC System-21 H) using polystyrene as a standard substance and THF as an eluent. Moreover, the measuring method of an acid value was measured based on JISK 0070.

Synthesis Example 9 Synthesis of Blue Color Material α
(1) Synthesis of Intermediate 1 Referring to the method for producing Intermediate 3 and Intermediate 4 described in WO 2012/144521, 15.9 g of Intermediate 1 represented by the following Chemical Formula (1) Yield 70%).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 511 (+), Divalent Elemental Analysis: CHN found (78.13%, 7.48%, 7.78%); theoretical value (78.06%) , 7.75%, 7.69%)

(2) Synthesis of Blue Coloring Material α The above Intermediate 1 5.00 g (4.58 mmol) was added to 300 ml of water and dissolved at 90 ° C. to prepare an Intermediate 1 solution. Next, 10.44 g (3.05 mmol) of phosphotungstic acid n hydrate H ₃ [PW ₁₂ O ₄₀ ] n H ₂ O (n = 30) (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.) is added to 100 ml of water, and 90 ° C. The solution was stirred to prepare an aqueous solution of phosphotungstic acid. The prepared phosphotungstic acid aqueous solution was mixed with the above Intermediate 1 solution at 90 ° C., and the formed precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 13.25 g of a blue coloring material α of a metal lake color material of a triarylmethane basic dye represented by the following chemical formula (2).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 510 (+), Divalent Elemental Analysis: CHN found (41.55%, 5.34%, 4.32%); theoretical value (41.66%) , 5.17%, 4.11%)

Synthesis Example 10 Preparation of Azo Derivative 1
In 550 g of distilled water, 23.1 g of diazobarbituric acid and 19.2 g of barbituric acid were introduced. Then, it was adjusted to be azobarbituric acid (0.3 mol) using an aqueous potassium hydroxide solution, and mixed with 750 g of distilled water. 5 g of 30% hydrochloric acid were added dropwise. Thereafter, 38.7 g of melamine was introduced. Then, 0.39 molar nickel chloride solution and 0.21 molar zinc chloride solution were mixed and added, and stirred at a temperature of 80 ° C. for 8 hours. The pigment was isolated by filtration, washed, dried at 120 ° C. and ground in a mortar to obtain Azo derivative 1 (Ni-azo-1, azo pigment of Ni: Zn = 65: 35 (molar ratio)) .

Synthesis Example 11 Preparation of Azo Derivative 2
In the preparation of Azo derivative 1 of Synthesis Example 10, 0.42 mol of nickel chloride solution and 0.18 mol of zinc chloride solution are used instead of 0.39 mol of nickel chloride solution and 0.21 mol of zinc chloride solution. Azo derivative 2 (Ni-azo-2, azo pigment of Ni: Zn = 70: 30 (molar ratio)) was obtained in the same manner as in Synthesis Example 10 except that it was used.

Synthesis Example 12 Preparation of Azo Derivative 3
In the preparation of Azo derivative 1 of Synthesis Example 10, 0.3 mol of nickel chloride solution and 0.3 mol of zinc chloride solution are used instead of 0.39 mol of nickel chloride solution and 0.21 mol of zinc chloride solution. Azo derivative 3 (Ni-azo-3, azo pigment of Ni: Zn = 50: 50 (molar ratio)) was obtained in the same manner as in Synthesis Example 10 except that it was used.

Synthesis Example 13 Preparation of Azo Derivative 4
In the preparation of Azo derivative 1 of Synthesis Example 10, 0.18 molar nickel chloride solution and 0.42 molar zinc chloride solution are used instead of 0.39 molar nickel chloride solution and 0.21 molar zinc chloride solution. Azo derivative 4 (Ni-azo-4, azo pigment of Ni: Zn = 30: 70 (molar ratio)) was obtained in the same manner as in Synthesis Example 10 except that it was used.

Synthesis Example 14 Preparation of Azo Derivative 5
In preparation of Azo derivative 1 of Synthesis Example 10, 0.06 mol of nickel chloride solution and 0.54 mol of zinc chloride solution are used instead of 0.39 mol of nickel chloride solution and 0.21 mol of zinc chloride solution. Azo derivative 5 (Ni-azo-5, azo pigment of Ni: Zn = 10: 90 (molar ratio)) was obtained in the same manner as in Synthesis Example 10 except that it was used.

Synthesis Example 15 Synthesis of Potential Antioxidant (Compound a)
0.01 mol of a phenol compound represented by the following chemical formula (3), 0.05 mol of di-tert-butyl dicarbonate and 30 g of pyridine are mixed, 0.025 mol of 4-dimethylaminopyridine is added at room temperature under a nitrogen atmosphere, and 60 Stir at C for 3 hours. After cooling to room temperature, the reaction solution was poured into 150 g of ion exchanged water, and 200 g of chloroform was added to conduct oil-water separation. The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and 100 g of methanol was added to the residue for crystallization. The obtained white powdery crystals were dried under reduced pressure at 60 ° C. for 3 hours to obtain a latent antioxidant (compound a) represented by the chemical formula (a). In addition, the structure of the obtained latent antioxidant was confirmed by IR and NMR.

Example 1
(1) Production of Color Material Dispersion 1 5.1 parts by mass of block copolymer A of Synthesis Example 7 as a dispersant, 13.0 parts by mass of blue color material α obtained in Synthesis Example 9 as a colorant, 5.1 parts by mass in terms of solid content of the alkali-soluble resin A solution obtained in Synthesis Example 8 and 76.8 parts by mass of PGMEA and 100 parts by mass of zirconia beads with a particle diameter of 2.0 mm are put into mayonnaise bottle and pre-crushed Shake for 1 hour with a paint shaker (manufactured by Asada Iron Works, Ltd.), take out 2.0 mm zirconia beads, add 200 parts by mass of 0.1 mm zirconia beads, The dispersion was performed for 4 hours with a paint shaker to obtain a colorant dispersion 1.

(2) Production of photosensitive colored resin composition 1 for color filter 286.1 parts by mass of coloring material dispersion 1 obtained in the above (1), solid solution of alkali soluble resin A solution obtained in synthesis example 8 8.6 parts by mass in conversion, 18.2 parts by mass of a photopolymerizable compound (trade name: Alonix M-520D, manufactured by Toagosei Co., Ltd.), 2.0 parts by mass of dibutyl hydroxytoluene (BHT) as an antioxidant Part and 5.1 mass parts of compound A obtained by the synthesis example 1 as a photoinitiator, 42.2 mass parts of PGMEA were added, and the photosensitive colored resin composition 1 for color filters was obtained.

(Examples 2 to 13)
Photosensitive colored resin compositions 2 to 13 for color filters were obtained in the same manner as in Example 1 except that the photoinitiator was used in the type and amount shown in Table 1 in Example 1.

  In addition, OXE-01 used as a photoinitiator in Example 8 is an oxime ester photoinitiator (brand name Irgacure OXE-01, BASF make), and is a compound represented by following Chemical formula (4).

(Example 14)
Photosensitive coloring resin for color filter in the same manner as in Example 13 except that a bisphenol antioxidant (Adekastab AO-40, manufactured by ADEKA) was used instead of BHT as the antioxidant in Example 13. The composition 14 was obtained.

(Example 15)
Photosensitive coloring resin composition for a color filter in the same manner as in Example 13 except that a hindered phenol type antioxidant (Irg1010, manufactured by BASF) was used instead of BHT as the antioxidant. I got the thing 15.

(Example 16)
Photosensitivity for color filter in the same manner as in Example 13, except that Compound a which is a latent antioxidant obtained in Synthesis Example 15 was used in place of BHT as the antioxidant in Example 13. A colored resin composition 16 was obtained.

(Examples 17 to 21)
Photosensitive coloring for color filter in the same manner as in Example 1 except that the amounts of the alkali-soluble resin, the photopolymerizable compound, the photoinitiator and the antioxidant in Example 1 were changed to the amounts shown in Table 1. Resin compositions 17 to 21 were obtained.

(Comparative Examples 1 to 3)
In Example 21, in the same manner as in Example 21, except that the photoinitiator shown in Table 1 was used instead of the compound A obtained in Synthesis Example 1 as a photoinitiator, the photosensitivity for comparison color filter Colored resin compositions 1 to 3 were obtained.

  The photoinitiator used by the comparative example 1 is OXE-02 (made by BASF) represented by following Chemical formula (5).

  The photoinitiator used in Comparative Example 3 is a comparative compound A represented by the following chemical formula (6).

(Example 22)
Photosensitive colored resin composition for a color filter in the same manner as in Example 13 except that 37.2 parts by mass of pigment red 254 (PR254) was used in place of blue color material α as a coloring material in Example 13. I got 22.

(Comparative example 4)
In Example 22, without using Compound A obtained in Synthesis Example 1 as a photoinitiator, Compound E obtained in Synthesis Example 5 and Irg 819 (manufactured by BASF), OXE represented by the above-mentioned chemical formula (5) Comparative color filter in the same manner as in Example 22 except that 02 (manufactured by BASF) was used in the amount shown in Table 2, no antioxidant (BHT) was used, and 20.2 parts by mass of the photopolymerizable compound was used. A photosensitive colored resin composition 4 was obtained.

(Example 23)
In Example 13, except that 16.48 parts by mass of Pigment Green 59 (PG 59) and 20.72 parts by mass of Azo derivative 1 obtained in Synthesis Example 10 were used instead of blue color material α as a coloring material. In the same manner as in Example 13, a photosensitive colored resin composition 23 for color filter was obtained.

(Comparative example 5)
In Example 23, the compound A obtained in Synthesis Example 1 as the photoinitiator, the compound E obtained in Synthesis Example 5 and Irg 819 (manufactured by BASF) were not used, and the OXE represented by the chemical formula (5) was used. Comparative color filter in the same manner as in Example 23 except that 02 (manufactured by BASF) was used in the amount shown in Table 2, no antioxidant (BHT) was used, and 20.2 parts by mass of the photopolymerizable compound was used. A photosensitive colored resin composition 5 was obtained.

(Example 24)
In Example 13, in place of blue coloring material α as a coloring material, C.I. I. Photosensitive coloring for color filter in the same manner as in Example 13 except that 37.2 parts by mass of Solvent Yellow 162, 20.2 parts by mass of the photopolymerizable compound was used without using the antioxidant (BHT), and The resin composition 24 was obtained.

(Comparative example 6)
In Example 24, without using Compound A obtained in Synthesis Example 1 as a photoinitiator, Compound E obtained in Synthesis Example 5 and Irg 819 (manufactured by BASF), OXE represented by the above chemical formula (5) A photosensitive colored resin composition 6 for comparison color filter was obtained in the same manner as in Example 24 except that 02 (manufactured by BASF) was used in the amount shown in Table 2.

(Example 25)
Example 16 is an example except that 23.8 parts by mass of pigment green 58 and 13.4 parts by mass of Azo derivative 2 obtained in Synthesis Example 11 are used instead of blue color material α as a coloring material. In the same manner as in 16, a photosensitive colored resin composition 25 for color filter was obtained.

(Example 26)
Example 16 is an example except that 24.5 parts by mass of pigment green 58 and 12.7 parts by mass of Azo derivative 3 obtained in Synthesis Example 12 are used instead of blue color material α as a coloring material. In the same manner as in 16, a photosensitive colored resin composition 26 for color filter was obtained.

(Example 27)
In Example 16, 25.3 parts by mass of Pigment Green 58 and 11.9 parts by mass of Azo derivative 4 obtained in Synthesis Example 13 were used in place of blue color material α as a coloring material. In the same manner as in 16, a photosensitive colored resin composition 27 for color filter was obtained.

(Example 28)
Example 16 is an example except that 26.1 parts by mass of pigment green 58 and 11.1 parts by mass of Azo derivative 5 obtained in Synthesis Example 14 are used instead of blue color material α as a coloring material. In the same manner as in 16, a photosensitive colored resin composition 28 for color filter was obtained.

(Example 29)
A photosensitive colored resin composition 29 for a color filter was obtained in the same manner as in Example 27, except that BHT was used instead of the compound a as the antioxidant in Example 27.

(Example 30)
A photosensitive colored resin composition 30 for a color filter is obtained in the same manner as in Example 27 except that 20.2 parts by mass of the photopolymerizable compound is used without using the compound a of the antioxidant in Example 27. The

(Comparative example 7)
In Example 27, without using Compound A obtained in Synthesis Example 1 as a photoinitiator, Compound E obtained in Synthesis Example 5 and Irg 819 (manufactured by BASF), OXE represented by the above-mentioned chemical formula (5) Photosensitivity for comparison color filter in the same manner as in Example 27 except that 02 (manufactured by BASF) was used in the amount shown in Table 2, and no antioxidant was used, and 20.2 parts by mass of the photopolymerizable compound was used. Colored resin composition 7 was obtained.

[Evaluation]
The photosensitive colored resin composition obtained in each Example and each Comparative Example was coated on a glass substrate ("NH35" manufactured by NH Techno Glass Co., Ltd.) using a spin coater, and the thickness of the cured coating was 3 After coating to a thickness of 0 μm, it was dried at 80 ° C. for 3 minutes using a hot plate to form a coating on a glass substrate. This coating film is exposed to UV light of 40 mJ / cm ² using an ultra-high pressure mercury lamp through a pattern photomask (chromium mask) in which a 20 μm × 20 μm chromium mask is arranged at the center in an independent thin line of 90 μm × 300 μm. By exposure, a coating film after exposure was formed on the glass substrate. Next, spin development is carried out using a 0.05 wt% potassium hydroxide aqueous solution as a developer, and after making the developer indirect solution for 60 seconds, development is carried out by washing with pure water, and a coating film is formed I got Thereafter, post-baking was carried out in a clean oven at 230 ° C. for 25 minutes to form a colored layer in the form of an independent fine line pattern having micropores. The following evaluation was performed about the obtained colored layer.

<Optical characteristics evaluation>
The photosensitive colored resin composition obtained in each Example and each Comparative Example is coated on a glass substrate ("NA 35" manufactured by NH Techno Glass Co., Ltd.) using a spin coater, and then a hot plate is formed. It was dried at 80 ° C. for 3 minutes to form a coating on a glass substrate. The entire surface was irradiated with ultraviolet light of 60 mJ / cm ² using an ultra-high pressure mercury lamp without using a photomask to form a coated film after exposure. Subsequently, spin development was carried out using a 0.05 wt% aqueous potassium hydroxide solution as a developer, and the developer was made to be an indirect solution for 60 seconds and then washed with pure water to develop and form a coated film after development. After that, post-baking in a clean oven at 230 ° C for 25 minutes, y = 0.083 when using the blue coloring material α, x = 0.650 when using PR254, and PG59 / Azo derivative When y is used, y = 0.610, C.I. A cured coating (colored layer) was formed so that y = 0.503 when I solvent yellow 162 was used, and y = 0.630 when PG58 / Azo derivative was used. The chromaticity (x, y) and the luminance (Y) of the colored layer were measured using an Olympus microspectroscope OSP-SP200.

<Evaluation of developability>
[Linearity]
The width of the thin line pattern of the colored layer in a portion corresponding to the opening width 90 μm of the chromium mask used at the time of exposure was measured at five places with an optical microscope, and the linearity was evaluated by the variation of the line width.
A: Variation is within ± 0.1 μm B: Variation is above ± 0.1 μm ± 0.3 μm C: Variation is above ± 0.3 μm [Remaining film rate]
In the formation of the colored layer, in the process of forming a coating film, the film thickness after exposure (E) and the film thickness after development (D) were measured with a stylus profiler P-16 (manufactured by KLA-Tencor). The film thickness after development (D) / film thickness after exposure (E) was calculated as the residual film ratio.
The film thickness after development (D) / film thickness after exposure (E) is 90% or more, which is a range suitable for practical use.

The colored layer was observed with an optical microscope, and the shape, flicker and development residue of micropores were evaluated according to the following evaluation criteria.
[shape]
A: With respect to the size of the chromium mask arranged in the independent thin line pattern, the deviation of the size of the micropores formed in the colored layer is smaller than 2% in absolute value. B: The chromium mask arranged in the independent thin line pattern The displacement of the dimension of the micropores formed in the colored layer is 2% or more and 6% or less in absolute value with respect to the dimension of C. C: formed in the colored layer with respect to the dimension of the chromium mask disposed in the independent thin line pattern The dimensional deviation of the micropores is larger than 6% and 8% or less in absolute value D: The deviation of the micropores formed in the colored layer is smaller than the size of the chromium mask disposed in the independent thin line pattern The absolute value is larger than 8%. The dimensional deviation is calculated as the average value of the dimensional deviation of each side.
[Billitsuki]
A: The ten-point average roughness of the peripheral portion of the micropores formed in the colored layer is smaller than 0.1 B: The ten-point average roughness of the peripheral portion of the micropores formed in the colored layer is 0.1 or more .5 or less C: The ten-point average roughness of the peripheral portion of the micropores formed in the colored layer is larger than 0.5 The ten-point average roughness was measured in accordance with JIS B0601.
[Development residue]
AA: No coloration is observed in the inside of the micropores formed in the colored layer by observation with an optical microscope, and no transparent material is observed at the periphery of the micropores A: Inside of the micropores formed in the coloring layer by observation with an optical microscope Coloration is not observed, but some transparency is observed at the periphery of the micropores B: coloration is observed inside the micropores formed in the colored layer by observation with an optical microscope

The abbreviations in Tables 1 and 2 are as follows.
OXE-01: oxime ester photoinitiator (trade name Irgacure OXE-01, manufactured by BASF)
-OXE-02: oxime ester photoinitiator (trade name Irgacure OXE-02, manufactured by BASF)
Irg 369: α-amino ketone photoinitiator (Irgacure 369, manufactured by BASF)
Irg 907: α-amino ketone photoinitiator (Irgacure 907, manufactured by BASF)
-Mercapto type: Mercapto chain transfer agent (2-mercaptobenzothiazole, manufactured by Tokyo Kasei Co., Ltd.)
・ Biimidazole type: Biimidazole type photoinitiator (HABI, black gold chemical made)
-DETX: Thioxanthone photoinitiator (DOUBLECURE DETX, manufactured by Double Bond Chemical)
· Irg 819: Acyl phosphine oxide photoinitiator (Irgacure 819, manufactured by BASF · BHT: dibutyl hydroxytoluene · AO-40: bisphenol antioxidant (Adekastab AO-40, manufactured by ADEKA)
Irg1010: hindered phenolic antioxidant (IRGACURE 1010, manufactured by BASF)

<Summary of results>
The photosensitive colored resin compositions of Examples 1 to 30, which contain the oxime ester compound represented by the general formula (1) as a photoinitiator, are compared to the comparative photosensitive colored resin compositions using the same coloring material. In comparison, it was revealed that a colored layer with improved brightness can be formed. Moreover, the colored resin composition of Examples 1-30 had a high residual film rate, and the sensitivity was favorable. It was revealed that the photosensitive colored resin compositions of Examples 1 to 30 were excellent in the linearity of the fine line pattern and that it is easy to form desired micropores in the colored layer simultaneously when patterning the colored layer. In Examples 1 to 3 using the oxime ester compound in which Z in the general formula (1) is a hydrogen atom, the luminance and the residual film ratio are high, and in the general formula (1), Z is-(C = O Example 4 using the oxime ester compound which is R ^d ) had better solvent solubility of the oxime ester compound and compatibility with other components, and had better shape of micropores. When the cross section of the micropores of Example 1 and Example 2 was observed and compared, the taper angle was more gradual in Example 2 and the shape of the micropores was better.
In addition, the shape of the micropores became better by using the oxime ester compound represented by the general formula (1) and the oxime ester compound having a diphenyl sulfide skeleton in combination as the photoinitiator. Comparison of Example 1 with Example 5 and Comparison of Example 2 with Examples 6-8).
Further, as the photoinitiator, an oxime ester compound represented by the above general formula (1) and an oxime ester compound having a diphenyl sulfide skeleton are combined, and further, an α-amino ketone based photoinitiator, a biimidazole based photoinitiator The linearity of the fine line pattern is improved by containing at least one selected from a thioxanthone photoinitiator, an acylphosphine oxide photoinitiator, and a mercapto chain transfer agent, and the shape of the micropores is better. (Comparison of Example 5 with Examples 9 to 13).
In addition, the inclusion of the antioxidant further suppressed the flicker of the micropores and improved the luminance (comparison of Example 1 with Example 21, comparison of Examples 27 and 29 with Example 30). Among the antioxidants, when the latent antioxidant (compound a) was used, the residual film rate was as good as in the case where the antioxidant was not used while the flicker of the micropores was further suppressed. On the other hand, when the hindered phenol type antioxidant which is not the latent antioxidant is used, the luminance is more improved than when the latent antioxidant is used (Examples 27 and 29 and Example 30) Comparison).
On the other hand, in Comparative Example 1 and Comparative Examples 4 to 7 using the oxime ester compound having a carbazole skeleton without containing the oxime ester compound represented by the general formula (1) as a photoinitiator, the same coloring material is used The brightness was inferior to that of the example described above, and the linearity of the fine line pattern was inferior, and it was not possible to form micropores.
In addition, in Comparative Example 2 using Irg 907 (α-amino ketone photoinitiator) without containing the oxime ester compound represented by the above general formula (1) as a photoinitiator, the luminance and the residual film ratio are inferior. The
Comparative compound A which does not contain the oxime ester compound represented by the above general formula (1) as a photoinitiator, has a nitro group in the fluorene skeleton, and has an oxime ester group bonded to the fluorene skeleton without passing a carbonyl group. The luminance and the linearity were inferior in Comparative Example 3 using. The poor linearity of Comparative Example 3 is presumed to be due to the poor solvent solubility of Comparative Compound A and the poor compatibility with other components.

Reference Signs List 1 substrate 2 light shielding unit 3 colored layer 10 color filter 20 counter substrate 30 liquid crystal layer 40 liquid crystal display device 50 organic protective layer 60 inorganic oxide film 71 transparent anode 72 hole injection layer 73 hole transport layer 74 light emitting layer 75 electron injection layer 76 Cathode 80 Organic light emitter 100 Organic light emitting display

Claims (12)

Contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent,
The photosensitive coloring resin composition for color filters in which the said photoinitiator contains the oxime ester compound represented by following General formula (1).

(In the general formula (1), R ^a and R ^b are each independently a hydrogen atom or an alkyl group, R ^c is a thioether bond (-S-), an ether bond (-O-) and a carbonyl bond (- A hydrocarbon group which may contain at least one kind of divalent linking group selected from CO-), Z is a hydrogen atom or-(C = O) R ^d , and R ^d is an oxygen atom And a hydrocarbon group which may contain at least one selected from sulfur, or a heterocyclic group containing no nitrogen, at least one selected from oxygen and sulfur, R ^e Is a hydrocarbon group having 1 to 10 carbon atoms.)   The photosensitive coloring resin composition for color filters of Claim 1 in which the said photoinitiator contains 2 or more types of oxime ester compounds which do not have carbazole frame | skeleton.   The photosensitive coloring resin composition for color filters of Claim 1 or 2 in which the said photoinitiator contains the oxime ester compound which has a diphenyl sulfide frame further.   The photoinitiator is at least one selected from an α-amino ketone based photoinitiator, a biimidazole based photoinitiator, a thioxanthone based photoinitiator, an acyl phosphine oxide based photoinitiator, and a mercapto based chain transfer agent. The photosensitive colored resin composition for color filters as described in any one of the Claims 1 thru | or 3 containing these.   The photoinitiator is at least one selected from an α-amino ketone based photoinitiator, a biimidazole based photoinitiator, a thioxanthone based photoinitiator, an acyl phosphine oxide based photoinitiator, and a mercapto based chain transfer agent. The photosensitive coloring resin composition for color filters as described in any one of the Claims 1 thru | or 4 containing and the oxime ester compound which has diphenyl sulfide frame | skeleton.   Furthermore, the photosensitive coloring resin composition for color filters as described in any one of the Claims 1 thru | or 5 containing antioxidant.   A group consisting of a hindered phenolic antioxidant and a latent hindered phenolic antioxidant wherein the phenolic hydroxyl group of the hindered phenolic antioxidant is protected by a heat-removable protective group, as the antioxidant. The photosensitive colored resin composition for color filters according to claim 6, which is at least one selected from the group consisting of The composition according to any one of claims 1 to 7, further comprising a dispersant, wherein the dispersant comprises a polymer having a structure represented by the following general formula (I) and having an amine value of 40 mgKOH / g or more and 120 mgKOH / g or less. The photosensitive coloring resin composition for color filters as described in any one of-.

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, Q is a direct bond or a divalent linking group, R ² is an alkylene group having 1 to 8 carbon atoms,-[CH (R ⁵ ) -CH (R ⁶ ) -O] _x -CH (R ⁵ ) -CH (R ⁶ )-or-[(CH ₂ ) _y -O] _z- (CH ₂ ) _y- , R ³ and R ⁴ each independently represent a optionally substituted linear or cyclic hydrocarbon group, R ³ and R ⁴ form a ring structure by bonding with each other .R ⁵ and R ⁶ each independently represents a hydrogen atom or a methyl group.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )   The dispersant is a polymer having a structure represented by the general formula (I) and having an amine value of 40 mg KOH / g to 120 mg KOH / g, and an acid value of 1 mg KOH / g to 18 mg KOH / g The photosensitive colored resin composition for color filters according to claim 8.   The coloring material is at least one selected from the group consisting of a zinc phthalocyanine pigment, and an azo compound represented by the following general formula (ii) and an azo compound of a tautomeric structure thereof: di, tri and tetra anions And a yellow coloring material containing ions of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn; The photosensitive coloring resin composition for color filters as described in any one of Claims 1 thru | or 9.   A color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a photosensitive colored resin composition for a color filter according to any one of claims 1 to 10. A color filter that is a colored layer made of a cured product of a product.   A display device comprising the color filter according to claim 11.

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