WO2018062105A1

WO2018062105A1 - Photosensitive colored resin composition for color filter, color filter, and display device

Info

Publication number: WO2018062105A1
Application number: PCT/JP2017/034555
Authority: WO
Inventors: 琢実鈴木; 正幹大庭; 亘田尻; 山縣　秀明
Original assignee: 株式会社Ｄｎｐファインケミカル
Priority date: 2016-09-30
Filing date: 2017-09-25
Publication date: 2018-04-05
Also published as: JPWO2018062105A1; CN109642971B; TW201818154A; JP7008508B2; TWI742166B; CN109642971A

Abstract

The purpose of the present invention is to provide a photosensitive colored resin composition for a color filter, the composition exhibiting good sensitivity and enabling a colored layer having improved brightness to be formed. This photosensitive colored resin composition for a color filter contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent. The photoinitiator contains an oxime ester compound represented by general formula (1). (The reference symbols in general formula (1) are as described in the description.)

Description

Photosensitive colored resin composition for color filter, color filter, and display device

The present invention relates to a photosensitive colored resin composition for a color filter, 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 (cell phones, smartphones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding. Recently, an organic light-emitting display device such as an organic EL display having high visibility due to self-emission has been 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 in 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, the light passing through the color filter is colored as it is into the color of each pixel constituting the color filter, and the light of those colors is synthesized 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 the organic light emitting display device, a color filter is used for color adjustment.

As a recent trend, there is a demand for power saving of an image display device, and in order to improve the use efficiency of a backlight, a high brightness of a color filter is particularly demanded. This is a big problem especially for mobile displays (cell phones, smartphones, tablet PCs).

Here, the color filter is generally formed on the substrate to form the substrate, the colored layer formed of the three primary color patterns of red, green, and blue, and the respective colored patterns. A light shielding portion.
As a method for 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 colorant dispersion obtained by dispersing a colorant with a dispersant or the like. After coating on a glass substrate and drying, exposure is performed using a photomask, development is performed to form a colored pattern, and heating is performed to fix the pattern to form a colored layer. These steps are repeated for each color to form a color filter.

Even in the color filter, the demand for higher brightness is increasing, and the color material concentration in the colored layer of the color filter is higher than before, so that the components necessary for photopolymerization are relatively reduced and patterning is difficult. It has become to. Furthermore, in order to improve the productivity of the color filter, it is required to reduce the integrated exposure amount necessary for patterning, and how to secure the curability necessary for patterning is a big issue.

It has been proposed to use an oxime ester photoinitiator as a method for obtaining a colored resin composition capable of achieving high sensitivity. For example, Patent Document 1 proposes an oxime ester compound having a specific structure including 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 containing a diphenyl sulfide skeleton or a carbazole skeleton and having a specific substituent containing a cycloalkyl group in the oxime ester group.

Japanese Patent No. 3993725 JP-T-2015-523318 Chinese Patent Application No. 10293855

However, the conventional colored resin composition using the oxime ester photoinitiator tends to have insufficient luminance. In particular, conventional oxime ester photoinitiators with high sensitivity tend to lower the luminance. On the other hand, the sensitivity of the oxime ester photoinitiator, which tends to have relatively good brightness, is low, and the effect of the oxime ester photoinitiator on the sensitivity and the brightness has a trade-off relationship. Therefore, there is a demand for a colored resin composition that can achieve high sensitivity and can form a colored layer with higher brightness.

The present invention has been made in view of the above circumstances, and can form a colored layer with improved brightness, and has a good sensitivity, a photosensitive colored resin composition for a color filter, and the photosensitive colored resin composition for a 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 a color filter according to the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent.
The photoinitiator contains an oxime ester compound represented by the following general formula (1).

(In the general formula (1), R ^a and R ^b are each independently a hydrogen atom or an alkyl group, and R ^c is a thioether bond (—S—), an ether bond (—O—) and a carbonyl bond (— CO—) is a hydrocarbon group which may contain at least one divalent linking group selected from Z, Z is a hydrogen atom or — (C═O) R ^d , and R ^d is an oxygen atom And a hydrocarbon group that may contain at least one selected from sulfur atoms, or a heterocyclic group that does not contain a nitrogen atom and contains at least one selected from oxygen and sulfur atoms, and 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 made of a cured 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 with improved luminance, and a photosensitive color resin composition for color filters having good sensitivity, and a color formed using the photosensitive color 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 illustrating an example of the organic light emitting display device of the present invention.

Hereinafter, the photosensitive colored resin composition for a color filter, 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 having wavelengths in the visible and invisible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.
In the present invention, (meth) acryl represents each of acryl and methacryl, and (meth) acrylate represents each of acrylate and methacrylate.
In this specification, unless otherwise specified, 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 a color filter according to the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent.
The photoinitiator contains an oxime ester compound represented by the following general formula (1).

The photosensitive colored resin composition for a color filter according to the present invention can form a colored layer with improved brightness by using the oxime ester compound represented by the general formula (1) as a photoinitiator, which is good. Have high sensitivity. In addition, the photosensitive colored resin composition for color filter according to the present invention is one in which the development residue is suppressed, and it is easy to form desired micropores in the colored layer at the same time when the colored layer is patterned. There are benefits.

The photosensitive colored resin composition for a color filter according to the present invention uses the oxime ester compound represented by the general formula (1) as a photoinitiator, and as an effect that exhibits the above effects, Although it is clarified, it is estimated as follows.
The decrease in luminance of the colored layer may be caused by coloring due to the reaction residue of the photoinitiator. Conventionally, it is presumed that oxime ester-based initiators that increase the sensitivity but have insufficient brightness of the colored layer have a structure in which the reaction residue of the photoinitiator is easily colored, such as having a carbazole skeleton. The On the other hand, since the oxime ester compound represented by the general formula (1) used in the present invention has a structure having a high transmittance in which the reaction residue is unlikely to cause coloration, the coloring layer is colored by the reaction residue. As a result, it is considered that a colored layer with improved luminance can be formed.
In addition, since the oxime ester compound represented by the general formula (1) used in the present invention has a fluorene skeleton and an oxime ester group via a carbonyl group, the conjugated system of the structure has luminance 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 sensitivity. Furthermore, the oxime ester compound represented by the 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. Compared with, radical movement occurs more rapidly, so it is considered to have good sensitivity.
The photosensitive colored resin composition for a color filter of the present invention has a high affinity for the oxime ester compound represented by the general formula (1) or a reaction residue thereof in an alkaline aqueous solution during alkali development. Since it is easy, it is estimated that a development residue is easy to be suppressed.
Moreover, the photosensitive colored resin composition for color filters of this invention tends to form a desired fine hole simultaneously in a colored layer, when patterning a colored layer. When a more sensitive photoinitiator is used to form a colored layer, the radical moves to the unexposed area after the generation of radicals, while maintaining the shape of the unexposed area inside the exposed area and It is difficult to form the peripheral portion of the exposed portion without flaking. Therefore, in the conventional photosensitive resin composition, when a highly sensitive photoinitiator capable of forming a fine line pattern is used, it is difficult to form micropores even if the linearity of the fine line pattern is good. . Further, as shown in Comparative Example 2 to be described later, when a photoinitiator having a relatively low sensitivity is used, there is a problem that the remaining film rate is lowered even if 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 used in combination, micropores with a good shape can be formed more easily. Since the photosensitive colored resin composition for a color filter of the present invention easily forms desired fine holes in the colored layer, for example, in order to form a reflective color filter, a colored layer is formed on the TFT substrate, At the same time, it is also suitable for use in forming through holes for conduction in the colored layer.
Furthermore, the oxime ester compound represented by the general formula (1) used in the present invention has an oxime ester group via a carbonyl group in the fluorene skeleton, so that the oxime ester group does not pass through the carbonyl group via the carbonyl group. Compared with the oxime ester compound having a bonded structure, crystallinity is lowered, so that solvent solubility and solvent re-solubility are improved, and compatibility with other components is improved. By using a photoinitiator that is improved in solvent solubility, solvent re-solubility, and compatibility with other components, the linearity of the fine line pattern is improved, and the fluctuation of micropores is easily suppressed.
Moreover, since the oxime ester compound represented by the general formula (1) has a high thermal decomposition temperature, generation of outgas during heating of the coating film can be suppressed. Therefore, the reliability of the resist is high. For example, when another layer such as a conductive film is further laminated on the coating film, damage due to outgassing of the laminated layer can be suppressed.

The photosensitive colored resin composition for a color filter according to the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and impairs the effects of the present invention. Other components may be further contained within the range.
Hereinafter, each component of the colored resin composition of the present invention will be described in detail in order from the photoinitiator characteristic of the present invention.

[Photoinitiator]
<Oxime ester compound represented by the general formula (1)>
The photoinitiator used for this invention contains the oxime ester compound represented by the said 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 thereof. Examples of the alkyl group include 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, and methylcyclopentyl. Group, a cyclopentylmethyl group, a cyclohexyl group, etc. 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 a carbon number of 2 is more preferable. 4 to 4 linear alkyl groups.

In the general formula (1), R ^c includes at least one divalent linking group selected from a thioether bond (—S—), an ether bond (—O—), and a carbonyl bond (—CO—). It may be a hydrocarbon group.
Examples of the hydrocarbon group for R ^c include an alkyl group, an alkenyl group, an aryl group, and an aralkyl group. The alkyl group may be linear, branched or cyclic, and 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. Group, cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, cyclohexylmethyl group, cyclopentylethyl group, cyclohexylethyl group, bornyl group, isobornyl group, dicyclopentanyl group, adamantyl group, lower alkyl group-substituted adamantyl group, 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 a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group. As the hydrocarbon group for R ^c, a hydrocarbon group having 1 to 14 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, and a carbon group having 6 to 10 carbon atoms. An aryl group is more preferable, and an alkyl group having 1 to 10 carbon atoms is still more preferable. Further, the hydrocarbon group in R ^c is preferably 2 or more carbon atoms from the viewpoint of improving the shape of the micropore when forming the micropore in the colored layer. In addition, the hydrocarbon group in R ^c is preferably a structure containing cyclic and linear alkyl groups such as a cyclopentylmethyl group and a cyclohexylmethyl group from the viewpoint of solvent solubility and compatibility.
Moreover, in said ^Rc , when the said hydrocarbon group contains the said bivalent coupling group, solvent solubility and compatibility can be improved. In particular, the divalent linking group is preferably a thioether bond (—S—) or an ether bond (—O—) from the viewpoint of improving solvent solubility. In ^Rc , when the hydrocarbon group includes the divalent linking group, the hydrocarbon group may be bonded to a carbon atom of the oxime ester group via 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 R ^c , when the hydrocarbon group includes 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 may be carbonized. The case where it is the group which couple | bonded hydrogen groups with the said bivalent coupling group is mentioned. Examples of the group in which hydrocarbon groups are bonded to each other through the divalent linking group include, for example, a structure containing a thioether bond (—S—) such as an alkylthioalkyl group such as a methylthiomethyl group or an arylthioalkyl group; A structure containing an ether bond (—O—) such as a methoxycyclohexyl group, an alkoxyalkyl group or an aryloxyalkyl group; a structure containing a carbonyl bond (—CO—) such as an acetylmethyl group, a benzoylmethyl group or an acylalkyl group And the like.

In the general formula (1), Z is a hydrogen atom or — (C═O) R ^d , and R ^d is a hydrocarbon group that may contain at least one selected from an oxygen atom and a sulfur atom, Or it is a heterocyclic group which does not contain a nitrogen atom but contains at least 1 sort (s) 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 At least one linking group selected from a linking group containing an oxygen atom such as an ether bond (—O—) or a carbonyl bond (—CO—) and a linking group containing a sulfur atom such as a thioether bond (—S—) In particular, a hydrocarbon group having 1 to 14 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, and a carbon group having 6 to 10 carbon atoms. An aryl group is more preferred, and an aryl group having 6 to 10 carbon atoms is still more preferred.
Examples of the heterocyclic ring in the heterocyclic group that does not include a nitrogen atom and includes at least one selected from an oxygen atom and a sulfur atom include, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a thienothiophene ring, Examples include a furofuran ring and a thienofuran ring. The hydrocarbon group or the heterocyclic group in R ^d preferably has 1 to 10 carbons from the viewpoint of developability.
Above all, Z is preferably a hydrogen atom from the viewpoint of developability and brightness. 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 include those having 1 to 10 carbon atoms among the hydrocarbon groups described in the above R ^c . The 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 more preferably 1 to 4 carbon atoms from the viewpoint of improving sensitivity. Are more preferable, and a methyl group is particularly preferable.

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. It is preferable.

Examples of the oxime ester compound represented by the general formula (1) include that R ^a and R ^b are both alkyl groups having 1 to 4 carbon atoms, and R ^c is an alkyl group having 1 to 4 carbon atoms, A compound 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 cyclic A compound having 4 to 10 carbon atoms in combination with an alkyl group, Z is a hydrogen atom, and R ^e is an alkyl group having 1 to 4 carbon atoms; both R ^a and R ^b are hydrogen atoms or carbon atoms An alkyl group having 1 to 4 carbon atoms, 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 the oxime ester compound represented by the general formula (1), at least one selected from the following compounds (1-1) to (1-4) is more preferable.

The oxime ester compound represented by the general formula (1) refers to, for example, JP-T-2012-526185, and uses fluorene or a derivative thereof instead of diphenyl sulfide or a derivative thereof, depending on the material used. It can be synthesized by appropriately selecting the solvent, reaction temperature, reaction time, purification method and the like.

In the colored resin composition of the present invention, when the photoinitiator contains two or more oxime ester compounds having no carbazole skeleton, it is possible to form a colored layer with improved brightness, good sensitivity, and pattern formation. This is preferable from the viewpoint of easy adjustment of the line width. An oxime ester compound that does not have a carbazole skeleton can suppress a reduction in luminance of the colored layer because the reaction residue is unlikely to cause coloration. In addition, it includes an oxime ester compound represented by the general formula (1), and by appropriately selecting and combining two or more oxime ester compounds having different sensitivities, while maintaining good sensitivity, The line width can be adjusted. When the colored resin composition of the present invention contains two or more oxime ester compounds having no carbazole skeleton, it is sufficient to include at least one oxime ester compound represented by the general formula (1). The oxime ester compound represented by 1) may contain two or more oxime ester compounds represented by the general formula (1), and the carbazole different from the oxime ester compound represented by the general formula (1) A combination of oxime ester compounds having no skeleton may also be included.

Among them, the combination of the oxime ester compound represented by the general formula (1) and the oxime ester compound having a diphenyl sulfide skeleton can be used without reducing the brightness, developability, and sensitivity significantly. This is preferable because the shape can be easily improved.
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 preferably used.

(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—)). And a divalent linking group of 1 to 14 carbon atoms, Z ¹ is a hydrogen atom, a nitro group or — (C═O) R ^{d ′} , and R ^{d ′} is It is a hydrocarbon group that may contain at least one selected from an oxygen atom and a sulfur atom, or a heterocyclic group that 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). Examples of the hydrocarbon group having 1 to 14 carbon atoms which may contain thioether bond (—S—), ether bond (—O—) and carbonyl bond (—) in R ^c of the general formula (1) Among the hydrocarbon groups that may contain at least one divalent linking group selected from CO-), the same as those having 1 to 14 carbon atoms are exemplified. As R ^{c ′} in the general formula (2), those preferably used as R ^{c in the} general formula (1) can be preferably used as well. R ^f in the general formula (2) 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 from the viewpoint of improving sensitivity. An alkyl group having 1 to 4 carbon atoms is more preferable, and a 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 ′} may include at least one selected from an oxygen atom and a sulfur atom. A good hydrocarbon group or a heterocyclic group not containing a nitrogen atom and containing at least one selected from an oxygen atom and a sulfur atom. Examples of R ^{d ′} include R in the general formula (1) The thing similar to ^d is mentioned. Above all, Z ¹ is preferably a hydrogen atom or — (C═O) R ^{d ′} from the viewpoint of developability and luminance, and more preferably a hydrogen atom from the viewpoint of luminance.

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. It is preferable.

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 atom, and R ^f is an alkyl group having 1 to 4 carbon atoms; R c ^'is a linear alkyl group and the alkyl group of which the cyclic alkyl group and having 6 to 10 carbon atoms combining, Z ¹ is — (C═O) R ^{d ′} , wherein R ^{d ′} does not contain a nitrogen atom, is a heterocyclic group containing a sulfur atom, and R ^f is an alkyl group having 1 to 4 carbon atoms; etc. However, it is not limited to these.

As the oxime ester compound represented by the general formula (2), at least one selected from the following compounds (2-1) to (2-2) is more preferable.

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

The photosensitive colored resin composition for a color filter of the present invention may be used in combination with another photoinitiator different from the oxime ester compound described above 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>
Other photoinitiators include, for example, oxime ester photoinitiators different from oxime ester compounds having no carbazole skeleton including the oxime ester compound represented by the general formula (1), α-aminoketone photoinitiators Agents, biimidazole photoinitiators, thioxanthone photoinitiators, acylphosphine oxide photoinitiators, and mercapto chain transfer agents.
Above all, while improving brightness, when forming a fine line pattern, the linearity is further improved, the ability to form a fine line pattern as designed for the mask line width is improved, and the shape of the micro hole is improved In view of the above, to the oxime ester compound represented by the general formula (1), an α-aminoketone photoinitiator, a biimidazole photoinitiator, a thioxanthone photoinitiator, an acylphosphine oxide photoinitiator, and It is preferable to use a combination of at least one selected from mercapto chain transfer agents. Among them, it is preferable to use an acylphosphine oxide photoinitiator in combination because it is easy to form micropores with excellent dimensional accuracy by suppressing the wobble at the end of the pores when forming micropores. . Since acylphosphine oxide photoinitiators have a higher thermal decomposition temperature than other initiators, side reactions due to heating during pre-baking are unlikely to occur, and therefore, it is considered that billiness is suppressed.
“Improved linearity” means that the end of the colored layer formed in the development step after applying the colored composition has few irregularities and is linear or substantially linear. Further, the “billing” refers to a problem that the dimensional accuracy is deteriorated due to non-uniformity of straight lines or curves at the pattern end.

In addition, from the viewpoint of improving the shape of the micropores and suppressing billiness, the α-aminoketone photoinitiator, biimidazole photoinitiator, thioxanthone series are added to the oxime ester compound represented by the general formula (1). It is preferable to use a combination of at least one selected from a photoinitiator, an acylphosphine oxide photoinitiator, and a mercapto chain transfer agent and the oxime ester compound having the diphenyl sulfide skeleton. It is more preferable to use a combination of inhibitors.

Since the α-aminoketone photoinitiator has the property of curing the middle from the surface of the coating film and easily suppresses the deep film curability, when combined with the oxime ester compound represented by the general formula (1), It is preferable from the viewpoint of a high tendency to improve the deep film curability.
Examples of α-aminoketone photoinitiators include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (for example, Irgacure 907, manufactured by BASF), 2-benzyl-2- (Dimethylamino) -1- (4-morpholinophenyl) -1-butanone (eg Irgacure 369, manufactured by BASF), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [ 4- (4-morpholinyl) phenyl] -1-butanone (Irgacure 379EG, manufactured by BASF) and the like.
The α-aminoketone photoinitiator may be used alone or in combination of two or more, among which 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and 2-Benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone is preferred from the viewpoint of improving the remaining film rate, and 2-methyl-1- (4-methylthiophenyl) -2 -Morpholinopropan-1-one is more preferred from the viewpoint of suppressing micropore mottling.

The biimidazole photoinitiator has the property of curing the deep part of the coating film, is easy to suppress the coating film surface curability, and when combined with the oxime ester compound represented by the general formula (1), the coating film surface curing It is preferable because it has a high tendency to improve the property.
Examples of the biimidazole photoinitiator include 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 , 4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and the like.
As a biimidazole type photoinitiator, you may use individually or in combination of 2 or more types, and it is preferable to use it in combination with a mercapto type | system | group chain transfer agent especially from the point which improves coating-film hardening property.

Examples of the thioxanthone photoinitiator include 2,4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2,4-dichlorothioxanthone, and the like.
The thioxanthone photoinitiator may be used alone or in combination of two or more. Among them, 2,4-isopropylthioxanthone and 2,4-diethylthioxanthone are used because the transfer of radical generation is improved. preferable.

Acylphosphine oxide photoinitiators have the property of being less susceptible to yellowing due to heat, and are therefore suitable for improving brightness, but generally have low sensitivity and may not provide sufficient curability. However, when combined with the oxime ester compound represented by the general formula (1), the overall coating film curability is improved, and when the micropores are formed, the irregularity at the ends of the pores is suppressed and the dimensional accuracy is improved. It is preferable from the viewpoint of forming good micropores.
Examples of the acylphosphine oxide photoinitiator include benzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyl-diphenylphosphine 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-pentylphosphine oxide, bis (2,6-dimethylbenzoyl) -ethylphosphine oxide, and the like.
The acyl phosphine oxide photoinitiator may be used singly or in combination of two or more. Among them, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide may be used for coating film curability. Is preferable from the viewpoint of improvement.

A mercapto chain transfer agent has a property of receiving a radical from a slowly reacting radical and accelerates the reaction, and is particularly preferable when combined with a biimidazole photoinitiator because it tends to improve the reaction rate.
Examples of mercapto chain transfer agents include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 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-mercaptobuty Rate), pen Erythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate) and the like.
The mercapto chain transfer agent may be used alone or in combination of two or more, and among them, 2-mercaptobenzothiazole is preferably used from the viewpoint of improving the reaction rate.

The total content of the photoinitiator used in the photosensitive colored resin composition for a color filter of the present invention is not particularly limited as long as the effect of the present invention is not impaired, but the solid content of the photosensitive colored resin composition for a color filter is not limited. Preferably it is 0.1 mass% or more and 12.0 mass% or less with respect to the total amount, More preferably, it exists in the range of 1.0 mass% or more and 8.0 mass% or less. When this content is not less than the above lower limit, photocuring is sufficiently advanced and the exposed portion is prevented from being eluted during development. On the other hand, if it is not more than the above upper limit, the yellowing of the resulting colored layer becomes strong and the luminance Can be suppressed.
In addition, solid content is all except a solvent, and a liquid polyfunctional monomer etc. are also contained.

The content of the oxime ester compound represented by the general formula (1) used in the photosensitive colored resin composition for a color filter of the present invention is based on the total solid content of the photosensitive colored resin composition for a color filter. Preferably it is 0.1 mass% or more and 8.0 mass% or less, More preferably, it exists in the range of 0.5 mass% or more and 6.0 mass% or less. When this content is not less than the above lower limit, photocuring is sufficiently advanced and the exposed portion is prevented from being eluted during development. On the other hand, if the content is not more than the above upper limit, the yellowing of the resulting colored layer becomes strong and the luminance is reduced. Can be suppressed.

Moreover, the photosensitive colored resin composition for color filters of this invention includes the oxime ester compound represented by the said General formula (1), when a photoinitiator contains 2 or more types of oxime ester compounds which do not have a carbazole skeleton. The total content of two or more oxime ester compounds having no carbazole skeleton is 0.1% by mass or more and 12.0% by mass or less, more preferably, based on the total solid content of the photosensitive colored resin composition for color filters. Is preferably in the range of 1.0% by mass or more and 8.0% by mass or less from the viewpoint of sufficiently exerting the combined use effect with these photoinitiators.

Moreover, when combining the oxime ester compound which has the said diphenyl sulfide skeleton with the oxime ester compound represented by the said General formula (1) as a photoinitiator used for this invention, the oxime ester compound which has the said diphenyl sulfide skeleton of The content is preferably 0.1% by mass or more and 4.0% by mass or less, more preferably 0.3% by mass or more and 3.0% by mass, based on the total solid content of the photosensitive colored resin composition for color filters. It is preferable that it is within the following range from the viewpoint of sufficiently exerting the combined effect of the oxime ester compound represented by the general formula (1) and the oxime ester compound having the diphenyl sulfide skeleton.

When combining the oxime ester compound which has the said diphenyl sulfide skeleton with the oxime ester compound represented by the said General formula (1) as a photoinitiator used for this invention, the oxime ester represented by the said General formula (1) The ratio of the compound and the oxime ester compound having the diphenyl sulfide skeleton is 10 parts by mass of the oxime ester compound having the diphenyl sulfide skeleton with respect to 100 parts by mass of the oxime ester compound represented by the general formula (1). The amount is preferably 150 parts by mass or less, and more preferably 15 parts by mass or more and 120 parts by mass or less from the viewpoint of luminance and sensitivity. In terms of facilitating the formation of micropores, the oxime ester compound having the diphenyl sulfide skeleton is 10 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the oxime ester compound represented by the general formula (1). It is preferable that it is 15 parts by mass or more and 50 parts by mass or less.

Moreover, the photosensitive colored resin composition for color filters 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 The total content of the oxime ester compound having a total of 100 parts by mass of the photoinitiator used in the present invention is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and 50 parts by 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, from the viewpoint of sufficiently exerting the combined effect with the other photoinitiator, The total amount of the photoinitiator used in the present invention is preferably 95 parts by mass or less, more preferably 85 parts by mass or less, in a total of 100 parts by mass.

The photoinitiator used in the present invention is further selected from α-aminoketone photoinitiators, biimidazole photoinitiators, thioxanthone photoinitiators, acylphosphine oxide photoinitiators, and mercapto chain transfer agents. In the case of containing at least one selected from the above, the total content thereof is 0.1% by mass or more and 4.0% by mass or less, and further 0.5% with respect to the total solid content of the photosensitive colored resin composition for color filter. It is preferable that it is in the range of not less than 2.0% by mass and not more than 2.0% by mass in order to sufficiently exhibit the combined effect with these photoinitiators.

[Color material]
In the present invention, the color material is not particularly limited as long as it can form a desired color when a colored layer of a color filter is formed. Various organic pigments, inorganic pigments, dispersible dyes, and dyes are not particularly limited. Can be used alone or in admixture of two or more. Among these, organic pigments are preferably used because they have high color developability and high heat resistance. Examples of the organic pigment include compounds classified as pigments in the Color Index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (C.I. .) Can be listed with numbers.
In the following description, when color index names are described, when only color index names having 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, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 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, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 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 Black 1 and 7.

Specific examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, and oxidation. Examples thereof include chrome green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.

For example, when forming the pattern of the light shielding layer on the substrate of the 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 a 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.

Examples of the dispersible dye include dyes that can be dispersed by adding various substituents to the dye and insolubilizing the solvent, dyes that can be dispersed by using in combination with a solvent having low solubility, and solvents And a lake color material obtained by forming a salt with a counter ion to form an insoluble (rake) salt. By using a combination of such a dispersible dye and a dispersant, the dispersibility and dispersion stability of the dye can be improved.
As a guide, if the amount of 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 salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes. 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;

In the case of forming a blue colored layer, at least one of triarylmethane dyes, xanthene dyes, and cyanine dyes is preferable from the viewpoint of increasing the brightness, and from the viewpoint of high heat resistance, triatrimethane dyes are particularly preferable. At least one selected from a reel methane dye and a xanthene dye is preferable.
In the present invention, from the viewpoint of improving the brightness of the color filter, it is preferable to include a lake color material having a triarylmethane dye, and among these, a triarylmethane basic dye and a polyacid anion are included. preferable.

In the present invention, the rake colorant is excellent in heat resistance and light resistance, and achieves high brightness of the color filter. Among these, the rake colorant is a colorant represented by the following general formula (i). An association state is formed, which is preferable in that it exhibits superior heat resistance.

(In general formula (i), A is an a-valent organic group in which the carbon atom directly bonded to N does not have a π bond, and the organic group is saturated aliphatic carbonized at least at the terminal directly bonded to N. Represents an aliphatic hydrocarbon group having a hydrogen group or an aromatic group having the aliphatic hydrocarbon group, and may contain O, S and N in the carbon chain, and B ^c- represents a polyvalent polyvalent R ⁱ to R ^v each independently represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, 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 ~} R ^v and Ar ¹ each They 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. A plurality of e may be the same or different. )

The cation part of the color material represented by the general formula (i) may be the same as the cation part of the color material represented by the general formula (i) described in International Publication No. 2012/144521.
A in the general formula (i) is an a-valent organic group in which the carbon atom directly bonded to N (nitrogen atom) does not have a π bond, and the organic group is saturated at least at the terminal directly bonded to N. An aliphatic hydrocarbon group having an aliphatic hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group is represented, and O (oxygen atom), S (sulfur atom), and N (nitrogen atom) are present 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 the color tone and transmittance of the cationic coloring portion are not affected by the linking group A and other coloring portions, Similar colors can be retained.
In A, an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N is linear, branched or cyclic unless the terminal carbon atom directly bonded to N has a π bond. The carbon atom other than the terminal may have an unsaturated bond, may have a substituent, and the carbon chain contains O, S, and N. Also good. For example, a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group or the like may be contained, and a hydrogen atom may be further substituted with a halogen atom or the like.
The aromatic group having an 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 terminal directly bonded to N. And may have a substituent, and may be a heterocyclic ring containing O, S, and N.
Especially, it is preferable that A contains a cyclic | annular aliphatic hydrocarbon group or an aromatic group from the point of the robustness of frame | skeleton.
Among the cyclic aliphatic hydrocarbon groups, a bridged alicyclic hydrocarbon group is preferable from the viewpoint of skeleton fastness. The bridged alicyclic hydrocarbon group means a polycyclic aliphatic hydrocarbon group having a bridged structure in the aliphatic ring and having a polycyclic structure, for example, norbornane, bicyclo [2,2,2]. Examples include octane, dicyclopentadiene and adamantane. Among the bridged alicyclic hydrocarbon groups, norbornane is preferable. Moreover, as an aromatic group, the group containing a benzene ring and a naphthalene ring is mentioned, for example, Among these, the group containing a benzene ring is preferable.
From the viewpoint of easy availability of raw materials, A is preferably divalent to tetravalent, preferably divalent to trivalent, and more preferably divalent. For example, when A is a divalent organic group, an aromatic group in which two alkylene groups having 1 to 20 carbon atoms such as a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms or a xylylene group are substituted. Family groups and the like.

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

R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v are combined to form a ring structure. R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v form a ring structure through a nitrogen atom Say. The ring structure is not particularly limited, and examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring.

Among these, from the viewpoint of chemical stability, R ⁱ to R ^v are each independently 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 bonded to form a pyrrolidine ring, piperidine ring, or morpholine ring.

R ⁱ to R ^v can each independently have the above-described structure, and among these, R ⁱ is preferably a hydrogen atom from the viewpoint of color purity, and R ⁱⁱ to R ⁱⁱ from the viewpoint of ease of production and raw material procurement. More preferably, R ^v are all the same.

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 composed of a carbocyclic ring. As an aromatic hydrocarbon in the aromatic hydrocarbon group, in addition to a benzene ring, condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetralin ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring; biphenyl, terphenyl, Examples thereof include chain polycyclic hydrocarbons such as diphenylmethane, triphenylmethane, and stilbene. The chain polycyclic hydrocarbon may have O, S, and N in the chain skeleton such as diphenyl ether. On the other hand, the heterocyclic ring in the heterocyclic group includes 5-membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole and pyrazole; 6-membered heterocycles such as pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine and pyrazine. And condensed polycyclic heterocycles 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.

Examples of the substituent that the aromatic group may have include an alkyl group having 1 to 5 carbon atoms and a halogen atom.

Ar ¹ is preferably an aromatic group having 6 to 20 carbon atoms, and more preferably an aromatic group composed of a condensed polycyclic carbocycle having 10 to 14 carbon atoms. Among these, a phenylene group or a naphthylene group is more preferable because the structure is simple and the raw material is inexpensive.

A plurality of R ⁱ to R ^v and Ar ¹ in one molecule may be the same or different. In the case where a plurality of R ⁱ to R ^v and Ar ¹ are the same, the color development site exhibits the same color development, so that the same color as the single color development site can be reproduced, which is preferable from the viewpoint 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 types of monomers can be reproduced and adjusted to a desired color. it can.

The anion (B ^c− ) of the colorant represented by the general formula (i) is a polyacid anion having a valence of 2 or more.
Among them, the polyacid anion is preferably a polyacid anion containing at least one of tungsten (W) and molybdenum (Mo) from the viewpoint of high brightness and excellent heat resistance and light resistance, and contains at least tungsten. Further, a polyacid anion which may contain molybdenum is more preferable from the viewpoint of heat resistance.

In the polyacid anion containing at least tungsten (W), the content ratio of tungsten and molybdenum is not particularly limited, but the molar ratio of tungsten to molybdenum is particularly in the range of 100: 0 to 85:15 because of excellent heat resistance. Is preferably within the range of 100: 0 to 90:10.
As the polyacid anion (B ^c− ), the above-mentioned polyacid anions can be used singly or in combination of two or more. When two or more are used in combination, tungsten and molybdenum in the entire polyacid anion are used. The molar ratio is preferably within the above range.

The colorant represented by the general formula (i) may be a double salt containing other cations and anions as long as the effects of the present invention are not impaired. Specific examples of such cations include other basic dyes, organic compounds containing functional groups capable of forming salts with anions such as amino groups, pyridine groups, and imidazole groups, sodium ions, potassium ions, and magnesium ions. Metal ions such as calcium ion, copper ion and iron ion. Specific examples of anions include acid dyes, halide ions such as fluoride ions, chloride ions and bromide ions, and anions of inorganic acids. Examples of the anion of the inorganic acid include anions of oxo acids such as phosphate ions, sulfate ions, chromate ions, tungstate ions (WO ₄ ²⁻ ), molybdate ions (MoO ₄ ²⁻ ), and the like.
The color material represented by the general formula (i) can be prepared with reference to, for example, International Publication No. 2012/144520 pamphlet.

In the case of forming a green colored layer, C.I. which is a zinc phthalocyanine pigment. I. Pigment Green 59 (PG59) and C.I. I. A green color material obtained by further combining a yellow color material with Pigment Green 58 (PG58) can be preferably used.

As yellow color materials used in combination with zinc phthalocyanine pigments such as PG59 and PG58, C.I. I. Pigment Yellow 150 derivative pigments are preferred. C. I. As pigment pigments of CI Pigment Yellow 150, specifically, mono-, di-, tri- and tri-azo compounds of the azo compound according to the following general formula (ii) or one of its tautomeric structures serving as a host of at least one guest compound Tetraanions and metals 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 pigment yellow 150 pigment because the luminance is improved.

(In the 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, the yellow color material is at least one anion selected from the group consisting of mono-, di-, tri- and tetraanions of the azo compound represented by the general formula (ii) and the azo compound having a tautomer structure thereof And ions of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn improve brightness and increase contrast. It is preferable from the viewpoint of improvement.
By containing two or more kinds of metal ions, crystal growth of the colorant is suppressed and atomization is possible. Further, since it is used in combination with a dispersant described later, it is atomized in the colorant dispersion liquid and the contrast is increased. It is inferred that an improved colored layer can be formed.

Examples of the acyl group in the acylamino group in the general formula (ii) include, for example, an alkylcarbonyl group, a phenylcarbonyl group, an alkylsulfonyl group, a phenylsulfonyl group, an carbamoyl group optionally substituted with alkyl, phenyl, or naphthyl, an alkyl , Sulfamoyl group optionally substituted with phenyl or naphthyl, guanyl group optionally substituted with alkyl, phenyl or naphthyl, and the like. The alkyl group preferably has 1 to 6 carbon atoms. The alkyl group may be substituted with, for example, a halogen such as F, Cl, or Br, —OH, —CN, —NH ₂ , and / or an alkoxy group having 1 to 6 carbon atoms. The phenyl group and naphthyl group are, for example, halogen such as F, Cl, Br, —OH, —CN, —NH ₂ , —NO ₂ , an alkyl group having 1 to 6 carbon atoms, and / or 1 to carbon atoms. It may be substituted with 6 alkoxy groups.
The alkyl group in the alkylamino group in general formula (ii) preferably has 1 to 6 carbon atoms. The alkyl group may be substituted with, for example, a halogen such as F, Cl, or Br, —OH, —CN, —NH ₂ , and / or 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. These aryl groups include, for example, halogens such as F, Cl, and Br, —OH, and those having 1 to 6 carbon atoms. It may be substituted with an alkyl group, an alkoxy group having 1 to 6 carbon atoms, —NH ₂ , —NO _2, —CN and the like.

In the azo compound represented by the general formula (ii) and the azo compound having a tautomer structure thereof, each R ³¹ is independently —OH, —NH ₂ , —NH—CN, or alkylamino. This is preferable from the viewpoint of hue, and two R ^{31 s} may be the same or different.
In the general formula (ii), from the viewpoint of hue, the two R ³¹ are both —OH, both —NH—CN, or one —OH and one —NH—. More preferably, it is CN, and even more preferably both are —OH.

In the azo compound represented by the general formula (ii) and the azo compound having a tautomer structure thereof, R ³² is more preferably both —OH from the viewpoint of hue.

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

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

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

C. I. In the pigment yellow 150 pigment pigment, at least two types of metal ions may be included in the common crystal lattice, and at least two types of metal ions may be included in another crystal lattice. The case where the crystal | crystallization containing the metal ion of agglomerates is mentioned. Among them, the case where at least two kinds of metal ions are contained in a common crystal lattice is preferable from the viewpoint of further improving the contrast. Whether the common crystal lattice includes at least two kinds of metal ions or whether another crystal lattice includes one type of metal ion each aggregated. For example, it can be appropriately determined by using an X-ray diffraction method with reference to JP-A-2014-12838.

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

The color material used in the present invention can be produced by a known method such as a recrystallization method or a solvent salt milling method. Further, a commercially available color material may be used after being refined.

The total content of the coloring material may be blended at a ratio 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 filters. preferable. If it is at least the above lower limit, the colored layer has a sufficient color density when the photosensitive colored resin composition for color filters is applied to a predetermined film thickness (usually 1.0 μm to 5.0 μm). Moreover, if it is below the said upper limit, while being excellent in storage stability, the colored layer which has sufficient hardness and adhesiveness with a board | substrate can be obtained. In particular, when a colored layer having a high color material concentration is formed, the total content of the color material is preferably 15% by mass to 65% by mass with respect to the total solid content of the photosensitive color resin composition for color filters. Is preferably blended at a ratio of 25 mass% to 60 mass%.

[Alkali-soluble resin]
The alkali-soluble resin in the present invention has an acidic group, and can be appropriately selected from those that act as a binder resin and are soluble in an alkali developer used for pattern formation.
In the present invention, the alkali-soluble resin can be based on an acid value of 40 mgKOH / g or more.
A preferred alkali-soluble resin in the present invention is a resin having an acidic group, usually a carboxy group, and specifically, acrylic resins such as an acrylic copolymer having a carboxy group and a styrene-acrylic copolymer having a carboxy group. And epoxy (meth) acrylate resins 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. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. In addition, acrylic resins such as acrylic copolymers and styrene-acrylic copolymers, and epoxy acrylate resins may be used in combination.

An acrylic resin such as an acrylic copolymer having a constitutional unit having a carboxy group and a styrene-acrylic copolymer having a carboxy group includes, for example, a carboxy group-containing ethylenically unsaturated monomer and, if necessary, a copolymer. It is a (co) polymer obtained by (co) polymerizing other polymerizable monomers by a known method.
Examples of the carboxy group-containing ethylenically unsaturated monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. It is done. Also, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxy group. Among these, (meth) acrylic acid is particularly preferable from the viewpoints 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 has been found that the alkali-soluble resin has a hydrocarbon ring which is a bulky group, thereby suppressing the solvent resistance of the obtained colored layer, particularly the swelling of the colored layer. Although the action is unclear, the 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.
Examples of such a hydrocarbon ring include a cyclic aliphatic hydrocarbon ring which may have a substituent, an aromatic ring which may have a substituent, and combinations thereof. May have a substituent such as a carbonyl group, a carboxy group, an oxycarbonyl group, or an amide group. Especially, when an aliphatic ring is included, while the heat resistance and adhesiveness of a colored layer improve, the brightness | luminance of the obtained colored layer improves.
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), and adamantane. Rings: aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, fluorene; chain polycycles such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, stilbene, and cardo structures represented by the following chemical formula (A) It is done.

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

(In General Formula (B), R ^M is an optionally substituted hydrocarbon ring.)

When the alkali-soluble resin has a maleimide structure represented by the general formula (B), it is a polymer having a structural unit represented by the following general formula (I) 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 residue is improved.
In R ^M of the foregoing formula (B), specific examples of the optionally substituted hydrocarbon ring, those similar to the specific example of the hydrocarbon ring.

When an aliphatic ring is included as the hydrocarbon ring, it is preferable from the viewpoint of improving the heat resistance and adhesion of the colored layer and improving the luminance of the obtained colored layer.
Moreover, when including the cardo structure shown by the said Chemical formula (A), it is especially preferable from the point which the sclerosis | hardenability of a colored layer improves and 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 an acrylic copolymer having a constituent unit having a hydrocarbon ring separately from the constituent unit having a carboxy group. This is preferable because the amount of the structural unit having a hydrocarbon ring is increased to easily improve the function of the structural unit.
The acrylic copolymer having a structural unit having a carboxy group and the hydrocarbon ring is prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned “other monomer capable of copolymerization”. 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. , Isobornyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, styrene, and the like. From the point that the cross-sectional shape of the colored layer after development is highly effective in heat treatment, cyclohexyl ( (Meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable, and styrene is particularly preferable.
From the viewpoint of the effect of suppressing development residue, the ethylenically unsaturated monomer having a hydrocarbon ring is preferably a monomer having the maleimide structure and styrene, and particularly preferably styrene.

The alkali-soluble resin used in the present invention preferably 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 and the photopolymerizable compound can form a cross-linked bond in the curing step of the resin composition at the time of producing the 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, the development resistance is improved, and the thermal shrinkage of the cured film is suppressed. Excellent adhesion to the substrate.
The method for introducing an ethylenic double bond into the alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a method of introducing an ethylenic double bond into a side chain by adding a compound having both an epoxy group and an ethylenic double bond in the molecule, such as glycidyl (meth) acrylate, to the carboxy group of the alkali-soluble resin Or by 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 into the side chain. Etc.

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

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

The charging amount of the carboxy group-containing ethylenically unsaturated monomer is preferably 5% by mass or more and more preferably 10% by mass or more with respect to the total amount of the monomer from the viewpoint of obtaining a good pattern. On the other hand, from the viewpoint of suppressing film roughness on the pattern surface after development, the amount of the carboxy group-containing ethylenically unsaturated monomer is preferably 50% by mass or less, and 40% by mass or less, based on the total amount of monomers. More preferably.
The solubility of the coating film obtained when the ratio of the carboxy group-containing ethylenically unsaturated monomer is not less than the above lower limit is sufficient for the alkali developer, and the ratio of the carboxy group-containing ethylenically unsaturated monomer is the above upper limit. When it is below, there is a tendency that the formed pattern is not easily detached from the substrate and the pattern surface is not easily roughened during development with an alkali developer.

In addition, in an acrylic resin such as an acrylic copolymer having a structural unit having an ethylenic double bond and a styrene-acrylic copolymer, which is more preferably used as an alkali-soluble resin, an epoxy group and an ethylenic double bond are used. The amount of the compound having a 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, more preferably 3,000 to 20,000. If it is less than 1,000, the binder function after curing may be remarkably lowered. If it exceeds 50,000, pattern formation may be difficult during development with an alkali developer.
The weight average molecular weight (Mw) of the carboxy group-containing copolymer can be measured by a Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent.

Although it does not specifically limit as an epoxy (meth) acrylate resin which has a carboxy group, Epoxy (meth) obtained by making the reaction product of an epoxy compound and unsaturated group containing monocarboxylic acid react with an acid anhydride. Acrylate compounds are suitable.
The epoxy compound, unsaturated group-containing monocarboxylic acid, and acid anhydride can be appropriately selected from known ones. The epoxy (meth) acrylate resin having a carboxy group may be used alone or in combination of two or more.

As the alkali-soluble resin, it is preferable to select and use an acid-soluble resin having an acid value of 50 mgKOH / g or more from the viewpoint of developability (solubility) with respect to an alkaline aqueous 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) in an aqueous alkali solution used for the developer and adhesion to the substrate. It is preferable that they are 70 mgKOH / g or more and 280 mgKOH / g or less.
In the present invention, the acid value can be measured according to JIS K 0070.

When the ethylenically unsaturated bond equivalent in the case of having an ethylenically unsaturated group in the side chain of the alkali-soluble resin is combined with the oxime ester compound represented by the general formula (1) used in the present invention, The range of 100 to 2000 is preferable, and the range of 140 to 1500 is particularly preferable from the viewpoint of improving the film strength, improving the development resistance, and achieving excellent adhesion to the substrate. When the ethylenically unsaturated bond equivalent is 2000 or less, the development resistance and adhesion are excellent. Moreover, since the ratio of other structural units, such as the structural unit which has the said carboxy group, and the structural unit which has a hydrocarbon ring, can be relatively increased if it is 100 or more, it is excellent in developability and heat resistance. Yes. The oxime ester compound represented by the general formula (1) used in the present invention is preferably used in combination with the content described above.
Here, the ethylenically unsaturated bond equivalent is a 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 Formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of the ethylenic double bond contained in the alkali-soluble resin W (g).)

The ethylenically unsaturated bond equivalent is determined, 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 the 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 filters may be used singly or in combination of two or more, and the content is not particularly limited. The alkali-soluble resin is preferably in the range of 5% by mass to 60% by mass, more preferably in the range of 10% by mass to 40% by mass with respect to the total solid content of the photosensitive colored resin composition for filters. When the content of the alkali-soluble resin is not less than the above lower limit value, sufficient Akali developability can be obtained, and when the content of the alkali-soluble resin is not more than the above upper limit value, film roughening or chipping of the pattern can be caused during development. Can be suppressed.

[Photopolymerizable compound]
The photopolymerizable compound used in the photosensitive colored resin composition for a color filter is not particularly limited as long as it can be polymerized by the photoinitiator, and usually has two or more ethylenically unsaturated double bonds. It is preferable to use a polyfunctional (meth) acrylate having 2 or more acryloyl groups or methacryloyl groups.
Such polyfunctional (meth) acrylate may be appropriately selected from conventionally known ones. Specific examples include those described in JP2013-029832A.

These polyfunctional (meth) acrylates may be used alone or in combination of two or more. Moreover, when the photocurable (high sensitivity) excellent in the photosensitive coloring resin composition for color filters of this invention is requested | required, polyfunctional (meth) acrylate has three double bonds which can superpose | polymerize ( Trifunctional or higher polyhydric alcohol poly (meth) acrylates and their dicarboxylic acid-modified products are preferred, specifically, trimethylolpropane tri (meth) acrylate, Pentaerythritol tri (meth) acrylate, modified succinic acid 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 filters is not particularly limited, but the photopolymerizable compound is preferably based on the total solid content of the photosensitive colored resin composition for color filters. Is in the range of 5% to 60% by weight, more preferably 10% to 40% by weight. When the content of the photopolymerizable compound is not less than the above lower limit, photocuring sufficiently proceeds, the exposed portion can suppress elution during development, and the content of the photopolymerizable compound is not more than the above upper limit. Alkali developability is sufficient.
The content of the photopolymerizable compound used in the photosensitive colored resin composition for color filters and the content ratio of the photoinitiator are excellent in curability and residual film ratio, and further improved in electrical reliability. In view of the above, the total content of the photoinitiator is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and 40 parts by mass or less with respect to 100 parts by mass of the photopolymerizable compound. 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 that does not react with each component in the photosensitive colored resin composition for color filters and can dissolve or disperse them. A solvent can be used individually or in combination of 2 or more types.
Specific examples of the solvent include 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, etc. Tone solvents; glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, 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 and N-methylpyrrolidone; γ-butyrolactone, etc. 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; Examples include organic solvents such as aromatic hydrocarbons such as xylene. Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferably used from the viewpoint of solubility of other components. Among them, the solvent used in the present invention includes propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, In addition, one or more selected from the group consisting of 3-methoxybutyl acetate is preferable from the viewpoints of solubility of other components and coating suitability.

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 a range in which the colored layer can be formed with high accuracy. Usually, it is preferably in the range of 55% by mass to 95% by mass, more preferably in the range of 65% by mass to 88% by mass, based on the total amount of the photosensitive colored resin composition for color filters containing the solvent. More preferably. When the content of the solvent is within the above range, the coating property can be excellent.

[Dispersant]
In the photosensitive colored resin composition for a color filter of the present invention, the colorant is preferably used by being dispersed in a solvent with a dispersant. In the present invention, the dispersant can be appropriately selected from conventionally known dispersants. Examples of the dispersant that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Among the surfactants, a polymer dispersant is preferable because it can be uniformly and finely dispersed.

Examples of the polymer dispersant include (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid; (Partial) ammonium salts and (partial) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes Long chain polyaminoamide phosphates; polyethyleneimine derivatives (amides and their bases obtained by reaction of poly (lower alkylene imines) with free carboxy group-containing polyesters); polyallylamine derivatives (polyallylamine and free carboxy) Polyester, polyamide or ester-amide co-condensate having a group The reaction product obtained by reacting one or more compound selected from among the three compounds of the polyester amide)), and the like.

As the polymer dispersant, among them, a polymer dispersant containing a nitrogen atom in the main chain or side chain and having an amine value is preferable from the viewpoint that the colorant can be suitably dispersed and the dispersion stability is good. Among these, a polymer dispersant composed of a polymer containing a repeating unit having a tertiary amine is preferable from the viewpoint of good dispersibility, no precipitation of foreign matters when forming a coating film, and improvement of luminance and contrast.
The repeating unit having a tertiary amine is a site having an affinity for the colorant. The polymer dispersant made of a polymer containing a repeating unit having a tertiary amine usually contains a repeating unit that becomes a site having an affinity for a solvent. As a polymer containing a repeating unit having a tertiary amine, a block copolymer having a block part composed of a repeating unit having a tertiary amine and a block part having a solvent affinity is particularly preferable. It is preferable at the point which can form the coating film which is excellent in and high brightness.

The repeating unit having a tertiary amine only needs to 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 the side chain is preferable, and among them, the structure represented by the following general formula (I) is preferable because the main chain skeleton is hardly thermally decomposed and has high heat resistance. Is more preferable.

(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 ( A divalent organic group represented by 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 represents an optionally substituted chain or cyclic hydrocarbon group, or R ³ and R ⁴ are bonded to each other to form a cyclic structure, and R ⁵ and R ⁶ are Each independently represents a hydrogen atom or a methyl group.
x represents an integer of 1 to 18, y represents an integer of 1 to 5, and z represents an integer of 1 to 18. )

Examples of the divalent linking group Q in the general formula (I) include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, a —CONH— group, a —COO— group, an ether group having 1 to 10 carbon atoms (— R′—OR ″ —: R ′ and R ″ are each independently an alkylene group) and combinations thereof. Among these, Q is a —COO— group or —CONH— from the viewpoint of heat resistance of the polymer obtained, 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 in the 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. For example, methylene group, ethylene group, trimethylene group, propylene group, various butylene groups, various pentylene groups, various hexylenes. Groups, various octylene groups and the like.
R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group.
R ² is preferably an alkylene group having 1 to 8 carbon atoms from the viewpoint of dispersibility. Among them, R ² is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group. Groups are more preferred.

Examples of the cyclic structure formed by combining R ³ and R ^{4 in} the general formula (I) include a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a condensed ring formed by condensing two of these. It is done. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring.

Examples of the repeating unit represented by the general formula (I) include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, and other alkyl group-substituted amino groups. Examples include group-containing (meth) acrylates, alkyl group-substituted amino group-containing (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, and the like. Of these, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylamide can be preferably used in terms of improving dispersibility and dispersion stability.

In the block part composed of repeating units having a tertiary amine, it is preferable that three or more structural units represented by the general formula (I) are included. Among these, from the viewpoint of improving dispersibility and dispersion stability, it is preferably 3 to 100, more preferably 3 to 50, and even more preferably 3 to 30.

A block having a block part (hereinafter sometimes referred to as A block) composed of a repeating unit having a tertiary amine and a block part having solvent affinity (hereinafter sometimes referred to as B block). As the block part having solvent affinity in the polymer, from the viewpoint of improving solvent affinity and improving dispersibility, the block unit does not have the structural unit represented by the general formula (I), and the general formula (I A solvent-affinity block portion having a structural unit copolymerizable with I). In the present invention, the arrangement of each block of the block copolymer is not particularly limited, and for example, an AB block copolymer, an ABA block copolymer, a BAB block copolymer, and the like can be used. Among these, an AB block copolymer or an ABA block copolymer is preferable in terms of excellent dispersibility.
The B block may be the same as the B block of International Publication No. 2016/104493.

The number of structural units constituting the solvent affinity block may be appropriately adjusted within a range where the colorant dispersibility is improved. Among them, the number of structural units constituting the solvent-affinity block part is 10 to 200 from the viewpoint that the solvent-affinity part and the colorant affinity part act effectively and improve the dispersibility of the colorant. It is preferably 10 to 100, more preferably 10 to 70.

The solvent-affinity block part may be selected so as to function as a solvent-affinity site, and the repeating unit constituting the solvent-affinity block part may be composed of one kind, or two or more kinds. The repeating unit may be included.
In the block copolymer used as the dispersant of the present invention, the number of units m of the structural unit represented by the general formula (I) and the number of units n of other structural units constituting the solvent-affinity block unit 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 dispersibility and dispersion stability of the color material. .

Further, among them, in the present invention, the dispersant is a polymer having an amine value of 40 mgKOH / g or more and 120 mgKOH / g or less that includes the structure represented by the general formula (I), and has good dispersibility. It is preferable from the viewpoint of improving luminance and contrast without depositing foreign matters.
When the amine value is within the above range, the viscosity is excellent in stability over time and heat resistance, and is also excellent in alkali developability and solvent resolubility. When the amine value of the dispersant is high, the dispersibility and dispersion stability are improved, the solvent solubility and the solvent re-solubility are improved, the compatibility with other components is improved, and the fine line pattern of the colored layer The linearity is improved, and the fluctuation of micropores is easily suppressed. In the present invention, the amine value of the dispersant is preferably 80 mgKOH / g or more, more preferably 90 mgKOH / g or more. On the other hand, from the viewpoint of solvent resolubility, the amine value of the dispersant is preferably 110 mgKOH / g or less, more preferably 105 mgKOH / g or less.
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 a sample, and can be measured by the method defined in JIS-K7237. When measured by this method, even if it is an amino group that forms a salt with the organic acid compound in the dispersant, the organic acid compound usually dissociates, so that the block copolymer itself used as the dispersant is itself The amine value of can be measured.

The acid value of the dispersant used in the present invention is preferably 1 mgKOH / g or more as a lower limit from the viewpoint of the effect of suppressing development residue. Among them, the acid value of the dispersant is more preferably 2 mgKOH / g or more from the viewpoint of more excellent development residue suppression effect. In addition, the acid value of the dispersant used in the present invention can prevent deterioration in development adhesion and solvent resolubility, improve the linearity of the fine line pattern of the colored layer, and suppress the fluctuation of micropores. From the viewpoint of ease, the upper limit of the acid value of the dispersant is preferably 18 mgKOH / g or less. Among these, the acid value of the dispersant is more preferably 16 mgKOH / g or less, and even more preferably 14 mgKOH / g or less, from the viewpoint of improving the development adhesion and the solvent resolubility.
In the dispersant used in the present invention, the acid value of the block copolymer before salt formation is preferably 1 mgKOH / g or more, and more preferably 2 mgKOH / g or more. This is because the effect of suppressing the development residue is improved. The upper limit of the acid value of the block copolymer before salt formation is preferably 18 mgKOH / g or less, more preferably 16 mgKOH / g or less, and even more preferably 14 mgKOH / g or less. . This is because the development adhesiveness and the solvent resolubility are improved.

Moreover, in this invention, it is preferable that the glass transition temperature of a dispersing agent is 30 degreeC or more from the point which image development adhesiveness improves. That is, whether the dispersant is a block copolymer before salt formation or a salt block copolymer, the glass transition temperature is preferably 30 ° C. or higher. When the glass transition temperature of the dispersant is low, it is particularly close to the developer temperature (usually about 23 ° C.), and 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, resulting in poor development adhesion. When the glass transition temperature is 30 ° C. or higher, the molecular motion of the dispersant during development is suppressed, so that it is estimated that the decrease in development adhesion is suppressed.
The glass transition temperature of the dispersant is preferably 32 ° C. or higher, more preferably 35 ° C. or higher, from the viewpoint of development adhesion. On the other hand, the temperature is preferably 200 ° C. or lower from the viewpoint of operability during use, such as easy precision weighing.
The glass transition temperature of the dispersant in the present invention can be determined by measuring 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, it is assumed that n monomer components from i = 1 to n are copolymerized in the block portion. Xi is the weight fraction of the i-th monomer (ΣXi = 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ is the sum from i = 1 to n. As the value (Tgi) of the homopolymer glass transition temperature of each monomer, the value of Polymer Handbook (3rd Edition) (by J. Brandrup, EHImmergut (Wiley-Interscience, 1989)) can be adopted.

When the colorant concentration is increased and the dispersant content is increased, the amount of the binder is relatively decreased, so that the colored resin layer is easily peeled off from the base substrate during development. When the dispersant contains a B block containing a structural unit derived from a carboxy group-containing monomer and has the specific acid value and glass transition temperature, the development adhesion is improved. If the acid value is too high, the developability is excellent, but it is presumed that the polarity is too high and peeling easily occurs during development.

From the above, in the present invention, the dispersant 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. 1 mgKOH / g or more and 18 mgKOH / g or less and having a glass transition temperature of 30 ° C. or more improves the color material dispersion stability and improves the contrast, and includes the oxime ester compound represented by the general formula (1) When a colored resin composition is used, the generation of development residues is suppressed, the solvent resolubility is excellent, the development adhesion is high, and the micropores with excellent shape can be easily formed. It is preferable from the viewpoint that the fluctuation of holes and development residues are easily suppressed.

As the carboxy group-containing monomer, a monomer that can be copolymerized with a monomer having a structural unit represented by the general formula (I) and contains an unsaturated double bond and a carboxy group can be used. Examples of such monomers include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, 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 and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use acid anhydride group containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxy group. Among these, (meth) acrylic acid is particularly preferable from the viewpoints 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 is within the range of the specific acid value. Although not limited, it is preferably 0.05% by mass to 4.5% by mass, and preferably 0.07% by mass to 3.7% by mass with respect to the total mass of all the structural units of the block copolymer. Is more preferable.
Since 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 the development residue is expressed, and since it is not more than the upper limit value, the development adhesiveness is deteriorated and the solvent resolubility is reduced. Deterioration can be prevented.
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.

Moreover, the monomer whose glass transition temperature (Tgi) of the homopolymer of the monomer is 10 ° C. or higher from the viewpoint that the glass transition temperature of the dispersant used in the present invention is a specific value or higher and development adhesion is improved. Is preferably 75% by mass or more, and more preferably 85% by mass or more in the B block.

In the block copolymer, the ratio m / n of the unit number m of the structural unit of the A block and the unit number n of the structural unit of the B block is in the range of 0.05 to 1.5. The range of 0.1 to 1.0 is more preferable from the viewpoint of the dispersibility and dispersion stability of the color material.

The weight average molecular weight Mw of the block copolymer is not particularly limited, but is preferably 1000 to 20000, and preferably 2000 to 15000 from the viewpoint of good colorant dispersibility and dispersion stability. More preferably, it is more preferably 3000 to 12000.
Here, the weight average molecular weight is determined as a standard polystyrene conversion value by (Mw) and gel permeation chromatography (GPC). The macromonomer, salt-type block copolymer, and graft copolymer that are the raw materials for the block copolymer are also subjected to the above conditions.

As a specific example of a block copolymer having a block part composed of a repeating unit having a tertiary amine and a block part having a solvent affinity, for example, a block copolymer described in Japanese Patent No. 4911253 is used. It can be mentioned as a suitable thing.

In the case of dispersing the colorant using a polymer containing a repeating unit having a tertiary amine as a dispersant, the polymer containing a repeating unit having the tertiary amine with respect to 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. If it is in the said range, it is excellent in the dispersibility and dispersion stability, and the effect which improves a contrast becomes high.

In the present invention, from the viewpoint of dispersibility and dispersion stability of the coloring material, at least a part of the amino group in the polymer containing the repeating unit having the tertiary amine, an organic acid compound, and a halogenated hydrocarbon. It is also preferable to use a salt forming a salt as a dispersant (hereinafter, such a polymer may be referred to as a salt-type polymer).
Among them, the polymer containing a repeating unit having a tertiary amine is a block copolymer, and the organic acid compound is an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphinic acid. And preferred from the viewpoint of excellent dispersion stability. Specific examples of the organic acid compound used for such a dispersant include, for example, organic acid compounds described in JP 2012-236882 A and the like.
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 and dispersion stability of the coloring material.

The content in the case of using a dispersant is not particularly limited as long as it can uniformly disperse the coloring material. For example, the total solid content of the photosensitive colored resin composition for color filters is used. On the other hand, it can be used in an amount of 1 to 40% by mass. Further, it is preferably blended in an amount of 2 to 30% by weight, particularly preferably 3 to 25% by weight, based on the total solid content of the photosensitive colored resin composition for color filters. If it is more than the said lower limit, it is excellent in the storage stability of the dispersibility and dispersion stability of a color material, and the photosensitive coloring resin composition for color filters. Moreover, if it is below the said upper limit, developability will become favorable. In particular, when a colored layer having a high colorant concentration is formed, the content of the dispersant is 2% by mass to 25% by mass, more preferably based on the total solid content of the photosensitive colored resin composition for color filters. It is preferable to blend at a ratio of 3% by mass to 20% by mass.

[Antioxidant]
The photosensitive colored resin composition for a color filter 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 including an antioxidant in combination with the oxime ester compound represented by the general formula (1). Since it is possible to suppress the luminance decrease after post-baking, the luminance can be improved, and excessive radical chain reaction in the micropores can be controlled without impairing the curability when forming the micropores in the cured film, Micropores having a desired shape can be formed more easily.
The antioxidant used in the present invention is not particularly limited, and may be appropriately selected from conventionally known ones. Specific examples of antioxidants include, for example, hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, and the like. It is preferable to use a hindered phenol type antioxidant from the point which makes the shape of a point and a micropore favorable.

The hindered phenol antioxidant contains at least one phenol structure, and has a structure in which a substituent having 4 or more carbon atoms is substituted on at least one of the 2-position and 6-position of the hydroxyl group of the phenol structure. Means an antioxidant.
Specific examples of the hindered phenol antioxidant include, for example, dibutylhydroxytoluene (BHT), 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, manufactured by BASF), 1,2-bis [3- (4-hydroxy-3,5-di-tert-butylphenyl) propionyl] hydrazine (trade name: Irganox MD1024, 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 1520L, manufactured by BASF), N, N′-hexamethylenebis [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-tert-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5.5] undecane (trade name: ADK STAB AO-80 , Manufactured by Adeka), bis (3-tert-butyl-4-hydroxy-5-methylbenzenepropionic acid) ethylene bis (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-hydroxy Diethyl benzylphosphonate (trade name: Irgamod 195, manufactured by BASF), 2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl acrylate (trade name: Sumilizer GM, manufactured by Sumitomo Chemical Co., Ltd., 4,4'-thiobis (6-tert-butyl-m-cresol) (trade name: Sumilizer 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 exhibiting an antioxidant function when the protecting group is eliminated. Among them, those which are easy to remove the protecting 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 radicals generated from the photoinitiator, suppresses a decrease in sensitivity, suppresses line width thinning, and a remaining film ratio It is easy to improve. On the other hand, in the heating step performed after exposure, the protective group is eliminated and an antioxidant effect is exhibited, so that fading of a color material or the like is suppressed and a high-luminance colored layer is obtained.
The latent antioxidant suitably used in the present invention is a protection capable of detaching the phenolic hydroxyl group of the hindered phenolic antioxidant by heating from the viewpoint of heat resistance and good micropore shape. And latent hindered phenol antioxidants protected with a group, and specific examples thereof include the following chemical formulas (a) to (c), but are not limited thereto.

The method for producing the latent antioxidant is not particularly limited. For example, JP-A-57-111375, JP-A-3-173843, JP-A-6-128195, JP-A-7-207771, JP-A-7-252191, special table. Obtained by reacting a phenolic compound produced by the method described in each publication of 2004-501128 with an acid anhydride, acid chloride, Boc reagent, alkyl halide compound, silyl chloride compound, allyl ether compound, etc. Can do. Moreover, you may use a commercial item.
Examples of the protecting group that can be removed by heating include a reaction residue of an acid anhydride, an acid chloride, a Boc reagent, an alkyl halide compound, a silyl chloride compound, or an allyl ether compound. , T-butoxycarbonyl group.

The content when the antioxidant is used is not particularly limited. For example, the content is 0.1% by mass to 20% by mass with respect to the total solid content of the photosensitive colored resin composition for color filter. be able to. Further, it is preferably blended in an amount of 0.2% by mass to 10% by mass with respect to the total solid content of the photosensitive colored resin composition for a color filter, and the ratio is particularly preferably 0.3% by mass to 5% by mass. From the viewpoint of sufficiently exerting the combined effect with the photoinitiator.

In addition, when the photosensitive colored resin composition for a color filter of the present invention further contains an antioxidant, the photoinitiator used in the present invention is sufficiently effective for the combined use with the photoinitiator. 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.
On the other hand, from the standpoint of maintaining moderate sensitivity, it is preferably 300 parts by mass or less, and more preferably 200 parts by mass or less, with respect to 100 parts by mass in total of the photoinitiator used in the present invention.

[Optional components]
The photosensitive colored resin composition for color filters may contain various additives as necessary. Examples of the additive include a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an ultraviolet absorber, and an adhesion promoter.
Specific examples of the surfactant and the plasticizer include those described in JP2013-029832A.

The ratio of the mass (P) of the color material used in the present invention to the mass (V) of the solid content other than the color material (hereinafter sometimes referred to as “P / V ratio”) is the colored layer of the color filter. In this case, it is only necessary that the desired color can be produced, and it is not particularly limited, 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 forming a desired color can be obtained, and further, the above photosensitive colored resin composition for a color filter. It can be uniformly dispersed in the product.

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

<Method for Producing Photosensitive Colored Resin Composition for Color Filter>
The method for producing a photosensitive colored resin composition for a color filter of the present invention comprises a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, preferably a dispersant, and an antioxidant. From the point of improving contrast, it is preferable that the colorant can be uniformly dispersed in the solvent by a dispersant, containing various additive components used as desired, and mixing using a known mixing means Can be prepared.
As a method for preparing the resin composition, for example, (1) First, a color material and a dispersant are added to a solvent to prepare a color material dispersion, and the alkali-soluble resin, light, A method of mixing a polymerizable compound, a photoinitiator, and various additive components used as desired; (2) In a solvent, a coloring material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator (3) In a solvent, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a photoinitiator are optionally used. A method in which various additive components are added and mixed, and then a color material is added and dispersed; (4) A color material dispersion is prepared by adding a color material, a dispersant, and an alkali-soluble resin to a solvent. The dispersion is further mixed with 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 above methods (1) and (4) are preferable from the viewpoint that the aggregation of the coloring material can be effectively prevented and dispersed uniformly.

The method for preparing the colorant dispersion can be appropriately selected from conventionally known dispersion methods. For example, (1) A dispersant is mixed and stirred in advance to prepare a dispersant solution, and then an organic acid compound is mixed as necessary to form a salt between the amino group of the dispersant and the organic acid compound. Let A method of mixing this with a coloring material and other components as necessary, and dispersing the mixture using a known stirrer or disperser; (2) Mixing and stirring a dispersant in a solvent to prepare a dispersant solution; A method of mixing a coloring material and, if necessary, an organic acid compound and, if necessary, other components and dispersing the mixture using a known stirrer or disperser; (3) mixing and stirring a dispersant in a solvent. Then, the dispersant solution is prepared, then the colorant and other components are mixed as necessary, and the mixture is made into a dispersion using a known stirrer or disperser, and then an organic acid compound is added as necessary. The method etc. are mentioned.

Examples of the dispersing machine for performing the dispersion treatment include roll mills such as two rolls and three rolls, ball mills such as a ball mill and a vibration ball mill, bead mills such as a paint conditioner, a continuous disk type bead mill, and a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter to be used is preferably 0.03 mm to 2.00 mm, and 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, and at least one of the colored layers is a photosensitive for color filter according to the present invention. It has a colored layer made of a cured product of the 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 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 has a substrate 1, a light shielding part 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 made of a cured product of the photosensitive colored resin composition for color filters according to the present invention.
The colored layer is usually formed in an opening of a light shielding part on the substrate to be described later, and is usually composed of a colored pattern of three or more colors.
In addition, the arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used. Moreover, the width | variety, area, etc. of a colored layer can be set arbitrarily.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration, the viscosity, etc. of the photosensitive colored resin composition for a color filter, but is usually preferably in the range of 1 μm to 5 μm. .

The colored layer can be formed by the following method, for example.
First, the above-described photosensitive colored resin composition for color filters of the present invention is applied to a substrate described later using a coating means such as spray coating, dip coating, bar coating, roll coating, spin coating, or die coating. Apply on top to form a wet coating. Of these, spin coating and die coating can be preferably used.
Next, after drying the wet coating film using a hot plate or oven, it is exposed to light through a mask having a predetermined pattern, and an alkali-soluble resin and a photopolymerizable compound are subjected to a photopolymerization reaction. Let it be a cured coating film. Examples of the light source used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
Moreover, in order to promote a polymerization reaction after exposure, you may heat-process. 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, it develops using a developing solution, a coating film is formed with a desired pattern by melt | dissolving and removing an unexposed part. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to the alkaline solution.
Further, a general method can be adopted as the developing method.
After the development treatment, usually, the developer is washed and the cured coating film of the photosensitive colored resin composition for color filter is dried to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after image development processing. The heating conditions are not particularly limited and are appropriately selected depending on the application of the coating film.

In addition, when the color filter according to the present invention has a color filter-on-array structure, micropores may be formed in the colored layer during the development process. In the present invention, since the above-described photosensitive colored resin composition for a color filter is used, desired micropores can be easily formed in the colored layer. The shape of the micropore is appropriately selected according to the application and is not particularly limited. In the present invention, for example, a micropore having a size of about 10 μm × 10 μm to 30 μm × 30 μm can be formed. Moreover, the shape of a micropore is not specifically limited, For example, circular, an ellipse, a polygon etc. are mentioned.
As a method for forming micropores in the colored layer, for example, as a photomask used for forming the colored layer, a microhole for forming micropores in an opening pattern of a pattern photomask capable of forming a fine line pattern is used. There is a method using a pattern photomask in which a mask is arranged.

(Shading part)
The light shielding part in the color filter of the present invention is formed in a pattern on a substrate to be described later, and can be the same as that used as a light shielding part in a general color filter.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. The light shielding part may be a metal thin film such as chromium by sputtering, vacuum deposition or the like. Alternatively, the light shielding part 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, there are 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 the photosensitive resist, etc. is there.

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

(substrate)
As the substrate, a transparent substrate, a silicon substrate, and a transparent substrate or a substrate in which an aluminum, silver, silver / copper / palladium alloy thin film or the like is formed on a transparent substrate or a silicon substrate, which will be described later, 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 base material transparent to visible light, and a transparent substrate used for a general color filter can be used. Specifically, transparent flexible rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible flexible materials such as transparent resin films, optical resin plates, and flexible glasses. Materials.
The thickness of the transparent substrate is not particularly limited, but for example, a thickness of about 100 μm to 1 mm can be used according to the use of the color filter of the present invention.
The color filter of the present invention includes, for example, an overcoat layer, a transparent electrode layer, an alignment film, an alignment protrusion, a columnar spacer, etc., in addition to the substrate, the light shielding portion, and the colored layer. Also good.

III. Display Device A display device according to the present invention includes 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, such as a liquid crystal display device and an organic light emitting display device.

[Liquid Crystal Display]
The liquid crystal display device includes the above-described color filter according to the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter 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 illustrated in FIG. 2, the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
Note that the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, but can be a configuration generally known as a liquid crystal display device using a color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for a liquid crystal display device can be employed. Examples of such a drive method include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be preferably used.
Further, the counter substrate can be appropriately selected and used according to the driving method 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 mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention.

As a method for forming a liquid crystal layer, a method generally used as a method for producing 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-described method, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.

[Organic light emitting display]
An organic light emitting display device includes the above-described color filter according to the present invention and an organic light emitter.
Such an organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic view illustrating 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 includes a color filter 10 and an organic light emitter 80. An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80.

As a method for laminating the organic light emitter 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. Examples thereof include a method and a method in which an organic light emitter 80 formed on another substrate is bonded onto the inorganic oxide film 60. As the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other configurations in the organic light emitting body 80, known structures can be appropriately used. The organic light emitting display device 100 manufactured as described above can be applied to, for example, a passive drive type organic EL display or an active drive type organic EL display.
Note that the organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may be a known configuration as an organic light emitting display device that generally uses a color filter.

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.
The structure of the obtained compound was determined by 1H- and 13C-NMR spectra measured using a nuclear magnetic resonance apparatus (Bruker Biospin, AVANCE III HD 500 MHz), and a liquid chromatograph mass spectrometer (Shimadzu Corporation, LC- It was confirmed by mass spectrometry using 30A, Bruker Daltonics, MICROTOFQ2).

(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 were dissolved in 500 ml of anhydrous dimethyl sulfoxide under a nitrogen atmosphere and maintained at 15 ° C., and 1.33 mol of bromobutane was added. Slowly added in 2 hours and the reaction was stirred at 15 ° C. for 1 hour. Thereafter, 2 L of distilled water was added to the reaction product and stirred for about 30 minutes, and then the product was extracted with 2 L of dichloromethane, and the extracted organic layer was washed twice with 2 L of distilled water. Next, the collected organic layer is dried over anhydrous MgSO ₄ , and the product obtained by distilling the solvent under reduced pressure 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) was dissolved in 500 ml of dichloromethane and cooled to −5 ° C., then 0.13 mol of AlCl ₃ was gradually added, and the temperature of the reaction product was not raised. Thus, a solution consisting of 15 ml of dichloromethane and 0.13 mol of cyclohexylpropionyl chloride was gradually 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. Next, the product obtained by distilling the collected organic layer under reduced pressure 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 intermediate A2 (0.042 mol) was dissolved in 200 ml of tetrahydrofuran (THF), and 25 ml of 4N HCl dissolved in 1,4-dioxane and 0.063 mol of isobutyl nitrite were added in order. The product was stirred at 25 ° C. for 6 hours. Thereafter, 200 ml of ethyl acetate was added to the reaction solution and stirred for 30 minutes to separate the organic layer, followed by washing with 200 ml of distilled water. Next, the collected organic layer was dried over anhydrous MgSO ₄ , and the product obtained by distilling the solvent under reduced pressure was 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) was dissolved in 200 ml of N-methyl-2-pyrrolidinone (NMP) under a nitrogen atmosphere and maintained at −5 ° C., and 0.068 mol of triethylamine was added. 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 temperature of the reaction was not increased. Thereafter, 200 ml of distilled water was gradually added to the reaction product and stirred for 30 minutes to separate the organic layer. Next, the collected organic layer was dried over anhydrous MgSO ₄ , and the product obtained by distilling the solvent under reduced pressure was recrystallized using 1 L of ethanol and dried to obtain the following compound A.

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

(2) Synthesis of Intermediate B2 In Synthesis Example 1 (2), except that the same mole of the intermediate B1 was used instead of the intermediate A1, and the same mole of propionyl chloride was used instead of the cyclohexyl propionyl chloride, In the same manner as in Synthesis Example 1 (2), the following intermediate B2 was obtained.

(3) Synthesis of Intermediate B3 In Synthesis Example 1 (3), the same mole of Intermediate B2 was used instead of Intermediate A2, and instead of silica gel column chromatography, ethyl acetate: n-hexane (1: 6 The following intermediate B3 was obtained in the same manner as in (3) of Synthesis Example 1 except that it was recrystallized using a mixed solvent of

(4) Synthesis of Compound B In the same manner as in Synthesis Example 1 (4) except that the same mole of Intermediate B3 was used in place of Intermediate A3 in Synthesis Example 1 (4), Compound B below 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 mole of butyryl chloride was used in place of propionyl chloride in (2) of Synthesis Example 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 9 ml of dichloromethane was then added. And a solution consisting of 0.033 mol of propionyl chloride was gradually added over 1 hour so as not to raise the temperature of the reaction product 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 above intermediate D1 (0.010 mol) was dissolved in 30 ml of tetrahydrofuran (THF), and 4.5 ml of 4N HCl dissolved in 1,4-dioxane and 0.015 mol of isopentyl nitrite were 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 was dried over anhydrous MgSO ₄ , and the product obtained by distilling the solvent under reduced pressure was 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 intermediate D2 (0.006 mol) was dissolved in 25 ml of ethyl acetate under a nitrogen atmosphere to maintain the reaction at −5 ° C., and 0.007 mmol of triethylamine was added to the reaction solution 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 temperature of the reaction was not increased, and stirred for 30 minutes. Thereafter, 100 ml of distilled water was gradually added to the reaction product and stirred for about 30 minutes to separate the organic layer. Next, the recovered 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 pulverized AlCl ₃ and 150 ml of dichloroethane were added and stirred, and argon gas was passed in an ice bath. When the temperature was lowered to 0 ° C. by cooling, a solution consisting of 0.22 mol of cyclohexylpropionyl chloride and 42 g of dichloroethane began to be added dropwise, and was added over about 1.5 hours while adjusting the temperature to 10 ° C. or lower. The temperature was raised to 15 ° C., followed by stirring for 2 hours, and then the reaction solution was discharged.
The reaction solution is gradually added with stirring to dilute hydrochloric acid containing 400 g of ice and 65 ml of concentrated hydrochloric acid, and then the lower layer is separated using a separatory funnel, and the upper layer is extracted with 50 ml of dichloroethane. Combined with the liquid. Then, it was washed with a NaHCO ₃ solution containing 10 g of NaHCO ₃ and 200 g of water, further washed with 200 ml of water until the pH value became neutral, and dried with 60 g of anhydrous MgSO ₄ to remove moisture. Later, dichloroethane was evaporated by rotary evaporation. The solid powder remaining in the rotary evaporation bottle was put into 200 ml of petroleum ether, subjected to suction filtration, further put into 150 ml of absolute ethanol, heated and refluxed. Thereafter, the mixture was cooled to room temperature, further cooled with ice for 2 hours, suction filtered, and 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 above 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. Thereafter, the reaction solution was discharged.
The reaction solution was placed in a large beaker, and after adding 1000 ml of water and stirring, the mixture was allowed to stand overnight to separate the 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 put into 150 ml of petroleum ether, stirred and precipitated, and suction filtered to obtain a white powdery solid. Then, it dried at 60 degreeC for 5 hours, and obtained the following intermediate body E2.

(3) Synthesis of Compound E In a 1000 ml four-necked flask, 34 g of the above intermediate E2, 350 ml of dichloroethane, and 12.7 g of triethylamine were added and stirred, and cooled in an ice bath until the temperature reached 0 ° C. When lowered, a solution consisting of 15.7 g of acetic chloride and 15 g of dichloroethane began to be added dropwise and added over about 1.5 hours. Subsequently, after stirring for 1 hour, 500 ml of cold water was added dropwise, and the layers were separated using a separatory funnel. Wash once with 200 ml of 5% NaHCO ₃ solution, then twice with 200 ml of water until the pH value is neutral, then wash once with dilute hydrochloric acid containing 20 g of concentrated hydrochloric acid and 400 ml of water, followed by 200 ml of water. And then dried with 100 g of anhydrous MgSO ₄ , and the solvent was removed by rotary evaporation to obtain a viscous liquid. A white solid deposited by adding an appropriate amount of methanol to the viscous liquid 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 mole of [4- (phenylthio) phenyl] -2-thienyl-methanone was used instead of diphenylthioether in Synthesis Example 5 (1). did.

(Synthesis Example 7: Production of dispersant (block copolymer A))
Add 250 parts by weight of THF and 0.6 parts by weight of lithium chloride to a 500 mL round bottom 4-neck separable flask equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, and perform sufficient nitrogen replacement. It was. 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 part by mass of methyl isobutyrate were injected using a syringe. B block monomer 1-ethoxyethyl methacrylate (EEMA) 2.2 parts by weight, 2-hydroxyethyl methacrylate (HEMA) 18.7 parts by weight, 2-ethylhexyl methacrylate (EHMA) 12.8 parts by weight, methacryl 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 added dropwise using an addition funnel over 60 minutes. . After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for the 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, diluted with PGMEA to obtain a solid content solution of 30% by mass. 32.5 parts by mass of water was added, the temperature was raised to 100 ° C., and the reaction was carried out for 7 hours. The obtained block copolymer PGMEA solution is reprecipitated in hexane, purified by filtration and vacuum drying, and a structural unit derived from a block containing a structural unit represented by the general formula (I) and a carboxy group-containing monomer A block copolymer A (acid value: 8 mgKOH / g, Tg: 38 ° C.) containing a B block having solvophilic properties. The block copolymer A thus obtained was confirmed by GPC (gel permeation chromatography), and the weight average molecular weight Mw was 7730. The amine value was 95 mgKOH / g.

(Synthesis Example 8: Synthesis of alkali-soluble resin A solution)
A mixed liquid 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 was dropped into a polymerization tank containing 150 parts by mass of PGMEA at 100 ° C. for 3 hours in a nitrogen stream. did. After completion of dropping, the mixture was further heated at 100 ° C. for 3 hours to obtain a polymer solution. The weight average molecular weight of this polymer solution was 7000.
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 through the solution. The obtained alkali-soluble resin A is a resin in which a side chain having an ethylenic double bond is introduced into the main chain formed by copolymerization of styrene, MMA, and MAA using GMA, and has a solid content of 42.6 mass. %, Acid value 74 mgKOH / g, and weight average molecular weight 12000. The weight average molecular weight was measured with a Shodex GPC System-21H (polypropylene) using polystyrene as a standard substance and THF as an eluent. The acid value was measured based on JIS K 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 International Publication No. 2012/144521, 15.9 g of intermediate 1 represented by the following chemical formula (1) was obtained. Rate 70%).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 511 (+), divalent and elemental analysis values: CHN measured value (78.13%, 7.48%, 7.78%); theoretical value (78.06%) , 7.75%, 7.69%)

(2) Synthesis of Blue Color Material α 5.00 g (4.58 mmol) of the intermediate 1 was added to 300 ml of water and dissolved at 90 ° C. to obtain an intermediate 1 solution. Next, 10.44 g (3.05 mmol) of phosphotungstic acid · n hydrate H ₃ [PW ₁₂ O ₄₀ ] · nH ₂ O (n = 30) (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.) was placed in 100 ml of water, and 90 ° C. And a phosphotungstic acid aqueous solution was prepared. The aqueous phosphotungstic acid solution prepared in the intermediate 1 solution was mixed 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 color 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 value: CHN measured value (41.55%, 5.34%, 4.32%); theoretical value (41.66%) (5.17%, 4.11%)

(Synthesis Example 10: Preparation of Azo derivative 1)
23.1 g diazobarbituric acid and 19.2 g barbituric acid were introduced into 550 g distilled water. Subsequently, it adjusted so that it might become azobarbituric acid (0.3 mol) using potassium hydroxide aqueous solution, and mixed with 750 g of distilled water. 5 g of 30% hydrochloric acid was added dropwise. Thereafter, 38.7 g of melamine was introduced. Subsequently, 0.39 mol nickel chloride solution and 0.21 mol 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 (azo pigment of Ni-azo-1, 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, instead of 0.39 mol nickel chloride solution and 0.21 mol zinc chloride solution, 0.42 mol nickel chloride solution and 0.18 mol zinc chloride solution were used. Azo derivative 2 (azo pigment with 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 the Azo derivative 1 of Synthesis Example 10, 0.3 mol nickel chloride solution and 0.3 mol zinc chloride solution were used instead of 0.39 mol nickel chloride solution and 0.21 mol zinc chloride solution. Except that it was used, Azo derivative 3 (Ni-azo-3, azo pigment with Ni: Zn = 50: 50 (molar ratio)) was obtained in the same manner as in Synthesis Example 10.

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

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

(Synthesis Example 15: Synthesis of Latent Antioxidant (Compound a))
A phenol compound represented by the following chemical formula (3) 0.01 mol, di-tert-butyl dicarbonate 0.05 mol and 30 g of pyridine were mixed, and 0.025 mol of 4-dimethylaminopyridine was added at room temperature under a nitrogen atmosphere. Stir at 0 ° 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 perform 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 powder 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). 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 color material, The alkali-soluble resin A solution obtained in Synthesis Example 8 was put into a mayonnaise bin with 5.1 parts by mass in terms of solid content, 76.8 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle size of 2.0 mm. Shake with a paint shaker (manufactured by Asada Tekko Co., Ltd.) for 1 hour, then take out 2.0 mm zirconia beads with a particle size of 2.0 mm, add 200 parts by mass of zirconia beads with a particle size of 0.1 mm, Was dispersed for 4 hours in 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 the colorant dispersion 1 obtained in the above (1) and the alkali-soluble resin A solution obtained in Synthesis Example 8 as a solid content 8.6 parts by mass, 18.2 parts by mass of a photopolymerizable compound (trade name Aronix M-520D, manufactured by Toagosei Co., Ltd.) and 2.0 parts by mass of dibutylhydroxytoluene (BHT) as an antioxidant As a photoinitiator, 5.1 parts by mass of Compound A obtained in Synthesis Example 1 and 42.2 parts by mass of PGMEA were added to obtain a photosensitive colored resin composition 1 for a color filter.

(Examples 2 to 13)
In Example 1, photosensitive color 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 types and amounts shown in Table 1.

OXE-01 used as the photoinitiator in Example 8 is an oxime ester photoinitiator (trade name: Irgacure OXE-01, manufactured by BASF), and is a compound represented by the following chemical formula (4).

(Example 14)
In Example 13, a photosensitive colored resin for a color filter was used in the same manner as in Example 13 except that a bisphenol antioxidant (ADK STAB AO-40, manufactured by ADEKA) was used instead of BHT as an antioxidant. A composition 14 was obtained.

(Example 15)
In Example 13, a photosensitive colored resin composition for a color filter was used in the same manner as in Example 13 except that a hindered phenol antioxidant (Irg1010, manufactured by BASF) was used instead of BHT as an antioxidant. Product 15 was obtained.

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

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

(Comparative Examples 1 to 3)
In Example 21, the photoinitiator was used 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. Colored resin compositions 1 to 3 were obtained.

The photoinitiator used in Comparative Example 1 is OXE-02 (manufactured by BASF) represented by the following chemical formula (5).

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

(Example 22)
In Example 13, a photosensitive colored resin composition for a color filter was used in the same manner as in Example 13 except that 37.2 parts by mass of Pigment Red 254 (PR254) was used instead of the blue color material α as the color material. 22 was obtained.

(Comparative Example 4)
In Example 22, without using Compound A obtained in Synthesis Example 1, Compound E obtained in Synthesis Example 5 and Irg819 (manufactured by BASF) as a photoinitiator, OXE- represented by the above chemical formula (5) was used. 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, the antioxidant (BHT) was not 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, instead of the blue color material α as the color material, 16.48 parts by mass of Pigment Green 59 (PG59) and 20.72 parts by mass of the Azo derivative 1 obtained in Synthesis Example 10 were used. In the same manner as in Example 13, a photosensitive colored resin composition 23 for a color filter was obtained.

(Comparative Example 5)
In Example 23, without using Compound A obtained in Synthesis Example 1, Compound E obtained in Synthesis Example 5 and Irg819 (manufactured by BASF) as a photoinitiator, OXE-- represented by the above 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 amounts shown in Table 2, the antioxidant (BHT) was not 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, instead of the blue color material α as the color material, C.I. I. Photosensitive coloring for color filters in the same manner as in Example 13 except that 37.2 parts by mass of Solvent Yellow 162, no antioxidant (BHT), and 20.2 parts by mass of the photopolymerizable compound were used. A resin composition 24 was obtained.

(Comparative Example 6)
In Example 24, without using Compound A obtained in Synthesis Example 1, Compound E obtained in Synthesis Example 5 and Irg819 (manufactured by BASF) as a photoinitiator, OXE- represented by the above chemical formula (5) was used. A photosensitive colored resin composition 6 for a comparative color filter was obtained in the same manner as in Example 24 except that 02 (manufactured by BASF) was used in an amount shown in Table 2.

(Example 25)
In Example 16, in place of the blue color material α as the color material, 23.8 parts by mass of Pigment Green 58 and 13.4 parts by mass of the Azo derivative 2 obtained in Synthesis Example 11 were used. In the same manner as in No. 16, a photosensitive colored resin composition 25 for a color filter was obtained.

(Example 26)
In Example 16, instead of the blue color material α as the color material, 24.5 parts by mass of Pigment Green 58 and 12.7 parts by mass of the Azo derivative 3 obtained in Synthesis Example 12 were used. In the same manner as in No. 16, a photosensitive colored resin composition 26 for a color filter was obtained.

(Example 27)
In Example 16, instead of the blue color material α as a color material, 25.3 parts by mass of Pigment Green 58 and 11.9 parts by mass of the Azo derivative 4 obtained in Synthesis Example 13 were used. In the same manner as in No. 16, a photosensitive colored resin composition 27 for a color filter was obtained.

(Example 28)
In Example 16, instead of the blue color material α as the color material, 26.1 parts by mass of Pigment Green 58 and 11.1 parts by mass of Azo derivative 5 obtained in Synthesis Example 14 were used. In the same manner as in No. 16, a photosensitive colored resin composition 28 for a color filter was obtained.

(Example 29)
In Example 27, 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.

(Example 30)
In Example 27, the photosensitive colored resin composition 30 for color filters was obtained in the same manner as in Example 27 except that 20.2 parts by mass of the photopolymerizable compound was used without using the antioxidant compound a. It was.

(Comparative Example 7)
In Example 27, without using Compound A obtained in Synthesis Example 1, Compound E obtained in Synthesis Example 5 and Irg819 (manufactured by BASF) as a photoinitiator, OXE- represented by the above chemical formula (5) was used. Photosensitive compound for comparative color filter in the same manner as in Example 27 except that 02 (manufactured by BASF) was used in an amount shown in Table 2, an antioxidant was not used, and 20.2 parts by mass of a photopolymerizable compound was used. A 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 (NH Techno Glass Co., Ltd., “NA35”) using a spin coater to obtain a cured coating film having a thickness of 3 After coating to a thickness of 0.0 μm, it was dried at 80 ° C. for 3 minutes using a hot plate to form a coating film on the glass substrate. This coating film is irradiated with ultraviolet rays of 40 mJ / cm ² using an ultrahigh pressure mercury lamp through a pattern photomask (chrome mask) in which a chromium mask of 20 μm × 20 μm is arranged in the center of an independent thin line having an opening size of 90 μm × 300 μm. By exposing, a post-exposure coating film was formed on the glass substrate. Next, spin-develop with 0.05 wt% potassium hydroxide aqueous solution as a developer, develop it by indirect solution in the developer for 60 seconds, and then wash with pure water to form a coating film with an independent fine line pattern having micropores Got. After that, post-baking in a clean oven at 230 ° C. for 25 minutes was performed to form a colored layer having an independent fine line pattern having micropores. The following evaluation was performed about the obtained colored layer.

<Optical characteristic evaluation>
The photosensitive colored resin composition obtained in each example and each comparative example was applied on a glass substrate (NH Techno Glass Co., Ltd., “NA35”) using a spin coater, and then a hot plate was used. It was used and dried at 80 ° C. for 3 minutes to form a coating on the glass substrate. The whole surface was irradiated with 60 mJ / cm ² of ultraviolet light using an ultrahigh pressure mercury lamp without passing through a photomask to form a post-exposure coating film. Next, spin development was performed using a 0.05 wt% potassium hydroxide aqueous solution as a developer, and the resulting solution was indirectly developed for 60 seconds and then washed with pure water to form a post-development coating film. Thereafter, it was post-baked in a clean oven at 230 ° C. for 25 minutes, and the chromaticity was y = 0.083 when using the blue color material α, x = 0.650 when using PR254, and PG59 / Azo derivative. , Y = 0.610, C.I. A cured coating film (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 luminance (Y) of the colored layer were measured using an Olympus microscopic spectrophotometer OSP-SP200.

<Developability evaluation>
[Linearity]
The width of the fine line pattern of the colored layer at the portion corresponding to the opening width of 90 μm of the chromium mask used at the time of exposure was measured with an optical microscope, and the linearity was evaluated based on the variation in line width.
A: Variation within ± 0.1 μm B: Variation within ± 0.1 μm within ± 0.3 μm C: Variation over ± 0.3 μm [Residual film ratio]
In the formation of the colored layer, 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) in the process of forming a coating film. The film thickness after development (D) / the film thickness after exposure (E) was calculated as the remaining film ratio.
It should be noted that the film thickness after development (D) / the film thickness after exposure (E) is 90% or more, which is a range suitable for actual use.

The colored layer was observed with an optical microscope, and the shape of micropores, billiness and development residue were evaluated according to the following evaluation criteria.
[shape]
A: The deviation of the dimension of the minute holes formed in the colored layer is smaller than 2% in absolute value with respect to the dimension of the chromium mask arranged in the independent thin line pattern. B: The chromium mask arranged in the independent thin line pattern. Deviations in the size of the micropores formed in the colored layer with respect to the dimension of 2 to 6% in absolute value C: formed in the colored layer with respect to the dimension of the chrome mask arranged in the independent fine line pattern Deviation of the dimension of the formed micropore is larger than 6% and not more than 8% in absolute value. D: The dimension deviation of the microhole formed in the colored layer is different from the dimension of the chromium mask arranged in the independent thin line pattern. The absolute value is larger than 8%. Note that the dimensional deviation was calculated as an average value of the dimensional deviation of each side.
[Biritsuki]
A: Ten-point average roughness of the peripheral portion of the micropore formed in the colored layer is smaller than 0.1 B: Ten-point average roughness of the peripheral portion of the micropore formed in the colored layer is 0.1 or more and 0 .5 or less C: The ten-point average roughness of the peripheral edge of the micropore formed in the colored layer is greater than 0.5. The ten-point average roughness was measured in accordance with JIS B0601.
[Development residue]
AA: No coloring is observed inside the micropores formed in the colored layer by observation with an optical microscope, and no transparent material is observed at the periphery of the micropore A: Inside the micropores formed in the colored layer by observation with an optical microscope No coloration is observed, but some transparent material is observed at the periphery of the micropore B: Coloration is observed inside the micropore formed in the colored layer by observation with an optical microscope

Abbreviations in Table 1 and Table 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)
Irg369: α-aminoketone photoinitiator (Irgacure 369, manufactured by BASF)
Irg907: α-aminoketone photoinitiator (Irgacure 907, manufactured by BASF)
・ Mercapto series: Mercapto chain transfer agent (2-mercaptobenzothiazole, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Biimidazole series: Biimidazole series photoinitiator (HABI, manufactured by Kurokin Kasei)
DETX: thioxanthone photoinitiator (DOUBLECURE DETX, manufactured by Double Bond Chemical)
Irg819: acylphosphine oxide photoinitiator (Irgacure 819, manufactured by BASF, BHT: dibutylhydroxytoluene, AO-40: bisphenol-based antioxidant (Adekastab AO-40, manufactured by ADEKA)
Irg1010: hindered phenol antioxidant (Irgacure 1010, manufactured by BASF)

<Summary of results>
The photosensitive colored resin compositions of Examples 1 to 30 containing the oxime ester compound represented by the general formula (1) as a photoinitiator were used as comparative photosensitive colored resin compositions using the same color material. In comparison, it was revealed that a colored layer with improved luminance can be formed. In addition, the colored resin compositions of Examples 1 to 30 had a high residual film ratio and good sensitivity. It was clarified that the photosensitive colored resin compositions of Examples 1 to 30 were excellent in the linearity of the fine line pattern, and desired micropores were easily formed in the colored layer at the same time when the colored layer was patterned. 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 remaining film ratio are high, and Z in the general formula (1) is — (C═O ) example using an oxime ester compound is a R ^d 4 is compatibility with solvent solubility and other components of the oxime ester compound is better, the shape of the micropores was better. When the cross sections of the micropores of Example 1 and Example 2 were observed and compared, Example 2 had a gentler taper angle and a better micropore shape.
In addition, by using a combination of the oxime ester compound represented by the general formula (1) and the oxime ester compound having a diphenyl sulfide skeleton as a photoinitiator, the shape of the micropores was improved (implementation). Comparison between Example 1 and Example 5 and Comparison between Example 2 and Examples 6-8).
Further, as the photoinitiator, an oxime ester compound represented by the general formula (1) and an oxime ester compound having a diphenyl sulfide skeleton are combined, and an α-aminoketone photoinitiator or a biimidazole photoinitiator is further combined. , Containing at least one selected from thioxanthone photoinitiators, acylphosphine oxide photoinitiators, and mercapto chain transfer agents improves the linearity of the fine line pattern and improves the shape of the micropores (Comparison between Example 5 and Examples 9 to 13).
In addition, the inclusion of the antioxidant further suppressed the fluctuation of micropores and improved the brightness (comparison between Example 1 and Example 21, and comparison between Examples 27 and 29 and Example 30). Among the antioxidants, when the latent antioxidant (compound a) was used, the remaining film ratio was as good as when the antioxidant was not used while the micropores were more suppressed. On the other hand, when a hindered phenolic antioxidant that is not a latent antioxidant is used, the luminance is improved more than when a latent antioxidant is used (Examples 27 and 29 and Example 30). Comparison).
On the other hand, the same color material was used in Comparative Example 1 and Comparative Examples 4 to 7 which did not contain the oxime ester compound represented by the general formula (1) as a photoinitiator and used an oxime ester compound having a carbazole skeleton. The brightness was inferior to that of the previous example, the linearity of the fine line pattern was inferior, and micropores could not be formed.
Further, in Comparative Example 2 which does not contain the oxime ester compound represented by the general formula (1) as a photoinitiator and uses Irg907 (α-aminoketone photoinitiator), the luminance and the remaining film ratio are inferior. It was.
Comparative compound A which does not contain the oxime ester compound represented by the general formula (1) as a photoinitiator, has a nitro group in the fluorene skeleton, and the oxime ester group is bonded to the fluorene skeleton without a carbonyl group. In the comparative example 3 using the brightness and the linearity were inferior. The reason why the linearity of Comparative Example 3 was inferior is presumed that the solvent solubility of Comparative Compound A and the compatibility with other components were inferior.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Light-shielding part 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 device

Claims

Containing a coloring material, 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, and R c is a thioether bond (—S—), an ether bond (—O—) and a carbonyl bond (— CO—) is a hydrocarbon group which may contain at least one divalent linking group selected from Z, Z is a hydrogen atom or — (C═O) R d , and R d is an oxygen atom And a hydrocarbon group that may contain at least one selected from sulfur atoms, or a heterocyclic group that does not contain a nitrogen atom and contains at least one selected from oxygen and sulfur atoms, and R e Is a hydrocarbon group having 1 to 10 carbon atoms.)
The photosensitive colored resin composition for a color filter according to claim 1, wherein the photoinitiator includes two or more oxime ester compounds having no carbazole skeleton.
The photosensitive colored resin composition for a color filter according to claim 1 or 2, wherein the photoinitiator further contains an oxime ester compound having a diphenyl sulfide skeleton.
The photoinitiator is further at least one selected from α-aminoketone photoinitiators, biimidazole photoinitiators, thioxanthone photoinitiators, acylphosphine oxide photoinitiators, and mercapto chain transfer agents. The photosensitive coloring resin composition for color filters as described in any one of Claims 1 thru | or 3 containing this.
The photoinitiator is further at least one selected from α-aminoketone photoinitiators, biimidazole photoinitiators, thioxanthone photoinitiators, acylphosphine oxide photoinitiators, and mercapto chain transfer agents. The photosensitive coloring resin composition for color filters as described in any one of Claims 1 thru | or 4 containing the oxime ester compound which has a diphenyl sulfide skeleton.
Furthermore, the photosensitive coloring resin composition for color filters as described in any one of Claims 1 thru | or 5 containing antioxidant.
The antioxidant comprises a hindered phenolic antioxidant and a latent hindered phenolic antioxidant in which the phenolic hydroxyl group of the hindered phenolic antioxidant is protected with a protecting group that can be removed by heating. The photosensitive coloring resin composition for color filters of Claim 6 which is at least 1 sort (s) selected from.
The dispersant according to any one of claims 1 to 7, further comprising a dispersant, wherein the dispersant contains a polymer having a structure represented by the following general formula (I) and an amine value of 40 mgKOH / g or more and 120 mgKOH / g or less. A photosensitive colored resin composition for a color filter according to claim 1.

(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 ) A divalent organic group represented by —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 Each 6 is independently a hydrogen atom or a methyl group.
x represents an integer of 1 to 18, y represents an integer of 1 to 5, and z represents an integer of 1 to 18. )
The dispersant is a polymer having a structure represented by the general formula (I) and an amine value of 40 mgKOH / g or more and 120 mgKOH / g or less, and an acid value of 1 mgKOH / g or more and 18 mgKOH / g or less. The photosensitive colored resin composition for color filters according to claim 8, wherein
The colorant is at least one selected from the group consisting of a zinc phthalocyanine pigment, an azo compound represented by the following general formula (ii), and mono-, di-, tri-, and tetraanions of an azo compound having a tautomer structure thereof. A yellow color material containing a seed anion and ions of at least two kinds of 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 photosensitive colored resin composition for a color filter according to any one of claims 1 to 10, wherein the color filter comprises at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers. A color filter, which is a colored layer made of a cured product.
A display device comprising the color filter according to claim 11.