JP6949527B2 - Photosensitive colored resin composition, cured product, color filter, display device - Google Patents

Description

The present invention relates to a photosensitive colored resin composition and a cured product thereof, a color filter, and a display device.

In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays has been increasing. The penetration rate of mobile displays (mobile phones, smartphones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding more and more. Recently, organic light emitting display devices such as organic EL displays having high visibility due to self-luminous light have also attracted attention as next-generation image display devices. In terms of 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 displays and organic light emitting displays. For example, in the formation of a color image of a liquid crystal display device, the light that has passed through the color filter is colored as it is in the color of each pixel constituting the color filter, and the light of those colors is combined to form a color image. As the light source at that time, in addition to the conventional cold cathode fluorescent lamp, an organic light emitting element that emits white light or an inorganic light emitting element that emits white light may be used. Further, in the organic light emitting display device, a color filter is used for color adjustment and the like.
Under such circumstances, there is an increasing demand for color filters as well, such as higher brightness, higher contrast, and improved color reproducibility.

Here, the color filter is generally formed on a substrate, a colored layer formed on the substrate and composed of colored patterns of the three primary colors of red, green, and blue, and formed on the substrate so as to partition each colored pattern. It has a light-shielding part.
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 color material dispersion liquid in which a color material is dispersed with a dispersant or the like. After coating on a glass substrate and drying, it is exposed with a photomask and developed to form a colored pattern, and heated to fix the pattern to form a colored layer. These steps are repeated for each color to form a color filter.

As for color filters, the demand for higher brightness, higher contrast, and improved color reproducibility is increasing, and the density of colorants in the colored layer of the color filter is higher than before, resulting in relatively photopolymerization. The number of components required for this is decreasing, making patterning difficult. Further, in order to improve the productivity of the color filter, the integrated exposure amount required for patterning is reduced, and how to secure the curability required for patterning has become a big issue.

As a method for obtaining a colored resin composition capable of achieving high sensitivity, it has been proposed to use an oxime ester compound having one oxime ester group in the molecule as a photopolymerization initiator (for example, Patent Document 1).
Further, Patent Document 2 proposes to use an oxime ester compound having two oxime ester groups in the molecule as a photopolymerization initiator as a photosensitive resin composition capable of achieving high sensitivity.

Japanese Patent No. 3992725 Chinese Patent Application Publication No. 1046194940

Even if an oxime ester compound, which has been conventionally considered to be able to achieve high sensitivity, is used, for example, when the colorant concentration is high or the integrated exposure amount is small, the curability becomes insufficient and the residual film ratio becomes high. There was the problem that it tended to be inadequate. On the other hand, the oxime ester compound having two oxime ester groups in the molecule has low solvent solubility, and the oxime ester compound may be precipitated as a foreign substance in the colored layer.

The present invention has been made in view of the above circumstances, and provides a photosensitive colored resin composition having excellent curability, a high residual film ratio, and capable of forming a colored layer in which foreign substances are less likely to precipitate. With the goal. Another object of the present invention is to provide a cured product of the photosensitive colored resin composition and a color filter having a colored layer which is the cured product. Another object of the present invention is to provide a display device using the color filter.

The photosensitive coloring resin composition according to the present invention contains a coloring material, 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) and an acylphosphine oxide-based photoinitiator.
The coloring material includes a coloring material represented by the general formula (i) described later .

（一般式（１）において、Ｒ^ａは炭素数２以上４以下のアルキル基であり、Ｒ^ｂ及びＲ^ｃはそれぞれ独立に、水素原子又はニトロ基であり、Ｒ^ｄは炭素数５以上１０以下の直鎖状アルキル基であり、Ｒ^ｅは炭素数５以上１０以下の直鎖状アルキル基、シクロペンチルメチル基、シクロペンチルエチル基、シクロヘキシルメチル基及びシクロヘキシルエチル基からなる群から選ばれる１種である。）

(In the general formula (1), ^Ra is an alkyl group having 2 or more and 4 or less carbon atoms , R ^b and R ^c are independently hydrogen atoms or nitro groups, and R ^d is 5 or more and 10 or less carbon atoms. a linear alkyl group, R ^e is one selected from the group consisting of 5 or more 10 or less linear alkyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclohexylmethyl group and a cyclohexylethyl group having a carbon .)

The cured product according to the present invention is a cured product of the photosensitive colored resin composition according to the present invention.

The color filter according to the present invention is a color filter including at least a substrate and a colored layer provided on the substrate, and at least one of the colored layers is a cured product according to the present invention.
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 provide a photosensitive colored resin composition having excellent curability, a high residual film ratio, and capable of forming a colored layer in which foreign substances are less likely to precipitate. Further, according to the present invention, it is possible to provide a cured product of the photosensitive colored resin composition and a color filter having a colored layer which is the cured product. Further, according to the present invention, it is possible to provide a display device using the color filter.

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

Hereinafter, the photosensitive colored resin composition, the cured product, 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 radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.
In the present invention, (meth) acrylic represents each of acrylic and methacrylic, and (meth) acrylate represents each of acrylate and methacrylate.

I. Photosensitive Colored Resin Composition The photosensitive colored resin composition according to the present invention contains a coloring material, 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).

一般式（１）
（一般式（１）において、Ｒ^ａは炭素数１以上６以下の炭化水素基であり、Ｒ^ｂ及びＲ^ｃはそれぞれ独立に、水素原子又はニトロ基であり、Ｒ^ｄは炭素数５以上の直鎖状アルキル基であり、Ｒ^ｅは炭化水素基である。）

General formula (1)
(In the general formula (1), ^Ra is a hydrocarbon group having 1 or more carbon atoms and 6 or less carbon atoms, R ^b and R ^c are independently hydrogen atoms or nitro groups, and R ^d has 5 or more carbon atoms. It is a linear alkyl group, and ^Re is a hydrocarbon group.)

The photosensitive colored resin composition according to the present invention has excellent curability, a high residual film ratio, and a foreign substance by using the oxime ester compound represented by the general formula (1) as the photoinitiator. It is a photosensitive colored resin composition capable of forming a colored layer in which is difficult to precipitate. With the colored resin composition of the prior art, when the colorant density is high or the integrated exposure amount is small, the curability is excellent and it is difficult to increase the residual film ratio. However, the photosensitivity according to the present invention. The sex-colored resin composition is a photosensitive coloring resin composition that has excellent curability and can increase the residual film ratio even in such a case. Further, the conventional oxime ester compound having two oxime ester groups in the molecule has low solvent solubility, and the oxime ester compound precipitates when the concentration of the coloring material in the colored resin composition is increased. In some cases, foreign matter may be deposited on the colored layer. On the other hand, since the oxime ester compound represented by the general formula (1) has excellent solvent solubility, the oxime ester compound is precipitated in the colored layer even when the concentration of the coloring material in the colored resin composition is increased. It is suppressed and foreign matter is less likely to precipitate on the colored layer. Further, by using the oxime ester compound represented by the general formula (1), a high-luminance colored layer can be formed.
Further, the photosensitive colored resin composition according to the present invention has an advantage that the generation of development residue is suppressed, and it is easy to form desired micropores in the colored layer at the same time when patterning the colored layer. ..

By using the compound represented by the general formula (1) as the photoinitiator, the action of exerting the above-mentioned effects is unclear, but is presumed as follows.
First, since the compound represented by the general formula (1) used in the present invention has two oxime ester groups with respect to one carbazole ring which is an absorbent part, the amount of the photoinitiator added is increased. Can efficiently generate radicals. Therefore, it is presumed that excellent curability can be obtained and the residual film ratio can be improved even if the concentration of the coloring material in the colored resin composition is increased or the integrated exposure amount is small.
Further, the compound represented by the general formula (1) used in the present invention tends to have a structure having high crystallinity because the carbazole ring is rigid, and thus a ^{linear alkyl having R d} having 5 or more carbon atoms. Since it is a group and ^Re is a hydrocarbon group, it is considered that the crystallinity is lowered and the solvent solubility and compatibility are high.
Further, the compound represented by the general formula (1) used in the present invention has a dioxime structure and high sensitivity, so that excellent curability can be obtained and the heat resistance of the coating film is improved. By suppressing fading due to heating in a manufacturing process such as baking, a high-brightness colored layer can be formed.
Further, the photosensitive colored resin composition of the present invention tends to form desired fine pores in the colored layer at the same time when the colored layer is patterned. When a more sensitive photoinitiator is used to form a colored layer, the radicals move to the unexposed area after the radicals are generated, and the shape of the unexposed area inside the exposed area is maintained and not yet exposed. It is difficult to form the peripheral portion of the exposed portion without chattering. Therefore, in the conventional photosensitive resin composition, when a high-sensitivity 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 described later, when a photoinitiator having a relatively low sensitivity is used, there is a problem that the residual film ratio is lowered even if micropores can be formed. On the other hand, in the photosensitive colored resin composition of the present invention, by using the oxime ester compound represented by the general formula (1), it is easy to form micropores without lowering the residual film ratio. In particular, by adjusting the content of the photoinitiator and the content of the antioxidant used in combination, it is possible to more easily form micropores having a good shape. Since the photosensitive colored resin composition of the present invention easily forms desired fine pores in the colored layer, for example, in order to form a reflective color filter, a colored layer is formed on a TFT substrate, and at the same time, the coloring is performed. It is also suitable for applications where through holes for conduction are formed in the layer.
Further, since the oxime ester compound represented by the general formula (1) used in the present invention has decreased crystallinity, solvent solubility and solvent resolubility are improved, and compatibility with other components is good. As a result, the linearity of the fine line pattern is improved, and the chattering of micropores is easily suppressed.

The photosensitive coloring resin composition according to the present invention contains a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, as long as the effects of the present invention are not impaired. , Further other components may be contained.
Hereinafter, each component of such a colored resin composition of the present invention will be described in detail in order from the photoinitiator characteristic of the present invention.

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

In the general formula (1), ^Ra is a hydrocarbon group having 1 or more and 6 or less carbon atoms, and may be either a saturated or unsaturated aliphatic hydrocarbon group or an aromatic hydrocarbon group. ^{Above all, Ra} is preferably an alkyl group from the viewpoint of solvent solubility and compatibility with other components. The alkyl group may be 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. Examples thereof include a group, a cyclopentylmethyl group, a cyclohexyl group, and the like. Among them, an alkyl group having 2 or more and 6 or less carbon atoms is preferable, an alkyl group having 2 or more and 4 or less carbon atoms is more preferable, and carbon is more preferable. It is a linear alkyl group having a number of 2 or more and 4 or less.

In the general formula (1), R ^b and R ^c are independently hydrogen atoms or nitro groups, respectively, and at least of ^{R b} and R ^{c in terms of solvent solubility and compatibility with other components.} preferably one of a hydrogen atom, in terms of sensitivity and brightness, it is preferable that at least one of R ^b and R ^c is a nitro group, that both R ^b and R ^c is a nitro group More preferred.

In the general formula (1), R ^d is a linear alkyl group having 5 or more carbon atoms, and the linear alkyl group has 6 carbon atoms from the viewpoint of solvent solubility and compatibility with other components. The above is preferable. The carbon number of the linear alkyl group is not particularly limited, but is preferably 16 or less, and more preferably 10 or less, from the viewpoint of compatibility and coating film curability.

In the general formula (1), ^Re is a hydrocarbon group, and examples thereof include an alkyl group, an alkenyl group, an aryl group, and an aralkyl group. The alkyl group may be linear, branched, cyclic, or a combination thereof, or may be a combination of linear and cyclic. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, an n-decyl group and an n-dodecyl group. 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 and the like. can. The alkenyl group may be linear, branched, cyclic, or a combination thereof, 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 xsilyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group. Among them, ^Re is a hydrocarbon having 3 to 14 carbon atoms from the viewpoint of solvent solubility and compatibility with other components and the improvement of the shape of the micropores when forming micropores in the colored layer. It is preferably a group, more preferably an alkyl group having 3 or more and 14 or less carbon atoms, an aralkyl group having 7 or more and 14 or less carbon atoms, or an aryl group having 6 or more and 10 or less carbon atoms, among which 14 or more carbon atoms. The following alkyl groups are preferable, alkyl groups having 4 or more and 12 or less carbon atoms are more preferable, alkyl groups having 5 or more and 10 or less carbon atoms are more preferable, and linear alkyl groups having 5 or more and 10 or less carbon atoms are even more preferable. .. Further, in the present invention, since R ^d is a number of 5 or more linear alkyl group having a carbon, the R ^e, cyclopentylmethyl group, cyclopentylethyl group, cyclohexylmethyl group, a cyclic partial structure such as a cyclohexyl ethyl group An alkyl group containing an alkyl group is preferable from the viewpoint of solvent solubility and compatibility with other components. Further, it is preferable that ^Re is a ^{hydrocarbon group different from R d} from the viewpoint of solvent solubility and compatibility with other components.

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 further 800 or less, from the viewpoint of reducing the content of the photoinitiator. Is preferable.

As the oxime ester compound represented by the general formula (1), for example, ^Ra is an alkyl group having 1 or more carbon atoms and 4 or less carbon atoms, and R ^b and R ^c are independently hydrogen atoms or nitro groups. R ^d is a linear alkyl group having 5 to 10 carbon atoms, the compound R ^e is a linear alkyl group having 1 to 10 carbon atoms; R ^a is 1 to 4 alkyl group having a carbon number R ^b and R ^c are independent hydrogen atoms or nitro groups, R ^d is a linear alkyl group having 5 or more and 10 or less carbon atoms, and ^Re is 4 or more carbon atoms including a cyclic partial structure. Compounds having an alkyl group of 10 or less; and the like are preferable, but the compounds are not limited thereto.

As the oxime ester compound represented by the general formula (1), specifically, at least one selected from the following compounds (1-1) to (1-3) is more preferable. Further, among them, the following compound (1-1) is preferable from the viewpoint of being able to form a highly sensitive and bright colored layer, and the following compound is preferable from the viewpoint of solvent solubility and compatibility with other components. (1-2) is preferable.

For the oxime ester compound represented by the general formula (1), refer to, for example, Chinese Patent Application Publication No. 1038819583, using carbazole or a derivative thereof, and depending on the material used, the solvent, reaction temperature, and reaction time. , Purification method and the like can be appropriately selected for synthesis.

<Other photoinitiators>
Examples of other photoinitiators include an oxime ester-based photoinitiator different from the oxime ester compound represented by the general formula (1), an α-aminoketone-based photoinitiator, a biimidazole-based photoinitiator, and a thioxanthone-based photoinitiator. Examples thereof include a photoinitiator, an acylphosphine oxide-based photoinitiator, and a mercapto-based chain transfer agent.
Above all, while improving the brightness, when forming the fine line pattern, the linearity is further improved, the ability to form the fine line pattern according to the design of the mask line width is improved, and the shape of the micropores is improved. From this point of view, the oxime ester compound represented by the general formula (1) includes an α-aminoketone-based photoinitiator, a biimidazole-based photoinitiator, a thioxanthone-based photoinitiator, an acylphosphine oxide-based photoinitiator, and an acylphosphine oxide-based photoinitiator. It is preferable to further use at least one selected from the mercapto-based chain transfer agents in combination. Above all, it is preferable to further use an acylphosphine oxide-based photoinitiator in combination, because when forming micropores, chattering at the ends of the pores is suppressed and it is easy to form micropores with good dimensional accuracy. .. Since the acylphosphine oxide-based photoinitiator has a higher thermal decomposition temperature than other initiators, it is considered that vaccination is suppressed because side reactions due to heating during prebaking are unlikely to occur.
"Improved linearity" means that the unevenness of the end portion of the colored layer formed in the developing step after applying the coloring composition is small, and the colored layer is formed linearly or substantially linearly. Further, "blinking" refers to a problem in which the straight line or curve at the end of the pattern becomes non-uniform and the dimensional accuracy deteriorates.

Further, from the viewpoint of improving the shape of the micropores and suppressing chattering, the oxime ester compound represented by the general formula (1) includes an α-aminoketone-based photoinitiator, a biimidazole-based photoinitiator, and a thioxanthone-based compound. It is more preferable to use at least one selected from a photoinitiator, an acylphosphine oxide-based photoinitiator, and a mercapto-based chain transfer agent in combination with an antioxidant described later.

Since the α-aminoketone-based photoinitiator has the property of curing the middle part from the surface of the coating film and easily suppresses the deep curability of the coating film, it is combined with the oxime ester compound represented by the general formula (1). It is preferable because it has a high tendency to improve the deep curability of the coating film.
Examples of the α-aminoketone-based photoinitiator include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (for example, Irgacure 907, manufactured by BASF) and 2-benzyl-2-. (Dimethylamino) -1- (4-morpholinophenyl) -1-butanone (for example, 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 can be mentioned.
The α-aminoketone-based photoinitiator may be used alone or in combination of two or more, among which 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one and 2-Benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone is preferable from the viewpoint of improving the residual film ratio, and 2-methyl-1- (4-methylthiophenyl) -2. -Mophorinopropan-1-one is more preferable from the viewpoint of suppressing the chattering of micropores.

The biimidazole-based photoinitiator has the property of curing the deep part of the coating film, easily suppresses the surface curability of the coating film, and cures the surface of the coating film when combined with the oxime ester compound represented by the general formula (1). It is preferable because it has a high tendency to improve the property.
Examples of the biimidazole-based 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 '-Bimidazole and the like can be mentioned.
The biimidazole-based photoinitiator may be used alone or in combination of two or more, and among them, it is preferable to use it in combination with a mercapto-based chain transfer agent from the viewpoint of improving the coating film curability.

Examples of the thioxanthone-based photoinitiator include 2,4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2,4-dichlorothioxanthone and the like.
As the thioxanthone-based photoinitiator, it may be used alone or in combination of two or more. Among them, 2,4-isopropylthioxanthone and 2,4-diethylthioxanthone are used from the viewpoint of improving the transfer of radical generation. preferable.

Acylphosphine oxide-based photoinitiators have the property of being less yellowing due to heat, and are 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 forming micropores, the flicker at the ends of the pores is suppressed and the dimensional accuracy is improved. It is preferable because it is easy to form good micropores.
Examples of the acylphosphine oxide-based 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 acylphosphine oxide-based photoinitiator may be used alone or in combination of two or more. Among them, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is used for coating film curability. Is preferable from the viewpoint of improving.

The mercapto-based chain transfer agent has the property of receiving radicals from slow-reacting radicals to accelerate the reaction, and is particularly preferable because it tends to improve the reaction rate when combined with a biimidazole-based photoinitiator.
Examples of the mercapto-based chain transfer agent include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzoimidazole, 3-. Mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, 1,4-bis (3-mercaptobutylyloxy) butane, 1,3,5-tris (3- Mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylpropanthris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobuty) Rate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate) and the like.
As the mercapto chain transfer agent, it may be used alone or in combination of two or more, and among them, it is preferable to use 2-mercaptobenzothiazole from the viewpoint of improving the reaction rate.

The total content of the photoinitiator used in the photosensitive colored resin composition of the present invention is not particularly limited as long as the effect of the present invention is not impaired, but is based on the total solid content of the photosensitive colored resin composition. It is preferably in the range of 0.1% by mass or more and 12.0% by mass or less, and more preferably 1.0% by mass or more and 8.0% by mass or less. When this content is at least the above lower limit value, photocuring is sufficiently promoted and the exposed portion is suppressed from being eluted during development, while when it is at least the above upper limit value, the yellowing of the obtained colored layer becomes strong and the brightness becomes high. Can be suppressed from decreasing.
The solid content is anything other than the solvent, and includes a liquid polyfunctional monomer and the like.

The content of the oxime ester compound represented by the general formula (1) used in the photosensitive coloring resin composition of the present invention is preferably 0.1% by mass with respect to the total solid content of the photosensitive coloring resin composition. % Or more and 8.0% by mass or less, more preferably 0.5% by mass or more and 6.0% by mass or less. When this content is at least the above lower limit value, photocuring is sufficiently promoted and the exposed portion is suppressed from being eluted during development, while when it is at least the above upper limit value, the yellowing of the obtained colored layer becomes strong and the brightness becomes high. Can be suppressed from decreasing.

Further, in the photosensitive colored resin composition of the present invention, when the photoinitiator further contains the other photoinitiator, the content of the oxime ester compound represented by the general formula (1) is in the present invention. Of the total 100 parts by mass of the photoinitiator used, it is preferably 30 parts by mass or more, and more preferably 40 parts by mass or more.
On the other hand, the content of the oxime ester compound represented by the general formula (1) is 100% by mass in total of the photoinitiator used in the present invention from the viewpoint of sufficiently exerting the effect of combined use with the other photoinitiator. The amount is preferably 95 parts by mass or less, and more preferably 85 parts by mass or less.

The photoinitiator used in the present invention is further selected from an α-aminoketone-based photoinitiator, a biimidazole-based photoinitiator, a thioxanthone-based photoinitiator, an acylphosphine oxide-based photoinitiator, and a mercapto-based chain transfer agent. When at least one of these is contained, the total content thereof is 0.1% by mass or more and 4.0% by mass or less, and further 0.5% by mass or more, based on the total solid content of the photosensitive colored resin composition. It is preferably in the range of 2.0% by mass or less from the viewpoint of sufficiently exerting the combined effect with these photoinitiators.

[Color material]
In the present invention, the coloring material is not particularly limited as long as it can develop a desired color when the colored layer of the color filter is formed, and various organic pigments, inorganic pigments, dispersible dyes, and dyes are used. Can be used alone or in combination of two or more. Among them, organic pigments are preferably used because they have high color development and high heat resistance. Examples of the organic pigment include compounds classified as Pigments in the color index (CI; published by The Society of Dyers and Colorists), specifically, the following color index (CI). .) Numbered ones can be mentioned.
In addition, when the color index name is described below, when listing only the color index names having different numbers, only the number 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, 206, 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, 7.

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

For example, when a pattern of a light-shielding layer is formed on a substrate of a color filter by using the photosensitive coloring resin composition 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 triiron tetroxide, or an organic pigment such as cyanine black can be used.

Examples of the dispersible dye include a dye that can be dispersed by adding various substituents to the dye and insolubilizing it in a solvent, a dye that can be dispersed by using it in combination with a solvent having low solubility, and a solvent. Examples thereof include a rake coloring material in which a soluble dye is salt-formed with counter ions to insolubilize (lake). By using such a dispersible dye in combination with a dispersant, the dispersibility and dispersion stability of the dye can be improved.
As a guide, if the amount of the dye dissolved in 10 g of the solvent (or the mixed solvent) is 100 mg or less, it can be determined that the dye can be dispersed in the solvent (or the 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; etc. can be mentioned.

When forming a blue colored layer, at least one of a triarylmethane dye, a xanthene dye, and a cyanine dye is preferable from the viewpoint of high brightness, and from the viewpoint of high heat resistance, among others, Tria At least one selected from the reel methane dye and the xanthene dye is preferable.
In the present invention, it is preferable to include a rake coloring material having a triarylmethane dye from the viewpoint of improving the brightness of the color filter, and among them, a triarylmethane basic dye and a polyacid anion may be contained. preferable.

In the present invention, the rake coloring material is excellent in heat resistance and light resistance, and from the viewpoint of achieving high brightness of the color filter, it is a molecule that the rake coloring material is represented by the following general formula (i). It is preferable because it forms an associative state and exhibits better heat resistance.

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

(In the 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 at least saturated aliphatic hydrocarbon at the terminal directly bonded to N. It represents an aliphatic hydrocarbon group having a hydrogen group or an aromatic group having the aliphatic hydrocarbon group, and O, S, and N may be contained in the carbon chain. B ^c− is a c-valent poly. .R ⁱ to R ^v which represents an acid anion each independently represent a hydrogen atom, which may have an optionally substituted alkyl group or a 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 to R ^v and Ar ¹ each It may be the same or different.
a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. A plurality of e may be the same or different. )

The color material represented by the general formula (i) can be prepared by referring to, for example, International Publication No. 2012/144520 Pamphlet.

When forming a green colored layer, C.I. I. A green color material in which a yellow color material is further combined with Pigment Green 59 (PG59) can be preferably used.

Among the yellow color materials used in combination with PG59, C.I. I. Pigment Yellow 150 derivative pigments are preferred. C. I. As the derivative pigment of Pigment Yellow 150, specifically, mono, di, tri and azo compounds according to the following general formula (ii) or one of the tautomeric structures thereof, which acts 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. A metal complex can be mentioned. Such C.I. I. It is preferable to use the derivative pigment of Pigment Yellow 150 from the viewpoint of improving the brightness.

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

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

Among them, the yellow color material is at least one anion selected from the group consisting of mono, di, tri and tetra anions of the azo compound represented by the general formula (ii) and the azo compound having a tautomeric structure thereof. And the inclusion of at least two metal ions selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn improves brightness and contrast. It is preferable from the viewpoint of improvement.
By containing two or more types of metal ions, the crystal growth of the coloring material is suppressed and atomization becomes possible. Furthermore, since it is used in combination with a dispersant described later, it is atomized in the coloring material dispersion liquid and the contrast is improved. It is presumed that an improved colored layer can be formed.

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

In the azo compound represented by the general formula (ii) and the azo compound having a tautomeric structure thereof, R ³¹ is independently -OH, -NH ₂ , -NH-CN, or alkylamino. This is preferable from the viewpoint of hue, and the two R ^31s may be the same or different from each other.
In the general formula (ii), there may two for ^{R 31,} a from among them hue point, if both are -OH, when both are -NH-CN, or, one one with -OH -NH- It is more preferably CN, and even more preferably both −OH.

Further, in the azo compound represented by the general formula (ii) and the azo compound having a tautomeric structure thereof, ^{it is more preferable that both of R 32} are −OH from the viewpoint of hue.

Among the at least two metals in the case of containing ions of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn. It preferably contains at least one metal that becomes a divalent or trivalent cation, preferably contains at least one selected from the group consisting of Ni, Cu, and Zn, and further contains at least Ni. Is preferable.
Further, it is preferable to contain Ni and at least one metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu and Mn, and further, Ni Further, it is preferable to include at least one metal selected from the group consisting of Zn, Cu, Al and Fe. Among them, the at least two kinds of metals are preferably Ni and Zn or Ni and Cu.

When it contains ions of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, the content ratio of at least two metals is appropriate. It may be prepared.
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: other at least the above. The type 1 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 them, Ni and Zn are preferably contained in a molar ratio of Ni: Zn of 90:10 to 10:90, and more preferably contained in a molar ratio of 80:20 to 20:80.
Alternatively, Ni and Cu are preferably contained in a molar ratio of Ni: Cu of 97: 3 to 10:90, and more preferably in a molar ratio of 96: 4 to 20:80.

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

C. I. In the derivative pigment of Pigment Yellow 150, as an embodiment containing ions of at least two kinds of metals, there are cases where ions of at least two kinds of metals are contained in a common crystal lattice and one kind each in another crystal lattice. There is a case where crystals containing the metal ions of the above are agglomerated. Above all, it is preferable that ions of at least two kinds of metals are contained in the common crystal lattice from the viewpoint of further improving the contrast. It should be noted that whether the common crystal lattice contains at least two types of metal ions or the crystal containing one type of metal ion in each of the different crystal lattices is aggregated. For example, it can be appropriately determined by using the X-ray diffraction method with reference to Japanese Patent Application Laid-Open No. 2014-12838.

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

The coloring 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 coloring material may be used after being miniaturized.

The total content of the coloring material is preferably 3% by mass to 65% by mass, more preferably 4% by mass to 60% by mass, based on the total solid content of the photosensitive coloring resin composition. When it is at least the above lower limit value, the colored layer when the photosensitive colored resin composition is applied to a predetermined film thickness (usually 1.0 μm to 5.0 μm) has a sufficient color density. Further, if it is not more than the above upper limit value, it is possible to obtain a colored layer having excellent storage stability, sufficient hardness, and adhesion to a substrate. In particular, when forming a coloring layer having a high concentration of coloring material, the total content of the coloring material is 15% by mass to 65% by mass, more preferably 25% by mass, based on the total solid content of the photosensitive coloring resin composition. It is preferable to mix in a ratio of% to 60% by mass.

[Alkali-soluble resin]
The alkali-soluble resin in the present invention has an acidic group, and can be appropriately selected and used 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 referred to as having an acid value of 40 mgKOH / g or more as a guide.
The preferable alkali-soluble resin in the present invention is a resin having an acidic group, usually a carboxy group, and specifically, an acrylic such as an acrylic copolymer having a carboxy group and a styrene-acrylic copolymer having a carboxy group. Examples thereof include based resins and epoxy (meth) acrylate resins having a carboxy group. Among these, 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 are particularly preferable. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. In addition, two or more kinds of acrylic resins such as these acrylic copolymers and styrene-acrylic copolymers, and epoxy acrylate resins may be mixed and used.

Acrylic resins such as an acrylic copolymer having a structural unit having a carboxy group and a styrene-acrylic copolymer having a carboxy group are, for example, a carboxy group-containing ethylenically unsaturated monomer and, 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. Be done. Further, 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 acid anhydride, ω-carboxy-polycaprolactone. Mono (meth) acrylate and the like can also be used. Further, as a precursor of the carboxy group, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride, or citraconic anhydride may be used. Of 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 has a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer. It was found that the solvent resistance of the obtained colored layer, particularly the swelling of the colored layer, is suppressed by having the hydrocarbon ring which is a bulky group in the alkali-soluble resin. Although the action is unclear, the inclusion of a bulky hydrocarbon ring in the colored layer suppresses the movement of molecules in the colored layer, resulting in higher strength of the coating film and suppression of swelling due to the solvent. It is presumed to be.
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 a combination thereof. May have a substituent such as a carbonyl group, a carboxy group, an oxycarbonyl group, or an amide group. Above all, when an aliphatic ring is contained, the heat resistance and adhesion of the colored layer are improved, and the brightness of the obtained colored layer is improved.
Specific examples of hydrocarbon rings 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, and fluorene; chain polycycles such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilben, and cardo structures represented by the following chemical formula (A). Be done.

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

（一般式（Ｂ）において、Ｒ^Ｍは、置換されていてもよい炭化水素環である。）

(In the general formula (B), ^RM is a 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 general formula (I) described later because it has a nitrogen atom in the hydrocarbon ring. The compatibility with the basic dispersant is very good, and the effect of suppressing the 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 the hydrocarbon ring contains an aliphatic ring, it is preferable because the heat resistance and adhesion of the colored layer are improved and the brightness of the obtained colored layer is improved.
Further, when the cardo structure represented by the chemical formula (A) is contained, the curability of the colored layer is improved and the solvent resistance (suppression of NMP swelling) is improved, which is particularly preferable.

In the alkali-soluble resin used in the present invention, it is easier to adjust the amount of each structural unit by using an acrylic copolymer having a structural unit having a hydrocarbon ring in addition to the structural unit having a carboxy group. It is preferable because it is easy to improve the function of the structural unit by increasing the amount of the structural unit having a hydrocarbon ring.
The acrylic copolymer having a structural unit having a carboxy group and the above-mentioned hydrocarbon ring is prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned "other copolymerizable monomer". be able to.
Examples of the ethylenically unsaturated monomer having a hydrocarbon ring to be 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, etc., and cyclohexyl (meth) because it has a great effect of maintaining the cross-sectional shape of the colored layer after development even in heat treatment. Meta) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable, and styrene is particularly preferable.
Further, from the viewpoint of the effect of suppressing the development residue, the monomer having a maleimide structure and styrene are preferable, and styrene is particularly preferable, as the ethylenically unsaturated monomer having a hydrocarbon ring.

The alkali-soluble resin used in the present invention also preferably has an ethylenic double bond in the side chain. When it has an ethylenic double bond, the alkali-soluble resins or the alkali-soluble resin and a photopolymerizable compound can form a cross-linking bond in the curing step of the resin composition at the time of producing a color filter. By combining with the oxime ester compound represented by the general formula (1) used in the present invention, the film strength of the cured film is further improved, the development resistance is improved, and the heat 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 in which a compound having both an epoxy group and an ethylenic double bond, for example, glycidyl (meth) acrylate, is added to the carboxy group of the alkali-soluble resin to introduce an ethylenic double bond into the side chain. Alternatively, a method in which a structural unit having a hydroxyl group is introduced into a copolymer, a compound having an isocyanate group and an ethylenic double bond is added to the molecule, and an ethylenic double bond is introduced into a side chain. And so on.

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

The amount of the carboxy group-containing ethylenically unsaturated monomer charged is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total amount of the monomers, 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 charged is preferably 50% by mass or less, preferably 40% by mass or less, based on the total amount of the monomers. More preferably.
When the ratio of the carboxy group-containing ethylenically unsaturated monomer is at least the above lower limit value, the coating film obtained has sufficient solubility in an alkaline developer, and the ratio of the carboxy group-containing ethylenically unsaturated monomer is the above upper limit value. If it is as follows, there is a tendency that the formed pattern is less likely to fall off from the substrate or the surface of the pattern is roughened during development with an alkaline developer.

Further, in an acrylic resin such as an acrylic copolymer having a structural unit having an ethylenic double bond and a styrene-acrylic copolymer, which are more preferably used as an alkali-soluble resin, an epoxy group and an ethylenic double are used. The amount of the compound having a bond is preferably 10% by mass to 95% by mass, more preferably 15% by mass to 90% by mass, based on the amount of the carboxy group-containing ethylenically unsaturated monomer charged.

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 significantly deteriorated, and if it exceeds 50,000, it may be difficult to form a pattern during development with an alkaline developer.
The weight average molecular weight (Mw) of the carboxy group-containing copolymer can be measured by a Shodex GPC system-21H (Shodex GPC System-21H) using polystyrene as a standard substance and THF as an eluent.

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

It is preferable to select and use an alkali-soluble resin having an acid value of 50 mgKOH / g or more from the viewpoint of developability (solubility) in an alkaline aqueous solution used for a developing solution. 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 alkaline aqueous solution used for a developing solution and adhesion to a substrate. It is preferably 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: 1992.

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

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

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

The alkali-soluble resin used in the photosensitive coloring resin composition may be used alone or in combination of two or more, and the content thereof is not particularly limited, but the photosensitive coloring resin is used. The alkali-soluble resin is preferably in the range of 5% by mass to 60% by mass, more preferably 10% by mass to 40% by mass, based on the total solid content of the composition. When the content of the alkali-soluble resin is at least the above lower limit value, sufficient acari developability can be obtained, and when the content of the alkali-soluble resin is at least the above upper limit value, film roughness and pattern chipping occur during development. Can be suppressed.

[Photopolymerizable compound]
The photopolymerizable compound used in the photosensitive colored resin composition may be any compound as long as it can be polymerized by the photoinitiator, and is not particularly limited, and usually, a compound having two or more ethylenically unsaturated double bonds is used. It is preferably used, and in particular, a polyfunctional (meth) acrylate having two or more acryloyl groups or methacryloyl groups is preferable.
As such a polyfunctional (meth) acrylate, it may be appropriately selected and used from conventionally known ones. Specific examples include those described in Japanese Patent Application Laid-Open No. 2013-029832.

One of these polyfunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination. When the photosensitive colored resin composition of the present invention is required to have excellent photocurability (high sensitivity), the polyfunctional (meth) acrylate has three polymerizable double bonds (trifunctional). Those having the above are preferable, and poly (meth) acrylates of trivalent or higher polyhydric alcohols and their dicarboxylic acid-modified products are preferable. (Meta) acrylate, succinic acid modified product of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate ) A succinic acid-modified product of acrylate, dipentaerythritol hexa (meth) acrylate and the like are preferable.

The content of the photopolymerizable compound used in the photosensitive coloring resin composition is not particularly limited, but the photopolymerizable compound is preferably 5% by mass to 60% by mass based on the total solid content of the photosensitive coloring resin composition. It is in the range of% by mass, more preferably 10% by mass to 40% by mass. When the content of the photopolymerizable compound is at least the above lower limit, photocuring proceeds sufficiently, the exposed portion can suppress elution during development, and the content of the photopolymerizable compound is at least the above upper limit. Sufficient alkali developability.
The content of the photopolymerizable compound used in the photosensitive colored resin composition and the content ratio of the photoinitiator are excellent in terms of curability and residual film ratio, and further, in terms of improving electrical reliability. 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. Is preferable, and more preferably 30 parts by mass 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 and can dissolve or disperse them. The solvent can be used alone or in combination of two or more.
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; and carbitol solvents such as methoxy ethoxy ethanol and ethoxyethoxy ethanol; 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; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1 -Glycol ether acetate solvents such as butyl acetate, 3-methoxybutyl acetate and ethoxyethyl acetate; carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate and butyl carbitol acetate (BCA); propylene glycol diacetate , 1,3-butylene glycol diacetate and other diacetates; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, dipropylene glycol Glycol ether solvents such as dimethyl ether; aproton amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; 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; Organic solvents such as aromatic hydrocarbons such as toluene and xylene Can be mentioned. Among these solvents, glycol ether acetate-based solvent, carbitol acetate-based solvent, glycol ether-based solvent, and ester-based solvent are preferably used in terms of solubility of other components. Among them, as the solvent used in the present invention, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, etc. In addition, one or more selected from the group consisting of 3-methoxybutyl acetate is preferable from the viewpoint of solubility of other components and application suitability.

In the photosensitive colored resin composition 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. It is usually preferably in the range of 55% by mass to 95% by mass, and above all, in the range of 65% by mass to 88% by mass with respect to the total amount of the photosensitive colored resin composition containing the solvent. More preferred. When the content of the solvent is within the above range, the coatability can be made excellent.

[Dispersant]
In the photosensitive coloring resin composition of the present invention, it is preferable that the coloring material is used by being dispersed in a solvent with a dispersant. In the present invention, the dispersant can be appropriately selected and used from conventionally known dispersants. As the dispersant, for example, cationic, anionic, nonionic, amphoteric, silicone-based, and fluorine-based surfactants can be used. Among the surfactants, the 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 acids 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 polyacrylic acid esters and their modifications; polyurethanes; unsaturated polyamides; polysiloxane Classes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (amides obtained by the reaction of poly (lower alkyleneimine) with free carboxy group-containing polyesters and their bases); polyallylamine derivatives (polyallylamine and free carboxy) (Reaction product obtained by reacting one or more compounds selected from three kinds of compounds of polyester, polyamide or ester and amide cocondensate (polyester amide) having a group) and the like can be mentioned.

As the polymer dispersant, 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 coloring material can be preferably dispersed and the dispersion stability is good. Above all, a polymer dispersant made of a polymer containing a repeating unit having a tertiary amine is preferable because it has good dispersibility, does not precipitate foreign substances during coating film formation, and improves brightness and contrast.
The repeating unit having a tertiary amine is a site having an affinity for the coloring material. A polymer dispersant consisting of a polymer containing a repeating unit having a tertiary amine usually contains a repeating unit that serves as 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 portion composed of a repeating unit having a tertiary amine and a block portion having a solvent affinity is particularly heat resistant. It is preferable in that it is possible to form a coating film having excellent and high brightness.

The repeating unit having a tertiary amine may have a tertiary amine, and the tertiary amine may be contained in the side chain of the block polymer or may form a main chain.
Above all, it is preferable that it is a repeating unit having a tertiary amine in the side chain, and above all, it has a structure represented by the following general formula (I) because the main chain skeleton is hard to be thermally decomposed and has high heat resistance. However, it is more preferable.

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

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, Q is a divalent linking group, R ² is an alkylene group having 1 to 8 carbon atoms, and-[CH (R ⁵ ) -CH ( R ⁶ ) -O] _x- CH (R ⁵ ) -CH (R ⁶ )-or-[(CH ₂ ) _y- O] _z- (CH ₂ ) _y- divalent organic group, R ³ and R ⁴ each independently represent an optionally substituted linear or cyclic hydrocarbon group, .R ⁵ and R ⁶ R ³ and R ⁴ form a ring structure by bonding with each other is, Each is independently a hydrogen atom or a methyl group.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

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

The divalent organic group R ² of 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.
R ⁵ and R ⁶ are independently hydrogen atoms or methyl groups, respectively.
The R ² is preferably an alkylene group having 1 to 8 carbon atoms from the viewpoint of dispersibility, and more preferably R ² is a methylene group, an ethylene group, a propylene group or a butylene group, and the methylene group and ethylene. Groups are more preferred.

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

Examples of the repeating unit represented by the general formula (I) include alkyl group-substituted aminos such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and diethylaminopropyl (meth) acrylate. Examples thereof include group-containing (meth) acrylates, alkyl group-substituted amino group-containing (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide. 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 portion composed of the repeating unit having the tertiary amine, it is preferable that three or more structural units represented by the general formula (I) are contained. Among them, from the viewpoint of improving dispersibility and dispersion stability, it is preferable to contain 3 to 100 pieces, more preferably 3 to 50 pieces, and further preferably 3 to 30 pieces.

Both a block portion composed of a repeating unit having a tertiary amine (hereinafter, may be referred to as A block) and a block portion having a solvent affinity (hereinafter, may be referred to as B block). The block portion having solvent affinity in the polymer does not have the structural unit represented by the general formula (I) from the viewpoint of improving solvent affinity and improving dispersibility, and the general formula ( It has a solvent-affinity block portion having a structural unit copolymerizable with I).
The B block may be the same as the B block of International Publication No. 2016/104493.

The number of the structural units constituting the solvent-affinity block portion may be appropriately adjusted within the range in which the color material dispersibility is improved. Among them, the number of structural units constituting the solvent-affinity block portion is 10 to 200 from the viewpoint that the solvent-affinity portion and the color material-affinity portion act effectively to improve the dispersibility of the color material. It is preferably 10 to 100, more preferably 10 to 70, and even more preferably 10 to 70.

The solvent-affinity block portion may be selected so as to function as a solvent-affinity site, and the repeating unit constituting the solvent-affinity block portion may consist of one type or two or more types. May include repeating units of.

Further, among them, in the present invention, the dispersant is a polymer containing the structure represented by the general formula (I) and having an amine value of 40 mgKOH / g or more and 120 mgKOH / g or less, which has good dispersibility at the time of forming a coating film. It is preferable because it does not deposit foreign matter and improves brightness and contrast.
When the amine value is within the above range, the viscosity is excellent in stability over time and heat resistance, and also 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 resolubility are improved, the compatibility with other components is improved, and the fine line pattern of the colored layer is improved. The linearity of the solvent is improved, and the chattering of micropores is easily suppressed. In the present invention, the amine value of the dispersant is preferably 80 mgKOH / g or more, and 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, and more preferably 105 mgKOH / g or less.
The amine value refers to the number of mg of perchloric acid and equivalent potassium hydroxide required to neutralize the amine component contained in 1 g of the sample, and can be measured by the method defined in JIS-K7237: 1995. .. When measured by this method, even if the amino group is salt-formed with the organic acid compound in the dispersant, the organic acid compound usually dissociates, so that the block copolymer itself used as the dispersant 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 suppressing the development residue. Above all, the acid value of the dispersant is more preferably 2 mgKOH / g or more because the effect of suppressing the development residue is more excellent. On the other hand, the acid value of the dispersant is preferably 0 mgKOH / g from the viewpoint of dispersibility and dispersion stability. Further, the acid value of the dispersant used in the present invention can prevent deterioration of development adhesion and solvent resolubility, improve the linearity of the fine line pattern of the colored layer, and suppress the chattering of micropores. The upper limit of the acid value of the dispersant is preferably 18 mgKOH / g or less from the viewpoint of facilitation. Above all, the acid value of the dispersant is more preferably 12 mgKOH / g or less, and even more preferably 8 mgKOH / g or less, from the viewpoint of improving development adhesion and solvent resolubility.
In the dispersant used in the present invention, the acid value of the block copolymer before salt formation is preferably 1 mgKOH / g or more, and more preferably 2 mgKOH / g or more. This is because the effect of suppressing the development residue is improved. On the other hand, the acid value of the block copolymer before salt formation is preferably 0 mgKOH / g from the viewpoint of dispersibility and dispersion stability. The upper limit of the acid value of the block copolymer before salt formation is preferably 18 mgKOH / g or less, more preferably 12 mgKOH / g or less, and even more preferably 8 mgKOH / g or less. .. This is because the development adhesion and the solvent resolubility are improved.

When the concentration of the coloring material is increased and the content of the dispersant is increased, the amount of the binder is relatively reduced, so that the colored resin layer is easily peeled off from the underlying 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, 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 is likely to occur during development.

As the carboxy group-containing monomer, a monomer copolymerizable with a monomer having a structural unit represented by the general formula (I) and containing an unsaturated double bond and a carboxy group can be used. Examples of such a monomer include those similar to the carboxy group-containing ethylenically unsaturated monomer used in the synthesis of the above-mentioned acrylic copolymer having a carboxy group.

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 above-mentioned specific acid value range, and in particular. Although not limited, it is preferably 0.05% by mass to 4.5% by mass, and 0.07% by mass to 3.7% by mass, based on the total mass of all the constituent units of the block copolymer. Is more preferable.
When the content ratio of the structural unit derived from the carboxy group-containing monomer is at least the above lower limit value, the effect of suppressing the development residue is exhibited, and when it is at least the above upper limit value, the development adhesion is deteriorated and the solvent resolubility is deteriorated. Deterioration can be prevented.
The structural unit derived from the carboxy group-containing monomer may have the above-mentioned specific acid value, may consist of one type, or may contain two or more types of structural units.

In the block copolymer, the ratio m / n of the number of units m of the constituent units of the A block and the number of units n of the constituent units of the B block shall be within the range of 0.05 to 1.5. Is preferable, and the range is more preferably in the range of 0.1 to 1.0 from the viewpoint of dispersibility and dispersion stability of the coloring material.

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

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

When the coloring material is dispersed by using the polymer containing the repeating unit having the tertiary amine as a dispersant, the polymer containing the 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 within the above range, the dispersibility and dispersion stability are excellent, and the effect of improving the contrast is enhanced.

In the present invention, from the viewpoint of dispersibility and dispersion stability of the coloring material, at least a part of the amino groups in the polymer containing the repeating unit having the tertiary amine, an organic acid compound and a halogenated hydrocarbon are used. It is also preferable to use a polymer in which a salt is formed as a dispersant (hereinafter, such a polymer may be referred to as a salt-type polymer).
Among them, the dispersibility of the coloring material is that the polymer containing the 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. It is preferable from the viewpoint of excellent dispersion stability. Specific examples of the organic acid compound used in such a dispersant include the organic acid compounds described in JP-A-2012-236882.
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 when the dispersant is used is not particularly limited as long as the coloring material can be uniformly dispersed, but for example, it is 1 with respect to the total solid content of the photosensitive coloring resin composition. It can be used in an amount of% to 40% by mass. Further, it is preferably blended in an amount of 2% by mass to 30% by mass, particularly preferably in a proportion of 3% by mass to 25% by mass, based on the total solid content of the photosensitive colored resin composition. When it is at least the above lower limit value, the dispersibility and dispersion stability of the coloring material are excellent, and the storage stability of the photosensitive colored resin composition is excellent. Further, when it is not more than the above upper limit value, the developability is good. 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 3% by mass, based on the total solid content of the photosensitive coloring resin composition. It is preferable to blend in a proportion of ~ 20% by mass.

[Antioxidant]
The photosensitive colored resin composition according to the present invention may further contain an antioxidant. The photosensitive colored resin composition according to the present invention can improve heat resistance by containing an antioxidant in combination with the oxime ester compound represented by the general formula (1), and can be used as a cured film. Since the excessive radical chain reaction in the micropores can be controlled without impairing the curability when forming the micropores, the 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 the antioxidant include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like, and have heat resistance. It is preferable to use a hindered phenolic antioxidant from the viewpoint of improving the shape of the dots and the micropores.

A hindered phenolic antioxidant contains at least one phenolic structure and
It means an antioxidant having a structure in which a substituent having 4 or more carbon atoms is substituted at at least one of the 2-position and the 6-position of the hydroxyl group of the phenol structure.
Specific examples of the hindered phenol-based antioxidant include dibutylhydroxytoluene (BHT) and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Ilganox 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) mecitylene (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, manufactured by 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: Irga) Knox MD1024, manufactured by BASF), octyl 3- (4-hydroxy-3,5-diisopropylphenyl) propionate (trade name: Irganox 1135, manufactured by BASF), 4,6-bis (octylthiomethyl) -o-cresol (Product name: Irganox 1520L, manufactured by BASF), N, N'-hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanamide] (trade name: Irganox 1098, BASF), 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 259, manufactured by BASF), 1-dimethyl-2- [(3-T-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5.5] undecane (trade name: ADK STAB AO-80, Adeca) , Bis (3-tert-butyl-4-hydroxy-5-methylbenzenepropionic acid) Ethylenebis (oxyethylene) (trade name: Irganox 245, manufactured by BASF), 1,3,5-Tris [[4] -(1,1-Dimethylethyl) -3-hydroxy-2,6-dimethylphenyl] methyl] -1,3,5-triazi 2,4,6 (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- Diethyl 4-hydroxybenzylphosphonate (trade name: Irgamod 195, manufactured by BASF), 2-tert-butyl-4-methyl-6-acrylate (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl ( Product name: Sumilyzer GM, manufactured by Sumitomo Chemical Co., Ltd., 4,4'-thiobis (6-tert-butyl-m-cresol) (Product name: Sumilyzer WX-R, manufactured by Sumitomo Chemical Co., Ltd.), 6,6'-di-tert -Butyl-4,4'-butylideneji-m-cresol (trade name: Adecastab AO-40, manufactured by ADEKA) and the like can be mentioned. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

Further, 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 desorbed by heating, and exhibits an antioxidant function when the protecting group is desorbed. Of these, those in which the protecting group is easily removed by heating at 150 ° C. or higher are preferable.
Specific examples of the latent antioxidants preferably used in the present invention include, but are not limited to, the following chemical formulas (a) to (c).

The method for producing the latent antioxidant is not particularly limited. Obtained by reacting a phenolic compound produced by the methods described in each of the publications of 2004-501128 with an acid anhydride, a acid compound, a Bocation reagent, an alkyl halide compound, a silyl chloride compound, an allyl ether compound, or the like. Can be done. Moreover, you may use a commercially available product.

[Arbitrary additive component]
The photosensitive colored resin composition may contain various additives, if necessary. Examples of the additive include a polymerization inhibitor, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, a defoaming agent, a silane coupling agent, an ultraviolet absorber, an adhesion accelerator and the like.
Specific examples of the surfactant and the plasticizer include those described in JP2013-029832A.

The ratio of the mass (P) of the coloring material used in the present invention to the mass (V) of the solid content other than the coloring material (hereinafter, may be referred to as “P / V ratio”) is the colored layer of the color filter. However, the desired color development 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, it is possible to obtain a photosensitive colored resin composition capable of forming a colored layer capable of developing a desired color, and further, uniformly in the above photosensitive colored resin composition. Can be dispersed.

In the case of a red colored resin composition, the P / V ratio is preferably 0.50 or more, more preferably 0.60 or more, and even more 0.74 or more, from the viewpoint of desired color development. Is preferable. Further, it is preferably 1.0 or less.
In the case of a green colored resin composition, the P / V ratio is preferably 0.46 or more, more preferably 0.56 or more, still more preferably 0.68 or more, from the viewpoint of desired color development. Is preferable. Further, it is preferably 1.0 or less.
In the case of a blue colored resin composition, the P / V ratio is preferably 0.24 or more, more preferably 0.34 or more, still more preferably 0.41 or more, from the viewpoint of desired color development. Is preferable. Further, it is preferably 1.0 or less. When each is equal to or more than the above lower limit, the color density of the photosensitive coloring resin composition can be increased, and the color filter pixels can be made to have higher color rendering and lower film thickness. Further, if each is not more than the upper limit value, it is possible to obtain a colored layer having excellent storage stability, sufficient hardness, and adhesion to the substrate.

<Manufacturing method of photosensitive colored resin composition>
The method for producing the photosensitive colored resin composition of the present invention comprises a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, preferably a dispersant, an antioxidant, and optionally. A method that contains various additive components to be used and the coloring material can be uniformly dispersed in the solvent by a dispersant is preferable from the viewpoint of improving contrast, and is prepared by mixing using a known mixing means. can do.

As a method for preparing the color material dispersion liquid, a conventionally known dispersion method can be appropriately selected and used.
As a disperser for performing the dispersion treatment when preparing the color material dispersion liquid, roll mills such as two rolls and three rolls, ball mills, ball mills such as vibration ball mills, paint conditioners, continuous disc type bead mills, and continuous annular type A bead mill such as a bead mill can be mentioned. As a preferable dispersion condition of the bead mill, the bead diameter used is preferably 0.03 mm to 2.00 mm, more preferably 0.10 mm to 1.0 mm.

The photosensitive colored resin composition of the present invention is suitably used for color filter applications because it has excellent curability, has a high residual film ratio, and can form a colored layer in which foreign substances are less likely to precipitate.

II. Cured product The cured product according to the present invention is a cured product of the photosensitive colored resin composition according to the present invention.
The cured product according to the present invention can be obtained, for example, by forming a coating film of the photosensitive colored resin composition according to the present invention, drying the coating film, and then exposing the coating film. As a method for forming and exposing the coating film, for example, the same method as the method used for forming the colored layer provided in the color filter according to the present invention described later can be used.
Further, the cured product according to the present invention is suitably used as a colored layer of a color filter.

III. Color filter The color filter according to the present invention is a color filter including at least a substrate and a colored layer provided on the substrate, and at least one of the colored layers is the cured product according to the present invention.

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

(Colored layer)
At least one of the colored layers used in the color filter of the present invention is the cured product according to the present invention, that is, the cured product of the photosensitive colored resin composition according to the present invention.
The colored layer is usually formed in the opening of a light-shielding portion on a substrate, which will be described later, and is usually composed of a colored pattern of three or more colors.
The arrangement of the colored layers is not particularly limited, and may be, for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a 4-pixel arrangement type. Further, the width, area and the like of the colored layer can be arbitrarily set.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration and the viscosity of the photosensitive colored resin composition, etc., but is usually preferably in the range of 1 μm to 5 μm.

The colored layer can be formed, for example, by the following method.
First, the above-mentioned photosensitive colored resin composition of the present invention is applied onto a substrate described later by using a coating means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, and a die coating method. Then, a wet coating film is formed. Among them, the die coat method can be preferably used.
Next, the wet coating film is dried using a hot plate, an oven, or the like, and then exposed to the wet coating film through a mask having a predetermined pattern, and an alkali-soluble resin, a photopolymerizable compound, or the like is photopolymerized. Use as a cured coating. 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.
In addition, heat treatment may be performed in order to accelerate the polymerization reaction after exposure.

Next, a coating film is formed in a desired pattern by developing with a developing solution to dissolve and remove the unexposed portion. As the developing solution, a solution in which an alkali is usually dissolved in water or a water-soluble solvent is used. Moreover, a general method can be adopted as a developing method.
After the development treatment, the developer is usually washed and the cured coating film of the photosensitive coloring resin composition is dried to form a colored layer. After the development treatment, a heat treatment may be performed to sufficiently cure the coating film. The heating conditions are not particularly limited and are appropriately selected depending on the intended use of the coating film.

Further, when the color filter according to the present invention has a color filter-on-array structure or the like, micropores may be formed in the colored layer during the development process. In the present invention, since the above-mentioned photosensitive colored resin composition is used, desired micropores can be easily formed in the colored layer. The shape of the micropores is appropriately selected depending on the intended use and is not particularly limited, but in the present invention, for example, micropores having a size of about 10 μm × 10 μm to 30 μm × 30 μm can be formed. The shape of the micropores is not particularly limited, and examples thereof include a circular shape, an elliptical shape, and a polygonal shape.
As a method of forming micropores in the colored layer, for example, as a photomask used when forming a colored layer, a pattern capable of forming a fine line pattern. A method of using a pattern photomask in which a mask is arranged can be mentioned.

(Shading part)
The light-shielding portion in the color filter of the present invention is formed in a pattern on a substrate described later, and can be the same as that used as a light-shielding portion in a general color filter.
The pattern shape of the light-shielding portion is not particularly limited, and examples thereof include a striped shape and a matrix shape. The light-shielding portion may be a metal thin film such as chromium obtained by a sputtering method, a vacuum vapor deposition method, or the like. Alternatively, the light-shielding portion may be a resin layer in which light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in the resin binder.

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

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

The transparent substrate may be a substrate that is transparent to visible light, and is not particularly limited, and a transparent substrate used for a general color filter can be used. Specifically, a transparent rigid material having no flexibility such as quartz glass, non-alkali glass, or synthetic quartz plate, or a transparent flexible material having flexibility such as a transparent resin film, an optical resin plate, or a flexible glass. The material is mentioned.
The thickness of the transparent substrate is not particularly limited, but one of about 100 μm to 1 mm can be used depending on the use of the color filter of the present invention.
In addition to the above substrate, light-shielding portion, and colored layer, the color filter of the present invention has, for example, an overcoat layer, a transparent electrode layer, an alignment film, alignment protrusions, columnar spacers, and the like. May be good.

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

[Liquid crystal display]
The liquid crystal display device is characterized by having the above-mentioned color filter according to the present invention, a facing substrate, and a liquid crystal layer formed between the color filter and the facing 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 has a liquid crystal layer formed between a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and the color filter 10 and the counter substrate 20. It has 30 and.
The liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, and can be generally known as a liquid crystal display device using a color filter.

The drive system of the liquid crystal display device of the present invention is not particularly limited, and a drive system generally used for the liquid crystal display device can be adopted. Examples of such a drive system include a TN system, an IPS system, an OCB system, an MVA system, and the like. In the present invention, any of these methods can be preferably used.
Further, as the facing substrate, it can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention and the like.
Further, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and a mixture thereof can be used depending on the driving method of the liquid crystal display device of the present invention.

As a method for forming the 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 method, the enclosed liquid crystal can be oriented by slowly cooling the liquid crystal cell to room temperature.

[Organic light emission display device]
The organic light emitting display device is characterized by having the above-mentioned color filter according to the present invention and an organic light emitting body.
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 showing an example of the organic light emitting display device of the present invention. As illustrated in FIG. 3, the organic light emitting display device 100 of the present invention includes a color filter 10 and an organic light emitting body 80. An organic protective layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80.

As a method of laminating the organic light emitting body 80, for example, a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 are sequentially formed on the upper surface of the color filter. Examples thereof include a method and a method in which the organic light emitting body 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 of the organic light emitter 80, known ones can be appropriately used. The organic light emitting display device 100 produced in this manner can be applied to, for example, both a passive drive type organic EL display and an active drive type organic EL display.
The organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and can be generally known as an organic light emitting display device using a color filter.

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.
The structures of the obtained compounds were 1H- and 13C-NMR spectra measured using a nuclear magnetic resonance apparatus (Bruker Biospin, AVANCEIII HD500MHz), and a liquid chromatograph mass spectrometer (Shimadzu, LC-). It was confirmed by mass spectrometry using 30A, Bruker Daltonics, microOTOFQ2).

(Synthesis Example 1: Synthesis of Compound A)
1. 1-octane, 1,1'-(9-ethyl-1,8-dinitro-9H-carbazole-3,6-diyl) bis-1,1'-bisoxime 24.8 g, 100 g dichloromethane and 5. 1 g of triethylamine was mixed and stirred at room temperature for 5 minutes, then 6.1 g of acetic acid was added dropwise over 30 minutes and stirred at room temperature for 2 hours. After that, the pH was adjusted, a 5% _{aqueous solution of NaCO 3} was added so as to be neutral, the organic layer was separated with a separatory funnel, washed twice with 200 mL of water, and dried with 50 g of anhydrous magnesium sulfide. The solvent was evaporated to give a viscous liquid. By recrystallizing this liquid with methanol, 27.7 g of the following compound A was obtained as a white powder. The yield was 85% and the purity was 99%.

(Synthesis Example 2: Synthesis of Compound B)
In Synthesis Example 1, instead of 1-octane, 1,1'-(9-ethyl-1,8-dinitro-9H-carbazole-3,6-diyl) bis-1,1'-bisoxime 24.8 g. , 1-octane, 1,1'-(9-ethyl-1-nitro-9H-carbazole-3,6-diyl) bis-1,1'-bisoxime 22.8 g, but the above synthesis example 1 In the same manner as above, 25.8 g of the following compound B was obtained. The yield was 85% and the purity was 99%.

(Synthesis Example 3: Synthesis of Compound C)
In Synthesis Example 1, instead of 1-octane, 1,1'-(9-ethyl-1,8-dinitro-9H-carbazole-3,6-diyl) bis-1,1'-bisoxime 24.8 g. , 1-heptane, 1,1'-(6-methylcyclohexyl-9-ethyl-9H-carbazole-3-yl) bis-1,1'-bisoxime 23.1 g, except that 23.1 g of the above synthesis example 1 was used. Similarly, 24.0 g of the following compound B was obtained. The yield was 88% and the purity was 99%.

(Synthesis Example 4: Production of Dispersant (Block Copolymer A))
Add 250 parts by mass of THF and 0.6 parts by mass of lithium chloride to a 500 mL round bottom 4-port separable flask equipped with a cooling tube, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, and perform sufficient nitrogen substitution. rice field. After cooling the reaction flask to −60 ° C., 4.9 parts by mass of butyl lithium (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. 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA), 18.7 parts by mass of 2-hydroxyethyl methacrylate (HEMA), 12.8 parts by mass of 2-ethylhexyl methacrylate (EHMA), methacrylic acid for B block monomer 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 over 60 minutes using an addition funnel. .. After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, and diluted with PGMEA to obtain a solid content of 30% by mass. 32.5 parts by mass of water was added, the temperature was raised to 100 ° C., and the mixture was reacted for 7 hours to deprotect the constituent unit derived from EEMA to obtain a constituent unit derived from methacrylic acid (MAA). The obtained block copolymer PGMEA solution is reprecipitated in hexane, purified by filtration and vacuum drying, and is a structural unit derived from an 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 B block containing and having a solvent-like property was obtained. When the block copolymer A thus obtained was confirmed by GPC (gel permeation chromatography), the weight average molecular weight Mw was 7730. The amine value was 95 mgKOH / g.

(Synthesis Example 5: Synthesis of Alkali Soluble Resin A Solution)
A mixed solution of 40 parts by mass of styrene, 15 parts by mass of MMA, 25 parts by mass of MAA, and 3 parts by mass of AIBN was added dropwise to a polymerization tank containing 150 parts by mass of PGMEA at 100 ° C. for 3 hours. bottom. After completion of the 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 7,000.
Next, 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol were added to the obtained polymer solution, and the mixture was heated at 110 ° C. for 10 hours for reaction. Air was bubbled into the solution. The obtained alkali-soluble resin A is a resin in which a side chain having an ethylenic double bond is introduced into a main chain formed by copolymerization of styrene, MMA, and MAA using GMA, and has a solid content of 42.6 mass. %, The acid value was 74 mgKOH / g, and the weight average molecular weight was 12000. The weight average molecular weight was measured by a Shodex GPC system-21H (Shodex GPC System-21H) using polystyrene as a standard substance and THF as an eluent. The acid value was measured based on JIS K 0070: 1992.

(Synthesis example 6: Synthesis of blue color material α)
(1) Synthesis of Intermediate 1 With reference to the method for producing Intermediate 3 and Intermediate 4 described in International Publication No. 2012/144521, 15.9 g (yield) of Intermediate 1 represented by the following chemical formula (1) was obtained. Rate 70%) Obtained.
It was confirmed from the following analysis results that the obtained compound was the target compound.
-MS (ESI) (m / z): 511 (+), divalent / elemental analysis value: 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 above intermediate was added to 300 ml of water and dissolved at 90 ° C. to prepare one solution of the intermediate. Next, add 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 Chemicals Co., Ltd.) to 100 ml of water at 90 ° C. To prepare an aqueous solution of phosphotungstic acid. The aqueous solution of phosphotungstic acid prepared in the above 1 solution of the intermediate was mixed at 90 ° C., and the produced 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 as a metal lake color material of a triarylmethane-based basic dye represented by the following chemical formula (2).
It was confirmed from the following analysis results that the obtained compound was the target compound.
-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 7: Preparation of Azo Derivative 1)
23.1 g of diazobarbituric acid and 19.2 g of barbituric acid were introduced into 550 g of distilled water. Then, it was adjusted to azobarbituric acid (0.3 mol) using an aqueous potassium hydroxide solution, and mixed with 750 g of distilled water. 5 g of 30% hydrochloric acid was added dropwise. Then, 38.7 g of melamine was introduced. Then, 0.39 mol of nickel chloride solution and 0.21 mol of zinc chloride solution were mixed and added, and the mixture was stirred at a temperature of 80 ° C. for 8 hours. The pigment was isolated by filtration, washed, dried at 120 ° C., and ground in a mortar to obtain Azo derivative 1 (Ni-azo-1, Ni: Zn = 65: 35 (molar ratio) azo pigment). ..

( Reference example 1)
(1) Production of Coloring Material Dispersion Solution 3.85 parts by mass of block copolymer A of Synthesis Example 4 as a dispersant, 13 parts by mass of blue coloring material α obtained in Synthesis Example 6 as a coloring material, Synthesis Example 8.8 parts by mass (solid content 3.75 parts by mass) of the alkali-soluble resin A solution obtained in step 5, 74.35 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle size of 2.0 mm were placed in a mayonnaise bottle. As a preliminary crush, shake with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour, then take out zirconia beads having a particle size of 2.0 mm, add 200 parts by mass of zirconia beads having a particle size of 0.1 mm, and do the same. As the main crushing, dispersion was carried out with a paint shaker for 4 hours to obtain a color material dispersion liquid 1.

(2) Production of Photosensitive Colored Resin Composition 1 324.5 parts by mass of the colorant dispersion liquid 1 obtained in (1) above, and 23.78 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 5. (Solid content 10.13 parts by mass), photopolymerizable compound (trade name: Aronix M-520D, manufactured by Toa Synthetic Co., Ltd.) in 18.0 parts by mass, compound A obtained in Synthesis Example 1 as a photoinitiator. Was added by 5.0 parts by mass and PGMEA by 142.7 parts by mass to obtain a photosensitive colored resin composition 1.

(Reference Examples 2 to 13 and Example 14 )
In Reference Example 1, the photoinitiator was used in the types and amounts shown in Table 1, and in Reference Examples 10 and 11, except that the types and amounts of antioxidants shown in Table 1 were further added, the photoinitiators were different from Reference Example 1. Similarly, photosensitive colored resin compositions 2 to 14 were obtained.

(Comparative Examples 1 and 2)
In Reference Example 1, the comparative photosensitive colored resin composition is the same as in Reference Example 1 except that the photoinitiator shown in Table 1 is used instead of the compound A obtained in Synthesis Example 1. I got things 1 and 2.

The photoinitiator used in Comparative Example 1 is OXE-02 (manufactured by BASF) represented by the following chemical formula (3).

( Reference example 15)
In Reference Example 1, Pigment Red 254 was used as the color material instead of the blue color material α, and the amount of each component was changed as shown in Table 2, except that the photosensitive coloring was performed in the same manner as in Reference Example 1. A resin composition 15 was obtained.

(Comparative Example 3)
In Reference Example 15, the same as in Reference Example 15 except that OXE-02 (manufactured by BASF) represented by the chemical formula (3) was used instead of the compound A obtained in Synthesis Example 1 as the photoinitiator. The comparative photosensitive colored resin composition 3 was obtained.

( Reference example 16)
In Reference Example 1, instead of the blue color material α as the color material, 18.7 parts by mass of Pigment Green 59 and 23.5 parts by mass of the Azo derivative 1 obtained in Synthesis Example 7 were used, and the blending amount of each component was adjusted. A photosensitive colored resin composition 16 was obtained in the same manner as in Reference Example 1 except that the changes were made as shown in Table 2.

(Comparative Example 4)
In Reference Example 16, the same as in Reference Example 16 except that OXE-02 (manufactured by BASF) represented by the chemical formula (3) was used instead of the compound A obtained in Synthesis Example 1 as the photoinitiator. A comparative photosensitive colored resin composition 4 was obtained.

( Reference example 17)
In Reference Example 1, instead of the blue color material α as the color material, C.I. I. A photosensitive colored resin composition 17 was obtained in the same manner as in Reference Example 1 except that Solvent Yellow 162 was used and the blending amount of each component was changed as shown in Table 2.

(Comparative Example 5)
In Reference Example 17, the same as in Reference Example 17 except that OXE-02 (manufactured by BASF) represented by the chemical formula (3) was used instead of the compound A obtained in Synthesis Example 1 as the photoinitiator. The comparative photosensitive colored resin composition 5 was obtained.

[evaluation]
The photosensitive colored resin composition obtained in each Example and each Comparative Example was put on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") to form a cured coating film having a thickness of 3 using a spin coater. 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 a glass substrate. A pattern photomask (chrome mask) in which a chrome 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 is passed through this coating film with an ultraviolet ray of ^{40 mJ / cm 2 using an ultrahigh pressure mercury lamp.} By exposure, a post-exposure coating film was formed on the glass substrate. Next, spin-development is performed using a 0.05 wt% potassium hydroxide aqueous solution as a developer, the developer is indirectly liquidated for 60 seconds, and then the developer is washed with pure water for development treatment. Got Then, by post-baking in a clean oven at 230 ° C. for 25 minutes, an independent fine line pattern-like colored layer having micropores was formed. The obtained colored layer was evaluated as follows.

<Evaluation of optical characteristics>
The chromaticity (x, y) and brightness (Y) of the colored layer were measured using an Olympus microspectroscopy measuring device OSP-SP200.

<Developability evaluation>
[Linearity]
The width of the fine line pattern of the colored layer in the portion corresponding to the opening width of 90 μm of the chrome mask used at the time of exposure was measured at five points with an optical microscope, and the linearity was evaluated based on the variation in the line width.
A: Variation within ± 0.1 μm B: Variation exceeds ± 0.1 μm within ± 0.3 μm C: Variation exceeds ± 0.3 μm [Residual film ratio]
In the formation of the colored layer, in the process of forming the coating film, the film thickness (E) after exposure and the film thickness (D) after development were measured with a stylus profiler P-16 (manufactured by KLA-Tencor). , The film thickness (D) after development / the film thickness (E) after exposure was calculated as the residual film ratio.
When the film thickness (D) after development / the film thickness (E) after exposure is 90% or more, it is in a range suitable for actual use.

The colored layer was observed with an optical microscope, and the shape, chattering, and development residue of the micropores were evaluated according to the following evaluation criteria.
[shape]
A: The dimensional deviation of the micropores formed in the colored layer is smaller than 2% in absolute value with respect to the dimensions of the chrome mask arranged in the independent fine line pattern. B: The chrome mask arranged in the independent fine line pattern. The absolute value of the deviation of the dimensions of the micropores formed in the colored layer is 2% or more and 6% or less with respect to the dimensions of C: formed in the colored layer with respect to the dimensions of the chrome mask arranged in the independent fine line pattern. The dimensional deviation of the micropores formed is greater than 6% and 8% or less in absolute value. D: The dimensional deviation of the micropores formed in the colored layer is larger than the dimensional deviation of the chrome mask arranged in the independent fine line pattern. The absolute value is larger than 8%. The dimensional deviation was calculated as the average value of the dimensional deviation of each side.
[Billitsuki]
A: The ten-point average roughness of the peripheral edge of the micropores formed in the colored layer is less than 0.1 B: The ten-point average roughness of the peripheral edge of the micropores 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 micropores formed in the colored layer is larger than 0.5. The ten-point average roughness was measured according to JIS B0601.
[Development residue]
A: No coloring is observed inside the micropores formed in the colored layer by observation with an optical microscope B: Coloring is observed inside the micropores formed in the colored layer by observation with an optical microscope.

The abbreviations in Tables 1 and 2 are as follows.
OXE-02: Oxime ester-based photoinitiator (trade name: Irgacure OXE-02, manufactured by BASF)
-Irg369: α-aminoketone-based photoinitiator (Irgacure 369, manufactured by BASF)
-Irg907: α-aminoketone-based photoinitiator (Irgacure 907, manufactured by BASF)
・ Mercapto-based: Mercapto-based chain transfer agent (2-mercaptobenzothiazole, manufactured by Tokyo Kasei)
-Biomidazole-based: Biimidazole-based photoinitiator (HABI, manufactured by Kurogane Kasei)
-DETX: Thioxanthone-based photoinitiator (DOUBLECURE DETX, Double Bond Chemical)
-Irg819: Acylphosphine oxide-based photoinitiator (Irgacure 819, manufactured by BASF) -Irg1010: Hindered phenol-based antioxidant (Irgacure 1010, manufactured by BASF)
-BHT: Dibutylhydroxytoluene

The photosensitive coloring resin compositions of Examples or Reference Examples 1 to 17 containing the oxime ester compound represented by the general formula (1) as the photoinitiator are comparative photosensitive coloring resins using the same coloring material. It was clarified that it is possible to form a colored layer having excellent curability, a high residual film ratio, and high brightness as compared with the composition. Further, it is clear that the photosensitive colored resin compositions of Examples or Reference Examples 1 to 17 are excellent in the linearity of the fine line pattern, and it is easy to form desired micropores in the colored layer at the same time when the colored layer is patterned. Was done.
Further, as the photoinitiator, at least one selected from an α-aminoketone-based photoinitiator, a biimidazole-based photoinitiator, a thioxanthone-based photoinitiator, an acylphosphine oxide-based photoinitiator, and a mercapto-based chain transfer agent. By containing the seed, the shape of the micropores became better ( comparison between Reference Example 1 and Examples or Reference Examples 8 to 14).
On the other hand, in Comparative Example 1 and Comparative Examples 3 to 5 in which the oxime ester compound represented by the general formula (1) was not contained as the photoinitiator and the monooxime ester compound was used, Examples using the same color material were used. The residual film ratio and brightness were inferior to those of the above, the linearity of the fine line pattern was inferior, and micropores could not be formed.
Further, in Comparative Example 2 in which Irg907 (α-aminoketone-based photoinitiator) was used without containing the oxime ester compound represented by the general formula (1) as the photoinitiator, the residual film ratio and the brightness were inferior. rice field.

(Comparative Synthesis Example 1: Synthesis of Comparative Compound A)
82.1 g of N-ethyl 1,8-nitrocarbazole was dissolved in 800 ml of chloroform, 128.6 g of aluminum chloride was further added, and the mixture was stirred at 0 ° C., and 60.5 g of 2- (cyclohexyloxy) acetyl chloride was added to 300 ml of chloroform. The solution dissolved in 1 was added dropwise over 2 hours. After completion of the dropping, the mixture was stirred at 25 ° C. for 4 hours. The reaction mixture was stirred again at 0 ° C., and a solution prepared by dissolving 36.8 g of pentanoyl chloride in 200 ml of chloroform was added dropwise over 2 hours. After completion of the dropping, the mixture was stirred at 25 ° C. for 3 hours. The reaction mixture was poured into 1800 g of ice water and extracted with 2000 ml of chloroform. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was recrystallized from chloroform / methanol to obtain 127.4 g of the comparative compound (AA) (yield 86. 9%).
Next, from the obtained comparative compound (AA), the comparative compound (AB) was synthesized as follows. A mixture of 98.1 g of the comparative compound (AA), 1000 ml of tetrahydrofuran and 500 ml of concentrated hydrochloric acid was dissolved, and 18.9 g of hydroxylamine was added dropwise over 1 hour under stirring at room temperature. After completion of the dropping, the mixture was stirred at room temperature for 5 hours. The reaction mixture was poured into 1600 ml of ice water and extracted with 1600 ml of chloroform. The organic layer was washed with water (500 ml x 3 times), dried over magnesium sulfate, the desiccant was filtered to remove the solvent, and the residue was washed with n-hexane to obtain the comparative compound (AB). 88.8 g (yield 85.7%).
Next, using the obtained comparative compound (AB), comparative compound A was synthesized as follows. Acetic anhydride and sodium acetate were added to the mixture of 40.1 g of the comparative compound (AB) stirred in 500 ml of ethyl acetate, and the mixture was heated under reflux for 3 hours. Then, the reaction solution is poured into 500 ml of ice water, the product is extracted with ethyl acetate, the organic layer is washed with water (400 ml × 3 times), dried with magnesium sulfate, and the desiccant is filtered to distill off the solvent. The residue was recrystallized from ethyl acetate-hexane to synthesize 48.4 g of Comparative Compound A represented by the following chemical formula (yield 90.0%).

<Solvent solubility test of dioxime ester initiator>
Compound A, Compound B and Compound C, which are oxime ester compounds represented by the general formula (1), and the compound represented by the general formula (1) are represented by a total of 10 g of propylene glycol monomethyl ether acetate (PGMEA). 0.1 g of each of Comparative Compound A, which is different from the oxime ester compound, was added and stirred at 25 ° C. for 30 minutes, the dissolution state was visually confirmed, and the solvent solubility was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 3.
A: The initiator dissolves after stirring at 25 ° C. for 30 minutes and precipitation does not occur. B: The initiator does not dissolve after stirring at 25 ° C. for 30 minutes and precipitation occurs.

Further, when the solubility of Compound A, Compound B and Compound C in 100 g of PGMEA at 25 ° C. was measured, Compound A was 5 g / 100 g-PGMEA, Compound B was 7 g / 100 g-PGMEA, and Compound C was 2 g / 100 g-PGMEA. Met.

(Comparative Example 6)
In Reference Example 1, comparative photosensitivity was obtained in the same manner as in Reference Example 1 except that Comparative Compound A obtained in Comparative Synthesis Example 1 was used instead of Compound A obtained in Synthesis Example 1 as the photoinitiator. A sex-colored resin composition 6 was obtained.

<Foreign matter evaluation>
The photosensitive colored resin compositions 1 to 3 of Reference Examples 1 to 3 and the comparative photosensitive colored resin composition 6 of Comparative Example 6 are placed on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.), respectively. The cured coating film was applied to a thickness of 3.0 μm using a spin coater, and then dried at 80 ° C. for 3 minutes using a hot plate to form a coating film on a glass substrate. An ultra-high pressure mercury lamp was used to irradiate the entire surface with ultraviolet rays of ^{40 mJ / cm 2 without using a photomask to form a coating film after exposure.} Then, a 0.05 wt% potassium hydroxide aqueous solution was spin-developed as a developing solution, and the developer was indirectly liquid-developed for 60 seconds and then washed with pure water to develop and form a coating film after development. Then, it was post-baked in a clean oven at 230 ° C. for 25 minutes to form a cured coating film (colored layer) having a thickness of 3.0 μm. When the surface of the colored layer was observed with an optical microscope, the colored layer formed by using the photosensitive colored resin compositions 1 to 3 had no or almost no precipitation of foreign matter on the surface, whereas it was comparatively photosensitive. Foreign matter was deposited on the surface of the colored layer formed by using the colored resin composition 6, which was not suitable for actual use.

1 Substrate 2 Light-shielding part 3 Colored layer 10 Color filter 20 Opposite substrate 30 Liquid crystal layer 40 Liquid crystal display 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 emission display device

Claims (7)

It contains a coloring material, 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) and an acylphosphine oxide-based photoinitiator.
A photosensitive coloring resin composition, wherein the coloring material contains a coloring material represented by the following general formula (i).

(In the general formula (1), ^Ra is an alkyl group having 2 or more and 4 or less carbon atoms, R ^b and R ^c are independently hydrogen atoms or nitro groups, and R ^d is 5 or more and 10 or less carbon atoms. a linear alkyl group, R ^e is one selected from the group consisting of 5 or more 10 or less linear alkyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclohexylmethyl group and a cyclohexylethyl group having a carbon .)

(In the 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 at least saturated aliphatic hydrocarbon at the terminal directly bonded to N. It represents an aliphatic hydrocarbon group having a hydrogen group or an aromatic group having the aliphatic hydrocarbon group, and O, S, and N may be contained in the carbon chain. B ^c− is a c-valent poly. .R ⁱ to R ^v which represents an acid anion each independently represent a hydrogen atom, which may have an optionally substituted alkyl group or a 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 to R ^v and Ar ¹ each It may be the same or different.
a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. A plurality of e may be the same or different. ) The content of the oxime ester compound represented by the general formula (1) is 0.5% by mass or more and 8.0% by mass or less with respect to the total solid content of the photosensitive colored resin composition, and the acylphosphine oxide The photosensitive colored resin composition according to claim 1, wherein the content of the system photoinitiator is 0.1% by mass or more and 4.0% by mass or less. The photosensitive colored resin composition according to claim 1 or 2 , further containing an antioxidant. Any of claims 1 to 3 , further comprising a dispersant, wherein the dispersant contains a polymer having a structure represented by the following general formula (I) and having an amine value of 40 mgKOH / g or more and 120 mgKOH / g or less. The photosensitive colored resin composition according to item 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, and-[CH (R ⁵ )). −CH (R ⁶ ) −O] _x −CH (R ⁵ ) −CH (R ⁶ ) − or − [(CH ₂ ) _y −O] _z − (CH ₂ ) _y − , R ³ and R ⁴ each independently represent a optionally substituted linear or cyclic hydrocarbon group, R ³ and R ⁴ form a ring structure by bonding with each other .R ⁵ and R ⁶ is an independent hydrogen atom or methyl group, respectively.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. ) A cured product of the photosensitive colored resin composition according to any one of claims 1 to 4. A color filter comprising a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is the cured product according to claim 5. A display device having the color filter according to claim 6.

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