JP7059009B2 - Photosensitive colored resin composition, color filter and its manufacturing method, and display device - Google Patents

Description

The present invention relates to a photosensitive colored resin composition, a color filter and a method for producing the same, and a display device.

Many thin image display devices such as displays, so-called flat panel displays, have been put on the market because they are thinner than CRT displays and do not take up space in the depth direction. The market price is becoming more affordable year by year with the evolution of production technology, the demand is further expanding, and the production volume is also increasing year by year. In particular, color LCD TVs have almost reached the mainstream of TV. 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 such as improvement in contrast and color reproducibility are strongly desired.
Color filters are used in these liquid crystal displays and organic light emission display devices. For example, in the case of a color liquid crystal display, a backlight is used as a light source, the amount of light is controlled by electrically driving the liquid crystal, and the light passes through a color filter to express colors. Therefore, color filters are indispensable for the color expression of LCD TVs, and they also play a major role in determining the performance of displays. Further, in the organic light emitting display device, there are cases where the color adjustment of the pixels is performed by using a color filter, and there are cases where a color filter is used for the organic light emitting element of white light emission to form a color image in the same manner as the liquid crystal display device.

As a trend in recent years, there is a demand for power saving of image display devices, and in particular, there is a demand for higher brightness of color filters in order to improve the utilization efficiency of the backlight. This is a major issue especially for mobile displays (mobile phones, smartphones, tablet PCs).
Although the battery capacity has increased due to technological evolution, the amount of electricity stored in mobile devices is still finite, while the power consumption tends to increase as the screen size increases. An image display device including a color filter influences the design and performance of the mobile terminal because it is directly linked to the usable time and charging frequency of the mobile terminal.

Here, the color filter is generally formed on the substrate, a colored layer 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 one of the methods for forming such a colored layer, a method of applying a photosensitive resin composition containing a coloring material and a photopolymerizable compound on a substrate and curing it by irradiating with ultraviolet rays or the like is known. ing.
Pigments and dyes are used as the coloring material of the photosensitive resin composition. Pigments are generally superior in heat resistance and light resistance to dyes, but they cannot sufficiently prevent fading during high-temperature heating in the color filter manufacturing process, resulting in a decrease in brightness. ..
Further, in recent years, from the viewpoint of further increasing the brightness of a color filter, a photosensitive resin composition for a color filter using a dye having a high transmittance has been generally studied, and the heat resistance and light resistance of the dye have been improved. It is also being considered to use a rake colorant in which the dye is insolubilized. However, since dyes have poor heat resistance and light resistance as compared with pigments, there is a problem that the chromaticity tends to change and the brightness of the colored layer tends to decrease during high-temperature heating or light irradiation in the color filter manufacturing process. was there.

As one of the methods for solving the above problems, the use of a resin composition containing an antioxidant has been studied.
For example, Patent Document 1 describes a blue color filter containing a blue colorant, an alkali-soluble resin, a polyfunctional monomer, a specific photopolymerization initiator, and a specific antioxidant in a specific ratio. Sensitive radiation compositions are disclosed. According to Patent Document 1, blue pixels having high luminance can be formed.

Further, Patent Document 2 discloses a colored resin composition for a color filter containing a lake pigment, a specific dispersant, a hindered phenolic antioxidant, a binder component, and a solvent. According to Patent Document 2, the heat resistance is improved by the hindered phenolic antioxidant, and a high-brightness colored layer can be formed.

On the other hand, Patent Document 3 discloses a colored photosensitive composition containing a specific latent antioxidant and a specific organic dye as a colored photosensitive composition having excellent heat resistance.

Japanese Unexamined Patent Publication No. 2014-160254 Japanese Unexamined Patent Publication No. 2014-153569 International Publication No. 2014/021023 Pamphlet

Generally, the colored layer for the color filter is patterned on the substrate. When a colored layer is formed using the photosensitive colored resin composition, for example, after forming a coating film of the photosensitive colored resin composition on a substrate, exposure is performed through a predetermined mask pattern, and then development processing is performed. This makes it possible to obtain a patterned colored layer.
The present inventors have studied the formation of a colored layer by the above-mentioned method using a photosensitive colored resin composition containing an antioxidant. As a result, the present inventors have found that when the photosensitive resin composition containing the antioxidant is used, the colored layer as designed may not be formed.

The present invention has been made based on the above findings, and is a photosensitive colored resin composition capable of forming a high-luminance colored layer and suppressing a change in line width, the photosensitive colored resin composition. It is an object of the present invention to provide a high-luminance color filter formed by using the above color filter and a display device having excellent display characteristics using the color filter.

The photosensitive coloring resin composition according to the present invention contains a coloring material, a photopolymerizable compound, an initiator, a latent antioxidant, and a solvent, and the coloring material is made of a dye and a rake coloring material. It comprises one or more selected species, and the latent antioxidant contains a compound represented by the following general formula (1).

（一般式（１）中の各符号は、後述のとおりである。）

(Each reference numeral in the general formula (1) is as described later.)

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 curing of the photosensitive colored resin composition according to the present invention. It is characterized by being a thing.
The method for manufacturing a color filter according to the present invention is a method for manufacturing a color filter including at least a substrate and a colored layer provided on the substrate.
It is characterized by having a step of forming at least one of the colored layers by using the photosensitive colored resin composition according to the present invention.

Further, the display device according to the present invention is characterized by having the color filter according to the present invention.

According to the present invention, a photosensitive colored resin composition capable of forming a high-brightness colored layer and suppressing a change in line width, and a high-brightness color formed by using the photosensitive colored resin composition. It is possible to provide a filter and a display device having excellent display characteristics using the color filter.

FIG. 1 is a schematic cross-sectional view showing an example of the color filter of the present invention. FIG. 2 is a schematic cross-sectional view showing an example of the display device of the present invention. FIG. 3 is a schematic cross-sectional view showing another example of the display device of the present invention.

Hereinafter, the photosensitive colored resin composition, the color filter, and the display device according to the present invention will be described in order.
In the present invention, the light includes electromagnetic waves having wavelengths in the visible and invisible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it refers to an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.
In the present invention, (meth) acrylic represents each of acrylic and methacrylic, and (meth) acrylate represents each of acrylate and methacrylate.
In the present invention, the organic group means a group having one or more carbon atoms.
Further, in the present invention, the solid content means all components other than the solvent constituting the resin composition, and for example, even a liquid monomer is contained in the solid content.

1. 1. Photosensitive Colored Resin Composition The photosensitive colored resin composition according to the present invention contains a coloring material, a photopolymerizable compound, an initiator, a latent antioxidant, and a solvent. It contains one or more selected from dyes and lake colorants, and the latent antioxidant contains a compound represented by the following general formula (1).

（一般式（１）中、環Ａは、五員環又は六員環の炭化水素環又は複素環であり、
Ｒ^１は、それぞれ独立に、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシ基、置換基を有していてもよい炭素原子数１～４０のアルキル基、置換基を有していてもよい炭素原子数６～２０のアリール基、置換基を有していてもよい炭素原子数７～２０のアリールアルキル基、又は置換基を有していてもよい炭素原子数２～２０の複素環含有基であるか、又は、複数のＲ^１同士が結合してベンゼン環若しくはナフタレン環を形成し、
Ｒ^２は、炭素原子数１～２０のアルキル基、炭素原子数２～２０のアルケニル基、炭素原子数６～２０のアリール基、炭素原子数７～２０のアリールアルキル基、炭素原子数２～２０の複素環含有基、又はトリアルキルシリル基であり、
Ｒ^１及びＲ^２が有するアルキル基中に、炭素－炭素二重結合、－Ｏ－、－Ｓ－、－Ｃ（＝Ｏ）－、－Ｏ－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－Ｏ－、－Ｓ－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｓ－、－Ｓ－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－Ｓ－、－Ｃ（＝Ｏ）－ＮＨ－、－ＮＨ－Ｃ（＝Ｏ）－、－ＮＨ－Ｃ（＝Ｏ）－Ｏ－、－ＮＲ’－、－Ｓ－Ｓ－又は－ＳＯ_２－を有してもよく、Ｒ’は、水素原子又は炭素原子数１～８のアルキル基であり、複数あるＲ^１及びＲ^２はそれぞれ同一であっても異なっていてもよい。
Ｘは、ａ価の基であって、直接結合、窒素原子、酸素原子、硫黄原子、リン原子、（－Ｏ）_３Ｐ＝Ｏ、＞Ｃ＝Ｏ、＞ＮＲ^３、－ＯＲ^３、－ＳＲ^３、－Ｎ（Ｒ^３）（Ｒ^４）、置換基を有していてもよい炭素原子数１～１２０の脂肪族炭化水素基、置換基を有していてもよい炭素原子数６～３５の芳香環含有炭化水素基、又は、置換基を有していてもよい炭素原子数２～３５の複素環含有基であり、Ｒ^３及びＲ^４は、それぞれ独立に、水素原子、置換基を有していてもよい炭素原子数１～３５の脂肪族炭化水素基、置換基を有していてもよい炭素原子数６～３５の芳香環含有炭化水素基、又は置換基を有していてもよい炭素原子数２～３５の複素環含有基である。Ｘにおける前記脂肪族炭化水素基、及び前記芳香環含有炭化水素基中に、炭素－炭素二重結合、－Ｏ－、－Ｓ－、－Ｃ（＝Ｏ）－、－Ｏ－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－Ｏ－、－Ｓ－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｓ－、－Ｓ－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－Ｓ－、－Ｃ（＝Ｏ）－ＮＨ－、－ＮＨ－Ｃ（＝Ｏ）－、－ＮＨ－Ｃ（＝Ｏ）－Ｏ－、－ＮＲ’－、－Ｓ－Ｓ－、－ＳＯ_２－又は窒素原子を有してもよい。
ａは、１～１０の整数を表し、ｂは、１～４の整数を表し、ｃは、１～３の整数を表す。）

(In the general formula (1), the ring A is a 5-membered ring or a 6-membered ring hydrocarbon ring or a heterocycle.
R ¹ may independently have a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxy group, and an alkyl group having 1 to 40 carbon atoms and a substituent. Contains an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms which may have a substituent, or a heterocyclic ring having 2 to 20 carbon atoms which may have a substituent. It is a group, or a plurality of R1s are bonded to ^each other to form a benzene ring or a naphthalene ring.
^R2 has an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and 2 to 2 carbon atoms. 20 heterocyclic-containing groups or trialkylsilyl groups.
In the alkyl group of R ¹ and R ² , carbon-carbon double bond, -O-, -S-, -C (= O)-, -OC (= O)-, -C (= O) ) -O-, -OC (= O) -O-, -SC (= O)-, -C (= O) -S-, -SC (= O) -O-,- OC (= O) -S-, -C (= O) -NH-, -NH-C (= O)-, -NH-C (= O) -O-, -NR'-, -S It may have —S— or _—SO2- , where R ′ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and the plurality of ^R1 and ^R2 are different even if they are the same. You may.
X is an a-valent group, which is a direct bond, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, (-O) ₃ P = O,> C = O,> NR ³ , -OR ³ , -SR. ³ , -N (R ³ ) (R ⁴ ), an aliphatic hydrocarbon group having 1 to 120 carbon atoms which may have a substituent, and 6 to 35 carbon atoms which may have a substituent. Aromatic ring-containing hydrocarbon group or a heterocyclic ring-containing group having 2 to 35 carbon atoms which may have a substituent, and R ³ and R ⁴ independently have a hydrogen atom and a substituent, respectively. It has an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms which may have a substituent, or a substituent. It is also a hydrocarbon-containing group having 2 to 35 carbon atoms. In the aliphatic hydrocarbon group in X and the aromatic ring-containing hydrocarbon group, a carbon-carbon double bond, -O-, -S-, -C (= O)-, -OC (= O) )-, -C (= O) -O-, -OC (= O) -O-, -SC (= O)-, -C (= O) -S-, -SC ( = O) -O-, -OC (= O) -S-, -C (= O) -NH-, -NH-C (= O)-, -NH-C (= O) -O- , -NR'-, -SS-, -SO _2- or may have a nitrogen atom.
a represents an integer of 1 to 10, b represents an integer of 1 to 4, and c represents an integer of 1 to 3. )

The photosensitive colored resin composition according to the present invention has an effect that a high-luminance colored layer can be formed and that a change in line width is suppressed during development.

Although there are some unclear points about the action of obtaining the above effect by the configuration of the present invention, it is presumed as follows.
Conventionally, as a method for improving heat resistance and light resistance, it has been studied to add an antioxidant to a photosensitive resin composition. Generally, an antioxidant can suppress the oxidation of a coloring material or the like by inactivating radicals or the like generated during heating or exposure. However, the present inventors have a case where a coating film of a colored photosensitive resin composition containing an antioxidant is exposed through a predetermined mask pattern and then developed to obtain a patterned colored layer. It was found that the line width is narrower than that of the conventional photosensitive colored resin composition having no antioxidant. As a cause, since the antioxidant also inactivates the radicals generated from the initiator at the time of exposure, it is speculated that the photopolymerization reaction does not proceed sufficiently and the sensitivity is insufficient by using the antioxidant.
In order to obtain the fine line pattern as designed without changing the mask pattern, for example, it was considered to add a large amount of the initiator. However, in such a method, the content ratio of the coloring material is relatively lowered, and there is a problem that the desired chromaticity cannot be achieved.
The photosensitive colored resin composition of the present invention contains a latent antioxidant represented by the general formula (1). In the latent antioxidant, a phenolic hydroxyl group exhibiting an antioxidant effect is protected by a protecting group. Since the latent antioxidant does not have an antioxidant function at the time of exposure, it does not inactivate radicals generated from the initiator, suppresses a decrease in sensitivity, and suppresses line width thinning. On the other hand, in the heating step performed after exposure, the protecting group is desorbed and the antioxidant effect is exhibited, so that fading of the coloring material or the like is suppressed, and a high-luminance colored layer can be obtained.

The photosensitive coloring resin composition of the present invention contains at least a coloring material, a photopolymerizable compound, an initiator, a latent antioxidant, and a solvent, and does not impair the effects of the present invention. As long as it is necessary, other components may be further contained.
Hereinafter, each component of the colored resin composition for a color filter of the present invention will be described in detail in order.

[Latent Antioxidant]
In the present invention, the latent antioxidant is a compound having a protecting group that can be desorbed by heating, and is a compound that exhibits an antioxidant function when the protecting group is desorbed. Of these, those that facilitate the removal of protecting groups by heating at 150 ° C. or higher are preferable.

In the present invention, as such a latent antioxidant, a compound represented by the following general formula (1) is used.

（一般式（１）中の各符号は、前述のとおりである。）

(Each reference numeral in the general formula (1) is as described above.)

The latent antioxidant represented by the general formula (1) has a structure in which a specific group is bonded to a specific atom or group having a valence represented by X. The a groups may be the same or different from each other. The value of a is 1 to 10, preferably 2 to 6 from the viewpoint of ease of synthesis.

The ring A in the above general formula (1) is a 5-membered ring or a 6-membered ring hydrocarbon ring or a heterocycle.
Examples of the five-membered hydrocarbon ring include an alicyclic ring such as a cyclopentane ring and a cyclopentene ring, and an aromatic ring such as cyclopentadiene and ferrocene.
Examples of the five-membered ring heterocycle include furan, thiophene, pyrrole, pyrrolidine, pyrazolidine, pyrazole, imidazole, imidazolidine, oxazole, isoxazole, isooxazolidine, thiazole, isothiazole, and isothiazolidine.
Examples of the six-membered hydrocarbon ring include a six-membered alicyclic ring such as a cyclohexane ring, a cyclohexene ring, and a cyclohexadiene ring, and a six-membered aromatic ring such as benzene, naphthalene, anthracene, fluorene, perylene, and pyrene. Be done.
Examples of the six-membered ring heterocycle include piperidine, piperazine, morpholine, thiomorpholin, pyridine, pyrazine, pyrimidine, pyridazine, triazine and the like.
These rings may be condensed or substituted with other rings, and may constitute, for example, quinoline, isoquinoline, indole, urolysine, benzoxazole, benzotriazole, azulene and the like.
In the present invention, the ring A is a six-membered aromatic ring or a heterocycle, from the viewpoint that a photosensitive colored resin composition capable of forming a high-luminance colored layer and suppressing a change in line width can be obtained. It is more preferable that the aromatic ring is a six-membered ring, and it is even more preferable that the aromatic ring is selected from benzene, naphthalene, anthracene, and pyrene.

Among R ¹ in the above general formula (1), examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Among R ¹ , alkyl groups having 1 to 40 carbon atoms which may have a substituent include, for example, methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl and iso-. Butyl, amyl, iso-amyl, tert-amyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1 -Octyl, iso-octyl, tert-octyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, adamantyl, 1-adamantyl, 2-adamantyl, 2-methyl- Examples thereof include 1-adamantyl, 2-methyl-2-adamantyl, 2-ethyl-1-adamantyl, 2-ethyl-2-adamantyl, 2-norbornyl, 2-norbornylmethyl and the like.

Among R ¹ , examples of the aryl group having 6 to 20 carbon atoms include phenyl, naphthyl, anthracenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, and 3-iso-propyl. Phenyl, 4-iso-propylphenyl, 4-butylphenyl, 4-iso-butylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) Phenyl, 4-stearylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2 , 4-Di-tert-butylphenyl, 2,5-di-tert-butylphenyl, 2,6-di-tert-butylphenyl, 2,4-di-tert-pentylphenyl, 2,5-di-tert -Amilphenyl, 2,5-di-tert-octylphenyl, 2,4-dicumylphenyl, 4-cyclohexylphenyl, (1,1'-biphenyl) -4-yl, 2,4,5-trimethylphenyl, Examples include ferrocenyl and the like.

Among R ¹ , heterocyclic-containing groups having 2 to 20 carbon atoms include, for example, pyridyl, pyrimidyl, pyridadyl, piperidin, pyranyl, pyrazolyl, triazil, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzoimidazolyl, triazolyl, frill, and furanyl. , Benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolidine, benzoxazolyl, isothiazolyl, isooxazolidine, indolyl, 2-pyrrolidinone-1-yl, 2-piperidin-1-yl, 2,4- Examples thereof include dioxyimidazolidine-3-yl and 2,4-dioxyoxazolidine-3-yl.

Further, among R ¹ , as a substituent for substituting the hydrogen atom of the alkyl group, the aryl group and the heterocyclic ring-containing group, an ethylenically unsaturated group such as vinyl, allyl, acrylic and methacryl; fluorine, chlorine, bromine and iodine. Halogen atoms such as: acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t. -Acyl groups such as butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl; acyloxy groups such as acetyloxy, benzoyloxy; amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, Anilino, chlorophenylamino, toluidino, anisidino, N-methyl-anilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, lauroylamino, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, Substituent amino groups such as phenoxycarbonylamino, sulfamoylamino, N, N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino; sulfonamide group, sulfonyl group, carboxy group, cyano group, sulfo group , A hydroxyl group, a nitro group, a mercapto group, an imide group, a carbamoyl group, a sulfonamide group, a phosphonic acid group, a phosphoric acid group or a carboxy group, a sulfo group, a phosphonic acid group, a salt of a phosphoric acid group and the like.

Examples of the alkyl group having 1 to 20 carbon atoms in R ² in the general formula (1) include an alkyl group having 1 to 20 carbon atoms among the alkyl groups exemplified in R ¹ above. ..
Among ^R2 , the alkenyl groups having 2 to 20 carbon atoms include vinyl, 1-methylethene-1-yl, propene-1-yl, propene-2-yl, propene-3-yl and butene-1-yl. , Buten-2-yl, 2-methylpropene-3-yl, 1,1-dimethylethane-2-yl, 1,1-dimethylpropene-3-yl, 3-butenyl, 1-methyl-3-butenyl, Examples thereof include isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl, octenyl, decenyl, pentadecenyl, eicosenyl, tricoseni and the like.
Among R ² , the aryl group having 6 to 20 carbon atoms, the arylalkyl group having 7 to 20 carbon atoms, and the heterocycle-containing group having 2 to 20 carbon atoms are the same as those exemplified in R ¹ . Things can be mentioned.
Further, among R ² , examples of the trialkylsilyl group include trimethylsilane, triethylsilane, ethyldimethylsilane and the like.

Further, when the R ¹ and R ² have an alkyl group, a carbon-carbon double bond, -O-, -S-, -C (= O)-, and -OC (= O) are contained in the alkyl chain. )-, -C (= O) -O-, -OC (= O) -O-, -SC (= O)-, -C (= O) -S-, -SC ( = O) -O-, -OC (= O) -S-, -C (= O) -NH-, -NH-C (= O)-, -NH-C (= O) -O- , -NR'-, -S-S- or -SO _2- .
The R'of the -NR'-group is an alkyl group having 1 to 8 carbon atoms. Specifically, among the alkyl groups exemplified in R ¹ , the alkyl group has 1 to 8 carbon atoms. The group is mentioned.
When the above structure is contained in the alkyl chain, it is preferable that the alkyl chain does not have a structure (—O—O—) in which oxygen atoms are linked to each other.

In the present invention, R ¹ is preferably an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms from the viewpoint of easy synthesis. Further, R ¹ is preferably a substituent having 4 or more carbon atoms, from the viewpoint of being excellent in heat resistance and light resistance as a latent antioxidant. Specific examples of substituents having 4 or more carbon atoms include tertiary alkyl groups such as t-butyl group, t-pentyl group and t-hexyl group; secondary alkyl groups such as sec-butyl group and sec-pentyl group. Branched primary alkyl groups such as i-butyl group and i-pentyl group; cycloalkyl groups such as cyclohexyl group and cyclopentyl group, and tertiary alkyl groups are more preferable from the viewpoint of reactivity with radicals. , T-Butyl groups are particularly preferred.

Further, in the present invention, R ² having —C (= O) —O— bonded to the terminal on the oxygen atom side of an alkyl group having 2 to 8 carbon atoms is efficiently used as a latent additive. It is preferable because it expresses a function. That is, the substituent —OR ² in the general formula (1) is preferably —OC (= O) —OR ”(R” is an alkyl group having 1 to 7 carbon atoms).

The structure of the a-valent aliphatic hydrocarbon group having 1 to 120 carbon atoms, which may have a substituent and is represented by X in the general formula (1), is not particularly limited. The aliphatic hydrocarbon group may be a linear chain, a branched chain, a cyclic (alicyclic hydrocarbon) or a combination thereof. Further, the aliphatic hydrocarbon group has a carbon-carbon double bond, -O-, -S-, -C (= O)-, and -OC (= O) in the aliphatic hydrocarbon group. -, -C (= O) -O-, -OC (= O) -O-, -SC (= O)-, -C (= O) -S-, -SC (= O) -O-, -OC (= O) -S-, -C (= O) -NH-, -NH-C (= O)-, -NH-C (= O) -O-, It may have -NR'-, -SS-, -SO _2- or a nitrogen atom. For example, the monovalent aliphatic hydrocarbon group includes methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, secondary butyl, tertiary butyl, isobutyl, amyl, isoamyl, tertiary amyl, cyclopentyl, hexyl, 2-. Hexyl, 3-hexyl, cyclohexyl, bicyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, Alkyl groups such as decyl; methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, secondary butyloxy, tertiary butyloxy, isobutyloxy, amyloxy, isoamyloxy, tertiary amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyl Alkoxy groups such as oxy, tertiary heptyloxy, n-octyloxy, isooctyloxy, tertiary octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy; methylthio, ethylthio, propylthio, isopropylthio, butylthio, secondary butylthio, first. Alkylthio groups such as tributylthio, isobutylthio, amilthio, isoamylthio, tertiary amilthio, hexylthio, cyclohexylthio, heptylthio, isoheptylthio, tertiary heptylthio, n-octylthio, isooctylthio, tertiary octylthio, 2-ethylhexylthio; vinyl , 1-methylethenyl, 2-methylethenyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl , Octenyl, decenyl, pentadecenyl, eicosenyl, tricosenyl and the like, or a combination of these groups and the following substituents, etc., and the divalent or higher aliphatic hydrocarbon group is the above monovalent aliphatic hydrocarbon group. The structure in which a part of the hydrogen atom is removed can be mentioned.

The structure of the a-valent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms which may have a substituent in X is not particularly limited. For example, examples of the monovalent aromatic ring-containing hydrocarbon group include arylalkyl groups such as benzyl, phenethyl, diphenylmethyl, triphenylmethyl, styryl and cinnamyl; aryl groups such as phenyl and naphthyl; aryloxy such as phenoxy and naphthyloxy. Group; Arylthio groups such as phenylthio and naphthylthio, or combinations of these groups with the following substituents, etc., and divalent or higher aliphatic hydrocarbon groups are a part of hydrogen atoms of the above monovalent aromatic ring-containing hydrocarbon groups. There is a structure in which is removed. Further, the aromatic ring-containing hydrocarbon group contains a carbon-carbon double bond, —O—, —S—, —C (= O) −, —OC (=) in the aromatic ring-containing hydrocarbon group. O)-, -C (= O) -O-, -OC (= O) -O-, -SC (= O)-, -C (= O) -S-, -SC (= O) -O-, -OC (= O) -S-, -C (= O) -NH-, -NH-C (= O)-, -NH-C (= O) -O -, -NR'-, -SS-, -SO _2- or may have a nitrogen atom.

The structure of the a-valent heterocyclic group having 2 to 35 carbon atoms which may have a substituent in X is not particularly limited. For example, the monovalent heterocyclic-containing group includes pyridyl, pyrimidyl, pyridadyl, piperidil, pyranyl, pyrazolyl, triazil, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzoimidazolyl, triazolidine, frill, furanyl, benzofuranyl, thienyl, thiophenyl, benzothio. Phenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolidine, isothiazolyl, isooxazolidine, indrill, 2-pyrrolidinone-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidine-3-yl, 2,4-Dioxyoxazolidine-3-yl, benzotriazoyl, etc. or a combination of these groups and the following substituents may be mentioned. A divalent or higher valent heterocycle-containing group is hydrogen of the above monovalent heterocyclic-containing group. The structure in which a part of the atom is removed can be mentioned.

Substituents that X may have include ethylenically unsaturated groups such as vinyl, allyl, acrylic and methacryl; halogen atoms such as fluorine, chlorine, bromine and iodine; acetyl, 2-chloroacetyl, propionyl and octanoyl. Acryl groups such as acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl and the like. Acyloxy groups such as acetyloxy and benzoyloxy; amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, anisidino, N-methyl-anilino, Diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, lauroylamino, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonyl Amino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N, N-dimethylamino Substituent amino groups such as sulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino; sulfonamide group, sulfonyl group, carboxy group, cyano group, sulfo group, hydroxyl group, nitro group, mercapto group, imide group, carbamoyl group, Examples thereof include a sulfonamide group, a phosphonic acid group, a phosphoric acid group or a carboxy group, a sulfo group, a phosphonic acid group, a salt of a phosphoric acid group, and the like, and these groups may be further substituted. Further, the carboxy group and the sulfo group may form a salt.

Further, among X, in R ³ and R ⁴ in> NR ³ , -OR ³ , -SR ³ , -N (R ³ ) (R ⁴ ), an aliphatic hydrocarbon group having 1 to 35 carbon atoms, The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and the heterocyclic ring-containing group having 2 to 35 carbon atoms include the monovalent aliphatic hydrocarbon group and the monovalent aromatic ring-containing hydrocarbon, respectively. Among the groups exemplified as the monovalent heterocyclic-containing group, those satisfying the number of carbon atoms can be mentioned.

In the present invention, among the compounds represented by the general formula (1), one or more selected from the following general formulas (1A) to (1E) is preferable from the viewpoint of excellent heat resistance.

（一般式（１Ａ）中、環Ａ’は、六員環の脂環、芳香環又は複素環であり、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、及びＲ^１５は、それぞれ独立に、水素原子又は前記一般式（１）におけるＲ^１と同様の基であり、Ｒ^２は前記一般式（１）におけるＲ^２と同様である。但し、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、及びＲ^１５のうち少なくとも一つは、一般式（１）におけるＲ^１と同様の基である。）

(In the general formula (1A), the ring A'is a 6-membered alicyclic ring, an aromatic ring or a heterocycle, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are independently hydrogen. It is an atom or a group similar to R ¹ in the general formula (1), and R ² is the same as R ² in the general formula (1), except that R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ . At least one of R ¹⁵ is a group similar to R ¹ in the general formula (1).)

（一般式（１Ｂ）中、Ｘ^１は、下記一般式（３）で表される基であり、環Ａ’、Ｒ^２、Ｒ^１１、Ｒ^１２、Ｒ^１３、及びＲ^１４は、一般式（１Ａ）と同様である。）

(In the general formula (1B), X ¹ is a group represented by the following general formula (3), and rings A', R ² , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are general formulas (1B). Same as 1A).)

（一般式（１Ｃ）中、ｍは２～６の整数であり、Ｘ^１は、ｍ＝２のとき下記一般式（３）で表される基であり、ｍ＝３のとき下記一般式（４）で表される基であり、ｍ＝４のとき下記一般式（５）で表される基であり、ｍ＝５のとき下記一般式（６）で表される基であり、ｍ＝６のとき下記一般式（７）で表される基であり、環Ａ’、Ｒ^２、Ｒ^１１、Ｒ^１２、Ｒ^１３、及びＲ^１４は、一般式（１Ａ）と同様である。）

(In the general formula (1C), m is an integer of 2 to 6, X ¹ is a group represented by the following general formula (3) when m = 2, and the following general formula (when m = 3). It is a group represented by 4), a group represented by the following general formula (5) when m = 4, a group represented by the following general formula (6) when m = 5, and m =. In the case of 6, it is a group represented by the following general formula (7), and the rings A', R ² , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are the same as those in the general formula (1A).

（一般式（１Ｄ）中、ｍ、Ｘ^１、環Ａ’、Ｒ^２、Ｒ^１１、Ｒ^１２、Ｒ^１３、及びＲ^１４は、一般式（１Ｃ）と同様である。）

(In the general formula (1D), m, X ¹ , ring A', R ² , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are the same as those in the general formula (1C).)

（一般式（１Ｅ）中、ｍ’は３～６の整数であり、一般式（１Ｃ）のｍが３～６の場合とそれぞれ同様である。Ｘ^１、環Ａ’、Ｒ^２、Ｒ^１１、Ｒ^１２、Ｒ^１３、及びＲ^１４は、一般式（１Ｃ）と同様である。）

(In the general formula (1E), m'is an integer of 3 to 6, which is the same as the case where m in the general formula (1C) is 3 to 6, respectively. X ¹ , ring A', R ² , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are the same as in the general formula (1C).)

（一般式（３）中、Ｑ^１は、－ＮＲ^３２－、二価の炭素原子数１～３５の脂肪族炭化水素基、二価の炭素原子数６～３５の芳香環含有炭化水素基若しくは二価の炭素原子数２～３５の複素環含有基又は下記（３－１）～（３－３）の何れかで表される置換基を表し、
Ｑ^１で表される脂肪族炭化水素基中のメチレン基は、－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－又はこれらを組み合わせた基で置き換わっていてもよく、Ｚ^１及びＺ^２は、それぞれ独立に、直接結合、－Ｏ－、－Ｓ－、－ＳＯ_２－、－ＳＯ－、－ＮＲ^３２－、－ＰＲ^３３－を表し、Ｒ^３２及びＲ^３３は、それぞれ独立に、水素原子、炭素原子数１～８のアルキル基、炭素原子数６～２０のアリール基又は炭素原子数７～２０のアリールアルキル基を表し、Ｒ^３２及びＲ^３３で表されるアルキル基、アリール基及びアリールアルキル基は、ハロゲン原子、水酸基又はニトロ基で置換されていてもよく、Ｒ^３２及びＲ^３３で表されるアルキル基及びアリールアルキル基中のメチレン基は、－ＣＯＯ－、－Ｏ－、－ＯＣＯ－、－ＮＨＣＯ－、－ＮＨ－又は－ＣＯＮＨ－で置き換わっていてもよい。
但し、上記一般式（３）で表される基は炭素原子数１～３５の範囲内である。）

(In the general formula (3), Q ¹ is -NR ^32- , an aliphatic hydrocarbon group having a divalent carbon atom number of 1 to 35, an aromatic ring-containing hydrocarbon group having a divalent carbon atom number of 6 to 35, or the like. Represents a divalent heterocyclic group having 2 to 35 carbon atoms or a substituent represented by any of the following (3-1) to (3-3).
The methylene group in the aliphatic hydrocarbon group represented by ^Q1 is replaced with -O-, -S-, -CO-, -COO-, -OCO-, -NH- or a combination thereof. Often, Z ¹ and Z ² independently represent direct binding, -O-, -S-, -SO _2- , -SO-, -NR ^32- , ^-PR 33-, R ³² and R, respectively. ³³ independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms, and is represented by R ³² and R ³³ , respectively. The alkyl group, aryl group and arylalkyl group to be formed may be substituted with a halogen atom, a hydroxyl group or a nitro group, and the methylene group in the alkyl group represented by R ³² and R ³³ and the aryl alkyl group is-. It may be replaced by COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-.
However, the group represented by the above general formula (3) is in the range of 1 to 35 carbon atoms. )

（式（３－１）中、Ｒ^３４は水素原子、炭素原子数１～１０のアルキル基若しくは炭素原子数１～１０のアルコキシ基により置換されてもよいフェニル基又は炭素原子数３～１０のシクロアルキル基を表し、Ｒ^３５は炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基、炭素原子数２～１０のアルケニル基又はハロゲン原子を表し、Ｒ^３４及びＲ^３５で表されるアルキル基、アルコキシ基及びアルケニル基は、ハロゲン原子で置換されているか又は無置換であり、ｄは０～５の整数である。）

(In formula (3-1), R ³⁴ has a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, which may be substituted with a phenyl group or 3 to 10 carbon atoms. Representing a cycloalkyl group, ^R35 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, and R ³⁴ and R ³⁵ represent. The represented alkyl group, alkoxy group and alkenyl group are substituted or unsubstituted with a halogen atom, and d is an integer of 0 to 5).

（式（３－３）中、Ｒ^３６及びＲ^３７は、それぞれ独立に、炭素原子数１～１０のアルキル基、炭素原子数６～２０のアリール基、炭素原子数６～２０のアリールオキシ基、炭素原子数６～２０のアリールチオ基、炭素原子数８～２０のアリールアルケニル基、炭素原子数７～２０のアリールアルキル基、炭素原子数２～２０の複素環含有基又はハロゲン原子を表し、Ｒ^３６及びＲ^３７で表されるアルキル基、アリール基、アリールオキシ基、アリールチオ基、アリールアルケニル基、アリールアルキル基及び複素環含有基は、ハロゲン原子で置換されているか又は無置換であり、Ｒ^３６及びＲ^３７で表されるアルキル基及びアリールアルキル基中のメチレン基は、不飽和結合、－Ｏ－又は－Ｓ－で置き換わっていてもよく、Ｒ^３６は、隣接するＲ^３６同士で環を形成していてもよく、ｅは０～４の数を表し、ｆは０～８の数を表し、ｇは０～４の数を表し、ｈは０～４の数を表し、ｇとｈの数の合計は２～４である。）

(In formula (3-3), R ³⁶ and R ³⁷ are independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms, respectively. Represents an arylthio group having 6 to 20 carbon atoms, an arylalkenyl group having 8 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or a halogen atom. The alkyl group, aryl group, aryloxy group, arylthio group, arylalkenyl group, arylalkyl group and heterocyclic-containing group represented by R ³⁶ and R ³⁷ are substituted with or unsubstituted from a halogen atom and are R. The methylene groups in the alkyl and arylalkyl groups represented by ³⁶ and R ³⁷ may be replaced by unsaturated bonds, —O— or —S—, where R ³⁶ forms a ring between adjacent R ^36s . It may be formed, where e represents a number from 0 to 4, f represents a number from 0 to 8, g represents a number from 0 to 4, h represents a number from 0 to 4, and g and h. The total number of is 2-4.)

（一般式（４）～（７）中、Ｑ^２は、Ｒ^３８で置換された炭素原子、三価の炭素原子数１～３５の脂肪族炭化水素基、三価の炭素原子数６～３５の芳香環含有炭化水素基又は三価の炭素原子数２～３５の複素環含有基を表し、Ｒ^３８は、水素原子、炭素原子数１～８のアルキル基、炭素原子数６～２０のアリール基又は炭素原子数７～２０のアリールアルキル基を表し、Ｑ^３は、炭素原子、四価の炭素原子数１～３５の脂肪族炭化水素基、四価の炭素原子数６～３５の芳香環含有炭化水素基又は四価の炭素原子数２～３５の複素環含有基を表し、Ｑ^４は、五価の炭素原子数２～３５の脂肪族炭化水素基、五価の炭素原子数６～３５の芳香環含有炭化水素基又は五価の炭素原子数２～３５の複素環含有基を表し、Ｑ^５は、六価の炭素原子数２～３５の脂肪族炭化水素基、六価の炭素原子数６～３５の芳香環含有炭化水素基又は六価の炭素原子数２～３５の複素環含有基を表し、Ｑ^２、Ｑ^４、Ｑ^５、Ｑ^６で表される脂肪族炭化水素基中のメチレン基は、－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－又はこれらを組み合わせた基で置き換わっていてもよく、Ｚ^１～Ｚ^６は、それぞれ独立に、上記一般式（３）におけるＺ^１及びＺ^２で表される基と同じである。但し、上記一般式（４）又は（５）で表わされる基はそれぞれ炭素原子数１～３５の範囲内であり、上記一般式（６）又は（７）で表される基はそれぞれ炭素原子数２～３５の範囲内である。）

(In the general formulas (4) to (7), ^Q2 is a carbon atom substituted with R ³⁸ , an aliphatic hydrocarbon group having a trivalent carbon atom number of 1 to 35, and a trivalent carbon atom number of 6 to 35. Represents an aromatic ring-containing hydrocarbon group or a trivalent heterocyclic group having 2 to 35 carbon atoms, and R ³⁸ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an aryl having 6 to 20 carbon atoms. It represents a group or an arylalkyl group having 7 to 20 carbon atoms, and ^Q3 is a carbon atom, an aliphatic hydrocarbon group having 1 to 35 tetravalent carbon atoms, and an aromatic ring having 6 to 35 tetravalent carbon atoms. Represents a hydrocarbon-containing group or a heterocyclic group having a tetravalent carbon atom number of 2 to 35, and ^Q4 is an aliphatic hydrocarbon group having a pentavalent carbon atom number of 2 to 35 and a pentavalent carbon atom number of 6 to 35. Represents 35 aromatic ring-containing hydrocarbon groups or ^pentavalent heterocyclic groups having 2 to 35 carbon atoms, and Q5 is a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms and hexavalent carbon. An aromatic ring-containing hydrocarbon group having 6 to 35 atoms or a heterocyclic ring-containing group having ^hexavalent carbon atoms of 2 to 35, represented by ^Q2 , ^Q4 , ^Q5 , and Q6. The methylene groups in the group may be replaced with -O-, -S-, -CO-, -COO-, -OCO-, -NH- or a combination thereof, and Z ¹ to Z ⁶ are each replaced. Independently, it is the same as the group represented by Z ¹ and Z ² in the above general formula (3). However, the group represented by the above general formula (4) or (5) has 1 to 35 carbon atoms, respectively. It is within the range, and the groups represented by the above general formula (6) or (7) are each within the range of 2 to 35 carbon atoms.)

As the alicyclic, aromatic ring or heterocycle of the 6-membered ring represented by the ring A'in the general formula (1A) to the general formula (1E), those exemplified in the explanation of A in the general formula (1) are used. Can be mentioned.
In the general formulas (1A) to (1E), R ¹¹ to R ¹⁵ are independently hydrogen atoms or groups similar to R ¹ in the general formula (1), and are of R ¹¹ to R ¹⁵ . At least one of them is a group similar to ^R1 . In the present invention, it is particularly preferable that the carbon atom adjacent to the carbon atom substituted with —OR ² has a group similar to that of R ¹ , and above all, a substituent having 4 or more carbon atoms is preferable. -Because the carbon atom adjacent to the carbon atom substituted with OR ² has a bulky substituent, it is excellent in heat resistance and light resistance as a latent antioxidant, and is also excellent in antioxidant effect.

Examples of the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by ^Q1 in the general formula (3) include methane, ethane, propane, iso-propane, butane, sec-butane and tert-butane. , Iso-butane, hexane, 2-methylhexane, 3-methylhexane, heptane, 2-methylheptane, 3-methylheptane, iso-heptane, tert-heptane, 1-methyloctane, iso-octane, tert-octane, Divalent groups in which groups such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, 2,4-dimethylcyclobutane, 4-methylcyclohexane ^are replaced with Z1 and Z2, cyclooctyl, cyclodecanyl, ^1- Adamanthyl, 2-adamantyl, noradamantyl, 2-methyladamantyl, norbornyl, isonorbornyl, perhydronaphthyl, perhydroanthrasenyl, bicyclo [1.1.0] butyl, bicyclo [1.1.1] pentyl, bicyclo [ 2.1.0] pentyl, bicyclo [3.1.0] hexyl, bicyclo [2.1.1] hexyl, bicyclo [2.2.0] hexyl, bicyclo [4.1.0] heptyl, bicyclo [ 3.2.0] heptyl, bicyclo [3.1.1] heptyl, bicyclo [2.2.1] heptyl, bicyclo [5.1.0] octyl, bicyclo [4.2.0] octyl, bicyclo [ 4.1.1] Octyl, Bicyclo [3.3.0] Octyl, Bicyclo [3.2.1] Octyl, Bicyclo [2.2.2] Octyl, Spiro [4,4] Nonanyl, Spiro [4, 5] Divalent groups in which groups such as decanyl, decalin, tricyclodecanyl, tetracyclododecanyl, ^sedrol , and cyclododecanyl ^are substituted with Z1 and Z2, and combinations thereof can be mentioned. The methylene group in the hydrocarbon group may be replaced with -O-, -S-, -CO-, -COO-, -OCO-, -NH- or a group combining these, or a group combining these. Represents, for example, -COO-O-, -COO-S-, -O-OCO-, -S-OCO-, -CO-NH-, -NH-CO-, etc., among which -COO-, It is preferably replaced with -O-, -OCO-, -NHCO-, -NH-, -CONH-, -O-CONH- or -NHCO-O-.
As the aromatic ring-containing hydrocarbon group having a divalent carbon atom number of 6 to 35 represented by ^Q1 , a divalent group in which a group such as phenyl, naphthyl, or biphenyl is substituted with Z ¹ and Z ² is used. Can be mentioned.
Examples of the heterocyclic group having a divalent carbon atom number of 2 to 35 represented by ^Q1 include pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, hexahydrotriazine, furan, tetrahydrofuran, chromane, xanthene and thiophene. , A divalent group in which a group such as thiolan is substituted with Z ¹ and Z ² can be mentioned.
These groups may be further substituted with a halogen atom, a cyano group, a nitro group or an alkoxy group having 1 to 8 carbon atoms.
The alkyl group having 1 to 8 carbon atoms represented by R ³² and R ³³ has a predetermined carbon number among the groups exemplified as the alkyl group having 1 to 40 carbon atoms represented by R ¹ and R ² . The group that satisfies is mentioned.
Examples of the aryl group having 6 to 20 carbon atoms represented by R ³² and R ³³ include the groups exemplified as the aryl group having 6 to 20 carbon atoms represented by R ¹ , R ² and R ⁴ .
Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ³² and R ³³ include the groups exemplified as the aryl alkyl group having 7 to 20 carbon atoms represented by R ¹ , R ² and R ⁴ . Be done.
Further, examples of the halogen atom in which the alkyl group represented by R ³² and R ³³ , the aryl group and the aryl alkyl group may be substituted include the groups exemplified as the halogen atom represented by R ¹ and R ² . ..

In the substituent represented by (3-1) above, the phenyl group represented by ^R34 and the cycloalkyl group having 3 to 10 carbon atoms may be substituted with the alkyl group having 1 to 10 carbon atoms and R. Examples of the alkyl group having 1 to 10 carbon atoms represented by ³⁵ include groups satisfying a predetermined carbon number among the groups exemplified as the alkyl groups having 1 to 40 carbon atoms represented by R ¹ and R ² . Can be mentioned. The phenyl group represented by R ³⁴ and the cycloalkyl group having 3 to 10 carbon atoms may be substituted. The alkoxy group having 1 to 10 carbon atoms and R ³⁵ are represented. Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, s-butyloxy, t-butyloxy, isobutyloxy, pentyloxy, isoamyloxy, t-amyloxy, and hexyloxy. Examples thereof include cyclohexyloxy, cyclohexylmethyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy and the like.
Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by R ³⁴ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohebutyl, cyclooctyl and the like, and the above-mentioned alkyl group or carbon having 1 to 10 carbon atoms. Examples thereof include a group substituted with an alkoxy group having 1 to 10 atoms.
Examples of the alkenyl group having 2 to 10 carbon atoms represented by ^R35 include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-octenyl and the like. ..
The halogen atom represented by R ³⁵ and the halogen atom represented by R ³⁴ and R ³⁵ which may be substituted with the alkyl group, the alkoxy group and the alkenyl group include the halogen atom represented by R ¹ and R ² . Examples are given.
The substitution position of the halogen atom which may substitute the alkyl group, the alkoxy group and the alkenyl group represented by ^R35 is not limited.

Among the substituents represented by (3-3) above, the alkyl groups having 1 to 10 carbon atoms represented by R ³⁶ and R ³⁷ include 1 to 40 carbon atoms represented by R ¹ and R ² . Among the groups exemplified as the alkyl group of the above, a group satisfying a predetermined carbon number and the like can be mentioned.
Examples of the aryl group having 6 to 20 carbon atoms represented by R ³⁶ and R ³⁷ include the groups exemplified as the aryl group having 6 to 20 carbon atoms represented by R ¹ , R ² and R ⁴ . ..
Examples of the aryloxy group having 6 to 20 carbon atoms represented by R ³⁶ and R ³⁷ include phenyloxy, naphthyloxy, 2-methylphenyloxy, 3-methylphenyloxy, 4-methylphenyloxy and 4-vinylphenyl. Dioxy, 3-iso-propylphenyloxy, 4-iso-propylphenyloxy, 4-butylphenyloxy, 4-tert-butylphenyloxy, 4-hexylphenyloxy, 4-cyclohexylphenyloxy, 4-octylphenyl Oxy, 4- (2-ethylhexyl) phenyloxy, 2,3-dimethylphenyloxy, 2,4-dimethylphenyloxy, 2,5-dimethylphenyloxy, 2.6-dimethylphenyloxy, 3.4-dimethylphenyl Oxy, 3.5-Dimethylphenyloxy, 2,4-G-tert-butylphenyloxy, 2,5-G-tert-butylphenyloxy, 2,6-G-tert-butylphenyloxy, 2.4-G-tert- Groups such as pentylphenyloxy, 2,5-tert-amylphenyloxy, 4-cyclohexylphenyloxy, 2,4,5-trimethylphenyloxy, ferrosenyloxy and these groups were substituted with halogen atoms. The foundation is dedicated.
As the arylthio group having 6 to 20 carbon atoms represented by R ³⁶ and R ³⁷ , the oxygen atom of the aryloxy group having 6 to 20 carbon atoms which may be substituted with the halogen atom is replaced with a sulfur atom. The foundation is dedicated.
As the arylalkenyl group having 8 to 20 carbon atoms represented by R ³⁶ and R ³⁷ , the oxygen atom of the aryloxy group having 6-20 carbon atoms which may be substituted with the halogen atom is vinyl, allyl, or the like. Examples thereof include groups substituted with alkenyl groups such as 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl and 2-octenyl.
Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ³⁶ and R ³⁷ include a group exemplified as an aryl alkyl group having 7 to 20 carbon atoms represented by R ¹ , R ² and R ⁴ . Can be mentioned.
Examples of the heterocyclic group having 2 to 20 carbon atoms represented by R ³⁶ and R ³⁷ include pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, hexahydrotriazine, furan, tetrahydrofuran, chroman, xanthene and thiophene. , A group such as thiofuran and a group in which these groups are substituted with a halogen atom and the like can be mentioned.
Examples of the halogen atom in which the alkyl group, aryl group, aryloxy group, arylthio group, arylalkenyl group, arylalkyl group and heterocyclic-containing group represented by R ³⁶ and R ³⁷ may be substituted include R ¹ and R. Examples of the halogen atom represented by ² are the groups exemplified.

An aliphatic hydrocarbon group having a trivalent carbon atom number of 1 to 35 represented by ^Q2 in the general formula (4), an aromatic ring-containing hydrocarbon group having a trivalent carbon atom number of 6 to 35, or a trivalent carbon. As the heterocyclic group having 2 to 35 atoms, the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group, and the heterocyclic ring-containing group exemplified in the explanation of ^Q1 in the above general formula (3) are Z ¹ respectively. , Z ² and Z ³ substituted trivalent groups and the like.
The alkyl group having 1 to 8 carbon atoms, the aryl group having 6 to 20 carbon atoms, or the arylalkyl group having 7 to 20 carbon atoms represented by R ³⁸ is represented by R ³² and R ³³ . Examples thereof include an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a group similar to an arylalkyl group having 7 to 20 carbon atoms.

An aliphatic hydrocarbon group having 1 to 35 tetravalent carbon atoms represented by ^Q3 in the above general formula (5), an aromatic ring-containing hydrocarbon group having 6 to 35 tetravalent carbon atoms, or a tetravalent carbon. As the heterocyclic group having 2 to 35 atoms, the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group, and the heterocyclic ring-containing group exemplified in the explanation of ^Q1 in the above general formula (3) are Z ¹ respectively. , Z ² , Z ³ and Z ⁴ substituted tetravalent groups and the like.

An aliphatic hydrocarbon group having a pentavalent carbon number of 2 to 35 represented by ^Q4 in the general formula (6), an aromatic ring-containing hydrocarbon group having a pentavalent carbon atom number of 6 to 35, or a pentavalent carbon. As the heterocyclic-containing group having 2 to 35 atoms, the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group, and the heterocyclic ring-containing group exemplified in the explanation of ^Q1 in the above general formula (3) are Z ¹ respectively. , Z ² , Z ³ , Z ⁴ and Z ⁵ substituted pentavalent groups and the like.

An aliphatic hydrocarbon group having ⁶ to 35 hexavalent carbon atoms represented by Q5 in the general formula (7), an aromatic ring-containing hydrocarbon group having 6 to 35 hexavalent carbon atoms, or a hexavalent carbon. As the heterocyclic group having 2 to 35 atoms, the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group, and the heterocyclic ring-containing group exemplified in the explanation of X1 in the above general formula (3) are Z ^{1 respectively} . , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ substituted hexavalent groups and the like.

Specific examples of the latent antioxidant preferably used in the present invention include a structure in which the hydrogen of the phenol group of the hindered phenolic antioxidant is replaced with a carbamate-based protecting group such as a t-butoxycarbonyl group. , For example, the following chemical formulas (A) to (C) and the like can be mentioned, but the present invention is not limited thereto.

The method for producing the compound represented by the general formula (1) is not particularly limited, and for example, JP-A-57-11375, JP-A-3-173843, JP-A-6-128195, JP-A-7-206771, JP-A-7- Reaction of a phenolic compound produced by the methods described in 252191 and JP-A-2004-501128 with an acid anhydride, acid acid compound, chloride reagent, alkyl halide compound, silyl chloride compound, allyl ether compound and the like. Can be obtained. Further, a commercially available product may be used.

[Color material]
In the present invention, the coloring material may be any as long as it can develop a desired color when the colored layer of the color filter is formed, and is not particularly limited, and various organic pigments, inorganic pigments, dyes and the like may be used alone or. Two or more kinds can be mixed and used. The dye may be a dispersible dye as well as a dye which is used by dissolving it in a solvent. The dispersible dye is excellent in heat resistance and light resistance when combined with a dispersant described later.

Organic pigments are preferably used because of their 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). .) Examples include those with numbers.

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, and C.I. I. Pigment Yellow 150 derivative pigment;
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 white, 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 iron tetraoxide, or an organic pigment such as cyanine black can be used.

The dispersible dyes include dyes that can be dispersed by adding various substituents to the dyes and insolubilizing them in a solvent, dyes that can be dispersed by using them in combination with a solvent having low solubility, and solvents. 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 10 mg or less, it can be determined that the dye can be dispersed in the solvent (or the mixed solvent).

In the present invention, it is particularly preferable to use the rake coloring material from the viewpoint of improving the luminance and contrast. The rake coloring material can usually be obtained by mixing a dye soluble in a solvent and a rake agent described later in a solvent. As the dye soluble in the solvent, it is preferable to use a dye having a high transmittance from the viewpoint of increasing the brightness of the color filter. The dye may be appropriately selected according to a desired color tone, and may be appropriately selected from azo dyes, metal complex salt azo dyes, anthraquinone dyes, triarylmethane dyes, xanthene dyes, cyanine dyes, indigo dyes, naphthoquinone dyes, etc. It may be a dye having any basic skeleton (coloring site) such as a quinone imine dye, a methine dye, and a phthalocyanine dye. Further, the dye may be a dye classified into any of the following categories, such as an acid dye having an anionic substituent and a basic dye having a cationic substituent.
When forming a blue colored layer, at least one of a triarylmethane dye, a xanthene dye, and a cyanine dye is preferable, and a triarylmethane dye is more preferable, from the viewpoint of increasing the brightness. preferable.

Examples of the acid dye include C.I. I. Acid Violet 29,31,33,34,36,36: 1,39,41,42,43,47,51,63,76,103,118,126, C.I. I. Acid Blue 2,8,14,25,27,35,37,40,41,41: 1,41: 2,43,45,46,47,49,50,51,51,53,54,55, 56, 57, 58, 62, 62: 1,63,64,65,68,69,70,78,79,80,81,96,111,124,127,127: 1,129,137,138, 143,145,150,175,176,183,198,203,204,205,208,215,220,221,225,226,227,230,231,232,233,235,239,245,247, 253,257,258,260,261,264,266,270,271,272,273,274,277,277: 1,278,280,281,228,286,287,288,289,290,291 292,293,294,295,298,301,302,304,305,306,307,313,316,318,322,324,327,331,333,336,339,340,343,344,350, C. I. Anthraquinones such as acid green 10,17,25,25: 1,27,36,37,38,40,41,42,44,54,59,69,71,81,84,95,101,110,117 Acid dyes; C.I. I. Acid Violet 15, 16, 17, 19, 21, 23, 24, 25, 38, 49, 72, C.I. I. Acid Blue 1, 3, 5, 7, 9, 19, 22, 83, 90, 93, 100, 103, 104, 109, C.I. I. Acid greens 3,5,6,7,8,9,11,13,14,15,16,18,22,50,50: 1 etc. Triarylmethane acid dyes; C.I. I. Acid Red 50, 51, 52, 87, 92, 94, 289, 388, C.I. I. Examples thereof include xanthene-based acid dyes such as Acid Violet 9, 30, 102, Sulforhodamine G, Sulforhodamine B, Sulforhodamine 101, and Sulforhodamine 640. Xanthene-based acid dyes include, among others, C.I. I. Acid Red 50, C.I. I. Acid Red 52, C.I. I. Acid Red 289, C.I. I. Acid Violet 9, C.I. I. Acid Violet 30, C.I. I. It is preferably a rhodamine-based acid dye such as Acid Blue 19.
Further, as a commercially available basic dye, for example, C.I. I. Basic Violet 1,3,14, C.I. I. Basic Blue 1,5,7,8,11,26, C.I. I. Triarylmethane basic dyes such as Basic Greens 1 and 4; C.I. I. Basic Yellow 13, C.I. I. Cyanine-based basic dyes such as Basic Red 14; C.I. I. Azo-based basic dyes such as Basic Red 29; C.I. I. Examples thereof include xanthene-based basic dyes such as Basic Violet 11. Triarylmethane-based basic dyes include, among others, C.I. I. Basic blue 1,5,7,8,11,26 is preferable. Further, as the triarylmethane-based basic dye in the present invention, a dye having a cation of a coloring material represented by the general formula (I') described later is also preferable.
These dyes can be used alone or in combination of two or more.

In the lake color material, the counter ion differs depending on the type of the dye, the counter ion of the acid dye is a cation, and the counter ion of the basic dye is an anion. Therefore, the rake agent is appropriately selected and used according to the dye. That is, in the case of insolubilizing the acid dye, a compound that produces a counter cation of the dye is used as a rake agent, and in the case of insolubilizing the basic dye, a counter anion of the dye is generated as a rake agent. Compounds are used.

Examples of the counter cation of the acid dye include ammonium cation, metal cation, inorganic polymer and the like.
As the rake agent that generates ammonium ions, for example, a primary amine compound, a secondary amine compound, a tertiary amine compound and the like are preferable, and among them, the secondary amine compound is excellent in heat resistance and light resistance. It is preferable to use an amine compound or a tertiary amine compound.
Further, the rake agent that generates a metal cation may be appropriately selected from metal salts having a desired metal ion.
The counter cations of acid dyes can be used alone or in combination of two or more.

As the rake color material containing an acid dye, a rake color material containing a xanthene dye is particularly preferable from the viewpoint that high brightness can be achieved.
As the xanthene-based acid dye in the lake coloring material, it is preferable to have a compound represented by the following general formula (II), that is, a rhodamine-based acid dye.

（一般式（ＩＩ）中、Ｒ^Ｉ～Ｒ^ＩＶは、それぞれ独立に、水素原子、アルキル基、アリール基、又はヘテロアリール基を表し、Ｒ^ＩとＲ^ＩＩＩ、Ｒ^ＩＩとＲ^ＩＶが結合して環構造を形成してもよい。Ｒ^Ｖは、酸性基、Ｘは、ハロゲン原子を表す。ｍは０～５の整数を表す。一般式（ＩＩ）は酸性基を１個以上有するものであり、ｎは０以上の整数である。）

(In the general formula (II), ^{RI to RIV independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and RI and R III and R II and R IV are bonded to each} other. A ring structure may be formed. ^RV represents an acidic group, X represents a halogen atom, and m represents an integer of 0 to 5. The general formula (II) has one or more acidic groups. , N is an integer greater than or equal to 0.)

The alkyl group in ^RI to ^RIV is not particularly limited. For example, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent may be mentioned, and among them, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable. , A linear or branched alkyl group having 1 to 5 carbon atoms is more preferable. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group and the like, and examples of the substituted alkyl group include a benzyl group and the like, and further, a substituent and the like. It may have a halogen atom or an acidic group.
The aryl group in ^RI to ^RIV is not particularly limited. For example, an aryl group which may have a substituent having 6 to 20 carbon atoms can be mentioned, and among them, a group having a phenyl group, a naphthyl group and the like is preferable. ^Examples of the heteroaryl group in RI to ^RIV include a heteroaryl group which may have a substituent having 5 to 20 carbon atoms, and the heteroatom preferably contains a nitrogen atom, an oxygen atom, and a sulfur atom. ..
Examples of the substituent that the aryl group or the heteroaryl group may have include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an acidic group, a hydroxyl group, an alkoxy group, a carbamoyl group, a carboxylic acid ester group and the like. ..
In addition, ^{RI to RIV may} be the same or different.

Specific examples of the acidic group or a salt thereof include a carboxy group (-COOH), a carboxylato group (-COO- ⁾ , a carboxylic acid base (-COOM, where M represents a metal atom), and a sulfonate group (-SO). ₃ ⁻ ), sulfo group (-SO ₃ H), sulfonic acid base (-SO ₃ M, where M represents a metal atom) and the like, among which sulfonato group (-SO ₃ ⁻ ), sulfo group It is preferable to have at least one of (-SO ₃ H) or a sulfonic acid base (-SO ₃ M). Examples of the metal atom M include a sodium atom and a potassium atom.

As the compound represented by the general formula (II), acid red 50, acid red 52, acid red 289, acid violet 9, acid violet 30, acid blue 19 and the like are preferable from the viewpoint of increasing the brightness.
Further, from the viewpoint of heat resistance, the compound having a betaine structure having m = 1 and n = 0 in the general formula (II) is preferable.
Further, among them, m = 1 and n = 0, ^{RI and R II are} independently alkyl groups or aryl groups, respectively, and R ^III and R ^IV are independently aryl groups or heteroaryl groups, respectively. It is preferable from the viewpoint that a colored layer having excellent brightness and light resistance can be formed.
The method for producing the compound represented by the general formula (II) is not particularly limited, but can be obtained by referring to, for example, Japanese Patent Application Laid-Open No. 2010-21198.

As the metal lake coloring material of the xanthene acid dye, a material containing a metal atom is used as a lake agent. By using a rake agent containing a metal atom, the heat resistance of the coloring material is increased. As such a rake agent, a rake agent containing a metal atom that becomes a divalent or higher metal cation is preferable.

On the other hand, the counter anion of the basic dye may be an organic anion or an inorganic anion. Examples of the organic anion include organic compounds having an anionic group as a substituent.

Further, a known acid dye may be used as the organic anion. In this case, the rake coloring material has an acid dye and a basic dye as an ion pair.
Examples of the rake agent for generating these organic anions include the above-mentioned alkali metal salts of organic anions and alkaline earth metal salts.

On the other hand, examples of the inorganic anion include an ^oxo acid anion (phosphate ion, sulfate ion, chromic acid ion, tungstate ion (WO _4-2 ), molybdenate ion (MoO _4-2 ), etc.) and a plurality of ^oxo acid anions. Examples thereof include inorganic anions such as polyacid anions condensed with oxometal and mixtures thereof.
The polyacid may be an _isopolyacid anion ( _MmOn ) ^c- or a heteropolyacid anion _{( XlMmOn )} ^c- . In the above ionic formula, M represents a poly atom, X represents a hetero atom, m represents a composition ratio of a poly atom, and n represents a composition ratio of an oxygen atom. Examples of the poly atom M include Mo, W, V, Ti, Nb and the like. Examples of the heteroatom X include Si, P, As, S, Fe, and Co.
Above all, from the viewpoint of heat resistance, a polyacid anion containing at least one of molybdenum (Mo) and tungsten (W) is preferable, and a c-valent polyacid anion containing at least tungsten is more preferable.

Examples of the rake agent that generates an inorganic anion include an alkali salt and an alkali metal salt of the above-mentioned inorganic anion.
The counter anion of the basic dye in the rake coloring material can be used alone or in combination of two or more.
In the present invention, the rake color material is preferably a rake color material composed of a basic dye and an inorganic anion, and more preferably a basic dye and a polyacid anion, from the viewpoint of heat resistance and light resistance. .. In the case of a rake coloring material containing a polyacid anion, the silane coupling agent is susceptible to change over time, but in the present invention, the content ratio of the silane coupling agent is the total solid content in the colored resin composition. On the other hand, since it is 1% by mass or less, the influence of the change with time is small, while the heat resistance and light resistance are high, so that it is particularly preferably used as the rake coloring material of the present application.

In the present invention, the rake coloring material preferably contains a rake coloring material having a triarylmethane-based dye from the viewpoint of improving the brightness of the color filter, and among them, a triarylmethane-based basic dye and a polyacid. It preferably contains an anion.

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 in that 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－は少なくともタングステンを含む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, N may be contained in the carbon chain. B ^c- contains at least tungsten. Represents a c-valent polyacid anion. R ⁱ to R ^v each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ^{i i} . R ⁱⁱ , R ^iv and R ^v may be combined to form a ring structure. Ar ¹ represents a divalent aromatic group which may have a substituent. A plurality of R ⁱ to R ^v and Ar ¹ may be the same or different.
a and c represent integers of 2 or more, and b and d represent integers 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. )

As shown in FIG. 4, the coloring material represented by the general formula (I) contains a divalent or higher anion 202 and a divalent or higher cation 201. Therefore, in the aggregate of the coloring material, the anion is used. It is presumed that the cations do not simply have an ionic bond of one molecule to one molecule, but form a molecular assembly 210 in which a plurality of molecules are associated via an ionic bond 203. Therefore, the apparent molecular weight of the coloring material represented by the general formula (I) is significantly increased as compared with the molecular weight of the conventional rake coloring material. It is presumed that the formation of such molecular aggregates further enhances the cohesive force in the solid state, reduces the thermal motion, suppresses the dissociation of ion pairs and the decomposition of the cation portion, and improves the heat resistance.

A in the general formula (I) is an a-valent organic group in which the carbon atom directly bonded to N (nitrogen atom) does not have a π bond, and the organic group is at least a saturated fat at the terminal directly bonded to N. Represents an aliphatic hydrocarbon group having a group hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group, and O (oxygen atom), S (sulfur atom), N (nitrogen atom) are contained in the carbon chain. It may be. Since the carbon atom directly bonded to N does not have a π bond, the color characteristics such as color tone and transmittance of the cationic color-developing site are not affected by the linking group A and other color-developing sites, and are not affected by the monomer. Similar colors can be retained. From the viewpoint of heat resistance, it is preferable that A does not have a siloxane bond, and more preferably it does not have Si (silicon atom).
In A, an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N is linear, branched or cyclic if the carbon atom at the terminal directly bonded to N does not have a π bond. Any of these may be used, carbon atoms other than the terminal may have an unsaturated bond, or may have a substituent, and the carbon chain contains O, S, and N. May be good. For example, a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group and the like may be contained, and a hydrogen atom may be further substituted with a halogen atom or the like.
Further, in A, the aromatic group having an aliphatic hydrocarbon group is a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at a terminal that is directly bonded to at least N. It may be mentioned and may have a substituent, and may be a heterocycle containing O, S, N.
Above all, from the viewpoint of skeletal robustness, A preferably contains a cyclic aliphatic hydrocarbon group or an aromatic group.
As the cyclic aliphatic hydrocarbon group, the Aribashi alicyclic hydrocarbon group is particularly preferable from the viewpoint of the robustness of the skeleton. The alicyclic hydrocarbon group with a bridge refers to a polycyclic aliphatic hydrocarbon group having a bridging structure in the aliphatic ring and having a polycyclic structure, for example, norbornane, bicyclo [2,2,2]. Examples include octane and adamantane. Among the alicyclic hydrocarbon groups of Arihashi, norbornane is preferable. Examples of the aromatic group include a group containing a benzene ring and a naphthalene ring, and a group containing a benzene ring is preferable. For example, when A is a divalent organic group, a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms or an aromatic group in which two alkylene groups having 1 to 20 carbon atoms such as a xylylene group are substituted is substituted. And so on.

The valence a in the general formula (I) is the number of color-developing cation sites constituting the cation, and a is an integer of 2 or more. In the coloring material of the present invention, since the cation valence a is 2 or more, the heat resistance is excellent. The upper limit of a is not particularly limited, but from the viewpoint of ease of production, a is preferably 4 or less, and more preferably 3 or less.

The alkyl group in R ⁱ to R ^v is not particularly limited. For example, a linear or branched alkyl group having 1 to 20 carbon atoms can be mentioned, and among them, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable, and a direct chain having 1 to 5 carbon atoms is used. A chain or branched alkyl group is more preferable from the viewpoint of brightness and heat resistance. Of these, it is particularly preferable that the alkyl group in ^Ri to R ^v is an ethyl group or a methyl group. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group and the like, and examples of the substituted alkyl group include a benzyl group and the like.
The aryl group in R ⁱ to R ^v is not particularly limited. For example, a phenyl group, a naphthyl group and the like can be mentioned. Examples of the substituent that the aryl group may have include an alkyl group, a halogen atom and the like.
Among them, from the viewpoint of chemical stability, R ⁱ to R ^v are independently bonded to a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ⁱⁱ and R ⁱⁱ , and R ^iv and R ^v . It is preferable to form a pyrrolidine ring, a piperidine ring, and a morpholine ring.

R ⁱ to R ^v can each have the above-mentioned structure independently, but among them, it is preferable that R ⁱ is a hydrogen atom from the viewpoint of color purity, and further, from the viewpoint of ease of production and raw material procurement, R ^{i i} to It is more preferable that all ^Rvs are the same.

The divalent aromatic group in Ar ¹ is not particularly limited. The aromatic group in Ar ¹ can be the same as that listed in the aromatic group in A.
Ar ¹ is preferably an aromatic group having 6 to 20 carbon atoms, and more preferably an aromatic group consisting of a fused polycyclic carbon ring having 10 to 14 carbon atoms. Above all, a phenylene group or a naphthylene group is more preferable because the structure is simple and the raw material is inexpensive.

A plurality of R ⁱ to R ^v and Ar ¹ in one molecule may be the same or different. The desired color can be adjusted by the combination of R ⁱ to R ^v and Ar ¹ .

In the coloring material represented by the general formula (I), the anion portion (B ^c− ) represents a c-valent polyacid anion containing at least tungsten and may contain molybdenum.

As the polyacid anion in the coloring material represented by the general formula (I), the above-mentioned anions can be used alone or in combination of two or more, and when two or more are used in combination, the polyacid anion can be used. The ratio of tungsten to molybdenum as a whole is preferably 90:10 to 100: 0 from the viewpoint of heat resistance and light resistance.

In the general formula (I), b represents the number of cations, d represents the number of anions in the molecular assembly, and b and d represent integers of 1 or more. When b is 2 or more, a plurality of cations in the molecular assembly may be used alone or in combination of two or more. Further, when d is 2 or more, a plurality of anions in the molecular assembly may be used alone or in combination of two or more, and organic anions and inorganic anions may be used in combination. ..

E in the general formula (I) is an integer of 0 or 1. e = 0 represents a triarylmethane skeleton and e = 1 represents a xanthene skeleton. A plurality of e may be the same or different. That is, for example, it may be a cation moiety having only a triarylmethane skeleton or a plurality of xanthene skeletons, or may be a cation moiety containing both a triarylmethane skeleton and a xanthene skeleton in one molecule. From the viewpoint of color purity, it is preferable that the anion portion has only the same skeleton. On the other hand, the color material represented by the general formula (I) can be adjusted to a desired color by forming a cation portion containing both a triarylmethane skeleton and a xanthene skeleton.

In the present invention, it is easy to adjust to a desired color by using a color material represented by the following general formula (I') in which e in the color material represented by the general formula (I) is 0, that is, by using the color material represented by the following general formula (I'). More preferred.

（一般式（Ｉ’）中の各符号は、前記一般式（Ｉ）と同様である。）

(Each reference numeral in the general formula (I') is the same as the general formula (I).)

The method for producing the coloring material represented by the general formula (I) is not particularly limited. For example, it can be obtained by the manufacturing method described in Pamphlet No. 2012/144520.

In the present invention, the coloring material may be used alone or in combination of two or more.
In the present invention, the coloring material includes one or more selected from a rake coloring material having a xanthene skeleton, a rake coloring material having a triarylmethane skeleton, and a dye having a xanthene skeleton from the viewpoint of improving brightness and contrast. It is preferable, and one or more selected from the rake color material represented by the general formula (I), the rake color material containing the xanthene dye, and a combination thereof are particularly preferably used.

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 the coloring layer of the color filter is used, and varies depending on the type of coloring material used. Is preferably in the range of 10 nm or more and 200 nm or less, and more preferably 15 nm or more and 150 nm or less. When the average primary particle size of the coloring material is within the above range, the display device provided with the color filter manufactured by using the coloring 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.

[Photopolymerizable compound]
The photopolymerizable compound used in the photosensitive coloring resin composition of the present invention may be appropriately selected from conventionally known compounds, and is not particularly limited, and is usually a compound having two or more ethylenically unsaturated double bonds. 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, a conventionally known one may be appropriately selected and used. 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. Further, when the photosensitive coloring resin composition for a color filter of the present invention is required to have excellent photocurability (high sensitivity), the polyfunctional monomer 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.

[Initiator]
The initiator used in the photosensitive colored resin composition of the present invention is not particularly limited, and one or a combination of two or more of various conventionally known initiators can be used.

Examples of the initiator include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, α-aminoketones, biimidazoles, N, N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, thioxanthone and the like. Can be done. Specific examples of the initiator include aromatic ketones such as benzophenone, 4,4'-bisdiethylaminobenzophenone and 4-methoxy-4'-dimethylaminobenzophenone, benzoin ethers such as benzoin methyl ether, and benzoin such as ethylbenzoin. , 2- (o-Chlorophenyl) -4,5-phenylimidazole dimer and other biimidazoles, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazol and other halos Methyloxadiazole compound, halomethyl-S-triazine compound such as 2- (4-butoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1, 2-Diphenylethan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanol, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1,1-hydroxy-cyclohexyl-phenylketone, benzyl, benzoyl benzoic acid, methyl benzoyl benzoate, 4-benzoyl-4'-methyldiphenyl sulfide, benzyl methyl ketal, dimethyl aminobenzoate, p-dimethylamino benzoic acid Isoamyl, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 4-benzoyl-methyldiphenylsulfide, 1-hydroxy-cyclohexyl -Phenylketone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphinoxide, 2-methyl-1- [ 4- (Methylthio) phenyl] -2- (4-morpholinyl) -1-propanol and the like can be mentioned.
Among them, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1- Butanone, 4,4'-bis (diethylamino) benzophenone, diethylthioxanthone are preferably used. Furthermore, it is sensitive to combine an α-aminoacetophenone-based initiator such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one with a thioxane-based initiator such as diethylthioxanthone. It is preferable because it suppresses adjustment and water stains and improves development resistance.
When the α-aminoacetophenone-based initiator and the thioxane-based initiator are used, the total content thereof is preferably 5% by mass or more and 15% by mass or less with respect to the total solid content of the photosensitive colored resin composition. When the amount of the initiator is 15% by mass or less, the sublimated product in the manufacturing process is reduced, which is preferable. When the amount of the initiator is 5% by mass or more, the development resistance is improved.

In the present invention, the initiator preferably contains an oxime-based initiator, and more preferably contains an oxime ester-based photoinitiator, from the viewpoint of ensuring a margin for adjusting the line width.
The oxime ester-based photoinitiator preferably has an aromatic ring, and has a condensed ring containing an aromatic ring, from the viewpoint of reducing contamination of the colored resin composition for a color filter by decomposition products and contamination of the apparatus. It is more preferable to have a fused ring containing a benzene ring and a hetero ring.
Examples of the oxime ester-based photoinitiator are described in JP-A-2000-80068, JP-A-2001-233842, JP-A-2010-527339, JP-A-2010-527338, JP-A-2013-041153 and the like. Initiators and the like can be mentioned.

As the oxime ester-based photoinitiator used in the present invention, it is preferable to use an oxime ester-based photoinitiator that generates an aryl radical, particularly a phenyl radical, and further an oxime ester-based photoinitiator that generates an alkyl radical, particularly a methyl radical. It is preferable to use a photoinitiator because of its high sensitivity, small reduction in radical width when combined with a latent antioxidant, and excellent solvent resistance and development resistance. It is presumed that the radical transfer of the alkyl radical is more likely to be activated than that of the phenyl radical. Examples of the oxime ester-based photoinitiator that generates an alkyl radical include etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (o-acetyloxime). (Product name: Irgacure OXE-02, manufactured by BASF), Metanon, [8-[[(Acetyloxy) imino] [2- (2,2,3,3-tetrafluoropropoxy) phenyl] methyl] -11-( 2-Ethylhexyl) -11H-benzo [a] carbazole-5-yl]-, (2,4,6-trimethylphenyl) (trade name: Irgacure OXE-03, manufactured by BASF), Etanone, 1- [9-ethyl -6- (1,3-dioxolane, 4- (2-methoxyphenoxy) -9H-carbazole-3-yl]-, 1- (o-acetyloxime) (trade name: ADEKA OPT-N-1919, manufactured by ADEKA) ), Metanon, (9-ethyl-6-nitro-9H-carbazole-3-yl) [4- (2-methoxy-1-methylethoxy-2-methylphenyl]-, o-acetyloxime (trade name: Adecaarc) Luz NCI-831, manufactured by ADEKA), 1-Propanone, 3-Cyclopentyl-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (o-acetyl) Oxime) (trade name TR-PBG-304, manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.), 1-Propanone, 3-Cyclopentyl-1- [2- (2-pyrimidinylthio) -9H-carbazole-3-yl]-, 1- (o-Acetyloxyme) (trade name TR-PBG-314, manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), Etanone, 2-cyclohexyl-1- [2- (2-pyrimidinyloxy) -9H-carbazole-3-3 Il]-, 1- (o-Acetyloxyme) (trade name TR-PBG-326, manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), Etanone, 2-cyclohexyl-1- [2- (2-pyrimidinylthio) -9H- Carbazole-3-yl]-, 1- (o-acetyloxime) (trade name TR-PBG-331, manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), 1-octanone, 1- [4- [3- [1- [1] (Acetyloxy) imino] ethyl] -6- [4-[(4,6-dimethyl-2-pyrimidinyl) thio] -2-methylbenzoyl] -9H-carbazole-9-yl] phenyl]-, 1-( o-Acetyloxime) (trade name: EXTA-9, manufactured by Union Chemical); In addition, a diphenylsulfide skeleton Examples of the oxime ester-based photoinitiator to have include ADEKA ARCLUS NCI-930 (manufactured by ADEKA) and TR-PBG-3057 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.).
Specific examples of the initiator that generate a phenyl radical include Irgacure OXE-01 (manufactured by BASF).

As the oxime ester photoinitiator, it is preferable to use an oxime ester-based photoinitiator having a diphenylsulfide skeleton because the brightness is improved as compared with the case of having a carbazole skeleton.
Further, it is preferable to include at least two kinds of oxime-based initiators from the viewpoint of improving the sensitivity. Further, it is preferable to include at least two kinds of oxime-based initiators in terms of improving the development resistance and enhancing the effect of suppressing the generation of water stains. It is presumed that when at least two kinds of oxime-based initiators are contained, the wavelengths absorbed by each initiator are different, so that the light at the time of exposure can be effectively used at each absorption wavelength.
In addition, water stain means that when a component that enhances alkaline developability is used, traces of water stain are generated after alkaline development and rinsing with pure water. Such water stains disappear after post-baking, so there is no problem as a product, but there is a problem that it is detected as unevenness abnormality in the visual inspection of the patterning surface after development, and it is not possible to distinguish between normal products and abnormal products. Occurs. Therefore, if the inspection sensitivity of the inspection device is lowered in the visual inspection, the yield of the final color filter product is lowered as a result, which becomes a problem.

Further, it is preferable to use a photoinitiator having a tertiary amine structure in combination with the oxime ester-based photoinitiator from the viewpoint of improving sensitivity. Since the photoinitiator having a tertiary amine structure has a tertiary amine structure which is an oxygen quencher in the molecule, the radicals generated from the initiator are not easily deactivated by oxygen, and the sensitivity can be improved. be. Examples of commercially available photoinitiators having a tertiary amine structure include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (for example, Irgacure 907, manufactured by BASF). 2-Benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (eg, Irgacure 369, manufactured by BASF), 4,4'-bis (diethylamino) benzophenone (eg, Hycure ABP, etc.) Kawaguchi Pharmaceutical Co., Ltd.).

Further, from the viewpoint of easy adjustment of the sensitivity, it is preferable to combine the oxime ester-based photoinitiator with the α-aminoalkylphenone-based initiator, among which the alkyl radical-based oxime ester compound and the α-aminoalkylphenone are preferable. It is more preferable to combine it with a system initiator.

[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-based solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; Ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, Ester solvents such as ethyl lactate and cyclohexanol acetate; 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 solvent such as dimethyl ether; aprotonic amide solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; lactone solvent such as γ-butyrolactone; cyclic ether solvent such as tetrahydrofuran Saturated 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 solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents are preferably used in terms of the 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 present invention, from the viewpoint of solubility of other components and application suitability, propylene glycol monomethyl ether acetate is contained, and further, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, 3-methoxy-3 methyl-1-butanol are contained. , 3-methoxy-3-methyl-1-butyl acetate, and propylene glycol monomethyl ether acetate. It is preferable to use a mixed solvent containing at least one selected from these. The content ratio of propylene glycol monomethyl ether acetate in the mixed solvent is preferably 70% by mass or more and 99% by mass or less, and more preferably 80% by mass or more and 99% by mass or less with respect to the total amount of the solvent.

[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. Further, the dispersant may be used alone or in combination of two or more. As the dispersant, for example, a cationic, anionic, nonionic, amphoteric, silicone-based, or fluorine-based surfactant can be used. Among the surfactants, the polymer dispersant is preferable because it can be dispersed uniformly and finely.

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; polysiloxanes Classes; long-chain polyaminoamide phosphates; polyethylene imine derivatives (amides obtained by the reaction of poly (lower alkylene imine) with free carboxy group-containing polyesters and their bases); polyallylamine derivatives (polyallylamine and free carboxy). Examples thereof include reaction products obtained by reacting one or more compounds selected from three kinds of compounds of a polyester having a group, a polyamide, or a cocondensate of an ester and an amide (polyester amide).

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 because the coloring material can be suitably 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 at the time of forming a coating film, and improves brightness and contrast.
The repeating unit having a tertiary amine is a site having an affinity with the coloring material. Polymers containing repeating units with tertiary amines usually contain repeating units that serve as sites that have an affinity for the solvent. As the 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 constitute the 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 is a repeating unit (a) represented by the following general formula (2) because the main chain skeleton is difficult to thermally decompose and has high heat resistance. ) Is more preferable.

（一般式（２）中、Ｒ^４１は、水素原子又はメチル基、Ｌは、２価の連結基、Ｒ^４２は、炭素数１～８のアルキレン基、－［ＣＨ（Ｒ^４５）－ＣＨ（Ｒ^４６）－Ｏ］_ｘ－ＣＨ（Ｒ^４５）－ＣＨ（Ｒ^４６）－又は－［（ＣＨ_２）_ｙ－Ｏ］_ｚ－（ＣＨ_２）_ｙ－で示される２価の有機基、Ｒ^４３及びＲ^４４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^４３及びＲ^４４が互いに結合して環状構造を形成する。Ｒ^４５及びＲ^４６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 (2), R ⁴¹ is a hydrogen atom or a methyl group, L is a divalent linking group, R ⁴² is an alkylene group having 1 to 8 carbon atoms, and-[CH (R ⁴⁵ ) -CH ( R ⁴⁶ ) -O] _x -CH (R ⁴⁵ ) -CH (R ⁴⁶ )-or-[(CH ₂ ) _y -O] _z- (CH ₂ ) _y- , a divalent organic group represented by R ⁴³ . And R ⁴⁴ each independently represent a chain or cyclic hydrocarbon group which may be substituted, or R ⁴³ and R ^{44 combine} with each other to form a ^cyclic structure. 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 L of the general formula (2) 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, L is -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 ⁴² of the above general formula (2) is an alkylene group having 1 to 8 carbon atoms,-[CH (R ⁴⁵ ) -CH (R ⁴⁶ ) -O] _x -CH (R ⁴⁵ ) -CH. (R ⁴⁶ )-or-[(CH ₂ ) _y -O] _z- (CH ₂ ) _y- . The alkylene group having 1 to 8 carbon atoms may be linear or branched.
R ⁴⁵ and R ⁴⁶ are independently hydrogen atoms or methyl groups, respectively.
The R ⁴² is preferably an alkylene group having 1 to 8 carbon atoms from the viewpoint of dispersibility, and more preferably R ⁴² is a methylene group, an ethylene group, a propylene group or a butylene group, and a methylene group and an ethylene group. Groups are more preferred.

Examples of the cyclic structure formed by bonding R ⁴³ and R ⁴⁴ of the above general formula (2) 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 is preferably one having no aromaticity, and more preferably a saturated ring.

The repeating unit represented by the general formula (2) is an alkyl group-substituted amino such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and diethylaminopropyl (meth) acrylate. Examples thereof include group-containing (meth) acrylate, dimethylaminoethyl (meth) acrylamide, alkyl group-substituted amino group-containing (meth) acrylamide such as dimethylaminopropyl (meth) acrylamide, and the like. Of these, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylamide can be preferably used in terms of improving dispersibility and dispersion stability.

In the block portion composed of the repeating unit having the tertiary amine, it is preferable that three or more structural units represented by the general formula (2) 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 consisting of a repeating unit having a tertiary amine (hereinafter, may be referred to as A block) and a block portion having a solvent-affinitive block portion (hereinafter, may be referred to as B block). The block portion having the solvent affinity in the polymer does not have the structural unit represented by the general formula (2) from the viewpoint of improving the solvent affinity and improving the dispersibility, and the general formula ( It has a solvent-affinity block portion having a structural unit copolymerizable with 2). In the present invention, the arrangement of each block of the block copolymer is not particularly limited, and for example, an AB block copolymer, an ABA block copolymer, a BAB block copolymer, or the like can be used. Of these, AB block copolymers or ABA block copolymers are preferable because they are excellent in dispersibility.
As the structural unit that can be copolymerized with the general formula (2), the structural unit represented by the following general formula (8) is described from the viewpoint of improving the dispersibility and dispersion stability of the coloring material while also improving the heat resistance. Is preferable.

（一般式（８）中、Ｒ^４７は、水素原子又はメチル基、Ａは、直接結合又は２価の連結基、Ｒ^４８は、炭素数１～１８のアルキル基、炭素数２～１８のアルケニル基、アラルキル基、アリール基、－［ＣＨ（Ｒ^４９）－ＣＨ（Ｒ^５０）－Ｏ］_ｘ－Ｒ^５１又は－［（ＣＨ_２）_ｙ－Ｏ］_ｚ－Ｒ^５１で示される１価の基である。Ｒ^４９及びＲ^５０は、それぞれ独立に水素原子又はメチル基であり、Ｒ^５１は、水素原子、あるいは炭素数１～１８のアルキル基、炭素数２～１８のアルケニル基、アラルキル基、アリール基、－ＣＨＯ、－ＣＨ_２ＣＨＯ、又は－ＣＨ_２ＣＯＯＲ^５２で示される１価の基であり、Ｒ^５２は水素原子又は炭素数１～５の直鎖状、分岐状、又は環状のアルキル基である。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 (8), R ⁴⁷ is a hydrogen atom or a methyl group, A is a direct bond or a divalent linking group, R ⁴⁸ is an alkyl group having 1 to 18 carbon atoms, and an alkenyl having 2 to 18 carbon atoms. Group, aralkyl group, aryl group, monovalent group represented by-[CH (R ⁴⁹ ) -CH (R ⁵⁰ ) -O] _x -R ⁵¹ or-[(CH ₂ ) _y -O] _z -R ⁵¹ . R ⁴⁹ and R ⁵⁰ are independent hydrogen atoms or methyl groups, respectively, and R ⁵¹ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, and the like. It is a monovalent group represented by an aryl group, -CHO, -CH ₂ CHO, or -CH ₂ COOR ⁵² , and R ⁵² is a hydrogen atom or a linear, branched, or cyclic alkyl having 1 to 5 carbon atoms. The group. X is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18.

The divalent linking group A of the general formula (8) can be the same as L in the general formula (2), and the heat resistance of the obtained polymer and propylene glycol preferably used as a solvent can be used. A is preferably a -COO- group because of its solubility in monomethyl ether acetate (PGMEA) and its relatively inexpensive material.

In R ⁴⁸ , the alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic.
Of these, R ⁴⁸ is preferably a methyl group, various butyl groups, various hexyl groups, a benzyl group, a cyclohexyl group, and a hydroxyethyl group from the viewpoint of dispersibility and substrate adhesion.

Examples of the aryl group which may have a substituent include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xsilyl group and the like. The aryl group preferably has 6 to 24 carbon atoms, and more preferably 6 to 12 carbon atoms.
Examples of the aralkyl group which may have a substituent include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like. The carbon number of the aralkyl group is preferably 7 to 20, and more preferably 7 to 14.
Examples of the substituent of the aromatic ring such as the aryl group and the aralkyl group include a linear and branched alkyl groups having 1 to 4 carbon atoms, an alkenyl group, a nitro group, a halogen atom and the like.

Further, the R ⁵¹ may have a hydrogen atom or a substituent, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -CHO and -CH ₂ CHO. , Or -CH ₂ COOR ⁵² is a monovalent group, and R ⁵² is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms.
In the monovalent group represented by R ⁵¹ , examples of the substituent that may be possessed include a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, and a halogen atom such as F, Cl, Br. And so on.
Of the R ⁵¹ , the alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 18 carbon atoms, the aralkyl group, and the aryl group are as shown in R ⁴⁸ .
In the above R ⁴⁸ , x, y and z are the same as R ⁴² in the general formula (2).

The number of the structural units constituting the solvent-affinitive block portion may be appropriately adjusted within the range in which the dispersibility of the coloring material is improved. Above all, the number of constituent units constituting the solvent-affinitive block portion is 10 or more and 200 or less 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 or more and 100 or less, and further preferably 10 or more and 70 or less.

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.
In the block copolymer used as the dispersant of the present invention, the ratio of the number of units m of the structural unit represented by the general formula (2) to the number n of the other structural units constituting the solvent-friendly block portion. The m / n is preferably in the range of 0.01 or more and 1 or less, and in the range of 0.05 or more and 0.7 or less, from the viewpoint of dispersibility and dispersion stability of the coloring material. preferable.

Further, among them, in the present invention, the dispersant is a polymer containing the structure represented by the general formula (2) 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. 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, from the viewpoint of dispersibility and dispersion stability. 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 the effect 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. Further, the acid value of the dispersant used in the present invention is 18 mgKOH / g or less as the upper limit of the acid value of the dispersant from the viewpoint of preventing deterioration of development adhesion and solvent resolubility. preferable. Above all, the acid value of the dispersant is more preferably 16 mgKOH / g or less, further preferably 14 mgKOH / g or less, and even more preferably 12 mgKOH / g, from the viewpoint of improving development adhesion and solvent resolubility. It is particularly preferable that it is g or less.
In the dispersant used in the present invention, the acid value of the block copolymer before salt formation is preferably 1 mgKOH / g or more, and more preferably 2 mgKOH / g or more. This is because the effect of suppressing the development residue is improved. The upper limit of the acid value of the block copolymer before salt formation is preferably 18 mgKOH / g or less, more preferably 16 mgKOH / g or less, and even more preferably 14 mgKOH / g or less. , 12 mgKOH / g or less is particularly preferable. 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 and glass transition temperature, the development adhesion is improved. It is presumed that if the acid value is too high, the developability is excellent, but the polarity is too high and peeling is likely to occur during development.

From the above, in the present invention, the dispersant is a polymer containing the structure represented by the general formula (2) and having an amine value of 40 mgKOH / g or more and 120 mgKOH / g or less, and has an acid value of 40 mgKOH / g or more. When the glass transition temperature is 30 ° C. or higher at 1 mgKOH / g or more and 18 mgKOH / g or less, the colorant dispersion stability is excellent, the contrast is improved, and the generation of development residue is suppressed when the colored resin composition is prepared. However, it is preferable because it has excellent solvent resolubility and high development adhesion.

As the carboxy group-containing monomer, a monomer copolymerizable with a monomer having a structural unit represented by the general formula (2) and containing an unsaturated double bond and a carboxy group can be used. Examples of such a monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer and the like. 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 acid anhydride group-containing monomer such as maleic anhydride, itaconic anhydride, and citraconic anhydride may be used. Among them, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, glass transition temperature and the like.

In the block copolymer before salt formation, the content ratio of the structural unit derived from the carboxy group-containing monomer may be appropriately set so that the acid value of the block copolymer is within the range of the specific acid value, and in particular. Although not limited, it is preferably 0.05% by mass or more and 4.5% by mass or less, and 0.07% by mass or more and 3.7% by mass or less, based on the total mass of all the constituent units of the block copolymer. It is more preferable to have.
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. It can prevent deterioration.
The structural unit derived from the carboxy group-containing monomer may have the above-mentioned specific acid value, may be composed of one kind, or may contain two or more kinds 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 is within the range of 0.05 or more and 1.5 or less. It is preferable, and it is more preferable that it is in the range of 0.1 or more and 1.0 or less 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 or more and 20000 or less, and preferably 2000 or more and 15000 or less, from the viewpoint of improving the dispersibility and dispersion stability of the coloring material. It is more preferable, and more preferably 3000 or more and 12000 or less.
Here, the weight average molecular weight (Mw) is determined by gel permeation chromatography (GPC) as a standard polystyrene-equivalent value. 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.

The method for producing the block copolymer is not particularly limited. The block copolymer can be produced by a known method, but it is particularly preferable to produce the block copolymer by the living polymerization method.

As a specific example of a block copolymer having a block portion composed of a repeating unit having such 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 the above is preferably 15 parts by mass or more and 300 parts by mass or less, and more preferably 20 parts by mass or more and 250 parts by mass or less. 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 present. 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).
Above all, 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. As a specific example of the organic acid compound used for such a dispersant, for example, the organic acid compound described in JP-A-2012-236882 can be mentioned as a suitable one.
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.

[Alkali-soluble resin]
The alkali-soluble resin in the present invention has an acidic group, can act as a binder resin, and can be appropriately selected and used from those that are soluble in the alkaline developer used for pattern formation. It can be used alone or in combination of two or more.
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, 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. Further, 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, and citraconic anhydride may be used. Of these, (meth) acrylic acid is particularly preferable in terms of copolymerizability, cost, solubility, glass transition temperature, and the like.

The alkali-soluble resin preferably has a hydrocarbon ring from the viewpoint of excellent heat resistance and light resistance of the colored layer. It was found that the solvent resistance, heat resistance and light resistance of the obtained colored layer are improved by using an alkali-soluble resin having a hydrocarbon ring, and in particular, the swelling of the colored layer is suppressed. 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, an amide group and the like. Above all, when the 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 the hydrocarbon ring include aliphatic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, tricyclo [5.2.1.0 (2,6)] decane (dicyclopentane), and adamantan. 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 (9). Be done.

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 (9) is contained, it is particularly preferable because the curability of the colored layer is improved and the solvent resistance (suppression of NMP swelling) is improved.

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 increase the amount of the structural unit having the hydrocarbon ring to improve the function of the structural unit.
The acrylic copolymer having the 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 a latent antioxidant include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl. Examples thereof include (meth) acrylate, phenoxyethyl (meth) acrylate, and styrene, which have excellent heat resistance and light resistance. Therefore, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, and benzyl. (Meta) acrylate and styrene are preferable.

The alkali-soluble resin used in the present invention also preferably has an ethylenic double bond in the side chain. When it has an ethylenically double bond, the alkali-soluble resins or the alkali-soluble resin and the polyfunctional monomer may form a cross-linking bond in the curing step of the resin composition at the time of producing a color filter.
The method for introducing an ethylenic double bond into the alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a method of adding a compound having both an epoxy group and an ethylenic double bond in the molecule, for example, glycidyl (meth) acrylate, to the carboxy group of the alkali-soluble resin, and introducing 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 colored resin composition for a color filter, 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 having a structural unit having a carboxy group and a structural unit having a hydrocarbon ring, and a styrene-acrylic copolymer. 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, 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, from the viewpoint of suppressing the film roughness of the pattern surface after development. It is more preferable to have.
When the ratio of the carboxy group-containing ethylenically unsaturated monomer is 5% by mass or more, the solubility of the obtained coating film in an alkaline developer is sufficient. Further, when the ratio of the carboxy group-containing ethylenically unsaturated monomer is 50% by mass or less, it is possible to suppress the formed pattern from falling off from the substrate and the film surface roughness of the pattern 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 bond are used. The compound having a bond is preferably 10% by mass or more and 95% by mass or less, and more preferably 15% by mass or more and 90% by mass or less, based on the charged amount of the carboxy group-containing ethylenically unsaturated monomer.

The preferred weight average molecular weight (Mw) of the carboxy group-containing copolymer is preferably in the range of 1,000 or more and 50,000 or less, and more preferably 3,000 or more and 20,000 or less. When the weight average molecular weight (Mw) is 1,000 or more, the binder function after curing is excellent, and when it is 50,000 or less, pattern formation becomes easy 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 material 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.

When the side chain of the alkali-soluble resin has an ethylenically unsaturated group, the ethylenically unsaturated bond equivalent is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 or more and 1500 or less. 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 other structural units such as the structural unit having a carboxy group and the structural unit having a hydrocarbon ring can be relatively increased, so that the developability and heat resistance are excellent. There is.
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, for example, by measuring the number of ethylenically double bonds contained in 1 g of an alkali-soluble resin in accordance with the test method for iodine value as described in JIS K 0070: 1992. It may be calculated.

[Antioxidant]
The photosensitive colored resin composition of the present invention preferably further contains an antioxidant. By combining the latent antioxidant represented by the general formula (1) and a known antioxidant, the potential antioxidant is particularly excellent in light resistance as compared with the case of using the latent antioxidant alone, and it is exposed to ultraviolet rays. It is possible to suppress the decrease in the brightness of the colored layer, and the antioxidant and the latent antioxidant sequentially develop the antioxidant function, thereby suppressing the fading of the coloring material and the like in the entire process of manufacturing the color filter. be able to.

The antioxidant can be appropriately selected and used from conventionally known ones. The antioxidant may be used alone or in combination of two or more. Specific examples of the antioxidant include hindered phenolic antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like, and have heat resistance. From this point of view, it is preferable to use a hindered phenolic antioxidant.

A hindered phenol-based antioxidant is a structure containing at least one phenol structure in which a substituent having 4 or more carbon atoms is substituted at at least one of the 2- and 6-positions of the hydroxyl group of the phenol structure. It means an antioxidant having.
Specific examples of the hindered phenolic antioxidant include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1010, manufactured by BASF). , 1,3,5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris (4-hydroxy- 3,5-Di-tert-butylbenzyl) Mesitylen (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] ( Product name: Irganox 1035, manufactured by BASF), 1,2-bis [3- (4-hydroxy-3,5-di-tert-butylphenyl) propionyl] hydrazine (trade name: Irganox MD1024, manufactured by BASF), Octyl 3- (4-hydroxy-3,5-diisopropylphenyl) propionate (trade name: Irganox 1135, manufactured by BASF), 4,6-bis (octylthiomethyl) -o-cresol (trade name: Irganox 1520L) , BASF), N, N'-hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanamide] (trade name: Irganox 1098, manufactured by BASF), 1,6 -Hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 259, manufactured by BASF), 1-dimethyl-2-[(3-t-butyl) -4-Hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5.5] undecane (trade name: ADK STAB AO-80, manufactured by 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-dimethyl) Ethyl) -3-hydroxy-2,6-dimethylphenyl] methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -to Rion (trade name: Irganox 1790, manufactured by BASF), 2,2'-methylenebis (6-tert-butyl-4-methylphenol) (trade name: Sumilyzer MDP-S, manufactured by Sumitomo Chemical), 6,6'- Thiobis (2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl (trade name: Irgamod 195, BASF) (Manufactured by), 2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl acrylate (trade name: Sumilyzer GM, manufactured by Sumitomo Chemical), 4,4' -Ciobis (6-tert-butyl-m-cresol) (trade name: Sumilyzer WX-R, manufactured by Sumitomo Chemical Co., Ltd.) and the like can be mentioned. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

[Arbitrary additive component]
The photosensitive colored resin composition of the present invention 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.

<Mixing ratio of each component of the photosensitive colored resin composition>
In the photosensitive colored resin composition of the present invention, the blending ratio of each component is not particularly limited, and it can be appropriately prepared according to the intended use and the like as long as the effect of the present invention is not impaired.
The content ratio of the coloring material may be appropriately adjusted according to the desired color, but from the viewpoint of increasing the brightness, it is 10% by mass or more with respect to the total solid content of the photosensitive coloring resin composition. It is preferably 60% by mass or less, and more preferably 12% by mass or more and 50% by mass or less.
In the present invention, the solid content represents all components other than the solvent constituting the photosensitive colored resin composition, and for example, even a liquid photopolymerizable compound is included in the solid content.

The content ratio of the photopolymerizable compound is preferably 5% by mass or more and 60% by mass or less, and more preferably 10% by mass or more and 40% by mass or less, based on the total solid content of the photosensitive colored resin composition. preferable. If the content of the photopolymerizable compound is less than the above lower limit, photocuring may not proceed sufficiently and the exposed part may elute during development, and if the content of the photopolymerizable compound is more than the above upper limit, it is alkaline. Developability may decrease.

The content ratio of the initiator is preferably 1% by mass or more and 40% by mass or less, and more preferably 3% by mass or more and 30% by mass or less, based on the total solid content of the photosensitive colored resin composition. When the amount of the initiator is less than the above upper limit value, the pattern does not become too thick with respect to the mask opening, which is preferable. When the amount of the initiator is equal to or higher than the above lower limit, the solvent resistance is good.
Further, when at least two kinds of oxime-based initiators are contained as the initiator, the total content of the two or more kinds of oxime-based initiators is 0.1% by mass or more with respect to the total solid content of the photosensitive colored resin composition. It is preferably 12.0% by mass or less, more preferably 1.0% by mass or more and 8.0% by mass or less, from the viewpoint of sufficiently exerting the combined effect of these initiators.

The content ratio of the latent antioxidant represented by the general formula (1) is that a photosensitive colored resin composition capable of forming a high-luminance colored layer and suppressing a change in line width can be obtained. Therefore, it is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.1% by mass or more and 8% by mass or less with respect to the total solid content of the photosensitive colored resin composition.

When an alkali-soluble resin is used, the content ratio is preferably 5% by mass or more and 60% by mass or less, preferably 5% by mass or more and 50% by mass or less, based on the total solid content of the photosensitive colored resin composition from the viewpoint of developability. The following is more preferable, and 10% by mass or more and 40% by mass or less is even more preferable.
When the content of the alkali-soluble resin is at least the above lower limit, sufficient alkali developability can be obtained, and when the content of the alkali-soluble resin is at least the above upper limit, film roughness and pattern chipping occur during development. Can be suppressed.

The content when the dispersant is used is not particularly limited as long as it can uniformly disperse the coloring material, 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% by mass or more and 40% by mass or less. Further, it is preferably blended in an amount of 2% by mass or more and 30% by mass or less, and particularly preferably 3% by mass or more and 25% by mass or less, based on the total solid content of the photosensitive colored resin composition. When it is at least the above lower limit, 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 forming a colored layer having a high concentration of coloring material, the content of the dispersant is 2% by mass or more and 25% by mass or less, more preferably 3% by mass, based on the total solid content of the photosensitive coloring resin composition. It is preferable to mix in a proportion of% or more and 20% by mass or less.

Further, when a non-latent antioxidant is used in combination, the content ratio of the antioxidant is a photosensitive coloring resin capable of forming a high-brightness coloring layer and suppressing a change in line width. From the viewpoint of obtaining a composition, it is preferably 0.1% by mass or more and 10% by mass or less, and 0.1% by mass or more and 8% by mass or less, based on the total solid content of the photosensitive colored resin composition. It is more preferable, and it is even more preferable that it is 0.1% by mass or more and 5.0% by mass or less. If it is at least the above lower limit value, the combined effect is likely to be exhibited. On the other hand, if it is not more than the above upper limit value, a highly sensitive photosensitive resin composition can be obtained.
The content ratio of the latent antioxidant represented by the general formula (1) and the antioxidant is such that a high-brightness colored layer can be easily formed while suppressing a change in line width. It is preferably 0.1 part by mass or more and 10 parts by mass or less, and further 0.1 part by mass or more and 5.0 parts by mass or less with respect to 1 part by mass of the latent antioxidant represented by 1). Is preferable.

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 or more and 95% by mass or less with respect to the total amount of the photosensitive coloring resin composition for a color filter containing the solvent, and in particular, the range of 65% by mass or more and 88% by mass or less. It is more preferable to be inside. When the content of the solvent is within the above range, the coating property can be made excellent.

<Manufacturing method of photosensitive colored resin composition>
The method for producing a photosensitive colored resin composition of the present invention contains at least a coloring material, a photopolymerizable compound, an initiator, a latent antioxidant, and a solvent, and more preferably a dispersant. Can be prepared by mixing using a well-known mixing means as long as it contains an antioxidant and preferably an alkali-soluble resin and the coloring material can be uniformly dispersed or dissolved in the solvent. ..
As a method for preparing the resin composition, for example, (1) first, a coloring material and, if necessary, a dispersant are added to a solvent to prepare a coloring material dispersion liquid, and photopolymerization is performed on the dispersion liquid. A method of mixing a sex compound, an initiator, a latent antioxidant, and a biweekly additive component used as desired; (2) a coloring material, a photopolymerizable compound, an initiator, and potential in a solvent. Examples thereof include a method in which an antioxidant is added at the same time and mixed.
Among these methods, the method (1) is preferable because it can effectively prevent the agglomeration of the coloring material and disperse it uniformly.

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

Examples of the disperser for performing the dispersion treatment include a roll mill such as a two-roll and three-roll mill, a ball mill such as a ball mill and a vibrating ball mill, a paint conditioner, a continuous disc type bead mill, and a bead mill such as a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter used is preferably 0.03 mm or more and 2.00 mm or less, and more preferably 0.10 mm or more and 1.0 mm or less.

Specifically, pre-dispersion may be performed with 2 mm zirconia beads having a relatively large bead diameter, and then main dispersion may be performed with 0.1 mm zirconia beads having a relatively small bead diameter. Further, after dispersion, it is preferable to filter with a membrane filter of 0.5 μm or more and 2 μm or less.

2. 2. 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 has a photosensitive colored resin composition according to the present invention. It is a hardened product.
The method for manufacturing a color filter according to the present invention is a method for manufacturing a color filter including at least a substrate and a colored layer provided on the substrate.
It has a step of forming at least one of the colored layers by using the photosensitive colored resin composition 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 a colored layer made of a 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, the viscosity, etc. of the photosensitive coloring resin composition for a color filter, but is usually in the range of 1 μm or more and 5 μm or less. preferable.

The colored layer can be formed, for example, by the following method.
First, the above-mentioned photosensitive coloring resin composition of the present invention is applied onto a substrate to be 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 spin coating method and the die coating 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 the alkali-soluble resin, the polyfunctional monomer, or the like is subjected to a photopolymerization reaction to be cured. Use as a coating. Examples of the light source used for exposure include ultraviolet rays such as low-pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps, electron beams, and the like. 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. The heating conditions are appropriately selected depending on the mixing ratio of each component in the photosensitive colored resin composition to be used, the thickness of the coating film, and the like.

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 obtained by dissolving an alkali in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to this alkaline solution. Further, a general method can be adopted as the developing method.
After the development treatment, usually, the developer is washed and the cured coating film of the photosensitive coloring resin composition is dried to form a colored layer. After the development treatment, a heat treatment may be performed in order to sufficiently cure the coating film. The heating conditions are not particularly limited and may be appropriately selected depending on the intended use of the coating film.

(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 stripe 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. In the case of a resin layer containing light-shielding particles, a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, etc. be.

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 or a silicon substrate described later, or a substrate on which an aluminum, silver, silver / copper / palladium alloy thin film or the like is formed is 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 in the color filter of the present invention may be any base material 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 flexible glass. The material is mentioned.
The thickness of the transparent substrate is not particularly limited, but for example, one having a thickness 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 substrate, the light-shielding portion, and the 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.

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

[Liquid crystal display device]
The liquid crystal display device is characterized by 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 facing substrate 20 having a TFT array substrate and the like, and the color filter 10 and the facing 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 method of the liquid crystal display device of the present invention is not particularly limited, and a drive method generally used for a liquid crystal display device can be adopted. 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 suitably used.
Further, as the facing substrate, it can be appropriately selected and used according to the drive method and the like of the liquid crystal display device of the present invention.
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 has a color filter 10 and an organic light emitting body 80. An organic protective layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the organic illuminant 80.

As a method of laminating the organic illuminant 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 a color filter. Examples thereof include a method and a method in which an organic light emitter 80 formed on another substrate is bonded onto an 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 way 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. In the following synthesis and preparation, the operation was repeated as necessary to obtain a desired amount.
In the following Examples 1, 2, 7, 8 , 10, 11, 12 , 13, 14 , 15 , 16, 18, 20 , 21 , 22 , 23 will be referred to as reference examples.

(Synthesis of color material A)
(1) Synthesis of Intermediate 1 1-iodonaphthalene manufactured by Wako Pure Chemical Industries, Ltd. 15.2 g (60 mmol), norbornane diamine (NBDA) manufactured by Mitsui Chemicals, Inc. (CAS No. 56602-77-8) 4.
63 g (30 mmol), sodium-tert-butoxide 8.07 g (84 mmol), manufactured by Aldrich 2-dicyclohexylphosphino-2', 6', -dimethoxybiphenyl 0.09 g (0.2 mmol), manufactured by Wako Pure Chemical Industries, Ltd. It was dispersed in 0.021 g (0.1 mmol) of palladium acetate and 30 mL of xylene and reacted at 130-135 ° C. for 48 hours. After completion of the reaction, the mixture was cooled to room temperature, water was added, and the mixture was extracted. Then, it was dried over magnesium sulfate and concentrated to obtain 18.5 g (yield 70%) of the intermediate represented by the following chemical formula (i).
It was confirmed from the following analysis results that the obtained compound was the target compound.
-MS (ESI) (m / z): 407 (M + H),
-Elemental analysis value: CHN measured value (85.47%, 8.02%, 6.72%); theoretical value (8)
5.26%, 8.11%, 6.63%)

(2) Synthesis of Intermediate 2 Intermediate 1 8.46 g (20.8 mmol), Tokyo Chemical Industry 4,4'-bis (dimethylamino) benzophenone 13.5 g (41.6 mmol) Toluene 60 mL was added and 45-50. Stirred at ° C. 6.38 g (51.5 mmol) of phosphorus oxychloride manufactured by Wako Pure Chemical Industries, Ltd. was added dropwise, and the mixture was refluxed for 2 hours and cooled. After completion of the reaction, toluene was decanted. The resinous precipitate was dissolved by adding 40 mL of chloroform, 40 mL of water and concentrated hydrochloric acid, and the chloroform layer was separated. The chloroform layer was washed with water, dried over magnesium sulfate, and concentrated. 65 mL of ethyl acetate was added to the concentrate and the mixture was refluxed. After cooling, the precipitate was filtered to obtain 15.9 g (yield 70%) of Intermediate 2 (BB7-Nb-dimer) represented by the following chemical formula (ii).
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 (7)
8.06%, 7.75%, 7.69%)

(3) Synthesis of Coloring Material A 5.00 g (4.58 mmol) of Intermediate 2 was added to 300 ml of water and dissolved at 90 ° C. to prepare an Intermediate 2 solution. Next, add 10.44 g (3.05 mmol) of phosphotungstic acid / n _- hydrate H3 [PW ₁₂ O ₄₀ ] / nH ₂ O (n = 30) manufactured by Nippon Inorganic Chemicals Co., Ltd. to 100 mL of water and stir at 90 ° C. Then, an aqueous solution of phosphotungstic acid was prepared. An aqueous solution of phosphotungstic acid was mixed with the above two intermediate solutions at 90 ° C., and the resulting precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 13.25 g (yield 98%) of the coloring material A represented by the following chemical formula (iii).
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%)
Further, it was confirmed by ³¹ P-NMR that the polyacid structure of phosphotungstic acid was maintained even after becoming the coloring material A.

(Synthesis Example 2: Synthesis of Color Material B)
5.0 g of Acid Red 289 (AR289, manufactured by Tokyo Kasei Co., Ltd.) represented by the following formula was added to 500 ml of water and dissolved at 80 ° C. to prepare a dye solution. Polyaluminum chloride ("trade name: Takibine # 1500" manufactured by Taki Chemical Co., Ltd., Al ₂ (OH) ₅ Cl, basicity 83.5% by mass, alumina content 23.5% by mass) 3.85 g in 200 ml of water And stirred at 80 ° C. to prepare a polyaluminum chloride aqueous solution. The prepared aqueous solution of polyaluminum chloride was added dropwise to the dye solution at 80 ° C. over 15 minutes, and the mixture was further stirred at 80 ° C. for 1 hour. The resulting precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 6.30 g (yield 96.2%) of a metal lake coloring material (coloring material B) of a rhodamine-based acid dye.

(Synthesis Example 3: Synthesis of Color Material C)
In a 500 ml four-necked flask, 40.2 parts by mass of the sulfofluorane compound of the following chemical formula (iv), 312 parts by mass of methanol, 6.8 parts by mass of N-methyl-2,6-xylidine and N-methyl-o- 6.0 parts by mass of toluidine was charged and refluxed for 30 hours. After filtering this reaction solution at 60 ° C. to remove insoluble matter, the solvent was removed under reduced pressure until the reaction solution became about 70 ml, and the mixture was poured into 200 parts by mass of 6% hydrochloric acid. Then, 600 parts by mass of water was added, and the mixture was stirred at room temperature for 30 minutes, and then the wet cake was collected by filtration. This wet cake is suspended in 100 parts by mass of water, stirred at 60 ° C. for 2 hours, collected again, washed with hot water at 60 ° C., and dried to obtain a coloring material C represented by the following formula. 27.4 parts by mass was obtained.

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

(Synthesis Example 5: Synthesis 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, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer to sufficiently replace nitrogen. 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, which is a monomer for B block. 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 units derived from EEMA to obtain constituent units 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 (2) and a carboxy group-containing monomer. A block copolymer A (acid value 8 mgKOH / g) containing B block having a pro-solvent 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 6: Synthesis of Alkali Soluble Resin A)
150 parts by mass of PGMEA was charged in the polymerization tank, the temperature was raised to 100 ° C. under a nitrogen atmosphere, and then 21 parts by mass of methacrylic acid (MAA), 15 parts by mass of methyl methacrylate (MMA), and 50 parts by mass of cyclohexyl methacrylate (CHMA). 6 parts by mass of Perbutyl O (manufactured by Nichiyu Co., Ltd.) and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. Then, the reaction was continued at 100 ° C., and 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor 2 hours after the completion of dropping of the main chain forming mixture to terminate the polymerization.
Next, while blowing air, 14 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound was added, the temperature was raised to 110 ° C., 0.8 part by mass of triethylamine was added, and the temperature was 110 ° C. for 15 hours. The addition reaction was carried out to obtain an alkali-soluble resin A (weight average molecular weight (Mw) 9020, acid value 90 mgKOH / g, solid content 40% by mass).
In the above method for measuring the weight average molecular weight, polystyrene was used as a standard substance and THF was used as an eluent to measure the weight average molecular weight by Shodex GPC System-21H (Shodex GPC System-21H). The acid value was measured based on JIS K 0070: 1992.

(Preparation Example 1: Preparation of Coloring Material Dispersion Liquid A)
In a 225 mL mayonnaise bottle, 68.8 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) and 2.7 parts by mass of block copolymer A (amine value 95 mgKOH / g) were placed and stirred. 2.45 parts by mass (0.7 mol equivalent to the tertiary amino group of the block copolymer) of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Co., Ltd.) was added thereto, and the mixture was stirred at room temperature for 30 minutes. A salt-type block copolymer solution was obtained.
Add 13.0 parts by mass of alkali-soluble resin A (solid content 40% by mass), stir at room temperature, add 13.0 parts by mass of the coloring material A and 100 parts by mass of zirconia beads having a particle size of 2.0 mm, and pre-crush. Shake with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour, then change to 200 parts of zirconia beads with a particle size of 0.1 mm and disperse with a paint shaker for 4 hours as the main crushing to obtain a color material dispersion liquid A. rice field.

(Preparation Example 2: Preparation of Coloring Material Dispersion Liquid B)
A color material dispersion liquid B was obtained in the same manner as in Preparation Example 1 except that the color material B was used instead of the color material A in the preparation example 1.

(Preparation Example 3: Preparation of Coloring Material Dispersion Liquid C)
To the flask, 1000 parts by mass of methanol was added to 100 parts by mass of the coloring material C and dissolved by a magnetic stirrer. After confirming the dissolution, 19 parts by mass of concentrated hydrochloric acid was added and stirred, and 1000 parts by mass of PGMEA was further added. Then, 198 parts by mass of the dispersant block copolymer A was added and stirred. Then, a reflux condenser was connected, the temperature was raised to 80 ° C. in a water bath, and the reaction was carried out for 4 hours after reaching 80 ° C. Then, methanol was distilled off at 45 ° C. in a water bath by an evaporator, 1000 parts by mass of PGMEA was added, and the mixture was left to cool at room temperature for 16 hours. Then, the filtrate obtained by filtration was recovered to obtain a colorant dispersion C in which the dye was uniformly dispersed.

(Production Example 1: Preparation of Photosensitive Binder A)
Dipentaerythritol penta (meth) acrylate (Aronix M403 (manufactured by Toa Synthetic)) 14 as a polyfunctional monomer with respect to 23.5 parts by mass of the alkali-soluble resin A solution (solid content 40% by mass) obtained in Synthesis Example 6. .1 part by mass, Irgacure 907 (photoinitiator having a tertiary amine structure: manufactured by BASF) 4.4 parts by mass, NCI-930 (oxym ester-based photoinitiator: manufactured by ADEKA) 1.5 parts by mass, A photosensitive binder A was obtained by adding 0.6 parts by mass of compound A (latent antioxidant) of Synthesis Example 4 and 55.9 parts by mass of PGMEA.

(Production Examples 2 to 6: Preparation of Photosensitive Binders B to F)
Photosensitive binders B to F were obtained in the same manner as in Production Example 1 except that the compounding ratio was changed as shown in Table 1 below in Production Example 1. The compound α in Table 1 represents the antioxidant IRGANOX 1010 manufactured by BASF.

(Comparative Production Examples 1 and 2: Preparation of Photosensitive Binders G and H)
In Production Example 1, photosensitive binders G to H were obtained in the same manner as in Production Example 1 except that the compounding ratio was changed as shown in Table 1 below.

(Example 1: Preparation of photosensitive colored resin composition 1)
24.6 parts by mass of the colorant dispersion A obtained in Preparation Example 1, 34.1 parts by mass of the photosensitive binder A obtained in Production Example 1, 0.16 parts by mass of the surfactant Megafuck R08MH (manufactured by DIC) , PGMEA 41.1 parts by mass were mixed to obtain the photosensitive colored resin composition 1 of Example 1.

(Examples 2 to 6: Preparation of photosensitive colored resin compositions 2 to 6)
In Example 1, the photosensitive colored resin compositions 2 to 6 were prepared in the same manner as in Example 1 except that the photosensitive binders B to F of Production Examples 2 to 6 were used instead of the photosensitive binder A. Obtained.

(Comparative Examples 1 and 2: Preparation of Photosensitive Colored Resin Compositions X1 and X2)
In Example 1, the photosensitive colored resin compositions X1 to X2 are the same as in Example 1 except that the photosensitive binders G to H of Comparative Production Examples 1 and 2 are used instead of the photosensitive binder A. Got

(Example 7: Preparation of photosensitive colored resin composition 7)
Except for the fact that in Example 1, instead of 24.6 parts by mass of the color material dispersion liquid A, 17.2 parts by mass of the color material dispersion liquid A and 7.4 parts by mass of the color material dispersion liquid B were used in combination. A photosensitive colored resin composition 7 was obtained in the same manner as in Example 1.

(Examples 8 to 9: Preparation of photosensitive colored resin compositions 8 to 9)
In Example 7, the photosensitive colored resin composition was the same as in Example 7, except that the photosensitive binder B of Production Example 2 and the photosensitive binder D of Production Example 4 were used instead of the photosensitive binder A. I got things 8-9.

(Comparative Examples 3 to 4: Preparation of Photosensitive Colored Resin Compositions X3 to X4)
In the same manner as in Example 7, the photosensitive colored resin compositions X3 to X4 are used in the same manner as in Example 7, except that the photosensitive binders G to H of Comparative Production Examples 1 and 2 are used instead of the photosensitive binder A. Got

(Example 10: Preparation of photosensitive colored resin composition 10)
In Example 1, instead of 24.6 parts by mass of the color material dispersion liquid A, 19.7 parts by mass of the color material dispersion liquid A and 8.3 parts by mass of the color material dispersion liquid C are used in combination, and a photosensitive binder is used. A photosensitive colored resin composition 10 was obtained in the same manner as in Example 1 except that the blending amount of A was changed to 33.9 parts by mass and the blending amount of PGMEA was changed to 37.9 parts by mass.

(Examples 11 to 12: Preparation of photosensitive colored resin compositions 11 to 12)
In Example 10, the photosensitive colored resin composition is the same as in Example 10, except that the photosensitive binder B of Production Example 2 and the photosensitive binder D of Production Example 4 are used instead of the photosensitive binder A. I got things 11-12.

(Comparative Examples 5 to 6: Preparation of Photosensitive Colored Resin Compositions X5 to X6)
In the same manner as in Example 10, the photosensitive colored resin compositions X5 to X6 were used in the same manner as in Example 10, except that the photosensitive binders G to H of Comparative Production Examples 1 and 2 were used instead of the photosensitive binder A. Got

(Example 13: Preparation of photosensitive colored resin composition 13)
In Example 1, instead of 24.6 parts by mass of the color material dispersion liquid A, 41.6 parts by mass of the color material dispersion liquid C was used, the amount of the photosensitive binder A was 33.1 parts by mass, and the amount of PGMEA was mixed. The photosensitive colored resin composition 13 was obtained in the same manner as in Example 1 except that the amount was changed to 25.2 parts by mass.

(Examples 14 to 15: Preparation of photosensitive colored resin compositions 14 to 15)
In Example 13, the photosensitive colored resin composition is the same as in Example 13 except that the photosensitive binder B of Production Example 2 and the photosensitive binder D of Production Example 4 are used instead of the photosensitive binder A. I got things 14-15.

(Comparative Examples 7 to 8: Preparation of Photosensitive Colored Resin Compositions X7 to X8)
In Example 13, the photosensitive colored resin compositions X7 to X8 are the same as in Example 13, except that the photosensitive binders G to H of Comparative Production Examples 1 and 2 are used instead of the photosensitive binder A, respectively. Got

(Brightness evaluation)
The photosensitive colored resin compositions of Examples and Comparative Examples were each applied on a glass substrate (manufactured by NH Techno Glass Co., Ltd., “NA35”) having a thickness of 0.7 mm using a spin coater. After heat-drying on a hot plate at 80 ° C. for 3 minutes, ultraviolet rays of 60 mJ / cm ² were irradiated using an ultra-high pressure mercury lamp. Then, it was post-baked in a clean oven at 230 ° C. for 75 minutes. Before and after the irradiation with the ultraviolet rays, the chromaticity of the colored film (x, y) and the brightness (Y) were measured, respectively. The chromaticity and brightness were measured using a "microspectroscopy measuring device OSP-SP200" manufactured by Olympus Corporation. The results are shown in Tables 2-5.

(Evaluation of line width increase / decrease rate)
The photosensitive colored resin composition obtained in each Example and each Comparative Example was subjected to a cured coating film having a thickness of 3 on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) 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. The coating film was exposed to ultraviolet rays of 60 mJ / cm ² using an ultra-high pressure mercury lamp via an independent fine line pattern photomask with a line width of 1 μm to 100 μm to form a coating film after exposure on a glass substrate. Next, spin-development using a 0.05 wt% potassium hydroxide aqueous solution as a developing solution, indirect solution in the developing solution for 60 seconds, washing with pure water for development treatment, and then posting in a clean oven at 230 ° C. for 25 minutes. It was baked and formed a fine line pattern. Of the formed fine line patterns, the width of the fine line pattern in the portion where the opening width of the chrome mask at the time of exposure corresponds to 90 μm is measured with an optical microscope, and the following is based on the line width of the comparative example to which no antioxidant is added. The line width increase / decrease rate was calculated by the formula (2). The results are shown in Tables 2-5.
Formula (2): (L-L ₀ ) / L ₀ x 100 (%)
In the formula (2), L ₀ represents the line width of the comparative example to which the antioxidant is not added, and L represents the line width of the example or the comparative example to be evaluated.
<Evaluation criteria>
A: -3% or more for the line width without the addition of antioxidant B: -10% or more and less than -3% for the line width without the addition of the antioxidant C: For the line width without the addition of the antioxidant Less than -10%

[Summary of results in Tables 2 to 5]
The colored layer using the photosensitive colored resin composition of Comparative Examples 2, 4, 6 and 8 using the conventional antioxidant is compared with Comparative Examples 1, 3, 5 and 7 not using the antioxidant. , It became clear that the line width change was large. On the other hand, in Comparative Examples 1, 3, 5 and 7, since the antioxidant was not contained, the change in the line width was suppressed, but the brightness was lowered. The photosensitive resin compositions of Examples 1 to 15 using the latent antioxidant have higher brightness than the comparative examples containing the same coloring material, and the comparative examples using the conventional antioxidant. It was clarified that the change in line width was suppressed. From these results, it has been clarified that according to the present invention, a photosensitive colored resin composition capable of forming a high-luminance colored layer and suppressing a change in line width can be obtained.
As shown in the results in Table 2, by combining the latent antioxidant and the antioxidant, the light resistance is improved as compared with the case where the latent antioxidant alone is used while suppressing the change in line width. It was shown that the decrease in the brightness of the colored layer due to the irradiation with ultraviolet rays can be suppressed.
Further, as shown in the results of Table 5, the photosensitive colored resin composition containing the coloring material C, which is a dye, tends to have a narrow line width. It is presumed that this is because the color material C, which is a dye, lowered the sensitivity. In particular, the colored layer using the colored resin composition of Comparative Example 8 has insufficient sensitivity even in an exposed portion due to the combination of such a coloring material C and an antioxidant, and has a hardness that can withstand development. Was not obtained and a fine line pattern was not formed. As shown in Examples 13 to 15, the photosensitive colored resin composition of the present invention using a latent antioxidant can obtain good sensitivity even when such a dye is contained, and has a line width. It became clear that the change was suppressed.

(Production Example 7: Preparation of Photosensitive Binder I)
Dipentaerythritol penta (meth) acrylate (Aronix M403 (manufactured by Toa Synthetic)) 14 as a polyfunctional monomer with respect to 23.5 parts by mass of the alkali-soluble resin A solution (solid content 40% by mass) obtained in Synthesis Example 6. .1 part by mass, Irgacure 907 (photoinitiator having a tertiary amine structure: manufactured by BASF) 2.9 parts by mass, NCI-930 (oxym ester-based photoinitiator: manufactured by ADEKA) 1.5 parts by mass, 1.5 parts by mass of PBG3057 (oxym ester-based photoinitiator, manufactured by Joshu Strong Electronics New Materials Co., Ltd., "TR-PBG-3057"), 0.6 parts by mass of compound A (potential antioxidant) of Synthesis Example 4. , PGMEA 55.9 parts by mass was added to obtain a photosensitive binder I.

(Production Example 8, Comparative Production Example 3: Preparation of Photosensitive Binders J and K)
Photosensitive binders J and K were obtained in the same manner as in Production Example 7 except that the compounding ratio was changed as shown in Table 6 below in Production Example 7. The compound α in Table 6 represents the antioxidant IRGANOX 1010 manufactured by BASF.

(Example 16: Preparation of photosensitive colored resin composition 16)
24.6 parts by mass of the colorant dispersion A obtained in Preparation Example 1, 34.1 parts by mass of the photosensitive binder I obtained in Production Example 7, 0.16 parts by mass of the surfactant Megafuck R08MH (manufactured by DIC) , PGMEA 41.1 parts by mass were mixed to obtain the photosensitive colored resin composition 16 of Example 16.

(Example 17, Comparative Example 9: Preparation of Photosensitive Colored Resin Composition 17, X9)
In Example 16, the photosensitive colored resin composition 17 is the same as in Example 16 except that the photosensitive binders J and K of Production Example 8 and Comparative Production Example 3 are used instead of the photosensitive binder I, respectively. , X9 was obtained.

(Example 18: Preparation of photosensitive colored resin composition 18)
Except for the fact that in Example 16, instead of 24.6 parts by mass of the color material dispersion liquid A, 17.2 parts by mass of the color material dispersion liquid A and 7.4 parts by mass of the color material dispersion liquid B were used in combination. A photosensitive colored resin composition 18 was obtained in the same manner as in Example 16.

(Example 19, Comparative Example 10: Preparation of photosensitive colored resin composition 19, X10)
In Example 18, the photosensitive colored resin composition 19 is the same as in Example 18, except that the photosensitive binders J and K of Production Example 8 and Comparative Production Example 3 are used instead of the photosensitive binder I, respectively. , X10 was obtained.

(Example 20: Preparation of photosensitive colored resin composition 20)
In Example 16, instead of 24.6 parts by mass of the color material dispersion liquid A, 19.7 parts by mass of the color material dispersion liquid A and 8.3 parts by mass of the color material dispersion liquid C were used in combination, and a photosensitive binder was used. A photosensitive colored resin composition 20 was obtained in the same manner as in Example 16 except that the blending amount of I was changed to 33.9 parts by mass and the blending amount of PGMEA was changed to 37.9 parts by mass.

(Example 21, Comparative Example 11: Preparation of Photosensitive Colored Resin Composition 21, X11)
In Example 20, the photosensitive colored resin composition 21 is the same as in Example 20, except that the photosensitive binders J and K of Production Example 8 and Comparative Production Example 3 are used instead of the photosensitive binder I, respectively. , X11 was obtained.

(Example 22: Preparation of photosensitive colored resin composition 22)
In Example 16, instead of 24.6 parts by mass of the coloring material dispersion liquid A, 41.6 parts by mass of the coloring material dispersion liquid C was used, the amount of the photosensitive binder I was 33.1 parts by mass, and the amount of PGMEA was mixed. The photosensitive colored resin composition 22 was obtained in the same manner as in Example 16 except that the amount was changed to 25.2 parts by mass.

(Example 23, Comparative Example 12: Preparation of photosensitive colored resin composition 23, X12)
In Example 22, the photosensitive colored resin composition 23 is the same as in Example 22 except that the photosensitive binders J and K of Production Example 8 and Comparative Production Example 3 are used instead of the photosensitive binder I, respectively. , X12 was obtained.

The obtained photosensitive colored resin compositions of Examples 16 to 23 and Comparative Examples 9 to 12 were subjected to luminance evaluation and line width increase / decrease rate evaluation in the same manner as in the photosensitive colored resin composition of Example 1. .. The results are shown in Table 7.

The obtained photosensitive colored resin compositions of Examples 1, 7, 10, 13, 16, 18, 20, and 22 were evaluated for water stain and development resistance as follows. The results are shown in Table 8.

(Water stain evaluation)
The photosensitive coloring resin composition for a color filter is placed on a glass substrate (“NA35” manufactured by NH Technoglass Co., Ltd.) to form a colored layer having a thickness of 1.6 μm after post-baking using a spin coater. After coating with a film thickness, it is dried at 60 ° C. for 3 minutes using a hot plate, and the glass substrate is colored by irradiating the entire surface with ultraviolet rays of 60 mJ / cm ² using an ultrahigh pressure mercury lamp without using a photomask. Formed a layer. Then, 0.05 wt% potassium (KOH) was spin-developed as a developer, and the developer was indirectly liquided for 60 seconds and then washed with pure water for development treatment. The washed substrate was rotated for 10 seconds to add water. Immediately after centrifugation, the contact angle of pure water was measured as shown below to evaluate water stains.
To measure the contact angle of pure water, a droplet of 1.0 μL of pure water is dropped on the surface of the colored layer immediately after the water is centrifugally removed, and the static contact angle 30 seconds after the droplet is applied is determined according to the θ / 2 method. I measured it. The measuring device was measured using a contact angle meter DM 500 manufactured by Kyowa Interface Science Co., Ltd.
<Evaluation criteria>
A: Contact angle 80 degrees or more B: Contact angle 65 degrees or more and less than 80 degrees C: Contact angle 50 degrees or more and less than 65 degrees D: Contact angle less than 50 degrees If the water stain evaluation standard is A or B, it can be practically used. However, if the evaluation result is A, the effect is better.

(Development resistance evaluation)
The photosensitive coloring resin composition for a color filter was applied onto a glass substrate (manufactured by NH Techno Glass Co., Ltd., “NA35”) having a thickness of 0.7 mm using a spin coater. After heat-drying on a hot plate at 80 ° C. for 3 minutes, ultraviolet rays of 30 mJ / cm ² were irradiated using an ultra-high pressure mercury lamp. The film thickness at this point is measured and set to T1 (μm). Then, shower development was carried out using a 0.05 mass% potassium hydroxide aqueous solution as an alkaline developer. The film thickness after development is measured and set to T2 (μm). T2 / T1 × 100 (%) was calculated.
(Development resistance evaluation criteria)
A: 95% or more B: 90% or more and less than 95% C: less than 90% If the evaluation result is B, it can be practically used, but if the above evaluation standard is A, the effect is more excellent.

[Summary of results in Tables 7 to 8]
From the results in Table 7, it was shown that the line width was increased and the sensitivity was improved when at least two kinds of oxime-based initiators were contained. In addition, from the results in Table 8, it was shown that when at least two kinds of oxime-based initiators were contained, the development resistance was improved and the effect of suppressing the generation of water stains was enhanced.

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 (10)

It contains a coloring material, a photopolymerizable compound, an initiator, a latent antioxidant, and a solvent.
The color material is one or more selected from the rake color materials, and the color material is one or more.
The latent antioxidant contains a compound represented by the following general formula (1), and contains the compound.
Further, a photosensitive colored resin composition containing a hindered phenolic antioxidant.

(In the general formula (1), the ring A is a 5-membered ring or a 6-membered ring hydrocarbon ring or a heterocycle.
R ¹ is an alkyl group having 1 to 40 carbon atoms, which may independently have a substituent.
R ² is a t-butoxycarbonyl group and
The plurality of R ^1s may be the same or different from each other.
X is an a-valent group, which is a direct bond, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, (-O) ₃ P = O,> C = O,> NR ³ , -OR ³ , -SR. ³ , -N (R ³ ) (R ⁴ ), an aliphatic hydrocarbon group having 1 to 120 carbon atoms which may have a substituent, and 6 to 35 carbon atoms which may have a substituent. Aromatic ring-containing hydrocarbon group or a heterocyclic ring-containing group having 2 to 35 carbon atoms which may have a substituent, and R ³ and R ⁴ independently have a hydrogen atom and a substituent, respectively. It has an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms which may have a substituent, or a substituent. It is also a hydrocarbon-containing group having 2 to 35 carbon atoms. In the aliphatic hydrocarbon group in X and the aromatic ring-containing hydrocarbon group, a carbon-carbon double bond, -O-, -S-, -C (= O)-, -OC (= O) )-, -C (= O) -O-, -OC (= O) -O-, -SC (= O)-, -C (= O) -S-, -SC ( = O) -O-, -OC (= O) -S-, -C (= O) -NH-, -NH-C (= O)-, -NH-C (= O) -O- , -NR'-, -SS-, -SO _2- or a nitrogen atom, where R'is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
a represents an integer of 1 to 10, b represents an integer of 1 to 4, and c represents an integer of 1 to 3. ) The invention according to claim 1, wherein the hindered phenolic antioxidant is 0.1 part by mass or more and 10 parts by mass or less with respect to 1 part by mass of the latent antioxidant represented by the general formula (1). Photosensitive colored resin composition. The photosensitive colored resin composition according to claim 1 or 2, further comprising a dispersant, wherein the dispersant is a polymer containing at least a repeating unit (a) represented by the following general formula (2).

(In the general formula (2), R ⁴¹ is a hydrogen atom or a methyl group, L is a divalent linking group, R ⁴² is an alkylene group having 1 to 8 carbon atoms, and-[CH (R ⁴⁵ ) -CH ( R ⁴⁶ ) -O] _x -CH (R ⁴⁵ ) -CH (R ⁴⁶ )-or-[(CH ₂ ) _y -O] _z- (CH ₂ ) _y- , a divalent organic group represented by R ⁴³ . And R ⁴⁴ each independently represent a chain or cyclic hydrocarbon group which may be substituted, or R ⁴³ and R ^{44 combine} with each other to form a ^cyclic structure. 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. ) The photosensitive color material according to any one of claims 1 to 3, wherein the color material comprises at least one selected from a lake color material having a xanthene skeleton and a lake color material having a triarylmethane skeleton. Colored resin composition. The solvent contains propylene glycol monomethyl ether acetate, and further includes diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, 3-methoxy-3 methyl-1-butanol, 3-methoxy-3-methyl-1-butyl acetate, and The photosensitive colored resin composition according to any one of claims 1 to 4, which comprises one or more selected from propylene glycol monomethyl ether acetate. The photosensitive colored resin composition according to any one of claims 1 to 5, wherein the initiator contains an oxime-based initiator. The photosensitive colored resin composition according to any one of claims 1 to 6, wherein the initiator contains at least two kinds of oxime-based initiators. A color filter including at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers cures the photosensitive colored resin composition according to any one of claims 1 to 7. A color filter that is a thing. A method for manufacturing a color filter including at least a substrate and a colored layer provided on the substrate.
A method for producing a color filter, comprising a step of forming at least one of the colored layers using the photosensitive colored resin composition according to any one of claims 1 to 7. A display device having the color filter according to claim 8.

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