WO2017170263A1

WO2017170263A1 - Photosensitive coloring resin composition, color filter and method for producing same, and display device

Info

Publication number: WO2017170263A1
Application number: PCT/JP2017/012133
Authority: WO
Inventors: 裕史大島; 崇岩澤
Original assignee: 株式会社Ｄｎｐファインケミカル
Priority date: 2016-03-31
Filing date: 2017-03-24
Publication date: 2017-10-05
Also published as: TW201807485A; CN108780273B; JP7308993B2; TWI714746B; JP2022062022A; JP7059009B2; JPWO2017170263A1; CN108780273A

Abstract

Provided is a photosensitive coloring resin composition which is capable of forming a colored layer that has high luminance, and which is suppressed in line width change. A photosensitive coloring resin composition which contains a colorant, a photopolymerizable compound, an initiator, a latent antioxidant and a solvent, and wherein: the colorant contains one or more materials selected from among dyes and lake colorants; and the latent antioxidant contains a compound represented by general formula (1). (In general formula (1), the symbols are as defined in the description.) AA general formula (1)

Description

Photosensitive colored resin composition, color filter, method for producing the same, and display device

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

Many thin image display devices represented by displays and the like, so-called flat panel displays, have been put on the market, characterized by being thinner than a cathode ray tube type display and taking up little space in the depth direction. The market price has become affordable year by year with the evolution of production technology, the demand has further expanded, and the production volume has been increasing year by year. In particular, color LCD TVs have almost reached the mainstream of TV. Recently, an organic light-emitting display device such as an organic EL display having high visibility due to self-emission has been attracting attention as a next-generation image display device. In the performance of these image display devices, further improvement in image quality such as improvement in contrast and color reproducibility and reduction in power consumption are strongly desired.
Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, in the 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 color expression is performed by the light passing through a color filter. Therefore, a color filter must be present in the color representation of a liquid crystal television and plays a major role in determining the performance of the display. Further, in an organic light emitting display device, color adjustment of pixels may be performed using a color filter, or a color image may be formed in the same manner as a liquid crystal display device using a color filter for a white light emitting organic light emitting element.

As a recent trend, there is a demand for power saving of an image display device, and in order to improve the utilization efficiency of a backlight, a high brightness of a color filter is particularly demanded. This is a big problem especially for mobile displays (cell phones, smartphones, tablet PCs).
Although the battery capacity has increased due to technological evolution, the amount of electricity stored in the mobile is still limited, while the power consumption tends to increase as the screen size increases. An image display device including a color filter affects the design and performance of a mobile terminal in order to be directly linked to the usable time and charging frequency of the mobile terminal.

Here, the color filter is generally formed on the substrate to form the substrate, the colored layer formed of the three primary colors of red, green, and blue, and the respective colored patterns. A light shielding portion.
As one method for forming such a colored layer, there is known a method in which a photosensitive resin composition containing a colorant and a photopolymerizable compound is applied onto a substrate and cured by irradiating ultraviolet rays or the like. ing.
As the coloring material of the photosensitive resin composition, pigments and dyes are used. Although the pigments are generally superior in heat resistance and light resistance compared to dyes, fading could not be sufficiently prevented during high-temperature heating in the color filter manufacturing process, and brightness was reduced. .
In recent years, photosensitive resin compositions for color filters using dyes with high transmittance have been studied from the viewpoint of further increasing the brightness of color filters, and the heat resistance and light resistance of dyes have been improved. In order to achieve this, the use of a rake color material in which a dye is insolubilized has been studied. However, since dyes have poor heat resistance and light resistance compared to pigments, the chromaticity is likely to change during high-temperature heating and light irradiation in the color filter manufacturing process, and the brightness of the colored layer is likely to decrease. was there.

As one of the techniques for solving the above problems, it has been studied to use a resin composition containing an antioxidant.
For example, Patent Document 1 discloses 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. Radiation sensitive compositions for use are disclosed. According to Patent Document 1, it is said that a blue pixel with high luminance can be formed.

Patent Document 2 discloses a colored resin composition for a color filter containing a lake pigment, a specific dispersant, a hindered phenol antioxidant, a binder component, and a solvent. According to Patent Document 2, heat resistance is improved by a hindered phenol-based antioxidant, and a high-luminance 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.

JP 2014-160254 A JP 2014-1553569 A International Publication No. 2014/021023 Pamphlet

In general, a colored layer for a color filter is patterned on a substrate. When forming a colored layer using the photosensitive colored resin composition, for example, after forming a coating film of the photosensitive colored resin composition on the substrate, it is exposed through a predetermined mask pattern, and then developed. Thus, a patterned colored layer can be obtained.
The present inventors have studied to form a colored layer by the above-described method using a photosensitive colored resin composition containing an antioxidant. As a result, the present inventors have found that when a photosensitive resin composition containing the antioxidant is used, a colored layer as designed may not be formed.

The present invention has been made on the basis of the above knowledge, and can form a high-brightness colored layer, and a photosensitive colored resin composition in which a change in line width is suppressed, and the photosensitive colored resin composition. It is an object of the present invention to provide a high-luminance color filter formed using the above and a display device having excellent display characteristics using the color filter.

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, and the coloring material is composed of a dye and a lake coloring material. 1 or more types selected, The said latent antioxidant contains the compound represented by following General formula (1), It is characterized by the above-mentioned.

(Each symbol 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 cured cured photosensitive colored resin composition according to the present invention. It is a thing.
A method for producing a color filter according to the present invention is a method for producing a color filter comprising at least a substrate and a colored layer provided on the substrate,
It has the process of forming at least 1 of the said colored layer using the photosensitive colored resin composition which concerns on the said this invention, It is characterized by the above-mentioned.

The display device according to the present invention includes the color filter according to the present invention.

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, and a high-luminance color formed using the photosensitive colored resin composition A filter and a display device having excellent display characteristics using the color filter can be provided.

FIG. 1 is a schematic sectional view showing an example of the color filter of the present invention. FIG. 2 is a schematic 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, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.
In the present invention, (meth) acryl represents each of acryl and methacryl, and (meth) acrylate represents each of acrylate and methacrylate.
In the present invention, the organic group means a group having one or more carbon atoms.
Moreover, in this invention, solid content means all components other than the solvent which comprises a resin composition, for example, even if it is a liquid monomer, it shall be contained in the said solid content.

1. Photosensitive Colored Resin Composition The photosensitive colored resin composition according to the present invention contains a color material, a photopolymerizable compound, an initiator, a latent antioxidant, and a solvent, and the color material is 1 or more types selected from dye and lake color material, The said latent antioxidant contains the compound represented by following General formula (1), It is characterized by the above-mentioned.

(In general formula (1), ring A is a 5-membered or 6-membered hydrocarbon ring or heterocyclic ring,
R ¹ each independently has a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxy group, an alkyl group having 1 to 40 carbon atoms which may have a substituent, or a substituent. 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 Or a plurality of R ¹ are bonded to each other to form a benzene ring or a naphthalene ring,
R ² is 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, or 2 to 2 carbon atoms. 20 heterocycle-containing groups, or trialkylsilyl groups,
In the alkyl group of R ¹ and R ² , a carbon-carbon double bond, —O—, —S—, —C (═O) —, —O—C (═O) —, —C (═O ) —O—, —O—C (═O) —O—, —S—C (═O) —, —C (═O) —S—, —S—C (═O) —O—, — OC (═O) —S—, —C (═O) —NH—, —NH—C (═O) —, —NH—C (═O) —O—, —NR′—, —S -S- or -SO ₂ -may be present, R 'is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ¹ and R ² may be the same or different. May be.
X is an a-valent group, and is a direct bond, nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, (—O) ₃ P═O,>C═O,> NR ³ , —OR ³ , —SR ³ , —N (R ³ ) (R ⁴ ), an optionally substituted aliphatic hydrocarbon group having 1 to 120 carbon atoms, and optionally having 6 to 35 carbon atoms An aromatic ring-containing hydrocarbon group or a heterocyclic group having 2 to 35 carbon atoms which may have a substituent, and R ³ and R ⁴ each independently represents a hydrogen atom or a substituent. An aliphatic hydrocarbon group having 1 to 35 carbon atoms that may have, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms that may have a substituent, or a substituent. It is also a heterocyclic group having 2 to 35 carbon atoms. In the aliphatic hydrocarbon group and the aromatic ring-containing hydrocarbon group in X, a carbon-carbon double bond, —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'-, -SS-, -SO _2-, or 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 a change in line width is suppressed during development.

Although there is an unclear part about the effect | action which said effect is acquired by the structure of this invention, it estimates as follows.
Conventionally, addition of an antioxidant to a photosensitive resin composition has been studied as a method for improving heat resistance and light resistance. In general, an antioxidant can suppress oxidation of a coloring material or the like by deactivating radicals generated during heating or exposure. However, the present inventors have exposed a coated film of a colored photosensitive resin composition containing an antioxidant through a predetermined mask pattern and then developed it to form a patterned colored layer. The present inventors have found that the line width is narrower than in the case where a photosensitive colored resin composition having no conventional antioxidant is used. As a cause, since the antioxidant also deactivates radicals generated from the initiator at the time of exposure, it was speculated that by using the antioxidant, the photopolymerization reaction does not sufficiently proceed and the sensitivity is insufficient.
In order to obtain a designed fine line pattern without changing the mask pattern, for example, it was considered to add a large amount of an initiator. However, such a method has a problem that the content ratio of the coloring material is relatively lowered, and a desired chromaticity cannot be achieved.
The photosensitive coloring resin composition of this invention contains the latent antioxidant represented by General formula (1). In the latent antioxidant, a phenolic hydroxyl group that exhibits 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 deactivate radicals generated from the initiator, suppresses a decrease in sensitivity, and suppresses a reduction in line width. On the other hand, in the heating step performed after exposure, the protective group is eliminated and an antioxidant effect is exhibited, so that fading of a color material or the like is suppressed and a high-luminance colored layer is obtained.

The photosensitive colored resin composition of the present invention contains at least a colorant, 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, it may further contain other components.
Hereinafter, each component of the colored resin composition for a color filter of the present invention will be described in detail in order.

[Latent antioxidants]
In the present invention, the latent antioxidant is a compound having a protecting group that can be removed by heating, and exhibiting an antioxidant function when the protecting group is eliminated. Among them, those which are easy to remove the protecting group by heating at 150 ° C. or higher are preferable.

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

(Each symbol 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 as or different from each other. The value of a is 1 to 10, and preferably 2 to 6 from the viewpoint of ease of synthesis.

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

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

Among R ^1, the optionally substituted alkyl group having 1 to 40 carbon atoms is, for example, methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, 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- 1- Examples thereof include adamantyl, 2-methyl-2-adamantyl, 2-ethyl-1-adamantyl, 2-ethyl-2-adamantyl, 2-norbornyl, 2-norbornylmethyl and the like.

Examples of the aryl group having 6 to 20 carbon atoms in R ¹ 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-butyl Ruphenyl, 2,6-di-tert-butylphenyl, 2,4-di-tert-pentylphenyl, 2,5-di-tert-amylphenyl, 2,5-di-tert-octylphenyl, 2,4- Examples include dicumylphenyl, 4-cyclohexylphenyl, (1,1′-biphenyl) -4-yl, 2,4,5-trimethylphenyl, and ferrocenyl.

Examples of the heterocyclic group containing 2 to 20 carbon atoms in R ¹ include pyridyl, pyrimidyl, pyridazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, and furanyl. , Benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidinon-1-yl, 2-piperidone-1-yl, 2,4- Examples include dioxyimidazolidin-3-yl and 2,4-dioxyoxazolidine-3-yl.

In R ¹ , the substituent for substituting the hydrogen atom of the alkyl group, aryl group, or heterocyclic group includes ethylenically unsaturated groups such as vinyl, allyl, acrylic, and methacryl; fluorine, chlorine, bromine, 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, cyclo Pentylamino, 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-octadecyloxy Carbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino Substituted amino groups such as N, N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino; sulfonamide group, sulfonyl group, carboxy group, cyano group, sulfo group, hydroxyl group, nitro group, mercapto group, Examples thereof include imide groups, carbamoyl groups, sulfonamido groups, phosphonic acid groups, phosphoric acid groups or carboxy groups, sulfo groups, phosphonic acid groups, and salts of phosphoric acid groups.

Among R ² in the general formula (1), examples of the alkyl group having 1 to 20 carbon atoms include alkyl groups having 1 to 20 carbon atoms among the alkyl groups exemplified for R ¹ above. .
Among R ² , an alkenyl group having 2 to 20 carbon atoms includes vinyl, 1-methylethen-1-yl, propen-1-yl, propen-2-yl, propen-3-yl, and buten-1-yl. Buten-2-yl, 2-methylpropen-3-yl, 1,1-dimethylethen-2-yl, 1,1-dimethylpropen-3-yl, 3-butenyl, 1-methyl-3-butenyl, Examples 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 heterocyclic-containing group having 2 to 20 carbon atoms are the same as those exemplified for R ¹ . Things.
In R ² , examples of the trialkylsilyl group include trimethylsilane, triethylsilane, and ethyldimethylsilane.

Further, when R ¹ and R ² have an alkyl group, the alkyl chain includes a carbon-carbon double bond, —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′—, —SS— or —SO ₂ —.
R ′ of the —NR′— group is an alkyl group having 1 to 8 carbon atoms, and specifically, an alkyl group having 1 to 8 carbon atoms among the alkyl groups exemplified as R ¹ above. Groups.
Note that in the case where the alkyl chain includes the above structure, the alkyl chain preferably does not have a structure in which oxygen atoms are connected (—O—O—).

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. R ¹ is preferably a substituent having 4 or more carbon atoms from the viewpoint of excellent heat resistance and light resistance as a latent antioxidant. Specific examples of the substituent having 4 or more carbon atoms include tertiary alkyl groups such as t-butyl, t-pentyl and t-hexyl; secondary alkyl groups such as sec-butyl and sec-pentyl. A branched primary alkyl group such as an i-butyl group and an i-pentyl group; a cycloalkyl group such as a cyclohexyl group and a cyclopentyl group; The t-butyl group is particularly preferred.

In the present invention, R ² is an alkyl group having 2 to 8 carbon atoms in which —C (═O) —O— is bonded to the terminal on the oxygen atom side efficiently as a latent additive. It is preferable because it exhibits a function. That is, the substituent —OR ² in the general formula (1) is preferably —O—C (═O) —O—R ″ (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, represented by X in the general formula (1) is not particularly limited. The aliphatic hydrocarbon group may be linear, branched, cyclic (alicyclic hydrocarbon), or a combination thereof. The aliphatic hydrocarbon group includes a carbon-carbon double bond, —O—, —S—, —C (═O) —, —O—C (═O) in the aliphatic hydrocarbon group. —, —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—, It may have —NR′—, —SS—, —SO ₂ — or a nitrogen atom. For example, monovalent aliphatic hydrocarbon groups include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-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, sec-butyloxy, tert-butyloxy, isobutyloxy, amyloxy, isoamyloxy, tert-amyloxy, hexyloxy, cyclohexyl Alkoxy groups such as oxy, heptyloxy, isoheptyloxy, tertiary heptyloxy, n-octyloxy, isooctyloxy, tertiary octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy; methylthio, ethylthio, propylthio, isopropylthio, Butylthio, sec-butylthio, tert-butylthio, isobutylthio, amylthio, isoamylthio, tert-amylthio, hexylthio, cyclohexylthio, heptylthio, isoheptylthio, tert-heptylthio, n-octylthio, isooctylthio, tert-octylthio, 2-ethylhexyl Alkylthio groups such as thio; vinyl, 1-methylethenyl, 2-methylethenyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl Examples include alkenyl groups such as isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl, octenyl, decenyl, pentadecenyl, eicosenyl, and tricosenyl, and combinations of these groups with the following substituents. Examples of the aliphatic hydrocarbon group include a structure in which a part of hydrogen atoms of the monovalent aliphatic hydrocarbon group is removed.

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, monovalent aromatic ring-containing hydrocarbon groups include arylalkyl groups such as benzyl, phenethyl, diphenylmethyl, triphenylmethyl, styryl, and cinnamyl; aryl groups such as phenyl and naphthyl; aryloxy groups such as phenoxy and naphthyloxy Groups: arylthio groups such as phenylthio and naphthylthio, or combinations of these groups with the following substituents, and the like. The divalent or higher aliphatic hydrocarbon group is a part of the hydrogen atoms of the monovalent aromatic ring-containing hydrocarbon group. Is a structure that is off. In addition, the aromatic ring-containing hydrocarbon group includes a carbon-carbon double bond, —O—, —S—, —C (═O) —, —O—C (= O)-, -C (= O) -O-, -O-C (= O) -O-, -SC (= O)-, -C (= O) -S-, -SC (═O) —O—, —O—C (═O) —S—, —C (═O) —NH—, —NH—C (═O) —, —NH—C (═O) —O It may have —, —NR′—, —SS—, —SO ₂ — or 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, monovalent heterocycle-containing groups include pyridyl, pyrimidyl, pyridazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiol. Phenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidinon-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidine-3-yl, benzotriazoyl and the like, or combinations of these groups with the following substituents, and the like. Examples of the bivalent or higher heterocyclic group include hydrogen of the above monovalent heterocyclic group. original It includes partially out structure is.

Examples of the substituent 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 Acyl groups such as acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl Acyloxy groups such as acetyloxy and benzoyloxy; amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamine , Anilino, chlorophenylamino, toluidino, anisidino, N-methyl-anilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, lauroylamino, carbamoyl Amino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonyl Amino, phenoxycarbonylamino, sulfamoylamino, N, N-dimethylaminosulfonylamino, methylsulfur Substituted amino groups such as nylamino, butylsulfonylamino, phenylsulfonylamino; sulfonamide group, sulfonyl group, carboxy group, cyano group, sulfo group, hydroxyl group, nitro group, mercapto group, imide group, carbamoyl group, sulfonamide group, phosphone Examples thereof include an 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. Moreover, the carboxy group and the sulfo group may form a salt.

Further, in X, 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, Examples of 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 those exemplified as the group and the monovalent heterocyclic ring-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), at least one selected from the following general formulas (1A) to (1E) is preferable from the viewpoint of excellent heat resistance.

(In General Formula (1A), ring A ′ is a six-membered alicyclic ring, aromatic ring or heterocyclic ring, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ are each independently hydrogen. is the same group as ^{R 1} in atom or the general formula (1), ^{R 2} is the same as ^{R 2} in the general formula (1). ^{^{^{However, R 11, R 12, R}}} 13, R 14 and, At least one of R ¹⁵ is the same group as R ¹ in the general formula (1).)

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

(In 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 (3 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 = 6 is a group represented by the following general formula (7), and ring A ′, R ² , R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are the same as in general formula (1A).)

(In General Formula (1D), m, X ¹ , Ring A ′, R ² , R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are the same as in General Formula (1C).)

(In the general formula (1E), m ′ is an integer of 3 to 6, which is the same as in the case where m in the general formula (1C) is 3 to 6. 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).)

(In General Formula (3), Q ¹ is —NR ³² —, a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, a divalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or 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 Q ¹ is replaced with —O—, —S—, —CO—, —COO—, —OCO—, —NH— or a combination thereof. Z ¹ and Z ² each independently represent a direct bond, —O—, —S—, —SO ₂ —, —SO—, —NR ³² —, —PR ³³ —, wherein R ³² and R Table ³³ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group or an arylalkyl group having 7 to 20 carbon atoms of 6 to 20 carbon ^atoms, with ^{R 32} and ^{R 33} The alkyl group, aryl group and arylalkyl group which may be substituted with a halogen atom, a hydroxyl group or a nitro group, and the methylene group in the alkyl group and arylalkyl group represented by R ³² and R ³³ are: COO-, -O-,- CO -, - NHCO -, - NH- or it may be replaced by -CONH-.
However, the group represented by the general formula (3) is in the range of 1 to 35 carbon atoms. )

(In the formula (3-1), R ³⁴ represents a hydrogen atom, a phenyl group optionally substituted by an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, or a group having 3 to 10 carbon atoms. R ³⁵ represents an cycloalkyl group, R ³⁵ 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 (The alkyl group, alkoxy group, and alkenyl group represented are substituted or unsubstituted with a halogen atom, and d is an integer of 0 to 5.)

(In the formula (3-3), R ³⁶ and R ³⁷ are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms. 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 heterocyclic-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 group-containing group represented by R ³⁶ and R ³⁷ are substituted with a halogen atom or unsubstituted, and R The methylene group in the alkyl group and arylalkyl group represented by ³⁶ and R ³⁷ may be replaced with an unsaturated bond, —O— or —S—, and R ³⁶ is Adjacent R ³⁶ may form a ring, e represents a number of 0 to 4, f represents a number of 0 to 8, g represents a number of 0 to 4, and h represents 0 to 4 The total number of g and h is 2 to 4.)

(In the general formulas (4) to (7), Q ² represents a carbon atom substituted by R ³⁸ , a trivalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, or a trivalent carbon atom having 6 to 35 carbon atoms. An aromatic ring-containing hydrocarbon group or a trivalent heterocyclic ring-containing group having 2 to 35 carbon atoms, wherein R ³⁸ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl having 6 to 20 carbon atoms. A group or an arylalkyl group having 7 to 20 carbon atoms, Q ³ is a carbon atom, a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, or an aromatic ring having 4 to 35 carbon atoms. Represents a hydrocarbon-containing group or a tetravalent heterocyclic group having 2 to 35 carbon atoms, and Q ⁴ represents a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms and a pentavalent carbon atom having 6 to 6 carbon atoms. represents 35 aromatic ring-containing hydrocarbon group or a pentavalent heterocyclic containing group having a carbon number of 2 to 35, Q ⁵ is hexavalent carbon atoms Aliphatic hydrocarbon group having to 35, represents a hexavalent aromatic ring-containing hydrocarbon group or hexavalent heterocyclic containing group having a carbon number of 2 to 35 carbon atoms ^{6 ~ 35, Q 2, Q} 4, Q ⁵ , the methylene group in the aliphatic hydrocarbon group represented by Q ⁶ is replaced with —O—, —S—, —CO—, —COO—, —OCO—, —NH— or a combination thereof. Z ¹ to Z ⁶ are each independently the same as the groups represented by Z ¹ and Z ² in the general formula (3), provided that the general formula (4) or (5) And each group represented by the general formula (6) or (7) is within a range of 2 to 35 carbon atoms.)

Examples of the six-membered alicyclic, aromatic or heterocyclic ring represented by the ring A ′ in the general formula (1A) to the general formula (1E) include those exemplified in the description of A in the general formula (1). Can be mentioned.
The general formula (1A) ~ the general formula ^{^{(1E), R 11 ~ R}} 15 are each independently a group similar to ^{R 1} in the hydrogen atom or a general formula ^(1), the R 11 ^{~ R 15} At least one of them is the same group as R ¹ . In the present invention, among them, a carbon atom adjacent to the carbon atom substituted with —OR ² preferably has the same group as R ^1, and among them, a substituent having 4 or more carbon atoms is preferable. Since 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 also in an antioxidant effect.

Examples of the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Q ¹ 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, A divalent group in which a group such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, 2,4-dimethylcyclobutane, 4-methylcyclohexane, etc. is substituted with Z ¹ and Z ² , cyclooctyl, cyclodecanyl, 1- Adamantyl, 2-adamantyl, noradamantyl, 2-methyladam Nthyl, norbornyl, isonorbornyl, perhydronaphthyl, perhydroanthracenyl, 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] decanyl, decalin, trisi Rodekaniru, tetracyclododecanyl, cedrol, group such cyclododecanyl is a divalent group which is substituted by Z ¹ and Z ^2, and combinations thereof, the methylene group in the aliphatic hydrocarbon group, —O—, —S—, —CO—, —COO—, —OCO—, —NH— or a combination thereof may be substituted. Examples of the combination thereof include —COO—O —, —COO—S—, —O—OCO—, —S—OCO—, —CO—NH—, —NH—CO—, etc., among others, —COO—, —O—, —OCO—, — Those substituted with NHCO-, -NH-, -CONH-, -O-CONH- or -NHCO-O- are preferred.
Examples of the divalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Q ¹ include divalent groups in which groups such as phenyl, naphthyl, and biphenyl are substituted with Z ¹ and Z ^2. Can be mentioned.
The divalent heterocyclic ring-containing group having a carbon number of 2 to 35 represented by Q ^1, pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, hexahydrotriazine, furan, tetrahydrofuran, chroman, xanthene, thiophene And divalent groups in which a group such as thiolane is substituted with Z ¹ and Z ² .
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.
As the alkyl group having 1 to 8 carbon atoms represented by R ³² and R ³³ , among the groups exemplified as the alkyl group having 1 to 40 carbon atoms represented by R ¹ and R ² , a predetermined carbon number The group which satisfy | fills is mentioned.
Examples of the aryl group having 6 to 20 carbon atoms represented by R ³² and R ³³ include 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 groups exemplified as the arylalkyl group having 7 to 20 carbon atoms represented by R ¹ , R ² and R ^4. It is done.
Examples of the halogen atom that may be substituted for the alkyl group, aryl group, and arylalkyl group represented by R ³² and R ³³ 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 R ³⁴ and the alkyl group having 1 to 10 carbon atoms which may be substituted with the cycloalkyl group having 3 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 , etc. Is mentioned. The phenyl group represented by R ³⁴ and the alkoxy group having 1 to 10 carbon atoms which may be substituted with the cycloalkyl group having 3 to 10 carbon atoms and R ³⁵ are also 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, hexyloxy, Examples 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, cyclohexyl, cyclooctyl and the like, and these groups are the above alkyl groups having 1 to 10 carbon atoms or carbon atoms. And 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 R ³⁵ 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 that may substitute the alkyl group, alkoxy group and alkenyl group represented by R ³⁴ and R ³⁵ are the halogen atom represented by R ¹ and R ^2. The exemplified groups are mentioned.
Incidentally, the substitution position of alkyl group, halogen atom be substituted alkoxy group and alkenyl group represented by R ^35, it is not limited.

In the substituent represented by the above (3-3), the alkyl group having 1 to 10 carbon atoms represented by R ³⁶ and R ³⁷ may have 1 to 40 carbon atoms represented by R ¹ and R ^2. Among the groups exemplified as the alkyl group, 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 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, 4-vinylphenyl 2-oxy, 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-di-tert-butylphenyloxy, 2,5-di-tert-butylphenyloxy, 2,6-di-tert-butylphenyloxy, 2.4-di-tert-pentylphenyloxy, 2,5-tert -Groups such as amylphenyloxy, 4-cyclohexylphenyloxy, 2,4,5-trimethylphenyloxy, ferrocenyloxy, etc., and groups in which these groups are substituted with halogen atoms, etc. are used.
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 above halogen atom is substituted with a sulfur atom. The foundation etc. are offered.
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 to 20 carbon atoms which may be substituted with the above halogen atom may be vinyl, allyl, Examples include groups substituted with alkenyl groups such as 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-octenyl and the like.
Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ³⁶ and R ³⁷ include groups exemplified as the arylalkyl group having 7 to 20 carbon atoms represented by R ¹ , R ² and R ^4. Can be mentioned.
Examples of the heterocyclic group containing 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, thiophene. And groups such as thiofuran and groups in which these groups are substituted with a halogen atom.
As the halogen atom which may be substituted for the alkyl group, aryl group, aryloxy group, arylthio group, arylalkenyl group, arylalkyl group and heterocyclic group represented by R ³⁶ and R ³⁷ , R ¹ and R ^The group illustrated as a halogen atom represented by ² is mentioned.

The trivalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Q ² in the general formula (4), the aromatic hydrocarbon group containing 6 to 35 carbon atoms having a trivalent carbon atom, or trivalent carbon. As the heterocyclic group having 2 to 35 atoms, the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocyclic group-containing group exemplified in the description of Q ¹ in the general formula (3) are each Z ^1. , Z ² and Z ³ substituted trivalent groups and the like.
Further, 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 a group similar to 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.

The general formula tetravalent aliphatic hydrocarbon group having a carbon number of 1 to 35 in (5) represented by Q ^3, tetravalent aromatic ring-containing hydrocarbon group or a tetravalent carbon carbon atoms 6-35 As the heterocyclic group having 2 to 35 atoms, the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocyclic group-containing group exemplified in the description of Q ¹ in the general formula (3) are each Z ^1. , Z ² , Z ^3, and a tetravalent group substituted with Z ⁴ .

The pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by Q ⁴ in the general formula (6), the aromatic hydrocarbon group containing 5 to 35 carbon atoms, or the pentavalent carbon. As the heterocyclic group having 2 to 35 atoms, the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocyclic group-containing group exemplified in the description of Q ¹ in the general formula (3) are each Z ^1. , Z ² , Z ³ , Z ⁴ and Z ⁵ , and the like.

The hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by Q ⁵ in the general formula (7), the aromatic hydrocarbon group containing 6 to 35 carbon atoms having 6 to 35 carbon atoms or hexavalent carbon. As the heterocyclic group having 2 to 35 atoms, each of the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group, and the heterocyclic group-containing group exemplified in the description of X ¹ in the general formula (3) is Z ^1. , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ and the like.

Specific examples of the latent antioxidant suitably used in the present invention include a structure in which the hydrogen of the phenol group of the hindered phenol antioxidant is substituted with a carbamate protecting group such as a t-butoxycarbonyl group. Examples thereof include the following chemical formulas (A) to (C), but are not limited thereto.

The method for producing the compound represented by the general formula (1) is not particularly limited. For example, JP-A-57-111375, JP-A-3-173843, JP-A-6-128195, JP-A-7-206771, JP-A-7- Reaction of phenolic compounds produced by the methods described in each publication of Japanese Patent No. 252191 and Special Tables 2004-501128 with acid anhydrides, acid chlorides, Boc reagents, alkyl halide compounds, silyl chloride compounds, allyl ether compounds, etc. Can be obtained. Moreover, you may use a commercial item.

[Color material]
In the present invention, the color material is not particularly limited as long as it can form a desired color when forming a colored layer of a color filter, and various organic pigments, inorganic pigments, dyes, and the like can be used alone or Two or more kinds can be mixed and used. The dye may be a dye that can be dispersed in addition to a dye that is dissolved in a solvent. Dispersible dyes are excellent in heat resistance and light resistance when combined with a dispersant described later.

Organic pigments are preferably used because of their high color developability and high heat resistance. Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (C.I. .) Can be listed with numbers.

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, 06,207,208,209,215,216,220,224,226,242,243,245,254,255,264,265;
C. I. Pigment blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Pigment green 7, 36, 58, 59;
C. I. Pigment brown 23, 25;
C. I. Pigment Black 1 and 7.

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

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

Examples of the dispersible dye include dyes that can be dispersed by adding various substituents to the dye and insolubilizing the solvent, dyes that can be dispersed by using in combination with a solvent having low solubility, and solvents And a lake color material obtained by forming a salt with a counter ion to form an insoluble (rake) salt. By using a combination of such a dispersible dye and a dispersant, the dispersibility and dispersion stability of the dye can be improved.
As a guide, if the amount of dye dissolved in 10 g of solvent (or mixed solvent) is 10 mg or less, it can be determined that the dye can be dispersed in the solvent (or mixed solvent).

In the present invention, it is particularly preferable to use the rake color material from the viewpoint of improving luminance and contrast. The rake colorant can be usually 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, a dye having a high transmittance is preferably used from the viewpoint of increasing the brightness of the color filter. What is necessary is just to select the said dye suitably according to a desired color tone, an azo dye, a metal complex azo dye, an anthraquinone dye, a triarylmethane dye, a xanthene dye, a cyanine dye, an indigo dye, a naphthoquinone dye, It may be a dye having any basic skeleton (coloring portion) such as a quinoneimine dye, a methine dye, or a phthalocyanine dye. The dye may be a dye classified into any one of an acidic dye having an anionic substituent and a basic dye having a cationic substituent.
In the case of forming a blue colored layer, from the viewpoint of increasing the brightness, among them, at least one of a triarylmethane dye, a xanthene dye, and a cyanine dye is preferable, and a triarylmethane dye is more preferable. 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, 282, 286 87,288,289,290,291,292,293,294,295,298, 301,302,304,305,306,307,313,316,318,322,324,327,331,333,336 339, 340, 343, 344, 350, C.I. I. 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, etc. System acid dyes; C.I. I. Acid Violet 15, 16, 17, 19, 21, 21, 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 Green 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 18, 22, 50, 50: 1, etc. triarylmethane acid dyes; I. Acid Red 50, 51, 52, 87, 92, 94, 289, 388, C.I. I. Acid violet 9, 30, 102, sulforhodamine G, sulforhodamine B, sulforhodamine 101, xanthene acid dyes such as sulforhodamine 640 and the like. Among the xanthene acid dyes, 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. A rhodamine acid dye such as Acid Blue 19 is preferred.
Examples of commercially available basic dyes include 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 Green 1, 4; I. Basic Yellow 13, C.I. I. Cyanine basic dyes such as Basic Red 14; C.I. I. Azo basic dyes such as Basic Red 29; I. And xanthene-based basic dyes such as Basic Violet 11. Triarylmethane basic dyes are C.I. I. Basic blue 1, 5, 7, 8, 11, 26 are preferred. Moreover, as a triarylmethane type | system | group basic dye in this invention, the dye which has the cation of the coloring material represented by general formula (I ') mentioned later is also mentioned as a suitable thing.
These dyes can be used alone or in combination of two or more.

In the rake 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 depending on the dye. That is, when the acid dye is insolubilized, a compound that generates a counter cation of the dye is used as a rake agent. When the basic dye is insolubilized, a counter anion of the dye is generated as a rake agent. A compound is used.

Examples of the counter cation of the acid dye include an ammonium cation, a metal cation, and an inorganic polymer.
As a rake agent that generates ammonium ions, for example, primary amine compounds, secondary amine compounds, tertiary amine compounds, and the like are preferable. Among them, secondary amines are preferred because of their excellent heat resistance and light resistance. It is preferable to use an amine compound or a tertiary amine compound.
Moreover, what is necessary is just to select suitably from the metal salt which has a desired metal ion as a lake agent which generate | occur | produces a metal cation.
The counter cation of the acid dye can be used alone or in combination of two or more.

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

(In the general formula (II), R ^I to R ^IV each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and R ^I and R ^III , R ^II and R ^IV are bonded to each other. R ^V represents an acidic group, X represents a halogen atom, m represents an integer of 0 to 5. The general formula (II) has one or more acidic groups. , N is an integer of 0 or more.)

The alkyl group in R ^I to R ^IV is not particularly limited. Examples thereof include a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent. Among them, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable. More preferably, it is a linear or branched alkyl group having 1 to 5 carbon atoms. 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 the substituted alkyl group includes a benzyl group, and further, a substituent. May have a halogen atom or an acidic group.
The aryl group in R ^I to R ^IV is not particularly limited. For example, an aryl group which may have a substituent having 6 to 20 carbon atoms is exemplified, and among them, a group having a phenyl group, a naphthyl group or the like is preferable. ^Examples of the heteroaryl group in R ^I to R ^IV include heteroaryl groups which may have a substituent having 5 to 20 carbon atoms, and those containing a nitrogen atom, an oxygen atom or a sulfur atom as the hetero atom are preferable. .
Examples of the substituent that the aryl group or 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, and a carboxylic acid ester group. .
R ^I to R ^IV may be the same or different.

Specific examples of the acidic group or a salt thereof include a carboxy group (—COOH), a carboxylate group (—COO ⁻ ), a carboxylate group (—COOM, where M represents a metal atom), a sulfonate group (—SOO). ₃ ^-), a sulfo group _(-SO 3 H), sulfonate _(-SO 3 M, wherein M represents a metal atom), and among them, a sulfonato group (-SO ₃ ^-.), a sulfo group It is preferable to have at least one of (—SO ₃ H) or a sulfonate group (—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 brightness.
From the viewpoint of heat resistance, a compound having a betaine structure in which m = 1 and n = 0 in general formula (II) is preferable.
Moreover, among them, m = 1 and n = 0, R ^I and R ^II are each independently an alkyl group or an aryl group, and R ^III and R ^IV are each independently an aryl group or a heteroaryl group. It is preferable from the viewpoint that a colored layer excellent in luminance and light resistance can be formed.
The method for producing the compound represented by the general formula (II) is not particularly limited, and can be obtained by referring to, for example, JP2010-211198A.

The metal lake color material of the xanthene acid dye includes a metal atom-containing material 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 valent 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.

Moreover, you may use a well-known acidic dye as an organic anion. In this case, the lake color material is an acid dye and a basic dye present as an ion pair.
Examples of rake agents that generate these organic anions include alkali metal salts and alkaline earth metal salts of the above organic anions.

On the other hand, as the inorganic anion, for example, an anion of oxo acid (phosphate ion, sulfate ion, chromate ion, tungstate ion (WO ₄ ²⁻ ), molybdate ion (MoO ₄ ²⁻ ), etc.) Mention may be made of inorganic anions such as polyacid anions condensed with oxo acids and mixtures thereof.
The polyacid may be an isopolyacid anion (M _m O _n ) ^c- or a heteropoly acid anion (X _l M _m O _n ) ^c- . In the above ionic formula, M represents a poly atom, X represents a hetero atom, m represents a composition ratio of poly atoms, and n represents a composition ratio of oxygen atoms. Examples of the poly atom M include Mo, W, V, Ti, and Nb. Examples of the hetero atom X include Si, P, As, S, Fe, and Co.
Among these, 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 rake agents that generate inorganic anions include alkali salts and alkali metal salts of the above inorganic anions.
The counter anion of the basic dye in the lake color 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, more preferably a basic dye and a polyacid anion, from the viewpoint of heat resistance and light resistance. . In the case of a lake color material containing a polyacid anion, the silane coupling agent is easily changed over time, but in the present invention, the content 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 suitably used as a rake color material of the present application.

In the present invention, it is preferable that the lake color material includes a lake color material having a triarylmethane dye from the viewpoint that the brightness of the color filter can be improved. Among them, a triarylmethane basic dye, a polyacid, It preferably contains an anion.

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

(In general formula (I), A is an a-valent organic group in which the carbon atom directly bonded to N has no π bond, and the organic group is saturated aliphatic carbonized at least at the terminal directly bonded to N. Represents an aliphatic hydrocarbon group having a hydrogen group or an aromatic group having the aliphatic hydrocarbon group, and may contain O, S, and N in the carbon chain, and B ^c- includes at least tungsten. c-valent polyacid anion R ⁱ to R ^v each independently represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, and R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v may combine 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 an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. A plurality of e may be the same or different. )

As shown in FIG. 4, the color material represented by the general formula (I) includes a divalent or higher valent anion 202 and a divalent or higher cation 201. It is presumed that the cation and the cation are not simply ion-bonded by one molecule to one molecule but form a molecular aggregate 210 in which a plurality of molecules are associated through the ion bond 203. Therefore, the apparent molecular weight of the color material represented by the general formula (I) is remarkably increased as compared with the molecular weight of the conventional lake color material. It is presumed that the formation of such molecular aggregates increases the cohesive force in the solid state, lowers the thermal motion, suppresses dissociation of ion pairs and decomposition of the cation part, and improves 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 saturated at least at the terminal directly bonded to N. Represents an aliphatic hydrocarbon group having an aromatic hydrocarbon group, or an aromatic group having the aliphatic hydrocarbon group, and includes O (oxygen atom), S (sulfur atom), and N (nitrogen atom) 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 the color tone and transmittance of the cationic coloring portion are not affected by the linking group A and other coloring portions, Similar colors can be retained. From the viewpoint of heat resistance, A preferably does not have a siloxane bond, and more preferably does not have Si (silicon atom).
In A, an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N is linear, branched or cyclic unless the terminal carbon atom directly bonded to N has a π bond. The carbon atom other than the terminal may have an unsaturated bond, may have a substituent, and the carbon chain contains O, S, and N. Also good. For example, a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group or the like may be contained, and a hydrogen atom may be further substituted with a halogen atom or the like.
The aromatic group having an aliphatic hydrocarbon group in A is a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N. And may have a substituent, and may be a heterocyclic ring containing O, S, and N.
Especially, it is preferable that A contains a cyclic | annular aliphatic hydrocarbon group or an aromatic group from the point of the robustness of frame | skeleton.
Among the cyclic aliphatic hydrocarbon groups, a bridged alicyclic hydrocarbon group is preferable from the viewpoint of skeleton fastness. The bridged alicyclic hydrocarbon group means a polycyclic aliphatic hydrocarbon group having a bridged structure in the aliphatic ring and having a polycyclic structure, for example, norbornane, bicyclo [2,2,2]. Examples include octane and adamantane. Among the bridged alicyclic hydrocarbon groups, norbornane is preferable. Moreover, as an aromatic group, the group containing a benzene ring and a naphthalene ring is mentioned, for example, Among these, the group containing a benzene ring is preferable. 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 substituted with two alkylene groups having 1 to 20 carbon atoms such as a xylylene group Etc.

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

The alkyl group for R ⁱ to R ^v is not particularly limited. Examples thereof include straight-chain or branched alkyl groups having 1 to 20 carbon atoms. Among them, straight-chain or branched alkyl groups having 1 to 8 carbon atoms are preferable, and straight chain having 1 to 5 carbon atoms. A chain or branched alkyl group is more preferable from the viewpoint of luminance and heat resistance. Of these, the alkyl group in R ⁱ to R ^v is particularly preferably an ethyl group or a methyl group. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, and a hydroxyl group, and examples of the substituted alkyl group include a benzyl group.
The aryl group in R ⁱ to R ^v is not particularly limited. For example, a phenyl group, a naphthyl group, etc. are mentioned. Examples of the substituent that the aryl group may have include an alkyl group and a halogen atom.
Among these, from the viewpoint of chemical stability, R ⁱ to R ^v are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ⁱⁱ and R ⁱⁱⁱ , or R ^iv and R ^v. Thus, it is preferable to form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

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

The divalent aromatic group in Ar ¹ is not particularly limited. As the aromatic group for Ar ^1, the same aromatic groups as those described for the aromatic group for A can be used.
Ar ¹ is preferably an aromatic group having 6 to 20 carbon atoms, more preferably an aromatic group composed of a condensed polycyclic carbocycle having 10 to 14 carbon atoms. Among these, a phenylene group or a naphthylene group is more preferable because the structure is simple and the raw material is inexpensive.

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

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 optionally containing molybdenum.

The polyacid anion in the colorant represented by the general formula (I) can be used alone or in combination of two or more of the above-mentioned anions. The overall ratio of tungsten to molybdenum is preferably 90:10 to 100: 0 from the viewpoint of heat resistance and light resistance.

In general formula (I), b represents the number of cations, d represents the number of anions in the molecular aggregate, and b and d represent an integer of 1 or more. When b is 2 or more, a plurality of cations in the molecular aggregate may be one kind alone, or two or more kinds may be combined. When d is 2 or more, the anion present in the molecular aggregate may be a single anion or a combination of two or more, and an organic anion and an inorganic anion 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, an anion portion having only the same skeleton is preferable. On the other hand, the color material represented by the general formula (I) can be adjusted to a desired color by using a cation portion including both a triarylmethane skeleton and a xanthene skeleton.

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

(The symbols in general formula (I ′) are the same as those in general formula (I).)

The method for producing the color material represented by the general formula (I) is not particularly limited. For example, it can be obtained by the production method described in International Publication No. 2012/144520 pamphlet.

In the present invention, the color materials can be used singly or in combination of two or more.
In the present invention, the color material includes at least one selected from a lake color material having a xanthene skeleton, a lake color material having a triarylmethane skeleton, and a dye having a xanthene skeleton from the viewpoint of improving luminance and contrast. It is preferable that at least one selected from a lake color material represented by the general formula (I), a lake color material containing the xanthene dye, and a combination thereof is particularly preferably used.

The average primary particle size of the color material used in the present invention is not particularly limited as long as it can produce a desired color when it is used as a color layer of a color filter, and varies depending on the type of color material used. Is preferably in the range of 10 nm to 200 nm, more preferably 15 nm to 150 nm. When the average primary particle diameter of the color material is in the above range, the display device including the color filter manufactured using the color material dispersion according to the present invention has high contrast and high quality. it can.

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

[Photopolymerizable compound]
The photopolymerizable compound used in the photosensitive colored resin composition of the present invention may be appropriately selected from conventionally known compounds, and is not particularly limited. Usually, a compound having two or more ethylenically unsaturated double bonds Is preferably used, and is particularly preferably a polyfunctional (meth) acrylate having two or more acryloyl groups or methacryloyl groups.
Such polyfunctional (meth) acrylate may be appropriately selected from conventionally known ones. Specific examples include those described in JP2013-029832A.

These polyfunctional (meth) acrylates may be used alone or in combination of two or more. When the photosensitive colored resin composition for color filter of the present invention requires excellent photocurability (high sensitivity), the polyfunctional monomer has three polymerizable double bonds (trifunctional). Preferred are poly (meth) acrylates of polyhydric alcohols having three or more valences and their dicarboxylic acid-modified products, specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tris. (Meth) 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) ) Succinic acid modified product of acrylate, dipen Hexa (meth) acrylate are preferable.

[Initiator]
There is no restriction | limiting in particular as an initiator used in the photosensitive coloring resin composition of this invention, From the conventionally known various initiators, it can be used 1 type or in combination of 2 or more types.

Initiators include aromatic ketones, benzoin ethers, halomethyl oxadiazole compounds, α-amino ketones, biimidazoles, N, N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, thioxanthone, etc. Can do. 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. , Biimidazoles such as 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, halo such as 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole Methyloxadiazole compounds, halomethyl-S-triazine compounds such as 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1, 2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2 Morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4 -Benzoyl-4'-methyldiphenyl sulfide, benzylmethyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone 2,4-dimethylthioxanthone, isopropylthioxanthone, 4-benzoyl-methyldiphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 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) phosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1- For example, propanone.
Among them, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1- Butanone, 4,4′-bis (diethylamino) benzophenone, and diethylthioxanthone are preferably used. Further, the sensitivity is obtained by combining an α-aminoacetophenone initiator such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one with a thioxan initiator such as diethylthioxanthone. It is preferable from the viewpoint of suppressing adjustment and water stain and improving development resistance.
When the α-aminoacetophenone initiator and the thioxan initiator are used, the total content thereof is preferably 5% by mass or more and 15% by mass or less based on the total solid content of the photosensitive colored resin composition. An initiator amount of 15% by mass or less is preferable because sublimates during the production process are reduced. When the initiator amount is 5% by mass or more, 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 that a margin for adjusting the line width can be secured.
As the oxime ester-based photoinitiator, those having an aromatic ring are preferable from the viewpoint of reducing contamination of the colored resin composition for color filters and degradation of the apparatus due to decomposition products, and having condensed rings including aromatic rings. More preferred are those having a condensed ring containing a benzene ring and a heterocycle.
Examples of the oxime ester photoinitiator include oxime ester light described in JP-A No. 2000-80068, JP-A No. 2001-233842, JP-T 2010-527339, JP-T 2010-527338, JP-A 2013-041153, and the like. An initiator etc. are mentioned.

The oxime ester photoinitiator used in the present invention is preferably an oxime ester photoinitiator that generates an aryl radical, particularly a phenyl radical, and more preferably an oxime ester type that generates an alkyl radical, particularly a methyl radical. It is preferable to use a photoinitiator because it has high sensitivity, and when combined with a latent antioxidant, the reduction in line width is small, and solvent resistance and development resistance are excellent. It is presumed that the alkyl radical is more easily activated by radical movement than the phenyl radical. Examples of oxime ester photoinitiators that generate alkyl radicals include ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) (Product name: Irgacure OXE-02, manufactured by BASF), Methanone, [8-[[(Acetyloxy) imino] [2- (2,2,3,3-tetrafluoropropoxy) phenyl] methyl] -11- ( 2-ethylhexyl) -11H-benzo [a] carbazol-5-yl]-, (2,4,6-trimethylphenyl) (trade name: Irgacure OXE-03, manufactured by BASF), ethanone, 1- [9-ethyl -6- (1,3-Dioxolane, 4- (2-methoxyphenoxy) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) ADEKA OPT-N-1919, manufactured by ADEKA), methanone, (9-ethyl-6-nitro-9H-carbazol-3-yl) [4- (2-methoxy-1-methylethoxy-2-methylphenyl]- , O-acetyloxime (trade name Adeka Arcles NCI-831, manufactured by ADEKA), 1-propanone, 3-cyclopentyl-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3- Yl]-, 1- (o-acetyloxime) (trade name TR-PBG-304, manufactured by Changzhou Power Electronics New Materials), 1-propanone, 3-cyclopentyl-1- [2- (2-pyrimidinylthio)- 9H-carbazol-3-yl]-, 1- (o-acetyloxime) (trade name TR-PBG-314, manufactured by Changzhou Power Electronics New Materials Co., Ltd.), Ethanone, 2 Cyclohexyl-1- [2- (2-pyrimidinyloxy) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) (trade name TR-PBG-326, manufactured by Changzhou Power Electronics New Materials Co., Ltd.), Etanone, 2-cyclohexyl-1- [2- (2-pyrimidinylthio) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) (trade name TR-PBG-331, Changzhou Power Electronics New Material 1) -octanone, 1- [4- [3- [1-[(acetyloxy) imino] ethyl] -6- [4-[(4,6-dimethyl-2-pyrimidinyl) thio] -2 -Methylbenzoyl] -9H-carbazol-9-yl] phenyl]-, 1- (o-acetyloxime) (trade name: EXTA-9, manufactured by Union Chemical); Oxime ester-based photoinitiator, (manufactured by ADEKA Corporation), ADEKA arc LUZ NCI-930, and the like TR-PBG-3057 (Changzhou made strong electron new materials Co.).
Specific examples of the initiator that generates a phenyl radical include Irgacure OXE-01 (manufactured by BASF).

As the oxime ester photoinitiator, it is preferable to use an oxime ester photoinitiator having a diphenyl sulfide skeleton from the viewpoint of improving luminance as compared with the case having a carbazole skeleton.
Moreover, it is preferable from the point which a sensitivity improves that at least 2 sorts of oxime system initiators are included. Further, the inclusion of at least two oxime-based initiators is preferable in terms of improving the development resistance and enhancing the effect of suppressing the occurrence of water stains. When at least two kinds of oxime initiators are included, the wavelengths absorbed by the respective initiators are different, so that it is presumed that the light at the time of exposure can be used effectively at the respective absorption wavelengths.
In addition, water stain means that, when a component that enhances alkali developability is used, a trace of water stain is generated after rinsing with pure water after alkali development. Such a water stain disappears after post-baking, so there is no problem as a product. Arise. Therefore, if the inspection sensitivity of the inspection apparatus is lowered in the appearance inspection, the yield of the final color filter product is lowered as a result, which becomes a problem.

In addition, it is preferable to use a photoinitiator having a tertiary amine structure in combination with the oxime ester photoinitiator from the viewpoint of improving sensitivity. Since the photoinitiator having a tertiary amine structure has a tertiary amine structure that is an oxygen quencher in the molecule, radicals generated from the initiator are hardly deactivated by oxygen, and sensitivity can be improved. is there. Examples of commercially available photoinitiators having the tertiary amine structure include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (for example, Irgacure 907, manufactured by BASF), 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (eg Irgacure 369, manufactured by BASF), 4,4′-bis (diethylamino) benzophenone (eg Hycure ABP, Kawaguchi Pharmaceutical).

From the viewpoint of easy sensitivity adjustment, it is preferable to combine an oxime ester photoinitiator with an α-aminoalkylphenone initiator, and among them, an alkyl radical oxime ester compound and an α-aminoalkylphenone. It is more preferable to combine 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. A solvent can be used individually or in combination of 2 or more types.
Specific examples of the solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol, and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; Ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, Ester solvents such as ethyl lactate and cyclohexanol acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc. Tone solvents; glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate; methoxyethoxyethyl acetate, ethoxy Carbitol acetate solvents such as ethoxyethyl acetate and butyl carbitol acetate (BCA); diacetates such as propylene glycol diacetate and 1,3-butylene glycol diacetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene Glycol ether solvents such as glycol diethyl ether, propylene glycol monomethyl ether and dipropylene glycol dimethyl ether; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; γ-butyrolactone, etc. Lactone solvents; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane; Examples include organic solvents such as aromatic hydrocarbons such as xylene. Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferably used from the viewpoint of solubility of other components. Among them, the solvent used in the present invention includes propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, In addition, one or more selected from the group consisting of 3-methoxybutyl acetate is preferable from the viewpoints of solubility of other components and coating suitability.

In the present invention, from the viewpoint of solubility of other components and application suitability, among them, propylene glycol monomethyl ether acetate is included, and further, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol. It is preferable to use a mixed solvent containing one or more selected from 3-methoxy-3-methyl-1-butyl acetate and propylene glycol monomethyl ether acetate. The content ratio of propylene glycol monomethyl ether acetate in the mixed solvent is preferably 70% by mass to 99% by mass and more preferably 80% by mass to 99% by mass with respect to the total amount of the solvent.

[Dispersant]
In the photosensitive colored resin composition of the present invention, the colorant is preferably used by being dispersed in a solvent with a dispersant. In the present invention, the dispersant can be appropriately selected from conventionally known dispersants. Moreover, a dispersing agent can be used individually by 1 type or in combination of 2 or more types. Examples of the dispersant that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Among the surfactants, a polymer dispersant is preferable because it can be uniformly and finely dispersed.

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

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

The repeating unit having a tertiary amine only needs to have a tertiary amine, and the tertiary amine may be contained in the side chain of the block polymer or may constitute the main chain.
Among them, a repeating unit having a tertiary amine in the side chain is preferable, and among them, the repeating unit (a) represented by the following general formula (2) is preferable because the main chain skeleton is hardly thermally decomposed and has high heat resistance. ) Is more preferable.

(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, — [CH (R ⁴⁵ ) —CH ( A divalent organic group represented by R ⁴⁶ ) —O] _x —CH (R ⁴⁵ ) —CH (R ⁴⁶ ) — or — [(CH ₂ ) _y —O] _z — (CH ₂ ) _y —, R ⁴³ and ^{R 44,} each independently, represent a substituted optionally also be a chain or cyclic hydrocarbon ^group, ^{.R 45} and ^{R 46} ^{R 43} and ^{R 44} form a ring structure by bonding with each other is, Each independently represents a hydrogen atom or a methyl group.
x represents an integer of 1 to 18, y represents an integer of 1 to 5, and z represents an integer of 1 to 18. )

Examples of the divalent linking group L in the general formula (2) include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, a —CONH— group, a —COO— group, an ether group having a carbon number of 1 to 10 (— R′—OR ″ —: R ′ and R ″ are each independently an alkylene group) and combinations thereof. Among them, L is a —COO— group or a —CONH— group because of the heat resistance of the polymer obtained, solubility in propylene glycol monomethyl ether acetate (PGMEA) which is suitably used as a solvent, and a relatively inexpensive material. It is preferably a group.

The divalent organic group R ⁴² in the 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 each independently a hydrogen atom or a methyl group.
R ⁴² is preferably an alkylene group having 1 to 8 carbon atoms from the viewpoint of dispersibility, and among them, R ⁴² is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group. Groups are more preferred.

Examples of the cyclic structure formed by combining R ⁴³ and R ^{44 in} the general formula (2) with each other include a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a condensed ring formed by condensing two of these. It is done. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring.

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

In the block part composed of repeating units having a tertiary amine, it is preferable that three or more structural units represented by the general formula (2) are included. Among these, from the viewpoint of improving dispersibility and dispersion stability, it is preferably 3 to 100, more preferably 3 to 50, and even more preferably 3 to 30.

A block having a block part (hereinafter sometimes referred to as A block) composed of a repeating unit having a tertiary amine and a block part having solvent affinity (hereinafter sometimes referred to as B block). As a block part having solvent affinity in the polymer, from the point of improving solvent affinity and improving dispersibility, the polymer does not have the structural unit represented by the general formula (2), and the general formula ( 2) It has a solvent-affinity block part having a structural unit copolymerizable with. In the present invention, the arrangement of each block of the block copolymer is not particularly limited, and for example, an AB block copolymer, an ABA block copolymer, a BAB block copolymer, and the like can be used. Among these, an AB block copolymer or an ABA block copolymer is preferable in terms of excellent dispersibility.
The structural unit copolymerizable with the general formula (2) is a structural unit represented by the following general formula (8) from the viewpoint of improving the heat resistance while improving the dispersibility and dispersion stability of the coloring material. It is preferable that

(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 group having 2 to 18 carbon atoms. Group, an aralkyl group, an aryl group, a 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 each independently a hydrogen atom or a methyl group, and R ⁵¹ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, A monovalent group represented by an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁵² , wherein R ⁵² is a hydrogen atom or a linear, branched, or cyclic alkyl having 1 to 5 carbon atoms. X is an integer from 1 to 18, and y is an integer from 1 to 5. The number z represents an integer of 1-18.

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

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.
Among these, R ⁴⁸ is preferably a methyl group, various butyl groups, various hexyl groups, benzyl groups, cyclohexyl groups, or hydroxyethyl groups 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, and a xylyl group. The aryl group preferably has 6 to 24 carbon atoms, 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, and a biphenylmethyl group. The aralkyl group preferably has 7 to 20 carbon atoms, more preferably 7 to 14 carbon atoms.
Examples of the substituent of the aromatic ring such as an aryl group and an aralkyl group include an alkenyl group, a nitro group, and a halogen atom in addition to a linear or branched alkyl group having 1 to 4 carbon atoms.

R ⁵¹ may be a hydrogen atom or an optionally substituted alkyl group having 1 to 18 carbon atoms, alkenyl group having 2 to 18 carbon atoms, aralkyl group, aryl group, —CHO, —CH ₂ CHO. Or a monovalent group represented by —CH ₂ COOR ⁵² , wherein 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 included include linear, branched or cyclic alkyl groups having 1 to 4 carbon atoms, and halogen atoms such as F, Cl and Br. And so on.
The alkyl group having 1 to 18 carbon atoms and the alkenyl group, aralkyl group and aryl group having 2 to 18 carbon atoms in R ⁵¹ are the same as those described for R ⁴⁸ above.
In the R ⁴⁸ , x, y and z are the same as R ⁴² in the general formula (2).

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

The solvent-affinity block part may be selected so as to function as a solvent-affinity site, and the repeating unit constituting the solvent-affinity block part may be composed of one kind, or two or more kinds. The repeating unit may be included.
In the block copolymer used as the dispersant of the present invention, the ratio between the number m of the structural unit represented by the general formula (2) and the number n of other structural units constituting the solvent-affinity block unit m / n is preferably in the range of 0.01 to 1 and more preferably in the range of 0.05 to 0.7 from the viewpoint of the dispersibility and dispersion stability of the color material. preferable.

In particular, in the present invention, the dispersant is a polymer having a structure represented by the general formula (2) and having an amine value of 40 mgKOH / g or more and 120 mgKOH / g or less. It is preferable from the viewpoint of improving luminance and contrast without depositing foreign matters.
When the amine value is within the above range, the viscosity is excellent in stability over time and heat resistance, and is also excellent in alkali developability and solvent resolubility. In the present invention, the amine value of the dispersant is preferably 80 mgKOH / g or more, 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, more preferably 105 mgKOH / g or less.
The amine value is the number of mg of potassium hydroxide equivalent to perchloric acid required to neutralize the amine component contained in 1 g of a sample, and can be measured by the method defined in JIS-K7237: 1995. . When measured by this method, even if it is an amino group that forms a salt with the organic acid compound in the dispersant, the organic acid compound usually dissociates, so that the block copolymer itself used as the dispersant is itself The amine value of can be measured.

The acid value of the dispersant used in the present invention is preferably 1 mgKOH / g or more as a lower limit from the viewpoint of the effect of suppressing development residue. Among them, the acid value of the dispersant is more preferably 2 mgKOH / g or more from the viewpoint of more excellent development residue suppression effect. In addition, the acid value of the dispersant used in the present invention is 18 mgKOH / g or less as the upper limit of the acid value of the dispersant from the viewpoint of preventing deterioration in development adhesion and solvent resolubility. preferable. Among them, the acid value of the dispersant is more preferably 16 mgKOH / g or less, even more preferably 14 mgKOH / g or less, from the viewpoint that the development adhesiveness and the solvent re-solubility are good. It is particularly preferred 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 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 still more preferably 14 mgKOH / g or less. , 12 mgKOH / g or less is particularly preferable. This is because the development adhesiveness and the solvent resolubility are improved.

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

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

As the carboxy group-containing monomer, a monomer that can be copolymerized with a monomer having a structural unit represented by the general formula (2) and contains an unsaturated double bond and a carboxy group can be used. Examples of such monomers include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and the like. Also, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use acid anhydride group containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxy group. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, glass transition temperature, and the like.

In the block copolymer before salt formation, the content ratio of the structural unit derived from the carboxy group-containing monomer may be appropriately set so that the acid value of the block copolymer is within the range of the specific acid value. Although it is not limited, it is preferable that it is 0.05 mass% or more and 4.5 mass% or less with respect to the total mass of all the structural units of a block copolymer, and is 0.07 mass% or more and 3.7 mass% or less. More preferably.
Since the content ratio of the structural unit derived from the carboxy group-containing monomer is not less than the lower limit value, the effect of suppressing the development residue is expressed, and since it is not more than the upper limit value, the development adhesiveness is deteriorated and the solvent resolubility is reduced. Deterioration can be prevented.
In addition, the structural unit derived from a carboxy group containing monomer should just become said specific acid value, may consist of 1 type, and may contain 2 or more types of structural units.

In the block copolymer, the ratio m / n of the unit number m of the structural unit of the A block and the unit number n of the structural unit of the B block is in the range of 0.05 to 1.5. In view of the dispersibility and dispersion stability of the coloring material, it is more preferably within the range of 0.1 to 1.0.

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 colorant dispersibility and dispersion stability. More preferably, it is more preferably 3000 or more and 12000 or less.
Here, the weight average molecular weight is determined as a standard polystyrene conversion value by (Mw) and gel permeation chromatography (GPC). The macromonomer, salt-type block copolymer, and graft copolymer that are the raw materials for the block copolymer are also subjected to the above conditions.

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

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

In the case of dispersing the colorant using a polymer containing a repeating unit having a tertiary amine as a dispersant, the polymer containing a repeating unit having the tertiary amine with respect to 100 parts by mass of the coloring material. 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 in the said range, it is excellent in the dispersibility and dispersion stability, and the effect which improves a contrast becomes high.

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

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

An acrylic resin such as an acrylic copolymer having a constitutional unit having a carboxy group and a styrene-acrylic copolymer having a carboxy group includes, for example, a carboxy group-containing ethylenically unsaturated monomer and, if necessary, a copolymer. It is a (co) polymer obtained by (co) polymerizing other polymerizable monomers by a known method.
Examples of the carboxy group-containing ethylenically unsaturated monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. It is done. Also, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxy group. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, glass transition temperature, and the like.

The alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of excellent heat resistance and light resistance of the colored layer. It was found that by using an alkali-soluble resin having a hydrocarbon ring, the solvent resistance, heat resistance, and light resistance of the obtained colored layer were improved, and in particular, swelling of the colored layer was suppressed. Although the action is unclear, the bulky hydrocarbon ring in the colored layer suppresses the movement of molecules in the colored layer, resulting in an increase in the strength of the coating and suppression of swelling by the solvent. It is estimated that.
Examples of such a hydrocarbon ring include a cyclic aliphatic hydrocarbon ring which may have a substituent, an aromatic ring which may have a substituent, and combinations thereof. May have a substituent such as a carbonyl group, a carboxy group, an oxycarbonyl group, or an amide group. Especially, when an aliphatic ring is included, while the heat resistance and adhesiveness of a colored layer improve, the brightness | luminance of the obtained colored layer improves.
Specific examples of the hydrocarbon ring include aliphatic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, tricyclo [5.2.1.0 (2,6)] decane (dicyclopentane), and adamantane. Rings: aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, fluorene; chain polycycles such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, stilbene, and cardo structures represented by the following chemical formula (9) It is done.

When an aliphatic ring is included as the hydrocarbon ring, it is preferable from the viewpoint of improving the heat resistance and adhesion of the colored layer and improving the luminance of the obtained colored layer.
Moreover, when the cardo structure shown by the said Chemical formula (9) is included, it is especially preferable from the point which the sclerosis | hardenability of a colored layer improves and solvent resistance (NMP swelling suppression) improves.

In the alkali-soluble resin used in the present invention, it is easy to adjust the amount of each constituent unit by using an acrylic copolymer having a constituent unit having a hydrocarbon ring separately from the constituent unit having a carboxy group. This is preferable because the amount of the structural unit having a hydrocarbon ring is increased to easily improve the function of the structural unit.
The acrylic copolymer having a structural unit having a carboxy group and the hydrocarbon ring is prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned “other monomer capable of copolymerization”. be able to.
Examples of the ethylenically unsaturated monomer having a hydrocarbon ring combined with a latent antioxidant include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, benzyl Examples include (meth) acrylate, phenoxyethyl (meth) acrylate, and styrene. From the viewpoint of excellent heat resistance and light resistance, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (Meth) acrylate and styrene are preferred.

The alkali-soluble resin used in the present invention preferably has an ethylenic double bond in the side chain. In the case of having an ethylenic double bond, the alkali-soluble resins, or the alkali-soluble resin and the polyfunctional monomer can form a cross-linked bond in the curing step of the resin composition at the time of producing the 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 introducing an ethylenic double bond into a side chain by adding a compound having both an epoxy group and an ethylenic double bond in the molecule, such as glycidyl (meth) acrylate, to the carboxy group of the alkali-soluble resin Or by introducing a structural unit having a hydroxyl group into a copolymer, adding a compound having an isocyanate group and an ethylenic double bond in the molecule, and introducing an ethylenic double bond into the side chain. Etc.

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

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

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

The charging amount of the carboxy group-containing ethylenically unsaturated monomer is preferably 5% by mass or more and more preferably 10% by mass or more with respect to the total amount of the monomer from the viewpoint of obtaining a good pattern. On the other hand, from the viewpoint of suppressing film roughness on the pattern surface after development, the amount of the carboxy group-containing ethylenically unsaturated monomer is preferably 50% by mass or less, and 40% by mass or less, based on the total amount of monomers. More preferably.
When the proportion of the carboxy group-containing ethylenically unsaturated monomer is 5% by mass or more, the resulting coating film has sufficient solubility in an alkaline developer. Further, when the ratio of the carboxy group-containing ethylenically unsaturated monomer is 50% by mass or less, dropping of the formed pattern from the substrate and film roughness on the pattern surface can be suppressed during development with an alkali developer.

In addition, in an acrylic resin such as an acrylic copolymer having a structural unit having an ethylenic double bond and a styrene-acrylic copolymer, which is more preferably used as an alkali-soluble resin, an epoxy group and an ethylenic double bond are used. The 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 weight average molecular weight (Mw) of the carboxy group-containing copolymer is preferably in the range of 1,000 to 50,000, and more preferably 3,000 to 20,000. When the weight average molecular weight (Mw) is 1,000 or more, the binder function after curing is excellent, and when the weight average molecular weight (Mw) is within 50,000, pattern formation is facilitated 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 using polystyrene as a standard substance and THF as an eluent.

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

The alkali-soluble resin is preferably selected from those having an acid value of 50 mgKOH / g or more from the viewpoint of developability (solubility) with respect to an alkaline aqueous solution used for the developer. The alkali-soluble resin preferably has an acid value of 70 mgKOH / g or more and 300 mgKOH / g or less from the viewpoint of developability (solubility) with respect to an aqueous alkali solution used for the developer and adhesion to the substrate. It is preferable that they are 70 mgKOH / g or more and 280 mgKOH / g or less.
In the present invention, the acid value can be measured according to JIS K 0070: 1992.

In the case where 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 to 1500. When the ethylenically unsaturated bond equivalent is 2000 or less, the development resistance and adhesion are excellent. Moreover, since the ratio of other structural units, such as the structural unit which has the said carboxy group, and the structural unit which has a hydrocarbon ring, can be relatively increased if it is 100 or more, it is excellent in developability and heat resistance. Yes.
Here, the ethylenically unsaturated bond equivalent is a weight average molecular weight per mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (1).

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

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

[Antioxidant]
It is preferable that the photosensitive colored resin composition of the present invention further contains an antioxidant. By combining the latent antioxidant represented by the general formula (1) and a known antioxidant, the light resistance is particularly superior to that obtained when the latent antioxidant is used alone. In addition to suppressing the decrease in luminance of the colored layer, the antioxidant and the latent antioxidant sequentially exhibit the antioxidant function, thereby suppressing the fading of color materials and the like in all the steps of manufacturing the color filter. be able to.

The antioxidant can be appropriately selected from conventionally known ones. An antioxidant can be used individually by 1 type or in combination of 2 or more types. Specific examples of antioxidants include, for example, hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, and the like. From the viewpoint, it is preferable to use a hindered phenol-based antioxidant.

The hindered phenol antioxidant contains at least one phenol structure, and has a structure in which a substituent having 4 or more carbon atoms is substituted on at least one of the 2-position and 6-position of the hydroxyl group of the phenol structure. Means an antioxidant.
Specific examples of the hindered phenol antioxidant include, for example, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1010, manufactured by BASF). 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris (4-hydroxy- 3,5-di-tert-butylbenzyl) mesitylene (trade name: Irganox 1330, manufactured by BASF), 6- (4-hydroxy-3,5-di-tert-butylanilino) -2,4-bis (octylthio) -1,3,5-triazine (trade name: Irganox 565, manufactured by BASF), 2,2′-thiodiethylbi [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1035, manufactured by BASF), 1,2-bis [3- (4-hydroxy-3,5 -Di-tert-butylphenyl) propionyl] hydrazine (trade name: Irganox MD1024, manufactured by BASF), 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, manufactured by BASF), N, N′-hexamethylenebis [3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propanamide] (trade name: Irganox 1098, manufactured by BASF), 1,6-hexa Didiol [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 Adeka), bis (3-tert-butyl -4-hydroxy-5-methylbenzenepropionic acid) ethylene bis (oxyethylene) (trade name: Irganox 245, manufactured by BASF), 1,3,5-tris [[4- (1,1-dimethylethyl)- 3-hydroxy-2,6-dimethylphenyl] methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trio (Trade name: Irganox 1790, manufactured by BASF), 2,2′-methylenebis (6-tert-butyl-4-methylphenol) (trade name: Sumilizer MDP-S, manufactured by Sumitomo Chemical), 6,6′-thiobis (2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate (trade name: Irgamod 195, manufactured by BASF) ), 2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl acrylate (trade name: Sumilizer GM, manufactured by Sumitomo Chemical), 4,4′- And thiobis (6-tert-butyl-m-cresol) (trade name: Sumilizer WX-R, manufactured by Sumitomo Chemical Co., Ltd.). In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

[Optional components]
The photosensitive colored resin composition of the present invention may contain various additives as necessary.
Examples of the additive include a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an ultraviolet absorber, and an adhesion promoter.

<Combination ratio of each component of 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 can be appropriately prepared according to the use and the like within a range not impairing the effects of the present invention.
The content ratio of the color 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 colored 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. For example, even a liquid photopolymerizable compound is included in the solid content.

The content of the photopolymerizable compound is preferably 5% by mass or more and 60% by mass or less, 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, the photocuring may not proceed sufficiently, and the exposed part may be eluted during development, and if the content of the photopolymerizable compound is greater than the above upper limit, There is a possibility that developability may be lowered.

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 with respect to the total solid content of the photosensitive colored resin composition. If the amount of initiator is less than the above upper limit value, it is preferable because the pattern does not become too thick with respect to the mask opening. If the amount of initiator is not less than the above lower limit, the solvent resistance is good.
Moreover, the total content of two or more oxime initiators when containing at least two oxime initiators as the initiator is 0.1% by mass or more based on 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 highly colored layer can be formed and a photosensitive colored resin composition in which a change in line width is suppressed can be obtained. Therefore, the content 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, based on the total solid content of the photosensitive colored resin composition.

In the case of using an alkali-soluble resin, the content is preferably 5% by mass or more and 60% by mass or less, and preferably 5% by mass or more and 50% by mass with respect to the total solid content of the photosensitive colored resin composition from the viewpoint of developability. The following is more preferable, and 10 mass% or more and 40 mass% or less are still more preferable.
If the content of the alkali-soluble resin is not less than the above lower limit value, sufficient alkali developability can be obtained, and if the content of the alkali-soluble resin is not more than the above upper limit value, film roughness or pattern chipping may occur during development. Can be suppressed.

The content in the case of using the dispersant is not particularly limited as long as it can uniformly disperse the coloring material. For example, the content is 1 with respect to the total solid content of the photosensitive colored resin composition. It can be used in the range of from mass% to 40 mass%. Furthermore, it is preferable to mix | blend in 2 to 30 mass% with respect to the solid content whole quantity of the photosensitive coloring resin composition, and it is preferable to mix | blend especially in the ratio of 3 to 25 mass%. If it is more than the said lower limit, it is excellent in the dispersibility and dispersion stability of a coloring material, and is excellent in the storage stability of the photosensitive coloring resin composition. Moreover, if it is below the said upper limit, developability will become favorable. In particular, when a colored layer having a high colorant concentration is formed, the content of the dispersant is 2% by mass or more and 25% by mass or less, more preferably 3% by mass with respect to the total solid content of the photosensitive colored resin composition. It is preferable to mix | blend in the ratio of% -20 mass%.

Further, when used in combination with a non-latent antioxidant, the content of the antioxidant is a photosensitive colored resin capable of forming a high-brightness colored layer and suppressing a change in line width. In terms of obtaining the composition, it is preferably 0.1% by mass or more and 10% by mass or less, and preferably 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 that the content is 0.1% by mass or more and 5.0% by mass or more. If it is more than the said lower limit, a combined use effect will be easy to be exhibited. On the other hand, if it is below the said upper limit, it can be set as the highly sensitive photosensitive resin composition.
The content ratio between the latent antioxidant represented by the general formula (1) and the antioxidant is that the above general formula ( 1 to 10 parts by mass, preferably 0.1 to 5.0 parts by mass, based on 1 part by mass of the latent antioxidant represented by 1) Is preferred.

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. The total amount of the photosensitive colored resin composition for color filters containing the solvent is usually preferably in the range of 55% by mass to 95% by mass, and more preferably in the range of 65% by mass to 88% by mass. More preferably, it is within. When the content of the solvent is within the above range, the coating property can be excellent.

<Method for producing photosensitive colored resin composition>
The method for producing the photosensitive colored resin composition of the present invention comprises at least a colorant, a photopolymerizable compound, an initiator, a latent antioxidant, and a solvent, and more preferably a dispersant, Can be prepared by mixing using a known mixing means as long as it contains an antioxidant and preferably an alkali-soluble resin and the colorant can be uniformly dispersed or dissolved in the solvent. .
As a method for preparing the resin composition, for example, (1) First, a color material and a dispersant as necessary are added to a solvent to prepare a color material dispersion, and photopolymerization is performed on the dispersion. A method of mixing an optional compound, an initiator, a latent antioxidant, and an optional biweekly addition component; (2) a coloring material, a photopolymerizable compound, an initiator, and a latent in a solvent Examples thereof include a method in which an antioxidant is simultaneously added and mixed.
Among these methods, the method (1) is preferable because it can effectively prevent aggregation of the color material and can be uniformly dispersed.

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

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

Specifically, preliminary dispersion is performed with 2 mm zirconia beads having a relatively large bead diameter, and the main dispersion is further performed with 0.1 mm zirconia beads having a relatively small bead diameter. Moreover, it is preferable to filter with a membrane filter of 0.5 μm or more and 2 μm or less after dispersion.

2. Color filter The color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is the photosensitive colored resin composition according to the present invention. It is a cured product.
A method for producing a color filter according to the present invention is a method for producing a color filter comprising at least a substrate and a colored layer provided on the substrate,
It has the process of forming at least 1 of the said colored layer using the photosensitive colored resin composition which concerns on the said this invention.

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

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

The colored layer can be formed by the following method, for example.
First, the above-described photosensitive colored resin composition of the present invention is applied onto a substrate to be described later using an application means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, or a die coating method. Then, a wet coating film is formed. Of these, spin coating and die coating can be preferably used.
Next, after drying the wet coating film using a hot plate or an oven, it is exposed through a mask having a predetermined pattern and cured by photopolymerization of an alkali-soluble resin and a polyfunctional monomer. Let it be a coating film. Examples of the light source used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
Further, heat treatment may be performed in order to accelerate the polymerization reaction after exposure. The heating conditions are appropriately selected depending on the blending ratio of each component in the photosensitive colored resin composition to be used, the thickness of the coating film, and the like.

Next, it develops using a developing solution, a coating film is formed with a desired pattern by melt | dissolving and removing an unexposed part. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to the alkaline solution. Further, a general method can be adopted as the developing method.
After the development treatment, the developer is usually washed and the cured coating film of the photosensitive colored resin composition is dried to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after image development processing. The heating conditions are not particularly limited and are appropriately selected depending on the application of the coating film.

(Shading part)
The light shielding part in the color filter of the present invention is formed in a pattern on a substrate to be described later, and can be the same as that used as a light shielding part in a general color filter.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. The light shielding part may be a metal thin film such as chromium by sputtering, vacuum deposition or the like. Alternatively, the light shielding part may be a resin layer in which light shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in a resin binder. In the case of a resin layer containing light-shielding particles, a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring the photosensitive resist, etc. is there.

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

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

The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used. Specifically, transparent flexible rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible flexible materials such as transparent resin films, optical resin plates, and flexible glasses. Materials.
The thickness of the transparent substrate is not particularly limited, but for example, a thickness of about 100 μm to 1 mm can be used according to the use of the color filter of the present invention.
The color filter of the present invention includes, for example, an overcoat layer, a transparent electrode layer, an alignment film, an alignment protrusion, a columnar spacer, etc., in addition to the substrate, the light shielding portion, and the colored layer. Also good.

3. Display Device A display device according to the present invention includes the color filter according to the present invention. In the present invention, the configuration of the display device is not particularly limited, and can be appropriately selected from conventionally known display devices, such as a liquid crystal display device and an organic light emitting display device.

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

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

As a method for forming a liquid crystal layer, a method generally used as a method for producing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method. After forming the liquid crystal layer by the above-described method, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.

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

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

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention. In addition, in the following synthesis | combination and preparation, operation was repeated as needed and the desired amount was obtained.

(Synthesis of colorant A)
(1) Synthesis of Intermediate 1 1-Iodonaphthalene 15.2 g (60 mmol) manufactured by Wako Pure Chemical Industries, Ltd. Norbornanediamine (NBDA) (CAS No. 56602-77-8) manufactured by Mitsui Chemicals, Inc.
63 g (30 mmol), sodium-tert-butoxide 8.07 g (84 mmol), Aldrich 2-dicyclohexylphosphino-2 ′, 6 ′,-dimethoxybiphenyl 0.09 g (0.2 mmol), manufactured by Wako Pure Chemical Industries, Ltd. 0.021 g (0.1 mmol) of palladium acetate and 30 mL of xylene were dispersed and reacted at 130-135 ° C. for 48 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted with water. Next, it was dried with magnesium sulfate and concentrated to obtain 8.5 g of intermediate 1 represented by the following chemical formula (i) (yield 70%).
The obtained compound was confirmed to be the target compound from the following analysis results.
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 46 (46. 6 g, 20.8 mmol), Tokyo Chemical Industry 4,4'-bis (dimethylamino) benzophenone (13.5 g, 41.6 mmol) and toluene (60 mL) were added. Stir at ° C. 6.38 g (51.5 mmol) of phosphorus oxychloride manufactured by Wako Pure Chemical Industries, Ltd. was added dropwise, refluxed for 2 hours and cooled. After completion of the reaction, toluene was decanted. The resinous precipitate was dissolved by adding chloroform (40 mL), water (40 mL) 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 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).
The obtained compound was confirmed to be the target compound from the following analysis results.
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 Colorant A Intermediate 2 5.00 g (4.58 mmol) was added to 300 ml of water and dissolved at 90 ° C. to obtain Intermediate 2 solution. Next, 10.44 g (3.05 mmol) of phosphotungstic acid · n hydrate H ₃ [PW ₁₂ O ₄₀ ] · nH ₂ O (n = 30) manufactured by Nippon Inorganic Chemical Industry Co., Ltd. was added to 100 mL of water and stirred at 90 ° C. An aqueous phosphotungstic acid solution was prepared. The intermediate 2 solution was mixed with an aqueous phosphotungstic acid solution 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 coloring material A represented by the following chemical formula (iii).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 510 (+), divalent, elemental analysis value: CHN measured value (41.55%, 5.34%, 4.32%); theoretical value (41.66%) (5.17%, 4.11%)
In addition, it was confirmed by ³¹ P-NMR that the polyacid structure of phosphotungstic acid was maintained even after becoming colorant A.

(Synthesis Example 2: Synthesis of Color Material B)
Acid Red 289 (AR289, manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following formula was added to 500 ml of water and dissolved at 80 ° C. to prepare a dye solution. 3.85 g of polyaluminum chloride (“trade name: Takibaine # 1500” manufactured by Taki Chemical Co., Ltd., Al ₂ (OH) ₅ Cl, basicity 83.5 mass%, alumina content 23.5 mass%) in 200 ml of water The mixture was stirred at 80 ° C. to prepare a polyaluminum chloride aqueous solution. The prepared polyaluminum chloride aqueous solution was added dropwise to the dye solution at 80 ° C. over 15 minutes, and further stirred at 80 ° C. for 1 hour. The formed 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 color material (color material B) of a rhodamine acid dye.

(Synthesis Example 3: Synthesis of Color Material C)
In a 500 ml four-necked flask, 40.2 parts by mass of a 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. The reaction solution was filtered at 60 ° C. to remove insoluble components, and then the solvent was removed under reduced pressure until the reaction solution reached about 70 ml, and the mixture was poured into 200 parts by mass of 6% hydrochloric acid. Next, after adding 600 parts by mass of water and stirring for 30 minutes at room temperature, the wet cake was collected by filtration. The wet cake was suspended in 100 parts by mass of water, stirred at 60 ° C. for 2 hours, filtered again, washed with hot water at 60 ° C., and then dried, whereby a colorant C represented by the following formula: 27.4 parts by mass were obtained.

(Synthesis Example 4: Synthesis of latent antioxidant)
A phenol compound represented by the following chemical formula (vi) (0.01 mol), di-tert-butyl dicarbonate (0.05 mol) and pyridine (30 g) were mixed, and in a nitrogen atmosphere, 0.025 mol of 4-dimethylaminopyridine was added at room temperature. Stir at 0 ° C. for 3 hours. After cooling to room temperature, the reaction solution was poured into 150 g of ion-exchanged water, and 200 g of chloroform was added to perform oil / water separation. The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and 100 g of methanol was added to the residue for crystallization. The obtained white powder crystal was 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 weight of THF and 0.6 parts by weight of lithium chloride to a 500 mL round bottom 4-neck separable flask equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, and perform sufficient nitrogen replacement. It was. After cooling the reaction flask to −60 ° C., 4.9 parts by mass of butyllithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine and 1.0 part by mass of methyl isobutyrate were injected using a syringe. B block monomer 1-ethoxyethyl methacrylate (EEMA) 2.2 parts by weight, 2-hydroxyethyl methacrylate (HEMA) 18.7 parts by weight, 2-ethylhexyl methacrylate (EHMA) 12.8 parts by weight, methacryl 13.7 parts by mass of n-butyl acid (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA), and 17.5 parts by mass of methyl methacrylate (MMA) were added dropwise using an addition funnel over 60 minutes. . After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for the A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, diluted with PGMEA to obtain a solid content solution of 30% by mass. 32.5 parts by mass of water was added, the temperature was raised to 100 ° C., and the mixture was allowed to react for 7 hours. The structural unit derived from EEMA was deprotected to obtain a structural unit derived from methacrylic acid (MAA). The obtained block copolymer PGMEA solution is reprecipitated in hexane, purified by filtration and vacuum drying, and a structural unit derived from a block containing a structural unit represented by the general formula (2) and a carboxy group-containing monomer A block copolymer A (acid value: 8 mgKOH / g) containing B block having solvophilic property was obtained. The block copolymer A thus obtained was confirmed by GPC (gel permeation chromatography), and the weight average molecular weight Mw was 7730. The amine value was 95 mgKOH / g.

(Synthesis Example 6: Synthesis of alkali-soluble resin A)
A polymerization tank was charged with 150 parts by mass of PGMEA and heated to 100 ° C. in 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). And 6 parts by mass of perbutyl O (manufactured by NOF Corporation) and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. Thereafter, the reaction was continued while maintaining 100 ° C., and after 2 hours from the completion of dropping of the main chain forming mixture, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization.
Next, while blowing air, 14 parts by mass of glycidyl methacrylate (GMA) was added as an epoxy group-containing compound, and the temperature was raised to 110 ° C. Then, 0.8 parts by mass of triethylamine was added and the mixture was heated at 110 ° C. for 15 hours. By addition reaction, alkali-soluble resin A (weight average molecular weight (Mw) 9020, acid value 90 mgKOH / g, solid content 40% by mass) was obtained.
The weight average molecular weight was measured by a Shodex GPC System-21H (Shorex GPC System-21H) using polystyrene as a standard substance and THF as an eluent. The acid value was measured based on JIS K 0070: 1992.

(Preparation Example 1: Preparation of colorant dispersion 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 added and stirred. Thereto, 2.45 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Co., Ltd.) (0.7 molar equivalent to the tertiary amino group of the block copolymer) was added and 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 coloring material A, and 100 parts by mass of zirconia beads having a particle size of 2.0 mm, and pre-crush Shake for 1 hour with a paint shaker (manufactured by Asada Tekko Co., Ltd.), then change to 200 parts of zirconia beads with a particle size of 0.1 mm and disperse for 4 hours with the paint shaker as the main crushing to obtain a colorant dispersion A It was.

(Preparation Example 2: Preparation of colorant dispersion B)
A color material dispersion B was obtained in the same manner as in Preparation Example 1 except that Color Material B was used instead of Color Material A in Preparation Example 1.

(Preparation Example 3: Preparation of colorant dispersion C)
To the flask, 1000 parts by mass of methanol was added to 100 parts by mass of the coloring material C, and dissolved with a magnetic stirrer. After confirming dissolution, 19 parts by mass of concentrated hydrochloric acid was added and stirred, and 1000 parts by mass of PGMEA was further added. Next, 198 parts by mass of dispersant block copolymer A was added and stirred. Thereafter, a reflux condenser was connected, the temperature was raised to 80 ° C. with a water bath, and the reaction was performed for 4 hours after reaching 80 ° C. Thereafter, methanol was distilled off by an evaporator at a water bath of 45 ° C., 1000 parts by mass of PGMEA was added, and the mixture was allowed to cool at room temperature for 16 hours. Next, the filtrate obtained by filtration was collected 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 Toagosei Co., Ltd.)) 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 tertiary amine structure: manufactured by BASF) as an initiator, 4.4 parts by mass, NCI-930 (oxime ester photoinitiator: manufactured by ADEKA), 1.5 parts by mass, 0.6 parts by mass of Compound A (latent antioxidant) of Synthesis Example 4 and 55.9 parts by mass of PGMEA were added to obtain a photosensitive binder A.

(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 blending ratio in Production Example 1 was changed as shown in Table 1 below. In addition, the compound (alpha) in Table 1 represents the antioxidant IRGANOX1010 by BASF Corporation.

(Comparative Production Examples 1 and 2: Preparation of photosensitive binders G to H)
Photosensitive binders G to H were obtained in the same manner as in Production Example 1 except that the blending ratio in Production Example 1 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, and 0.16 parts by mass of the surfactant Megafac R08MH (manufactured by DIC) 41.1 parts by mass of PGMEA were mixed to obtain a photosensitive colored resin composition 1 of Example 1.

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

(Comparative Examples 1 and 2: Preparation of photosensitive colored resin compositions X1 and X2)
In Example 1, photosensitive colored resin compositions X1 to X2 were used in the same manner as in Example 1 except that the photosensitive binders G to H of Comparative Production Examples 1 and 2 were used in place of the photosensitive binder A, respectively. Got.

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

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

(Comparative Examples 3 to 4: Preparation of photosensitive colored resin compositions X3 to X4)
In Example 7, photosensitive colored resin compositions X3 to X4 were used in the same manner as in Example 7 except that the photosensitive binders G to H of Comparative Production Examples 1 and 2 were used in place of the photosensitive binder A, respectively. 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 A, 19.7 parts by mass of the color material dispersion A and 8.3 parts by mass of the color material dispersion C were used in combination. A photosensitive colored resin composition 10 was obtained in the same manner as in Example 1 except that the amount of A was changed to 33.9 parts by mass and the 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, a photosensitive colored resin composition was used in the same manner as in Example 10 except that instead of the photosensitive binder A, the photosensitive binder B of Production Example 2 and the photosensitive binder D of Production Example 4 were used. Items 11-12 were obtained.

(Comparative Examples 5 to 6: Preparation of photosensitive colored resin compositions X5 to X6)
In Example 10, 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 in place of the photosensitive binder A, respectively. Got.

(Example 13: Preparation of photosensitive colored resin composition 13)
In Example 1, 41.6 parts by mass of the colorant dispersion C was used instead of 24.6 parts by mass of the colorant dispersion A, and the compounding amount of the photosensitive binder A was 33.1 parts by mass, and the compounding amount of PGMEA Except having changed into 25.2 mass parts, it carried out similarly to Example 1, and obtained the photosensitive colored resin composition 13.

(Examples 14 to 15: Preparation of photosensitive colored resin compositions 14 to 15)
In Example 13, a photosensitive colored resin composition was prepared in the same manner as in Example 13 except that instead of the photosensitive binder A, the photosensitive binder B of Production Example 2 and the photosensitive binder D of Production Example 4 were used. Items 14 to 15 were obtained.

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

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

(Evaluation of line width change rate)
The photosensitive colored resin composition obtained in each example and each comparative example was coated on a glass substrate (NH Techno Glass Co., Ltd., “NA35”) using a spin coater to obtain a cured coating film having a thickness of 3 After coating to a thickness of 0.0 μm, it was dried at 80 ° C. for 3 minutes using a hot plate to form a coating film on the glass substrate. By exposing the coating film with ultraviolet light of 60 mJ / cm ² using an ultrahigh pressure mercury lamp through an independent fine line pattern photomask having a line width of 1 μm to 100 μm, a post-exposure coating film is formed on the glass substrate, Next, 0.05 wt% aqueous potassium hydroxide solution is spin-developed as a developing solution, the developing solution is subjected to an indirect solution for 60 seconds and then washed with pure water, followed by post-processing for 25 minutes in a 230 ° C. clean oven. Baking was performed to form a fine line pattern. Among the formed fine line patterns, the width of the fine line pattern of the portion where the opening width of the chromium mask at the time of exposure corresponds to 90 μm is measured with an optical microscope, and based on the line width of the comparative example in which no antioxidant is added, The line width increase / decrease rate was calculated according to Equation (2). The results are shown in Tables 2-5.
Formula (2): (L−L ₀ ) / L ₀ × 100 (%)
In Formula (2), L ₀ represents the line width of the comparative example to which no antioxidant is added, and L represents the line width of the example or comparative example to be evaluated.
<Evaluation criteria>
A: -3% or more with respect to the line width to which no antioxidant is added B: -10% to less than -3% with respect to the line width to which no antioxidant is added C: against the line width to which no antioxidant is added Less than -10%

[Summary of results in Table 2 to Table 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 using no antioxidant. It was revealed that the line width change was large. On the other hand, since Comparative Examples 1, 3, 5 and 7 did not contain an antioxidant, the change in line width was suppressed, but the luminance 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 color material, and the comparative examples using the conventional antioxidant It was revealed that the line width change was suppressed as compared with. From these results, it became clear 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 of Table 2, by combining the latent antioxidant and the antioxidant, the light resistance is improved as compared with the case where the latent antioxidant is used alone while suppressing the change in the line width. As a result, it was shown that the decrease in luminance of the colored layer due to ultraviolet irradiation can be suppressed.
Further, as shown in the results of Table 5, the photosensitive colored resin composition containing the coloring material C as a dye tended to have a narrow line width. This is presumably because the coloring material C, which is a dye, has decreased sensitivity. In particular, the colored layer using the colored resin composition of Comparative Example 8 has such a combination that the color material C and the antioxidant are insufficient in sensitivity even in the exposed portion, 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 the latent antioxidant can obtain good sensitivity even when such a dye is contained, and has a line width of It became clear that the change was suppressed.

(Production Example 7: Preparation of photosensitive binder I)
Dipentaerythritol penta (meth) acrylate (Aronix M403 (manufactured by Toagosei Co., Ltd.)) 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 tertiary amine structure: manufactured by BASF) 2.9 parts by mass as an initiator, NCI-930 (oxime ester photoinitiator: manufactured by ADEKA) 1.5 parts by mass, 1.5 parts by mass of PBG3057 (oxime ester photoinitiator, Changzhou Power Electronics New Materials Co., Ltd., “TR-PBG-3057”), 0.6 parts by mass of Compound A (latent antioxidant) of Synthesis Example 4 And 55.9 parts by mass of PGMEA were added to obtain a photosensitive binder I.

(Production Example 8, Comparative Production Example 3: Preparation of photosensitive binders J and K)
In Production Example 7, photosensitive binders J and K were obtained in the same manner as Production Example 7 except that the blending ratio was changed as shown in Table 6 below. In addition, the compound (alpha) in Table 6 represents the antioxidant IRGANOX1010 by BASF Corporation.

(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, and 0.16 parts by mass of the surfactant MegaFac R08MH (manufactured by DIC) 41.1 parts by mass of PGMEA were mixed to obtain a photosensitive colored resin composition 16 of Example 16.

(Example 17, Comparative Example 9: Preparation of photosensitive colored resin composition 17, X9)
In Example 16, photosensitive colored resin composition 17 was prepared in the same manner as in Example 16 except that photosensitive binders J and K of Production Example 8 and Comparative Production Example 3 were used instead of photosensitive binder I. X9 was obtained.

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

(Example 19, Comparative Example 10: Preparation of photosensitive colored resin composition 19, X10)
In Example 18, the photosensitive colored resin composition 19 was used in the same manner as in Example 18 except that instead of the photosensitive binder I, the photosensitive binders J and K of Production Example 8 and Comparative Production Example 3 were used, 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 A, 19.7 parts by mass of the color material dispersion A and 8.3 parts by mass of the color material dispersion C were used in combination. A photosensitive colored resin composition 20 was obtained in the same manner as in Example 16, except that the amount of I was changed to 33.9 parts by mass and the 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 was used in the same manner as in Example 20 except that instead of the photosensitive binder I, the photosensitive binders J and K of Production Example 8 and Comparative Production Example 3 were used, respectively. X11 was obtained.

(Example 22: Preparation of photosensitive colored resin composition 22)
In Example 16, in place of 24.6 parts by mass of the color material dispersion A, 41.6 parts by mass of the color material dispersion C was used, the blending amount of the photosensitive binder I was 33.1 parts by mass, and the blending amount of PGMEA. A 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 was obtained in the same manner as in Example 22 except that the photosensitive binders J and K of Production Example 8 and Comparative Production Example 3 were used instead of the photosensitive binder I. X12 was obtained.

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

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

(Water stain evaluation)
A colored layer having a thickness of 1.6 μm is formed on the glass substrate (NH Techno Glass Co., Ltd., “NA35”) after post-baking the photosensitive colored resin composition for color filter using a spin coater. After coating with a film thickness, it is dried at 60 ° C. for 3 minutes using a hot plate, and colored on the glass substrate by irradiating the entire surface with 60 mJ / cm ² ultraviolet rays using an ultrahigh pressure mercury lamp without using a photomask. A layer was formed. Next, spin development is performed using 0.05 wt% potassium (KOH) as a developer, the developer is subjected to an indirect solution for 60 seconds and then washed with pure water, and the washed substrate is rotated for 10 seconds to remove water. Immediately after centrifugation, the contact angle of pure water was measured as described below to evaluate water stain.
The contact angle of pure water is measured by dropping 1.0 μL of pure water on the surface of the colored layer immediately after removing the water by centrifugation, and determining the static contact angle 30 seconds after the landing according to the θ / 2 method. Measured. The measuring device was measured using a contact angle meter DM 500 manufactured by Kyowa Interface Science Co., Ltd.
<Evaluation criteria>
A: Contact angle of 80 ° or more B: Contact angle of 65 ° or more and less than 80 ° C: Contact angle of 50 ° or more and less than 65 ° D: Contact angle of less than 50 ° If the water stain evaluation standard is A or B, it can be used practically. However, if the evaluation result is A, the effect is more excellent.

(Development resistance evaluation)
The photosensitive colored resin composition for a color filter was applied on a glass substrate having a thickness of 0.7 mm (“NA35” manufactured by NH Techno Glass Co., Ltd.) using a spin coater. After heating and drying on an 80 ° C. hot plate for 3 minutes, ultraviolet rays of 30 mJ / cm ² were irradiated using an ultrahigh pressure mercury lamp. The film thickness at this point is measured and set to T1 (μm). Thereafter, shower development was performed using a 0.05% by mass aqueous potassium hydroxide 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 used practically, but if the evaluation criterion is A, the effect is more excellent.

[Summary of results in Tables 7 to 8]
From the results of Table 7, it was shown that when at least two oxime initiators were included, the line width was increased and the sensitivity was improved. In addition, the results shown in Table 8 indicate that when at least two oxime initiators are included, the development resistance is improved, and the effect of suppressing the occurrence of water stains is enhanced.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Light-shielding part 3 Colored layer 10 Color filter 20 Counter substrate 30 Liquid crystal layer 40 Liquid crystal display device 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection layer 73 Hole transport layer 74 Light emitting layer 75 Electron injection layer 76 Cathode 80 Organic light emitter 100 Organic light emitting display device

Claims

A colorant, a photopolymerizable compound, an initiator, a latent antioxidant, and a solvent, wherein the colorant includes one or more selected from a dye and a lake colorant, The photosensitive coloring resin composition in which antioxidant contains the compound represented by following General formula (1).

(In general formula (1), ring A is a 5-membered or 6-membered hydrocarbon ring or heterocyclic ring,
R 1 each independently has a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxy group, an alkyl group having 1 to 40 carbon atoms which may have a substituent, or a substituent. 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 Or a plurality of R 1 are bonded to each other to form a benzene ring or a naphthalene ring,
R 2 is 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, or 2 to 2 carbon atoms. 20 heterocycle-containing groups, or trialkylsilyl groups,
In the alkyl group of R 1 and R 2 , a carbon-carbon double bond, —O—, —S—, —C (═O) —, —O—C (═O) —, —C (═O ) —O—, —O—C (═O) —O—, —S—C (═O) —, —C (═O) —S—, —S—C (═O) —O—, — OC (═O) —S—, —C (═O) —NH—, —NH—C (═O) —, —NH—C (═O) —O—, —NR′—, —S -S- or -SO 2 -may be present, R 'is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R 1 and R 2 may be the same or different. May be.
X is an a-valent group, and is a direct bond, nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, (—O) 3 P═O,>C═O,> NR 3 , —OR 3 , —SR 3 , —N (R 3 ) (R 4 ), an optionally substituted aliphatic hydrocarbon group having 1 to 120 carbon atoms, and optionally having 6 to 35 carbon atoms An aromatic ring-containing hydrocarbon group or a heterocyclic group having 2 to 35 carbon atoms which may have a substituent, and R 3 and R 4 each independently represents a hydrogen atom or a substituent. An aliphatic hydrocarbon group having 1 to 35 carbon atoms that may have, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms that may have a substituent, or a substituent. It is also a heterocyclic group having 2 to 35 carbon atoms. In the aliphatic hydrocarbon group and the aromatic ring-containing hydrocarbon group in X, a carbon-carbon double bond, —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'-, -SS-, -SO 2-, or 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. )
Furthermore, the photosensitive coloring resin composition of Claim 1 containing a hindered phenolic antioxidant.
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, — [CH (R 45 ) —CH ( A divalent organic group represented by R 46 ) —O] x —CH (R 45 ) —CH (R 46 ) — or — [(CH 2 ) y —O] z — (CH 2 ) y —, R 43 and R 44, each independently, represent a substituted optionally also be a chain or cyclic hydrocarbon group, .R 45 and R 46 R 43 and R 44 form a ring structure by bonding with each other is, Each independently represents a hydrogen atom or a methyl group.
x represents an integer of 1 to 18, y represents an integer of 1 to 5, and z represents an integer of 1 to 18. )
The color material includes one or more selected from a lake color material having a xanthene skeleton, a lake color material having a triarylmethane skeleton, and a dye having a xanthene skeleton. The photosensitive colored resin composition described in 1.
The solvent includes 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 coloring resin composition as described in any one of Claims 1 thru | or 4 containing 1 or more types selected from propylene glycol monomethyl ether acetate.
The photosensitive colored resin composition according to any one of claims 1 to 5, wherein the initiator includes an oxime 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 initiators.
A color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured cured photosensitive colored resin composition according to any one of claims 1 to 7. Color filters that are things.
A method for producing a color filter comprising at least a substrate and a colored layer provided on the substrate,
The manufacturing method of a color filter which has the process of forming at least 1 of the said colored layer using the photosensitive colored resin composition as described in any one of Claims 1 thru | or 7.
A display device comprising the color filter according to claim 8.