TW201807485A - Photosensitive color resin composition, color filter and production method thereof, and display device - Google Patents

Abstract

The present invention provides a photosensitive color resin composition that can form a high-luminance color layer and inhibits a change in line width. Disclosed is a photosensitive color resin composition including a color material, a photopolymerizable compound, an initiator, a latent antioxidant and a solvent, wherein the color material contains one or more selected from dyes and lake color materials, and the latent antioxidant contains a compound represented by the following general formula (1): (the symbols in the formula are as described in the specification.).

Description

Photosensitive colored resin composition, color filter, manufacturing method thereof and display device

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

A thin image display device typified by a display or the like, that is, a so-called flat panel display, is characterized in that it is thinner than a cathode ray tube type display and does not occupy a space in the depth direction, and has been widely marketed. Its market price is steadily increasing year by year with the evolution of production technology, and the demand is expanding, and the production volume is increasing year by year. In particular, color LCD TVs have become the mainstream of TV. In addition, an organic light-emitting display device such as an organic EL display having high visibility from self-luminous light has recently attracted attention as a next-generation video display device. In view of the performance of these image display devices, it is strongly desired to further improve image quality or power consumption, such as improvement in contrast or color reproducibility.

Color filters are used in such liquid crystal display devices or organic light emitting display devices. For example, in the case of a color liquid crystal display, a backlight is used as a light source, and the amount of light is controlled by electrically driving the liquid crystal, and the light passes through the color filter, thereby performing color expression. Therefore, color filters are indispensable for the color performance of LCD TVs and play an important role in the performance of left and right displays. Further, in the organic light-emitting display device, a color filter is used to adjust the color of the pixel, or a color filter is used for the white light-emitting organic light-emitting device, and a color image is formed in the same manner as the liquid crystal display device.

As a trend in recent years, power saving of an image display device is required, and in order to improve the utilization efficiency of a backlight, high luminance of a color filter is particularly required. Especially in mobile displays (mobile phones, smart phones, tablet PCs) has become a big issue.

Although the battery capacity has increased due to technological evolution, the power storage capacity of the mobile terminal is still limited, and on the other hand, there is a tendency to increase power consumption as the screen size increases. Since it is directly related to the usable time or charging frequency of the mobile terminal, the image display device including the color filter will design the left or right mobile terminal or the performance.

Here, the color filter generally has a substrate, a coloring layer formed on the substrate and including a color pattern of three primary colors of red, green, and blue, and a light blocking portion formed on the substrate to divide each colored pattern.

As one of the methods for forming such a coloring layer, a method of applying a photosensitive resin composition containing a color material and a photopolymerizable compound to a substrate and curing it by irradiation with ultraviolet rays is known.

As the color material of the photosensitive resin composition, a pigment or a dye is used. In contrast to dyes, pigments generally have superior heat resistance and light resistance, but when heated at a high temperature in the color filter manufacturing step, fading cannot be sufficiently prevented, and the luminance is lowered.

In addition, in recent years, from the viewpoint of the further high-intensity of the color filter, the photosensitive resin composition for a color filter using a dye having a high general transmittance has been reviewed, and To improve the heat resistance or light resistance of the dye, it is also reviewed to use a lake color material in which the dye is insolubilized. However, since the dye is inferior in heat resistance and light resistance compared to the pigment, there is a problem that the chromaticity is liable to change or the luminance of the colored layer is liable to be lowered during high-temperature heating or light irradiation in the color filter manufacturing step.

As one of the methods for solving the above problems, it has been reviewed to use a resin composition containing an antioxidant.

For example, Patent Document 1 discloses a radiation sensitive linear composition for a blue color filter, which contains a blue colorant, an alkali-soluble resin, a polyfunctional monomer, a specific photopolymerization initiator, and a specific ratio according to a specific ratio. Antioxidants. According to Patent Document 1, a blue pixel having high luminance can be formed.

Further, Patent Document 2 discloses a colored resin composition for a color filter, which comprises a lake pigment, a specific dispersant, a hindered phenol-based antioxidant, a binder component, and a solvent. According to Patent Document 2, a high-luminance coloring layer can be formed by improving the heat resistance by a hindered phenol-based antioxidant.

On the other hand, according to Patent Document 3, as a coloring photosensitive composition having excellent heat resistance, a coloring photosensitive composition containing a specific latent antioxidant and a specific organic dye is disclosed.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2014-160254

Patent Document 2: Japanese Patent Laid-Open Publication No. 2014-153569

Patent Document 3: International Publication No. 2014/021023

In general, a color filter is patterned on a substrate by a color layer. When a coloring layer is formed using a photosensitive colored resin composition, for example, a coating film of a photosensitive colored resin composition can be formed on a substrate, and then exposed through a predetermined mask pattern, followed by development processing, thereby producing a Patterned color layer.

The present inventors have directed to the use of a photosensitive colored resin containing an antioxidant. The matter, through the above methods to form the color layer for review. As a result, the present inventors have found that when the photosensitive resin composition containing an antioxidant is used, there is a case where a coloring layer cannot be formed as designed.

The present invention has been made in view of the above-described findings, and an object of the invention is to provide a coloring resin composition capable of forming a high-luminance coloring 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 excellent in display characteristics using the color filter.

The photosensitive colored resin composition of the present invention contains a color material, a photopolymerizable compound, a starter, a latent antioxidant, and a solvent, and the color material contains one or more selected from the group consisting of a dye and a lake color material. The latent antioxidant is a compound represented by the following general formula (1);

(The symbols in the general formula (1) are as follows.)

The color filter of the present invention includes at least a substrate and a coloring layer provided on the substrate, and at least one of the colored layers is a cured product of the photosensitive colored resin composition of the present invention.

A method of producing a color filter according to the present invention is a method of manufacturing a color filter including at least a substrate and a coloring layer provided on the substrate, wherein There is a step of forming at least one of the colored layers by using the photosensitive colored resin composition of the present invention described above.

Further, the display device of the present invention is characterized by having the above-described color filter of the present invention.

According to the present invention, it is possible to provide a coloring resin composition capable of forming a high-luminance coloring layer and suppressing a change in line width, a high-intensity color filter formed using the photosensitive colored resin composition, and using the color filter A color filter is used to display a display device having superior characteristics.

1‧‧‧Substrate

2‧‧‧Lighting Department

3‧‧‧Colored layer

10‧‧‧Color filters

20‧‧‧ opposite substrate

30‧‧‧Liquid 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‧‧‧Lighting layer

75‧‧‧Electronic injection layer

76‧‧‧ cathode

80‧‧‧Organic emitters

100‧‧‧Organic light-emitting display device

Fig. 1 is a schematic cross-sectional view showing an example of a color filter of the present invention.

Fig. 2 is a schematic cross-sectional view showing an example of a 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 of the present invention will be described in order.

Still, in the present invention, the light includes electromagnetic waves of wavelengths of visible and non-visible regions, and further includes radiation, and the radiation system 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, the (meth)acrylic acid means acrylic acid and methacrylic acid, respectively, and the (meth)acrylic acid ester means acrylate and methacrylate, respectively.

The term "organic group" as used in the present invention means a group having one or more carbon atoms.

Further, the term "solid content" as used in the present invention means a solvent other than the solvent constituting the resin composition. All ingredients, such as even liquid monomers, are considered to be included in the solid portion.

1. Photosensitive colored resin composition

The photosensitive colored resin composition of the present invention contains a color material, a photopolymerizable compound, a starter, a latent antioxidant, and a solvent, and the color material contains one or more selected from the group consisting of a dye and a lake color material. The latent antioxidant is a compound represented by the following general formula (1).

(In general formula (1), ring A is a five-membered or six-membered hydrocarbon ring or a heterocyclic ring; and R ^{1 is} independently a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, or a carbon which may have a substituent. An alkyl group having 1 to 40 atomic atoms, an aryl group having 6 to 20 carbon atoms which may have a substituent, an arylalkyl group having 7 to 20 carbon atoms which may have a substituent, or a substituent a heterocyclic group having 2 to 20 carbon atoms, or a plurality of R ¹ 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, and carbon An aryl group having 6 to 20 atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a trialkylsulfonyl group; and an alkane having R ¹ and R ² In the base, it may also have a carbon-carbon double bond, -O-, -S-, -C(=O)-, -OC(=O)-, -C(=O)-O-, -OC(= O)-O-, -SC(=O)-, -C(=O)-S-, -SC(=O)-O-, -OC(=O)-S-, -C(=O) -NH-, -NH-C(=O)-, -NH-C(=O)-O-, -NR'-, -SS- or -SO ₂ -, R' is a hydrogen atom or a carbon atom ~8 alkyl, the plural R ¹ and R ² respectively may be the same or different; X is a valence group, which is a direct bond, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, (-O ₃ P=O, >C=O, >NR ³ , -OR ³ , -SR ³ , -N(R ³ )(R ⁴ ), an aliphatic hydrocarbon group having 1 to 120 carbon atoms which may have a substituent Further, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms of the substituent or the heterocyclic group having 2 to 35 carbon atoms which may have a substituent; R ³ and R ⁴ are each independently a hydrogen atom; An aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, an aromatic cyclic hydrocarbon group having 6 to 35 carbon atoms which may have a substituent, or a heterocyclic ring having 2 to 35 carbon atoms which may have a substituent The above-mentioned aliphatic hydrocarbon group in X and the above aromatic-containing hydrocarbon group may have a carbon-carbon double bond, -O-, -S-, -C(=O)-, -OC(=O)- , -C(=O)-O-, -OC(=O)-O-, -SC(=O)-, -C(=O)-S-, -SC(=O)-O-,- OC(=O)-S-, -C(=O)-NH-, -NH-C(=O)-, -NH-C(=O)-O-, -NR'-, -SS- or -SO ₂ - or a nitrogen atom; a represents an integer from 1 to 10, b represents an integer from 1 to 4, and c represents an integer from 1 to 3.)

The photosensitive colored resin composition of the present invention has an effect of forming a coloring layer having high luminance and suppressing a change in line width at the time of development.

The effect of obtaining the above effects according to the constitution of the present invention has not been clarified, but it can be inferred as follows.

Conventionally, as a method for improving heat resistance and light resistance, it has been reviewed that an antioxidant is added to a photosensitive resin composition. In general, the antioxidant suppresses oxidation of a color material or the like by deactivating radicals or the like generated during heating or exposure. However, the present inventors have found that a coating film of a coloring photosensitive resin composition containing an antioxidant is used. Exposure by a predetermined mask pattern, followed by development processing to form a patterned coloring layer, and line width compared to the case of using a photosensitive colored resin composition which does not contain an antioxidant Thinner. The reason for this is presumed to be that the antioxidant is deactivated by the radical from the initiator at the time of exposure. Therefore, the photopolymerization reaction is not sufficiently carried out by using an antioxidant, and the sensitivity is insufficient.

In order to obtain a fine line pattern as designed without changing the mask pattern, it is considered to add, for example, a large amount of the initiator. However, in such a method, the ratio of the color material is relatively lowered, and there is a problem that the desired chromaticity cannot be achieved.

The photosensitive colored resin composition of the present invention contains a latent antioxidant represented by the general formula (1). The latent antioxidant protects the phenolic hydroxyl group which exhibits an antioxidant effect by a protecting group. Since the latent antioxidant does not have an antioxidant function at the time of exposure, the radical derived from the initiator is not deactivated, the suppression sensitivity is lowered, and the line width is suppressed from being reduced. On the other hand, in the heating step performed after the exposure, the protective group is detached to exhibit an antioxidant effect, so that fading of the color material or the like is suppressed, and a high-luminance coloring layer is obtained.

The photosensitive colored resin composition of the present invention contains at least a color material, a photopolymerizable compound, a starter, a latent antioxidant, and a solvent, and may be further included before the effect of the present invention is not impaired, and may be further contained as necessary. Other ingredients.

The components of the colored resin composition for a color filter of the present invention will be described in detail below.

[latent antioxidants]

The term "latent antioxidant" as used in the present invention refers to a compound having a protective group which can be removed by heating, and which exhibits an antioxidant function by being detached from the protective group. Among them, it is preferred to cause the protective group to be easily separated by heating at 150 ° C or higher.

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

(The symbols in the general formula (1) are as described above.)

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

Ring A in the above general formula (1) is a hydrocarbon ring or a heterocyclic ring of a five-membered or six-membered ring.

Examples of the hydrocarbon ring of the five-membered ring include an alicyclic ring such as a cyclopentane ring or a cyclopentene ring, or an aromatic ring such as cyclopentadiene or ferrocene.

Examples of the heterocyclic ring of the five-membered ring include furan, thiophene, pyrrole, pyrrolidine, pyrazole, pyrazole, imidazole, and imidazolium. Azole Azole Zolidine, thiazole, isothiazole, isothiazolidine and the like.

The hydrocarbon group of the six-membered ring may, for example, be a six-membered ring alicyclic ring such as a cyclohexane ring, a cyclohexene ring or a cyclohexadiene ring, or a six-membered member such as benzene, naphthalene, anthracene, anthracene, anthracene or anthracene. The aromatic ring of the ring.

The heterocyclic ring of the six-membered ring may, for example, be piperidine or piperidine. , Porphyrin, thio Porphyrin, pyridine, pyridyl Pyrimidine ,three Wait.

These rings may also be condensed or substituted with other rings, for example, may also constitute quinoline, isoquinoline, anthracene, Pyrrolidine Oxazole, benzotriazole, hydrazine, and the like.

In the present invention, the ring A is preferably a six-membered ring aromatic ring or a heterocyclic ring, from the viewpoint of obtaining a photosensitive coloring resin composition capable of forming a high-luminance coloring layer and suppressing a change in line width. The aromatic ring of the six-membered ring is more preferably an aromatic ring selected from the group consisting of benzene, naphthalene, anthracene and anthracene.

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

In R ¹ , the alkyl group having 1 to 40 carbon atoms which may have a substituent may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group or a third butyl group. Isobutyl, pentyl, isopentyl, third pentyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3- Heptyl, isoheptyl, third heptyl, 1-octyl, isooctyl, trioctyl, decyl, isodecyl, fluorenyl, eleven, twelve, thirteen, iso Tris, tetradecyl, fifteen, hexadecyl, heptadecyl, octadecyl, adamantyl, 1-adamantyl, 2-adamantyl, 2-methyl-1-gold steel alkyl , 2-methyl-2-adamantyl, 2-ethyl-1-adamantyl, 2-ethyl-2-adamantyl, 2-lower Base, 2-low Methyl group and the like.

In R ¹ , examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthalene group, a fluorenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, and a 4-vinyl group. Phenylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4-(2-ethylhexyl)phenyl, 4-stearylphenyl, 2,3-dimethylphenyl, 2,4-dimethyl Phenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di Tributylphenyl, 2,5-di-t-butylphenyl, 2,6-di-t-butylphenyl, 2,4-di-t-pentylphenyl, 2,5-di-third Phenylphenyl, 2,5-di-t-octylphenyl, 2,4-diisopropylphenylphenyl, 4-cyclohexylphenyl, (1,1'-biphenyl)-4-yl, 2,4,5-trimethylphenyl, ferrocene, and the like.

In R ¹ , examples of the heterocyclic group having 2 to 20 carbon atoms include a pyridyl group, a pyrimidinyl group and an anthracene group. Base, piperidinyl, piperidyl, pyrazolyl, tri , pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furyl, benzofuranyl, thienyl, phenylthio, benzophenylthio, Thiadiazolyl, thiazolyl, benzothiazolyl, Azolyl, benzo Azolyl, isothiazolyl, iso Azyl, fluorenyl, 2-pyrrolidone-1-yl, 2-piperidin-1-yl, 2,4-dioxaimidazolyl-3-yl, 2,4-dioxo Zyridin-3-yl and the like.

Further, in R ¹ , examples of the substituent of the substituted alkyl group, the aryl group or the hydrogen atom containing a heterocyclic group include an ethylenically unsaturated group such as a vinyl group, an allyl group, an acryl group or a methacryl group; a halogen atom such as fluorine, chlorine, bromine or iodine; an ethyl fluorenyl group, a 2-chloroethyl fluorenyl group, a propyl fluorenyl group, a octyl decyl group, an acryl fluorenyl group, a methacryl fluorenyl group, a phenylcarbonyl group (benzhydryl group), an anthracene Sulfhydryl, 4-trifluoromethylbenzhydryl, trimethylethenyl, sulfonyl, oxalinyl, stearyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, positive a mercapto group such as an octadecyloxycarbonyl group or an amine carbenyl group; a decyloxy group such as an ethoxycarbonyl group or a benzhydryloxy group; an amine group, an ethylamino group, a dimethylamino group, and a diethylamine; Base, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, chlorophenylamino group, toluidine group, methoxyaniline group, N-methyl group Anilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, ethylamino, benzhydrylamine, formazan Amino group, trimethyl ethinylamine Base, laurylamine, amine mercaptoamine, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, Polinylcarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino , phenoxycarbonylamino, aminesulfonylamino, N,N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonate Substituted amine group such as arylamino group; sulfonylamino group, sulfonyl group, carboxyl group, cyano group, fluorenyl group, hydroxyl group, nitro group, fluorenyl group, fluorenylene group, amine carbaryl group, sulfonylamino group, sulfonic acid a salt such as a phosphate group or a carboxyl group, a sulfhydryl group, a sulfonic acid group or a phosphoric acid group.

In the R ² in the above general formula (1), examples of the alkyl group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms in the alkyl group exemplified in the above R ¹ .

In R ² , examples of the alkenyl group having 2 to 20 carbon atoms include a vinyl group, a 1-methylvinyl-1-yl group, a propen-1-yl group, a propen-2-yl group, a propen-3-yl group, and a butyl group. Alken-1-yl, buten-2-yl, 2-methylpropen-3-yl, 1,1-dimethylvinyl-2-yl, 1,1-dimethylpropen-3-yl, 3 -butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl, octenyl, Decenyl, pentadecenyl, nonenyl, indolyl and the like.

In R ² , the aryl group having 6 to 20 carbon atoms, the arylalkyl group having 7 to 20 carbon atoms, and the heterocyclic group having 2 to 20 carbon atoms are, for example, the same as those exemplified as R ¹ . By.

Further, examples of the trialkylsulfonyl group in R ² include trimethyldecane, triethyldecane, and ethyldimethyldecane.

Further, in the case where the above R ¹ and R ² have an alkyl group, they may have a carbon-carbon double bond, -O-, -S-, -C(=O)-, -OC(= in the alkyl chain. O)-, -C(=O)-O-, -OC(=O)-O-, -SC(=O)-, -C(=O)-S-, -SC(=O)-O -, -OC(=O)-S-, -C(=O)-NH-, -NH-C(=O)-, -NH-C(=O)-O-, -NR'-, - SS- or -SO ₂ -.

R' of the above -NR'- group is an alkyl group having 1 to 8 carbon atoms, and specific examples thereof include an alkyl group having 1 to 8 carbon atoms in the alkyl group exemplified in the above R ¹ .

Further, in the case where the above structure is contained in the alkyl chain, it is preferred that the structure (O-O-) in which oxygen atoms are bonded to each other is not provided.

In the present invention, R ^{1 is} preferably an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms from the viewpoint of easy synthesis. Further, R ¹ is preferably a substituent having 4 or more carbon atoms from the viewpoint of excellent heat resistance and light resistance as a latent antioxidant. Specific examples of the substituent having 4 or more carbon atoms include a tertiary alkyl group such as a third butyl group, a third pentyl group or a third hexyl group; and a second alkyl group such as a second butyl group and a second pentyl group. a branched alkyl group such as an isobutyl group or an isopentyl group; a cycloalkyl group such as a cyclohexyl group or a cyclopentyl group; and a 3-stage alkyl group from the viewpoint of reactivity with a radical; Particularly preferred is a third butyl group.

Further, in the present invention, R ^{2 is} bonded to -C(=O)-O- at the end of the oxygen atom side of the alkyl group having 2 to 8 carbon atoms, and is preferably used as a latent property. The function of the additive. That is, the substituent -OR ² in the general formula (1) is preferably -OC(=O)-OR"(R" is an alkyl group having 1 to 7 carbon atoms).

The structure of the aliphatic hydrocarbon group represented by X in the above general formula (1) and having a substituent having a carbon atomic number of from 1 to 120 is not particularly limited. The aliphatic hydrocarbon group may be any of a linear chain, a branched chain, a cyclic (alicyclic hydrocarbon), and the like. Further, the aliphatic hydrocarbon group is in the aliphatic hydrocarbon group, and may have a carbon-carbon double bond, -O-, -S-, -C(=O)-, -OC(=O)-, -C( =O)-O-, -OC(=O)-O-, -SC(=O)-, -C(=O)-S-, -SC(=O)-O-, -OC(=O )-S-, -C(=O)-NH-, -NH-C(=O)-, -NH-C(=O)-O-, -NR'-, -SS- or -SO ₂ - Or a nitrogen atom. For example, examples of the monovalent aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, a second butyl group, a third butyl group, an isobutyl group, and a pentyl group. Isoamyl, third amyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, bicyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, Alkyl groups such as isoheptyl, third heptyl, n-octyl, isooctyl, trioctyl, 2-ethylhexyl, decyl, isodecyl, fluorenyl, etc.; methoxy, ethoxy, Propyloxy, isopropoxy, butoxy, second butoxy, tert-butoxy, isobutoxy, pentyloxy, isopentyloxy, third pentyloxy, hexyloxy, ring Hexyloxy, heptyloxy, isoheptyloxy, third heptyloxy, n-octyloxy, isooctyloxy, trioctyloxy, 2-ethylhexyloxy, decyloxy, decyloxy Alkoxy; methylthio, ethylthio, propylthio, isopropylthio, butylthio, second butylthio, tert-butylthio, isobutylthio, pentylthio, isova Sulfur, third pentylthio, hexylthio, cyclohexylthio, heptylthio, isoheptylthio, third heptane Alkylthio group such as n-octylthio, isooctylthio, trioctylthio, 2-ethylhexylthio; vinyl, 1-methylvinyl, 2-methylvinyl, 2- Propylene, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, An alkenyl group such as a cyclohexene group, a heptenyl group, an octenyl group, a nonenyl group, a pentacenyl group, a nonenyl group, a decyl group, or the like; or a combination of the above groups with the following substituents; The above aliphatic hydrocarbon group may have a structure in which a part of hydrogen atoms of one of the above monovalent aliphatic hydrocarbon groups are removed.

The structure of the aromatic ring-containing hydrocarbon group having a substituent of a carbon atom having 6 to 35 carbon atoms in the substituent X may not be particularly limited. For example, examples of the monovalent aromatic-containing cyclic hydrocarbon group include an arylalkyl group such as a benzyl group, a phenethyl group, a diphenylmethyl group, a triphenylmethyl group, a styryl group or a cinnamyl group; a phenyl group and a naphthalene group; An aryl group such as a phenoxy group or a naphthyloxy group; an arylthio group such as a phenylthio group or a naphthylthio group; or a combination of the above groups and the following substituents; The hydrocarbon group may have a structure in which, for example, a part of the hydrogen atom of the monovalent aromatic-containing cyclic hydrocarbon group is removed. Further, the aromatic ring-containing hydrocarbon group may be a carbon-carbon double bond, -O-, -S-, -C(=O)-, -OC(=O)-, in the aromatic ring-containing hydrocarbon group. -C(=O)-O-, -OC(=O)-O-, -SC(=O)-, -C(=O)-S-, -SC(=O)-O-, -OC (=O)-S-, -C(=O)-NH-, -NH-C(=O)-, -NH-C(=O)-O-, -NR'-, -SS- or - SO ₂ - or a nitrogen atom.

The structure of the heterocyclic group having a valence of a carbon atom having 2 to 35 carbon atoms which may have a substituent in X is not particularly limited. For example, examples of the monovalent heterocyclic group include a pyridyl group, a pyrimidinyl group and an anthracene group. Base, piperidinyl, piperidyl, prazolyl, tri , pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furyl, benzofuranyl, thienyl, phenylthio, benzophenylthio, Thiadiazolyl, thiazolyl, benzothiazolyl, oxygen Azoyl, phenoxy Azolyl, isothiazolyl, iso Azyl, fluorenyl, 2-pyrrolidone-1-yl, 2-piperidin-1-yl, 2,4-dioxaimidazolyl-3-yl, 2,4-dioxo a combination of a oxazolidin-3-yl group, a phenoxytriazolyl group, or the like, or a combination of the above substituents, and the like, and the divalent or higher heterocyclic group may, for example, be a part of the above-mentioned monovalent heterocyclic group-containing hydrogen atom. Construction.

Examples of the substituent which X may have include an ethylenically unsaturated group such as a vinyl group, an allyl group, an acryl group or a methacryl group; a halogen atom such as fluorine, chlorine, bromine or iodine; an ethyl fluorenyl group; - chloroethyl fluorenyl, propyl fluorenyl, octyl decyl, acryl fluorenyl, methacryl fluorenyl, phenylcarbonyl (benzylidene), fluorenyl, 4-trifluoromethylbenzylidene, trimethyl a mercapto group such as an ethenyl group, a sulfonyl group, a sulfhydryl group, a stearyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, an n-octadecyloxycarbonyl group, an amine carbaryl group; a decyloxy group such as a decyloxy group or a benzyl methoxy group; an amine group, an ethylamino group, a dimethylamino group, a diethylamino group, a butylamino group, a cyclopentylamino group, and a 2-ethyl group; Hexylamino, dodecylamino, anilino, chlorophenylamino, toluidine, methoxyanilino, N-methyl-anilino, diphenylamino, naphthylamino, 2-pyridine Amino group, methoxycarbonylamino group, phenoxycarbonylamino group, acetylamino group, benzhydrylamino group, formylamino group, trimethylethylamino group, lauryl amine group Aminomethylamino, N, N-di Amino carbonyl amino group, N, N- diethylamino-carbonyl group, Polinylcarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino , phenoxycarbonylamino, aminesulfonylamino, N,N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonate Substituted amine group such as arylamino group; sulfonylamino group, sulfonyl group, carboxyl group, cyano group, fluorenyl group, hydroxyl group, nitro group, fluorenyl group, fluorenylene group, amine carbaryl group, sulfonylamino group, sulfonic acid a salt of a phosphate group, a phosphate group or a carboxyl group, a sulfhydryl group, a sulfonic acid group, a phosphoric acid group or the like; and these groups may be further substituted. Further, a carboxyl group and a thiol group may form a salt.

Further, in X, in R ³ and R ⁴ of >NR ³ , -OR ³ , -SR ³ and -N(R ³ )(R ⁴ ), the aliphatic hydrocarbon group having 1 to 35 carbon atoms and the number of carbon atoms Examples of the aromatic ring-containing hydrocarbon group of 6 to 35 and the heterocyclic group having 2 to 35 carbon atoms include, for example, the above-mentioned monovalent aliphatic hydrocarbon group, the above-mentioned monovalent aromatic ring-containing hydrocarbon group, and the above-mentioned monovalent content. The number of carbon atoms is satisfied in the exemplified by the heterocyclic group.

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

(In the general formula (1A), the ring A' is a six-membered ring alicyclic ring, an aromatic ring or a heterocyclic ring, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or a general formula (1) the R ¹ Similarly the group, R ² system and the (1) of R in the above general formula ² Likewise, ^{wherein, R 11, R 12, R} 13, R 14 and R ¹⁵ in at least one of the general The same group of R ¹ in the formula (1).)

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

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

[Chemistry 7]

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

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

General formula (3)-Z ¹ -Q ¹ -Z ² -

(In the general formula (3), Q ¹ represents -NR ³² -, a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, a divalent carbon atom-containing hydrocarbon group having 6 to 35 carbon atoms or a divalent carbon atom a substituent represented by a heterocyclic group of 2 to 35 or any one of the following (3-1) to (3-3); a methylene group in the aliphatic hydrocarbon group represented by Q ¹ may also be - O-, -S-, -CO-, -COO-, -OCO-, -NH- or a combination of these groups; Z ¹ and Z ² independently represent direct bonding, -O-, -S- , -SO ₂ -, -SO-, -NR ³² -, -PR ³³ -, R ³² and R ³³ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an aryl group having 6 to 20 carbon atoms. or 7 to 20 carbon atoms, the aryl group, alkyl group represented by R ³² and R ^33, the alkyl and aryl groups may be replaced by a halogen atom, a hydroxyl group or a nitro group; R ³² and R ³³ shown in FIG. The methylene group in the alkyl group and the arylalkyl group may also be substituted by -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-.

Here, the group represented by the above 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 which may be substituted by an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, or a carbon number of 3 to 10; a 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 an alkane represented by R ³⁴ and R ³⁵ ; The group, alkoxy group and alkenyl group are substituted or unsubstituted by a halogen atom, and d is an integer of 0 to 5.)

(In the formula (3-3), R ³⁶ and R ³⁷ each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or a carbon atom. a 6 to 20 arylthio group, an arylalkenyl group having 8 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms or a halogen atom; R ³⁶ As shown in the alkyl group and R ^37, aryl group, aryloxy group, arylthio group, arylalkenyl group, arylalkyl and heterocyclic ring-containing group, a substituted or unsubstituted with a halogen-based atom; R ³⁶ and R ³⁷ Suo The methylene group in the alkyl group and the arylalkyl group may be substituted by an unsaturated bond, -O- or -S-; R ³⁶ may also form a ring with the adjacent R ³⁶ ; e represents 0~4 The number, f represents the number of 0~8, g represents the number of 0~4, h represents the number of 0~4, and the total of the number of g and h is 2~4.)

(In the general formulae (4) to (7), Q ² represents a carbon atom substituted by R ³⁸ , an aliphatic hydrocarbon group having a trivalent carbon number of 1 to 35, and a trivalent carbon atom having a carbon number of 6 to 35. a cyclic hydrocarbon group or a trivalent heterocyclic group having 2 to 35 carbon atoms; R ³⁸ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms or a carbon number of 7 to 20 An arylalkyl group; Q ³ represents a carbon atom, a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, a tetravalent carbon atom having 6 to 35 atomic aromatic hydrocarbon groups or a tetravalent carbon atom having 2 to 35 carbon atoms; The heterocyclic group is contained; Q ⁴ represents a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, a pentavalent carbon group having 6 to 35 atomic aromatic hydrocarbon groups or a pentavalent carbon atom having 2 to 35 carbon atoms; a ring group; Q ⁵ represents a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms; a hexavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms; or a hexavalent heterocyclic group having 2 to 35 carbon atoms; The methylene group in the aliphatic hydrocarbon group represented by Q ² , Q ⁴ , Q ⁵ or Q ⁶ may also be -O-, -S-, -CO-, -COO-, -OCO-, -NH- or a combination the group of such substituted; Z ¹ ~ Z ⁶ are each independently the same group in the above general formula (3) Z ¹ and Z ² as shown in the; wherein, The groups represented by the general formula (4) or (5) are each in the range of 1 to 35 carbon atoms, and the groups represented by the above general formula (6) or (7) are each in the range of 2 to 35 carbon atoms. Inside.)

The alicyclic ring, the aromatic ring or the hetero ring of the six-membered ring represented by the ring A' in the general formula (1A) to the general formula (1E) may, for example, be described in the description of A in the above general formula (1). Example.

In the above general formula (1A) to general formula (1E), R ¹¹ to R ¹⁵ are each independently a hydrogen atom or a group having the same R ¹ in the above general formula (1), and at least one of R ¹¹ to R ¹⁵ is The same base of R ¹ . In the present invention, it is preferred that the carbon atom adjacent to the carbon atom substituted with -OR ² 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 large volume of substituents, it is excellent in heat resistance and light resistance as a latent antioxidant, and is excellent in oxidation resistance.

The divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Q ¹ in the above general formula (3) may, for example, be methane, ethane, propane, isopropane, butane or second butane. Tributane, isobutane, hexane, 2-methylhexane, 3-methylhexane, heptane, 2-methylheptane, 3-methylheptane, isoheptane, third heptane , 1-methyloctane, isooctane, third octane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, 2,4-dimethylcyclobutane, 4-methyl a divalent group, a cyclooctyl group, a cyclodecyl group, a 1-adamantyl group, a 2-adamantyl group, a n-adamantyl group, a 2-methyl hexanyl group substituted by a group such as a cyclohexane or the like by Z ¹ and Z ² Alkyl, descending Base Base, perhydronaphthyl, perhydroindolyl, bicyclo[1.1.0] butyl, bicyclo[1.1.1]pentyl, bicyclo[2.1.0]pentyl, bicyclo[3.1.0]hexyl , hydrazine [2.1.1] hexyl, bicyclo [2.2.0] hexyl, bicyclo [4.1.0] heptyl, bicyclo [3.2.0] heptyl, bicyclo [3.1.1] heptyl, hydrazine Ring [2.1.1] heptyl, bicyclo [5.1.0] octyl, bicyclo [4.2.0] octyl, bicyclo [4.1.1] octyl, bicyclo [3.3.0] octyl, hydrazine Ring [3.2.1] octyl, bicyclo [2.2.2] octyl, spiro[4,4]decyl, spiro[4,5]decyl, decahydronaphthalene, tricyclodecyl, tetracyclic a divalent group in which a group such as a base, a cedarol, a cyclododeyl group or the like is substituted by Z ¹ and Z ² , and a combination thereof; the methylene group in the aliphatic hydrocarbon group may also be -O-, -S-, - CO-, -COO-, -OCO-, -NH- or a combination of these groups, the so-called combination of such groups, for example, -COO-O-, -COO-S-, -O-OCO-, -S-OCO-, -CO-NH-, -NH-CO-, etc., preferably -COO-, -O-, -OCO-, -NHCO-, -NH-, -CONH-, -O Replaced with -CONH- or -NHCO-O-.

The aromatic ring-containing hydrocarbon group having a divalent carbon number of 6 to 35 represented by Q ¹ may, for example, be a divalent group substituted with Z ^{1 or} Z ² such as a phenyl group, a naphthyl group or a biphenyl group.

The divalent heterocyclic hydrocarbon group having 2 to 35 carbon atoms represented by Q ¹ may, for example, be pyridine or pyridyl. Piperidine, piperazine Pyrimidine ,three Hexahydrogen , furan, tetrahydrofuran, alkyl, a divalent group substituted with a group such as thiophene or tetrahydrothiophene via Z ¹ and Z ² .

These groups may be further substituted by a halogen atom, a cyano group, a nitro group or an alkoxy group having 1 to 8 carbon atoms.

The alkyl group having 1 to 8 carbon atoms represented by R ³² and R ³³ may, for example, be a group exemplified as the alkyl group having 1 to 40 carbon atoms represented by R ¹ and R ² and satisfying a predetermined carbon number. base.

Examples of the aryl group having 6 to 20 carbon atoms represented by R ³² and R ³³ include, for example, those exemplified as the aryl group having 6 to 20 carbon atoms represented by R ¹ , R ² and R ⁴ .

The arylalkyl group having 7 to 20 carbon atoms represented by R ³² and R ³³ may, for example, be exemplified as an arylalkyl group having 7 to 20 carbon atoms represented by R ¹ , R ² and R ⁴ . base.

Further, the halogen atom which may be substituted with an alkyl group, an aryl group or an arylalkyl group represented by R ³² and R ³³ may, for example, be a group exemplified as the halogen atom represented by R ¹ and R ² .

In the substituent represented by the above (3-1), an alkyl group having 1 to 10 carbon atoms and R ^{35 which may} be substituted with a phenyl group represented by R ³⁴ and a cycloalkyl group having 3 to 10 carbon atoms; The alkyl group having 1 to 10 carbon atoms as shown, for example, a group satisfying a predetermined carbon number among the groups exemplified as the alkyl group having 1 to 40 carbon atoms represented by R ¹ and R ² . The alkoxy group having 1 to 10 carbon atoms and the alkoxy group having 1 to 10 carbon atoms represented by R ³⁵ may be substituted with a phenyl group represented by R ³⁴ and a cycloalkyl group having 3 to 10 carbon atoms. The base may, for example, be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a second butoxy group, a third butoxy group, an isobutoxy group, a pentyloxy group or an isopentyloxy group. A group, a third pentyloxy group, a hexyloxy group, a cyclohexyloxy group, a cyclohexylmethoxy group, a tetrahydrofuranyloxy group, a tetrahydropyranyloxy group or the like.

Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by R ³⁴ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cycloheptyl group, a cyclooctyl group, etc., and the above-mentioned carbon atoms are 1~. A group in which an alkyl group of 10 or an alkoxy group having 1 to 10 carbon atoms is substituted.

Examples of the alkenyl group having 2 to 10 carbon atoms represented by R ³⁵ include a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, and a 1,3-butadienyl group. 2-pentenyl, 2-octenyl and the like.

The halogen atom may also be a halogen atom on the R, and R ³⁴ and R ³⁵ shown in the alkyl, alkoxy and alkenyl substituted FIG ³⁵ includes, for example, as R ¹ and R ² of the halogen atom shown in FIG. The base of the illustration.

Further, the position of substitution of the halogen atom to which the alkyl group, the alkoxy group and the alkenyl group represented by R ³⁵ are substituted may not be 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, for example, be 1 to 40 carbon atoms represented by R ¹ and R ² . A group satisfying a predetermined carbon number among the groups exemplified by the alkyl group.

Examples of the aryl group having 6 to 20 carbon atoms represented by R ³⁶ and R ³⁷ include, for example, a group exemplified as an 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 a phenoxy group, a naphthyloxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, and 4 Methylphenoxy, 4-vinylphenoxy, 3-isopropylphenoxy, 4-isopropylphenoxy, 4-butylphenoxy, 4-tert-butylphenoxy, 4-hexylphenoxy, 4-cyclohexylphenoxy, 4-octylphenoxy, 4-(2-ethylhexyl)phenoxy, 2,3-dimethylphenoxy, 2,4 - dimethylphenoxy, 2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy Base, 2,4-di-t-butylphenoxy, 2,5-di-t-butylphenoxy, 2,6-di-t-butylphenoxy, 2,4-di-t-pentyl a group such as a phenoxy group, a 2,5-tripentylphenoxy group, a 4-cyclohexylphenoxy group, a 2,4,5-trimethylphenoxy group, a ferroceneoxy group, or the like A group substituted with a halogen atom or the like.

The arylthio group having 6 to 20 carbon atoms represented by R ³⁶ and R ³⁷ may, for example, be substituted with a sulfur atom of an arylthio group having 6 to 20 carbon atoms which may be substituted by a halogen atom. Base.

Examples of the arylalkenyl group having 8 to 20 carbon atoms represented by R ³⁶ and R ³⁷ include an oxygen atom of an aryloxy group having 6 to 20 carbon atoms which may be substituted by a halogen atom, and a vinyl group. A group substituted with an alkenyl group such as allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl or 2-octenyl.

Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ³⁶ and R ³⁷ include, for example, an arylalkyl group having 7 to 20 carbon atoms represented by R ¹ , R ² and R ⁴ . Base.

Examples of the heterocyclic group having 2 to 20 carbon atoms represented by R ³⁶ and R ³⁷ include pyridine, piperidine and piperidin. Piperidine, pyrimidine, pyrene ,three Hexahydrogen , furan, tetrahydrofuran, alkyl, a group such as thiophene or tetrahydrothiophene, and a group in which these groups are substituted by a halogen atom.

The halogen atom which may be substituted with an alkyl group, an aryl group, an aryloxy group, an arylthio group, an arylalkenyl group, an arylalkyl group or a heterocyclic group represented by R ³⁶ and R ³⁷ may, for example, be mentioned as The group represented by the halogen atom represented by R ¹ and R ² .

The trivalent carbon atom having 1 to 35 carbon atoms represented by Q ² in the above general formula (4), the trivalent carbon atom having 6 to 35 carbon atoms or the trivalent carbon atom number 2 The heterocyclic group of the group of ~35, for example, the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group, and the heterocyclic group containing the aromatic group represented by the description of Q ¹ in the above general formula (3) are respectively Z ¹ , Z ² and Z. ³ substituted trivalent groups and the like.

Moreover, as the number of carbon atoms in R 1 to 8 of the alkyl group, an aryl group or a number of carbon atoms of 6 to 20 carbon atoms, arylalkyl group having 7 to 20 of ^{FIG. 38} includes, for example with R ³² and R ³³ Suo The alkyl group having 1 to 8 carbon atoms, the aryl group having 6 to 20 carbon atoms or the same arylalkyl group having 7 to 20 carbon atoms are shown.

The tetravalent carbon atom having 1 to 35 carbon atoms represented by Q ³ in the above general formula (5), the tetravalent carbon atom having 6 to 35 carbon atoms or the tetravalent carbon atom number 2 The heterocyclic group of the group of ~35, for example, the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group, and the heterocyclic group containing the aromatic group represented by the description of Q ¹ in the above general formula (3) are respectively Z ¹ , Z ² , and Z. ³ and a tetravalent group substituted by Z ⁴ or the like.

The pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by Q ⁴ in the above general formula (6), the aromatic ring-containing hydrocarbon group having a pentavalent carbon number of 6 to 35 or the pentavalent carbon atom number 2 The heterocyclic group of the group of ~35, for example, the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group, and the heterocyclic group containing the aromatic group represented by the description of Q ¹ in the above general formula (3) are respectively Z ¹ , Z ² , and Z. ^3. A pentavalent group substituted by 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 above general formula (7), the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or the hexavalent carbon atom number 2 The heterocyclic group of the group of ~35, for example, the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group, and the heterocyclic group containing the aromatic group represented by the description of Q ¹ in the above general formula (3) are respectively Z ¹ , Z ² , and Z. ³ , a hexavalent group substituted by Z ⁴ , Z ⁵ and Z ⁶ , and the like.

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

[Chemistry 13]

The method for producing the compound of the general formula (1) is not particularly limited, and for example, it is disclosed in Japanese Patent Laid-Open No. Sho 57-111375, Japanese Patent Application Laid-Open No. Hei No. Hei. - 251191, the phenolic compound produced by the method described in each of the publications of JP-A-2004-501128, reacted with an acid anhydride, an acid chloride, a Boc reagent, an alkyl halide compound, a mercapto halogen compound, an allyl ether compound, or the like. Available. Further, a commercially available product can also be used.

[color material]

In the present invention, the color material is not particularly limited as long as it can form a desired color when forming the color layer of the color filter, and various organic pigments, inorganic pigments, dyes, and the like can be used alone or in combination. Used above. The dye system may be a dispersible dye in addition to being dissolved in a solvent. The dispersible dye is excellent in heat resistance or light resistance by being combined with a dispersing agent to be described later.

From the viewpoint of high color developability and high heat resistance, an organic pigment is suitably used. The organic pigment may, for example, be a compound classified as a pigment in a color index (C.I., issued by The Society of Dyers and Colourists), and specific examples thereof include the following coloring index (C.I.) number.

CI 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 CI pigment yellow 150 derivative pigment; CI pigment orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49 , 51, 61, 63, 64, 71, 73; CI pigment purple 1, 19, 23, 29, 32, 36, 38; CI pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9 , 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48 :3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63 : 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265; CI Pigment Blue 15, 15: 3, 15 : 4, 15: 6, 60; CI pigment green 7, 36, 58, 59; CI pigment brown 23, 25; CI pigment black 1, 7.

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

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

The dispersible dye may be a dispersible dye by adding various substituents to the dye to be insolubilized in a solvent, or may be used as a dispersible dye in combination with a solvent having a low solubility, or A dye-soluble dye and a counter ion are salt-formed to form an insoluble (paste-forming) lake color material. Such dispersible dyes are used in combination with dispersants to enhance the dispersibility or dispersion stability of the dye.

Further, as a standard, if the amount of the dye dissolved is 10 mg or less with respect to 10 g of the solvent (or the mixed solvent), it can be judged that the dye is acceptable in the solvent (or mixed solvent). dispersion.

In the present invention, it is preferred to use the above-described lake color material from the viewpoint of enhancing the luminance and contrast. The lake color material can usually be obtained by mixing a solvent which is soluble in a solvent with a post-coating agent described later in a solvent. As the dye which is soluble in the solvent, it is preferred to use a dye having a high transmittance from the viewpoint of high luminance of the color filter. The dye may be appropriately selected in accordance with a desired color tone, and may be an azo dye, a metal complex salt azo dye, an anthraquinone dye, or a triarylmethane dye. A dye having any basic skeleton (chromophoric moiety) such as a dye, a cyanine dye, a indigo dye, a naphthoquinone dye, a quinone imine dye, a methylene dye, a phthalocyanine dye, or the like. Further, the dye may be a dye classified as either an acid dye having an anionic substituent or a basic dye having a cationic substituent.

In the case of forming a blue colored layer, among them, a triarylmethane dye is preferable from the viewpoint of high luminance. At least one of a dye and a cyanine dye is more preferred, and a triarylmethane dye is more preferred.

As the acid dye, for example, CI Acid Violet 29, 31, 33, 34, 36, 36:1, 39, 41, 42, 43, 47, 51, 63, 76, 103, 118, 126, CI Acid Blue 2 , 8, 14, 25, 27, 35, 37, 40, 41, 41:1, 41:2, 43,45,46,47,49,50,51,53,54,55,56,57,58 , 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, 287, 288, 289, 290, 291, 292, 293, 294 , 295, 298, 301, 302, 304, 305, 306, 307, 313, 316, 318, 322, 324, 327, 331, 333, 336, 339, 340, 343, 344, 350, CI 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 and the like lanthanide acid dye; CI acid purple 15, 16, 17, 19, 21, 23, 24, 25, 38, 49, 72; CI Acid Blue 1, 3, 5, 7, 9, 19, 22, 83, 90, 93, 100, 103, 104 , 109, CI acid green 3,5,6,7,8,9,11,13,14,15,16,18,22,50, 50:1 triarylmethane acid dye; CI acid red 50 , 51, 52, 87, 92, 94, 289, 388, CI Acid Violet 9, 30, 102, mineral acid rose red G, sulfonic acid rose red B, sulfonic acid rose red 101, sulfonic acid rose red 640, etc. It is an acid dye or the like. Among the acid dyes, preferred are rose red acid dyes such as CI Acid Red 50, CI Acid Red 52, CI Acid Red 289, CI Acid Violet 9, CI Acid Violet 30, and CI Acid Blue 19.

Further, as a commercially available basic material, CI basic violet 1, 3, 14, CI basic blue 1, 5, 7, 8, 11, 26, CI basic green 1, 4, etc. triarylmethane system can be exemplified. Basic dyes; CI basic yellow 13, CI alkaline red 14 and other cyanine basic dyes; CI alkaline red 29 and other azo basic dyes; CI alkaline purple 11 etc. It is a basic dye or the like. Among the triarylmethane-based basic dyes, CI basic blue 1, 5, 7, 8, 11, and 26 are preferred. Moreover, as the triarylmethane-based basic dye in the present invention, for example, a dye having a cation of a color material represented by the following general formula (I') is preferable.

These dyes may be used alone or in combination of two or more.

In the lake color material, the relative ion type varies depending on the type of the dye, the relative ion of the acid dye is a cation, and the relative ion of the basic dye is an anion. Therefore, the above-mentioned laking agent is appropriately selected and used in combination with the above dye. That is, in the case of insolubilizing the above acid dye, a compound which produces a relative cation of the dye is used. It is a lake forming agent; in the case of insolubilizing the above basic dye, a compound which produces a relative anion of the dye is used as a lake forming agent.

The relative cation of the acid dye may, for example, be a metal ion or an inorganic polymer in addition to the ammonium cation.

As a coloring agent which produces an aluminum ion, a 1st-order amine compound, a 2nd-grade amine compound, and a tertiary-grade amine compound are preferable, and it is preferable to use 2 from a viewpoint of the heat resistance and the light resistance. Amine compound or a tertiary amine compound.

Further, as the coloring agent for producing metal cations, it may be appropriately selected from metal salts having a desired metal ion.

The relative ions of the acid dye may be used alone or in combination of two or more.

As a lake color material containing an acid dye, from the viewpoint of achieving high luminance, it is preferable to contain A dye-based lake color material.

As the color lake material The acid dye is preferably a compound represented by the following general formula (II), that is, a rosin-based acid dye.

(In general formula (II), R ^I to R ^IV each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and R ^I and R ^III , R ^II and R ^IV may also bond to form a ring structure. R ^V It represents an acidic group, and X represents a halogen atom. m represents an integer of 0 to 5. The general formula (II) has one or more acidic groups, and n is an integer of 0 or more.

The alkyl group in R ^I to R ^IV is not particularly limited. For example, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, and the like, preferably a linear or branched alkyl group having 1 to 8 carbon atoms, more preferably a carbon number of 1 a linear or branched alkyl group of ~5. The substituent which the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, and a hydroxyl group. The substituted alkyl group may, for example, be a benzyl group or the like, or may have a halogen atom or an acidic group. Substituent.

The aryl group in R ^I to R ^IV is not particularly limited. For example, an aryl group having a carbon number of 6 to 20 which may have a substituent may be mentioned, and among them, a group having a phenyl group, a naphthyl group or the like is preferable. The heteroaryl group in R ^I to R ^IV may, for example, be a heteroaryl group which may have a substituent of 5 to 20 carbon atoms, and preferably contains a nitrogen atom, an oxygen atom or a sulfur atom as a hetero atom.

The aryl group or the heteroaryl group may have a substituent, and examples thereof include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an acidic group, a hydroxyl group, an alkoxy group, an aminomethyl group, and a carbonate group.

Also, R ^I ~ R ^IV may be the same or different.

Specific examples of the acidic group or a salt thereof include a carboxyl group (-COOH), a carboxyl group (-COO ^- ), a carboxylate group (-COOM, wherein M represents a metal atom), and a sulfonate group (-SO ₃ ). ^- ), a sulfonic acid group (-SO ₃ H), a sulfonate group (-SO ₃ M, wherein M represents a metal atom), etc.; among them, preferably having a sulfonate group (-SO ₃ ^- ), a sulfonic acid group At least one of a group (-SO ₃ H) or a sulfonate group (-SO ₃ M). Further, the metal atom M may, for example, be a sodium atom or a potassium atom.

The compound represented by the general formula (II) is preferably acid red 50, acid red 52, acid red 289, acid violet 9, acid violet 30, acid blue 19 or the like from the viewpoint of high luminance.

Further, from the viewpoint of heat resistance, in the general formula (II), it is preferred to have m=1. And a compound of betaine structure with n=0.

Further, among them, from the viewpoint of forming a coloring layer excellent in luminance and light resistance, m=1 and n=0, and R ^I and R ^II are each independently an alkyl group or an aryl group, and R ^III and R are respectively. ^{IV is} independently an aryl or heteroaryl group.

The method for producing the compound of the above formula (II) is not particularly limited, and can be obtained, for example, from Japanese Patent Laid-Open Publication No. 2010-211198.

Above A metal lake coloring material which is an acid dye, which uses a metal atom as a lake former. By using a coloring agent containing a metal atom, the heat resistance of the color material becomes high. As such a lake-forming agent, a lake-forming agent containing a metal atom which is a metal cation of two or more valences is preferable.

On the other hand, the relative anion of the basic dye may be an organic anion or an inorganic anion. The organic anion may, for example, be an organic compound having an anionic group as a substituent.

Further, a known acid dye can also be used as the organic anion. At this time, the lake color material is an acid dye and the basic dye is present as an ion pair.

Examples of the lake forming agent which produces an organic anion include an alkali metal salt or an alkaline earth metal salt of the above organic anion.

On the other hand, examples of the inorganic anion include an anion of an oxyacid (phosphoric acid ion, sulfate ion, chromic acid ion, tungstic acid ion (WO ₄ ^2- ), molybdate ion (MoO ₄ ^2- ), etc.), or plural An inorganic anion of a condensed polyoxometalate anion or the like, or a mixture thereof.

The polyoxo acid may be a heteropolymer ion (M _m O _n ) ^c- or a heteropolymer ion (X ₁ 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 a poly atom, and n represents a composition ratio of oxygen atoms. Examples of the poly atom M include Mo, W, V, Ti, Nb, and the like. Further, examples of the hetero atom X include Si, P, As, S, Fe, Co, and the like.

Among them, from the viewpoint of heat resistance, it is preferred to contain at least one polyoxometalate anion of molybdenum (Mo) and tungsten (W), and more preferably a c-valent polyoxometallate containing at least tungsten. Anion.

The coloring agent which produces an inorganic anion may, for example, be an alkali salt or an alkali metal salt of the above inorganic anion.

The relative anions of the basic dye in the lake coloring material may be used alone or in combination of two or more.

In the present invention, the coloring material is preferably a coloring material composed of a basic dye and an inorganic anion, more preferably a basic dye and a polyoxometalate, from the viewpoint of heat resistance and light resistance. Salt anion. In the case of a lake color material containing a polyoxometallate anion, the decane coupling agent is susceptible to change with time, but in the present invention, the content ratio of the decane coupling agent is relative to the total solid content in the colored resin composition. When the amount is 1% by mass or less, the influence of the change over time is small, and on the other hand, since the heat resistance and the light resistance are high, it is particularly suitable to use the lake color material as the present invention.

In the present invention, the above-mentioned lake color material is preferably a lake color material having a triarylmethane dye, and preferably a triarylmethane type alkalinity, from the viewpoint of enhancing the luminance of the color filter. Dyes, and polyoxometalate anions.

In the present invention, the lake coloring material is excellent in heat resistance and light resistance, and the high luminance of the color filter is obtained. When the coloring material is represented by the following general formula (I), the molecule is formed. The state of rendezvous is preferable from the viewpoint of exhibiting superior heat resistance.

[化15]

(In the general formula (I), the carbon atom directly bonded to the A system and N is an a-valent organic group having no π bond, and the organic group means a fat having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N. The hydrocarbon group or the aromatic group having the aliphatic hydrocarbon group may further contain O, S, and N in the carbon chain. B ^c- represents a polyvalent metal oxylate anion containing at least c-valent tungsten. R ⁱ to R ^v respectively The hydrogen atom independently represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ⁱⁱ may be bonded to R ⁱⁱⁱ , R ^iv and R ^v to form a ring structure. Ar ¹ may also have a substitution. The divalent aromatic group of the group may have the same or different R ¹ to R ^v and Ar ¹ , respectively.

a and c are integers of 2 or more, and b and d are integers of 1 or more. e is 0 or 1, and when there is 0, there is no bond. The plural e can be the same or different. )

As shown in Fig. 4, the color material shown in the above general formula (I) is presumed to contain an anion 202 having a valence of two or more and a cation 201 having a valence of two or more. Therefore, in the aggregate of the color material, the anion and the cation are not simple. One molecule is ion-bonded to one molecule, and a molecular conjugation 210 in which a plurality of molecules meet is formed via the ionic bond 203. Therefore, the molecular weight of the appearance of the color material represented by the general formula (I) is particularly increased as compared with the molecular weight of the conventional lake color material. It is presumed that due to the formation of such a molecular confluence, the cohesive force in the solid state is further improved, the thermal motion is lowered, and the ion pair dissociation or the cation portion can be suppressed. Decomposition to improve heat resistance.

The carbon atom directly bonded to the A system and the N (nitrogen atom) in the general formula (I) is an a-valent organic group having no π bond, and the organic group means a saturated aliphatic group at least at the end directly bonded to N. The aliphatic hydrocarbon group of the hydrocarbon group or the aromatic group having the aliphatic hydrocarbon group may further contain O (oxygen atom), S (sulfur atom), or N (nitrogen atom) in the carbon chain. Since the carbon atom directly bonded to N does not have a π bond, the color characteristics such as hue or transmittance of the cationic color-developing portion are not affected by the linking group A or other color-developing portions, and can be maintained. The same color of the monomer. Further, from the viewpoint of heat resistance, A preferably does not have a siloxane coupling, and more preferably does not have Si (germanium atom).

In A, an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N may have a π bond as long as the carbon atom at the terminal directly bonded to N may be a straight chain, a branch or a ring. Any one of the carbon atoms other than the terminal may have an unsaturated bond and may have a substituent, and the carbon chain may further contain O, S, and N. For example, a carbonyl group, a carboxyl group, an oxycarbonyl group, a decylamino group or the like may be contained, and a hydrogen atom may be further substituted with a halogen atom.

Further, in the above, the aromatic group having an aliphatic hydrocarbon group may, for example, be a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N, It may have a substituent or a hetero ring containing O, S or N.

Among them, from the viewpoint of the firmness of the skeleton, A preferably contains a cyclic aliphatic hydrocarbon group or an aromatic group.

The cyclic aliphatic hydrocarbon group is preferably a bridged alicyclic hydrocarbon group from the viewpoint of the robustness of the skeleton. The bridged alicyclic hydrocarbon group refers to a polycyclic aliphatic hydrocarbon group having a crosslinked structure and a polycyclic structure in an aliphatic ring, and for example, Alkane, bicyclo[2,2,2]octane, adamantane, and the like. Among the bridged alicyclic hydrocarbon groups, it is preferred to lower alkyl. Further, the aromatic group may, for example, be a group containing a benzene ring or a naphthalene ring, and among them, a group containing a benzene ring is preferred. For example, in the case where A is a divalent organic group, for example, a linear, branched, or cyclic alkyl group having a carbon number of 1 to 20 or an alkylene group having a carbon number of 1 to 20 such as a fluorene group may be mentioned. The valence number a in the general formula (I) is a number of chromogenic cation sites constituting a 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, heat resistance is excellent. The upper limit of a is not particularly limited, and a is preferably 4 or less, more preferably 3 or less from the viewpoint of easiness of production.

The alkyl group in R ⁱ to R ^v is not particularly limited. For example, a linear or branched alkyl group having 1 to 20 carbon atoms may be used. Among them, a linear or branched alkyl group having 1 to 8 carbon atoms is preferred, and from the viewpoint of luminance and heat resistance, it is more preferable. A linear or branched alkyl group having 1 to 5 carbon atoms. Among them, the alkyl group in R ⁱ to R ^v is particularly preferably an ethyl group or a methyl group. The substituent which the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, and a hydroxyl group. 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. The substituent which the aryl group may have may, for example, be an alkyl group or a halogen atom.

Wherein, from the viewpoint of chemical stability, R ⁱ to R ^{v are} preferably independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v bonds. Forming a pyrrolidine ring, a piperidine ring, A porphyrin ring.

R ⁱ to R ^v can independently form the above-mentioned structures, wherein, in terms of color purity, R ⁱ is preferably a hydrogen atom, and further, in terms of ease of manufacture and supply of raw materials, R ⁱⁱ to R ^v are more preferable. the same.

The divalent aromatic group in Ar ¹ is not particularly limited. The aromatic group in Ar ¹ can be the same as those exemplified as the aromatic group of A.

Ar ^{1 is} preferably an aromatic group having 6 to 20 carbon atoms, more preferably an aromatic group having a condensed polycyclic carbocyclic ring having 10 to 14 carbon atoms. Among them, in terms of simple structure and low raw material cost, it is more preferably a phenyl or a naphthyl group.

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

In the color material of the general formula (I), the anion portion (B ^c- ) represents a c-valent polyoxometallate anion which contains at least tungsten and may also contain molybdenum.

In the case of the polyoxometalate anion in the color material of the general formula (I), one or a combination of the above anions may be used alone or two or more of them may be used in combination, and from the viewpoint of heat resistance and light resistance. In general, the ratio of tungsten to molybdenum in the total polyoxometallate anion is preferably 90:10 to 100:0.

In the general formula (I), b is the number of cations, d is the number of anions in the molecular confluence, and b and d are integers of 1 or more. When b is 2 or more, the plural cations in the molecular complex may be used alone or in combination of two or more. In the case where d is 2 or more, the plurality of anions in the molecular combination may be used alone or in combination of two or more. The organic anion may be used in combination with an inorganic anion.

In the general formula (I), e is an integer of 0 or 1, and e=0 represents a triarylmethane skeleton, and e=1 represents skeleton. The plural e can be the same or different. That is, it may be a plurality of triarylmethane skeletons, or only plural The cation portion of the skeleton may also contain a triarylmethane skeleton in one molecule and a cationic portion of both sides of the skeleton. From the viewpoint of color purity, it is preferred to have only an anion portion having the same skeleton. On the other hand, by making a triaryl methane skeleton In the cation portion of both the skeletons, the color material represented by the general formula (I) can be adjusted to a desired color.

In the present invention, from the viewpoint of easy adjustment to a desired color, it is preferred In the color material represented by the general formula (I), e is 0, that is, a color material represented by the following general formula (I').

(The symbols in the general formula (I') are the same as the above 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 produced by the manufacturing method described in the specification of International Publication No. 2012/144520.

In the present invention, the color materials may be used alone or in combination of two or more.

In the present invention, the color material is preferably selected from the viewpoints of enhancing brightness and contrast. a color lake material of a skeleton, a lake color material having a triaryl methane skeleton, and One or more kinds of the dyes of the skeleton are particularly preferably selected from the group consisting of the above-mentioned general formula (I), and containing the above-mentioned One or more kinds of the coloring material of the dye and the combination of these.

The average primary particle diameter of the color material used in the present invention is not particularly limited as long as it is a coloring layer of a color filter, and the color is preferably used. The type of the material varies, but is preferably in the range of 10 nm or more and 200 nm or less, more preferably 15 nm or more and 150 nm or less. By using the average primary particle diameter of the color material to be in the above range, the invention can be used. The display device of the color filter manufactured by the color material dispersion liquid has high contrast and high quality.

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. Moreover, the commercially available color material can also be used for miniaturization.

[Photopolymerizable compound]

The photopolymerizable compound to be used in the photosensitive colored resin composition of the present invention is appropriately selected from conventionally known ones, and is not particularly limited. Usually, a compound having two or more ethylenically unsaturated double bonds is preferably used. It is a polyfunctional (meth)acrylate which has two or more of an acryl fluorenyl group or a methacryl fluorenyl group.

Such a polyfunctional (meth) acrylate can be appropriately selected from the conventionally known ones. Specific examples include those described in Japanese Laid-Open Patent Publication No. 2013-029832.

These polyfunctional (meth) acrylates may be used alone or in combination of two or more. Further, in the case where the photosensitive coloring resin composition for a color filter of the present invention is required to have excellent photocurability (high sensitivity), the polyfunctional monomer preferably has three (three or more) functional double bonds. Preferred are poly(meth)acrylates of polyvalent alcohols having a valence of 3 or more or modified dicarboxylic acids, and specific examples thereof include trimethylolpropane tri(meth)acrylate and pentaerythritol III ( Methyl) acrylate, succinic acid modification of pentaerythritol tri(meth) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, A succinic acid modification of pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or the like.

[starting agent]

The initiator to be used for the photosensitive coloring resin composition of the present invention is not particularly limited, and it may be used alone or in combination of two or more kinds from various conventionally known initiators.

As the initiator, for example, aromatic ketones, benzoin ethers, and halomethyl groups are mentioned. Diazole compound, α-amino ketone, biimidazole, N,N-dimethylaminodiphenyl ketone, halomethyl-S-three Compound, sulfur Wait. Specific examples of the initiator include diphenyl ketone, 4,4'-bisdiethylaminodiphenyl ketone, and 4-methoxy-4'-dimethylaminodiphenyl ketone. Such as aromatic ketones, benzoin ethers such as benzoin methyl ether, benzoin such as ethyl benzoin, and bisimidazoles such as 2-(o-chlorophenyl)-4,5-phenylimidazole 2, 2 -trichloromethyl-5-(p-methoxystyryl)-1,3,4- Halomethyl group such as oxadiazole Diazole compound, 2-(4-butoxy-naphthalen-1-yl)-4,6-bis-trichloromethyl-S-three Halomethyl-S-three Compound, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2- Polinylacetone, 1,2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzoin benzoic acid, benzoin benzoic acid methyl ester, 4-benzoin-4'-methyldiphenylsulfide, benzyl Methyl acetal, dimethylamino benzoate, p-dimethylamino benzoic acid isoamyl ester, 2-n-butoxyethyl-4-dimethylamino benzoate, 2 -Chlorosulfur 2,4-diethyl sulphide 2,4-dimethylsulfur Isopropyl sulfide , 4-benzylidene-methyldiphenylsulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-(dimethylamino)-1-[4-(4- Phenyl)phenyl]-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Phenyl)phenyl]-1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzylidene)phosphine oxide, 2- Methyl-1-[4-(methylthio)phenyl]-2-(4- Polinyl)-1-propanone and the like.

Among them, 2-methyl-1-[4-(methylthio)phenyl]-2- can be preferably used. Lolinylpropan-1-one, 2-benzyl-2-(dimethylamino)-1-(4- Polinylphenyl)-1-butanone, 4,4'-bis(diethylamino)diphenyl ketone, diethyl sulphate . It is more preferable to combine 2-methyl-1-[4-(methylthio)phenyl]-2- from the viewpoints of sensitivity adjustment, suppression of water bleeding, and improvement of development resistance. 啉-ylpropan-1-one-like α-aminoacetophenone-based initiator and diethylsulfide Sulphur Is the initiator.

In the use of α-aminoacetophenone-based initiator and sulfur In the case of the initiator, the total content of these is preferably 5% by mass or more and 15% by mass or less based on the total amount of the solid content of the photosensitive colored resin composition. If the starting dose is 15% by mass or less, the sublimate in the manufacturing process is reduced, which is preferable. When the amount of the initiator is 5% by mass or more, the development resistance is improved.

In the present invention, the initiator is preferably an oxime-based initiator, and more preferably an oxime-based photoinitiator, from the viewpoint of ensuring the margin of the line width adjustment.

The oxime ester-based photoinitiator is preferably one having an aromatic ring or more preferably from the viewpoint of reducing contamination of the colored resin composition for a color filter or device contamination caused by the decomposition product. The condensed ring containing an aromatic ring is more preferably a condensed ring containing a benzene ring and a hetero ring.

Examples of the oxime ester-based photoinitiator include those described in JP-A-2000-80068, JP-A-2001-233842, JP-A-2010-527339, JP-A-2010-527338, JP-A-2013-041153, and the like. An oxime ester photoinitiator or the like.

The oxime ester-based photoinitiator used in the present invention is preferably high in sensitivity and is preferably combined with a latent antioxidant to reduce the line width, to improve solvent resistance and developability. An oxime ester photoinitiator which produces an aryl radical, particularly a phenyl radical, is used, and an oxime ester photoinitiator which produces an alkyl radical, especially a methyl radical, is more preferably used. Presumed alkyl radicals It is easier to activate free radical movement. As the oxime ester-based photoinitiator which generates an alkyl radical, for example, 1-(o-ethylindenyl) 1-[9-ethyl-6-(2-methylbenzylidene)-9H- Carbazole-3-yl]-ethanone (trade name: Irgacure OXE-02, manufactured by BASF), (2,4,6-trimethylphenyl)[8-[[(ethyloxy)imino) [2-(2,2,3,3-tetrafluoropropoxy)phenyl]methyl]-11(2-ethylhexyl)-11H-benzo[a]carbazol-5-yl]- Methyl ketone (trade name: Irgacure OXE-03, manufactured by BASF), 1-(o-ethyl fluorenyl) 1-[9-ethyl-6-(1,3-dioxolan, 4-(2-methyl) Oxyphenoxy)-9H-carbazol-3-yl]-ethanone (trade name: ADEKA OPT-N-1919, manufactured by ADEKA), o-ethenyl hydrazine (9-ethyl-6-nitro- 9H-carbazol-3-yl)[4-(2-methoxy-1-methylethoxy-2-methylphenyl]-methanone (trade name: ADEKA AKLS NCI-831, manufactured by ADEKA) , 1-(o-ethenyl hydrazide) 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-carbazol-3-yl]-1-propanone (trade name TR-PBG-304, manufactured by Changzhou Qiang Electronics New Material Co., Ltd.), 1-(o-ethylidene oxime) 3-cyclopentyl-1-[2-(2-pyrimidinylthio)-9H-carazole -3-yl]-1-propanone (trade name TR-PBG-314, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 1-(o-ethylidene oxime) 2-ring Hexyl-1-[2-(2-pyrimidinyloxy)-9H-indazol-3-yl]-ethanone (trade name: TR-PBG-326, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 1-(o Ethyl hydrazide) 2-cyclohexyl-1-[2-(2-pyrimidinylthio)-9H-carbazol-3-yl]-ethanone (trade name TR-PBG-331, Changzhou Power Electronic New Material Co., Ltd.) , 1-(o-ethylidene hydrazide) 1-[4-[3-[1-[(ethyloxy)imino]ethyl]-6-[4-[(4,6-di) Methyl-2-pyrimidinyl]thio]-2-methylbenzylidene]-9H-carbazol-9-yl]phenyl]-1-octanone (trade name EXTA-9, manufactured by UNION CHEMICAL) Further, as the oxime ester photoinitiator having a diphenylsulfide skeleton, for example, ADEKA AKLS NCI-930 (made by Adeka Co., Ltd.), TR-PBG-3057 (made by Changzhou Strong Electronic New Materials Co., Ltd.), etc. are mentioned.

Further, as a starting agent for generating a phenyl radical, a specific example thereof is Irgacure OXE-01 (manufactured by BASF).

As the oxime ester photoinitiator, an oxime ester photoinitiator having a diphenylsulfide skeleton is preferably used from the viewpoint of enhancing the luminance compared to the case of having a carbazole skeleton.

Further, from the viewpoint of enhancing sensitivity, it is preferred to contain at least two kinds of lanthanide initiators. Further, from the viewpoint of improving development resistance and improving the effect of suppressing water bleeding, it is preferred to contain at least two kinds of lanthanide initiators. If at least two kinds of lanthanide initiators are contained, it is presumed that the wavelengths absorbed by the respective initiators are different, so that light at the time of exposure can be effectively used at each absorption wavelength.

In addition, the term "water permeation" refers to a phenomenon in which, as a component for improving alkali developability, a trace such as water permeation occurs after rinsing with pure water after alkali development. Since such water permeation disappears after post-baking, there is no problem as a product. However, when the appearance of the pattern surface is examined after development, an abnormality is detected, and the problem that the normal product and the abnormal product cannot be distinguished is generated. . Therefore, if the inspection sensitivity of the inspection apparatus is lowered during the visual inspection, the result is that the yield of the final color filter manufacturing is lowered, which is a problem.

Further, in the oxime ester photoinitiator, it is preferred to use a photoinitiator having a tertiary amine structure in combination from the viewpoint of sensitivity improvement. The reason for this is that a photoinitiator having a tertiary amine structure has a tertiary amine structure belonging to an oxygen quencher in the molecule, so that the radical generated by the initiator is not easily deactivated by oxygen, and the sensitivity can be improved. Caused. As a commercially available product of the above-mentioned photoinitiator having a tertiary amine structure, for example, 2-methyl-1-(4-methylthiophenyl)-2- Lolinylpropan-1-one (for example, Irgacure 907, manufactured by BASF Corporation), 2-benzyl-2-(dimethylamino)-1-(4- Polinylphenyl)-1-butanone (for example, Irgacure 369, manufactured by BASF Corporation), 4,4'-bis(diethylamino)diphenyl ketone (for example, Hicure ABP, manufactured by Kawaguchi Pharmaceutical Co., Ltd.), and the like.

Further, from the viewpoint of easy adjustment of sensitivity, it is preferred to fluorenyl ester light. The initiator is a combination of an α-aminoalkylbenzophenone-based initiator, and preferably an alkyl radical oxime ester compound and an α-aminoalkylbenzophenone-based initiator are combined.

[solvent]

The solvent to be used in the present invention is not particularly limited as long as it is an organic solvent which does not react with each component in the photosensitive colored resin composition and can be dissolved or dispersed. The solvent may be used singly or in combination of two or more.

Specific examples of the solvent include alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, methoxy alcohol, and ethoxylated alcohol; methoxyethoxyethanol and ethoxyethoxy group; A carbitol solvent such as ethanol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate , esters of ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, cyclohexanol acetate, etc.; acetone, A a ketone solvent such as ketoethyl ketone, methyl isobutyl ketone, cyclohexanone or 2-heptanone; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy- a glycol ether acetate solvent such as 3-methyl-1-butyl acetate, 3-methoxybutyl acetate or ethoxyethyl acetate; methoxyethoxy B Carbitol acetate solvent such as acetoxyacetate, ethoxyethoxyethyl acetate, butyl carbitol acetate (BCA); propylene glycol diacetate, 1,3-butyl Diacetate such as diol diacetate; ethylene glycol single Ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl a glycol ether solvent such as ether or dipropylene glycol dimethyl ether; aproticity such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone a solvent such as a lactone solvent; a lactone solvent such as γ-butyrolactone; a cyclic ether solvent such as tetrahydrofuran; an unsaturated hydrocarbon solvent such as benzene, toluene, xylene or naphthalene; A saturated hydrocarbon solvent such as heptane, N-hexane or N-octane; or an organic solvent such as an aromatic hydrocarbon such as toluene or xylene. Among these solvents, the glycol ether acetate solvent, the carbitol acetate solvent, the glycol ether solvent, and the ester solvent are preferably used from the viewpoint of solubility of other components. Among them, the solvent used in the present invention is preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether or butyl carbitol from the viewpoint of solubility or coating suitability of other components. Group consisting of ester (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate and 3-methoxybutyl acetate Choose one or more of them.

In the present invention, from the viewpoints of solubility of other components and coating suitability, among them, propylene glycol monomethyl ether acetate is preferably contained, and more preferably contains diethylene glycol ethyl methyl ether. , propylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methyl-1-butyl acetate and propylene glycol monomethyl ether acetate One or more mixed solvents. In the mixed solvent, the content ratio of propylene glycol monomethyl ether acetate is preferably 70% by mass or more and 99% by mass or less, and more preferably 80% by mass or more and 99% by mass or less based on the total amount of the solvent.

[Dispersant]

In the photosensitive colored resin composition of the present invention, the color material is preferably used by being dispersed in a solvent in a dispersing agent. In the present invention, the dispersing agent can be appropriately selected from among the well-known dispersing agents. Further, the dispersing agent may be used alone or in combination of two or more. As the dispersing agent, for example, a surfactant such as a cationic system, an anionic system, a nonionic system, an amphoteric, a polyfluorene-based or a fluorine-based surfactant can be used. Among the surfactants, a polymer dispersant is preferred from the viewpoint of being uniformly and finely dispersed.

Examples of the polymer dispersant include unsaturated carboxylic acids such as polyacrylate. a (co)polymer of an acid ester; a (partial) amine salt, a (partial) ammonium salt or a (partial) alkylamine salt of a (co)polymer of an unsaturated carboxylic acid such as polyacrylic acid; a hydroxyl group-containing polyacrylic acid; a (co)polymer of a hydroxyl group-containing unsaturated carboxylic acid ester such as an ester or a modified substance thereof; a polyurethane; an unsaturated polyamine; a polyoxyalkylene; a long-chain polyamine amide Phosphate; polyethylenimine derivative (anthracene or a base obtained by the reaction of poly(lower alkylene imine) with a polyester containing a free carboxyl group); polyallylamine a derivative (reacting a polyallylamine, a compound selected from a compound selected from the group consisting of a polyester having a free carboxyl group, a polycondensate or a copolycondensate of a polyester and a decylamine (polyester decylamine); The obtained reaction product) and the like.

The polymer dispersant is preferably a polymer dispersant having a nitrogen atom and having an amine valence in a main chain or a side chain, from the viewpoint of preferably dispersing the color material and having good dispersion stability. From the viewpoint of good dispersibility, no precipitation of foreign matter, formation of a coating film, and improvement of luminance and contrast, a polymer dispersant comprising a polymer having a repeating unit of a tertiary amine is preferred.

A repeating unit having a 3-stage amine, which is a moiety having affinity with the above-mentioned color material. A polymer containing a repeating unit having a tertiary amine usually contains a repeating unit which is a site having affinity with a solvent. As a polymer containing a repeating unit having a tertiary amine, it is preferable to have a block portion composed of repeating units having a tertiary amine from the viewpoint of excellent heat resistance and a high-thickness coating film. A block copolymer with a block having solvent affinity.

The repeating unit having a tertiary amine may have a tertiary amine, and the tertiary amine may be contained in a side chain of the block polymer or may constitute a main chain.

In particular, it is preferable to have a repeating unit of a tertiary amine in a side chain, and it is more preferable to contain the following general formula (2) from the viewpoint that the main chain skeleton is not easily thermally decomposed and has high heat resistance. Repeat unit (a) shown.

(In the general formula (2), R ⁴¹ represents a hydrogen atom or a methyl group, L represents a divalent linking group, R ⁴² represents 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 divalent organic group, R ⁴³ and R ⁴⁴ respectively Independently, it may represent a substituted chain or cyclic hydrocarbon group, or R ⁴³ and R ^{44 may} be bonded to each other to form a cyclic structure; and R ⁴⁵ and R ⁴⁶ are each independently a hydrogen atom or a methyl group.

x represents an integer from 1 to 18, y represents an integer from 1 to 5, and z represents an integer from 1 to 18. )

The divalent linking group of the above general formula (2) may, for example, be an alkylene group having 1 to 10 carbon atoms, an extended aryl group, a -CONH- group, a -COO- group or an ether group having 1 to 10 carbon atoms (- R'-OR"-: R' and R" are each independently an alkylene group) and combinations thereof. Among them, L is preferably -COO-based or - in terms of heat resistance of the obtained polymer or solubility in the use of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, or a relatively inexpensive material. CONH-based.

The divalent organic group R ^{42 of the} above general formula (2) is an alkylene group having 1 to 8 carbon atoms, -[CH(R ⁴⁵ )-CH(R ⁴⁶ )-O] _x -CH(R ⁴⁵ )-CH (R ⁴⁶ )- or -[(CH ₂ ) _y -O] _z -(CH ₂ ) _y -. The above alkylene group having 1 to 8 carbon atoms may be either linear or branched.

R ⁴⁵ and R ⁴⁶ are each independently a hydrogen atom or a methyl group.

The above R ⁴² is preferably a C 1-8 alkylene group from the viewpoint of dispersibility, wherein R ^{42 is} preferably a methylene group, an ethyl group, a propyl group, a butyl group, or the like. It is preferably a methylene group and an ethyl group.

The cyclic structure in which R ⁴³ and R ^{44 in the} above general formula (2) are bonded to each other may, for example, be a nitrogen-containing heterocyclic monocyclic ring having a 5- to 7-membered ring or a condensed ring obtained by condensing the two. The nitrogen-containing heterocyclic ring is preferably one which does not have aromaticity, and more preferably a saturated ring.

The repeating unit represented by the above general formula (2) may, for example, be dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate or diethyl (meth)acrylate. (meth) acrylate containing an alkyl-substituted amine group, such as an aminoethyl ester or diethylaminopropyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, and A (meth)acrylamide or the like containing an alkyl-substituted amine group such as methylaminopropyl (meth) acrylamide. Among them, from the viewpoint of improvement in dispersibility and dispersion stability, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylamino group are preferably used. Propyl (meth) acrylamide.

In the block portion composed of the repeating unit having a tertiary amine, the constituent unit represented by the general formula (2) preferably contains three or more. Among them, from the viewpoint of improving dispersibility and dispersion stability, it is preferably 3 to 100, more preferably 3 to 50, and still more preferably 3 to 30.

The block copolymer having a block portion (hereinafter referred to as A block) composed of a repeating unit having a tertiary amine and a block portion having a solvent affinity (hereinafter sometimes referred to as a B block) In the above, the block portion having the solvent affinity is not limited to the above-described general formula (2), and has the above-mentioned general point of view, from the viewpoint of improving solvent affinity and improving dispersibility. Formula (2) copolymerization A solvent affinity block at the position. In the present invention, the arrangement of the respective blocks of the block copolymer is not particularly limited, and examples thereof include an AB block copolymer, an ABA block copolymer, and a BAB block copolymer. Among them, from the viewpoint of superior dispersibility, an AB block copolymer or an ABA block copolymer is preferred.

The constituent unit which can be copolymerized with the above general formula (2) is preferably a general formula (8) as shown in the following general formula (8) from the viewpoint of improving the dispersibility and dispersion stability of the color material and improving heat resistance. Constitute unit.

(In the general formula (8), R ⁴⁷ represents a hydrogen atom or a methyl group, A represents a direct bond or a divalent linking group, and R ⁴⁸ represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and an aromatic group. Alkyl, aryl, -[CH(R ⁴⁹ )-CH(R ⁵⁰ )-O] _x -R ⁵¹ - or -[(CH ₂ ) _y -O] _z -R ⁵¹ represents a monovalent group. R ⁴⁹ and R ⁵⁰ are each independently a hydrogen atom or a methyl group, and R ⁵¹ is a hydrogen atom, or an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -CHO, -CH ₂ CHO or a monovalent group represented by -CH ₂ COOR ⁵² , and R ⁵² is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms. X represents an integer of 1 to 18, y represents an integer from 1 to 5, and z represents an integer from 1 to 18.

The divalent linking group A of the above general formula (8) may, for example, be the same as L in the above general formula (2), and may have heat resistance of the obtained polymer or propylene glycol monomethyl ether B as a solvent. A is preferably a -COO- group in terms of solubility of the acid ester (PGMEA) or a relatively inexpensive material.

In R ⁴⁸ , the alkyl group having 1 to 18 carbon atoms may be any of a linear chain, a branched chain, and a cyclic group.

The alkenyl group having 2 to 18 carbon atoms may be any of a linear chain, a branched chain, and a cyclic chain.

Among them, 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 carbon number of the aryl group is preferably from 6 to 24, more preferably from 6 to 12.

Examples of the aralkyl group which may have a substituent include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, and the like. The carbon number of the aralkyl group is preferably from 7 to 20, more preferably from 7 to 14.

The substituent of the aromatic ring such as an aryl group or an aralkyl group may, for example, be an alkyl group, a nitro group or a halogen atom, in addition to a linear or branched alkyl group having 1 to 4 carbon atoms.

Further, the above R ⁵¹ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms which may have a substituent, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -CHO, -CH ₂ CHO or -CH ₂ A monovalent group represented by COOR ⁵² , and R ⁵² is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms.

The monovalent group represented by the above R ⁵¹ may, for example, be a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, or a halogen such as F, Cl or Br. Atoms, etc.

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 the above R ⁵¹ are as shown in the above R ⁴⁸ .

In the above R ⁴⁸ , x, y and z are the same as R ⁴² in the above general formula (2).

The number of constituent units of the block portion constituting the solvent affinity can be appropriately adjusted in the range of improving the dispersibility of the color material. Among them, the solvent affinity part and the color material pro The number of constituent units of the block portion constituting the solvent affinity is preferably 10 or more and 200 or less, more preferably 10 or more and 100 or less, from the viewpoint of effectively acting on the functional portion and improving the dispersibility of the color material. It is preferably 10 or more and 70 or less.

The block portion of the solvent affinity may be a function of a solvent affinity portion, and the repeating unit of the block portion constituting the solvent affinity may be composed of one type or two or more types of repeat units.

In the block copolymer of the present invention, the ratio m/n of the unit number m of the constituent unit represented by the general formula (2) and the unit number n of other constituent units of the block portion constituting the solvent affinity is m/n. In the range of preferably 0.01 or more and 1 or less, from the viewpoint of dispersibility of the color material and dispersion stability, it is more preferably in the range of 0.05 or more and 0.7 or less.

In addition, in the present invention, the dispersant is preferably composed of the above general formula (2) and has an amine value of 40 mgKOH from the viewpoint of good dispersibility, no precipitation of foreign matter during coating film formation, and improvement in brightness and contrast. /g or more and 120 mgKOH/g or less.

When the amine value is in the above range, the viscosity stability or heat resistance is excellent, and alkali developability and solvent resolubility are also excellent. In the present invention, the amine valence of the dispersing agent is preferably from 80 mgKOH/g or more, more preferably 90 mgKOH/g or more, in terms of dispersibility and dispersion stability. On the other hand, in terms of solvent resolubility, the amine value of the dispersing agent 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 the amount of perchloric acid required for neutralizing the amine component contained in 1 g of the sample, and can be measured by a method defined in JIS-K7237:1995. In the measurement by this method, even if the amine group which forms a salt with the organic acid compound in the dispersing agent is usually dissociated from the organic acid compound, the amine valence of the block copolymer itself used as the dispersing agent can be measured.

The acid value of the dispersing agent used in the present invention is preferably 1 mgKOH/g or more in terms of the effect of suppressing the development residue. Among them, the acid value of the dispersant is more preferably 2 mgKOH/g or more from the viewpoint that the effect of suppressing the development residue is further superior. Moreover, the acid value of the dispersing agent used in the present invention is preferably 18 mg KOH/g or less from the viewpoint of preventing deterioration of development adhesiveness or deterioration of solvent resolubility. In particular, the acid value of the dispersing agent is preferably 16 mgKOH/g or less, more preferably 14 mgKOH/g or less, and particularly preferably 12 mgKOH/g or less from the viewpoint of good development adhesiveness and solvent resolubility.

In the dispersant used in the present invention, the acid value of the block copolymer before salt formation is preferably 1 mgKOH/g or more, more preferably 2 mgKOH/g or more. This is due to the effect of suppressing the development residue. Further, 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, still more preferably 14 mgKOH/g or less, and particularly preferably 12 mgKOH/g or less. This is because the development adhesiveness and the solvent resolubility are good.

When the concentration of the color material is increased and the content of the dispersant is increased, since the amount of bonding is relatively reduced, the colored resin layer is easily peeled off from the base substrate during development. When the dispersant contains a B block containing a constituent unit derived from a carboxyl group-containing monomer and has the above specific acid value and glass transition temperature, the development adhesiveness is improved. If the acid value is too high, the developability is excellent, but when the polarity is too high, peeling tends to occur at the time of development.

According to the above, in the present invention, the dispersing stability of the color material is superior and the contrast is improved, and the dispersing property is suppressed as a colored resin composition, and the solvent resolubility is excellent, and further, the above-mentioned dispersion is obtained from the viewpoint of high developing adhesiveness. The agent preferably contains a polymer having a structure of the above formula (2) and an amine value of 40 mgKOH/g or more and 120 mgKOH/g or less, and the acid value is 1 mgKOH/g or more and 18 mgKOH/g or less. The transfer temperature is above 30 °C.

As the carboxyl group-containing monomer, a monomer copolymerizable with a monomer having a structural unit represented by the general formula (2) and containing an unsaturated double bond and a carboxyl group can be used. Examples of such a monomer include (meth)acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, and the like. Cinnamic acid, acrylic acid dimer, and the like. Further, an addition reactant of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, a cyclic anhydride such as maleic anhydride or decanoic anhydride or cyclohexane dicarboxylic anhydride, or ω- may be used. Carboxy-polycaprolactone mono(meth)acrylate and the like. Further, as the carboxyl group precursor, an acid anhydride group-containing monomer such as maleic anhydride, itaconic anhydride or citraconic anhydride may be used. Among them, (meth)acrylic acid is particularly preferred 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 constituent unit derived from the carboxyl group-containing monomer is not particularly limited as long as the acid value of the block copolymer is within the range of the specific acid value. The total mass of the total constituent units of the block copolymer is preferably 0.05% by mass or more and 4.5% by mass or less, more preferably 0.07% by mass or more and 3.7% by mass or less.

When the content ratio of the constituent unit derived from the carboxyl group-containing monomer is at least the above lower limit value, the effect of suppressing the development residue is exhibited, and when it is at most the above upper limit value, deterioration of development adhesiveness or solvent re-protection can be prevented. Deterioration of solubility.

In addition, the constituent unit derived from the carboxyl group-containing monomer may be one type of the specific acid value, and may contain two or more types of constituent units.

In the block copolymer, the ratio m/n of the unit number m of the constituent units of the A block and the number N of the constituent units of the B block is preferably 0.05 or more and 1.5 or less. The concept of dispersibility and dispersion stability of color materials In terms of points, it is more preferably in the range of 0.1 or more and 1.0 or less.

The weight average molecular weight Mw of the above-mentioned block copolymer is not particularly limited, and is preferably 1,000 or more and 20,000 or less, more preferably 2,000 or more and 15,000 or less, and more preferably from the viewpoint of improving dispersibility and dispersion stability of the color material. Good 3000 or more and 12,000 or less.

Here, the weight average molecular weight (Mw) is determined by gel chromatography (GPC) in terms of standard polystyrene. Further, the macromonomer, the salt block copolymer, and the graft copolymer which are the raw materials of the block copolymer are also subjected to the above conditions.

The method for producing the above block copolymer is not particularly limited. The block copolymer can be produced by a known method, and among them, a living polymerization method is preferred.

Specific examples of the block copolymer having a block portion composed of a repeating unit having a tertiary amine and a block portion having a solvent affinity include, for example, block copolymerization described in Japanese Patent No. 4911253. Fit is preferred.

When the above-mentioned color material is dispersed by using the above-mentioned polymer containing a repeating unit having a tertiary amine as a dispersing agent, the content of the polymer containing the repeating unit having a tertiary amine is higher than 100 parts by mass of the coloring material. It is preferably 15 parts by mass or more and 300 parts by mass or less, more preferably 20 parts by mass or more and 250 parts by mass or less. When it is in the above range, the dispersibility and dispersion stability are excellent, and the effect of improving the contrast becomes high.

In the present invention, from the viewpoint of dispersibility or dispersion stability of the color material, it is preferred to use at least a part of the amine group in the polymer containing the repeating unit having a tertiary amine as the dispersing agent, and the organic acid. The compound or the halogenated hydrocarbon is formed by a salt (hereinafter, such a polymer is sometimes referred to as a salt type polymer).

Among them, from the viewpoint of superior dispersibility and dispersion stability of the color material, it is preferred that the polymer having a repeating unit having a tertiary amine be a block copolymer, and the above organic acidification The compound is an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphoric acid. Specific examples of the organic acid compound to be used in the above-mentioned dispersing agent include, for example, an organic acid compound described in JP-A-2012-236882.

In addition, as the halogenated hydrocarbon, at least one of a halogenated allyl group such as a brominated allyl group or a benzyl chloride group and a halogenated alkyl group is preferred from the viewpoint of excellent dispersibility and dispersion stability of the color material. .

[alkali soluble resin]

The alkali-soluble resin in the present invention has an acidic group, and may be used as it is as a binder resin and is soluble in the alkali developer used for pattern formation, and may be used singly or in combination. 2 or more types.

In the present invention, the alkali-soluble resin may be based on an acid value of 40 mgKOH/g or more.

The alkali-soluble resin which is preferable in the invention is a resin having an acidic group and usually a carboxyl group, and specific examples thereof include an acrylic resin having a carboxyl group and an acrylic resin having a carboxyl group such as a styrene-acrylic copolymer, and having a carboxyl group. An epoxy group (meth) acrylate resin or the like. Among these, a photopolymerizable functional group having a carboxyl group in the side chain and an ethylenically unsaturated group in the side chain is particularly preferable. This is because the film strength of the cured film formed by the photopolymerizable functional group is improved. Further, two or more kinds of the acrylic resin and the epoxy acrylate resin such as the acryl-based copolymer and the styrene-acrylic copolymer may be used in combination.

An acrylic resin having an acryl-based copolymer having a carboxyl group and a styrene-acrylic copolymer having a carboxyl group, for example, a carboxyl group-containing ethylenically unsaturated monomer and, if necessary, other copolymerizable copolymers Monomer, known Method A (co)polymer obtained by (co)polymerization.

Examples of the carboxyl group-containing ethylenically unsaturated monomer include (meth)acrylic acid, vinylbenzoic acid, maleic acid, alkyl maleate, fumaric acid, itaconic acid, and the like. Butenoic acid, cinnamic acid, acrylic acid dimer, and the like. Further, an addition reactant of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, a cyclic anhydride such as maleic anhydride or decanoic anhydride or cyclohexane dicarboxylic anhydride, or ω- may be used. Carboxy-polycaprolactone mono(meth)acrylate and the like. Further, as the carboxyl group precursor, an acid anhydride group-containing monomer such as maleic anhydride, itaconic anhydride or citraconic anhydride may be used. Among them, (meth)acrylic acid is particularly preferred 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 has been known that by using an alkali-soluble resin having a hydrocarbon ring, solvent resistance, heat resistance, light resistance, and particularly swelling of the colored layer can be improved. Although the effect has not been elucidated, it is presumed that the molecular movement in the colored layer is suppressed by the large-volume hydrocarbon ring in the colored layer, and as a result, the strength of the coating film is increased, and swelling due to the solvent is suppressed.

The hydrocarbon ring may, for example, be a cyclic aliphatic hydrocarbon ring which may have a substituent, an aromatic ring which may have a substituent, or a combination thereof; the hydrocarbon ring may have a carbonyl group, a carboxyl group or an oxycarbonyl group. a substituent such as a guanamine group. Among them, in the case of containing an aliphatic ring, the brightness of the obtained colored layer is improved while improving the heat resistance or adhesion of the colored layer.

Specific examples of the hydrocarbon ring include cyclopropane, cyclobutane, cyclopentane, cyclohexane, and descending. An aliphatic hydrocarbon ring of alkane, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane), adamantane or the like; an aromatic ring of benzene, naphthalene, anthracene, phenanthrene, anthracene or the like; biphenyl, A chain polycyclic ring such as terphenyl, diphenylmethane, triphenylmethane or hydrazine; or a cardo structure represented by the following chemical formula (9).

When the aliphatic ring is contained, it is particularly preferable from the viewpoint of improving the heat resistance or adhesion of the colored layer and improving the luminance of the obtained colored layer.

Moreover, in the case of containing the cardo structure represented by the above chemical formula (9), it is particularly preferable from the viewpoint of improving the curability of the colored layer and improving the solvent resistance (NMP swelling inhibition).

In the alkali-soluble resin used in the present invention, it is preferred to have a carboxyl group from the viewpoint of easily adjusting the respective constituent unit amounts and increasing the constituent unit amount of the hydrocarbon ring to easily improve the function of the constituent unit. In addition to the unit, an acrylic copolymer having the above constituent unit having a hydrocarbon ring is additionally used.

The constitutive unit having a carboxyl group and the above-mentioned acrylic copolymer having a hydrocarbon ring can be prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned "other monomer copolymerizable".

Examples of the ethylenically unsaturated monomer having a hydrocarbon ring in combination with a latent antioxidant include cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and adamantyl (meth)acrylate. (meth)acrylic acid Ester, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, styrene, etc.; from the viewpoint of superior heat resistance and light resistance, cyclohexyl (meth)acrylate, ( Methyl)dicyclopentanyl acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate, styrene.

The alkali-soluble resin used in the present invention preferably has an ethylenic double bond in a side chain. In the case of having an ethylenic double bond, in the hardening step of the resin composition at the time of production of the color filter, the alkali-soluble resins or the alkali-soluble resin and the polyfunctional monomer may form a cross-linking bond.

The method of introducing an ethylenic double bond into the alkali-soluble resin may be appropriately selected by a conventionally known method. For example, a compound having an epoxy group and an ethylenic double bond in a component, such as a carboxyl group having an epoxy group and an ethylenic double bond, may be added to the side chain to introduce an ethylenic double bond. Or a method in which a compound having a hydroxyl group is introduced into a copolymer, a compound having an isocyanate group and an ethylenic double bond is added to the molecule, and a vinyl double bond is introduced into the side chain.

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

The alkali-soluble resin of the present invention preferably has an acrylic resin having a constituent unit of a carboxyl group, an acrylic copolymer having a structural unit of a hydrocarbon ring, and a styrene-acrylic copolymer; more preferably, it has a carboxyl group. An acrylic resin such as a constituent unit, a constituent unit having a hydrocarbon ring, an acrylic copolymer having a constituent unit having an ethylenic double bond, and a styrene-acrylic copolymer.

The alkali-soluble resin can be used as an alkali-soluble resin having desired properties by appropriately adjusting the amount of each constituent unit.

The amount of the carboxyl group-containing ethylenically unsaturated monomer to be filled is preferably 5% by mass or more, more preferably 10%, based on the total amount of the monomers. More than % by mass. On the other hand, the amount of the carboxyl group-containing ethylenically unsaturated monomer to be filled is preferably 50% by mass or less, more preferably from the viewpoint of suppressing the film roughness of the surface of the pattern after development. 40% by mass or less.

When the proportion of the carboxyl group-containing ethylenically unsaturated monomer is 5% by mass or more, the solubility of the obtained coating film to the alkali developing solution is sufficient. In addition, when the ratio of the carboxyl group-containing ethylenically unsaturated monomer is 50% by mass or less, when the image is developed by the alkali developing solution, the formed pattern can be prevented from falling off from the substrate or the film on the pattern surface can be roughened.

In addition, it is more preferable to use an acrylic resin such as an acrylic copolymer having a structural unit of an ethylenic double bond and an acryl-based copolymer such as a styrene-acrylic copolymer, which has an epoxy group and an ethylenic double bond. The compound is preferably contained in an amount of 10% by mass or more and 95% by mass or less, more preferably 15% by mass or more and 90% by mass or less based on the amount of the carboxyl group-containing ethylenically unsaturated monomer.

The preferred weight average molecular weight (Mw) of the carboxyl group-containing copolymer is preferably in the range of 1,000 or more and 50,000 or less, more preferably in the range of from 3,000 to 20,000. When the weight average molecular weight (Mw) is 1,000 or more, the binder after curing is excellent in function; and if it is within 50,000, pattern formation by the alkali developer is easy.

Further, the above weight average molecular weight (Mw) of the carboxyl group-containing copolymer can be measured by using Shodex GPC System-21H using styrene as a standard substance and THF as an eluent.

The epoxy group (meth) acrylate resin having a carboxyl group is not particularly limited, and is preferably an epoxy group obtained by reacting an epoxy compound with a reaction product of an unsaturated group-containing monocarboxylic acid and an acid anhydride ( Methyl) acrylate compound.

An epoxy compound, an unsaturated group-containing monocarboxylic acid, and an acid anhydride, which are appropriately known in the art Choose to use. The epoxy group (meth) acrylate resin having a carboxyl group may be used alone or in combination of two or more.

The alkali-soluble resin is preferably one having an acid value of 50 mgKOH/g or more from the viewpoint of developability (solubility) of the aqueous alkali solution used for the developer. The alkali-soluble resin is preferably 70 mg KOH/g or more and 300 mg KOH/g or less from the viewpoints of developability (solubility) of the aqueous alkali solution used for the developer and adhesion to the substrate. It is preferably 70 mgKOH/g or more and 280 mgKOH/g or less.

Further, in the present invention, the acid value can be measured in accordance with JIS K 0070:1992.

When the side chain of the alkali-soluble resin has an ethylenically unsaturated group, the ethylenically unsaturated bond equivalent is preferably in the range of from 100 to 2,000, particularly preferably in the range of from 140 to 1,500. When the ethylenically unsaturated bond equivalent is 2,000 or less, development resistance or adhesion is excellent. In addition, when the ratio is 100 or more, the ratio of the constituent unit having the carboxyl group or the other constituent unit having the constituent unit of the hydrocarbon ring can be relatively increased, so that the developability or heat resistance is excellent.

Here, the ethylenically unsaturated bond equivalent is a weight average molecular weight per one mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (1).

Formula (1) Ethylene Unsaturated Bond Equivalent (g/mol)=W(g)/M(mol)

(In the formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the molar number (mol) of the ethylenic double bond contained in the alkali-soluble resin W (g).

The ethylenically unsaturated bond equivalent can be determined, for example, by measuring the iodine value described in JIS K 0070:1992, by measuring the alkali-soluble resin per 1 g. Calculated by the number of ethylenic double bonds contained.

[Antioxidants]

The photosensitive colored resin composition of the present invention preferably further contains an antioxidant. By combining the latent antioxidant represented by the above general formula (1) with a known antioxidant, it is particularly excellent in light resistance compared to the case where a latent antioxidant is used alone, and the coloring layer caused by ultraviolet irradiation can be suppressed. The brightness is lowered, and the antioxidant and the latent antioxidant sequentially exhibit an antioxidant function, thereby suppressing fading of the color material and the like in all steps of the color filter manufacturing.

The antioxidant can be appropriately selected and used by a person skilled in the art. The antioxidant may be used alone or in combination of two or more. Specific examples of the antioxidant include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and lanthanoid antioxidants, and from the viewpoint of heat resistance, it is preferably blocked. Phenolic antioxidants.

The hindered phenol-based antioxidant means an antioxidant having a structure containing at least one phenol structure and having a substituent of at least one carbon atom at the 2-position and the 6-position of the hydroxyl group of the phenol structure.

Specific examples of the hindered phenol-based antioxidant include quinone pentaerythritol [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF). 1,3,5-paran (3,5-di-t-butyl-4-hydroxybenzyl)-trimeric isocyanate (trade name: IRGANOX 3114, manufactured by BASF), 2,4,6-gin (4-hydroxy- 3,5-di-t-butylbenzyl) 1,3,5-trimethylbenzene (trade name: IRGANOX 1330, manufactured by BASF), 6-(4-hydroxy-3,5-di-t-butylanilinyl) -2,4-bis(octylthio)-1,3,5-three (trade name: IRGANOX 565, manufactured by BASF), 2,2'-thiodiethyl bis[3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate] (trade name: IRGANOX) 1035, manufactured by BASF), 1,2-bis[3-(4-hydroxy-3,5-di-t-butylphenyl)propanyl]anthracene (trade name: IRGANOX MD1024, manufactured by BASF), 3-( Octyl 4-hydroxy-3,5-diisopropylphenyl)propanoate (trade name: IRGANOX 1135, manufactured by BASF), 4,6-bis(octylthiomethyl)-o-cresol (trade name: IRGANOX) 1520L, manufactured by BASF), N, N'-hexamethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propane decylamine] (trade name: IRGANOX 1098, manufactured by BASF) 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 259, manufactured by BASF), 1-dimethyl -2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propanyloxy]ethyl]2,4,8,10 oxaoxaspiro[5.5]undecane ( Product name: ADK STAB AO-80, manufactured by ADEKA), bis(3-tert-butyl-4-hydroxy-5-methylphenylpropionic acid) ethylene bis(oxyethylene) (trade name: IRGANOX 245, manufactured by BASF) ), 1,3,5-gin[[4-(1,1-dimethylethyl)-3-hydroxy-2,6-dimethylphenyl]methyl]-1,3,5-three -2,4,6(1H,3H,5H)-trione (trade name: IRGANOX 1790, manufactured by BASF), 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (trade name: SUMILIZER MDP-S, manufactured by Sumitomo Chemical Co., Ltd.), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: IRGANOX 1081, manufactured by BASF), 3,5- Di-tert-butyl-4-hydroxybenzyl sulfonate (trade name: IRGAMOD 195, manufactured by BASF), 2-tert-butyl-4-methyl-6-(2-hydroxy-3-yl acrylate Tributyl-5-methylbenzyl)phenyl ester (trade name: SUMILIZER GM, manufactured by Sumitomo Chemical Co., Ltd.), 4,4'-thiobis(6-t-butyl-m-cresol) (trade name: SUMILIZER WX- R, Sumitomo Chemical Co., Ltd., etc. Other oligomer type and polymer type compounds having a hindered phenol structure can also be used.

[optional addition]

In the photosensitive colored resin composition of the present invention, various additives may be contained as needed. Additives.

Examples of the additive include a polymerization stopper, a chain shifting agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a decane coupling agent, an ultraviolet absorber, a dense adhesion promoter, and the like.

<Preparation ratio of each component of the photosensitive colored resin composition>

In the photosensitive colored resin composition of the present invention, the blending ratio of each component is not particularly limited, and can be appropriately adjusted in accordance with the use and the like without departing from the scope of the effects of the present invention.

The content ratio of the coloring material is preferably 10% by mass or more and 60% by mass or less based on the total amount of the solid content of the photosensitive colored resin composition, in terms of high luminance. More preferably, it is 12 mass % or more and 50 mass % or less.

In the present invention, the solid portion indicates all components other than the solvent constituting the photosensitive colored resin composition. For example, even a liquid photopolymerizable compound is included in the solid portion.

The content ratio of the photopolymerizable compound is preferably 5% by mass or more and 60% by mass or less, and more preferably 10% by mass or more and 40% by mass or less based on the total amount of the solid content of the photosensitive colored resin composition. When the content ratio of the photopolymerizable compound is less than the above lower limit, the photocuring is not sufficiently performed, and the exposed portion is eluted during development; and when the content ratio of the photopolymerizable compound is more than the above upper limit, The alkali developability is 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 based on the total amount of the solid content of the photosensitive colored resin composition. If the starting dose is less than the above upper limit, then It is preferred that the mask is open and the pattern is not too thick. When the starting dose is at least the above lower limit value, the solvent resistance is improved.

Further, in the case where at least two kinds of oxime-based initiators are contained as the initiator, the total content of two or more kinds of the lanthanide initiator is relative to the total amount of the solid content of the photosensitive resin composition, and such From the viewpoint of the synergistic effect of the agent, the content is preferably 0.1% by mass or more and 12.0% by mass or less, more preferably 1.0% by mass or more and 8.0% by mass or less. The content ratio of the latent antioxidant represented by the above general formula (1) is based on the viewpoint of obtaining a coloring layer having a high luminance and obtaining a photosensitive colored resin composition having a suppressed line width change. The total amount of the solid content of the colored resin composition is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 8% by mass or less.

When the alkali-soluble resin is used, the content ratio thereof is preferably 5% by mass or more and 60% by mass or less based on the total amount of the solid content of the photosensitive colored resin composition from the viewpoint of developability, and more preferably 5 mass% or more and 50 mass% or less are more preferably 10 mass% or more and 40 mass% or less.

When the content of the alkali-soluble resin is at least the above lower limit value, sufficient alkali developability can be obtained. Further, when the content of the alkali-soluble resin is at most the above upper limit value, film roughness or pattern defects can be suppressed at the time of development.

The content of the dispersant is not particularly limited as long as the color material can be uniformly dispersed. For example, the content of the solid content of the photosensitive colored resin composition can be 1% by mass or more and 40% by mass or less. . Further, the total amount of the solid content of the photosensitive colored resin composition is preferably 2% by mass or more and 30% by mass or less, particularly preferably 3% by mass or more and 25% by mass or less. If it is above When the value is more than the limit, the dispersibility and dispersion stability of the color material are excellent, and the storage stability of the photosensitive colored resin composition is excellent. Moreover, when it is below the said upper limit, the developability is favorable. In particular, in the case of forming a coloring layer having a high color material concentration, the content of the dispersing agent is preferably 2% by mass or more and 25% by mass or less, more preferably 3 parts by mass based on the total amount of the solid content of the photosensitive colored resin composition. The ratio is 5% by mass or more and 20% by mass or less.

Further, when the non-latentified antioxidant is further used in combination, the content ratio of the antioxidant is obtained from a coloring layer capable of forming a high luminance and a photosensitive colored resin composition having a suppressed line width change. The total amount of the solid content of the photosensitive colored resin composition is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 8% by mass or less, still more preferably 0.1% by mass or more and 5.0. Below mass%. When it is more than the above lower limit value, it is easy to exhibit the effect of use in combination. On the other hand, when it is at most the above upper limit value, a photosensitive resin composition having high sensitivity can be obtained.

The content ratio of the latent antioxidant represented by the above general formula (1) to the antioxidant is latent with respect to the general formula (1) in terms of suppressing the change in line width and easily forming a high-luminance coloring layer. The amount of the antioxidant is 1 part by mass, preferably 0.1 part by mass or more and 10 parts by mass or less, more preferably 0.1 part by mass or more and 5.0 parts by mass or less.

In the photosensitive colored resin composition of the present invention, the content of the solvent is appropriately set within a range in which the coloring layer can be formed with high precision. The total amount of the photosensitive colored resin composition for a color filter containing the solvent is usually in the range of 55 mass% or more and 95 mass% or less, and more preferably 65 mass% or more and 88 mass% or less. Within the scope. When the content of the above solvent is within the above range, it is possible to obtain a coating property superior.

<Method for Producing Photosensitive Colored Resin Composition>

The method for producing a photosensitive colored resin composition of the present invention contains at least a color material, a photopolymerizable compound, a starter, a latent antioxidant, and a solvent, and more preferably contains a dispersant, preferably an antioxidant, preferably. The method of containing an alkali-soluble resin and uniformly dispersing or dissolving the color material in a solvent may be prepared by mixing using a known mixing means.

As a method of preparing the resin composition, for example, (1) First, a color material and a dispersing agent are added to a solvent to prepare a color material dispersion, and a photopolymerizable compound and a starter are mixed in the dispersion. a latent antioxidant, a method of adding various components as needed, and (2) a method of mixing a color material, a photopolymerizable compound, a starter, and a latent antioxidant in a solvent; .

Among these methods, the method of the above (1) is preferable from the viewpoint of effectively preventing aggregation and uniform dispersion of the color material.

The method of preparing the color material dispersion can be appropriately selected and used by a conventionally known dispersion method. For example, (1) the dispersant is mixed with a solvent in advance and stirred to prepare a dispersant solution, and then the organic acid compound is mixed as necessary to form a salt of the amine group of the dispersant with the organic acid compound. Mixing this with a color material and other components as needed, and dispersing it using a known mixer or disperser; (2) mixing the dispersant into a solvent and stirring to prepare a dispersant solution, then coloring the material and optionally a method of mixing an organic acid compound and, if necessary, other components, and dispersing it using a known mixer or disperser; (3) mixing the dispersant into a solvent and stirring to prepare a dispersant solution, followed by coloring materials and optionally A method in which an organic acid compound is added as needed after mixing other components and using a known agitator or disperser to form a dispersion.

As the dispersing machine for performing the dispersion treatment, for example, a two-roll mill Ball mills such as roller mills, ball mills, vibrating ball mills, etc., ball mills, paint shakers, continuous disk bead mills, continuous ring bead mills, etc. 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, more preferably 0.10 mm or more and 1.0 mm or less.

Specifically, for example, it is preliminarily dispersed by a 2 mm zirconia bead having a large bead diameter, and then uniformly dispersed by a 0.1 mm zirconia bead having a small bead diameter. Further, after the dispersion, it is preferably filtered through a membrane filter of 0.5 μm or more and 2 μm or less.

2. Color filter

The color filter of the present invention includes at least a substrate and a colored layer provided on the substrate, and at least one of the colored layers is a cured product of the photosensitive colored resin composition of the present invention.

A method of producing a color filter according to the present invention is a method of producing a color filter including at least a substrate and a coloring layer provided on the substrate, comprising: forming the photosensitive coloring resin composition of the present invention The step of at least one of the colored layers.

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

(colored layer)

At least one of the coloring layers used in the color filter of the present invention is a coloring layer containing the cured product of the photosensitive colored resin composition of the present invention.

The colored layer is usually formed on the opening of the light-shielding portion on the substrate to be described later, and is usually composed of three or more colored patterns.

In addition, the arrangement of the colored layer is not particularly limited, and may be, for example, a general arrangement such as a stripe type, a mosaic type, a triangular type, or a four-pixel arrangement type. Further, the width, area, and the like of the colored layer can be arbitrarily set.

The thickness of the colored layer can be appropriately suppressed by adjusting the coating method, the solid content concentration or the viscosity of the photosensitive colored resin composition for a color filter, and the like, and is usually preferably in the range of 1 μm or more and 5 μm or less.

The colored layer can be formed by, for example, the following method.

First, the photosensitive colored resin composition of the present invention is applied onto a transparent substrate to be described later by a coating means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method or a die coating method to form a wet film. Coating film. Among them, a spin coating method or a die coating method is preferably used.

Then, the wet coating film is dried by a hot plate or an oven, and then exposed to a mask of a predetermined pattern, and an alkali-soluble resin, a polyfunctional monomer, or the like is photopolymerized to form a cured coating film. Examples of the light source used for the 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 thickness of the light source or coating film to be used and the like.

Further, after the exposure, in order to promote the polymerization reaction, heat treatment may be performed. 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, development treatment is carried out using a developing solution to dissolve and remove the unexposed portion, thereby forming a coating film in a desired pattern. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. In this alkaline solution, a surfactant or the like may be added in an appropriate amount. Further, the development method can employ a general 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. Further, after the development treatment, heat treatment may be performed in order to sufficiently cure the coating film. The heating conditions are not particularly limited and may be appropriately selected depending on the use of the coating film.

(lighting part)

The light-shielding portion of the color filter of the present invention is formed into a pattern on a substrate to be described later, and can be the same as that used for a light-shielding portion in a general color filter.

The pattern shape of the light shielding portion is not particularly limited, and may be, for example, a stripe shape or a matrix shape. The light shielding portion may be a metal thin film such as chromium which is caused by a sputtering method or a vacuum evaporation method. Alternatively, the light-shielding portion may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in the resin binder. In the case of a resin layer containing light-shielding particles, there is a method of patterning by development using a photosensitive photoresist, a method of patterning using an inkjet ink containing light-blocking particles, and heat of a photosensitive photoresist. Transfer method, etc.

The film thickness of the light-shielding portion is about 0.2 μm to 0.4 μm in the case of the metal thin film, and is 0.5 μm to 2 μm or less in order to disperse or dissolve the black pigment in the binder resin.

(substrate)

As the substrate, a transparent substrate or a tantalum substrate to be described later is used, and an aluminum, silver, silver/copper/palladium alloy thin film or the like is formed on the substrate. On such substrates, other color filter layers, resin layers, TFTs such as TFTs, circuits, and the like can be formed.

As a transparent substrate in the color filter of the present invention, if it is visible The light-transparent substrate is not particularly limited, and a transparent substrate used for a general color filter can be used. Specifically, for example, a transparent rigid material such as quartz glass, an alkali-free glass, or a synthetic quartz plate, or a flexible transparent material such as a transparent resin film, an optical resin plate, or a flexible glass can be used.

The thickness of the transparent substrate is not particularly limited, and for the use of the color filter of the present invention, for example, a thickness of about 100 μm to 1 mm can be used.

Further, in addition to the substrate, the light shielding portion, and the coloring layer, the color filter of the present invention may form, for example, a top coat layer or a transparent electrode layer, and further an alignment film, an alignment protrusion, a columnar spacer, or the like.

3. Display device

A display device of the present invention is characterized by comprising the above-described color filter of the present invention. The configuration of the display device in the present invention is not particularly limited, and may be appropriately selected from known display devices, and examples thereof include a liquid crystal display device and an organic light-emitting display device.

[Liquid Crystal Display Device]

The liquid crystal display device is characterized by comprising the above-described color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.

The liquid crystal display device of the present invention will be described below with reference to the drawings. Fig. 2 is a schematic view showing an example of a liquid crystal display device of the present invention. As shown in FIG. 2, the liquid crystal display device 40 of the present invention has a color filter 10, an opposite substrate 20 having a TFT array substrate, and the like, and a liquid crystal layer formed between the color filter 10 and the opposite substrate 20. 30.

Further, the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, A known configuration of a liquid crystal display device used for a general color filter can be used.

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 driving 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 suitably 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 or the like.

In addition, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and a mixture thereof can be used according to the driving method of the liquid crystal display device of the present invention.

As a method of forming the liquid crystal layer, a method generally used as a method of producing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method. After the liquid crystal layer is formed by the above method, the liquid crystal cell is slowly cooled to a normal temperature, whereby the sealed liquid crystal can be aligned.

[Organic light-emitting display device]

The organic light-emitting display device is characterized by comprising the above-described color filter of the present invention and an organic light-emitting body.

The organic light-emitting display device of the present invention will be described below with reference to the drawings. Fig. 3 is a schematic cross-sectional view showing an example of the organic light-emitting display device of the present invention. As shown in FIG. 3, the organic light-emitting display device 100 of the present invention has a color filter 10 and an organic light-emitting body 80. An organic protective layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the organic light-emitting body 80.

As a method of laminating the organic light-emitting body 80, for example, color filter 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 successively formed on the light sheet, or the organic light-emitting body 80 formed on the other substrate is attached. A method of bonding to the inorganic oxide film 60 or the like. The transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 75, and the cathode 76 in the organic light-emitting body 80, and other configurations can be suitably used. The organic light-emitting display device 100 thus fabricated can be applied to, for example, an organic EL display in a passive driving mode or an organic EL display in an active driving mode.

In addition, the organic light-emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and can be generally configured as an organic light-emitting display device using a color filter.

[Examples]

Hereinafter, the embodiments will be specifically described with reference to the present invention. However, the present invention is not limited to these descriptions. Further, in the following synthesis and modulation, the operation is repeated as needed to obtain the desired amount.

(Synthesis of color material A) (1) Synthesis of Intermediate 1

1.1 iodine naphthalene (15.2 g (60 mmol) and Mitsui Chemicals Co., Ltd.) Alkyldiamine (NBDA) (CAS No. 56602-77-8) 4.63 g (30 mmol), sodium butoxide 8.07 g (84 mmol), 2-dicyclohexylphosphino-2', 6', from Aldrich. 0.09 g (0.2 mmol) of dimethoxybiphenyl and 0.021 g (0.1 mmol) of palladium acetate produced by Wako Pure Chemical Industries Co., Ltd. were dispersed in 30 mL of xylene, and reacted at 130-135 ° C for 48 hours. After the reaction was completed, it was cooled to room temperature and extracted with water. Then, it was dried over magnesium sulfate and concentrated, whereby 8.5 g of the intermediate 1 (yield 70%) of the following formula (i) was obtained.

The obtained compound was confirmed to be the target compound by the following analysis.

‧MS(ESI)(m/z):407(M+H)

‧ Elemental analysis values: CHN measured values (85.47%, 8.02%, 6.72%); theoretical values (85.26%, 8.11%, 6.63%)

(2) Synthesis of intermediate 2

8.46 g of the intermediate 1 (20.8 mmol) and 13.5 g (41.6 mmol) of 4,4'-bis(dimethylamino)diphenyl ketone manufactured by Tokyo Chemical Industry Co., Ltd. were added to 60 mL of toluene at 45-50 ° C with stirring. 6.38 g (51.5 mmol) of phosphonium chloride was prepared by the Wako Pure Chemical Industries, and refluxed for 2 hours and cooled. After the reaction was completed, toluene was decanted. The resinous precipitate was added to 40 mL of chloroform, 40 mL of water, and concentrated hydrochloric acid to dissolve, 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 to reflux. After cooling, the precipitate was filtered to obtain 15.9 g of the intermediate 2 (BB7-Nb-dimer) of the following formula (ii) (yield 70%).

The obtained compound was confirmed to be the target compound by the following analysis.

‧MS(ESI)(m/z): 511(+), 2 price

‧ Elemental analysis values: CHN measured values (78.13%, 7.48%, 7.78%); theoretical values (78.06%, 7.75%, 7.69%)

(3) Synthesis of color material A

5.00 g (4.58 mmol) of the intermediate 2 was added to 300 ml of water, and dissolved at 90 ° C to prepare an intermediate 2 solution. Next, a phosphotungstic acid ‧n hydrate H ₃ [PW ₁₂ O ₄₀ ]‧nH ₂ O (n=30) 10.44 g (3.05 mmol) manufactured by Nippon Chemical Industry Co., Ltd. was added to 100 mL of water, and stirred at 90 ° C to prepare a phosphorus tungsten Aqueous acid solution. The aqueous solution of the phosphotungstic acid was mixed with the previous intermediate 2 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 the color material A represented by the following chemical formula (iii).

The obtained compound was confirmed to be the target compound by the following analysis.

‧MS(ESI)(m/z): 510(+), 2 price

‧ Elemental analysis values: CHN measured values (41.55%, 5.34%, 4.32%); theoretical values (41.66%, 5.17%, 4.11%)

Further, it was confirmed by ³¹ P-NMR that the polyoxo acid structure of the phosphotungstic acid was retained after the color material A was formed.

(Synthesis Example 2: Synthesis of color material B)

5.0 g of Acid Red 289 (AR289, manufactured by Tokyo Kasei Co., Ltd.) shown in the following formula was added to 500 ml of water, and dissolved at 80 ° C to prepare a dye solution. Next, polyaluminum chloride ("trade name: Takibine #1500", manufactured by Toki Chemical Co., Ltd., Al ₂ (OH) ₅ Cl, alkalinity of 83.5 mass%, and alumina content of 23.5 mass%) was added to 3.85 g of water to 200 ml. The mixture was dissolved, and stirred at 80 ° C to prepare an aqueous solution of polyaluminum chloride. The prepared aqueous solution of polyaluminum chloride was dropped into the above dye solution at 80 ° C for 15 minutes, and further stirred at 80 ° C for 1 hour. The resulting precipitate was filtered off and washed with water. The obtained cake was dried to obtain 6.30 g (yield 96.2%) of a metallic lake color material (color material B) of a rose-red acid dye.

[化23]

(Synthesis Example 3: Synthesis of color material C)

4 parts by mass of a sulfonic acid-based fluorescent yellow mother compound of the following chemical formula (iv), 312 parts by mass of methanol, and 6.8 parts by mass of N-methyl-2,6-dimethylaniline, were placed in a 500-ml four-necked flask. 6.0 parts by mass of N-methyl-o-toluidine and refluxed for 30 hours. After the reaction solution was filtered at 60 ° C to remove the insoluble portion, the solvent was removed under reduced pressure until it became about 70 ml, and was poured into 200 parts by mass of 6% hydrochloric acid. Next, 600 parts by mass of water was added and stirred at room temperature for 30 minutes, and then the wet cake was filtered off. The cake was suspended in 100 parts by mass of water and stirred at 60 ° C for 2 hours, and then filtered again, washed with water at 60 ° C, and then dried, whereby a coloring material C 27.4 of the following formula was obtained. Parts by mass.

[化25]

(Synthesis Example 4: Synthesis of latent antioxidants)

0.01 mol of the phenol compound represented by the following chemical formula (vi), 0.05 mol of dibutyl butyl carbonate, and 30 g of pyridine were mixed, and 4-dimethylaminopyridine 0.025 mol was added at room temperature under a nitrogen atmosphere. Stir at °C for 3 hours. After cooling to room temperature, the reaction solution was poured into 150 g of ion-exchanged water, and 200 g of chloroform was added thereto to carry out oil-water separation. After drying the organic layer with anhydrous sodium sulfate, the solvent was distilled off, and 100 g of methanol was added to the residue for crystallization. The obtained white powdery crystals were dried under reduced pressure at 60 ° C for 3 hours to obtain a latent antioxidant (compound A) represented by the above formula (A). Further, the structure of the obtained latent antioxidant was confirmed by IR and NMR.

(Synthesis Example 5: Synthesis of Dispersant (Block Copolymer A))

To a 500 mL round bottom four-neck separation flask equipped with a cooling tube, an addition funnel, a nitrogen gas inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added, and nitrogen substitution was sufficiently performed. After cooling the reaction flask to -60 ° C, 4.9 parts by mass of butyllithium (15 mass% hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 part by mass of methyl isocyanate were injected using a syringe. 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA) of the B block, 18.7 parts by mass of 2-hydroxyethyl methacrylate (HEMA), 2-ethylhexyl methacrylate ( EHMA) 12.8 parts by mass, 13.7 parts by mass of n-butyl methacrylate (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA), and 17.5 parts by mass of methyl methacrylate (MMA), using an addition funnel for 60 minutes Drip. After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for the A block, was dropped over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to terminate the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, and diluted with PGMEA to prepare a 30% by mass solid solution. 32.5 parts by mass of water was added, and the mixture was heated to 100 ° C for 7 hours, and the constituent unit derived from EEMA was deprotected to obtain a constituent unit derived from methacrylic acid (MAA). The obtained block copolymer PGMEA solution is reprecipitated in hexane, and purified by filtration and vacuum drying to obtain an A block containing a constituent unit represented by the general formula (2) and a constituent unit containing a carboxyl group-containing monomer. Further, it has a solvent-soluble B block block copolymer A (acid value: 8 mgKOH/g). The block copolymer A thus obtained was confirmed by GPC (gel permeation chromatography), and as a result, the weight average molecular weight Mw was 7730. Further, the amine value was 95 mgKOH/g.

(Synthesis Example 6: Synthesis of alkali-soluble resin A)

150 parts by mass of PGMEA was filled in the polymerization tank, and the temperature was raised to 100 in a nitrogen atmosphere. After the temperature of C, 21 parts by mass of methacrylic acid (MAA), 15 parts by mass of methyl methacrylate (MMA), 50 parts by mass of cyclohexyl methacrylate (CHMA), and PERBUTYL O (manufactured by Nippon Oil Co., Ltd.) 6 The mass parts and the chain shifting agent (n-dodecyl hydrazine) 2 parts by mass were continuously dropped over 1.5 hours. Thereafter, the reaction was continued at 100 ° C, and after completion of the dropwise addition of the above-mentioned main chain-forming mixture for 2 hours, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibiting agent to stop the polymerization.

Next, 14 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound was added while blowing air, and the temperature was raised to 110 ° C, and 0.8 parts by mass of triethylamine was added thereto, and the mixture was added at 110 ° C. After reacting for 15 hours, an alkali-soluble resin A (weight average molecular weight (Mw): 9020, an acid value of 90 mgKOH/g, and a solid content of 40% by mass) was obtained.

Further, the method for measuring the weight average molecular weight is a polystyrene standard material, and THF is used as an eluent, and the weight average molecular weight is measured by Shodex GPC System-21H). Further, the method for measuring the acid value is measured in accordance with JIS K 0070:1992.

(Modulation Example 1: Modulation of Color Material Dispersion A)

To 225 mL of a cannabis bottle, 68.8 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) and 2.7 parts by mass of block copolymer A (amine price: 95 mgKOH/g) were added and stirred. 2.45 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Co., Ltd.) was added thereto (0.7 molar equivalent to the tertiary amine group of the block copolymer), and stirred at room temperature for 30 minutes to obtain a salt form. Block copolymer solution.

13.0 parts by mass of the alkali-soluble resin A (solid content: 40% by mass) was added, and after stirring at room temperature, 100 parts by mass of the above-mentioned color material A and 3.0 parts by mass of zirconia beads having a particle diameter of 2.0 mm were added by a coating shaker. (manufactured by Asada Iron Works Co., Ltd.) was shaken for 1 hour as a preliminary crush, and then changed to a particle size of 0.1 mm zirconia beads 200 parts by a pigment oscillator. The dispersion was carried out for 4 hours as an official pulverization, and a color material dispersion A was obtained.

(Preparation Example 2: Modulation of Color Material Dispersion B)

In the above-described preparation example 1, the color material dispersion liquid B was obtained in the same manner as in the preparation example 1 except that the color material B was used instead of the color material A.

(Preparation Example 3: Modulation of Color Material Dispersion C)

In a beaker, 1000 parts by mass of methanol was added to 100 parts by mass of the color material C and dissolved by a magnetic stir bar. After confirming the dissolution, 19 parts by mass of concentrated hydrochloric acid was added and stirred, and then 1000 parts by mass of PGMEA was added. Next, 198 parts by mass of the dispersant block copolymer A was added and stirred. Thereafter, the reflux cooling tube was connected, and the temperature was raised to 80 ° C by a water bath, and the reaction was carried out for 4 hours after reaching 80 ° C. Thereafter, methanol was distilled off by a water bath at 45 ° C in an evaporator to 1000 parts by mass of PGMEA, and then left to stand at room temperature for 16 hours. Then, the obtained filtrate was collected by filtration to obtain a color material dispersion C in which the dye was uniformly dispersed.

(Manufacturing Example 1: Modulation of Photosensitive Adhesive A)

14.2 parts by mass of dipentaerythritol penta(meth)acrylate (ARONIX M403 (manufactured by Toagosei Co., Ltd.)) as a polyfunctional monomer was added to 23.5 parts by mass of the alkali-soluble resin A solution (solid content: 40% by mass) obtained in Synthesis Example 6. 144 parts by mass of IRGACURE 907 (light initiator having a tertiary amine structure: manufactured by BASF), 1.5 parts by mass of NCI-930 (an oxime ester photoinitiator: manufactured by ADEKA), and a compound of Synthesis Example 4 A (latent antioxidant) 0.6 parts by mass and PGMEA 55.9 parts by mass to obtain a photosensitive adhesive A.

(Manufacturing Example 2 to 6: Modulation of Photosensitive Adhesive B to F)

In Production Example 1, the blending ratio was changed in the same manner as in Production Example 1 except that the blending ratio was changed, for example, in the following Table 1, and photosensitive adhesives B to F were obtained. Further, the compound α in Table 1 represents an antioxidant IRGANOX 1010 manufactured by BASF Corporation.

(Comparative Production Example 1 to 2: Modulation of Photosensitive Adhesive G~H)

In Production Example 1, the blending ratio was changed in the same manner as in Production Example 1 except that the blending ratio was changed, for example, in the following Table 1, and the photosensitive adhesives G to H were obtained.

(Example 1: Preparation of photosensitive colored resin composition 1)

24.6 parts by mass of the color material dispersion A obtained in Preparation Example 1, 34.1 parts by mass of the photosensitive adhesive A obtained in Production Example 1, 0.16 parts by mass of the surfactant MAGAFAC R08MH (manufactured by DIC), and 41.1 parts by mass of PGMEA were mixed and obtained. The photosensitive colored resin composition 1 of Example 1.

(Examples 2 to 6: Preparation of photosensitive colored resin compositions 2 to 6)

In the first embodiment, the photosensitive colored resin compositions 2 to 6 were obtained in the same manner as in Example 1 except that the photosensitive adhesives A to B were used instead of the photosensitive adhesives B to F.

(Comparative Example 1 to 2: Modulation of photosensitive colored resin composition X1 to X2)

In the first embodiment, the photosensitive colored resin compositions X1 to X2 were obtained in the same manner as in Example 1 except that the photosensitive adhesives A to Comparative Examples 1 and 2 were used instead of the photosensitive adhesives A.

(Example 7: Preparation of photosensitive colored resin composition 7)

In the same manner as in Example 1, except that 17.2 parts by mass of the color material dispersion liquid A and 7.4 parts by mass of the color material dispersion liquid B were used in combination, the photosensitive coloring resin was obtained in the same manner as in Example 1. Composition 7.

(Examples 8 to 9: Preparation of photosensitive colored resin composition 8 to 9)

In Example 7, instead of the photosensitive adhesive A, the feeling of Production Example 2 was used. The photosensitive adhesive composition 8 to 9 was obtained in the same manner as in Example 7 except that the photosensitive adhesive B and the photosensitive adhesive D of Production Example 4 were used.

(Comparative Examples 3 to 4: Modulation of photosensitive coloring resin composition X3 to X4)

In the same manner as in Example 7, except that the photosensitive adhesives G to H of Comparative Production Examples 1 and 2 were used instead of the photosensitive adhesive A, the photosensitive colored resin compositions X3 to X4 were obtained.

(Example 10: Preparation of photosensitive colored resin composition 10)

In the first embodiment, in place of the color material dispersion A 24.6 parts by mass, 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, and the amount of the photosensitive adhesive A was changed to 33.9 mass. In the same manner as in Example 1, except that the amount of the PGMEA was changed to 37.9 parts by mass, the photosensitive colored resin composition 10 was obtained.

(Examples 11 to 12: Preparation of photosensitive colored resin compositions 11 to 12)

In the same manner as in Example 10 except that the photosensitive adhesive B of the production example 2 and the photosensitive adhesive D of the production example 4 were used instead of the photosensitive adhesive A, the photosensitive colored resin composition was obtained. Object 11~12.

(Comparative Examples 5 to 6: Modulation of photosensitive coloring resin composition X5 to X6)

In the same manner as in Example 10 except that the photosensitive adhesives G to H of Comparative Production Examples 1 and 2 were used, the photosensitive colored resin compositions X5 to X6 were obtained in the same manner as in Example 10 except that the photosensitive adhesives A were used.

(Example 13: Modulation of photosensitive colored resin composition 13)

In the first embodiment, 42.6 parts by mass of the color material dispersion A was used instead of the color material dispersion A 24.6 parts by mass, and the amount of the photosensitive adhesive A was changed to 33.1 parts by mass, and the PGMEA amount was changed to 25.2 mass. The photosensitive colored resin composition 13 was obtained in the same manner as in Example 1 except for the portion.

(Examples 14 to 15: Preparation of photosensitive colored resin compositions 14 to 15)

In the same manner as in Example 13, except that the photosensitive adhesive B of the production example 2 and the photosensitive adhesive D of the production example 4 were used instead of the photosensitive adhesive A, the photosensitive colored resin composition was obtained. Matter 14~15.

(Comparative Examples 7 to 8: Modulation of photosensitive colored resin composition X7 to X8)

In the same manner as in Example 13, except that the photosensitive adhesives A of Comparative Examples 1 and 2 were used instead of the photosensitive adhesive A, the photosensitive colored resin compositions X7 to X8 were obtained.

(luminance evaluation)

The photosensitive colored resin compositions of the examples and the comparative examples were each coated on a glass substrate (manufactured by NH Techno Glass, "NA35") having a thickness of 0.7 mm using a spin coater. After heating and drying on a hot plate at 80 ° C for 3 minutes, ultraviolet rays of 60 mJ/cm ^{2 were} irradiated with an ultrahigh pressure mercury lamp. Thereafter, post-baking was performed for 75 minutes in a 230 ° C clean room. The chromaticity (x, y) and luminance (Y) of the colored film were measured before and after the irradiation of the ultraviolet rays. The chromaticity and the luminance were measured using a "microscopic spectroscopic measuring device OSP-SP200" manufactured by Olympus Co., Ltd. The results are shown in Tables 2 to 5.

(Linewidth increase and decrease rate evaluation)

The photosensitive colored resin composition obtained in each of the examples and the comparative examples was applied to a glass substrate ("NA35" manufactured by NH Techno Glass Co., Ltd.) by a spin coater so as to have a thickness of 3.0 μm. Thereafter, it was dried at 80 ° C for 3 minutes using a hot plate to form a coating film on the glass substrate. The coating film was exposed to ultraviolet light of 60 mJ/cm ² through an ultra-high pressure mercury lamp through an independent fine-line pattern mask having a line width of 1 μm to 100 μm, thereby forming an exposed coating film on the glass substrate, followed by 0.05 wt% of hydrogen. The sodium oxide aqueous solution was subjected to rotational development as a developing solution, and the developer was liquid-contacted for 60 seconds, and then washed with pure water to carry out development treatment. Thereafter, the solution was post-baked in a clean room at 230 ° C for 25 minutes to form a fine line pattern. In the thin line pattern formed, the width of the thin line pattern corresponding to the opening width of the chrome mask at the time of exposure was 90 μm by an optical microscope, and the line width of the comparative example in which no antioxidant was added was used as the reference. Equation (2) calculates the line width increase and decrease rate. The results are shown in Tables 2 to 5.

Equation (2): (LL ₀ ) / L ₀ × 100 (%)

In the formula (2), L ₀ represents the line width of the comparative example in which no antioxidant is added, and L represents the line width of the example or the comparative example to be evaluated.

<Evaluation criteria>

A: The line width is -3% or more with respect to the unadded antioxidant

B: the line width is -10% or more and less than -3% with respect to the unadded antioxidant

C: the line width is less than -10% relative to the line without added antioxidant

[Table 2 to Table 5 results integration]

The coloring layer of the photosensitive colored resin composition of Comparative Examples 2, 4, 6 and 8 using the conventional antioxidants was used, compared with Comparative Examples 1, 3, 5 and 7 in which no antioxidant was used, and the line width thereof. The change is significantly larger. On the other hand, in Comparative Examples 1, 3, 5, and 7, since the antioxidant was not contained, although the change in the line width was suppressed, the luminance was lowered. The photosensitive colored resin compositions of Examples 1 to 15 using latent antioxidants have higher luminance than the comparative examples containing the same color materials; and, compared with the use of conventional antioxidants For example, the change in line width is significantly suppressed. As a result of the above, according to the present invention, it is possible to obtain a photosensitive colored resin composition capable of forming a high-luminance coloring layer and suppressing variations in line width.

As shown in the results in Table 2, by combining latent antioxidants and antioxidants, the change in line width can be suppressed, and the light resistance is improved as compared with the case where the latent antioxidant is used alone, and the ultraviolet irradiation can be suppressed. The brightness of the colored layer is lowered.

Further, as shown in the results of Table 5, the photosensitive colored resin composition containing the color material C belonging to the dye tends to have a narrower line width. It is presumed that this is due to the decrease in sensitivity due to the color material C belonging to the dye. In particular, since the coloring layer of the colored resin composition of Comparative Example 8 was used, since the antioxidant was combined, the sensitivity of the exposed portion was insufficient, and the hardness sufficient for development could not be obtained, and the fine line pattern could not be formed. As shown in Examples 13 to 15, the photosensitive colored resin composition of the present invention using a latent antioxidant significantly suppressed the change in line width.

(Manufacturing Example 7: Modulation of Photosensitive Adhesive I)

The alkali-soluble resin A solution obtained in Synthesis Example 6 (solid content 40 mass) In an amount of 14.5 parts by mass, 14.1 parts by mass of dipentaerythritol penta(meth)acrylate (ARONIX M403 (manufactured by Toagosei Co., Ltd.)) as a polyfunctional monomer, and IRGACURE 907 (a light having a tertiary amine structure) Starting agent: 2.9 parts by mass, NCI-930 (an oxime-based photoinitiator: manufactured by ADEKA) 1.5 parts by mass, PBG3057 (an oxime-based photoinitiator, manufactured by Changzhou Strong Electronic New Materials Co., Ltd., "TR- PBG-3057") 1.5 parts by mass of Compound A of Synthesis Example 4 (0.6 parts by weight of latent antioxidant and 55.9 parts by mass of PGMEA), and photosensitive adhesive I was obtained.

(Manufacturing Example 8 and Comparative Production Example 3: Modulation of photosensitive adhesives J and K)

In Production Example 7, the blending ratios were changed in the same manner as in Production Example 7, except that the blending ratio was changed, for example, in the following Table 6, and photosensitive adhesives J and K were obtained. Further, the compound α in Table 6 represents an antioxidant IRGANOX 1010 manufactured by BASF Corporation.

(Example 16: Preparation of photosensitive colored resin composition 16)

24.6 parts by mass of the color material dispersion A obtained in Preparation Example 1, 34.1 parts by mass of the photosensitive adhesive I obtained in Production Example 7, and the surfactant MAGAFAC R08MH (DIC) 0.16 parts by mass and 41.1 parts by mass of PGMEA were mixed to obtain a photosensitive colored resin composition 16 of Example 16.

(Example 17 and Comparative Example 9: Preparation of photosensitive colored resin composition 17 and X9)

In the same manner as in Example 16, except that the photosensitive adhesives J and the photosensitive adhesives J and K of Comparative Production Example 3 were used in the same manner as in Example 16, the photosensitive colored resin composition 17 was obtained. X9.

(Example 18: Preparation of photosensitive colored resin composition 18)

In the same manner as in Example 16 except that 17.2 parts by mass of the color material dispersion liquid A and 7.4 parts by mass of the color material dispersion liquid B were used in combination, the photosensitive coloring resin was obtained. Composition 18.

(Example 19, Comparative Example 10: Preparation of photosensitive colored resin composition 19, X10)

In the same manner as in Example 18 except that the photosensitive adhesives J of Comparative Example 3 and the photosensitive adhesives J and K of Comparative Production Example 3 were used in the same manner as in Example 18, the photosensitive colored resin composition 19 was obtained. X10.

(Example 20: Preparation of photosensitive colored resin composition 20)

In Example 16, in place of the color material dispersion A 24.6 parts by mass, 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, and the amount of the photosensitive adhesive I was changed to 33.9 mass. The photosensitive colored resin composition 20 was obtained in the same manner as in Example 16 except that 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 the same manner as in Example 20, except that the photosensitive adhesives J of the production example 8 and the comparative production example 3 were used in the same manner as in the example 20, the photosensitive colored resin composition 21 was obtained. X11.

(Example 22: Preparation of photosensitive colored resin composition 22)

In the same manner as in Example 16, the color material dispersion liquid C was used in an amount of 44.6 parts by mass, and the color material dispersion liquid C was used in an amount of 41.6 parts by mass, and the amount of the photosensitive adhesive agent I was changed to 33.1 parts by mass, and the PGMEA amount was changed to 25.2 mass. The photosensitive colored resin composition 22 was obtained in the same manner as in Example 16 except for the portion.

(Example 23, Comparative Example 12: Preparation of photosensitive colored resin composition 23, X12)

In the same manner as in Example 22 except that the photosensitive adhesives J and K of Comparative Example 3 were used in the same manner as in Example 22, the photosensitive colored resin composition 23 was obtained. X12.

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

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

(water infiltration evaluation)

The color filter was used as a film of a coloring layer having a thickness of 1.6 μm on a glass substrate ("NA35" manufactured by NH Techno Glass Co., Ltd.) and post-baked using a spin coater. After coating with a thickness, it was dried at 60 ° C for 3 minutes using a hot plate, and an ultraviolet ray of 60 mJ/cm ^{2 was} entirely irradiated with an ultrahigh pressure mercury lamp through a mask to form a colored layer on the glass substrate. Next, rotation development was carried out using 0.05 wt% of potassium hydroxide (KOH) as a developing solution, and the developer was liquid-contacted for 60 seconds, and then washed with pure water to carry out development treatment, and the washed substrate was rotated for 10 seconds to be centrifuged. Immediately after the water was removed, the contact angle of the pure water was measured as described below to evaluate the water bleeding.

The contact angle of pure water was measured by dropping 1.0 μL of pure water onto the surface of the colored layer immediately after the above-mentioned centrifugal removal of water, and the static contact angle after 30 seconds of dropping was measured by the θ/2 method. The measurement apparatus was measured using a contact angle meter DM 500 manufactured by Kyowa Interface Science Co., Ltd.

<Evaluation criteria>

A: The contact angle is 80 degrees or more.

B: The contact angle is 65 degrees or more and less than 80 degrees.

C: The contact angle is 50 degrees or more and less than 65 degrees.

D:: The contact angle is less than 50 degrees

If the water infiltration evaluation standard is A or B, it is available for practical use, but if the evaluation result is A, the effect is more superior.

<Development resistance evaluation>

The color filter was used as a photosensitive colored resin composition, and coated on a glass substrate (manufactured by NH Techno Glass, "NA35") having a thickness of 0.7 mm, using a spin coater. After heating and drying on a hot plate at 80 ° C for 3 minutes, ultraviolet rays of 30 mJ/cm ^{2 were} irradiated with an ultrahigh pressure mercury lamp. The film thickness at this time was measured as T1 (μm). Thereafter, shower development was carried out using a 0.05% by mass aqueous potassium hydroxide solution as an alkali developing solution. The film thickness after development was measured as T2 (μm). Calculate T2/T1×100 (%).

(Development resistance evaluation standard)

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. If the evaluation criterion is A, the effect is more excellent.

[Table 7 to Table 8 results integration]

From the results of Table 7, it was revealed that if at least two kinds of oxime-based initiators are contained, the line width becomes large and the sensitivity is improved. Further, as a result of Table 8, it was revealed that when at least two kinds of oxime-based initiators are contained, the development resistance is improved and the water permeation suppressing effect is increased.

Claims (10)

A photosensitive colored resin composition comprising a color material, a photopolymerizable compound, a starter, a latent antioxidant, and a solvent, wherein the color material contains one or more selected from the group consisting of a dye and a lake color material, and the above The latent antioxidant contains a compound represented by the following general formula (1); (In general formula (1), ring A is a five-membered or six-membered hydrocarbon ring or a heterocyclic ring; and R ^{1 is} independently a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, or a carbon which may have a substituent. An alkyl group having 1 to 40 atomic atoms, an aryl group having 6 to 20 carbon atoms which may have a substituent, an arylalkyl group having 7 to 20 carbon atoms which may have a substituent, or a substituent a heterocyclic group having 2 to 20 carbon atoms, or a plurality of R ¹ bonded to each other to form a benzene ring or a naphthalene ring; and R ² is an alkyl group having 1 to 20 carbon atoms and 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, a heterocyclic group having 2 to 20 carbon atoms, or a trialkylsulfonyl group; and having R ¹ and R ² The alkyl group may also have a carbon-carbon double bond, -O-, -S-, -C(=O)-, -OC(=O)-, -C(=O)-O-, -OC ( =O)-O-, -SC(=O)-, -C(=O)-S-, -SC(=O)-O-, -OC(=O)-S-, -C(=O )-NH-, -NH-C(=O)-, -NH-C(=O)-O-, -NR'-, -SS- or -SO ₂ -, R' is a hydrogen atom or a carbon atom The alkyl group of 1~8, the plural R ¹ and R ² respectively may be the same or different; X is a group of a valence, which is a direct bond, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, (-O) ₃ P=O, >C=O, >NR ³ , -OR ³ , -SR ³ , -N(R ³ )(R ⁴ ), or a carbon atom having a substituent of 1 to 120 An aliphatic hydrocarbon group, an aromatic cyclic hydrocarbon group having 6 to 35 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 35 carbon atoms which may have a substituent; and R ³ and R ⁴ are each independently hydrogen. An atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, an aromatic cyclic hydrocarbon group having 6 to 35 carbon atoms which may have a substituent, or a carbon atom which may have a substituent of 2 to 35 The heterocyclic group-containing group; the above aliphatic hydrocarbon group in X and the above aromatic-containing hydrocarbon group may have a carbon-carbon double bond, -O-, -S-, -C(=O)-, -OC(= O)-, -C(=O)-O-, -OC(=O)-O-, -SC(=O)-, -C(=O)-S-, -SC(=O)-O -, -OC(=O)-S-, -C(=O)-NH-, -NH-C(=O)-, -NH-C(=O)-O-, -NR'-, - SS- or -SO ₂ - or a nitrogen atom; a represents an integer from 1 to 10, b represents an integer from 1 to 4, and c represents an integer from 1 to 3). The photosensitive colored resin composition of claim 1, which further contains a hindered phenol-based antioxidant. The photosensitive colored resin composition of claim 1, further comprising a dispersant containing at least a polymer of the repeating unit (a) represented by the following general formula (2); (In the general formula (2), R ⁴¹ represents a hydrogen atom or a methyl group, L represents a divalent linking group, R ⁴² represents 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 divalent organic group, R ⁴³ and R ⁴⁴ respectively Independently represents a chain or cyclic hydrocarbon group which may be substituted, or R ⁴³ and R ⁴⁴ are bonded to each other to form a cyclic structure; R ⁴⁵ and R ⁴⁶ are each independently a hydrogen atom or a methyl group; and x represents an integer of 1 to 18; , y represents an integer from 1 to 5, and z represents an integer from 1 to 18. The photosensitive colored resin composition of claim 1, wherein the color material is selected from the group consisting of a color lake material of a skeleton, a lake color material having a triaryl methane skeleton, and One or more kinds of dyes of the skeleton. The photosensitive colored resin composition of claim 1, wherein the solvent comprises propylene glycol monomethyl ether acetate; and further comprises diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, and 3- One or more of methoxy-3-methyl-1-butanol, 3-methoxy-3-methyl-1-butyl acetate, and propylene glycol monomethyl ether acetate. The photosensitive colored resin composition of claim 1, wherein the above initiator comprises a lanthanide initiator. The photosensitive colored resin composition of claim 1, wherein the above initiator comprises at least two lanthanide initiators. A color filter comprising at least one of a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured product of the photosensitive colored resin composition according to any one of claims 1 to 7. A method of producing a color filter, comprising: a substrate, and a color filter for forming a color filter provided on the substrate, comprising: the photosensitive coloring resin according to any one of claims 1 to 7; The step of forming at least one of the colored layers by the composition. A display device having the color filter of claim 8.