WO2023026894A1

WO2023026894A1 - Photosensitive colored resin composition, color filter, and display device

Info

Publication number: WO2023026894A1
Application number: PCT/JP2022/030921
Authority: WO
Inventors: 力飛塚本; 渚井上
Original assignee: 株式会社Ｄｎｐファインケミカル
Priority date: 2021-08-23
Filing date: 2022-08-16
Publication date: 2023-03-02
Also published as: JPWO2023026894A1; TW202313742A; CN117795419A

Abstract

This photosensitive colored resin composition contains: a color material including a phthalocyanine compound represented by general formula (1); a sulfonic acid group-containing pigment derivative; an alkali soluble resin; a photopolymerizable compound; a photoinitiator; and a solvent. (The symbols in formula (1) are as defined in the description.)

Description

Photosensitive colored resin composition, color filter, and display device

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

In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays is increasing. The penetration rate of mobile displays (mobile phones, smart phones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding more and more. An organic light-emitting display device such as an organic EL display, which has high visibility due to self-luminescence, is also attracting attention as a next-generation image display device.
Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, when forming a color image in a liquid crystal display device, the light passing through the color filter is colored into the color of each pixel constituting the color filter as it is, and the light of these colors is combined to form a color image. As a light source in that case, in addition to a conventional cold cathode tube, an organic light emitting element emitting white light or an inorganic light emitting element emitting white light may be used. An organic light-emitting display device uses a color filter for color adjustment.

Here, the color filter is generally formed on a substrate, a colored layer formed on the substrate and composed of colored patterns of the three primary colors of red, green, and blue, and formed on the substrate so as to partition each colored pattern. and a light shielding part.
As a method for forming a colored layer in a color filter, for example, a photosensitive colored resin obtained by adding an alkali-soluble resin, a photopolymerizable compound and a photoinitiator to a coloring material dispersion liquid in which a coloring material is dispersed using a dispersing agent or the like. After the composition is applied to a glass substrate and dried, it is exposed to light using a photomask and developed to form a colored pattern, which is fixed by heating to form a colored layer. These steps are repeated for each color to form a color filter.

Pigments are generally used as colorants from the standpoint of heat resistance and light resistance, but pigments are no longer able to meet market demands, especially for high brightness. Therefore, dyes have been widely investigated. Dyes are excellent in enhancing the hue and brightness of a displayed image due to the color purity of the dye itself and the vividness of its hue. On the other hand, dyes generally have poor heat resistance and solvent resistance, and have low solubility in solvents, and thus have the problem of depositing foreign substances in the resulting colored layer, and are said to be difficult to put into practical use. As for the green colored layer, the use of a specific phthalocyanine-based dye as the dye has been studied (see Patent Documents 1 to 3, for example).

JP 2009-051896 A JP 2014-125460 A Japanese Patent No. 2020-42263

For example, when forming a pattern of a colored layer during the production of a color filter, after exposing the coating film of the photosensitive colored resin composition, the unexposed area is developed with a developer, but the developer waste contains the photosensitive colored resin composition. Ingredients included. Therefore, in a factory, usually, a flocculant is added to the developer waste liquid to flocculate the components of the photosensitive colored resin composition containing the colorant, and then the agglomerate is recovered and the pH-adjusted water is drained. Therefore, it is necessary that the filtrate after recovery of the aggregates does not contain a coloring material and is not colored.
However, when the coloring material contains a phthalocyanine dye as in the photosensitive colored resin compositions described in Patent Documents 1 to 3, the developer waste liquid is not sufficiently aggregated even if a coagulant is added, and coagulates. A problem arises that the filtrate after recovering the substance is colored with the color of the phthalocyanine dye.

The present invention has been made in view of the above circumstances, and provides a photosensitive colored resin composition from which the coloring material can be easily recovered during waste liquid treatment after development even when the coloring material contains a specific phthalocyanine dye. intended to Moreover, an object of this invention is to provide the color filter and display apparatus which were formed using the said photosensitive colored resin composition.

The photosensitive colored resin composition according to the present invention includes a coloring material containing a phthalocyanine compound represented by the following general formula (1), a sulfonic acid group-containing dye derivative, an alkali-soluble resin, a photopolymerizable compound, and light It contains an initiator and a solvent.

(In general formula (1), X ¹ to X ¹⁶ each independently represent a hydrogen atom, a halogen atom, or -Y-R ^D , and -Y- is -O-, -S-, or -NH- and R ^D represents a monovalent organic group, provided that one or more of X ¹ to X ¹⁶ represents —Y—R ^D. )

The color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured photosensitive colored resin composition according to the present invention. It is a thing.
The present invention also provides a display device having the color filter according to the present invention.

According to the present invention, it is possible to provide a photosensitive colored resin composition from which the coloring material can be easily recovered during waste liquid treatment after development, even when the coloring material contains a specific phthalocyanine dye. Moreover, according to this invention, the color filter and display apparatus which were formed using the said photosensitive colored resin composition can be provided.

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

Hereinafter, the photosensitive colored resin composition, color filter, and display device according to the present invention will be described in detail in order.
In the present invention, light includes electromagnetic waves having wavelengths in the visible and non-visible regions, and radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves with a wavelength of 5 μm or less and electron beams.
In the present invention, (meth)acryloyl represents acryloyl and methacryloyl, (meth)acryl represents acrylic and methacrylic, and (meth)acrylate represents acrylate and methacrylate.
Also, in this specification, the term "to" indicating a numerical range is used to include the numerical values before and after it as lower and upper limits.

I. Photosensitive colored resin composition The photosensitive colored resin composition according to the present invention includes a coloring material containing a phthalocyanine compound represented by the following general formula (1), a sulfonic acid group-containing dye derivative, an alkali-soluble resin, and light It contains a polymerizable compound, a photoinitiator and a solvent.

The photosensitive colored resin composition according to the present invention uses a coloring material containing a phthalocyanine compound represented by the general formula (1) in combination with a sulfonic acid group-containing dye derivative to obtain a specific phthalocyanine dye as a coloring material. Even if it contains, it is possible to provide a photosensitive colored resin composition that is easy to collect the coloring material during waste liquid treatment after development.
Coloring materials contained in conventional photosensitive colored resin compositions are usually pigments. Pigments are insoluble in solvents and exist in the form of particles. Compared with dyes, pigments have a larger particle diameter and are surface-charged in an aqueous solution. In the case of a pigment that exists in the form of particles in an aqueous solution and has a surface charge, it was easy to aggregate and recover the pigment with other resin components by adding a charged flocculant to the waste developer. .
On the other hand, solvent-soluble dyes such as the phthalocyanine compound represented by the general formula (1) tend to exist at the molecular level, and have little or no surface charge even in an aqueous solution. Therefore, in the case of a photosensitive colored resin composition containing a phthalocyanine compound represented by the general formula (1) as a coloring material, even if a flocculant is added to the developer waste liquid, the flocculant hardly acts on the phthalocyanine compound, and free phthalocyanine It is presumed that the compound is generated, and the filtrate after collecting the aggregate is colored with the color of the phthalocyanine compound.
On the other hand, when a sulfonic acid group-containing dye derivative is used in combination with the specific phthalocyanine compound, it is presumed that the sulfonic acid group-containing dye derivative interacts with the phthalocyanine compound to impart anionicity to the surface of the phthalocyanine compound. be. Therefore, in the case of a photosensitive colored resin composition containing a combination of a sulfonic acid group-containing dye derivative and the specific phthalocyanine compound, if a flocculant is added to the developer waste liquid, the flocculant easily acts on the phthalocyanine compound, and other resins It is presumed that it easily aggregates together with the components, etc., makes it difficult to generate free phthalocyanine compounds, and makes it easy to recover the coloring material.

It was also found that the photosensitive colored resin composition according to the present invention suppresses residue after development by using the above-mentioned specific phthalocyanine compound in combination with a sulfonic acid group-containing dye derivative. It is presumed that the phthalocyanine compound, which tends to become a residue during development, is easily washed away by the developer during development due to its interaction with the sulfonic acid group-containing dye derivative, and is easily dissolved even after forming a coating film.

The photosensitive colored resin composition according to the present invention contains a colorant, a sulfonic acid group-containing dye derivative, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and the present It may further contain other components as long as the effects of the invention are not impaired.
Each component of the colored resin composition of the present invention will be described in detail below.

[Color material]
In the present invention, the coloring material contains the phthalocyanine compound represented by the general formula (1).
In the phthalocyanine compound represented by the general formula (1), X ¹ to X ¹⁶ each independently represent a hydrogen atom, a halogen atom, or -Y-R ^D , and -Y- is -O-, -S represents - or -NH-, and ^RD represents a monovalent organic group. However, one or more of X ¹ to X ¹⁶ represent -Y-R ^D.

In X ¹ to X ¹⁶ , the halogen atom includes, for example, fluorine atom, chlorine atom, bromine atom, iodine atom and the like. When the above formula (1) has two or more halogen atoms, the plurality of halogen atoms may be the same or different. The halogen atoms in X ¹ to X ¹⁶ preferably contain at least fluorine atoms, more preferably all fluorine atoms, from the viewpoint of color.

The number of halogen atoms in X ¹ to X ¹⁶ is preferably 4 or more, more preferably 6 or more, still more preferably 7 or more, from the viewpoint of high brightness. The number of halogen atoms in X ¹ to X ¹⁶ is preferably 12 or less, more preferably 10 or less, and even more preferably 9 or less. The number of halogen atoms in X ¹ to X ¹⁶ may be eight.
Among them, 6 to 10, especially 7 to 9 of X ¹ to X ¹⁶ are preferably fluorine atoms in terms of color and maximum absorption wavelength range.

X ¹ to X ¹⁶ may be hydrogen atoms. The number of hydrogen atoms among X ¹ to X ¹⁶ may be appropriately selected by adjusting the color, and may be 0 to 8, 0 to 4, or 0 to 2. It's fine.

-Y- in -Y-R ^D represents -O-, -S-, or -NH-, and from the point of obtaining the desired transmission spectrum, -O- or -S- is preferable, -O - is more preferred.
When two or more -Y-R ^D are present in the above formula (1), the plurality of -Y-R ^D may be the same or different.

R ^D in -YR ^D is a monovalent organic group. Here, an organic group means a group containing carbon atoms. R ^D includes an optionally substituted hydrocarbon group or heterocyclic group. Hydrocarbon groups include linear, branched, or cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. The linear or branched aliphatic hydrocarbon group may be a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the cyclic aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 3 to 20 carbon atoms. It may be a cyclic hydrocarbon group, the aromatic hydrocarbon group may be an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the heterocyclic group may be a nitrogen-containing heterocycle, a sulfur-containing heterocycle, an oxygen containing heterocycles, etc., and may be either an aromatic ring or a non-aromatic ring.

Examples of linear or branched aliphatic hydrocarbon groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc. Examples of alicyclic hydrocarbon groups include cyclopentyl group. , a cyclohexyl group, and the like.
Moreover, examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and a biphenyl group.
Further, the heterocyclic group includes, for example, a furan ring, a thiophene ring, a pyrrole ring, a 2H-pyran ring, a 4H-thiopyran ring, a pyridine ring, a 1,3-oxazole ring, and an isoxazole ring having one free valence. groups such as ring, 1,3-thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, pyrazine ring, pyrimidine ring and pyridazine ring;

When the hydrocarbon group or heterocyclic group of R ^D has a substituent, the substituent includes a halogen atom, —OR ^d0 , —COR ^d0 , —COOR ^d0 (wherein R ^d0 is a hydrocarbon group or a heterocyclic ring group) and the like. —OR ^d0 , —COR ^d0 and —COOR ^d0 (wherein R ^d0 is a hydrocarbon group or a heterocyclic group) are specifically alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl and the like.

R ^D in -Y-R ^D is an aromatic hydrocarbon group that may have a substituent, among others, from the viewpoint of crystallinity control (precipitation suppression of foreign matter) during coating film curing (baking) and imparting solubility. and preferably a monovalent group represented by the following formula (2).

(In formula (2), -W- is a single bond or -O-, R ^d1 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, a substituent is an alicyclic hydrocarbon group having 3 to 12 carbon atoms which may be substituted, or ^an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, p is an integer of 1 to 3, and q is an integer of 0 to 2. However, when p is 2 or 3, a plurality of W and R ^d1 may be the same or different, and when m is 2, a plurality of R ^d2 may be the same or different.
-Y- represents -O-, -S-, or -NH-, and * indicates the bonding position with the phthalocyanine skeleton in formula (1). )

In the above formula (2), examples of substituents for the aliphatic hydrocarbon group, alicyclic hydrocarbon group and aromatic hydrocarbon group include alkoxy groups having 1 to 5 carbon atoms. R ^d1 is preferably an optionally substituted aliphatic hydrocarbon group having 1 to 10 carbon atoms, and an optionally substituted alkyl group having 1 to 10 carbon atoms. is particularly preferred. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 5 carbon atoms. When R ^d1 is a substituted alkyl group, it is preferably a group having an alkoxy group having 1 to 5 carbon atoms as a substituent.
As for p, 1 or 2 is preferable and 1 is more preferable. When p=1, -CO-WR ^d1 is preferably bonded to -Y- at the 3- or 4-position, more preferably at the 4-position. When p = 2, the two -CO-WR ^d1 are preferably bonded to the 3,5-position or 2,4-position to -Y-, and bonded to the 3,5-position It is more preferable to be
q is preferably 0 or 1, more preferably 0.
Preferred specific examples of the group represented by the above formula (2) include groups represented by the following formulas (2-1) to (2-10), but are not limited thereto. do not have.

(In formulas (2-1) to (2-10), -Y- represents -O-, -S-, or -NH-, * is a bond with the phthalocyanine skeleton in formula (1) position.)

The number of —Y—R ^D in X ¹ to X ¹⁶ is the point of obtaining the desired transmission spectrum (high brightness), and the crystallinity control (precipitation suppression of foreign matter) peculiar to the phthalocyanine compound during coating curing (baking). From the point of view, the number is preferably 4 or more, more preferably 6 or more, and even more preferably 7 or more. The number of —Y—R ^D in X ¹ to X ¹⁶ is preferably 12 or less, more preferably 10 or less, even more preferably 9 or less. The number of —Y—R ^D in X ¹ to X ¹⁶ may be eight.
X ¹ to X ¹⁶ are at least four of X ² , X ³ , X ⁶ , X ⁷ , X ¹⁰ , X ¹¹ , X ¹⁴ and X ¹⁵ in order to obtain a desired transmission spectrum (high luminance) is -Y-R ^D , X ² , X ³ , X ⁶ , X ⁷ , X ¹⁰ , X ¹¹ , X ¹⁴ and X ¹⁵ are all groups -Y-R ^D and the remainder ( X ¹ , X ⁴ , X ⁵ , X ⁸ , X ⁹ , X ¹² , X ¹³ and X ¹⁶ ) are particularly preferably halogen atoms.

Preferable specific examples of the phthalocyanine compound represented by the general formula (1) include compounds represented by the following formulas (1-1) to (1-6), but are not limited thereto. .

As a method for producing the halogenated phthalocyanine colorant, conventionally known production methods can be appropriately selected and used. For example, a method of cyclizing a phthalonitrile compound and a metal salt in a molten state or in an organic solvent can be preferably used. can be manufactured. The phthalonitrile compound used as a starting material can also be synthesized by appropriately selecting a conventionally known production method, and a commercially available product may be used.

In the present invention, the coloring material may further contain other coloring materials in addition to the phthalocyanine compound represented by the general formula (1).
The other coloring material is not particularly limited as long as it is capable of developing a desired color, and various organic pigments, inorganic pigments, dyes, salt-forming compounds of dyes, etc. may be used alone or in combination of two or more. can be used. Among them, organic pigments are preferably used because of their high color developability and high heat resistance. Examples of organic pigments include compounds classified as pigments in the Color Index (C.I.; published by The Society of Dyers and Colorists). .) numbered ones can be mentioned.

As a yellow coloring material, for example, C.I. I.

Pigment Yellow

1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175, 185, 231, and yellow pigments such as derivative pigments thereof, coumarin dyes, cyanine dyes, merocyanine dyes, azo dyes, methine dyes, azomethine dyes, quinophthalone dyes, etc. and yellow dyes.

As the yellow colorant, a quinophthalone-based colorant is preferable because of its excellent heat resistance and light resistance and high transmittance. In addition, the quinophthalone-based colorant is also preferable in that it has a hue suitable for use in color filters.
A quinophthalone-based colorant refers to a colorant synthesized by condensation of a quinoline derivative such as quinaldine and a phthalic anhydride derivative or a naphthalic anhydride derivative, and may be any of pigments, dyes, and salt-forming compounds of dyes. good.
Among quinophthalone colorants, quinophthalone pigments include, for example, C.I. I. Pigment Yellow 138 and the like.
Examples of quinophthalone dyes include C.I. I. Disperse Yellow 54, 64, 67, 134, 149, 160, C.I. I. Solvent Yellow 114, 157 and the like.

Other green colorants include C.I. I.

Pigment Green

1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, etc. green pigments, squarylium, triarylmethane, anthraquinone, coumarin, cyanine, or green dyes such as azo dyes.
From the viewpoint of easiness of adjusting chromaticity, the other green coloring material different from the halogenated phthalocyanine compound is preferably a phthalocyanine green pigment.
Examples of the phthalocyanine green pigment include C.I. I. Pigment Green 7, 36, 58, 59, 62, 63 and the like. From the viewpoint of easiness in adjusting luminance, C.I. I. Pigment Green 7, 58, 59, 62 or 63 is preferred, C.I. I. Pigment Green 58, 59, 62 or 63 is preferred, C.I. I. Pigment Green 59 is more preferred.

Further, as an orange colorant, C.I. I.

Pigment Orange

1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73;
As a blue colorant, C.I. I. Pigment Blue 15, 15:3, 15:4, 15:6, 60;
As a purple colorant, C.I. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and the like.

Since the phthalocyanine compound represented by the general formula (1) usually exhibits a green color, the other colorant is preferably one or more selected from the group consisting of yellow colorants and other green colorants. be done.

In the photosensitive colored resin composition of the present invention, the content ratio of the phthalocyanine compound represented by the general formula (1) with respect to the entire colorant may be appropriately adjusted according to the desired chromaticity, and is not particularly limited. , may be 100% by mass with respect to the entire coloring material containing the phthalocyanine compound represented by the general formula (1). In the photosensitive colored resin composition of the present invention, if it contains another colorant, from the viewpoint of desired chromaticity adjustment, for the entire colorant containing the phthalocyanine compound represented by the general formula (1) It may contain 30 to 95% by mass, 40 to 85% by mass, or 50 to 80% by mass of the phthalocyanine compound represented by the general formula (1).

When the photosensitive colored resin composition of the present invention contains a yellow colorant, the yellow colorant is appropriately selected and used singly or in combination of two or more.
In the photosensitive colored resin composition of the present invention, the content ratio of the yellow colorant to the halogenated phthalocyanine colorant of the present invention may be appropriately adjusted according to the desired chromaticity, and is not particularly limited. Among them, from the viewpoint of desired chromaticity adjustment, the phthalocyanine compound represented by the general formula (1) may contain 5 to 233 parts by mass of a yellow colorant per 100 parts by mass, and 18 to 150 It may be contained in parts by mass, and may be contained in 25 to 100 parts by mass.

In the photosensitive colored resin composition of the present invention, if it contains a green colorant different from the phthalocyanine compound represented by the general formula (1), a green color different from the phthalocyanine compound represented by the general formula (1) Colorants are appropriately selected and used singly or in combination of two or more.
In the photosensitive colored resin composition of the present invention, the content ratio of the green colorant different from the phthalocyanine compound represented by the general formula (1) with respect to the phthalocyanine compound represented by the general formula (1) is the desired There is no particular limitation as long as the chromaticity is appropriately adjusted. Among them, from the viewpoint of desired chromaticity adjustment and brightness adjustment, a green color different from the phthalocyanine compound represented by the general formula (1) is added to 100 parts by mass of the phthalocyanine compound represented by the general formula (1). The coloring material may be contained in 5 to 233 parts by mass, 18 to 150 parts by mass, or 25 to 100 parts by mass.

Further, in the photosensitive colored resin composition of the present invention, when further containing a green colorant other than the phthalocyanine compound represented by the general formula (1), represented by the general formula (1) for the entire colorant The content of the green colorant containing the phthalocyanine compound is not particularly limited as long as it is appropriately adjusted according to the desired chromaticity. Among them, from the viewpoint of desired chromaticity adjustment and brightness adjustment, it is preferable to contain 30 to 95% by mass of a green colorant containing a phthalocyanine compound represented by the general formula (1) with respect to the entire colorant, It is more preferable to contain 50 to 80% by mass.
Moreover, the content ratio of the yellow colorant to the green colorant containing the halogenated phthalocyanine colorant of the present invention may be appropriately adjusted according to the desired chromaticity, and is not particularly limited. Among them, from the viewpoint of desired chromaticity adjustment and brightness adjustment, 5 to 70 parts by mass of a yellow colorant is contained with respect to 100 parts by mass of a green colorant containing a phthalocyanine compound represented by the general formula (1). more preferably 20 to 50 parts by mass.

Further, in the photosensitive colored resin composition of the present invention, the colorant may further contain a colorant other than the green colorant and the yellow colorant as long as the effects of the present invention are not impaired. However, the total content of the green colorant containing the phthalocyanine compound represented by the general formula (1) and the yellow colorant may be 70 to 100% by mass with respect to the entire colorant, especially 80 It may be up to 100% by mass.

The content of the coloring material in the photosensitive colored resin composition according to the present invention is not particularly limited. The total content of the colorant, from the viewpoint of dispersibility and dispersion stability, relative to the total solid content of the photosensitive colored resin composition, for example preferably 3% by mass to 65% by mass, more preferably 4% by mass to It is within the range of 60% by mass. If it is at least the above lower limit, the colored layer will have a sufficient color density when the photosensitive colored resin composition is applied to a predetermined film thickness (usually 1.0 μm to 5.0 μm). Moreover, if it is below the said upper limit, while being excellent in storage stability, the coloring layer which has sufficient hardness and adhesiveness with a board|substrate can be obtained. Especially when forming a colored layer having a high colorant concentration, the total content of the colorant is preferably 15% by mass to 65% by mass, more preferably 15% by mass to 65% by mass, based on the total solid content of the photosensitive colored resin composition. It is in the range of 25% by mass to 60% by mass.
In the present invention, the solid content refers to all substances other than the solvent, which will be described later, and includes monomers and the like dissolved in the solvent.

[Sulfonic Acid Group-Containing Dye Derivative]
A dye derivative is a compound that has a role of imparting a functional group to a dye skeleton and adding various functions to the dye. In the present invention, a dye derivative having a sulfonic acid group (--SO ₃ H) is used as the dye derivative. The sulfonic acid group-containing dye derivative preferably has a dye skeleton of a coloring material such as various pigments used in the colored layer of a color filter.

Examples of the dye skeleton of the dye derivative used in the present invention include a phthalocyanine skeleton, a quinophthalone skeleton, a triarylmethane skeleton, a xanthene skeleton, a coumarin skeleton, a naphthol azo skeleton, a diketopyrrolopyrrole skeleton, and a quinacridone skeleton. As the dye skeleton of the dye derivative used in the present invention, a dye skeleton having an aromatic ring is preferable because it is likely to interact with the compound represented by the general formula (1) through π-π stacking.

In the dye derivative having a sulfonic acid group (--SO ₃ H), the sulfonic acid group (--SO ₃ H) may be directly bonded to the dye skeleton, for example --SO ₂ NH--(CH ₂ ) _m -- A sulfonic acid group may be bonded to the dye skeleton via a linking group such as SO ₃ H (here, m is an integer of 1 to 6).
The sulfonic acid group (--SO ₃ H) may be directly bonded to the dye skeleton from the viewpoint of easy action on the target component.

In addition, in the dye derivative having a sulfonic acid group (—SO ₃ H), the number of sulfonic acid group substitutions per molecule may be 1 to 4, preferably 1 to 2, and particularly 1. is preferable because it is difficult to lower the luminance.

A coloring material containing a halogenated phthalocyanine coloring material represented by the general formula (1) is used to form a green colored layer. , a dye derivative having a dye skeleton of a blue colorant, or a dye derivative having a dye skeleton of a yellow colorant.

The dye skeleton of the dye derivative used in the present invention is, among others, a phthalocyanine skeleton or a A quinophthalone skeleton is more preferred.

Examples of dyes having a phthalocyanine skeleton include metal-free phthalocyanine dyes, copper phthalocyanine dyes, nickel phthalocyanine dyes, aluminum phthalocyanine dyes, cobalt phthalocyanine dyes, and zinc phthalocyanine dyes. As a dye having a phthalocyanine skeleton, the phthalocyanine does not have to have a substituent, but the phthalocyanine may have a known substituent such as an alkyl group or a halogen atom.
As a dye having a phthalocyanine skeleton, a phthalocyanine dye or a copper phthalocyanine dye is preferable, and a copper phthalocyanine dye may be used, because the raw material is easily available.

On the other hand, examples of dyes having a quinophthalone skeleton include C.I. I. Pigment Yellow 138, such as quinophthalone pigments such as C.I. I. Disperse Yellow 54, 64, 67, 134, 149, 160, C.I. I. Quinophthalone dyes such as Solvent Yellow 114 and 157 are included.
As a dye having a quinophthalone skeleton, C.I. I. Pigment Yellow 138 or Pigment Yellow 231 is preferred, and C.I. I. Pigment Yellow 138 may be used.

As a method for introducing a sulfonic acid group into a dye, it can be prepared by using known sulfonation. The sulfonic acid group of the dye can be introduced, for example, by introducing a dye such as copper phthalocyanine into concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, or a mixture of these to carry out a sulfonation reaction. After the sulfonation reaction, the reaction solution is diluted with a large amount of water, and the resulting suspension is filtered, washed with an aqueous washing solution, and dried.

When sulfonation is performed by the above method, the amount of sulfonic acid groups introduced per molecule can be controlled by adjusting the reaction solution concentration, reaction temperature, reaction time, and the like.

The sulfonic acid group-containing dye derivative can be used singly or in combination of two or more. For example, two or more sulfonic acid group-containing dye derivatives having different substitution positions or numbers of sulfonic acid groups may be used in combination.
Alternatively, for example, a sulfonic acid group-containing copper phthalocyanine derivative and a sulfonic acid group-containing C.I. I. Pigment Yellow 138 derivative may be used as a mixture of two or more dye derivatives having a dye skeleton.

In the present invention, the sulfonic acid group-containing dye derivative is preferably contained in an amount of 1% by mass to 15% by mass, and 2% by mass to 10% by mass, based on the total content of the compounds represented by the general formula (1). It is more preferably contained in an amount of 3% by mass to 9% by mass. By using such a content, even if the coloring material contains a specific phthalocyanine dye, the coloring material can be easily recovered during waste liquid treatment after development without significantly changing the hue.

In the photosensitive colored resin composition according to the present invention, the total content of the sulfonic acid group-containing dye derivative is, for example, 0.03% by mass to 9.75% by mass with respect to the total solid content of the photosensitive colored resin composition. may be 0.12 wt% to 9.0 wt%, preferably 1.0 wt% to 5.0 wt%, more preferably 2.5 wt% to 3.5 wt% Within range. When the content is at least the above lower limit, even when the coloring material contains a specific phthalocyanine dye, the coloring material can be easily recovered during waste liquid treatment after development. Further, when the content is equal to or less than the above upper limit value, the optical properties (brightness) and dye solubility are hardly affected.

[Alkali-soluble resin]
The alkali-soluble resin used in the present invention has an acidic group, and can be appropriately selected and used from those that act as a binder resin and are soluble in an alkali developer used for pattern formation. can.
In the present invention, the alkali-soluble resin can be defined as having an acid value of 40 mgKOH/g or more.

A carboxy group is mentioned as an acidic group which alkali-soluble resin has, for example. Examples of the alkali-soluble resin having a carboxy group include a carboxy group-containing copolymer having a carboxy group and an epoxy (meth)acrylate resin having a carboxy group. Examples of the carboxy group-containing copolymer include (meth) acrylic copolymers having a carboxy group and styrene-(meth) acrylic copolymers having a carboxy group. .
In addition, these (meth)acrylic copolymers, styrene-(meth)acrylic copolymers having a carboxyl group, (meth)acrylic copolymers such as (meth)acrylic copolymers, and epoxy (meth)acrylate resins are a mixture of two or more. can be used as

A (meth)acrylic copolymer such as a (meth)acrylic copolymer having a carboxy group and a styrene-(meth)acrylic copolymer having a carboxy group is, for example, a carboxy group-containing ethylenically unsaturated monomer, and, if necessary, other copolymerizable monomers are (co)polymerized by a known method.

Carboxy group-containing ethylenically unsaturated monomers include, for example, (meth)acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, (meth)acrylic acid dimer etc. In addition, addition reaction products of monomers having a hydroxy group such as 2-hydroxyethyl (meth)acrylate and cyclic anhydrides such as maleic anhydride, phthalic anhydride and cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone mono (Meth)acrylates and the like can also be used. Anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride may also be used as precursors of carboxyl groups. Among them, (meth)acrylic acid is particularly preferable from the viewpoint of copolymerizability, cost, solubility, glass transition temperature, and the like.

The alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of excellent adhesion to the substrate. By having a hydrocarbon ring, which is a bulky group, in the alkali-soluble resin, shrinkage during curing is suppressed, peeling from the substrate is alleviated, and substrate adhesion is improved. Further, by using an alkali-soluble resin having a hydrocarbon ring which is a bulky group, the solvent resistance of the resulting colored layer is improved, and in particular swelling of the colored layer is suppressed, which is also preferable.
Examples of such hydrocarbon rings include cyclic aliphatic hydrocarbon rings which may have substituents, aromatic rings which may have substituents, and combinations thereof, and hydrocarbon rings may have a substituent such as a carbonyl group, a carboxyl group, an oxycarbonyl group or an amide group.

Specific examples of hydrocarbon rings include aliphatic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane), and adamantane. Ring: Aromatic hydrocarbon ring such as benzene, naphthalene, anthracene, phenanthrene, fluorene, etc.; Chain polycyclic ring such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, stilbene, cardo structure (9,9-diarylfluorene), etc. is mentioned.

Among them, when an aliphatic hydrocarbon ring is contained as the hydrocarbon ring, the heat resistance and adhesion of the colored layer are improved, and the brightness of the obtained colored layer is also preferably improved.
In addition, when a structure (cardo structure) in which two benzene rings are bonded to a fluorene skeleton is included, the curability of the colored layer is improved, the solvent resistance is improved, and swelling against NMP is particularly suppressed. preferable.
The hydrocarbon ring may be contained as a monovalent group or may be contained as a divalent or higher group.

In the alkali-soluble resin used in the present invention, using a (meth)acrylic copolymer having a structural unit having a hydrocarbon ring, in addition to a structural unit having a carboxy group, adjusts the amount of each structural unit. It is preferable from the viewpoint that it is easy to improve the function of the structural unit by increasing the amount of the structural unit having a hydrocarbon ring.
In the (meth)acrylic copolymer having a structural unit having a carboxy group and the above hydrocarbon ring, an ethylenically unsaturated monomer having a hydrocarbon ring is used as the above-mentioned "other copolymerizable monomer". can be prepared by

Ethylenically unsaturated monomers having a hydrocarbon ring used in alkali-soluble resins having a hydrocarbon ring include, for example, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, isobornyl (meth)acrylate, ) acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, styrene, a monomer having a cardo structure and an ethylenically unsaturated group, and the like can be preferably used. Among them, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate, styrene, the cardo structure and the ethylenically unsaturated group and are preferred.

The alkali-soluble resin used in the present invention also preferably has an ethylenically unsaturated bond in its side chain. In the case of having an ethylenically unsaturated bond, the alkali-soluble resins may form cross-linked bonds with each other, or between the alkali-soluble resin and the polyfunctional monomer in the step of curing the resin composition during the production of the color filter. The film strength of the cured film is further improved, the development resistance is improved, and the heat shrinkage of the cured film is suppressed, resulting in excellent adhesion to the substrate.
The ethylenically unsaturated group means a radically polymerizable group containing a carbon-carbon double bond, and examples thereof include (meth)acryloyl group, vinyl group and allyl group.
A method for introducing an ethylenically unsaturated bond into an alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a method of adding a compound having both an epoxy group and an ethylenically unsaturated bond in the molecule, such as glycidyl (meth)acrylate, to the carboxyl group of the alkali-soluble resin to introduce an ethylenically unsaturated bond into the side chain. Alternatively, a structural unit having a hydroxy group is introduced into the copolymer, a compound having an isocyanate group and an ethylenically unsaturated bond is added in the molecule, and an ethylenically unsaturated bond is introduced into the side chain. methods and the like.

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

The alkali-soluble resin used in the present invention is a (meth)acrylic copolymer and a styrene-(meth)acrylic copolymer having a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring ( It is preferably a meth)acrylic resin, and a (meth)acrylic copolymer and styrene having a structural unit having a carboxyl group, a structural unit having a hydrocarbon ring, and a structural unit having an ethylenically unsaturated bond - (Meth)acrylic resins such as (meth)acrylic copolymers are more preferred.

The desired performance of the alkali-soluble resin used in the present invention can be obtained by appropriately adjusting the charged amount of the monomer that induces each structural unit.

The copolymerization ratio of the carboxy group-containing ethylenically unsaturated monomer in the carboxy group-containing copolymer is usually 5% to 50% by mass, preferably 10% to 40% by mass. In this case, when the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is 5% by mass or more, the decrease in the solubility of the obtained coating film in an alkaline developer can be suppressed, and pattern formation is facilitated. Further, when the copolymerization ratio is 50% by mass or less, chipping of the pattern and film roughness on the pattern surface are less likely to occur during development with an alkaline developer. In addition, the said copolymerization ratio is a value calculated from the preparation amount of each monomer.

In addition, (meth)acrylic resins such as (meth)acrylic copolymers and styrene-(meth)acrylic copolymers having structural units having ethylenically unsaturated bonds, which are more preferably used as alkali-soluble resins , The charged amount of the monomer having both an epoxy group and an ethylenically unsaturated bond is preferably 10% by mass to 95% by mass with respect to 100% by mass of the charged amount of the carboxyl group-containing ethylenically unsaturated monomer. More preferably, it is in the range of 90% by mass to 90% by mass.

A preferred weight average molecular weight (Mw) of the carboxy group-containing copolymer is in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. When the weight average molecular weight of the carboxyl group-containing copolymer is 1,000 or more, sufficient curability of the coating film can be obtained, and when it is 50,000 or less, pattern formation becomes easy during development with an alkaline developer.
Incidentally, the weight average molecular weight (Mw) in the present invention is obtained as a standard polystyrene conversion value by gel permeation chromatography (GPC).

Specific examples of the (meth)acrylic copolymer having a carboxy group include those described in JP-A-2013-029832.

The epoxy (meth)acrylate resin having a carboxy group is not particularly limited. ) acrylate compounds are suitable. Epoxy compounds, unsaturated group-containing monocarboxylic acids, and acid anhydrides can be appropriately selected from known ones and used.
Among the epoxy (meth)acrylate resins having a carboxyl group, those containing the cardo structure in the molecule improve the effect of suppressing display defects, improve the curability of the colored layer, and reduce the residue of the colored layer. It is preferable from the point that the film ratio becomes high.

The alkali-soluble resin more preferably has an acid value of 40 mgKOH/g or more from the viewpoint of developability (solubility) in an alkaline aqueous solution used as a developer. The carboxyl group-containing copolymer has an acid value of 50 mgKOH/g or more and 300 mgKOH/g or less in terms of developability (solubility) in an alkaline aqueous solution used in the developer and adhesion to a substrate. more preferably 60 mgKOH/g or more and 280 mgKOH/g or less, and even more preferably 70 mgKOH/g or more and 250 mgKOH/g or less.
Incidentally, in the present invention, the acid value can be measured according to JIS K 0070.

The ethylenically unsaturated bond equivalent when the side chain of the alkali-soluble resin has an ethylenically unsaturated group is 100 or more and 2000 or less from the viewpoint that the film strength of the cured film is improved and the deposition of the coloring material can be further suppressed. A range is preferable, and a range of 140 or more and 1500 or less is particularly preferable. If the ethylenically unsaturated bond equivalent is 2000 or less, the development resistance and adhesion are excellent. Also, if it is 100 or more, the ratio of other structural units such as structural units having a carboxy group and structural units having a hydrocarbon ring can be relatively increased, so that excellent developability and heat resistance can be obtained. there is Here, the ethylenically unsaturated bond equivalent is the weight average molecular weight per mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (1).

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

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

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

[Photopolymerizable compound]
The photopolymerizable compound used in the photosensitive colored resin composition of the present invention refers to a compound having a photopolymerizable group in its molecule. The photopolymerizable group is not particularly limited as long as it can be polymerized by a photoinitiator, and includes an ethylenically unsaturated bond, such as a vinyl group, an allyl group, an acryloyl group or a methacryloyl group. be done. As the photopolymerizable group, an acryloyl group or a methacryloyl group is preferably used from the viewpoint of ultraviolet curability.
As the photopolymerizable compound, from the viewpoint of curability, it is preferable to contain a compound having two or more photopolymerizable groups in one molecule, and a compound having three or more photopolymerizable groups in one molecule is contained. is more preferable.

The photopolymerizable compound is not particularly limited as long as it can be polymerized by the photoinitiator described later, and usually a compound having two or more ethylenically unsaturated bonds is used, particularly an acryloyl group or a methacryloyl group. It is preferably a polyfunctional (meth)acrylate having two or more.
As such a polyfunctional (meth)acrylate, it may be appropriately selected and used from conventionally known ones. Specific examples include those described in JP-A-2013-029832.

These photopolymerizable compounds may be used singly or in combination of two or more. Further, when excellent photocurability (high sensitivity) is required for the photosensitive colored resin composition of the present invention, the photopolymerizable compound has three polymerizable ethylenically unsaturated bonds (trifunctional). Those having the above are preferable, and poly (meth) acrylates of trihydric or higher polyhydric alcohols and dicarboxylic acid-modified products thereof are preferable. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth)acrylate, succinic acid-modified pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol penta(meth) ) succinic acid-modified acrylate, dipentaerythritol hexa(meth)acrylate and the like are preferred.

The content of the photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited, but relative to the total solid content of the photosensitive colored resin composition, for example preferably 5% by mass to 60% by mass, More preferably, it is within the range of 10% by mass to 40% by mass. If the content of the photopolymerizable compound is at least the above lower limit, photocuring will proceed sufficiently, and the exposed portion will be able to suppress elution during development. Adequate alkali developability.

[Photoinitiator]
Examples of photoinitiators include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, α-aminoketones, biimidazoles, N,N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, thioxanthone, and the like. be able to. Specific examples of photoinitiators include aromatic ketones such as benzophenone, 4,4′-bisdiethylaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, benzoin ethers such as benzoin methyl ether, and ethylbenzoin. benzoin, biimidazoles such as 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole and the like halomethyloxadiazole compounds, halomethyl-S-triazine compounds such as 2-(4-butoxy-naphth-1-yl)-4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1 , 2-diphenylethan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl )-butanone-,, 1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide, benzyl methyl ketal, dimethylaminobenzoate, p-dimethylaminobenzoate isoamyl acid, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 4-benzoyl-methyldiphenylsulfide, 1-hydroxy- Cyclohexyl-phenyl ketone, 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl ]-1-[4-(4-morpholinyl)phenyl]-1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-methyl-1- [4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone, 1-(9,9-dibutyl-9H-fluoren-2-yl)-2-methyl-2-(4-morpholinyl) -1-propanone and the like.
Among them, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1- Butanone, 4,4'-bis(diethylamino)benzophenone and diethylthioxanthone are preferably used. Furthermore, combining an α-aminoacetophenone initiator such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one with a thioxanthone initiator such as diethylthioxanthone can improve sensitivity. It is preferable from the viewpoint of adjustment, suppressing water staining, and improving development resistance.
When using an α-aminoacetophenone-based initiator and a thioxanthone-based initiator, the total content thereof is, for example, preferably 5% by mass to 15% by mass with respect to the total solid content of the photosensitive colored resin composition. If the content is equal to or less than the upper limit, the amount of sublimate during the manufacturing process is reduced, which is preferable. When it is at least the lower limit value, development resistance such as water staining is improved.

In the present invention, the photoinitiator preferably contains an oxime ester photoinitiator, among others, from the viewpoint of being able to improve the sensitivity. In addition, by using an oxime ester-based photoinitiator, in-plane variations in line width can be easily suppressed when a fine line pattern is formed. Furthermore, the use of an oxime ester-based photoinitiator tends to improve the residual film rate and enhance the effect of suppressing the occurrence of water stains.
As the oxime ester photoinitiator, from the viewpoint of reducing contamination of the photosensitive colored resin composition and contamination of the device due to decomposition products, among them, those having an aromatic ring are preferable, and those having a condensed ring containing an aromatic ring is more preferred, and it is even more preferred to have a condensed ring containing a benzene ring and a hetero ring.
Oxime ester photoinitiators include 1,2-octadione-1-[4-(phenylthio)-, 2-(o-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazol-3-yl]-,1-(o-acetyloxime), JP-A-2000-80068, JP-A-2001-233842, JP-T-2010-527339, JP-T-2010-527338, It can be appropriately selected from oxime ester photoinitiators described in JP-A-2013-041153 and the like. Commercially available products include Irgacure OXE-01 having a diphenyl sulfide skeleton, Adeka Arcules NCI-930 and TR-PBG-3057, Irgacure OXE-02 having a carbazole skeleton, Adeka Arcules NCI-831, TR-PBG-304 and TR. -PBG-345, TR-PBG-365 having a fluorene skeleton, etc. may be used (Irgacure series manufactured by BASF, Adeka Arcles series manufactured by ADEKA, and TR series manufactured by Changzhou Tenryu Denshi New Materials Co., Ltd.). In particular, it is preferable to use an oxime ester photoinitiator having a diphenyl sulfide skeleton or a fluorene skeleton from the viewpoint of brightness. Moreover, it is preferable to use an oxime ester photoinitiator having a carbazole skeleton from the viewpoint of high sensitivity. From the viewpoint of sensitivity and brightness, it is preferable to use an oxime ester photoinitiator having a diphenyl sulfide skeleton and an oxime ester photoinitiator having a fluorene skeleton in combination. From the viewpoint of sensitivity and brightness, it is preferable to use a combination of an oxime ester photoinitiator having a diphenyl sulfide skeleton and an oxime ester photoinitiator having a carbazole skeleton.

From the viewpoint of suppressing water staining and improving sensitivity, the oxime ester photoinitiator may be used in combination with a photoinitiator having a tertiary amine structure. A photoinitiator having a tertiary amine structure has a tertiary amine structure, which is an oxygen quencher, in the molecule, so that radicals generated from the initiator are less likely to be deactivated by oxygen, and sensitivity can be improved. be. Commercially available photoinitiators having a tertiary amine structure include, for example, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (eg Irgacure 907, manufactured by BASF), 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone (eg Irgacure 369, manufactured by BASF), 4,4′-bis(diethylamino)benzophenone (eg Hycure ABP, Kawaguchi Pharmaceutical Co., Ltd.) and the like.
In addition, from the viewpoint of adjusting sensitivity, suppressing water staining, and improving development resistance, the oxime ester photoinitiator may be combined with a thioxanthone initiator. Two or more kinds of oxime ester photoinitiators may be combined with a thioxanthone photoinitiator from the viewpoints of being easy to use, having a high effect of suppressing the occurrence of water stains, and improving development resistance.

The content of the photoinitiator in the photosensitive colored resin composition is, for example, preferably 0.1% by mass to 15% by mass, more preferably 1% by mass to the total solid content of the photosensitive colored resin composition. It is within the range of 10% by mass. When the content of the photoinitiator is at least the above lower limit, curing proceeds sufficiently, and when the content of the initiator is at most the above upper limit, side reactions can be suppressed and stability over time can be maintained. can.

[solvent]
The solvent used in the present invention is not particularly limited as long as it does not react with each component in the photosensitive colored resin composition and is capable of dissolving or dispersing them. A solvent can be used individually or in combination of 2 or more types.
Specific examples of solvents include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ester solvents such as ethyl lactate and cyclohexanol acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1 -glycol ether acetate solvents such as butyl acetate, 3-methoxybutyl acetate and ethoxyethyl acetate; carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate and butyl carbitol acetate (BCA); propylene glycol diacetate , 1,3-butylene glycol diacetate and other diacetates; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, dipropylene glycol Glycol ether solvents such as dimethyl ether; Aprotic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; Lactone solvents such as γ-butyrolactone; Cyclic ether solvents such as tetrahydrofuran unsaturated hydrocarbon solvents such as benzene, toluene, xylene and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane and N-octane; organic solvents such as aromatic hydrocarbons such as toluene and xylene are mentioned. Among these solvents, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents are preferably used in terms of solubility of other components. Among them, the solvent used in the present invention includes propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and one or more selected from the group consisting of 3-methoxybutyl acetate, from the viewpoint of solubility of other components and applicability.

In the present invention, since the acid group-containing dye derivative is contained, the inclusion of a solvent containing an alcoholic hydroxyl group as the solvent improves the solubility of the entire composition and suppresses the deposition of foreign substances in the coating film. It is preferable from the viewpoint of improving the contrast.
As the solvent containing an alcoholic hydroxyl group, alkylene glycol monoalkyl ether is preferable, and for example, one or more selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, and propylene glycol monomethyl ether. is preferred, and propylene glycol monomethyl ether is more preferred.
Among them, it is preferable to contain at least one of a glycol ether acetate solvent, a carbitol acetate solvent, and an ester solvent, and at least one solvent containing an alcoholic hydroxyl group, and at least one glycol ether acetate solvent. and at least one solvent containing an alcoholic hydroxyl group.
The content of the solvent containing an alcoholic hydroxyl group is preferably 15% by mass to 35% by mass, more preferably in the range of more than 20% by mass to 30% by mass or less, based on the total amount of the solvent.

In the photosensitive colored resin composition according to the present invention, the content of the solvent may be appropriately set within a range in which the colored layer can be formed with high accuracy. The content of the solvent is usually in the range of preferably 55% by mass to 95% by mass, more preferably 65% by mass to 88% by mass, based on the total amount of the photosensitive colored resin composition containing the solvent. When the content of the solvent is within the above range, excellent applicability can be obtained.

[Optional additional ingredients]
The photosensitive colored resin composition may contain various additives as necessary. Additives include, for example, dispersants, sensitizers, antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, UV absorbers, adhesion Accelerators and the like are included.
Specific examples of surfactants and plasticizers include those described in JP-A-2013-029832.

<Dispersant>
In the photosensitive colored resin composition of the present invention, when the colorant is dispersed, a dispersant may be further included from the viewpoint of colorant dispersibility and colorant dispersion stability.
In the present invention, the dispersant can be appropriately selected and used from conventionally known dispersants. As the dispersant, for example, cationic, anionic, nonionic, amphoteric, silicone, or fluorine surfactants can be used. Among surfactants, polymer dispersants are preferred because they can be uniformly and finely dispersed.

Examples of polymer dispersants include (co)polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid; (Partial) ammonium salts and (partial) alkylamine salts; (co)polymers of hydroxy group-containing unsaturated carboxylic acid esters such as hydroxy group-containing polyacrylic acid esters and modified products thereof; polyurethanes; unsaturated polyamides; Polysiloxanes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (amides obtained by reacting poly(lower alkyleneimine) with free carboxy group-containing polyesters and their bases); polyallylamine derivatives (polyallylamine and free A reaction product obtained by reacting one or more compounds selected from three types of compounds: a polyester, a polyamide, or a co-condensation product of an ester and an amide (polyesteramide) having a carboxy group). .

In the present invention, since the sulfonic acid group-containing dye derivative is included, the polymer dispersant may be, for example, a polymer dispersant containing a nitrogen atom in the main chain or side chain and having an amine value, Above all, it may be a polymeric dispersant comprising a polymer containing a repeating unit having a tertiary amine. In the present invention, since the sulfonic acid group-containing dye derivative is included, when the main chain or side chain includes a nitrogen atom and a polymer dispersant having an amine value is included, when the flocculant is added to the flocculation waste liquid Furthermore, the phthalocyanine compound tends to aggregate, and the coloring material can be easily recovered from the waste developer.
Polymer dispersants containing nitrogen atoms in the main chain or side chains and having an amine value are described, for example, in JP-A-2016-224447, because the main chain skeleton is difficult to thermally decompose and the heat resistance is high. and a block having a structural unit represented by the following general formula (I) as described in WO 2016/104493. A dispersant that is at least one of a copolymer and a salt-type block copolymer may be used.

(In general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent linking group, R ² and R ³ are each independently a hydrogen atom, or a hydrocarbon optionally containing a hetero atom. group, and R ² and R ³ may combine with each other to form a ring structure.)

In general formula (I), A is a divalent linking group. As the divalent linking group, for example, a linear, branched or cyclic alkylene group, a linear, branched or cyclic alkylene group having a hydroxyl group, an arylene group, -CONH- group, -COO- group, -NHCOO- groups, ether groups (--O--groups), thioether groups (--S--groups), and combinations thereof. In the present invention, the bonding direction of the divalent linking group is arbitrary. That is, when -CONH- is included in the divalent linking group, -CO may be on the carbon atom side of the main chain and -NH may be on the nitrogen atom side of the side chain, on the contrary, -NH is the main chain --CO may be on the nitrogen atom side of the side chain.
Among them, from the viewpoint of dispersibility, A in the general formula (I) is preferably a divalent linking group containing a -CONH- group or a -COO- group, a -CONH- group or a -COO- group, A divalent linking group containing an alkylene group having 1 to 10 carbon atoms is more preferable.

Examples of the hydrocarbon group in the hydrocarbon group optionally containing a heteroatom for R ² and R ³ include an alkyl group, an aralkyl group, an aryl group and the like.
Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2-ethylhexyl group, cyclopentyl group, cyclohexyl group and the like, and the number of carbon atoms in the alkyl group is 1. to 18 are preferable, and among them, a methyl group or an ethyl group is more preferable.
The aralkyl group includes, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like. The number of carbon atoms in the aralkyl group is preferably 7-20, more preferably 7-14.
Aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl groups. The number of carbon atoms in the aryl group is preferably 6-24, more preferably 6-12. In addition, the number of carbon atoms of the substituent is not included in the preferable number of carbon atoms.
A hydrocarbon group containing a heteroatom has a structure in which a carbon atom in the hydrocarbon group is replaced with a heteroatom, or a structure in which a hydrogen atom in the hydrocarbon group is replaced by a substituent containing a heteroatom. have Examples of the heteroatom that the hydrocarbon group may contain include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom and the like.
Further, hydrogen atoms in the hydrocarbon group may be substituted with halogen atoms such as fluorine, chlorine and bromine atoms.

That R ² and R ³ are bonded to each other to form a ring structure means that R ² and R ³ form a ring structure via a nitrogen atom. A heteroatom may be included in the ring structure formed by R ² and R ³ . Although the ring structure is not particularly limited, examples thereof include pyrrolidine ring, piperidine ring, morpholine ring and the like.

In the present invention, among others, R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, or R ² and R ³ are bonded to form a pyrrolidine ring, piperidine It preferably forms a ring or a morpholine ring.

Examples of monomers that derive structural units represented by the general formula (I) include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, and the like. Alkyl group-substituted amino group-containing (meth)acrylates, alkyl group-substituted amino group-containing (meth)acrylamides such as dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, and the like can be mentioned. Among them, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylamide can be preferably used in terms of improving dispersibility and dispersion stability.
In the polymer, the structural unit represented by formula (I) may consist of one type, or may contain two or more types of structural units.

Further, the structural unit functioning as the coloring material adsorption site is selected from the group consisting of at least part of the nitrogen site possessed by the structural unit represented by the general formula (I), an organic acid compound, and a halogenated hydrocarbon. At least one of them may form a salt (such a copolymer is sometimes referred to as a salt-type copolymer).
As the organic acid compound, among others, a compound represented by the following general formula (A) and a compound represented by the following general formula (C) are preferable, and as the halogenated hydrocarbon, among others, the following general formula (B ) are preferred. That is, at least one compound selected from the group consisting of the organic acid compound and the halogenated hydrocarbon is one or more compounds selected from the group consisting of the following general formulas (A), (B) and (C). It can be preferably used.

(In the general formula (A), R ^a is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or a benzyl group, or -O- Represents R ^e , R ^e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group which may have a substituent or a benzyl group, or a C 1 to 4 represents a (meth)acryloyl group via an alkylene group.In the general formula (B), R ^b , R ^b′ , and R ^b″ each independently represent a hydrogen atom, an acidic group or an ester group thereof, or a substituent. a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group which may have a substituent, a phenyl group which may have a substituent or a benzyl group, or -O- R ^f represents an optionally substituted linear, branched or ^cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group optionally having a substituent, a substituted may be a phenyl group or a benzyl group, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms, and X represents a chlorine atom, a bromine atom, or an iodine atom. , R ^c and R ^d are each independently a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or a benzyl group, Alternatively, —O—R ^e , where R ^e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or a benzyl group, or a carbon number represents a (meth)acryloyl group via 1 to 4 alkylene groups, provided that at least one of R ^c and R ^d contains a carbon atom.)

The symbols of the general formulas (A), (B) and (C) are the same as the symbols of the general formulas (1), (2) and (3) of WO 2016/104493. you can
It is preferable that the organic acid compound is an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphinic acid from the viewpoint of excellent dispersibility and dispersion stability of the coloring material. Specific examples of the organic acid compound used in such a dispersant include, for example, organic acid compounds described in JP-A-2012-236882 and the like as suitable ones.
The halogenated hydrocarbon is preferably at least one selected from allyl halides such as allyl bromide and benzyl chloride, and aralkyl halides, from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.

In the salt-type copolymer, the content of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons forms a salt with the terminal nitrogen moiety of the structural unit represented by general formula (I). Therefore, the total of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons is 0 for the terminal nitrogen portion of the structural unit represented by general formula (I) It is preferably 0.01 mol or more, more preferably 0.05 mol or more, still more preferably 0.1 mol or more, and particularly preferably 0.2 mol or more. When it is at least the above lower limit, the effect of improving the dispersibility of the coloring material by salt formation is likely to be obtained. Similarly, it is preferably 1 mol or less, more preferably 0.8 mol or less, even more preferably 0.7 mol or less, and particularly preferably 0.6 mol or less. When it is not more than the above upper limit, it can be excellent in development adhesion and solvent re-solubility.
At least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons may be used singly or in combination of two or more. When two or more are combined, the total content is preferably within the above range.

As a method for preparing the salt-type copolymer, at least one selected from the group consisting of the organic acid compound and the halogenated hydrocarbon is added to the solvent in which the copolymer before salt formation is dissolved or dispersed, and the mixture is stirred. and a method of heating if necessary.
The terminal nitrogen portion of the structural unit represented by the general formula (I) of the copolymer and at least one selected from the group consisting of the organic acid compound and the halogenated hydrocarbon form a salt. and the ratio thereof can be confirmed by a known method such as NMR.

From the viewpoint of dispersibility and dispersion stability, the copolymer having the structural unit represented by the general formula (I) has the structural unit represented by the general formula (I), and the graft polymer chain ( A graft copolymer having a meth)acrylate-derived structural unit, and a block having an A block containing a structural unit represented by the general formula (I) and a B block containing a (meth)acrylate-derived structural unit is more preferably at least one of copolymers.
In the graft copolymer, as a graft polymer chain having a structural unit derived from (meth)acrylate, a conventionally known structure can be appropriately selected and used. For example, at least one of the graft copolymer and the salt-type graft copolymer described in WO2021/006077 may be used.
Further, in the block copolymer, as the B block containing a structural unit derived from (meth)acrylate, a conventionally known structure can be appropriately selected and used. For example, at least one of block copolymers and salt-type block copolymers described in WO2016/104493 may be used.

Among the block copolymers used as dispersants, the A block containing the structural unit represented by the general formula (I) and the B block containing the structural unit derived from the carboxy group-containing monomer and the (meth)acrylate-derived structural unit and from the group consisting of at least part of the nitrogen moiety of the structural unit represented by the general formula (I) of the block copolymer, an organic acid compound, and a halogenated hydrocarbon At least one of the selected salt-type block copolymers forms a salt, and the block copolymer and at least one of the salt-type block copolymers have an acid value of 1 mgKOH/g to 18 mgKOH. /g and a glass transition temperature of 30°C or higher is preferable from the viewpoint that the substrate adhesion and solvent resistance of the cured film are improved even in low-temperature heat treatment, and the generation of development residues is suppressed.
The B block in this case contains a (meth)acrylate-derived structural unit as an essential component, and may be the same as the B block of WO 2016/104493.

A copolymer having a structural unit represented by the general formula (I) has an amine value of 40 mgKOH/g to 120 mgKOH/g and has good dispersibility and does not deposit foreign matter during coating film formation. , from the viewpoint of improving brightness and contrast.
When the amine value is within the above range, the viscosity stability over time and heat resistance are excellent, and alkali developability and solvent re-solubility are also excellent. In the present invention, the amine value of the copolymer having the structural unit represented by the general formula (I) is preferably 80 mgKOH/g or more, more preferably 90 mgKOH/g or more. preferable. On the other hand, from the viewpoint of solvent resolubility, the amine value of the copolymer having the structural unit represented by the general formula (I) is preferably 110 mgKOH/g or less, more preferably 105 mgKOH/g or less. more preferred.
The amine value refers to the number of mg of potassium hydroxide equivalent to perchloric acid required to neutralize the amine component contained in 1 g of sample, and can be measured by the method defined in JIS-K7237. When measured by this method, even if the amino group forms a salt with the organic acid compound in the dispersant, the organic acid compound usually dissociates, so the block copolymer itself used as the dispersant can be measured.

The content ratio (mol%) of each structural unit in the copolymer in the dispersant can be obtained from the amount of raw materials charged at the time of production, and can be measured using an analyzer such as NMR. Also, the structure of the dispersant can be measured using NMR, various mass spectrometry, and the like. In addition, if necessary, the dispersant is decomposed by thermal decomposition or the like, and the obtained decomposition product is subjected to high performance liquid chromatography, gas chromatograph mass spectrometer, NMR, elemental analysis, XPS / ESCA, TOF-SIMS, etc. can ask.

In the photosensitive colored resin composition according to the present invention, the content when using a dispersant may be selected so as to be excellent in the dispersibility and dispersion stability of the coloring material, and is not particularly limited, but the photosensitive colored resin For example, it is preferably in the range of 2% to 30% by mass, more preferably 3% to 25% by mass, relative to the total solid content in the composition. When it is at least the above lower limit, the dispersibility and dispersion stability of the coloring material are excellent, and the storage stability of the photosensitive colored resin composition is excellent. Moreover, if it is below the said upper limit, developability will become favorable. Especially when forming a cured film having a high colorant concentration, the content of the dispersant is, for example, preferably 2% by mass to 25% by mass, more preferably 2% by mass to 25% by mass, based on the total solid content of the photosensitive colored resin composition. It is within the range of 3% by mass to 20% by mass.

<Sensitizer>
In the present invention, the phthalocyanine compound represented by the general formula (1) diffused in the system absorbs the exposure light and tends to lose radicals generated from the initiator. It is preferred to include a sensitizer in combination with the initiator. Among them, from the viewpoint of good reactivity of the (meth)acrylic polymerization system, it is preferable to contain a thiol-based sensitizer, and it is more preferable to contain the oxime ester-based initiator in combination with a thiol-based sensitizer.

Examples of thiol-based sensitizers include monofunctional thiol compounds having one thiol group and polyfunctional thiol compounds having two or more thiol groups.
Examples of monofunctional thiol compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercapto propionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate and the like.
Examples of polyfunctional thiol compounds include 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2, 4,6(1H,3H,5H)-trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), di pentaerythritol hexakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate) and the like.

In the photosensitive colored resin composition of the present invention, the content when the sensitizer is included, from the viewpoint of the effect of improving the curability, relative to the total solid content of the photosensitive colored resin composition, for example 0.5 % to 10% by mass can be used. When the sensitizer is included, the content is more preferably 1% by mass to 6% by mass, more preferably 2% by mass to 5% by mass, relative to the total solid content of the photosensitive colored resin composition. is.

<Antioxidant>
It is preferable that the photosensitive colored resin composition of the present invention further contains an antioxidant from the viewpoint of suppressing the amount of line width shift. The photosensitive colored resin composition of the present invention, by containing an antioxidant in combination with the specific photoinitiator, because it is possible to control excessive radical chain reaction without impairing the curability when forming a cured film When forming a fine line pattern, the linearity is further improved, and the ability to form a fine line pattern as designed for the mask line width is improved. In addition, the heat resistance can be improved, and the decrease in luminance after exposure and post-baking can be suppressed, so that the luminance can be improved.
The antioxidant used in the present invention is not particularly limited, and may be appropriately selected from those conventionally known. Specific examples of antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and hydrazine-based antioxidants. It is preferable to use a hindered phenol-based antioxidant from the viewpoint of improving the ability to form a fine line pattern as designed and from the viewpoint of heat resistance. It may also be a latent antioxidant as described in WO 2014/021023.

Hindered phenol antioxidants include, for example, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX1010, manufactured by BASF), 1,3 ,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris(4-hydroxy-3,5- Di-tert-butylbenzyl)mesitylene (trade name: Irganox 1330, manufactured by BASF), 2,2′-methylenebis(6-tert-butyl-4-methylphenol) (trade name: Sumilizer MDP-S, manufactured by Sumitomo Chemical) ), 6,6′-thiobis(2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate ( trade name: Irgamod 195, manufactured by BASF) and the like. Among them, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX1010, manufactured by BASF) is preferable from the viewpoint of heat resistance and light resistance.

The content of the antioxidant is preferably 0.1% by mass to 10.0% by mass, more preferably 0.5% by mass to 5.0% by mass, based on the total solid content of the photosensitive colored resin composition. %. If it is at least the above lower limit, the ability to form a fine line pattern as designed with a mask line width is improved, and the heat resistance is excellent. On the other hand, if it is below the above upper limit, the photosensitive colored resin composition of the present invention can be made into a highly sensitive photosensitive resin composition.

<Method for producing a photosensitive colored resin composition>
The method for producing a photosensitive colored resin composition of the present invention includes a coloring material, a sulfonic acid group-containing dye derivative, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, and various kinds of materials optionally used. It can be prepared by mixing the additive components using a known mixing means.
As a method for preparing the resin composition, for example, (1) first, a coloring material, a sulfonic acid group-containing coloring matter derivative, and, if necessary, a dispersing agent are added to a solvent to prepare a coloring material liquid; A method of mixing an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and optionally various additive components into the colorant liquid; (2) a colorant and a sulfonic acid group-containing dye in a solvent; A method of simultaneously adding and mixing a derivative, optionally a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and optionally various additive components; (3) into a solvent, A method of adding and mixing an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and optionally various additive components, and then adding and mixing a coloring material and a sulfonic acid group-containing dye derivative; (4) A coloring material, a sulfonic acid group-containing dye derivative, and, if necessary, a dispersant and an alkali-soluble resin are added to a solvent to prepare a coloring material liquid, and the coloring material liquid is further added with an alkali. A method of adding and mixing a soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, and optionally various additive components;

II. Color filter The color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is the photosensitive colored resin composition according to the present invention. It is a hardened material.

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

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

The colored layer can be formed, for example, by the following method.
First, the photosensitive colored resin composition of the present invention described above is applied onto a substrate described later using a coating method 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 coating. Among them, the spin coating method and the die coating method can be preferably used.
Then, the wet coating film is dried by heating using a hot plate or oven, and then exposed through a mask having a predetermined pattern to photopolymerize the alkali-soluble resin, the photopolymerizable compound, and the like. to form a cured coating film. Light sources used for exposure include, for example, ultraviolet light from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and electron beams. The amount of exposure is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
Moreover, in order to accelerate the polymerization reaction after exposure, heat treatment may be performed. The heating conditions are appropriately selected according to the mixing ratio of each component in the photosensitive colored resin composition to be used, the thickness of the coating film, and the like.

Next, a coating film is formed in a desired pattern by developing with a developer to dissolve and remove the unexposed portions. As the developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to this alkaline solution.
Moreover, a general method can be adopted as the developing method.
After the development processing, the developing solution is usually washed and the cured coating film of the photosensitive colored resin composition is dried to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after development processing. The heating conditions are not particularly limited, and are appropriately selected according to the application of the coating film.
The colored layer may be a finely patterned colored layer with a line width of 40 μm or less, or may be a finely patterned colored layer with a line width of 20 μm or less.

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

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

(substrate)
As the substrate, a transparent substrate, a silicon substrate, and a transparent substrate or a silicon substrate on which an aluminum, silver, silver/copper/palladium alloy thin film or the like is formed are used. Other color filter layers, resin layers, transistors such as TFTs, circuits, and the like may be formed on these substrates.

The transparent substrate in the color filter of the present invention is not particularly limited as long as it is transparent to visible light, and transparent substrates used in general color filters can be used. Specifically, transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials such as transparent resin films, optical resin plates, and flexible glass. material.
Although the thickness of the transparent substrate is not particularly limited, a thickness of about 100 μm to 1 mm, for example, can be used depending on the application of the color filter of the present invention.
The color filter of the present invention includes, in addition to the above-described substrate, light shielding portion and colored layer, an overcoat layer, a transparent electrode layer, an alignment film, alignment protrusions, columnar spacers, and the like. good too.

(Processing of developer waste during color filter manufacturing)
As described above, when forming the pattern of the colored layer, after the coating film of the photosensitive colored resin composition is exposed, it is developed using a developer to dissolve and remove the unexposed portions. As the developer, an alkaline aqueous solution is usually used in which about 0.02 to 0.5% by mass of an alkali such as potassium hydroxide is dissolved in water or a water-soluble solvent. The developer waste liquid (developer waste liquid) generated in the process contains the components of the photosensitive colored resin composition in the unexposed portion. Therefore, usually, a flocculating agent is added to the developer waste liquid to flocculate the components of the photosensitive colored resin composition containing the colorant, and then the flocculated matter is recovered by filtration or the like, and the filtrate is neutralized to adjust the pH. Drain the water.
Conventionally, developer waste liquids containing phthalocyanine dyes were not sufficiently aggregated even when a flocculating agent was added, and there was a problem that the filtrate after collecting the aggregates was colored with the color of the phthalocyanine dyes. On the other hand, when the photosensitive colored resin composition of the present invention is used, the filtrate after the addition of the flocculant and the collection of aggregates can be prevented from containing dye and coloring.
The flocculant is not particularly limited as long as it is a flocculant that can be generally used when processing developer waste liquid at a color filter factory. As the flocculant, for example, a cationic inorganic flocculant such as polyaluminum chloride, an anionic polymer flocculant such as polyacrylamide, or the like can be used. For example, the development waste solution is flocculated with a cationic inorganic flocculant such as polyaluminum chloride to neutralize the repulsive negative charges on the colloidal surface present in the waste solution, and then the flocs are crosslinked with an anionic polymer flocculant. may coarsen and precipitate agglomerates.
Check the filtrate after collection of aggregates for coloration and foreign matter. Specifically, for example, the filtrate is checked for residual components derived from the photosensitive colored resin composition using a liquid chromatograph mass spectrometer.
Acids such as dilute hydrochloric acid can be used as the neutralizing agent used for neutralizing the filtrate after collecting the aggregates.

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

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

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for liquid crystal display devices can be adopted. Examples of such driving methods include the TN method, the IPS method, the OCB method, and the MVA method. Any of these methods can be suitably used in the present invention.
Also, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.
Further, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention.

As a method for forming the liquid crystal layer, a method generally used as a method for manufacturing 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 gradually cooled to room temperature, thereby aligning the enclosed liquid crystal.

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

As a lamination method of the organic light emitter 80, for example, a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 are sequentially formed on the upper surface of the color filter. method, and a method of bonding the organic light emitter 80 formed on another substrate onto the inorganic oxide film 60, and the like. As for the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other structures in the organic light emitter 80, known structures can be appropriately used. The organic light-emitting display device 100 manufactured in this way can be applied to, for example, a passive drive type organic EL display and an active drive type organic EL display.
The organic light-emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may have a known configuration as an organic light-emitting display device generally using color filters.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the invention.
The intermediate of the halogenated phthalocyanine compound was analyzed by LC-MS (quadrupole LC/MS manufactured by Agilent Technologies, Agilent 1260 Infinity).
Dye derivatives such as sulfonic acid group-containing dye derivatives and halogenated phthalocyanine compounds were analyzed by TOF-MS (manufactured by Shimadzu Corporation, MALDI-8020).

(Synthesis Example 1: Synthesis of phthalocyanine compound 1)
5.0 g (25.0 mmol) of tetrafluorophthalonitrile, 6.91 g (50 mmol) of potassium carbonate, and 25 ml of acetone were put into a 500 ml eggplant flask and stirred at room temperature until dissolved.
Next, 8.31 g (50.0 mmol) of ethyl 4-hydroxybenzoate dissolved in 25 ml of acetone was added to the eggplant flask with stirring in an ice bath over 1 hour using a dropping funnel. Stirred for 1 hour.
After completion of the reaction, potassium carbonate was removed by filtration, and the solvent was distilled off from the resulting reaction solution using an evaporator. The resulting oily product was dissolved in dichloromethane and subjected to liquid separation treatment with pure water. .
The organic layer after liquid separation was recrystallized in isopropyl alcohol to obtain intermediate 1.
Intermediate 1 had the following structure as analyzed by LC-MS. A representative chemical structural formula of Intermediate 1 is shown below.

5.00 g (10.15 mmol) of intermediate 1 and 15.0 ml of benzonitrile were added to a 50 ml flask and dissolved at about 100°C. The mixture was reacted with stirring at ℃ for 15 hours.
After the reaction solution was cooled to room temperature, the reaction solution was added dropwise to 150 ml of methanol, and the generated precipitate was stirred for 30 minutes, collected with filter paper, and repeatedly stirred in a beaker with methanol and filtered. was washed.
The obtained product was dried to obtain a halogenated phthalocyanine compound 1.
A representative chemical structural formula of the halogenated phthalocyanine compound 1 is shown below.

(Synthesis Example 2: Synthesis of phthalocyanine compound 2)
5.0 g (25.0 mmol) of tetrafluorophthalonitrile, 6.91 g (50 mmol) of potassium carbonate, and 25 ml of acetone were put into a 500 ml eggplant flask and stirred at room temperature until dissolved.
Next, 9.01 g (50.0 mmol) of n-propyl 4-hydroxybenzoate dissolved in 25 ml of acetone was added to the eggplant flask over 1 hour with stirring in an ice bath, After the addition, the mixture was stirred for 1 hour.
After completion of the reaction, potassium carbonate was removed by filtration, and the solvent was distilled off from the resulting reaction solution using an evaporator. The resulting oily product was dissolved in dichloromethane and subjected to liquid separation treatment with pure water. .
The organic layer after liquid separation was recrystallized in isopropyl alcohol to obtain an intermediate 2.
Intermediate 2 had the following structure when analyzed by LC-MS (Quadrupole LC/MS, Agilent 1260 Infinity, manufactured by Agilent Technologies). Furthermore, a representative chemical structural formula of Intermediate 2 is shown below.

5.28 g (10.15 mmol) of Intermediate 2 and 15.0 ml of benzonitrile were added to a 50 ml flask and dissolved at about 100°C. C. for 15 hours while stirring.
After cooling the reaction solution to room temperature, the reaction solution was added dropwise to 150 ml of methanol, and after stirring the generated precipitate for 30 minutes, it was collected with filter paper, and the reaction was repeated several times with methanol, stirring in a beaker, and filtration. was washed.
The obtained product was dried to obtain a halogenated phthalocyanine compound 2. Representative chemical structural formulas are shown below.

(Synthesis Example 3: Synthesis of sulfonic acid group-containing dye derivative A)
After adding 10.0 parts by weight of copper phthalocyanine to 266.7 parts by weight of 100% sulfuric acid, the mixture was stirred at 100° C. for 2 hours. After cooling to room temperature, the reaction solution was added to 800 parts by weight of ice water, and the precipitate was filtered. Then, it was washed twice with 800 parts by weight of water and vacuum-dried at 80° C. to obtain a blue product. The TOF-MS mass spectrometry result of this blue product (sulfonic acid group-containing dye derivative A) was consistent with the molecular weight (Mw=656.14) of the monosulfonic acid derivative of copper phthalocyanine having the following structure.

(Synthesis Example 4: Synthesis of sulfonic acid group-containing dye derivative B)
374.76 parts by mass of 11% by mass fuming sulfuric acid were stirred while cooling to 10°C, and C.I. I. Pigment Yellow 138 (PY138) 74.96 parts by weight was added. Then, the mixture was stirred at 90°C for 6 hours. The reaction solution was added to 1,600 parts by mass of ice water, stirred for 15 minutes, and the precipitate was filtered. The wet cake obtained was washed with 800 ml of water three times. The wet cake was vacuum dried at 80°C to obtain 81.55 parts by mass of a yellow product.
The TOF-MS mass spectrometry result of this yellow product (sulfonic acid group-containing dye derivative B) was consistent with the molecular weight (Mw=774.0) of the monosulfonic acid derivative of PY138 having the following structure.

(Synthesis Example 5: Synthesis of sulfonic acid group-containing dye derivative C)
Commercially available C.I. I. Pigment Red 254 (PR254) was added to 30 parts by mass of 20% fuming sulfuric acid and 300 parts by mass, followed by reaction at 40° C. for 4 hours. After cooling, the reaction mixture was precipitated in 3,000 parts by mass of ice water, filtered and washed with water to obtain a water paste. By drying this water paste, 26 parts by mass of a red product was obtained.
The TOF-MS mass spectrometry result of this red product (sulfonic acid group-containing dye derivative C) was consistent with the molecular weight (Mw=437.25) of the monosulfonic acid derivative of PR254 having the following structure.

(Synthesis Example 6: Synthesis of sulfonamide group-containing dye derivative D)
In a reaction vessel, 300 parts by mass of chlorosulfonic acid and 30 parts by mass of copper phthalocyanine were added and dissolved completely, then 24 parts by mass of thionyl chloride was added, and the temperature was gradually raised and reacted at 101° C. for 3 hours. The reaction solution was poured into 9000 parts by mass of ice water, stirred, filtered and washed with water. The obtained press cake is slurried with 300 parts by mass of water, 13 parts by mass of 1,1-diethyl-1,5-diazapentane is added, stirred at 65° C. for 4 hours, filtered, washed with water, dried, and turned into a blue color. The product was obtained.
The TOF-MS mass spectrometry result of this blue product (sulfonamide group-containing dye derivative D) was consistent with the molecular weight (Mw=768.35) of the sulfonamide derivative of copper phthalocyanine having the following structure.

(Synthesis Example 7: Synthesis of alkali-soluble resin A solution)
A mixture of 40 parts by mass of benzyl methacrylate (BzMA), 15 parts by mass of methyl methacrylate (MMA), 25 parts by mass of methacrylic acid (MAA), and 3 parts by mass of azobisisobutyronitrile (AIBN) was added to propylene glycol monomethyl ether acetate. (PGMEA) was added dropwise over 3 hours at 100° C. into a polymerization tank containing 150 parts by mass of PGMEA under a nitrogen stream. After completion of dropping, the mixture was further heated at 100° C. for 3 hours to obtain a polymer solution. The weight average molecular weight of this polymer solution was 7,000.
Next, 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol are added to the obtained polymer solution, and heated at 110° C. for 10 hours. , the reaction between the carboxylic acid group of main chain methacrylic acid and the epoxy group of glycidyl methacrylate was carried out. During the reaction, air was bubbled into the reaction solution to prevent polymerization of glycidyl methacrylate. The reaction was tracked by measuring the acid value of the solution. The resulting alkali-soluble resin A is a resin in which a side chain having an ethylenic double bond is introduced using GMA to the main chain formed by copolymerization of BzMA, MMA, and MAA, and has an acid value of 74 mgKOH/g. It had a weight average molecular weight of 12,000. The alkali-soluble resin A solution had a solid content of 40% by mass.

(Example 1)
(1) Production of colorant liquid G1 As a dispersant, dispersant b (salt-type block copolymer Coalescing) solution (solid content 40% by mass) was prepared.
8.13 parts by mass of the dispersant b solution as a dispersant, 11.96 parts by mass of the halogenated phthalocyanine compound 1 as the coloring material, and 1.04 parts by mass of the sulfonic acid group-containing dye derivative A obtained in Synthesis Example 7 14.63 parts by mass of the alkali-soluble resin A solution, 64.25 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were placed in a mayonnaise bottle and pre-crushed in a paint shaker (Asada Iron Works Co., Ltd.). ), then take out zirconia beads with a particle size of 2.0 mm, add 200 parts by mass of zirconia beads with a particle size of 0.1 mm, and similarly disperse for 4 hours with a paint shaker as main crushing. to obtain a coloring material liquid G1.

(2) Production of photosensitive colored resin composition G1 43.43 parts by mass of the colorant liquid G1 obtained in (1) above, 4.23 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 7, 3.95 parts by mass of polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), photoinitiator 1 (trade name TR-PBG-3057, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) at 0.95 parts by mass. 50 parts by mass, 0.50 parts by mass of photoinitiator 2 (trade name ADEKA Arkles NCI-831, manufactured by ADEKA), sensitizer (pentaerythritol tetrakis (3-mercaptobutyrate), trade name Karenz MT-PE1 , Showa Denko) 0.13 parts by mass, 0.03 parts by mass of a fluorine-based surfactant (trade name Megafac F559, manufactured by DIC Corporation), a silane coupling agent (trade name KBM503, manufactured by Shin-Etsu Silicone) 0.34 parts by mass of PGMEA, 26.24 parts by mass of PGMEA, and 20.65 parts by mass of propylene glycol monomethyl ether (PGME) were added to obtain a photosensitive colored resin composition G1.

(3) Formation of colored layer The photosensitive colored resin composition G1 obtained in (2) above is placed on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") having a thickness of 0.7 mm and a size of 100 mm x 100 mm. , After coating with a spin coater, dry at 80 ° C. for 3 minutes using a hot plate, irradiate ultraviolet rays of 60 mJ / cm ² using an ultra-high pressure mercury lamp, and then post in a clean oven at 230 ° C. for 30 minutes. By baking, the film thickness was adjusted to a film thickness of 2.5 μm to form the colored layer G1.

(Example 2)
(1) Production of Colorant Liquid G2 In (1) of Example 1, instead of the sulfonic acid group-containing dye derivative A, an equimolar amount of the sulfonic acid group-containing dye derivative B obtained above was used. Colorant liquid G2 was obtained in the same manner as in Example 1 (1).
(2) Production of photosensitive colored resin composition G2 In the same manner as in (2) of Example 1, except that the coloring material liquid G2 was used instead of the coloring material liquid G1 in (2) of Example 1, A photosensitive colored resin composition G2 was obtained.
(3) Formation of colored layer Same as (3) of Example 1, except that the photosensitive colored resin composition G2 was used instead of the photosensitive colored resin composition G1 in (3) of Example 1. to obtain a colored layer G2.

(Example 3)
(1) Production of Colorant Liquid G3 In (1) of Example 1, instead of the sulfonic acid group-containing dye derivative A, an equimolar amount of the sulfonic acid group-containing dye derivative C obtained above was used. Colorant liquid G3 was obtained in the same manner as in Example 1 (1).
(2) Production of photosensitive colored resin composition G3 In the same manner as in (2) of Example 1, except that the coloring liquid G3 was used instead of the coloring liquid G1 in (2) of Example 1, A photosensitive colored resin composition G3 was obtained.
(3) Formation of colored layer Same as (3) of Example 1, except that the photosensitive colored resin composition G3 was used instead of the photosensitive colored resin composition G1 in (3) of Example 1. to obtain a colored layer G3.

(Example 4)
(1) Production of Coloring Material Liquid G4 Except for using an equimolar amount of the halogenated phthalocyanine compound 2 obtained above instead of the halogenated phthalocyanine compound 1 as the coloring material in (1) of Example 1, the procedure was carried out. Colorant liquid G4 was obtained in the same manner as in Example 1 (1).
(2) Production of photosensitive colored resin composition G4 In the same manner as in (2) of Example 1, except that the coloring material liquid G4 was used instead of the coloring material liquid G1 in (2) of Example 1, A photosensitive colored resin composition G4 was obtained.
(3) Formation of colored layer Same as (3) of Example 1, except that the photosensitive colored resin composition G4 was used instead of the photosensitive colored resin composition G1 in (3) of Example 1. to obtain a colored layer G4.

(Example 5)
(1) Production of colorant liquid G5 In (1) of Example 1, the halogenated phthalocyanine compound 2 obtained above was used in an equimolar amount instead of the halogenated phthalocyanine compound 1 as the colorant, and the colorant contained a sulfonic acid group. A coloring material liquid G5 was obtained in the same manner as in Example 1 (1) except that the sulfonic acid group-containing coloring matter derivative B obtained above was used in an equimolar amount instead of the coloring matter derivative A.
(2) Production of photosensitive colored resin composition G5 In the same manner as in (2) of Example 1, except that the coloring material liquid G5 was used instead of the coloring material liquid G1 in (2) of Example 1, A photosensitive colored resin composition G5 was obtained.
(3) Formation of colored layer Same as (3) of Example 1, except that the photosensitive colored resin composition G5 was used instead of the photosensitive colored resin composition G1 in (3) of Example 1. to obtain a colored layer G5.

(Example 6)
(1) Production of colorant liquid G6 In (1) of Example 1, the halogenated phthalocyanine compound 2 obtained above was used in an equimolar amount instead of the halogenated phthalocyanine compound 1 as the colorant, and the colorant contained a sulfonic acid group. A coloring material liquid G6 was obtained in the same manner as in Example 1 (1), except that instead of the dye derivative A, the sulfonic acid group-containing dye derivative C obtained above was used in an equimolar amount.
(2) Production of photosensitive colored resin composition G6 In the same manner as in (2) of Example 1, except that the coloring material liquid G6 was used instead of the coloring material liquid G1 in (2) of Example 1, A photosensitive colored resin composition G6 was obtained.
(3) Formation of colored layer Same as (3) of Example 1, except that the photosensitive colored resin composition G6 was used instead of the photosensitive colored resin composition G1 in (3) of Example 1. to obtain a colored layer G6.

(Example 7)
(1) Production of colorant liquid G7 Except for using 12.87 parts by mass of the halogenated phthalocyanine compound 1 and 0.26 parts by mass of the sulfonic acid group-containing dye derivative A as the colorant in (1) of Example 1. obtained a coloring material liquid G7 in the same manner as in Example 1 (1).
(2) Production of photosensitive colored resin composition G7 In the same manner as in (2) of Example 1, except that the coloring material liquid G7 was used instead of the coloring material liquid G1 in (2) of Example 1, A photosensitive colored resin composition G7 was obtained.
(3) Formation of colored layer Same as (3) of Example 1, except that the photosensitive colored resin composition G7 was used instead of the photosensitive colored resin composition G1 in (3) of Example 1. to obtain a colored layer G7.

(Example 8)
(1) Production of colorant liquid G8 Except for using 11.70 parts by mass of the halogenated phthalocyanine compound 1 and 1.30 parts by mass of the sulfonic acid group-containing dye derivative A as the colorant in (1) of Example 1. obtained a coloring material liquid G8 in the same manner as in Example 1 (1).
(2) Production of photosensitive colored resin composition G8 In the same manner as in (2) of Example 1, except that the coloring material liquid G8 was used instead of the coloring material liquid G1 in (2) of Example 1, A photosensitive colored resin composition G8 was obtained.
(3) Formation of colored layer Same as (3) of Example 1, except that the photosensitive colored resin composition G8 was used instead of the photosensitive colored resin composition G1 in (3) of Example 1. to obtain a colored layer G8.

(Comparative example 1)
(1) Production of Comparative Colorant Liquid CG1 Comparative colorant liquid CG1 was prepared in the same manner as in Example 1(1), except that the sulfonic acid group-containing dye derivative A was not used in Example 1(1). got
(2) Production of Comparative Photosensitive Colored Resin Composition CG1 The procedure was the same as in (2) of Example 1, except that the comparative coloring liquid CG1 was used instead of the coloring liquid G1 in (2) of Example 1. Thus, a comparative photosensitive colored resin composition CG1 was obtained.
(3) Formation of colored layer In (3) of Example 1, instead of the photosensitive colored resin composition G1, except for using the comparative photosensitive colored resin composition CG1, and (3) of Example 1 A colored layer CG1 was obtained in the same manner.

(Comparative example 2)
(1) Production of Comparative Photosensitive Colored Resin Composition CG2 As the colorant liquid, comparative colorant liquid CG1 was used to prepare a comparative photosensitive colored resin composition with an increased alkali-soluble resin content.
Specifically, 43.43 parts by mass of the comparative colorant liquid CG1 obtained in (1) above, 8.47 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 4, and a polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.) 2.26 parts by mass, photoinitiator (trade name TR-PBG-3057, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) 0.50 parts by mass, photoinitiator 0.50 parts by mass of ADEKA Arkles NCI-831 (trade name, manufactured by ADEKA) and 0.50 parts by mass of a sensitizer (pentaerythritol tetrakis (3-mercaptobutyrate), trade name Karenz MT-PE1, manufactured by Showa Denko). 13 parts by mass, 0.03 parts by mass of a fluorine-based surfactant (trade name Megafac F559, manufactured by DIC Corporation), 0.34 parts by mass of a silane coupling agent (trade name KBM503, manufactured by Shin-Etsu Silicone), PGMEA and 20.65 parts by mass of propylene glycol monomethyl ether (PGME) were added to obtain a photosensitive colored resin composition CG2.
(2) Formation of colored layer In (3) of Example 1, instead of the photosensitive colored resin composition G1, except for using the comparative photosensitive colored resin composition CG2, and (3) of Example 1 A colored layer CG2 was obtained in the same manner.

(Comparative Example 3)
(1) Production of Comparative Colorant Liquid CG3 In (1) of Example 1, instead of the sulfonic acid group-containing dye derivative A, an equimolar amount of the sulfonamide group-containing dye derivative D obtained above was used. A comparative colorant liquid CG3 was obtained in the same manner as in Example 1 (1).
(2) Production of Comparative Photosensitive Colored Resin Composition CG3 The procedure was the same as in (2) of Example 1, except that the comparative coloring material liquid CG3 was used instead of the coloring material liquid G1 in (2) of Example 1. Thus, a comparative photosensitive colored resin composition CG3 was obtained.
(3) Formation of colored layer In (3) of Example 1, instead of the photosensitive colored resin composition G1, except for using the comparative photosensitive colored resin composition CG3, and (3) of Example 1 A colored layer CG3 was obtained in the same manner.

(Comparative Example 4)
(1) Production of Comparative Colorant Liquid CG4 In (1) of Example 1, an equimolar amount of the halogenated phthalocyanine compound 2 obtained above was used instead of the halogenated phthalocyanine compound 1 as the colorant, and the sulfonic acid group was A comparative colorant liquid CG4 was obtained in the same manner as in Example 1 (1), except that the dye-containing derivative A was not used.
(2) Production of Comparative Photosensitive Colored Resin Composition CG4 The procedure was the same as in (2) of Example 1, except that the comparative coloring liquid CG4 was used instead of the coloring liquid G1 in (2) of Example 1. Thus, a comparative photosensitive colored resin composition CG4 was obtained.
(3) Formation of colored layer In (3) of Example 1, instead of the photosensitive colored resin composition G1, except for using the comparative photosensitive colored resin composition CG4, and (3) of Example 1 A colored layer CG4 was obtained in the same manner.

(Comparative Example 5)
(1) Production of comparative colorant liquid CG5 In (1) of Example 1, an equimolar amount of the halogenated phthalocyanine compound 2 obtained above was used instead of the halogenated phthalocyanine compound 1 as the colorant, and the sulfonic acid group was A comparative colorant liquid CG5 was obtained in the same manner as in Example 1 (1), except that the sulfonamide group-containing dye derivative D obtained above was used in an equimolar amount instead of the dye-containing derivative A.
(2) Production of Comparative Photosensitive Colored Resin Composition CG5 The procedure was the same as in (2) of Example 1, except that the comparative coloring material liquid CG5 was used instead of the coloring material liquid G1 in (2) of Example 1. Thus, a comparative photosensitive colored resin composition CG5 was obtained.
(3) Formation of colored layer In (3) of Example 1, instead of the photosensitive colored resin composition G1, except for using the comparative photosensitive colored resin composition CG5, and (3) of Example 1 A colored layer CG5 was obtained in the same manner.

[Evaluation method]
(1) Developability Each of the photosensitive colored resin compositions of Examples and Comparative Examples was applied onto a 0.7 mm-thick glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") using a spin coater. . After that, it was dried by heating on a hot plate at 80° C. for 3 minutes. This colored layer was exposed to ultraviolet rays of 60 mJ/cm ² using an ultra-high pressure mercury lamp through an independent fine line pattern photomask with a line width of 1 μm to 100 μm, thereby forming a 2.0 μm thick film on a glass substrate. A colored layer was formed.
Next, spin development is performed using a 0.05% by mass potassium hydroxide (KOH) aqueous solution as a developer, and after contact with the developer, washing with pure water is performed for development processing, pattern formation, and developability. evaluated. In the above development processing, the time (unit: seconds) until the unexposed areas were dissolved and removed was measured.

(2) Development residue evaluation Each of the colored resin compositions of Examples and Comparative Examples was applied onto a 0.7 mm thick glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") using a spin coater. After that, a colored layer having a thickness of 2.5 μm was formed by drying at 60° C. for 3 minutes using a hot plate. The glass plate on which the colored layer was formed was subjected to shower development for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer. An unexposed portion (50 mm×50 mm) of the glass substrate after formation of the colored layer was observed with an optical microscope at a magnification of 200 with reflected light.
(Development residue evaluation criteria)
○: No colored residue was observed by optical microscope observation ×: Colored residue was confirmed by optical microscope observation

(3) Evaluation of developer waste liquid Development processing was performed in the same manner as in the evaluation of developability.
1 g of a cationic inorganic coagulant (polyaluminum chloride, manufactured by Taki Kagaku) was added to 500 mL of the colored waste liquid (alkaline developer) that had been developed, and the mixture was stirred for 30 minutes to flocculate the contained components. 1 g of an anionic polymer flocculant (polyacrylamide, manufactured by Asada Kagaku Kogyo Co., Ltd.) was further added to the colored waste liquid, and the mixture was stirred for 30 minutes to coarsen flocs and precipitate aggregates. Aggregates were removed from the waste liquid by filtering the aggregate-containing waste liquid through a 5 μm filter. A neutralizing agent (dilute hydrochloric acid) was added to the filtrate of the waste liquid to neutralize the pH to 7.
After neutralization, the filtrate was obtained by filtering through a 0.2 μm filter.
It was visually confirmed whether or not the obtained filtrate was colored. In addition, using a liquid chromatograph mass spectrometer (LC/MS, manufactured by Agilent Technologies, quadrupole LC/MS, Agilent 1260 Infinity), the resulting filtrate was checked for residual components of the photosensitive colored resin composition. bottom.
(Evaluation criteria for developer waste liquid)
○: There is no coloring in the filtrate, and the total content of solid components derived from the photosensitive colored resin composition is less than 0.001% by mass ×: There is coloring in the filtrate, and / or the photosensitive colored resin composition The total content of solid components derived from substances is 0.001% by mass or more

[Summary of results]
All of the photosensitive colored resin compositions of Comparative Examples 1 to 5, which do not contain a sulfonic acid group-containing dye derivative, contain a specific phthalocyanine dye in the coloring material, making it difficult to recover the coloring material during waste liquid treatment after development. , the coloring material remained in the waste liquid (filtrate) after collecting the aggregates, resulting in coloration. Furthermore, in the photosensitive colored resin compositions of Comparative Examples 1 to 5, the phthalocyanine dye is likely to be left behind during development, so it was shown that colored development residue is likely to remain.
Even in Comparative Example 2 in which the content of the alkali-soluble resin was increased, although the development time was shortened, the coloring material remained in the waste liquid (filtrate) after collecting the aggregates and was colored, and the phthalocyanine dye was left behind during development. It was easy to get wet, and a colored development residue was easy to remain.
Even in Comparative Examples 3 and 5 containing a basic sulfonamide group-containing dye derivative, the coloring material remained in the waste liquid (filtrate) after collecting the aggregates and was colored, and the phthalocyanine dye was easily left behind during development, resulting in coloring. Development residue was likely to remain.
On the other hand, the photosensitive colored resin compositions of Examples 1 to 8 containing the sulfonic acid group-containing dye derivative of the present invention contain a specific phthalocyanine dye in the coloring material, but the coloring material is recovered during waste liquid treatment after development. It was possible, the waste liquid (filtrate) was not colored, and there was no residue of the component of the photosensitive colored resin composition. Furthermore, the photosensitive colored resin compositions of Examples 1 to 8 showed that the phthalocyanine dye was less likely to be left behind during development, so that colored development residues were less likely to remain.

REFERENCE SIGNS LIST 1 substrate 2 light shielding part 3 colored layer 10 color filter 20 counter substrate 30 liquid crystal layer 40 liquid crystal display device 50 organic protective layer 60 inorganic oxide film 71 transparent anode 72 hole injection layer 73 hole transport layer 74 light emitting layer 75 electron injection layer 76 Cathode 80 Organic Light Emitting Body 100 Organic Light Emitting Display

Claims

A photosensitive material containing a coloring material containing a phthalocyanine compound represented by the following general formula (1), a sulfonic acid group-containing dye derivative, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent Colored resin composition.

(In the general formula (1), X 1 to X 16 each independently represent a hydrogen atom, a halogen atom, or -Y-R D , and -Y- is -O-, -S-, or -NH- and R D represents a monovalent organic group, provided that one or more of X 1 to X 16 represents —Y—R D. )
The photosensitive colored resin composition according to claim 1, wherein the sulfonic acid group-containing pigment derivative contains a phthalocyanine skeleton or a quinophthalone skeleton as a pigment skeleton.
A color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured product of the photosensitive colored resin composition according to claim 1 or 2. filter.
A display device having the color filter according to claim 3.