JP2013148850A - Colored film for image pickup device, colored film set, color filter, and image pickup device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored film for image pickup device, which contains no halogen atom, or contains only trace amounts of halogen atoms, to be able to cope with a safety and health problem and an environmental pollution problem, and have excellent spectral characteristics.SOLUTION: A colored film for image pickup device is formed by a coloring composition including a colorant [A] and a resin [B], and the halogen amount of the colored film is equal to or less than 1500 ppm relative to the whole colored film.

Description

The present invention relates to a color film that forms a color filter to be mounted on an image sensor typified by a C-MOS (Complementary Metal Oxide Semiconductor: Complementary Metal Oxide Semiconductor), CCD (Charge Coupled Device), The present invention relates to a colored film set, a color filter, and an image sensor.
The colored film for an image pickup device of the present invention is useful for applications requiring safety and health and environmental aspects, particularly in the above fields, because the colored film does not contain or contains a halogen atom.

  Color image sensors such as C-MOS and CCD are provided with color filters each having a primary color filter segment of additive mixture of B (blue), G (green), and R (red) on the light receiving element. Generally, color separation is performed. In recent years, the area per pixel is decreasing due to the reduction in size and increase in the number of pixels of a color image sensor. As a result, it is required to reduce the thickness of the color filter mounted on the image sensor and to increase the concentration of the coloring component.

  In recent years, the development of environmentally friendly products with low environmental impact has been actively promoted, and more stringent standards have been newly set in accordance therewith. Color materials used in current color filters for image sensors contain halogen atoms for each color, and halogen atoms are one of chemical substances that are desired to be removed as environmentally friendly products. However, since halogen atoms have a great influence on the colorant spectrum, it has been difficult to achieve both the spectral characteristics desired for the color filter for the image sensor and the removal of the halogen atoms.

  Currently, for the manufacture of image sensors, color mixing of halogen-containing colorants, which is not a problem with the current standards, is common, and color films for image sensors that achieve halogen-free can be provided. The current situation is not.

JP 2005-5419 A JP 2004-200360 A

  The colored film for an image sensor according to the present invention does not contain a halogen atom or is contained in a very small amount, so that the color filter for an image sensor is suitable for safety and hygiene and environmental pollution and has excellent spectral characteristics. The purpose is to provide.

  The colored film for an image pickup device of the present invention is a colored film formed of a colored composition containing a colorant [A] and a resin [B], and the halogen content of the colored film is relative to the entire colored film. It is characterized by being 1500 ppm or less.

  Further, in the present invention, when the coating composition is formed such that the coloring composition has a film thickness of 0.5 to 1.5 μm and the spectral transmittance at a wavelength of 580 nm is 50%, the coating composition has a wavelength of 430 nm to 560 nm. The present invention relates to the colored film for an image sensor, wherein the spectral transmittance in the range is 10% or less and the spectral transmittance at a wavelength of 600 nm is 75% or more.

[一般式（１）中、Ｒ¹、Ｒ²、Ｒ³は、それぞれ独立に−Ｈ、−ＣＨ₃、−ＯＣＨ₃、−ＣＯＯＣＨ₃、−ＣＯＯＣ₄Ｈ₉、−ＮＯ₂、−ＳＯ₂ＮＨＣＨ₃、または−ＣＯＮＨＣ₆Ｈ₅である。] The present invention also relates to the colored film for an image sensor, wherein the colored composition contains a benzimidazolone pigment represented by the following general formula (1).

[In the general formula (1), R ¹ , R ² and R ³ are each independently —H, —CH ₃ , —OCH ₃ , —COOCH ₃ , —COOC ₄ H ₉ , —NO ₂ , —SO ₂ NHCH. _3, or -CONHC ₆ H _5. ]

  In addition, the present invention provides a coating composition having a thickness of 0.5 to 1.5 μm and a spectral transmittance of 5% at a wavelength of 450 nm when the coating composition is formed on the short wavelength side of the coating film. The wavelength at which the transmittance is 50% is in the range from 480 nm to 510 nm, the wavelength at which the spectral transmittance on the long wavelength side is 50% is in the range from 570 nm to 610 nm, the wavelength 540 nm is 80% or more, and the wavelength is 650 nm. It has a spectral characteristic in which the spectral transmittance is 3% or less.

  The present invention also relates to the colored film for an image sensor, wherein the colored composition contains an aluminum phthalocyanine pigment.

  Further, in the present invention, when the coating composition is formed so that the coloring composition has a film thickness of 0.5 to 1.5 μm and a spectral transmittance of 3% at a wavelength of 570 nm, the spectral transmittance of the coating film is 50%. The color for the image sensor is characterized by having a spectral characteristic in which the wavelength is in the range of 490 nm to 510 nm, the spectral transmittance at a wavelength of 450 nm is 85% or more, and the spectral transmittance at a wavelength of 540 nm is 12% or less. Relates to the membrane.

  The present invention also relates to the colored film for an image sensor, wherein the colored composition contains a dye containing no halogen atom.

The present invention also relates to a colored film set for an image sensor, comprising at least two kinds of the colored films.
The present invention also relates to the colored film set for an image sensor, comprising a red colored film, a green colored film, and a blue colored film.

The present invention also relates to a color filter having the colored film for an image sensor.
The present invention also relates to an imaging device comprising the color filter.

  The colored film for an image pickup device of the present invention does not contain a halogen atom or contains a trace amount, so that it is useful for applications requiring safety and health and environmental aspects.

Hereinafter, the present invention will be described in detail.
In the present application, when “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” is particularly described, Unless otherwise indicated, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. It shall represent.
In addition, “CI” mentioned in the present specification means a color index (CI).

<Color filter>
First, the color filter of the present invention will be described.
The color filter of the present invention has a colored film formed of a colored composition containing a colorant [A] and a resin [B], and the halogen content of the colored film is 1500 ppm or less with respect to the entire colored film. More preferably, it is 700 ppm or less.

The film thickness of the colored film for the image sensor is required to be reduced to 0.5 μm to 1.5 μm, more preferably 0.5 μm to 1.2 μm. The content is large, and the content of the colorant [A] in 100% by weight of the coloring composition is preferably 1.5 to 20% by weight.
The content of the colorant [A] in 100% by weight of the colored film is preferably 10 to 50% by weight, more preferably 30 to 50% by weight, and the remainder is a resin provided by the colorant carrier. It consists essentially of a quality binder.

  Examples of the colored film for the imaging element include a red colored film, a green colored film, a blue colored film, a magenta colored film, a cyan colored film, and a yellow colored film.

  The color filter for an image pickup device of the present invention preferably includes at least two kinds of colored films having a halogen content of 1500 ppm or less based on the whole colored film, and further includes a red colored film, a green colored film, and It is preferable to include a blue colored film.

  The amount of halogen in the colored film for an image sensor in the present application is measured by diverting the measurement method described in the halogen-free copper-clad laminate test method (JPCA-ES01) to the colored film. In this measurement method, a sample pretreated by the flask combustion method is quantified by an ion chromatography method. Specifically, the halogen content is measured by first applying a photosensitive coloring composition on a transparent substrate to form a colored film, and then irradiating the film with ultraviolet rays. Next, the film is spray-developed with an alkaline developer, washed with ion-exchanged water, and the substrate is heated and allowed to cool to form a colored film on the substrate. The colored film is scraped off, the shaved colored film is pretreated by a flask combustion method, and the halogen content of the obtained sample is measured by ion chromatography.

  The color filter for an image sensor according to the present invention uses a colored film formed from a colored composition using a combination of a pigment and a dye having a specific structure, compared to a color filter formed by combining a conventional pigment. In addition to satisfying the spectrum desired for the imaging device, it is possible to provide a color filter excellent in safety and hygiene and environment because it contains no or even a halogen atom.

[Red colored film]
The red colored film can be formed using a red colored composition containing a red pigment and / or a red dye, a resin and / or a solvent, which will be described later. Moreover, an orange pigment and / or a yellow pigment can be used in combination with the red coloring composition. Also, an orange dye and / or a yellow dye can be used.
Especially, it is preferable from a viewpoint of spectral characteristics that the benzimidazolone pigment and / or xanthene acid dye which are shown by General formula (1) are included.

  Further, when a coating film is formed so that the spectral transmittance at a wavelength of 580 nm is 50% with a film thickness of 0.5 to 1.5 μm, the spectral transmittance in the wavelength range of 430 nm to 560 nm in the coating film is 10% or less. In addition, a colored film formed using a colored composition having a spectral characteristic having a spectral transmittance of 75% or more at a wavelength of 600 nm is excellent in spectral characteristics and is preferable.

[Green colored film]
The green colored film can be formed by using a green colored composition containing a blue pigment and a yellow pigment and / or a yellow dye, a resin and / or a solvent, which will be described later. Moreover, an orange pigment and / or an orange dye can also be used for a green coloring composition.
Among these, it is preferable from the viewpoint of spectral characteristics that an aluminum phthalocyanine pigment and / or a quinophthalone dye represented by the general formula (5) is included.

  Further, when the coating film is formed so that the spectral transmittance at a wavelength of 450 nm is 5% with a film thickness of 0.5 to 1.5 μm, the wavelength at which the spectral transmittance on the short wavelength side of the coating film becomes 50% is 480 nm. To 510 nm, the wavelength at which the spectral transmittance on the long wavelength side is 50% is in the range from 570 nm to 610 nm, the spectral transmittance at 540 nm is 80% or more, and the spectral transmittance at 650 nm is 3% or less. A colored film formed using a colored composition having spectral characteristics is excellent in spectral characteristics and is preferable.

[Blue colored film]
The blue colored film can be formed using a blue colored composition containing a blue pigment and / or a blue dye, a resin and / or a solvent, which will be described later. A purple pigment can be used in combination with the blue coloring composition. Red dyes and / or purple dyes can also be used.
Among these, it is preferable from the viewpoint of spectral characteristics that a xanthene acid dye and / or a triarylmethane basic dye are included.

  Further, when the coating film is formed so that the spectral transmittance at a wavelength of 570 nm is 3% with a film thickness of 0.5 to 1.5 μm, the wavelength at which the spectral transmittance of the coating film is 50% is in the range of 490 nm to 510 nm. The colored film is formed by using a colored composition having a spectral characteristic such that the spectral transmittance at a wavelength of 450 nm is 85% or more and the spectral transmittance at a wavelength of 540 nm is 12% or less. ,preferable.

[Magenta colored film]
The magenta colored film can be formed using a magenta colored composition containing a red pigment and / or a violet pigment and a resin and / or a solvent, which will be described later. Moreover, a red dye and / or a purple dye can be used in combination with the magenta colored composition.

[Cyan colored film]
The cyan colored film can be formed using a cyan colored composition containing a blue pigment and / or a blue dye and a resin and / or a solvent, which will be described later.

[Yellow colored film]
The yellow colored film can be formed by using a yellow colored composition containing a yellow pigment and / or yellow dye described later and a resin and / or a solvent.

  In the colored composition for forming the colored film for an image sensor in the present invention, the red colored composition preferably includes a benzimidazolone pigment represented by the general formula (1), and the green colored composition includes an aluminum phthalocyanine pigment. Preferably, the blue coloring composition contains a xanthene acid dye. These colorants satisfy the spectral characteristics desired for image sensor color filters and do not contain or contain halogen atoms, compared to conventional color films for image sensors using pigments and dyes. However, since it can be made into a very small amount of colored film, it is excellent in terms of safety and health and the environment, which is preferable.

Subsequently, a coloring composition for forming each colored film for an image sensor of the present invention will be described.
The coloring composition contains at least a colorant [A] and a resin [B].

<Colorant [A]>
In order to reduce the amount of halogen contained in the colored film for an image sensor to 1500 ppm or less, the colorant preferably contains no halogen, and is not particularly limited as long as the colorant does not contain halogen, and is generally commercially available. Pigments or dyes can be used.

(Red pigment)
Examples of red pigments include C.I. I. Pigment Red 1, 3, 12, 16, 17, 18, 22, 23, 31, 32, 41, 49, 54, 57: 1, 60: 1, 63, 64: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 81: 5, 81: 6, 83, 89, 95, 114, 119, 122, 123, 149, 150, 169, 170, 177, 178, 179, 190, 193, Mention may be made of red pigments such as 194, 206, 210, 213, 220, 224, 245, 247, 255, 260, 264, 266, 268, 272, 273, 274.
Not only the above organic pigments, but also inorganic pigments can be used as long as they satisfy the spectral characteristics desired for the color filter for the image sensor.
Moreover, it is preferable to use the benzimidazolone pigment represented by General formula (1) and / or the naphthol azo pigment represented by General formula (2) from a viewpoint which is excellent in a spectral characteristic also in a red pigment.

一般式（１）：
[一般式（１）中、Ｒ¹、Ｒ²、Ｒ³は、それぞれ独立に−Ｈ、−ＣＨ₃、−ＯＣＨ₃、−ＣＯＯＣＨ₃、−ＣＯＯＣ₄Ｈ₉、−ＮＯ₂、−ＳＯ₂ＮＨＣＨ₃、または−ＣＯＮＨＣ₆Ｈ₅である。] [Benzimidazolone pigment represented by general formula (1)]

General formula (1):
[In the general formula (1), R ¹ , R ² and R ³ are each independently —H, —CH ₃ , —OCH ₃ , —COOCH ₃ , —COOC ₄ H ₉ , —NO ₂ , —SO ₂ NHCH. _3, or -CONHC ₆ H _5. ]

  Benzimidazolone pigment is a water-insoluble pigment having excellent fastness to solvents and light, and by using this pigment, a coloring composition satisfying the spectral characteristics desired for a colored film for an image sensor You can get things.

  The benzimidazolone pigment is represented by a color index (CI) number as C.I. I. Pigment red 171, 175, 176, 185, 208 and the like. Among these, C.I. I. Pigment red 176 or C.I. I. Pigment Red 185 is preferable from the viewpoint of satisfying spectral characteristics desired for a colored film for an image sensor.

一般式（２）：
[一般式（２）中、Ａは、それぞれ独立して、水素原子、ベンズイミダゾロン基、置換基を有してもよいフェニル基、または置換基を有してもよい複素環基を表す。
Ｒ⁵¹は、水素原子、炭素数１〜４のアルキル基、−ＯＲ⁵⁷、または−ＣＯＯＲ⁵⁸を表す。Ｒ⁵²〜Ｒ⁵⁶は、それぞれ独立して、水素原子、シアノ基、ニトロ基、炭素数１〜４のアルキル基、−ＯＲ⁵⁹、−ＣＯＯＲ⁶⁰、−ＣＯＮＨＲ⁶¹、または−ＳＯ₂ＮＨＲ⁶²を表す。Ｒ⁵⁷〜Ｒ⁶²は、それぞれ独立して、水素原子、または炭素数１〜４のアルキル基を表す。］ [Naphthol azo pigment represented by the general formula (2)]

General formula (2):
[In General Formula (2), each A independently represents a hydrogen atom, a benzimidazolone group, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent.
R ⁵¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, —OR ⁵⁷ , or —COOR ⁵⁸ . R ^{52 to} R ⁵⁶ each independently represents a hydrogen atom, a cyano group, a nitro group, an alkyl group having 1 to 4 carbon atoms, —OR ⁵⁹ , —COOR ⁶⁰ , —CONHR ⁶¹ , or —SO ₂ NHR ⁶² . . R ^{57 to} R ⁶² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

  In general formula (2), in A, the “substituent” of the phenyl group which may have a substituent is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, cyano Monovalent to trivalent metal salt of an acidic group selected from a group, nitro group, hydroxyl group, carbamoyl group, N-substituted carbamoyl group, sulfamoyl group, N-substituted sulfamoyl group, carboxyl group, sulfo group, carboxyl group or sulfo group (For example, sodium salt, potassium salt, aluminum salt, etc.). Therefore, specific examples of the phenyl group which may have a substituent include a phenyl group, a p-methylphenyl group, a 4-tert-butylphenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, and a 3-carbamoyl group. Phenyl group, 2-chloro-4-carbamoylphenyl group, 2-methyl-4-carbamoylphenyl group, 2-methoxy-4-carbamoylphenyl group, 2-methoxy-4-methyl-3-sulfamoylphenyl group, 4 -Sulfophenyl group, 4-carboxyphenyl group, 2-methyl-4-sulfophenyl group and the like are exemplified, but not limited thereto.

  In addition, even if A has a substituent, the “substituent” of the heterocyclic group includes an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a cyano group, a tro group, a hydroxyl group, and carbamoyl. Group, N-substituted carbamoyl group, sulfamoyl group, N-substituted sulfamoyl group, carboxyl group, sulfo group, monovalent to trivalent metal salt of acidic group selected from carboxyl group or sulfo group (for example, sodium salt, potassium salt) , Aluminum salts, etc.). “Heterocycle” means an atom in which one or more heteroatoms other than carbon atoms are contained in the atoms constituting the ring system, and may be a saturated ring or an unsaturated ring. Further, it may be a single ring or a condensed ring. Therefore, the heterocyclic ring includes pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, isoxazole ring, isothiazole ring. , Triazole ring, thiadiazole ring, oxadiazole ring, quinoline ring, benzofuran ring, indole ring, morpholine ring, pyrrolidine ring, piperidine ring, tetrahydrofuran ring and the like. Therefore, the heterocyclic group means a monovalent group derived by removing a hydrogen atom from these heterocycles. Therefore, specific examples of the heterocyclic group which may have a substituent include 2-pyridyl. Group, 3-pyridyl group, 4-pyridyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 2-imidazolyl group, 2-oxazolyl group Group, 2-thiazolyl group, piperidino group, 4-piperidyl group, morpholino group, 2-morpholinyl group, N-indolyl group, 2-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 2-quinolino group, N -Carbazolyl group etc. are mentioned.

In addition, the alkyl group having 1 to 4 carbon atoms in R ^{51 to} R ⁶² may be linear or branched, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. , Sec-butyl group, and tert-butyl group.

As a naphthol azo pigment which can be used in the present invention, A is preferably a phenyl group which may have a substituent from the viewpoint of spectral characteristics. Furthermore, from the viewpoint of spectral characteristics and dispersibility, R ⁵¹ is preferably an alkyl group having 1 to 4 carbon atoms or —OR ⁶⁷ , and more preferably R ¹ is a methyl group or a methoxy group.

  The naphthol azo pigment of the present invention may have a chemical structure of the general formula (2), or a tautomer thereof, and may be a pigment having any crystal form. It may be a mixed crystal of pigments having a crystal form. The crystal form of these pigments can be confirmed by powder X-ray diffraction measurement or X-ray crystal structure analysis.

  Specific examples of the naphthol azo pigment of the present invention are listed below, but are not limited thereto.

  The naphthol azo pigment represented by the general formula (2) is a water-insoluble pigment having excellent fastness to solvent and light, and by using this pigment, a color filter having excellent spectral characteristics. A coloring composition can be obtained.

  As the colorant (a) in the coloring composition for a color filter of the present invention, a naphthol azo pigment can be used alone or in admixture of two or more.

(Blue pigment)
Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17: 1, 24, 24: 1, 25, 26, And blue pigments such as 56, 60, 61, 62, 63, 64, 75, and 79. Among these, from the viewpoint of satisfying the spectral characteristics desired for the color filter for the image sensor, C.I. I. It is preferable to use an aluminum phthalocyanine pigment such as CI Pigment Blue 79.
Not only the above organic pigments, but also inorganic pigments can be used as long as they satisfy the spectral characteristics desired for the color filter for the image sensor.

[Aluminum phthalocyanine pigment]
The aluminum phthalocyanine pigment is not particularly limited as long as it has a structure in which trivalent aluminum is coordinated at the center of the phthalocyanine ring. In an aluminum phthalocyanine pigment, aluminum is known to have a structure such as a dimer and a trimer in addition to a monomer, because it is trivalent and has a bond in addition to a bond with phthalocyanine. It is also known that the phthalocyanine ring can be chemically modified and can take various structures. The aluminum phthalocyanine pigment in the present invention may take any form such as not only a monomer but also a structure such as a dimer or a trimer, or a chemically modified phthalocyanine ring.

［一般式（３Ａ）中、Ｘ₁〜Ｘ₄はそれぞれ独立して、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいシクロアルキル基、置換基を有してもよい複素環基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルチオ基、または置換基を有してもよいアリールチオ基を表す。
Ｙ_l〜Ｙ₄はそれぞれ独立して、ニトロ基、置換基を有してもよいフタルイミドメチル基、または置換基を有してもよいスルファモイル基を表す。
Ｚは、水酸基、−ＯＰ（＝Ｏ）Ｒ⁴Ｒ⁵、または−Ｏ−ＳｉＲ⁶Ｒ⁷Ｒ⁸を表す。ここでＲ⁴〜Ｒ⁸はそれぞれ独立して、水素原子、水酸基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシル基、または置換基を有してもよいアリールオキシ基を表し、Ｒ同士が互いに結合して環を形成しても良い。ｍ₁〜ｍ₄、ｎ₁〜ｎ₄は、それぞれ独立して０〜４の整数を表し、ｍ₁＋ｎ₁、ｍ₂＋ｎ₂、ｍ₃＋ｎ₃、ｍ₄＋ｎ₄は、各々、０〜４で、同一でも異なっても良い。］ Among these, as the aluminum phthalocyanine pigment of the present invention, those represented by the structure of the following general formula (3A) or the following general formula (3B) are preferable in terms of color characteristics and dispersibility.

[In General Formula (3A), X _{1 to} X ₄ are each independently an alkyl group that may have a substituent, an aryl group that may have a substituent, or a cyclo that may have a substituent. An alkyl group, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or The arylthio group which may have a substituent is represented.
Y _{1 to} Y ₄ each independently represent a nitro group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group.
Z represents a hydroxyl group, —OP (═O) R ⁴ R ⁵ , or —O—SiR ⁶ R ⁷ R ⁸ . Here, R ^{4 to} R ⁸ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkoxyl group that may have a substituent. Or an aryloxy group which may have a substituent, and Rs may be bonded to each other to form a ring. m _{1 to} m ₄ and n _{1 to} n ₄ each independently represents an integer of 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ + n ₃ , m ₄ + n ₄ are each 0 to 4 may be the same or different. ]

［一般式（３Ｂ）中、Ｘ₅〜Ｘ₁₂はそれぞれ独立して、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいシクロアルキル基、置換基を有してもよい複素環基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルチオ基、または置換基を有してもよいアリールチオ基を表す。Ｙ₅〜Ｙ₁₂はそれぞれ独立して、ニトロ基、置換基を有してもよいフタルイミドメチル基、または置換基を有してもよいスルファモイル基を表す。
Ｌは、−Ｏ−ＳｉＲ⁹Ｒ¹⁰−Ｏ−、−Ｏ−ＳｉＲ⁹Ｒ¹⁰−Ｏ−ＳｉＲ¹¹Ｒ¹²−Ｏ−、または−Ｏ−Ｐ（＝Ｏ）Ｒ¹³−Ｏ−を表し、Ｒ⁹〜Ｒ¹³はそれぞれ独立して、水素原子、水酸基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシル基、または置換基を有してもよいアリールオキシ基を表す。ｍ₅〜ｍ₁₂、ｎ₅〜ｎ₁₂は、それぞれ独立して０〜４の整数を表し、ｍ₅＋ｎ₅、ｍ₆＋ｎ₆、ｍ₇＋ｎ₇、ｍ₈＋ｎ₈、ｍ₉＋ｎ₉、ｍ₁₀＋ｎ₁₀、ｍ₁₁＋ｎ₁₁、ｍ₁₂＋ｎ₁₂は、各々、０〜４で、同一でも異なっても良い。］

[In General Formula (3B), X _{5 to} X ₁₂ are each independently an alkyl group that may have a substituent, an aryl group that may have a substituent, or a cyclo that may have a substituent. An alkyl group, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or The arylthio group which may have a substituent is represented. Y _{5 to} Y ₁₂ each independently represent a nitro group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group.
L represents —O—SiR ⁹ R ¹⁰ —O—, —O—SiR ⁹ R ¹⁰ —O—SiR ¹¹ R ¹² —O—, or —O—P (═O) R ¹³ —O—, R ^{9 to} R ¹³ are each independently a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent. The aryloxy group which may have a group is represented. m _{5 to} m ₁₂ and n _{5 to} n ₁₂ each independently represents an integer of 0 to 4, and m ₅ + n ₅ , m ₆ + n ₆ , m ₇ + n ₇ , m ₈ + n ₈ , m ₉ + n ₉ , m ₁₀ + n ₁₀ , m ₁₁ + n ₁₁ , and m ₁₂ + n ₁₂ are each 0 to 4, and may be the same or different. ]

In General Formula (3A), X _{1 to} X ₄ may be the same or different, and specific examples thereof include an alkyl group that may have a substituent, an aryl group that may have a substituent, and a substituent. A cycloalkyl group that may have a group, a heterocyclic group that may have a substituent, an alkoxyl group that may have a substituent, an aryloxy group that may have a substituent, and a substituent. An alkylthio group that may be substituted, and an arylthio group that may have a substituent. When X _{1 to} X ₄ have a substituent, the substituents may be the same or different. Specific examples thereof include a characteristic group such as an amino group, a hydroxyl group, and a nitro group, an alkyl group, an aryl group, Examples thereof include a cycloalkyl group, an alkoxyl group, an aryloxy group, an alkylthio group, and an arylthio group. Moreover, there may be a plurality of these substituents.

  As the “alkyl group” of the alkyl group which may have a substituent, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, Examples include a linear or branched alkyl group such as an n-octyl group, a stearyl group, and a 2-ethylhexyl group. Examples of the “alkyl group having a substituent” include a 2-ethoxyethyl group, a 2-butoxyethyl group, and 2 -Nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group and the like.

  Examples of the “aryl group” of the aryl group which may have a substituent include a phenyl group, a naphthyl group, and an anthryl group, and the “aryl group having a substituent” includes a p-methylphenyl group, p- A nitrophenyl group, p-methoxyphenyl group, 2-aminophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, anthraquinonyl group, 2-aminoanthraquinonyl group and the like can be mentioned.

  Examples of the “cycloalkyl group” of the cycloalkyl group which may have a substituent include a cyclopentyl group, a cyclohexyl group, an adamantyl group and the like, and examples of the “cycloalkyl group having a substituent” include 2,5 -A dimethylcyclopentyl group, 4-tert- butyl cyclohexyl group, etc. are mentioned.

  Examples of the “heterocyclic group” of the heterocyclic group which may have a substituent include a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, an acridinyl group, and the like. "Includes 3-methylpyridyl group, N-methylpiperidyl group, N-methylpyrrolyl group and the like.

  As the “alkoxyl group” of the alkoxyl group which may have a substituent, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyloxy group, 2 , 3-dimethyl-3-pentyloxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group and the like linear and branched alkoxyl groups such as “alkoxyl having a substituent” Examples of the “group” include 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group and the like.

  Examples of the “aryloxy group” of the aryloxy group which may have a substituent include a phenoxy group, a naphthoxy group, an anthryloxy group, and the like, and the “aryloxy group having a substituent” includes p-methyl. Examples include phenoxy group, p-nitrophenoxy group, p-methoxyphenoxy group.

  Examples of the “alkylthio group” of the alkylthio group which may have a substituent include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, and an octadecylthio group. Examples of the “alkylthio group having a substituent” include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, a phenylcarbonylaminoethylthio group, and the like.

  Examples of the “arylthio group” of the arylthio group which may have a substituent include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group, and the like, and “an arylthio group having a substituent” , A cyanophenylthio group, a nitrophenylthio group, a 2-aminophenylthio group, a 2-hydroxyphenylthio group, and the like.

Next, specific examples of Y _{1 to} Y ₄ include a nitro group, an optionally substituted phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N—CH ₂ —), a sulfamoyl group (H ₂ NSO). _2- ). A phthalimidomethyl group having a substituent represents a structure in which a hydrogen atom in the phthalimidomethyl group is substituted by a substituent, and a sulfamoyl group having a substituent is a hydrogen atom in the sulfamoyl group substituted by a substituent. Represents the resulting structure. Preferred Y is a sulfamoyl group. A phthalocyanine compound in which m _{l to} m ₄ is 0 (that is, there is no Y _{l to} Y ₄ ) can also be suitably used. The “substituent” of the phthalimidomethyl group which may have a substituent and the sulfamoyl group which may have a substituent has the same meaning as the substituents of X _{1 to} X ₄ .

Z is a hydroxyl group, represented by —OP (═O) R ⁴ R ⁵ , or —O—SiR ⁶ R ⁷ R ⁸ , wherein R ⁴ and R ⁵ are a hydrogen atom, a hydroxyl group, and a substituent, respectively. Represents an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxyl group that may have a substituent, and an aryloxy group that may have a substituent, R ⁴ , R ⁵ May combine with each other to form a ring.

Here, as the alkyl group in R ⁴ and R ⁵ , methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group, n-octyl group , A linear or branched alkyl group such as a stearyl group or 2-ethylhexyl group, and the substituent when the alkyl group is an alkyl group having a substituent includes an alkoxyl group such as a methoxy group, a phenyl group, There are aromatic groups such as a tolyl group, and nitro groups. Further, there may be a plurality of substituents. Examples of the alkyl group having a substituent include a 2-ethoxyethyl group, a 2-butoxyethyl group, a 2-nitropropyl group, a benzyl group, a 4-methylbenzyl group, a 4-tert-butylbenzyl group, 4 -A methoxy benzyl group, 4-nitro benzyl group, etc. are mentioned.

As the aryl group in R ⁴ and R ⁵ , there are a phenyl group, a naphthyl group, an anthryl group, and the like. When the aryl group has a substituent, the substituent includes an alkyl group, an alkoxyl group, an amino group, a nitro group, and the like. is there. Further, there may be a plurality of substituents. Examples of the aryl group having a substituent include a p-tolyl group, p-nitrophenyl group, p-methoxyphenyl group, 2-dimethylaminophenyl group, 4-methoxy-1-naphthyl group, 6-methyl-2- Examples include naphthyl group and anthraquinonyl group.

Examples of the alkoxyl group in R ⁴ and R ⁵ include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyloxy group, 2,3-dimethyl-3- A linear or branched alkoxyl group such as a pentyloxy group, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group and the like can be mentioned. Examples thereof include aryl groups such as alkoxyl groups, phenyl groups, and tolyl groups, and nitro groups. Further, there may be a plurality of substituents. Examples of the alkoxyl group having a substituent include 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group and the like.

The aryloxy group in R ⁴ and R ⁵ includes a phenoxy group, a naphthaloxy group, an anthryloxy group, and the like. When the aryloxy group has a substituent, the substituent includes an alkyl group, an alkoxyl group, an amino group, There are nitro groups. Further, there may be a plurality of substituents. Examples of the aryloxy group having a substituent include a p-methylphenoxy group, a p-nitrophenoxy group, and a p-methoxyphenoxy group.

As the aluminum phthalocyanine pigment represented by the general formula (3A) used in the present invention, at least one of R ⁴ and R ⁵ may have a substituent from the viewpoint of dispersibility and color characteristics. An aryloxy group which may have an aryl group or a substituent is preferable. More preferably, R ⁴ and R ⁵ are both aryl groups or aryloxy groups. Further preferably, R ⁴ and R ⁵ are both phenyl groups or phenoxy groups.

In General Formula (3A), R ⁶ , R ⁷ and R ⁸ are each independently an alkyl group having 1 to 18 carbon atoms or an aromatic group having 4 or less rings. If the number of carbon atoms in the alkyl group exceeds 18 or the number of aromatic rings exceeds 4, the molecular weight increases and the extinction coefficient per unit weight decreases, so the pigment concentration in the coloring composition must be increased. It is not obtained and is not preferable.

As the alkyl group in R ⁶ , R ⁷ and R ^8, in addition to a straight chain, it may be branched or cyclic, and has a functional group within the total number of heteroatoms of 3 or less. Also good. For example, methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl Group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group 4-dimethylaminophenacyl group, 4-cyanophenacyl group 4-methylphenacyl group, 2-methylphenacyl group, 3-nitrophenacyl group, and the like.

As an aromatic group in R ⁶ , R ⁷ and R ⁸ , the aromatic ring may contain a hetero atom, and each aromatic ring may have a functional group in the range of 2 or less hetero atoms. . Illustrative examples include phenyl, biphenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 9-phenanthryl, 1-pyrenyl, 5-naphthacenyl, 1-indenyl, 2-azurenyl, 9 -Fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group , Quarternaphthalenyl group, heptalenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarteranthracene Nyl group, anthraquinolyl group, phenanthri Group, triphenylenyl group, a pyrenyl group, naphthacenyl group, pleiadenyl group, picenyl group, a perylenyl group, tetraphenylenyl les group, and coronenyl group and the like.

Among the phthalocyanine compounds represented by the general formula (3A) used in the present invention, Z is more preferably —OP (═O) R ⁴ R ⁵ from the viewpoint of heat resistance and light resistance.

In general formula (3B), X _{5 to} X ₁₂ may be the same or different. Specific examples thereof include an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. A cycloalkyl group that may have a group, a heterocyclic group that may have a substituent, an alkoxyl group that may have a substituent, an aryloxy group that may have a substituent, and a substituent. An alkylthio group that may be substituted, and an arylthio group that may have a substituent. When X _{5 to} X ₁₂ have a substituent, the substituents may be the same or different. Specific examples thereof include an alkyl group, an aryl group, a characteristic group such as an amino group, a hydroxyl group, and a nitro group. Examples thereof include a cycloalkyl group, an alkoxyl group, an aryloxy group, an alkylthio group, and an arylthio group. Moreover, there may be a plurality of these substituents.

  As the “alkyl group” of the alkyl group which may have a substituent, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, Examples include a linear or branched alkyl group such as an n-octyl group, a stearyl group, and a 2-ethylhexyl group. Examples of the “alkyl group having a substituent” include a 2-ethoxyethyl group, a 2-butoxyethyl group, and 2 -Nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group and the like.

  Examples of the “aryl group” of the aryl group which may have a substituent include a phenyl group, a naphthyl group, and an anthryl group, and the “aryl group having a substituent” includes a p-methylphenyl group, p- A nitrophenyl group, p-methoxyphenyl group, 2-aminophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, anthraquinonyl group, 2-aminoanthraquinonyl group and the like can be mentioned.

  Examples of the “cycloalkyl group” of the cycloalkyl group which may have a substituent include a cyclopentyl group, a cyclohexyl group, an adamantyl group and the like, and examples of the “cycloalkyl group having a substituent” include 2,5 -A dimethylcyclopentyl group, 4-tert- butyl cyclohexyl group, etc. are mentioned.

  Examples of the “heterocyclic group” of the heterocyclic group which may have a substituent include a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, an acridinyl group, and the like. "Includes 3-methylpyridyl group, N-methylpiperidyl group, N-methylpyrrolyl group and the like.

  As the “alkoxyl group” of the alkoxyl group which may have a substituent, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyloxy group, 2 , 3-dimethyl-3-pentyloxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group and the like linear and branched alkoxyl groups such as “alkoxyl having a substituent” Examples of the “group” include 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group and the like.

  Examples of the “aryloxy group” of the aryloxy group which may have a substituent include a phenoxy group, a naphthoxy group, an anthryloxy group, and the like, and the “aryloxy group having a substituent” includes p-methyl. Examples include phenoxy group, p-nitrophenoxy group, p-methoxyphenoxy group.

  Examples of the “alkylthio group” of the alkylthio group which may have a substituent include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, and an octadecylthio group. Examples of the “alkylthio group having a substituent” include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, a phenylcarbonylaminoethylthio group, and the like.

  Examples of the “arylthio group” of the arylthio group which may have a substituent include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group, and the like, and “an arylthio group having a substituent” , A cyanophenylthio group, a nitrophenylthio group, a 2-aminophenylthio group, a 2-hydroxyphenylthio group, and the like.

Next, as specific examples of Y _{5 to} Y ₁₂ , a nitro group, a phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N—CH ₂ —) which may have a substituent, a sulfamoyl group (H ₂ NSO) _2- ). A phthalimidomethyl group having a substituent represents a structure in which a hydrogen atom in the phthalimidomethyl group is substituted by a substituent, and a sulfamoyl group having a substituent is a hydrogen atom in the sulfamoyl group substituted by a substituent. Represents the resulting structure. Preferred Y is a sulfamoyl group. A phthalocyanine compound in which m _{1 to} m ₄ are 0 (that is, there is no Y _{5 to} Y ₁₂ ) can also be suitably used. The “substituent” of the phthalimidomethyl group which may have a substituent and the sulfamoyl group which may have a substituent has the same meaning as the substituent of X _{5 to} X ₁₂ .

In General Formula (3B), L represents —O—SiR ⁹ R ¹⁰ —O—, —O—SiR ⁹ R ¹⁰ —O—SiR ¹¹ R ¹² —O—, or —O—P (═O) R ¹³ —. O- represents, and R ^{9 to} R ¹³ each independently have a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. An alkoxyl group or an aryloxy group which may have a substituent is represented.

Here, as the alkyl group in R ^{9 to} R ¹³ , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, and an n-octyl group. , A linear or branched alkyl group such as a stearyl group or 2-ethylhexyl group, and the substituent when the alkyl group is an alkyl group having a substituent includes an alkoxyl group such as a methoxy group, a phenyl group, There are aromatic groups such as a tolyl group, and nitro groups. Further, there may be a plurality of substituents. Examples of the alkyl group having a substituent include a 2-ethoxyethyl group, a 2-butoxyethyl group, a 2-nitropropyl group, a benzyl group, a 4-methylbenzyl group, a 4-tert-butylbenzyl group, 4 -A methoxy benzyl group, 4-nitro benzyl group, etc. are mentioned.

As the aryl group in R ^{9 to} R ¹³ , there are a phenyl group, a naphthyl group, an anthryl group, and the like. When the aryl group has a substituent, the substituent includes an alkyl group, an alkoxyl group, an amino group, a nitro group, and the like. is there. Further, there may be a plurality of substituents. Examples of the aryl group having a substituent include a p-tolyl group, p-nitrophenyl group, p-methoxyphenyl group, 2-dimethylaminophenyl group, 4-methoxy-1-naphthyl group, 6-methyl-2- Examples include naphthyl group and anthraquinonyl group.

Examples of the alkoxyl group in R ^{9 to} R ¹³ include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyloxy group, 2,3-dimethyl-3- A linear or branched alkoxyl group such as a pentyloxy group, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group and the like can be mentioned. Examples thereof include aryl groups such as alkoxyl groups, phenyl groups, and tolyl groups, and nitro groups. Further, there may be a plurality of substituents. Examples of the alkoxyl group having a substituent include 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group and the like.

Examples of the aryloxy group in R ^{9 to} R ¹³ include a phenoxy group, a naphthaloxy group, an anthryloxy group, and the like. When the aryloxy group has a substituent, the substituent includes an alkyl group, an alkoxyl group, an amino group, There are nitro groups. Further, there may be a plurality of substituents. Examples of the aryloxy group having a substituent include a p-methylphenoxy group, a p-nitrophenoxy group, and a p-methoxyphenoxy group.

The phthalocyanine compound represented by the general formula (3B) used in the present invention includes at least one of R ^{9 to} R ¹⁰ and R ^{9 to} R ¹² and R ₁₃ from the viewpoint of the viscosity and color characteristics of the dispersion. Is preferably an aryl group which may have a substituent or an aryloxy group which may have a substituent. More preferably, R ^{9 to} R ¹⁰ , R ^{9 to} R ¹² , and R ¹³ are all aryl groups or aryloxy groups. Further preferably, R ^{9 to} R ¹⁰ , R ^{9 to} R ¹² , and R ¹³ are all phenyl groups or phenoxy groups.

(Orange or yellow pigment)
Examples of the orange pigment or yellow pigment include C.I. I. Pigment orange 1, 2, 3, 5, 15, 16, 17, 17: 1, 40, 43, 48, 49, 62, 64, 65, 68, 71, 73, 81 or the like, or C.I. I. Pigment Yellow 1, 4, 5, 7, 9, 18, 24, 61, 62, 65, 74, 100, 101, 104, 108, 115, 117, 120, 123, 129, 133, 139, 147, 150, 151, 153, 154, 155, 167, 169, 175, 177, 179, 180, 181, 182, 185, 191, 193, 194, 198, 199, 213 and the like.
Not only the above organic pigments, but also inorganic pigments can be used as long as they satisfy the spectral characteristics desired for the color filter for the image sensor.

(Purple pigment)
Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 13, 19, 25, 27, 29, 32, 37, 39, 44, 50, etc. Violet pigments.
Not only the above organic pigments, but also inorganic pigments can be used as long as they satisfy the spectral characteristics desired for the color filter for the image sensor.

(Red dye)
Examples of red dyes include xanthene, azo (pyridone, barbituric acid, metal complex, etc.), disazo, and anthraquinone dyes.

(Blue dye)
Examples of blue dyes include phthalocyanine, anthraquinone, triarylmethane, and methylene blue dyes.

(Orange or yellow dye)
Examples of orange dyes or yellow dyes include quinoline, azo (pyridone, barbituric acid, metal complex, etc.), disazo, methine, anthraquinone, cyanine, naphthoquinone, and quinophthalone dyes. It is done.

(Purple dye)
Examples of purple dyes include xanthene, methine, and triarylmethane dyes.

  Among these dyes, a salt forming compound of a xanthene acid dye and / or a salt forming compound of a triarylmethane basic dye and / or a general formula (from the viewpoint of satisfying spectral characteristics desired for a color filter for an image sensor) It is preferable to use a quinophthalone dye represented by 4).

[Salt-forming compound consisting of xanthene acid dye and quaternary ammonium salt compound]
The xanthene-based acid dye has a dye form and exhibits a red color or a purple color.
A red or purple color means C.I. I. Acid Red, C.I. Acid dyes such as I. Acid Violet, C.I. I. Direct Red, C.I. I. It belongs to direct dyes such as direct violet. Here, since the direct dye has a sulfonic acid group, it is regarded as synonymous with an acid dye in the present invention.
Further, the salt-forming compounds belong to salt-forming dyes that are salted and modified with these xanthene acid dyes (including direct dyes) and quaternary ammonium salt compounds that are cation components that act as counter ions.

《Xanthene acid dye》
The acidic dye of the xanthene dye will be described. Examples of acidic dyes of xanthene dyes include C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 289, Acid Rhodamine G, C.I. I. Acid Violet 9, C.I. I. It is preferable to use the acid violet 30.
Among them, C.I. I. Acid Red 52, C.I. I. It is preferable to use Acid Red 289.

  In the transmission spectrum, the xanthene acid dye used in the present invention has a transmittance of 90% or more in the region of 650 nm, a transmittance of 75% or more in the region of 600 nm, a transmittance of 5% or less in 550 nm, and a region of 400 nm. Those having a transmittance of 70% or more are preferred. More preferably, the transmittance is 95% or more in the region of 650 nm, the transmittance is 80% or more in the region of 600 nm, the transmittance of 550 nm is 10% or less, and the transmittance is 75% or more in the region of 400 nm.

  As the xanthene acid dye, a rhodamine acid dye is preferably used in terms of excellent color developability.

<Quaternary ammonium salt compound>
Next, the quaternary ammonium salt compound as the cation component of the xanthene acid dye will be described.

A preferable form of the quaternary ammonium salt compound which is a cation component of the salt-forming compound is colorless or white.
Here, colorless or white means a so-called transparent state, and is defined as a state where the transmittance is 95% or more, preferably 98% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Is. That is, it is necessary not to inhibit color development of the dye component and to cause no color change.

The molecular weight of the cation moiety that is the counter component of the quaternary ammonium salt compound is preferably in the range of 190-900. Here, the cation moiety corresponds to the (NR ¹⁴ R ¹⁵ R ¹⁶ R ¹⁷ ) + moiety in the following general formula (4). If the molecular weight is smaller than 190, light resistance and heat resistance may be lowered, and further solubility in a solvent may be lowered. On the other hand, when the molecular weight is larger than 900, the ratio of the coloring component in the molecule is lowered, the coloring property is lowered, and the spectral characteristics may be deteriorated. More preferably, the molecular weight of the cation moiety is in the range of 240-850. Particularly preferred is a molecular weight of the cationic moiety in the range of 350-800.
Here, the molecular weight was calculated based on the structural formula. The atomic weight of C was 12, the atomic weight of H was 1, and the atomic weight of N was 14.

[一般式（４）中、Ｒ¹⁴〜Ｒ¹⁷ は、それぞれ独立に、炭素数１〜２０のアルキル基またはベンジル基を示し、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷の少なくとも２つ以上がＣの数が５〜２０個である。Ｙ^-は無機または有機のアニオンを表す。] Moreover, what is represented by following General formula (4) is used as a quaternary ammonium salt compound.

[In General Formula (4), R ^{14 to} R ¹⁷ each independently represents an alkyl group having 1 to 20 carbon atoms or a benzyl group, and at least two of R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are The number of C is 5-20. Y ^- is representative of an inorganic or organic anion. ]

The solubility with respect to a solvent becomes favorable because the number of at least 2 or more C of R < ¹⁴ > -R < ¹⁷ > shall be 5-20. If the number of alkyl groups having a C number of less than 5 is 3 or more, the solubility in a solvent is deteriorated, and coating film foreign matter is likely to be generated. Further, if there is an alkyl group in which the number of C exceeds 20, the color forming property of the salt-forming compound is impaired.

  Specifically, tetramethylammonium chloride (molecular weight of the cation moiety is 74), tetraethylammonium chloride (molecular weight of the cation moiety is 122), monostearyltrimethylammonium chloride (molecular weight of the cation moiety is 312), distearyldimethylammonium chloride ( Cation portion molecular weight 550), tristearyl monomethylammonium chloride (cation portion molecular weight 788), cetyltrimethylammonium chloride (cation portion molecular weight 284), trioctylmethylammonium chloride (cation portion molecular weight 368), dioctyl Dimethylammonium chloride (cation part molecular weight 270), monolauryltrimethylammonium chloride (cation part molecule) 228), dilauryldimethylammonium chloride (cation part molecular weight 382), trilaurylmethylammonium chloride (cation part molecular weight 536), triamylbenzylammonium chloride (cation part molecular weight 318), trihexylbenzylammonium Chloride (cation part molecular weight 360), trioctylbenzylammonium chloride (cation part molecular weight 444), trilaurylbenzylammonium chloride (cation part molecular weight 612), benzyldimethylstearyl ammonium chloride (cation part molecular weight 388) ), And benzyldimethyloctylammonium chloride (the molecular weight of the cation moiety is 248), dialkyl (alkyl is C14 to C18) Dimethyl ammonium chloride (hydrogenated tallow) (molecular weight of the cationic moiety is from 438 to 550) is preferably used and the like.

The component of Y ⁻ constituting the anion may be an inorganic or organic anion, but is preferably a halogen, usually chlorine. The component of Y ⁻ constituting the anion forms a salt with a counter cation of the xanthene acid dye when salting with the xanthene acid dye, and is removed by washing with water or the like.

  Specific examples of the quaternary ammonium salt compound products include Cotamin 24P, Cotamin 86P Conch, Cotamin 60W, Cotamin 86W, Cotamin D86P, Sanizole C, Sanizole B-50, etc. manufactured by Lion Corp. 2C-75, 2HT-75, 2HT flakes, 2O-75I, 2HP-75, 2HP flakes, etc., among others, Cotamine D86P (distearyldimethylammonium chloride), Arcard 2HT-75 (dialkyl (alkyl is C14 to C18). ) Dimethylammonium chloride) is preferred.

  The quaternary ammonium salt compound is in the form of a resin having an amino group and an ammonium group in the side chain, and having a cationic group in the side chain that can react with a xanthene-based acid dye and form a salt by chlorination. May be.

《Chlorination treatment》
A salt-forming compound of a xanthene acid dye and a quaternary ammonium salt compound can be synthesized by a conventionally known method. A specific method is disclosed in Japanese Patent Laid-Open No. 11-72969.
For example, after the xanthene acid dye is dissolved in water, the quaternary ammonium salt compound is added and the chlorination treatment may be performed while stirring. Here, a salt-forming compound in which the sulfonic acid group (—SO ₃ H, —SO ₃ Na) portion in the xanthene-based acid dye and the ammonium group (NH ₄ +) portion of the quaternary ammonium salt compound are combined is obtained. In addition, instead of water, methanol and ethanol are also solvents that can be used for the chlorination.

  Salt-forming compounds are especially C.I. I. Acid Red 52 and C.I. I. By setting the molecular weight of the counter, which is a cationic component of Acid Red 289 and the quaternary ammonium salt compound, to 350 to 800, the solvent solubility is excellent, and the heat resistance, light resistance, and solvent resistance are excellent.

[Salt-forming compounds of triarylmethane basic dyes]
A salt-forming compound of a triarylmethane-based basic dye is blue or purple. That is, the salt-forming compound that can be preferably used in this coloring composition is C.I. I. Basic Blue, C.I. I. It is a salt-forming compound obtained by using a basic dye classified as basic violet and the like and an anionic compound, particularly a colorless anionic compound, as a counter.
Colorless in the present invention means a so-called transparent state, and is defined as a state in which the transmittance is 80% or more, preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. is there.

For example, the basic dye and the counter compound can form a salt-forming compound by dissolving both in an aqueous solution or an alcohol solution. Alternatively, it is also possible to obtain a salt-forming compound by melting and kneading them while heating them.
Although basic dyes have good spectral characteristics, they are extremely poor in light resistance and heat resistance like common dyes. That is, the basic dye has insufficient characteristics for use in a color filter of a color display device or a color imaging device that requires high reliability.
Therefore, it is preferable to replace the anion of the basic dye with an anion having a higher molecular weight. Preferably, this salt-forming compound is modified with a resin having an acid group.
The molecular weight of the counter compound is preferably in the range of 200-3500. The molecular weight of the counter compound is more preferably in the range of 250-3500, and more preferably in the range of 300-3500. Or it is preferable that the molecular weight of a counter compound exists in the range of 200-750. When a counter compound having a small molecular weight is used, it is difficult to achieve sufficient heat resistance and light resistance. When a counter compound having a large molecular weight is used, it is difficult for a salt-forming compound to exist in a large mole number in a unit volume, and sufficient color development is difficult.

《Triarylmethane basic dye》
Specific examples of the triarylmethane basic dye that can be used include C.I. I. Basic violet 1 (methyl violet), 3 (crystal violet), 14 (Magenta), C.I. Examples include I. Basic Blue 7 (Victoria Pure Blue BO) and 26 (Victoria Blue B conc.). Among them, C.I. I. Basic Blue 7, Violet 1 and Violet 3 are preferably used. The halogen component constituting the anion contained in the triphenylmethane-based basic dye forms a salt with the cation of the acidic counter compound during salt formation with the acidic counter compound, and is removed by washing or the like.

The triarylmethane basic dye develops color when the NH ₂ or OH group located in the para position with respect to the central carbon takes a quinone structure by oxidation. Depending on the number of NH ₂ and OH groups, it can be divided into the following three types. Among them, the triaminotriphenylmethane type basic dye is preferable in terms of good blue color development.
a) Diaminotriphenylmethane-based basic dye b) Triaminotriphenylmethane-based basic dye c) Rosolic acid-based basic dye having an OH group Triaminotriphenylmethane-based basic dye, Diaminotriphenylmethane-based basic dye The dye has a clear color tone and is excellent in sunlight fastness than the other dyes and is preferable. Further, diphenylnaphthylmethane basic dye and / or triphenylmethane basic dye are preferable.

  The blue triarylmethane basic dye has spectral characteristics having a high transmittance at 400 to 440 nm.

《Counter compound》
The counter compound used in the salt-forming compound of the triarylmethane-based basic dye is an anionic compound, and specifically includes, for example, heteropolyacids, organic sulfonic acids such as aromatic sulfonic acids, and aromatic carboxylic acids. Organic acids that are organic carboxylic acids such as acids and fatty acids, and acid dyes. The counter compound is preferably an organic sulfonic acid or an acid dye. Moreover, since the molecular weight of a counter compound is the range of 250-3500, since it is more excellent in terms of tolerance, it is preferable.

  The molecular weight and average molecular weight specified here are values obtained by rounding off the first decimal place of the theoretical value calculated based on the molecular structure and atomic weight. In addition, when the counter compound is a sodium salt, the molecular weight and the average molecular weight defined here mean a molecular value obtained by replacing sodium with hydrogen.

((Heteropolyacid))
Examples of the heteropolyacid include phosphotungstic acid H3 (PW12O40) .nH2O (n≈30; ≒ represents nearly equal) (molecular weight 3421), silicotungstic acid H4 (SiW12O40) .nH2O (n≈30) (molecular weight 3418) ), Phosphomolybdic acid H3 (PMo12O40) .nH2O (n.apprxeq.30) (molecular weight 2205), silicomolybdic acid H3 (SiMo12O40) .nH2O (n.apprxeq.30) (molecular weight 2202), phosphotungstomolybdate H3 (PW12-XMoXO40) NH2O (n≈30) (6 <X <12) and phosphovanadomolybdic acid H15-X (PV12-XMoXO40) nH2O (n≈30).
Lintangst molybdic acid, phosphovanadomolybdic acid, and silicotungsto molybdic acid have a molecular weight in the range of 2202 to 3421 by changing the content of components such as phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, and silicomolybdic acid. Can be adjusted.
When heteropolyacid is used as the counter compound, the average molecular weight is preferably in the range of 2820-3421. This is because when the counter compound contains molybdenum and tungsten, the proportion of tungsten is preferably more than 50%. In the case of phosphotungstomolybdic acid, a colorant having excellent transparency can be obtained by reducing the Mo content and containing a large amount of W.

((Organic acid))
As the organic sulfonic acid, for example, aromatic sulfonic acid can be used. Preferred compounds as the aromatic sulfonic acid include, for example, 1-naphthylamine-4,8-disulfonic acid (molecular weight 303), 1-naphthylamine-3,8-disulfonic acid (molecular weight 303), 1-naphthylamine-5,7-disulfone. Acid (molecular weight 303), 1-naphthylamine-3,6-disulfonic acid (molecular weight 303), 1-naphthylamine-3,6,8-trisulfonic acid (kofoic acid) (molecular weight 383), 2-naphthylamine-6,8 -Disulfonic acid (molecular weight 303), 2-naphthylamine-1,6-disulfonic acid (molecular weight 303), 2-naphthylamine-4,8-disulfonic acid (molecular weight 303), 2-naphthylamine-3,6-disulfonic acid (amino) -R acid) (molecular weight 303), 2-naphthylamine-5,7-disulfonic acid (amino J acid) (molecular weight) 03), 1-naphthol-4,8-disulfonic acid (molecular weight 304), 1-naphthol-3,8-disulfonic acid (ε acid) (molecular weight 304), 1-naphthol-3,6-disulfonic acid (molecular weight 304) ), 1-naphthol-3,6,8-trisulfonic acid (molecular weight 384), 2-naphthol-6,8-disulfonic acid (molecular weight 304), 2-naphthol-3,6-disulfonic acid (R acid) ( Molecular weight 304), 2-naphthol-3,6,8-trisulfonic acid (molecular weight 384), N-phenyl-1-naphthylamine-8-sulfonic acid (molecular weight 299), Np-tolyl-1-naphthylamine-8 -Sulfonic acid (molecular weight 313), N-phenyl-1-naphthylamine-5-sulfonic acid (molecular weight 299), N-phenyl-2-naphthylamine-6-sulfonic acid (min 299), N-acetyl-7-amino-1-naphthol-3-sulfonic acid (molecular weight 281), N-phenyl-7-amino-1-naphthol-3-sulfonic acid (molecular weight 315), N-acetyl -6-amino-1-naphthol-3-sulfonic acid (molecular weight 281), N-phenyl-6-amino-1-naphthol-3-sulfonic acid (molecular weight 315), 1,8-dihydro-3,6-disulfone Acid (chromotropic acid) (molecular weight 320), 8-amino-1-naphthol-3,6-disulfonic acid (molecular weight 319), 8-amino-1-naphthol-5,7-disulfonic acid (molecular weight 319), 1 , 6-Diamino-2-naphthol-4-sulfonic acid (molecular weight 254), 1-amino-2-naphthol-6,8-disulfonic acid (molecular weight 319), 1-amino-2 Naphthol-3,6-disulfonic acid (molecular weight 319), 2,8-diamino-1-naphthol-5,7-disulfonic acid (molecular weight 334), 2,7-diamino-1-naphthol-3-sulfonic acid (molecular weight) 254), 2,6-diamino-1-naphthol-3-sulfonic acid (molecular weight 254), 2,8-diamino-1-naphthol-3,6-disulfonic acid (molecular weight 334), and 2-amino-7- And phenylamino-1-naphthol-3-sulfonic acid (molecular weight 330).

  It is also preferable to use anthracene sulfonic acid (molecular weight 258), anthraquinone-2-sulfonic acid, or anthraquinone-1-sulfonic acid (molecular weight 288).

  When naphthylamine sulfonic acid having one amino group and one sulfonic acid group is used, excellent heat resistance and light resistance can be achieved. Examples of naphthylamine sulfonic acid include 2-amino-1-naphthalene sulfonic acid (tobias acid, molecular weight 223), 4-amino-1-naphthalene sulfonic acid (naphthoic acid, molecular weight 223), and 8-amino-1-naphthalene sulfone. Acid (peric acid, molecular weight 223), 2-amino-6-naphthalenesulfonic acid (brennic acid, molecular weight 223), 1-amino-5-naphthalenesulfonic acid (Lorentzic acid, molecular weight 223), 5-amino-2-naphthalene Sulfonic acid (molecular weight 223), 1-amino-6-naphthalenesulfonic acid (molecular weight 223), 6-amino-1-naphthalenesulfonic acid (molecular weight 223), and 3-amino-1-naphthalenesulfonic acid (molecular weight 223) Can be mentioned. Among these, 2-amino-1-naphthalenesulfonic acid (tobias acid, molecular weight 223) is particularly preferable in terms of color characteristics and resistance.

  It is also preferable to use hydroxynaphthalenesulfonic acid having one hydroxyl group and one sulfonic acid group. Examples of the hydroxy naphthalene sulfonic acid include 2-hydroxy-6-naphthalene sulfonic acid (shephatic acid, molecular weight 224), 1-hydroxy-4-naphthalene sulfonic acid (nevir-winter acid: NW acid, molecular weight 224), 1- Examples include hydroxy-5-naphthalenesulfonic acid (L acid, molecular weight 224), and 2-hydroxy-8-naphthalenesulfonic acid (croseinic acid, molecular weight 224).

  Among them, an organic sulfonic acid having 2 to 3 sulfonic acid groups is preferable in that it has good color developability and can achieve excellent spectral characteristics. When there are 4 or more sulfonic acids, environmental stability deteriorates and changes with time are likely to occur. With one sulfonic acid, the basic dye and the counter compound react in a 1: 1 ratio, and color is generated when the main color is used. May be worse.

  However, in the case of an organic sulfonic acid having a molecular weight in the range of 200 to 250, the molecular weight of the counter compound is small, so even if there is one sulfonic acid group per molecule, the color developability is not impaired. .

  As the organic carboxylic acid, for example, an aromatic carboxylic acid or a fatty acid can be used. Specific examples of the organic carboxylic acid include palmitic acid (molecular weight 257), stearic acid (molecular weight 285), arachidic acid (molecular weight 313), behenic acid (molecular weight 341), lignoceric acid (molecular weight 369), and oleic acid (molecular weight). 282), elaidic acid (molecular weight 282), erucic acid (molecular weight 339), nervonic acid (molecular weight 367), linoleic acid (molecular weight 280), gamolenic acid (molecular weight 278), arachidonic acid (molecular weight 305), α-linolenic acid ( Molecular weight 278), stearidonic acid (molecular weight 276), eicosapentaenoic acid (molecular weight 302), and docosahexaenoic acid (molecular weight 328).

((Acid dye))
The hue can also be controlled by using an acid dye as the counter compound.
Preferred acid dyes are C.I. I. Acid Red 52 (Acid Rhodamine B) (molecular weight 580), C.I. I. Acid Red 289 (molecular weight 676.7) and the like.

  In the case of an acid dye, a more preferable molecular weight range is 300 to 750. More preferably, it is the range of 350-700. By setting the molecular weight within this range, a colorant having a good balance between weather resistance and coloring power can be obtained, which is preferable.

<Additives to salt-forming compounds>
The salt-forming compound is a resin having an acid group, for example, a resin having an acid group such as rosin-modified maleic acid resin and rosin-modified fumaric acid resin, rosin ester, polyester resin, or acid value. When the styrene-acrylic copolymer and the like are added, the compatibility and dispersibility in the binder resin and the dispersibility in the solvent are greatly improved. As a result, further excellent color developability, heat resistance and light resistance can be realized. Here, the acid group is preferably a carboxyl group (—COOH) or a sulfonic acid group (for example, —SO 3 H or —SO 3 Na).
The weight average molecular weight of the resin having an acid group is preferably in the range of 400 to 12000, more preferably in the range of 400 to 6000, and in the range of 400 to 2000. Is more preferable. Such a resin is excellent in compatibility with the salt-forming compound. Therefore, when this resin is used, the dispersion of the salt-forming compound in the binder resin is improved.

The weight average molecular weight of the resin having an acid group is measured as follows.
Tetrahydrofuran (THF) is added to the specimen and left for 12 hours. Thereafter, the THF solution of the specimen is filtered, and the molecular weight of the specimen dissolved in the filtrate is measured. For measurement, gel permeation chromatography (GPC) method is used, and molecular weight is calculated from a calibration curve prepared using standard polystyrene. Below, an example of measurement conditions is described.
GPC device: HLC-8120GPC manufactured by Tosoh Corporation
Column: TOS Guard Co., Ltd. TSK Guardcolumn Super H-HT / SK-GEL / Super HM-M 3 flow rate: 1.0 ml / min (THF)
As the resin having an acid group, a rosin-modified maleic acid resin is preferably used. The rosin-modified maleic resin has an acid-containing polar group and a nonpolar rosin skeleton. The polar group having this acid is a carboxyl group derived from unreacted abietic acid and a carboxyl group of maleic acid, and reacts and is compatible with the polar group of the binder resin. On the other hand, the nonpolar rosin skeleton is compatible with the nonpolar part of the binder resin. Furthermore, the polar group having an acid of the rosin-modified maleic resin reacts with the amino group of the basic dye (unreacted basic dye in the salt-forming compound).

The acid value of the resin having an acid group is preferably in the range of 100 to 300 mgKOH / g. If the acid value is small, the compatibility between the resin and the salt-forming compound may be insufficient. Moreover, when an acid value is large, when this coloring composition is used as an alkali development type coloring resist mentioned later, it will be easy to produce image development defect. Here, the acid value is a value measured by a method defined in JIS K-0070.
Mixing of the salt-forming compound and the resin having an acid group is performed, for example, by the following method.
(1) A method of mixing a resin dissolved in a solvent and a salt-forming compound (2) A method of mixing a molten resin and a salt-forming compound Mixing may be performed by other methods.

Specific examples of the mixing methods (1) and (2) are described below. Here, an example using a triarylmethane basic dye and a rosin-modified maleic resin is shown.
(1) Method of mixing resin dissolved in solvent and salt-forming compound (1-1)
A triarylmethane-based basic dye is dissolved in water, and a counter compound such as an organic sulfonic acid is added to the solution while stirring the solution. As a result, the amino group (-NHC2H5) of the triarylmethane basic dye and the acid group of the counter compound are bonded to obtain a salt-forming compound. Prior to the salt formation reaction, the counter compound may be dissolved in an alkali solution such as sodium hydroxide and used, for example, in the form of sodium sulfonate (-SO3Na).
(1-2)
Next, the rosin-modified maleic resin is added to the previous liquid containing the salt-forming compound. Specifically, first, an alkaline aqueous solution such as an aqueous sodium hydroxide solution is added to the liquid containing the salt-forming compound to adjust the liquid to neutrality. Next, rosin-modified maleic resin dissolved in an alkaline aqueous solution is added to this solution, and this is stirred. Thereafter, mineral acid such as hydrochloric acid and sulfuric acid is added to the solution to adjust the solution to be acidic. This insolubilizes the rosin-modified maleic resin. Further, filtration, washing and drying are performed to obtain a colored composition. If necessary, the colored composition may then be pulverized to a desired particle size.

(2) Method of mixing molten resin and salt-forming compound A salt-forming compound and a resin having an acid group, here a rosin-modified maleic acid resin, are heated kneader, Banbury mixer, three roll mill, It puts into kneading machines, such as a two roll mill, a vibration mill, a ball mill, an attritor, and an extruder, and performs melt kneading at a temperature higher than the softening point of the resin having an acid group. Thereby, the salt-forming compound is uniformly dispersed in the resin having an acid group. In addition, the coloring composition obtained here exists in the form with which the resin which has an acid group was coat | covered with the salt-forming compound. Further, the coloring composition is crushed and pulverized to adjust to a desired particle size.

[一般式（５）中、Ｒ¹⁸〜Ｒ²³は、それぞれ独立に水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアリール基、または−ＯＲ²⁴を表す。
Ｒ²⁴は、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、または置換基を有してもよいアリール基である。
ただし、Ｒ¹⁸〜Ｒ²³が全て水素原子になる事はない。] [Quinophthalone dye represented by the general formula (5)]

[In General Formula (5), R ^{18 to} R ²³ may each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. aryl group or an -OR ^24,.
R ²⁴ is an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent.
However, R ^{18 to} R ²³ are not all hydrogen atoms. ]

The alkyl group which may have a substituent in R ^{18 to} R ²⁴ is a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or a case having 2 to 18 carbon atoms. Includes a linear, branched, monocyclic or condensed polycyclic alkyl group containing one or more ether bonds (—O—). Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, nonyl group, decyl group, dodecyl group, octadecyl group, trifluoromethyl group, isopropyl group, isobutyl group, isopentyl group, 2-ethylhexyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert- A pentyl group, a tert-octyl group, a neopentyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, a 4-decylcyclohexyl group, and the like can be mentioned. It is not something.

Specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and optionally including one or more ester bonds include —CH ₂ —CH ₂ —CH ₂ —COO—CH ₂ —CH ₃ , _{-CH 2 -CH (-CH 3) -CH} 2 -COO-CH 2 -CH 3, -CH 2 -CH 2 -CH 2 -OCO-CH 2 -CH 3, -CH 2 -CH 2 -CH 2 - _{CH 2 -COO-CH 2 -CH (} -CH 2 -CH 3) -CH 2 -CH 2 -CH 2 -CH 3, - (CH 2) 5 -COO- (CH 2) 11 -CH 3, -CH _{2 -CH 2 -CH 2 -CH (-COO} -CH 2 -CH 3) can be exemplified _2, etc., but is not limited thereto.

Specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and optionally including one or more ether bonds include —CH ₂ —O—CH ₃ , —CH ₂ —CH ₂ —. O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) n—CH ₃ (where n is 1 to 8). ), - (CH ₂ is _{-CH 2 -CH 2 -O) m-} CH 3 (m here is 5 _{1), - CH 2 -CH (} CH 3) -O-CH 2 -CH 3 -, Examples include —CH ₂ —CH— (OCH ₃ ) _2, but are not limited thereto.

Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and optionally including one or more ether bonds include the following, but are not limited thereto. Absent.

Examples of the alkenyl group which may have a substituent in R ^{18 to} R ²⁴ include a linear, branched, monocyclic or condensed polycyclic alkenyl group having 1 to 18 carbon atoms. They may have a plurality of carbon-carbon double bonds in the structure. Specific examples include vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4- Pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3-butadienyl group, cyclohexadienyl group, cyclopenta Although a dienyl group etc. can be mentioned, it is not limited to these.

The aryl group which may have a substituent in R ^{18 to} R ²⁴ is a substituted or unsubstituted monocyclic or condensed polycyclic aromatic group having 6 to 18 carbon atoms, such as a phenyl group, 1- Naphthyl group, 2-naphthyl group, p-biphenyl group, m-biphenyl group, 2-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 2-fluorenyl group, 3- Fluorenyl group, 9-fluorenyl group, 1-pyrenyl group, 2-pyrenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 4-methylbiphenyl group, terphenyl group, 4- Methyl-1-naphthyl group, 4-tert-butyl-1-naphthyl group, 4-naphthyl-1-naphthyl group, 6-phenyl-2-naphthyl group, 10-phenyl-9-an A tolyl group, a spirofluorenyl group, a 4-maleimidylphenyl group, a 2-benzocyclobutenyl group, and the like can be given.

  The specific quinophthalone dye can be obtained by reacting the corresponding 2-methylquinoline and naphthalenedicarboxylic anhydride in benzoic acid at a high temperature as shown in the following reaction formula.

  In addition, although the specific quinophthalone dye of the general formula (5) of the present invention has a tautomer, the tautomer is also within the scope of the right of the present invention.

  Although the specific example of the specific quinophthalone dye which can be used for the green coloring composition for color filters of this invention is given below, it is not limited to these.

(Miniaturization of pigment)
When the colorant used in the coloring composition of the present invention is a pigment, it can be refined by a salt milling process or the like. It is preferable that the average primary particle diameter calculated | required by TEM (transmission electron microscope) of a pigment is the range of 5-90 nm. If the thickness is smaller than 5 nm, dispersion in an organic solvent becomes difficult. If the thickness is larger than 90 nm, sufficient spectral characteristics may not be obtained. For these reasons, a more preferable average primary particle size is in the range of 10 to 70 nm.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

<Resin [B]>
[Binder resin]
The binder resin disperses, dyes, or penetrates the colorant, and examples thereof include a thermoplastic resin. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

  In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain as an alkali development type colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. As a result, the colorant is fixed, heat resistance is improved, and fading (deterioration of spectral characteristics) due to heat of the colorant can be suppressed. In addition, there is also an effect of suppressing aggregation and precipitation of the colorant component in the development process.

  The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When the binder resin is used as a photosensitive coloring composition for a color filter, a colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that acts as an affinity group for the colorant carrier and solvent, and The balance of the aromatic group is important for the dispersibility, penetrability, developability and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  The binder resin is preferably used in an amount of 20 parts by weight or more with respect to 100 parts by weight of the total weight of the colorant [A] because the film formability and various resistances are good, and the colorant concentration is high and good. Since color characteristics can be expressed, it is preferably used in an amount of 1000 parts by weight or less.

  Examples of the thermoplastic resin used for the binder resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate. , Polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. . Among them, it is preferable to use an acrylic resin.

Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group.
Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (i) and (ii).

[Method (i)]
As the method (i), for example, the side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers is used. Then, the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to convert the unsaturated ethylenic double bond and the carboxyl group into There is a way to introduce.

Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 2-glycidoxyethyl (meth).
An acrylate, 3,4 epoxy butyl (meth) acrylate, and 3,4 epoxy cyclohexyl (meth) acrylate are mentioned, These may be used independently or may use 2 or more types together. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth)
Acrylate is preferred.

Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro,
Examples thereof include monocarboxylic acids such as cyano-substituted products, and these may be used alone or in combination of two or more.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like.
More than one type may be used together. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of a carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an unsaturated ethylenic monomer having a hydroxyl group is used, and a monomer of an unsaturated monobasic acid having another carboxyl group or another monomer is copolymerized. There is a method of reacting an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group with a side chain hydroxyl group of the obtained copolymer.

Examples of the unsaturated ethylenic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3
-Or 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, or hydroxyalkyl (meth) acrylates such as cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in two types The above may be used together. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

[Thermosetting compound]
In the present invention, a thermosetting compound may be further contained in combination with the thermoplastic resin which is a binder resin.

  Examples of the thermosetting compound include epoxy compounds and / or resins, benzoguanamine compounds and / or resins, rosin-modified maleic acid compounds and / or resins, rosin-modified fumaric acid compounds and / or resins, melamine compounds and / or resins, Examples include urea compounds and / or resins, phenol compounds and / or resins, but the present invention is not limited thereto.

<Organic solvent>
In the coloring composition of the present invention, the coloring agent is sufficiently dispersed and permeated in the coloring agent carrier, and is applied onto a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent is included to facilitate the formation. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl- 1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, N, N-dimethyl Acetamide, N, N-dimethylformamide, n-butyl alcohol, n-butyl Benzene, n-propyl acetate, o-xylene, o-diethylbenzene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol Monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl Ether, ethylene glycol Dimonomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene Glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl Chill ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol Monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, Acetic acid Propyl, and dibasic acid esters.
These solvents can be used alone or in admixture of two or more at any ratio as required.

  Among them, the dispersibility of the coloring agent, the penetrability, and the coating property of the coloring composition are good, so that ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

  Moreover, since the organic solvent can adjust a coloring composition to an appropriate viscosity and can form the colored film of the target uniform film thickness, it is the quantity of 500-4000 weight part with respect to 100 weight part of colorants [A]. It is preferable to use in.

<Photopolymerizable monomer>
Photopolymerizable monomers that may be added to the colored composition of the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

  The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant [A], and 10 to 300 parts by weight from the viewpoint of photocurability and developability. Is more preferable.

<Photopolymerization initiator>
In the colored composition of the present invention, a photopolymerization initiator is added to form a filter segment by photolithography by curing the composition by ultraviolet irradiation, and a solvent development type or alkali development type photosensitive coloring composition is added. It can be prepared in the form of Further, the photopolymerization initiator used in the present invention preferably does not contain a halogen atom.

Examples of the photopolymerization initiator include diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- ( Methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone Or an acetophenone-based compound such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyldimethyl ketal Benzoin compounds such as benzophenone and benzoylbenzoate , Methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone Benzophenone compounds such as thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 1,2-octanedione, 1- [4- (phenylthio) )-, 2- (O-benzoyloxime)], or O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine and other oxime ester systems Conversion Phosphinic compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, etc. Quinone compounds; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The content of the photopolymerization initiator is preferably 2 to 200 parts by weight with respect to 100 parts by weight of the colorant [A], and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability. preferable.

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno And 4,4′-diethylaminobenzophenone.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the colored composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Antioxidant>
The coloring composition for a color filter of the present invention can contain an antioxidant. Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the color filter coloring composition from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. Can be high. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. In addition, the antioxidant used in the present invention preferably does not contain a halogen atom.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

  As the hindered phenol-based antioxidant, 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di- -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2'-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-butylidene-bis- (2-tert-butyl-5-methylphenol), 2,2'-thio- Su- (6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2′thiodiethylbis- (3,5-di-t-butyl-4-hydroxyphenyl) ) -Propionate, 1,1,3-tris- (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -butane, 2,2′-methylene-bis- (6- (1-methyl) -Cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydro Cinnamamide) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

  Examples of hindered amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4 -Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3, 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidi ) Imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2, 2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomer type having a hindered amine structure as well as Rimmer type of compounds and the like can also be used.

  Phosphorous antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 ′ isopropylidenediphenol phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2 , 4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidenebis (3-methyl-) 6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxyphosphonoxy) -ben Zen, ethylbisphosphite (2,4-ditert-butyl-6-methylphenyl), and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  As sulfur-based antioxidants, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

  As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.

  Specific examples of the benzophenone antioxidant include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2- Hydroxy-4-octadecyloxybenzophenone, 2,2′dihydroxy-4-methoxybenzophenone, 2,2′dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2- Hydroxy-4-methoxy-5sulfobenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone and the like can be mentioned. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  Examples of the triazine antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

  Examples of the salicylate ester antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

  These antioxidants can be used singly or in combination of two or more at any ratio as required.

  Further, the content of the antioxidant is more preferably 0.5 to 5.0% by weight based on the solid content weight of the photosensitive coloring composition for color filter because the spectral characteristics and sensitivity are good.

<Amine compound>
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

  Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivatives bicyclic amidine compounds and salts thereof (eg imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl) -4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus compounds (for example tri Phenylphosphine ), Guanamine compounds (for example, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino) -S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) Can do. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins.

<Other additive components>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

(Storage stabilizer)
Examples of the storage stabilizer include organic acids such as lactic acid and oxalic acid and methyl ether thereof, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

(Adhesion improver)
Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the colorant in the blue coloring composition.

(Multifunctional thiol)
The blue coloring composition of the present invention may contain a compound having two or more thiol (SH) groups as the polyfunctional thiol.
By using a polyfunctional thiol together with a photopolymerization initiator, a thiyl radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated in the radical polymerization process after light irradiation. Sensitivity. In particular, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable. Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropioate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibu Arylamino) -4,6-dimercapto--s- triazine and the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane tris thiopropionate, pentaerythritol tetrakis thiopropionate.

These polyfunctional thiols can be used individually by 1 type or in mixture of 2 or more types.
The content of the polyfunctional thiol is preferably 0.05 to 100 parts by weight, more preferably 1.0 to 50.0 parts by weight with respect to 100 parts by weight of the colorant. If the polyfunctional thiol content is less than 0.05 parts by weight, the effect of the chain transfer agent is small, and if it is more than 100 parts by weight, the polymerization initiating function is not improved, and developability, adhesion, etc. are insufficient. .

<Method for producing colored composition>
The coloring composition of the present invention comprises a colorant [A] in a colorant carrier such as a binder resin and / or a solvent, preferably together with a dispersion aid, a kneader, a two-roll mill, a three-roll mill, a ball mill, It can be produced by finely dispersing using various dispersing means such as a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). At this time, two or more kinds of colorants or the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. In addition, when the solubility of the colorant such as a dye is high, specifically, it is highly soluble in the solvent to be used. There is no need to manufacture.

  Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent development type or alkali development type coloring composition includes the pigment dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other pigment dispersants, additives, and the like. Can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

(Dispersing aid)
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a great effect of preventing re-aggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has spectral characteristics and viscosity stability. Will be better. In addition, as the dispersion aid used in the present invention, those containing no halogen atom are preferable.

  Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, etc. can be used. These can be used alone or in combination of two or more.

  The content of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant [A] from the viewpoint of improving dispersibility. is there. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, more preferably 35 parts by weight or less.

  The resin-type dispersant has a colorant-affinity part having the property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant to the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -SOLPERSE-3000, 9000, 1300 manufactured by Nippon Lubrizol Co., Ltd., such as P104, P104S, 220S, 6919, 21116, 21324, 21407, 21715 or Lactimon, Lactimon-WS or Bykumen , 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095 , 55000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, manufactured by Ciba Japan 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 501 , 5065,5066,5070,7500,7554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When a resin-type dispersant and a surfactant are added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant [A]. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the content is more than 55 parts by weight, the dispersion is affected by an excessive dispersant. May affect.

<Removal of coarse particles>
The colored composition of the present invention is prepared by means of centrifugal separation, filtration with a sintered filter or a membrane filter, and the like. Coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Color filter manufacturing method>
The color filter of the present invention can be produced by using a coloring composition by a printing method or a photolithography method.

  The formation of the colored film by the printing method can be patterned simply by repeating the printing and drying of the colored composition prepared as a printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When forming a colored film by a photolithography method, the colored composition prepared as the solvent development type or alkali development type colored resist material is spray coated, spin coated, slit coated, roll coated, etc. on a transparent substrate substrate. The coating method is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method or the like in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for manufacturing a color filter by using a transparent conductive film formed on a substrate and forming a colored film on the transparent conductive film by electrodeposition of colloidal particles. . The transfer method is a method in which a colored film is formed in advance on the surface of a peelable transfer base sheet, and this colored film is transferred to a desired substrate.

<Method for Manufacturing Image Sensor>
The manufacturing method of the image sensor of the present invention is not particularly limited, and a known method for manufacturing an image sensor can be used.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

  The average primary particle diameter of the pigment and the weight average molecular weight (Mw) of the resin are as follows.

(Average primary particle diameter of pigment)
The average primary particle diameter of the pigment was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission (TEM) electron microscope. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the primary pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size cube, and the volume average particle size was defined as the average primary particle size.

(Weight average molecular weight of resin (Mw))
The weight average molecular weight (Mw) of the resin was measured in terms of polystyrene measured using TSKgel column (manufactured by Tosoh Corporation) and GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector using THF as a developing solvent. It is a weight average molecular weight (Mw).

  Subsequently, binder resin solutions, thermosetting compounds, salt-forming dye resins, colorants, salt-forming compounds, coloring compositions, salt-forming compound-containing resin solutions, and photosensitive coloring compositions used in Examples and Comparative Examples The manufacturing method will be described.

<Method for producing binder resin solution>
(Acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Acrylic resin solution 1 was prepared by addition.

<Method for producing salt dye resin>
(Resin 1 having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2′-azobis (2,4-dimethylvaleronitrile) ) And 25.1 parts of methyl ethyl ketone were made uniform, charged in a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 6830, and the mixture was cooled to 50 ° C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thus, Resin 1 having a cationic group in the side chain of 47% by weight of the resin component was obtained. The ammonium salt value of the obtained resin was 34 mgKOH / g.

  Here, the ammonium salt value of the resin having a cationic group in the side chain was determined by titration with a 0.1N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and then converted into an equivalent of potassium hydroxide. It is a value and shows the ammonium salt value of the solid content.

<Method for producing colorant>
(Red colorant (R-1))
Benzimidazolone pigment C.I. I. 200 parts of Pigment Red 176 (“Novoperm Carmine HF3C” manufactured by Clariant), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a red colorant (R-1) was obtained. The average primary particle size was 39.8 nm.

(Red colorant (R-2))
Anthraquinone red pigment C.I. I. 200 parts of Pigment Red 177 (“Chromophthaled A2B” manufactured by Ciba Japan), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. , 190 parts of a red colorant (R-2) was obtained. The average primary particle size was 27.6 nm.

(Red colorant (R-3))
Diketopyrrolopyrrole red pigment C.I. I. 120 parts of Pigment Red 254 (“IRGAZIN RED 2030” manufactured by Ciba Japan Co., Ltd.), 1000 parts of crushed salt and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. The mixture was poured into 2000 parts of warm water and stirred for 1 hour while heating to 80 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 115 parts of red A colorant (R-3) was obtained. The average primary particle size was 24.8 nm.

(Yellow colorant (Y-1))
Isoindoline yellow pigment C.I. I. Pigment Yellow 139 (PY139) ("Irgafore Yellow 2R-CF" manufactured by Ciba Japan), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 100 ° C. Kneaded for 6 hours. Next, the kneaded product is poured into 5000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a yellow colorant (Y-1) was obtained. The average primary particle size was 36.0 nm.

(Yellow colorant (Y-2))
Nickel complex yellow pigment C.I. I. 100 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. The mixture was poured into 2000 parts of warm water and stirred for 1 hour while heating to 80 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 95 parts of yellow A colorant (Y-2) was obtained. The average primary particle size was 39.2 nm.

(Green colorant (G-1))
Phthalocyanine green pigment C.I. I. 100 parts of Pigment Green 58 (“FASTGEN GREEN A110” manufactured by DIC), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product is poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for a whole day and night. 97 parts of a colorant (G-1) were obtained. The average primary particle size was 28.2 nm.

(Green colorant (G-2))
Phthalocyanine green pigment C.I. I. 100 parts of Pigment Green 7 (“LIONOL GREEN Y-102” manufactured by Toyochem Co., Ltd.), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product is poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for a whole day and night. 97 parts of a colorant (G-2) were obtained. The average primary particle size was 31.5 nm.

(Blue colorant (B-1))
In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of anhydrous aluminum chloride were added to 1250 parts of n-amyl alcohol and stirred. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine. Further, 100 parts of chloroaluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid at room temperature in a reaction vessel. The mixture was stirred at 40 ° C. for 3 hours, and the sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. The blue precipitate was filtered, washed with water, and dried to obtain a blue colorant (B-1) represented by the following formula (6). The average primary particle size was 29.4 nm.

(Blue colorant (B-2))
In a reaction vessel, 100 parts of methanol and 100 parts of an aluminum phthalocyanine pigment represented by the formula (6) and 49.5 parts of diphenyl phosphate were added and heated to 40 ° C. and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain 114 parts of an aluminum phthalocyanine pigment represented by the following formula (7).

  A blue colorant (B-2) was obtained from the obtained aluminum phthalocyanine pigment represented by the formula (7) by the same salt milling method as that for the blue colorant (B-1). The average primary particle size was 31.2 nm.

(Blue colorant (B-3))
In a reaction vessel, 100 parts of methanol and 100 parts of an aluminum phthalocyanine pigment represented by the formula (6) and 43.2 parts of diphenylphosphinic acid were added to 1000 parts of methanol, heated to 40 ° C., and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain 112 parts of an aluminum phthalocyanine pigment represented by the following formula (8).
A blue colorant (B-3) was obtained from the obtained aluminum phthalocyanine pigment represented by the formula (8) by the same salt milling method as that for the blue colorant (B-1). The average primary particle size was 29.5 nm.

(Blue colorant (B-4))
Phthalocyanine blue pigment C.I. I. 100 parts of Pigment Blue 15: 6 (Toyochem "Lionol Blue ES"), 800 parts of crushed salt and 100 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 70 ° C for 12 hours. . The mixture was poured into 3000 parts of warm water and stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 98 parts of blue A colorant (B-4) was obtained. The average primary particle size was 28.3 nm.

(Purple colorant (V-1))
Dioxazine-based purple pigment C.I. I. 120 parts of Pigment Violet 23 (“Fast Violet RL” manufactured by Clariant), 1600 parts of ground sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 90 ° C. for 18 hours. The mixture was poured into 5000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 118 parts of purple A colorant (V-1) was obtained. The average primary particle size was 26.4 nm.

<Method for producing salt-forming compound>
(Salt-forming compound (A-1))
In the following procedure, C.I. I. A salt-forming compound (A-1) comprising Acid Red 289 and Resin 1 having a cationic group in the side chain was produced.
The resin 1 having a cationic group in the side chain of 51 parts is added to 2000 parts of water, and after sufficiently stirring and mixing, the mixture is heated to 60 ° C. On the other hand, 10 parts C.I. I. An aqueous solution in which Acid Red 289 is dissolved is prepared and added dropwise little by little to the resin solution. After dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer, and 32 parts of C.I. I. A salt-forming compound (A-1) between Acid Red 289 and Resin 1 having a cationic group in the side chain was obtained. At this time, C.I. in the salt-forming compound (A-2). I. The content of the effective pigment component derived from Acid Red 289 was 29% by weight.

<Method for producing colored composition>
(Red colored composition (DR-1 to 3), yellow colored composition (DY-1 to 2), green colored composition (DG-1 to 2), blue colored composition (DB-1 to 4), purple Preparation of coloring composition (DV-1))
After stirring and mixing the mixture of the composition (parts by weight) shown in Table 1 so as to be uniform, it is 5 with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm. After time dispersion, the mixture was filtered through a 5.0 μm filter and colored compositions (DR-1 to 3), (DY-1 to 2), (DG-1), (B-1 to 4), and (DV- 1) was produced.

In Table 1, EFKA4300 and BYK-LPN6919 are as follows.
EFKA4300: EFKA Chemical Co., amine value 56 mgKOH / g
BYK-LPN6919: manufactured by Big Chemie, amine value 74 mgKOH / g
The amine value was determined by potentiometric titration using a 0.1N aqueous hydrochloric acid solution, and then converted to an equivalent of potassium hydroxide. The amine value of the resin-type dispersant indicates the amine value of the solid content.

<Method for producing salt-forming compound-containing resin solution>
(Salt-forming compound-containing resin solution (DA-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a salt-forming compound-containing resin solution (D-1).

Salt-forming compound (A-1): 16.0 parts Acrylic resin solution 1: 20.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 64.0 parts

<Method for producing photosensitive coloring composition>
(Preparation of photosensitive coloring composition (RR-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a photosensitive coloring composition (RR-1).

Red colored composition (DR-1): 36.7 parts Red colored composition (DR-2): 13.3 parts Red colored composition (DR-3): 16.7 parts Acrylic resin solution 1: 4.3 Part Photopolymerization monomer: 4.2 parts "Aronix M402" manufactured by Toagosei Co., Ltd.
Photopolymerization initiator: 1.2 parts “Irgacure 907” manufactured by Ciba Japan
Sensitizer: 0.4 part "EAB-F" manufactured by Hodogaya Chemical Co., Ltd.
Solvent: 23.2 parts cyclohexanone

(Photosensitive coloring composition (RR-2, RG-1-4, RB-1, 2))
Hereinafter, the coloring composition, the salt-forming compound-containing resin solution, the acrylic resin solution, the photopolymerizable monomer, the photopolymerization initiator, the sensitizer, and the solvent are changed to the types and blending amounts (parts by weight) shown in Table 2. Except having carried out, it carried out similarly to the photosensitive coloring composition 1 (RR-1), and produced the photosensitive coloring composition (RR-2, RG-1-4, RB-1, 2).
In Table 2, “Aronix M402” manufactured by Toagosei Co., Ltd. is used as a photopolymerization monomer, “Irgacure 907” manufactured by Ciba Japan Co., Ltd. is used as a photopolymerization initiator, and Hodogaya is used as a sensitizer. “EAB-F” manufactured by Kagakusha was used.

[Examples 1-5, Reference Examples 1-3]
(Example 1, Reference Example 1)
The red photosensitive coloring composition (RR-1, 2) is applied to a glass substrate with a spin coater, dried, exposed, developed, and dried again to give a red colored film having a spectral transmittance of 50% at a wavelength of 580 nm. Got. The transmittance of the obtained red colored film was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) to measure the spectral transmittance in the wavelength range of 430 nm to 560 nm, the wavelength The spectral transmittance at 600 nm was measured. The thickness of the colored film thus obtained was measured using a surface shape measuring device “Dektak 8 (manufactured by Veeco)”. Furthermore, the halogen content of the colored film was measured. The results are shown in Table 3.

  Similar to the reference example, the red colored film used in the examples satisfies the spectral characteristics desired for the color filter for the image sensor, and has halogen atoms of 1500 ppm or less.

(Examples 2 to 4, Reference Example 2)
Green photosensitive coloring composition (RG-1 to 4) is coated on a glass substrate with a spin coater, dried, exposed, developed, and dried again to give a green colored film having a spectral transmittance of 5% at a wavelength of 450 nm Got. Microwave spectrophotometer (manufactured by Olympus Optical Co., Ltd.) has a wavelength at which the spectral transmittance on the short wavelength side of the colored film is 50%, a wavelength at which the spectral transmittance on the long wavelength side is 50%, and spectral transmittances at wavelengths of 540 nm and 650 nm. “OSP-SP100”). The thickness of the colored film thus obtained was measured using a surface shape measuring device “Dektak 8 (manufactured by Veeco)”. Furthermore, the halogen content of the colored film was measured. The results are shown in Table 4.

  Similar to the reference example, the green colored film used in the examples satisfies the spectral characteristics desired for the color filter for the image sensor, and has halogen atoms of 1500 ppm or less.

(Example 5, Reference Example 3)
Blue photosensitive coloring composition (RB-1 or 2) is applied to a glass substrate with a spin coater, dried, exposed, developed, and dried again, resulting in a blue colored film having a spectral transmittance of 3% at a wavelength of 570 nm Got. The wavelength at which the spectral transmittance of the colored film was 50% and the spectral transmittance at wavelengths of 450 nm and 540 nm were measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). The thickness of the colored film thus obtained was measured using a surface shape measuring device “Dektak 8 (manufactured by Veeco)”. Furthermore, the halogen content of the colored film was measured. The results are shown in Table 5.

  When the coating film is formed so that the coloring composition has a film thickness of 0.5 to 1.5 μm and the spectral transmittance at a wavelength of 570 nm is 3%, the wavelength at which the spectral transmittance of the coating film is 50% is from 490 nm. 2. The colored film for an image sensor according to claim 1, which has a spectral characteristic that is in a range of 510 nm and has a spectral transmittance of 85% or more at a wavelength of 450 nm and a spectral transmittance of 12% or less at a wavelength of 540 nm. .

  The blue colored film used in the examples satisfies the spectral characteristics desired for the color filter for the image sensor as in the reference example, and has halogen atoms of 1500 ppm or less.

  As described above, in the present invention, a colored film satisfying the spectrum desired for the color filter for an image sensor, which has 1500 ppm or less of halogen atoms, which are regarded as environmentally hazardous substances, was obtained.

(Preparation of colored film set for image sensor)
Furthermore, a red colored film, a green colored film, and a red colored film (RR-1), a green colored photosensitive composition (RG-1), and a blue colored colored film (RB-1) produced using the blue photosensitive colored composition (RB-1) When a colored film set for an image sensor was prepared using a blue colored film, a red photosensitive colored composition (RR-2), a green photosensitive colored composition (RG-4), and a blue photosensitive colored composition (RB-). Similar to the colored film set produced using 1), the film had good spectral characteristics, and the halogen content was greatly reduced to 1500 ppm or less.

  In addition, the color filter having the colored film for an image sensor of the present invention and the image sensor provided with the color filter are free from halogen atoms or are contained in a very small amount, so that they have a problem of health and safety and environmental pollution. In addition, a high-quality color filter for an image sensor and an image sensor were obtained.

Claims (11)

  A colored film formed from a colored composition containing a colorant [A] and a resin [B], wherein the halogen content of the colored film is 1500 ppm or less with respect to the entire colored film. Colored film for image sensor.   When the coating film was formed so that the coloring composition had a film thickness of 0.5 to 1.5 μm and the spectral transmittance at a wavelength of 580 nm was 50%, the spectral transmittance in the wavelength range of 430 nm to 560 nm in the coating film was 2. The colored film for an image sensor according to claim 1, which has a spectral characteristic of 10% or less and a spectral transmittance at a wavelength of 600 nm of 75% or more. The colored film for an image sensor according to claim 1 or 2, wherein the colored composition contains a benzimidazolone pigment represented by the following general formula (1).

[In the general formula (1), R ¹ , R ² and R ³ are each independently —H, —CH ₃ , —OCH ₃ , —COOCH ₃ , —COOC ₄ H ₉ , —NO ₂ , —SO ₂ NHCH. _3, or -CONHC ₆ H _5. ]   When the coating film is formed so that the coloring composition has a film thickness of 0.5 to 1.5 μm and the spectral transmittance at a wavelength of 450 nm is 5%, the spectral transmittance on the short wavelength side of the coating film is 50%. The wavelength is in the range from 480 nm to 510 nm, the wavelength at which the spectral transmittance on the long wavelength side is 50% is in the range from 570 nm to 610 nm, the spectral transmittance at 540 nm is 80% or more, and the spectral transmittance at wavelength 650 nm is 3 2. The colored film for an image sensor according to claim 1, having a spectral characteristic of not more than%.   The colored film for an image sensor according to claim 1 or 4, wherein the colored composition contains an aluminum phthalocyanine pigment.   When the coating film is formed so that the coloring composition has a film thickness of 0.5 to 1.5 μm and the spectral transmittance at a wavelength of 570 nm is 3%, the wavelength at which the spectral transmittance of the coating film is 50% is from 490 nm. 2. The colored film for an image sensor according to claim 1, which has a spectral characteristic that is in a range of 510 nm and has a spectral transmittance of 85% or more at a wavelength of 450 nm and a spectral transmittance of 12% or less at a wavelength of 540 nm. .   The colored film for an image sensor according to claim 1, wherein the colored composition contains a dye not containing a halogen atom.   A colored film set for an image sensor, comprising at least two kinds of colored films according to any one of claims 1 to 7.   The colored film set for an image pickup device according to claim 8, comprising a red colored film, a green colored film, and a blue colored film.   A color filter comprising the colored film for an image sensor according to claim 1.   An image sensor comprising the color filter according to claim 10.