JP2014164021A - Photosensitive colored composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive colored composition comprising a pigment containing a phthalocyanine ring, the photosensitive colored composition having high sensitivity and a high residual film ratio in spite of a high pigment content or high film thickness and being excellent in linearity, pattern shape, resolution and drug resistance; and a color filter using the same.SOLUTION: The photosensitive colored composition of the present invention can form a high sensitive and excellent filter segment pattern in spite of high pigment content or high thickness of a formed film in a filter segment, by using a pigment containing a phthalocyanine ring, a resin having a specific structure and a specific compound as a photoinitiator. Therefore, by using the photosensitive colored composition of the present invention, a high-quality color filter can be obtained.

Description

  The present invention relates to a photosensitive coloring composition, and more particularly to a highly sensitive photosensitive coloring composition useful for forming each color filter segment in a color filter used in a liquid crystal display device or a solid-state imaging device. The present invention also relates to a color filter formed using the photosensitive coloring composition.

A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting with each other on the surface of a transparent substrate such as glass, or the fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.
Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to form them generally at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher.

For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.
In the case of the pigment dispersion method, a photosensitive coloring composition (pigment resist) in which a pigment is dispersed in a photosensitive resin solution is applied to a transparent substrate such as glass, the solvent is removed by drying, and then pattern exposure of one filter color is performed. Next, the unexposed area is removed in the development process to form a pattern for the first color, and after processing such as heating as necessary, the same operation is sequentially repeated for all filter colors to produce a color filter. can do.

  In recent years, color liquid crystal display devices have formed a large market for liquid crystal color televisions, car navigation systems, personal computers, and portable terminals. In a color filter in which filter segments for each color are arranged, demands for high color reproducibility, high brightness, and high reliability (heat resistance, light resistance, voltage holding ratio) are increasing.

  In order to improve the color reproduction characteristics of the color filter, it is necessary to increase the pigment content in the photosensitive coloring composition or to increase the film thickness. However, in the method of increasing the pigment content, problems such as a decrease in sensitivity, developability, and resolution deteriorate. In the method of increasing the film thickness, the exposure light does not reach the bottom of the film, and problems such as poor pattern shape tend to occur. Then, in order to improve the sclerosis | hardenability in pattern formation, the coloring composition is a tendency of high sensitivity.

  Among the color filters, in the coloring composition for displaying green and blue, it is common to use green and blue pigments each containing a phthalocyanine skeleton. Conventionally, high sensitivity of color filters using these pigments has been achieved by (1) imparting a reactive double bond to the resin, (2) selecting or increasing the photopolymerization initiator and sensitizer, and (3) monomer. (4) Addition of a specific compound, etc. are studied, and examples thereof include Patent Documents 1 to 3. Further, in order to improve the color reproducibility of a green color filter containing a phthalocyanine ring, a method of using a new color material having a specific structure as in Patent Document 4 has been studied.

JP 2001-264530 A JP 2003-156842 A JP 2000-214580 A JP 2004-333817 A

However, improvement in sensitivity is limited only by the provision of a double bond of the resin and the selection of a photopolymerization initiator, a sensitizer, and a monomer. In particular, when the amount of the photopolymerization initiator is increased, coloring due to a color unique to the photopolymerization initiator, a decrease in heat resistance, a decrease in light transmittance, a decrease in resolution, and the like occur. Further, when the amount of the monomer is increased, problems such as tackiness occur. In addition, since the specific compound has a property of deactivating radicals generated by light irradiation, problems such as deterioration in curability in pattern formation and reduction in sensitivity occur. Furthermore, when a new color material is used, reliability such as heat resistance and light resistance may be insufficient.
Therefore, an object of the present invention is to provide a coloring composition having high sensitivity and excellent reliability, and a color filter using the same.

The photosensitive coloring composition of the present invention is highly sensitive when a coloring material containing a phthalocyanine ring is used, and has excellent linearity, pattern shape, resolution, and chemical resistance. It contains a resin (B1) containing the following structural units (a) to (c), a photopolymerization initiator (C) represented by the following general formula (5), and a photopolymerizable compound (D). .
That is, the present invention is a photosensitive coloring composition containing a pigment (A), a resin (B), a photopolymerization initiator (C), and a photopolymerizable compound (D),
Pigment (A) contains a phthalocyanine ring,
The resin (B) includes a resin (B1) including the following structural units (a) to (c),
It is related with the photosensitive coloring composition characterized by including a photoinitiator (C) represented by following General formula (5).
(A) Structural unit having a carboxyl group: 2 to 60% by weight
(B) Structural unit having an aromatic ring group represented by the following general formula (1) or general formula (2): 2 to 80% by weight
(C) Structural unit having an aliphatic cyclic group represented by the following formula (3) or formula (4): 2 to 40% by weight

General formula (1):

General formula (2):
[In General Formulas (1) and (2), R ₁ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. ]

General formula (3):

General formula (4):

General formula (5)
(In the formula (5), R ₁ represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl, Oxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted Or an unsubstituted arylsulfinyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted amino group, Substituted or unsubstituted phosphinoyl groups, substituted or It represents an unsubstituted carbamoyl group or a substituted or unsubstituted sulfamoyl group,.

R ₂ represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted A heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group Represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted acyloxy group, or a substituted or unsubstituted amino group.

R _{3 to} R ₅ are each independently a hydrogen atom, halogen atom, cyano group, nitro group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or Unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl Represents a group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group.
R _{6 to} R ₉ are each independently a hydrogen atom, halogen atom, cyano group, haloalkyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or Unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl Group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted amino group, or the following general formula The substituent which is (6) is represented.

General formula (6)
(In Formula (6), R _{1 ′} and R _{2 ′} have the same meanings as R ₁ and R _2. )
R _{10 to} R ₁₄ each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a haloalkyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkyl It represents a sulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group, and at least one of R _{10 to} R ₁₄ is a nitro group or the following general formula (7). )

General formula (7)
(In formula (7), R _{15 to} R ₁₉ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, Substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl Represents a sulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group.))

  The present invention also relates to the photosensitive coloring composition, wherein the resin (B1) is a photosensitive resin.

In the present invention, the resin (B1) is an epoxy resin obtained by polymerizing a precursor of the structural unit (b), a precursor of the structural unit (c), and an ethylenically unsaturated monomer having an epoxy group. The group-containing copolymer (i1-1) was obtained, and then the epoxy group of the obtained epoxy group-containing copolymer (i1-1) and the carboxyl group of the monocarboxyl group-containing ethylenically unsaturated monomer were used. A hydroxyl group-containing copolymer (i1-2) is obtained by reaction, and the hydroxyl group of the obtained hydroxyl group-containing copolymer (i1-2) is reacted with an acid anhydride group of a polybasic acid anhydride. Resin,
Alternatively, the precursor of the structural unit (a), the precursor of the structural unit (b), and the precursor of the structural unit (c) are polymerized to obtain a carboxyl group-containing copolymer (i2-1), Next, a resin obtained by reacting a part of the carboxyl groups of the obtained carboxyl group-containing copolymer (i2-1) with an epoxy group of an ethylenically unsaturated monomer having an epoxy group,
It is related with the said photosensitive coloring composition characterized by the above-mentioned.

  Furthermore, this invention relates to the color filter characterized by providing the filter segment formed from the said photosensitive coloring composition on a transparent substrate.

The photosensitive coloring composition of the present invention is a combination of a colorant containing a specific structure, a resin containing a specific structure, and an oxime ester compound containing a specific structure as a photopolymerization initiator. Even if the pigment content is high or the filter segment is formed with a large film thickness, it is possible to form a filter segment having high sensitivity and excellent linearity, pattern shape, resolution, and chemical resistance.
Therefore, a high quality color filter can be obtained by using the photosensitive coloring composition of the present invention.

First, the photosensitive coloring composition in this invention is demonstrated concretely.
The photosensitive coloring composition of the present invention is represented by the pigment (A) containing a phthalocyanine ring, the resin (B) containing the resin (B1) containing the structural units (a) to (c), and the general formula (5). A photopolymerization initiator (C) and a photopolymerizable compound (D).
The photosensitive coloring composition obtained by the above combination has high sensitivity, and a coating film having a particularly high residual film ratio can be obtained. Therefore, a photosensitive coloring composition excellent in production stability of the color filter can be obtained. Further, by using this photosensitive coloring composition, a filter segment having excellent linearity, pattern shape, resolution, and chemical resistance can be formed.

<Pigment (A)>
The pigment (A) contained in the photosensitive coloring composition of the present invention contains a phthalocyanine ring, and in addition, an organic or inorganic pigment can be mixed and used. Among the pigments, pigments having high color developability and high heat resistance are preferable, and organic pigments are usually used.
Below, the specific example of the organic pigment which can be used for the photosensitive coloring composition of this invention is shown with a color index number.
Examples of the pigment containing a phthalocyanine ring include green pigments such as CI Pigment Green 7, 36, 37 and 58, such as CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, Blue pigments such as 16 can be used.

Further, other pigments not containing a phthalocyanine ring may be used in combination, for example, CI Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81 : 2, 81: 3, 97, 122, 123, 144, 146, 149, 166, 168, 169, 176, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210 Red pigments such as 215, 216, 217, 220, 221, 223, 224, 226, 227, 228, 240, 242, 246, 254, 255, 264, 272, 279,
For example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 17 , Yellow pigments such as 177,179,180,181,182,185,187,188,193,194,199,213,214,
For example, CI Pigment orange 36, 38, 43, 51, 55, 59, 61, 71, 73, etc. Orange pigment, for example, CI Pigment Green 10, etc. Green pigment, for example, CI Pigment Blue 22, 60, 64, 80, etc. Purple pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, such as carbon black, aniline black, anthraquinone black pigment, perylene black pigment, etc. Specifically, CI pigment black 1, 6, 7, 12, 20, 31, etc. can be used.

Also, inorganic pigments include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber, titanium black. Examples thereof include metal oxide powders such as synthetic iron black, titanium oxide, and iron tetroxide, metal sulfide powders, and metal powders. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.
The photosensitive coloring composition of the present invention may contain a dye within a range that does not reduce heat resistance for color matching.

  Based on the total nonvolatile components of the photosensitive coloring composition of the present invention (100% by weight), the preferable concentration of the pigment (A) component is 10% by weight or more from the viewpoint of obtaining sufficient color reproducibility, more preferably It is 15% by weight or more, and most preferably 20% by weight or more. Further, since the stability of the photosensitive coloring composition is improved, the preferable concentration of the pigment (A) component is 90% by weight or less, more preferably 80% by weight or less, and most preferably 70% by weight or less. is there.

<Resin (B)>
The resin (B) contained in the photosensitive coloring composition of the present invention includes a resin (B1) containing the following structural units (a) to (c).
(A) Structural unit having a carboxyl group: 2 to 60% by weight
(B) Structural unit having an aromatic ring group represented by the following general formula (1) or general formula (2): 2 to 80% by weight
(C) Structural unit having an aliphatic ring group represented by the following general formula (3) or general formula (4): 2 to 40% by weight

General formula (1):

General formula (2):
[In General Formulas (1) and (2), R ₁ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. ]

General formula (3):

General formula (4):

Below, a structural unit (a), a structural unit (b), and a structural unit (c) are demonstrated in order.
In this specification, the content weight% of each structural unit is the weight% of the precursor that brings each structural unit to the resin (B1).

[(A) Structural unit having carboxyl group]
The structural unit (a) has a carboxyl group and functions as an alkali-soluble site during development. Based on the weight of all the structural units of the resin (B1), the structural unit (a) is 2 to 60% by weight from the viewpoint of developability. If it is less than 2% by weight, the removability of the unexposed portion by the alkaline developer becomes insufficient, and if it exceeds 60% by weight, the dissolution rate in the alkali developer is increased and the exposed portion is dissolved.

  Examples of the precursor of the structural unit (a) having a carboxyl group include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, and α-chloroacrylic acid, and unsaturated dicarboxylic acids such as maleic acid and fumaric acid. And compounds containing a carboxyl group such as an acid and having an ethylenically unsaturated double bond. Moreover, what half-esterified the anhydride of unsaturated dicarboxylic acid, such as maleic anhydride, with the (meth) acrylic compound which has hydroxyl groups, such as hydroxyalkyl (meth) acrylate, can also be used. Among these, (meth) acrylic acid is more preferable, and methacrylic acid is most preferable from the viewpoint of polymerizability (ease of control of molecular weight and the like). These can be used alone or in combination of two or more.

[(B) Structural unit having an aromatic ring group represented by general formula (1) or general formula (2)]
The structural unit (b) has a cyclic structure with an aromatic ring group represented by the general formula (1) or the general formula (2), and functions as an affinity site for the pigment or the resin-type dispersant. Based on the weight of all the structural units of the resin (B1), the structural unit (b) is 2 to 80% by weight from the viewpoints of dispersion stability, resistance and developability. If it is less than 2% by weight, the dispersion stability and resistance are lowered, and a high-quality color filter cannot be obtained. On the other hand, if it exceeds 80% by weight, the dissolution rate in an alkaline developer is slowed, and the development time is long and the productivity is deteriorated.

General formula (1):

General formula (2):
[In General Formulas (1) and (2), R ₁ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. ]

  Examples of the precursor of the structural unit (b) include styrene, α-methylstyrene, benzyl acrylate, benzyl methacrylate, or an ethylenically unsaturated monomer represented by the general formula (8).

General formula (8):
(In General Formula (8), R ₆ is a hydrogen atom or a methyl group, R ₇ is an alkylene group having 2 or 3 carbon atoms, and R ₈ is a carbon that may have a benzene ring. (It is an alkyl group of the number 1-20, and n is an integer of 1-15.)

Examples of the ethylenically unsaturated monomer represented by the general formula (8) include:
New Frontier CEA [EO-modified cresol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : methyl group, n = 1 or 2], NP-2 [n-nonylphenoxy polyethylene] Glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group, n = 2], N-177E [n-nonylphenoxypolyethylene glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene Group, R ₈ : n-nonyl group, n = 16 to 17], or PHE [phenoxyethyl acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1],
Daicel, IRR169 [ethoxylated phenyl acrylate (EO 1 mol), R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], or Ebecryl 110 [ethoxylated phenyl acrylate (EO 2 mol), R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 2],

Aronix M-101A manufactured by Toagosei Co., Ltd. [phenol EO modified (n≈2) acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n≈2], M-102 [phenol EO modified ( n≈4) acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n≈4], M-110 [paracumylphenol EO modified (n≈1) acrylate, R ₆ : hydrogen atom , R _7: an ethylene group, R _8: Parakumiru, n ≒ 1], M-111 [n- nonylphenol EO-modified (n ≒ 1) acrylate, R _6: a hydrogen atom, R _7: an ethylene group, R _8: n- Nonyl group, n≈1], M-113 [n-nonylphenol EO-modified (n≈4) acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group, n≈4], or M-117 [n-nonyl Phenol PO modified (n≈2.5) acrylate, R ₆ : hydrogen atom, R ₇ : propylene group, R ₈ : n-nonyl group, n≈2.5],
Kyoeisha light acrylate PO-A [phenoxyethyl acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], P-200A [phenoxypolyethylene glycol acrylate, R ₆ : hydrogen atom, R _7: an ethylene group, R _8: a hydrogen atom, n ≒ 2], NP-4EA [nonylphenol EO adduct acrylate, R _6: a hydrogen atom, R _7: an ethylene group, R _8: n-nonyl group, n ≒ 4 ], Or NP-8EA [[nonylphenol EO adduct acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group, n≈8], or light ester PO [phenoxyethyl methacrylate, R ₆ : Methyl group, R ₇ : propylene group, R ₈ : hydrogen atom, n = 1],

Manufactured by NOF Corporation Blemmer ANE-300 [nonylphenoxy polyethylene glycol acrylate, R _6: a hydrogen atom, R _7: an ethylene group, R _8: - nonyl group, n ≒ 5], ANP-300 [nonylphenoxy polypropylene glycol acrylate, R _6: a hydrogen atom, R _7: a propylene group, R _8: n-nonyl group, n ≒ 5], 43ANEP-500 [nonylphenoxy - polyethylene glycol - polypropylene glycol - acrylate, R _6: a hydrogen atom, R _7: an ethylene group And propylene group, R ₈ : -nonyl group, n≈5 + 5], 70ANEP-550 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group and propylene group, R ₈ : n -Nonyl group, n≈9 + 3], 75AN EP-600 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group and propylene group, R ₈ : n-nonyl group, n≈5 + 2], AAE-50 [phenoxypolyethylene glycol Acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], AAE-300 [phenoxypolyethylene glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen Atom, n≈5.5], PAE-50 [phenoxypolyethylene glycol methacrylate, R ₆ : methyl group, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], PAE-100 [phenoxypolyethylene glycol methacrylate, R _6: a methyl group, R _7: an ethylene group, R _8: a hydrogen atom, n = ], Or 43PAPE-600B [phenoxy - polyethylene glycol - polypropylene glycol - methacrylate, R _6: a methyl group, R _7: an ethylene group and a propylene group, R _8: a hydrogen atom, n ≒ 6 + 6],

Shin-Nakamura Chemical Co., Ltd. NK ESTER AMP-10G [phenoxy ethyleneglycol acrylate (EO1mol), R _6: a hydrogen atom, R _7: an ethylene group, R _8: a hydrogen atom, n = 1], AMP-20G [phenoxy ethyleneglycol acrylate (EO 2 mol), R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n≈2], AMP-60G [phenoxyethylene glycol acrylate (EO ₆ mol), R ₆ : hydrogen atom, R ₇ : ethylene group , R ₈ : hydrogen atom, n≈6], PHE-1G [phenoxyethylene glycol methacrylate (EO 1 mol), R ₆ : methyl group, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1],
Biscoat # 192 manufactured by Osaka Organic Chemical Co., Ltd. [phenoxyethyl acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], or
Nippon Kayaku SR-339A [2-phenoxy ethyleneglycol acrylate, R _6: a hydrogen atom, R _7: an ethylene group, R _8: a hydrogen atom, n = 1], or SR-504 (ethoxylated nonylphenol acrylate, R ₆ : Hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group] and the like, but not limited thereto, two or more kinds may be used in combination.

In the ethylenically unsaturated monomer represented by the general formula (8), the alkyl group represented by R ₈ has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. The alkyl group includes not only a linear alkyl group but also a branched alkyl group and an alkyl group having a benzene ring as a substituent. When the carbon number of the alkyl group of R ₈ is 1 to 10, the alkyl group becomes an obstacle and the penetration of ITO etching solution, molybdenum etching solution, etc. is suppressed and the acid resistance is increased. The obstacle effect becomes high and shows a tendency to prevent adhesion to the substrate. This tendency becomes more prominent as the carbon chain length of the alkyl group of R ₈ becomes longer. When the carbon number exceeds 20, the adhesion with the substrate is extremely lowered. Examples of the alkyl group having a benzene ring represented by R ₈ include a benzyl group and a 2-phenyl (iso) propyl group. By increasing one side chain benzene ring, acid resistance is further improved and developability is also improved.

  In the ethylenically unsaturated monomer represented by the general formula (8), n is preferably an integer of 1 to 15. When n exceeds 15, the hydrophilicity increases and the effect of solvation decreases, and the viscosity of the resin (B1) increases, and the viscosity of the photosensitive composition using the same also increases, affecting the fluidity. May give. From the viewpoint of solvation, n is particularly preferably 1 to 4.

  As the precursor of the structural unit (b), styrene, α-methylstyrene, benzyl acrylate, benzyl methacrylate, or the general formula (8) from the viewpoint of copolymerization with other precursors and the viewpoint of pigment dispersibility. The ethylenically unsaturated monomer shown by these is preferable. By introducing a benzene ring into the side chain of the binder resin (B), the side chain benzene ring is oriented to the pigment, thereby promoting the resin adsorption to the pigment and further suppressing the aggregation of the pigment. Furthermore, benzyl acrylate and / or benzyl methacrylate are most preferred from the viewpoints of developability and dispersion stability.

[(C) Structural unit having an aliphatic ring group represented by general formula (3) or general formula (4)]
The structural unit (c) has a cyclic structure with an aliphatic ring group represented by the formula (3) or the formula (4), and serves as an affinity site for the pigment or the resin-type dispersant and a hydrophobic site for the alkali developer. Function as. Based on the weight of all the structural units of the resin (B1), the structural unit (c) is 2 to 40% by weight from the viewpoints of developability, filter segment quality and dispersion stability. If it is less than 2% by weight, there will be a problem that the affinity site for the pigment or the resin-type dispersant is insufficient, a high-quality color filter cannot be obtained, and the storage stability of the color filter coloring composition is deteriorated. Further, since the hydrophobicity at the time of development is insufficient, there is a problem of pattern peeling or chipping in the pixel portion. If it exceeds 40% by weight, the dissolution rate in an alkaline developer will be slow, the development time will be long, and the productivity of the color filter will deteriorate.

General formula (3):

General formula (4):

Examples of the precursor of the structural unit (c) include an ethylenically unsaturated monomer represented by the general formula (9), an ethylenically unsaturated monomer represented by the general formula (10), and the like.
General formula (9):

General formula (10):
[In General Formula (9) and General Formula (10), R ₉ is a hydrogen atom or a methyl group, R ₁₀ is an alkylene group having 2 or 3 carbon atoms, and m is an integer of 1 to 15. It is. ]

Examples of the ethylenically unsaturated monomer represented by the general formula (9) include:
FANCLIL FA-513A [dicyclopentanyl acrylate, R ₉ : hydrogen atom, R ₁₀ : none, m = 0], or FA-513M [dicyclopentanyl methacrylate, R ₉ : methyl, R ₁₀ manufactured by Hitachi Chemical Co., Ltd. : None, m = 0] and the like, but not limited thereto, two or more kinds can be used in combination.

As an unsaturated ethylene monomer represented by the general formula (10), for example,
FANCLIL FA-511A [dicyclopentenyl acrylate, R ₉ : hydrogen atom, R ₁₀ : none, m = 0], FA-512A [dicyclopentenyloxyethyl acrylate, R ₉ : hydrogen atom, R ₁₀ : Ethylene group, m = 1], FA-512M [dicyclopentenyloxyethyl methacrylate, R ₉ : methyl group, R ₁₀ : ethylene group, m = 1], or FA-512MT [dicyclopentenyloxyethyl methacrylate, R _9: methyl group, R _10: an ethylene group, m = 1] and the like but can be exemplified, without limitation, can be used in combination of two or more kinds.

[Other structural units]
Other structural units are not limited as long as they are structural units other than the structural unit (a), the structural unit (b), and the structural unit (c). However, since the main function of the other structural unit is to provide developability, it takes a small structure with respect to the relatively large ring structure of the side chain of the structural unit (b) having an acid resistance function. It is preferable. Thereby, it is considered that developability can be imparted while maintaining the characteristics of the structural unit (b) having a large side chain having acid resistance.

Examples of other structural unit precursors include:
Methyl (meth) methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (Meth) acrylate, pentyl (meth) acrylate, isopentyl acrylate, neopentyl (meth) acrylate, t-pentyl (meth) acrylate, 1-methylbutyl (meth) acrylate, hexyl (meth) acrylate, hepta (meth) acrylate, octyl (Meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, Alkyl or alkenyl (meth) acrylates such as rohexyl (meth) acrylate, allyl (meth) acrylate, or oleyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (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, 1,6-hexanediol diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di Various acrylic and methacrylic esters such as (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isobornyl (meth) acrylate, ester acrylate, epoxy (meth) acrylate, urethane acrylate, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol Divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl- 2,2 '-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'-[oxybis (methylene)] bis-2- Examples of monomers and oligomers such as propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate include, but are not limited to, other ethylenically unsaturated monomers. Can be selected, and two or more types can be used in combination. As described above, methyl (meth) acryl methacrylate or ethyl (meth) acrylate is preferably used from the viewpoint of developability.

Examples of other ethylenically unsaturated monomers include:
(Meth) acrylates having a heterocyclic substituent such as tetrahydrofurfuryl (meth) acrylate or 3-methyloxetanyl (meth) acrylate;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate or ethoxypolyethylene glycol (meth) acrylate; or
(Meth) acrylamide (in the case of “(meth) acrylamide”, it means acrylamide and / or methacrylamide; the same shall apply hereinafter), N, N-dimethyl (meth) acrylamide, N, N -(Meth) acrylamides such as diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholine.

Moreover, as a monomer other than the acrylic monomer, for example,
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; or
Examples include vinyl acetate, and fatty acid vinyls such as vinyl propionate. The monomer other than the acrylic monomer can be used in combination with the acrylic monomer.

[Introduction of ethylenically unsaturated double bond]
The resin (B1) of the present invention is preferably a photosensitive resin having an ethylenically unsaturated double bond. In order to introduce an ethylenically unsaturated double bond, an ethylenically unsaturated monomer having an epoxy group or an ethylenically unsaturated monomer having a hydroxyl group is obtained by the following method (i) or method (ii). Can also be used. Since these may become structural units other than other structural units depending on the modification, the final weight ratio of the structural unit (a), the structural unit (b), and the structural unit (c) is taken into consideration. There is a need.

[Method (i)]
As the method (i), for example, the side of the copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other ethylenically unsaturated monomers The chain epoxy group is reacted with a carboxyl group of a monocarboxyl group-containing ethylenically unsaturated monomer (also referred to as an unsaturated monobasic acid), and the resulting hydroxyl group is reacted with a polybasic acid anhydride to produce ethylene. There is a method of introducing a carboxyl group having an alkali-soluble function while introducing a photosensitive unsaturated double bond to give the function of a photosensitive resin.

(Monocarboxyl group-containing ethylenically unsaturated monomer, polybasic acid anhydride)
Since the carboxyl group of the unsaturated monobasic acid used in this step forms an ester bond after the addition reaction to the epoxy group, the repeating unit (a) having a carboxyl group of the binder resin (B) in this specification includes Not applicable, corresponds to other structural units, and since the polybasic acid anhydride forms a carboxyl group after reaction with a hydroxyl group, the repeating unit (a) having a carboxyl group of the binder resin (B) in this specification It corresponds to.

Examples of the ethylenically unsaturated 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, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

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 be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

As a method similar to the method (i), for example, a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other ethylenically unsaturated monomers. There is a method of introducing an ethylenically unsaturated double bond and a carboxyl group by adding an ethylenically unsaturated monomer having an epoxy group to a part of the side chain carboxyl group of the coalescence.
In this case, only the structural unit corresponding to the carboxyl group that is not used for the addition reaction with the epoxy group corresponds to the repeating unit having the carboxyl group (a) of the resin (B) in this specification.

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

  Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. 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 ethylenically unsaturated 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.

The weight average molecular weight (Mw) of the resin (B1) is preferably in the range of 5,000 to 100,000, more preferably in the range of 5,000 to 80,000, still more preferably 5,000 to 30,000. Range. 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 weight average molecular weight (Mw) of the resin (B1) exceeds 100,000, the interaction between the resins becomes strong, and the viscosity of the photosensitive coloring composition becomes high, so that the handling tends to be difficult. Further, if the weight average molecular weight (Mw) is less than 5,000, problems may occur in developability and adhesion to a substrate such as glass.

  The acid value of the resin (B1) is preferably a resin having an acid value of 20 to 300 KOH-mg / g from the viewpoints of developability and resistance. When the acid value is less than 20 KOH-mg / g, the solubility in the developer is poor and it is difficult to form a fine pattern. If it exceeds 300 KOH-mg / g, a fine pattern may not remain.

  The resin (B1) is preferably used in an amount of 10 to 60% by weight in 100% by weight of the total solid content of the photosensitive coloring composition. When the resin (B1) is less than 10% by weight, sufficient adhesion improvement and high transmittance cannot be obtained. When the resin (B1) is more than 60% by weight, the content of the photocuring component is reduced and sufficient coating is achieved. It is difficult to obtain the hardness of the film.

《Other resins》
The photosensitive coloring composition of the present invention may further contain other resins other than the resin (B1). As the other resin, a resin having a transmittance of preferably 80% or more, more preferably 95% or more is preferable in the entire wavelength region of 400 to 700 nm in the visible light region. Other resins include thermoplastic resins, thermosetting resins, and photosensitive resins, and these can be used alone or in admixture of two or more.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Examples of the photosensitive resin include (meth) acrylic compounds having a reactive substituent such as an isocyanate group, an aldehyde group, and an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group, A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

  The resin (B) can be used in an amount of 20 to 400% by weight, preferably 50 to 250% by weight, based on 100% by weight of the pigment (A) in the photosensitive coloring composition.

<Photopolymerization initiator (C)>
The photopolymerization initiator (C) contained in the photosensitive coloring composition of the present invention is a compound represented by the above general formula (5). In general formula (5), R ₁ is substituted or unsubstituted. Alkenyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted Substituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl Group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted acyl group, substituted or unsubstituted Conversion acyloxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted phosphinoyl group, a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted sulfamoyl group,.

Examples of the substituted or unsubstituted alkenyl group for R ₁ include straight-chain, branched-chain, monocyclic or condensed polycyclic alkenyl groups having 1 to 18 carbon atoms. Specific examples include a 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- Examples thereof include butadienyl group, cyclohexadienyl group, cyclopentadienyl group and the like, but are not limited thereto.

The substituted or unsubstituted alkyl group in R ₁ is a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms and optionally one or more Examples thereof include a linear, branched, monocyclic or condensed polycyclic alkyl group interrupted by -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, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like, but are not limited thereto. Specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— 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 —CH ₂ —CH ₂ —O) _m —CH ₃ (where m is 1 to 5), —CH ₂ —CH (CH ₃ ) —O—CH ₂ —. Examples thereof include, but are not limited to, CH ₃ —, —CH ₂ —CH— (OCH ₃ ) _{2 and the} like.

  Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of -O- include the following, but are not limited thereto. Is not to be done.

The substituted or unsubstituted alkyloxy group in R ₁ is a linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms and optionally 1 Examples include a linear, branched, monocyclic or condensed polycyclic alkyloxy group interrupted by one or more —O—. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms include methyloxy group, ethyloxy group, propyloxy group, butyloxy group, pentyloxy group, hexyloxy Group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropyloxy group, isobutyloxy group, isopentyloxy group, sec-butyloxy group, tert-butyloxy group, sec-pentyl Oxy group, tert-pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boroni Group, 4-decyl cyclohexyl although group and the like, but is not limited thereto. Specific examples of the linear or branched alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more —O— include —O—CH ₂ —O—CH ₃ , _{-O-CH 2 -CH 2 -O-} CH 2 -CH 3, -O-CH 2 -CH 2 -CH 2 -O-CH 2 -CH 3, -O- (CH 2 -CH 2 -O) n -CH ₃ (wherein n is 1 to _{8), - O- (CH 2} -CH 2 -CH 2 -O) m -CH 3 ( here m is 5 1), - O-CH _{2 -CH (CH 3) -O-} CH 2 -CH 3 -, - OCH 2 -CH- (OCH 3) can be cited _2, etc., but is not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include the following. It is not limited.

Examples of the substituted or unsubstituted aryl group in R ₁ include monocyclic or condensed polycyclic aryl groups having 6 to 24 carbon atoms. Specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, 1 -Anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 2 -Fluorenyl group, 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,5-xylyl group, mesityl group, p-cumenyl group P-dodecylphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromopheny Group, p-hydroxyphenyl group, m-carboxyphenyl group, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, m-azidophenyl group, and the like, but are not limited thereto. It is not a thing.

Examples of the substituted or unsubstituted aryloxy group in R ₁ include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms, and specific examples include a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group. 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9- Although a fluorenyloxy group etc. can be mentioned, it is not limited to these.

Examples of the substituted or unsubstituted heterocyclic group for R ₁ include aromatic or aliphatic heterocyclic groups having 4 to 24 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Thienyl group, 2-benzothienyl group, naphtho [2,3-b] thienyl group, 3-thianthenyl group, 2-thianthrenyl group, 2-furyl group, 2-benzofuryl group, pyranyl group, isobenzofuranyl group, chromenyl Group, xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, 2- Indolyl group, 3-indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolidinyl group, isoquino Group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-carbolinyl group, phenanthridinyl group, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, Imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group, - quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathiinyl group, 3-coumarinyl of the group and the like, but is not limited thereto.

Examples of the substituted or unsubstituted heterocyclic oxy group in R ₁ include a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Examples include 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyloxy group , 3-carbazolyloxy group, 4-carbazolyloxy group, 9-acridinyloxy group and the like, but are not limited thereto.

Examples of the substituted or unsubstituted alkylsulfanyl group in R ₁ include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms. Specific examples include a methylthio group and an ethylthio group. Propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group and the like, but are not limited thereto.

Examples of the substituted or unsubstituted arylsulfanyl group in R ₁ include a monocyclic or condensed polycyclic arylthio group having 6 to 18 carbon atoms, and specific examples include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, Examples thereof include, but are not limited to, a 9-anthrylthio group and a 9-phenanthrylthio group.

The substituted or unsubstituted alkylsulfinyl group in R ₁ is preferably an alkylsulfinyl group having 1 to 20 carbon atoms, and specific examples include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, and a butylsulfinyl group. Group, hexylsulfinyl group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methyloxymethylsulfinyl group, etc. However, it is not limited to these.

  As the substituted or unsubstituted arylsulfinyl group, an arylsulfinyl group having 6 to 30 carbon atoms is preferable, and specific examples include a phenylsulfinyl group, a 1-naphthylsulfinyl group, a 2-naphthylsulfinyl group, a 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methyloxyphenylsulfinyl group, 2-butyloxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group Group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methyloxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfinyl group § sulfonyl phenylsulfinyl group, 4-dimethylaminophenyl sulfinyl but Le group and the like, but is not limited thereto.

The substituted or unsubstituted alkylsulfonyl group for R ₁ is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and specific examples include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, and a butylsulfonyl group. Hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methyloxymethylsulfonyl group and the like. It is not limited to these.

The substituted or unsubstituted arylsulfonyl group for R ₁ is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and specific examples include a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, and 2-chlorophenyl. Sulfonyl group, 2-methylphenylsulfonyl group, 2-methyloxyphenylsulfonyl group, 2-butyloxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3- Nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methyloxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfo Group, 4-but-dimethylaminophenyl sulfonyl group and the like, but is not limited thereto.

Examples of the substituted or unsubstituted acyl group for R ₁ include a hydrogen atom or a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or 2 to 20 carbon atoms. A carbonyl group substituted with an alkyloxy group, a carbonyl group bonded with a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms, or a carbonyl group substituted with a monocyclic or condensed polycyclic aryloxy group having 6 to 18 carbon atoms A carbonyl group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms, including a group, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom is bonded. Specific examples include a formyl group, an acetyl group Group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl , Stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group, cinnamoyl group benzoyl group, methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, butyloxy Carbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, trifluoromethyloxycarbonyl group, benzoyl group, toluoyl group, 1-naphthoyl group, 2-naphthoyl group, 9-anthryl Carbonyl group, phenyloxycarbonyl group, 4-methylphenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-dimethylaminophenyl Oxycarbonyl group, 2-methylsulfanylphenyloxycarbonyl group, 1-naphthoyloxycarbonyl group, 2-naphthoyloxycarbonyl group, 9-anthrylyloxycarbonyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, Although an isonicotinoyl group etc. can be mentioned, it is not limited to these.

Examples of the substituted or unsubstituted acyloxy group in R ₁ include an acyloxy group having 2 to 20 carbon atoms, and specific examples include an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, A fluoromethylcarbonyloxy group, a benzoyloxy group, a 1-naphthylcarbonyloxy group, a 2-naphthylcarbonyloxy group, and the like can be given.

Examples of the substituted or unsubstituted amino group in R ₁ include an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, a benzylamino group, and a dibenzylamino group.

  Here, as the alkylamino group, methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group , Octadecylamino group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentyl Amino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantami Group, and the like, but not limited thereto.

  Dialkylamino groups include dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, Dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, pyrrolidino group, piperidino group, Examples include, but are not limited to, piperazino groups.

  As an arylamino group, an anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4- A biphenylamino group, a 1-fluoreneamino group, a 2-fluoreneamino group, a 2-thiazoleamino group, a p-terphenylamino group, and the like are exemplified, but the invention is not limited thereto.

  Examples of the diarylamino group include, but are not limited to, a diphenylamino group, a ditolylamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group.

  Examples of the alkylarylamino group include N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, N-pentylanilino group, N -Ethylanilino group, N-methyl-1-naphthylamino group and the like are exemplified, but not limited thereto.

Examples of the substituted or unsubstituted phosphinoyl group in R ₁ include phosphinoyl groups having 2 to 50 carbon atoms. Specific examples thereof include dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenyl. Examples include, but are not limited to, phosphinoyl group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group. is not.

Examples of the substituted or unsubstituted carbamoyl group in R ₁ include a carbamoyl group having 1 to 30 carbon atoms, and specific examples thereof include N-methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N- Butylcarbamoyl group, N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group, N 2-chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3 -Cyanoff Nylcarbamoyl group, N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl Group, N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group, and the like, but are not limited thereto.

Examples of the substituted or unsubstituted sulfamoyl group in R ₁ include a sulfamoyl group having 0 to 30 carbon atoms, and specific examples include a sulfamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, an N N-dialkylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group and the like. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group and the like. It is not limited to.

R ₂ represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted A heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group A substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted acyloxy group, or a substituted or unsubstituted amino group.

R ₂ is a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted A heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, Examples of the substituted or unsubstituted alkylsulfonyl group, the substituted or unsubstituted arylsulfonyl group, the substituted or unsubstituted acyloxy group, and the substituted or unsubstituted amino group include the substituted or unsubstituted alkenyl group in R ¹ described above. Substituted or unsubstituted Alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or Unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl It is synonymous with a group, a substituted or unsubstituted acyloxy group, and a substituted or unsubstituted amino group.

R _{3 to} R ₅ are each independently a hydrogen atom, halogen atom, cyano group, nitro group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or Unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl A group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group.

As a halogen atom in R < ₃ > -R < ₅ >, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

A substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted in R _{3 to} R ₅ Unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted acyl group, and substituted or unsubstituted The amino group is a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group in R ¹ described above. Substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic group It is synonymous with a Si group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, and a substituted or unsubstituted amino group.

R _{6 to} R ₉ are each independently a hydrogen atom, halogen atom, cyano group, haloalkyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or Unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl Group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted amino group, or It is a substituent represented by Formula (6).

General formula (6)

(In Formula (6), R _{1 ′} and R _{2 ′} have the same meanings as R ₁ and R _2. )
The halogen atom in R < ₆ > -R < ₉ > is synonymous with the halogen atom in R < ³ > -R < ⁵ >.

Examples of the haloalkyl group in R _{6 to} R ₉ include an alkyl group having 1 to 15 carbon atoms in which all the hydrogen atoms are substituted with the halogen atoms described above, and specific examples include a trifluoromethyl group and a trichloromethyl group. , Tribromomethyl group, triiodomethyl group, pentafluoroethyl group, pentachloroethyl group, pentabromoethyl group, pentaiodoethyl group, trifluorodibromoethyl group, tribromodiiodoethyl group, heptafluoropropyl group, hepta Chloropropyl group, heptabromopropyl group, nonafluorobutyl group, nonachlorobutyl group, nonabromobutyl group, undecafluoropentyl group, undecachloropentyl group, undecabromopentyl group, tridecafluorohexyl group, tridecachlorohexyl Group, pentadecafluoro Examples thereof include, but are not limited to, a ptyl group, a heptadecafluorooctyl group, a nonadecafluorononyl group, a henicosafluorodecyl group, a tricosafluoroundecyl group, and a pentacosafluorododecyl group. .

  The haloalkyl group is more preferably a trifluoromethyl group or a pentafluoroethyl group from the viewpoint of the synthesis surface and the characteristics as a colored composition.

A substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, or a substituted group in R _{6 to} R ₉ Or an unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted aryl The sulfinyl group, the substituted or unsubstituted alkylsulfonyl group, the substituted or unsubstituted arylsulfonyl group, and the substituted or unsubstituted amino group are the substituted or unsubstituted alkyl group, substituted or unsubstituted in R ¹ described above. Alkyloxy group, substituted or unsubstituted A reel group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkylsulfanyl group, substituted or Unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, and substituted or unsubstituted Synonymous with amino group.

Examples of the substituent position of the substituent in R ₆ to R _9, from the characteristic surface of the synthetic surface and coloration composition, if substituted at the R ₇ is preferred.

R _{10 to} R ₁₄ each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a haloalkyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkyl Although they are a sulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group, all of R _{10 to} R ₁₄ do not become hydrogen atoms at the same time.

The haloalkyl group in R _{10 to} R ₁₄ has the same meaning as the haloalkyl group in R _{6 to} R ₉ described above, and is a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkylsulfonyl. group, a substituted or unsubstituted arylsulfonyl group, and a substituted or unsubstituted acyl group, a substituted or unsubstituted alkylsulfinyl group for R ¹ described above, a substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted It is synonymous with an alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, and a substituted or unsubstituted acyl group.

The haloalkyl group in R _{10 to} R ₁₄ is preferably a nitro group or a substituted or unsubstituted acyl group from the viewpoints of synthesis and coloring composition, and is a nitro group or the following general formula (7) Is more preferable.

General formula (7)

(In formula (7), R _{15 to} R ₁₉ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, Substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl A sulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group.)

The haloalkyl group in R _{15 to} R ₁₉ has the same meaning as the haloalkyl group in R _{6 to} R ₉ described above, and is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, Substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted An arylsulfanyl group, a substituted or unsubstituted acyl group, and a substituted or unsubstituted amino group are a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group in R ¹ , Substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group Substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted acyl group, and substituted or unsubstituted It is synonymous with the amino group.

Here, the substitution position of the nitro group in R _{10 to} R ₁₄ or the substituent represented by the formula (7) is more preferably substituted with R ₁₂ in view of the characteristics as a synthetic surface or a coloring composition. preferable.

The hydrogen atom of the substituent in R _{1 to} R ₁₉ described above may be further substituted with another substituent.

  Examples of such substituents include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, aryl groups such as phenoxy group and p-tolyloxy group. Oxy group, methoxycarbonyl group, butoxycarbonyl group, alkoxycarbonyl group such as phenoxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, Acyl group such as methoxalyl group, alkylsulfanyl group such as methylsulfanyl group, tert-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino group, cyclohexyla Alkyl groups such as alkyl groups, dimethylamino groups, diethylamino groups, morpholino groups, piperidino groups and other dialkylamino groups, phenylamino groups, p-tolylamino groups and other arylamino groups, methyl groups, ethyl groups, tert-butyl groups In addition to alkyl groups such as dodecyl groups, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, and other heterocyclic groups such as furyl groups and thienyl groups, hydroxy groups Group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, Trimethylammonium, dimethylsulfonium, trif Cycloalkenyl phenacyl phosphonium Niu mill group, and the like.

  Among the oxime ester photopolymerization initiators, the photopolymerization initiator (C) contained in the photosensitive coloring composition of the present invention has an electron-withdrawing substituent substituted on the phenyl group of the N-phenylcarbazole skeleton. It is a feature. Oxime ester-based photopolymerization initiators are believed to decompose the oxime ester moiety by absorbing ultraviolet rays to produce iminyl radicals and alkyloxy radicals, and the radicals of the active species produced by further decomposition cause the reaction. However, the photopolymerization initiator (C) contained in the photosensitive coloring composition of the present invention has a structure represented by the general formula (5), so that the decomposition efficiency by ultraviolet irradiation is very high, A pattern can be formed with a small exposure amount. Further, by combining with a pigment containing a phthalocyanine ring, a resin having a specific structure, and a photopolymerizable compound, high sensitivity and excellent linearity, pattern shape, resolution, and chemical resistance can be expressed.

  The photopolymerization initiator (C) containing the compound represented by the general formula (5) is 1 to 200% by weight, preferably 1 to 100% by weight with respect to 100% by weight of the pigment (A) in the photosensitive coloring composition. It can be used in an amount of 150% by weight.

<Other photopolymerization initiator (Y)>
In the photosensitive coloring composition of the present invention, other photopolymerization initiators can be used in combination with the compound represented by the above formula (5).
Other photopolymerization initiators (Y) include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, p-dimethylaminoacetophenone, 1- (4-isopropylphenyl) -2-hydroxy- 2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1- Acetophenone compounds such as butanone, benzoin, benzoin methyl ether, benzoin ethyl ether Benzoin compounds such as benzoin isopropyl ether and benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3, Benzophenone compounds such as 3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4- Thioxanthone compounds such as diethylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazi 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloro Methyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, Triazine compounds such as 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O -Benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine and the like, bis (2,4,4) 6-trimethylbenzoyl) phenylphosphine oxide, phosphine compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′- Tetraphenyl-1,2'-biimidazole, 2,2'-bis (o-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) Imidazole compounds such as -4,4 ', 5,5'-tetra (p-methylphenyl) biimidazole, 9,10-phenanthrenequinone, potassium And quinone-based compounds such as nephant quinone and ethylanthraquinone, borate-based compounds, carbazole-based compounds, titanocene-based compounds, and the like.

These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. The other photopolymerization initiator (Y) can be used in an amount of 1 to 200% by weight, preferably 1 to 150% by weight, based on 100% by weight of the pigment (A) in the photosensitive coloring composition.
Further, it can be used in an amount of 1 to 1000% by weight, preferably 5 to 600% by weight, based on 100% by weight of the photopolymerization initiator (C).

<Sensitizer (E)>
Furthermore, the sensitizer (E) can be contained in the photosensitive coloring composition of the present invention. The content of the sensitizer (E) is based on 100% by weight of the photopolymerization initiator (C) in the photosensitive coloring composition.
It can be used in an amount of 1-100% by weight.
As the sensitizer (E), unsaturated ketones represented by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives represented by 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 Body, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, annulene derivative, spiropyran derivative, Examples include spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, Michler ketone derivatives, and the like.

Specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special Examples include, but are not limited to, sensitizers described in “Functional Materials” (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.
Among the sensitizers (E), examples of the sensitizer capable of particularly suitably sensitizing the compound represented by the general formula (5) include thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.
The sensitizer (E) may contain two or more sensitizers in any ratio.

<Photopolymerizable compound (D)>
The photopolymerizable compound (D) contained in the photosensitive coloring composition of the present invention is a photopolymerizable monomer or oligomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 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, 1,6-hexanediol diglyme Sidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester Acrylate and methylolated melamine (meth) acrylic ester, epoxy (meth) acrylate, urethane acrylate and other acrylic and methacrylic esters, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol di Vinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformer De, acrylonitrile or photopolymerizable compounds represented by the following general formula (11), and the like. These can be used alone or in admixture of two or more.

Formula (11)
(In general formula (11), m represents an integer of 1 to 3, a represents an integer of 2 to 6, and b represents an integer of 0 to 4. However, a + b = 6.)

  The photopolymerizable compound (D) can be used in an amount of 10 to 400% by weight, preferably 10 to 300% by weight, based on 100% by weight of the pigment (A) in the photosensitive coloring composition.

In the photosensitive coloring composition, the ratio [I _a / M] of the weight [I _a ] of the photopolymerization initiator (C) and the weight [M] of the photopolymerizable compound (D) is 0.03 to 1. 00 is preferable, and 0.04 to 0.95 is more preferable.
Furthermore, when a photosensitive coloring composition contains a sensitizer (E) and other photoinitiators (Y), a photoinitiator (C), a sensitizer (E), and other photopolymerization The ratio [I _b / M] of the total weight (I _b ) of (Y) and the weight [M] of the photopolymerizable compound (D) is preferably 0.04 to 1.50, 0.05 More preferably, it is -1.45.
When [I _a / M] is 0.03 or more and [I _b / M] is 0.04 or more, the sensitivity is high and good. Further, when [I _a / M] is 1.00 or less and [I _b / M] is 1.50 or less, the linearity and resolution of the pattern shape are more excellent.

<Solvent>
In the photosensitive coloring composition of the present invention, the pigment (A) is sufficiently dispersed in a dye carrier such as a resin (B) or a photopolymerizable compound (D), and a dry film thickness is formed on a transparent substrate such as a glass substrate. In order to make it easy to form a filter segment by coating so as to be 0.2 to 10 μm, a solvent can be contained. Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 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, m-dichlorobenzene N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o- Xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, 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 mono Hexyl ether, ethylene glycol monomethyl ether Ter, ethylene glycol monomethyl 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, dip Pyrene glycol monomethyl 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, propyl acetate, include dibasic acid esters such as, used alone or in combination.
The solvent can be used in an amount of 100 to 10000% by weight, preferably 500 to 5000% by weight, based on 100% by weight of the pigment (A) in the coloring composition.

<Other ingredients>
The photosensitive coloring composition of the present invention can contain a polyfunctional thiol. A polyfunctional thiol is a compound having two or more thiol (SH) groups.
When the polyfunctional thiol is used together with the above-mentioned photopolymerization initiator (C), 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. The coloring property composition has high sensitivity. Especially, the polyfunctional thiol which has 2 or more of thiol (SH) groups is preferable at a highly sensitive point.
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, trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3- Mercaptopropionate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopropioate) Dipentaerythritol hexakis (3-mercaptopropionate), trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s -Triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine and the like. These polyfunctional thiols can be used individually by 1 type or in mixture of 2 or more types.

In addition, the photosensitive coloring composition of the present invention can contain an ultraviolet absorber or a polymerization inhibitor that functions to control the shape and resolution of the pattern.
Examples of the ultraviolet absorber include 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl). -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, etc. Hydroxyphenyltriazine, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, Benzotriazoles such as 2- (3-tbutyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,4- Benzophenone series such as hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, salicylate series such as phenyl salicylate, p-tert-butylphenyl salicylate, Cyanoacrylates such as ethyl-2-cyano-3,3′-diphenylacrylate, 2,2,6,6, -tetramethylpiperidine-1-oxyl (triacetone-amine-N-oxyl), bis (2, 2,6,6-tetramethyl-4-piperidyl) -sebacate, poly [[6-[(1,1,3,3-tetrabutyl) amino] -1,3,5-triazine-2,4-diyl] And hindered amines such as [(2,2,6,6-tetramethyl-4-piperidinyl) imino] and the like. Or in a mixture used. Examples of the polymerization inhibitor include methyl hydroquinone, t-butyl hydroquinone, 2,5-di-t-butyl hydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol. Hydroquinone derivatives and phenol compounds, amine compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate, etc. Copper and manganese salt compounds, 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxyl Nitroso compounds such as amine and an ammonium salt or an aluminum salt, and the like, can be used alone or in combination.

Moreover, the photosensitive coloring composition of this invention can be made to contain the storage stabilizer which has a function which stabilizes the time-dependent viscosity of a composition.
Examples of the storage stabilizer include 2,6-bis (1,1-dimethylethyl) -4-methylphenol, pentaerystyryl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl). Propionate], hindered phenols such as 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) 1,3,5-triazine, tetraethylphosphine, tri Organic phosphines such as phenylphosphine and tetraphenylphosphine, phosphites such as zinc dimethyldithiophosphate, zinc dipropyldithiophosphate and molybdenum dibutyldithiophosphate, sulfurs such as dodecyl sulfide and benzothiophene, benzyltrimethyl chloride, Quaternary ammonium chloride such as diethylhydroxyamine , Lactic acid, and organic acids and their methyl ethers such as oxalic acid and the like, can be used alone or in combination.

Moreover, the photosensitive coloring composition of this invention can be made to contain adhesion | attachment improvement agents, such as a silane coupling agent which has a function which improves the adhesiveness with a transparent substrate.
Examples of the silane coupling agent include vinyl silanes such as vinyl tris (β-methoxyethoxy) silane, vinyl ethoxy silane, and vinyl trimethoxy silane, (meth) acryl silanes such as γ-methacryloxypropyl trimethoxy silane, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxy (Cyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, epoxysilanes such as γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (Aminoethyl) γ-amino Propyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, Examples include aminosilanes such as N-phenyl-γ-aminopropyltriethoxysilane, thiosilanes such as γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane, and these may be used alone or in combination. Can do.

Moreover, the photosensitive coloring composition of the present invention can contain an amine compound having a function of reducing dissolved oxygen.
Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples thereof include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine and the like, and these can be used alone or in combination.

<Production method of photosensitive coloring composition>
The photosensitive coloring composition of the present invention uses various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor in the pigment (A) in a dye carrier such as the resin (B) and / or a solvent. The pigment dispersion is manufactured by finely dispersing the resin, and the pigment dispersion is coated with a resin (B), a photopolymerization initiator (C), a photopolymerizable compound (D), and in some cases other photopolymerization initiators (Y ), A sensitizer (E), a solvent, and other components can be mixed and stirred. In addition, the photosensitive coloring composition containing two or more pigments is prepared by mixing each pigment dispersion separately in a dye carrier and / or a solvent, and further mixing the resin (B), a photopolymerization initiator. (C), a photopolymerizable compound (D), and the like can be produced by mixing and stirring.

When the pigment is dispersed in the resin (B) and / or the solvent, a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a pigment derivative can be appropriately contained. Since the dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion, the photosensitivity obtained by dispersing the pigment in the resin (B) and / or solvent using the dispersion aid. When the coloring composition is used, a color filter having excellent transparency can be obtained.
The dispersion aid can be used in an amount of 0.1 to 55% by weight, preferably 0.1 to 45% by weight, based on 100% by weight of the pigment (A).

  The resin-type pigment dispersant has a pigment-affinity part that has the property of adsorbing to the pigment and a part that is compatible with the dye carrier, and adsorbs to the pigment to stabilize the dispersion of the pigment on the dye carrier. It works. Specific examples of resin-type pigment 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 alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, 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.

  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- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS, or Bykumen. 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, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 75 4,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, 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.

  The pigment derivative is a compound in which a substituent is introduced into an organic pigment, and the organic pigment also includes light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone that are not generally called pigments. Examples of the pigment derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used alone or in combination of two or more.

  The photosensitive coloring composition of the present invention can be prepared in the form of a solvent developing type or alkali developing type colored resist material. The colored resist material is obtained by dispersing the pigment (A) in a composition containing an alkali-soluble resin (B), a photopolymerization initiator (C), a photopolymerizable compound (D), and a solvent. is there.

  The photosensitive coloring composition is obtained by means of centrifugal separation, sintering filter, membrane filter or the like, coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more and mixed dust. Is preferably removed.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention is provided with a filter segment formed from the photosensitive coloring composition of the present invention on a transparent substrate, and a general color filter has at least one red filter segment and at least one green color. A filter segment and at least one blue filter segment, or at least one magenta filter segment, at least one cyan filter segment, and at least one yellow filter segment.

As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.
The dry film thickness of the filter segment is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

  The formation of each color filter segment by photolithography is performed by the following method. That is, the photosensitive coloring composition prepared as a solvent developing type or alkali developing type colored resist material has a dry film thickness of 0. 0 on a transparent substrate by a coating method such as spray coating, spin coating, slit coating or roll coating. It apply | coats so that it may become 2-10 micrometers. 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.

  Thereafter, the filter segment can be formed by immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern. Furthermore, in order to accelerate the polymerization of the filter segment formed by development, heating can be performed as necessary. According to the photolithography method, a filter segment with higher accuracy than the printing method can be formed.

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.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
In order to increase the UV exposure sensitivity, the photosensitive coloring composition is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to prevent polymerization inhibition due to oxygen. After forming, UV exposure can also be performed.

  EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In Examples and Comparative Examples, “parts” means “parts by weight” and “%” means “% by weight”.

First, prior to the examples, a method for producing the photopolymerization initiator (C) represented by the general formula (5), the acrylic resin solution, and the pigment dispersion used in the examples and comparative examples will be described.
In the synthesis of the photopolymerization initiator (C), an intermediate compound was first synthesized, then a precursor compound was synthesized from the intermediate compound, and the photopolymerization initiator was synthesized from the precursor compound. The obtained compounds were subjected to elemental analysis (C, H, N) (Perkin Elmer 2400 · CHN) and EI-MS (Thermo PolarisQ) to perform mass spectrometry, and the respective structures were confirmed.

  Further, the weight average molecular weight (Mw) of the resin was measured by using TSKgel column (manufactured by Tosoh Corp.) and GPC equipped with RI detector (manufactured by Tosoh Corp., HLC-8120GPC) using polystyrene as a developing solvent. It is a weight average molecular weight (Mw) in terms of conversion. The acid value of the resin was determined by adding 80 ml of acetone and 10 ml of water to 0.5 to 1 g of the resin solution, stirring and dissolving uniformly, and using a 0.1 mol / L KOH aqueous solution as a titrant, an automatic titrator (“COM -555 "manufactured by Hiranuma Sangyo Co., Ltd.) and the acid value of the resin solution was measured. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

<Method for producing photopolymerization initiator (C)>
[Synthesis of Photopolymerization Initiator (C1)]
Dissolve 100.0 g of N-benzophenoylcarbazole in 1000 ml of chloroform, add 85.0 g of aluminum chloride, and stir at 0 ° C., and then add a solution of 32.0 g of propionyl chloride in 500 ml of chloroform over 2 hours. It was dripped. After completion of dropping, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was poured into 2000 g of ice water and extracted with 2000 mL of chloroform. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was recrystallized from chloroform / methanol to obtain 113.0 g of the intermediate compound (a1). Next, 38.4 g of tert-butyl nitrite was added dropwise over 1 hour while stirring at room temperature when dissolved in a mixed solution of 100.0 g of compound (a1), 1000 ml of tetrahydrofuran and 500 ml of concentrated hydrochloric acid. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 ml of ice water and extracted with 1600 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered to remove the solvent, and the residue was washed with n-hexane to give precursor compound (b1) 99. .8 g was obtained. Next, 6.3 g of acetic anhydride and 10.6 g of sodium acetate were added to 30.0 g of compound (b1) in 300 ml of ethyl acetate, and the mixture was heated to reflux for 3 hours. Thereafter, the reaction solution was poured into 500 ml of ice water, the composition organism was extracted with ethyl acetate, the organic layer was washed with water (300 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered off and the solvent was distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 31.4 g of a photopolymerization initiator (C1).

Photopolymerization initiator (C1)

[Synthesis of Photopolymerization Initiator (C2)]
Dissolve 100.0 g of N-benzophenoylcarbazole in 1000 ml of chloroform, add 84.0 g of aluminum chloride and stir at 0 ° C., and then add a solution of 36.8 g of butanoyl chloride in 500 ml of chloroform over 2 hours. And dripped. After completion of dropping, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was poured into 2000 g of ice water and extracted with 2000 mL of chloroform. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was recrystallized from chloroform / methanol to obtain 109.3 g of the intermediate compound (a2). Next, 40.0 g of tert-butyl nitrite was added dropwise over 1 hour while stirring at room temperature when dissolved in a mixed solution of 100.0 g of compound (a2), 1000 ml of tetrahydrofuran and 500 ml of concentrated hydrochloric acid. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 ml of ice water and extracted with 1600 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and the residue was washed with n-hexane to give precursor compound (b2) 89 .3 g was obtained. Next, when 30.0 g of compound (b2) was stirred in 300 ml of ethyl acetate, 6.1 g of acetic anhydride and 10.3 g of sodium acetate were added, and the mixture was heated to reflux for 3 hours. Thereafter, the reaction solution was poured into 500 ml of ice water, the composition organism was extracted with ethyl acetate, the organic layer was washed with water (300 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered off and the solvent was distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 30.0 g of a photopolymerization initiator (C2).

Photopolymerization initiator (C2)

[Synthesis of Photopolymerization Initiator (C3)]
A solution in which 100.0 g of N- (p-nitrophenyl) carbazole was dissolved in 1000 ml of chloroform, 101.8 g of aluminum chloride was further added, and 44.3 g of butanoyl chloride was dissolved in 500 ml of chloroform was stirred at 0 ° C. It was dripped over 2 hours. After completion of dropping, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was poured into 2000 g of ice water and extracted with 2000 mL of chloroform. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was recrystallized from chloroform / methanol to obtain 113.6 g of an intermediate compound (a3). Next, 40.0 g of tert-butyl nitrite was added dropwise over 1 hour while stirring at room temperature when dissolved in a mixed solution of 100.0 g of compound (a3), 1000 ml of tetrahydrofuran and 500 ml of concentrated hydrochloric acid. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 ml of ice water and extracted with 1500 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and the residue was washed with n-hexane to give precursor compound (b3) 107. 0.2 g was obtained. Next, when 50.0 g of compound (b3) was stirred in 500 ml of ethyl acetate, 19.9 g of acetic anhydride and 11.7 g of sodium acetate were added, and the mixture was heated to reflux for 3 hours. Thereafter, the reaction solution is poured into 500 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant is filtered off, and the solvent is distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 57.6 g of a photopolymerization initiator (C3).

Photopolymerization initiator (C3)

[Synthesis of Photopolymerization Initiator (C4)]
Dissolve 100.0 g of N-benzophenoyl-1,3-dimethyl-carbazole in 1000 ml of chloroform, add 78.6 g of aluminum chloride and dissolve 29.6 g of propionyl chloride in 500 ml of chloroform with stirring at 0 ° C. The solution was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was poured into 2000 g of ice water and extracted with 2000 mL of chloroform. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was recrystallized from chloroform / methanol to obtain 111.8 g of intermediate compound (a4). Next, 35.7 g of tert-butyl nitrite was added dropwise over 1 hour while stirring at room temperature when dissolved in a mixed solution of 100.0 g of compound (a4), 1000 ml of tetrahydrofuran and 500 ml of concentrated hydrochloric acid. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 ml of ice water and extracted with 1600 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and the residue was washed with n-hexane to give precursor compound (b4) 98. .3 g was obtained. Next, when 30.0 g of compound (b4) was stirred in 300 ml of ethyl acetate, 5.9 g of acetic anhydride and 10.0 g of sodium acetate were added, and the mixture was heated to reflux for 3 hours. Thereafter, the reaction solution is poured into 500 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (300 ml × 3 times), dried over magnesium sulfate, the desiccant is filtered, and the solvent is distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 31.2 g of a photopolymerization initiator (C4).

Photopolymerization initiator (C4)

<Method for Producing Resin (B1) Solution>
(Preparation of resin solution (B1-1))
Place 100 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. A mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and 1.0 part of azobisisobutyronitrile was dropped over 2.5 hours from the dropping tube at a temperature to polymerize. Reaction was performed. Next, the inside of the flask was purged with air, 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 17.0 parts of acrylic acid, and the reaction was continued at 120 ° C. for 5 hours. Tetrahydrophthalic anhydride was further added. 30.4 parts and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 8000 and an acid value of 71 mgKOH / g. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether so that the nonvolatile content was 40% by weight in the previously synthesized resin solution. Acetate was added to prepare a resin solution (B1-1).

(Preparation of resin solution (B1-2))
Put 182 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube, and stirring device in a separable four-necked flask, and heat to 100 ° C. while injecting nitrogen gas into the vessel. Mixture of 70.5 parts of benzyl methacrylate, 22.0 parts of dicyclopentanyl methacrylate, 43.0 parts of methacrylic acid, 136 parts of propylene glycol monomethyl ether acetate, and 3.6 parts of azobisisobutyronitrile from a dropping tube at a temperature. Was added dropwise over 2 hours and further stirred at 100 ° C. for 5 hours to conduct a polymerization reaction. Next, the inside of the flask was purged with air, 0.9 part of trisdimethylaminomethylphenol and 0.145 part of hydroquinone were added to 35.5 parts of glycidyl methacrylate, the reaction was continued at 110 ° C. for 6 hours, and the weight average molecular weight 25000, An acrylic resin solution having an acid value of 88 mgKOH / g was obtained. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether so that the nonvolatile content was 40% by weight in the previously synthesized resin solution. Acetate was added to prepare a resin solution (B1-2).

(Preparation of resin solution (B1-3))
70.0 parts of propylene glycol monomethyl ether acetate was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable four-necked flask, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. Thereafter, a mixture of 69.5 parts of benzyl methacrylate, 15.5 parts of methacrylic acid, 15.0 parts of dicyclopentanyl methacrylate, and 0.4 part of 2,2′-azobisisobutyronitrile was added from the dropping tube over 2 hours. The solution was added dropwise to carry out a polymerization reaction. After completion of the dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 17100 and an acid value of 99 mgKOH / g. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether so that the nonvolatile content was 40% by weight in the previously synthesized resin solution. Acetate was added to prepare a resin solution (B1-3).

<Method for producing other resin (B2) solution>
(Preparation of resin solution (B2-1))
70.0 parts of propylene glycol monomethyl ether acetate was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable four-necked flask, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. Thereafter, 10.0 parts of methyl methacrylate, 25.0 parts of benzyl methacrylate, 20.0 parts of methacrylic acid, 15.0 parts of 2-hydroxyethyl methacrylate, 30.0 parts of n-butyl methacrylate, 2,2′- A mixture of 1.33 parts of azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 9300 and an acid value of 118 KOH-mg / g. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether so that the nonvolatile content was 40% by weight in the previously synthesized resin solution. Acetate was added to prepare a resin solution (B2-1).

In Table 1, the monomer composition of the resin (B1-1 to B1-3),
Table 2 shows the constituent unit ratios (% by weight) of the resins (B1-1 to B1-3).

Abbreviations in Tables 1 and 2 are shown below.
GMA + AA + THPA: A combination of a hydroxyl group generated by the addition reaction of glycidyl methacrylate and acrylic acid and a tetrahydrophthalic anhydride (bonding group is formed)
MAA: Methacrylic acid BzMA: Benzyl methacrylate St: Styrene DCPMA: Dicyclopentanyl methacrylate GMA: Glycidyl methacrylate GMA + AA: Glycidyl methacrylate and acrylic acid combined by addition reaction (formation of hydroxyl group)
GMA + MAA: Glycidyl methacrylate and methacrylic acid combined by addition reaction (generates hydroxyl group)

<Method for producing pigment dispersion>
[Preparation of Green Pigment Dispersion (P-1)]
After the mixture having the following composition is stirred and mixed uniformly, the mixture is dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A green pigment dispersion P-1 was prepared.
Green pigment: C.I. I. Pigment Green 58
(“FASTOGEN GREEN A110” manufactured by DIC) 8.95 parts Yellow pigment: C.I. I. Pigment Yellow 150
(“E4GN” manufactured by LANXESS) 2.75 parts Resin type dispersant (“EFKA4300” manufactured by BASF) 4.90 parts 83.40 parts propylene glycol monomethyl ether acetate

[Preparation of Green Pigment Dispersion (P-2)]
A green pigment dispersion P-2 was prepared in the same manner as the green pigment dispersion (P-1) using a mixture having the following composition.
Green pigment: C.I. I. Pigment Green 36
(Toyocolor Co., Ltd. “Lionol Green 6YK”) 8.95 parts Yellow Pigment: C.I. I. Pigment Yellow 150
(“E4GN” manufactured by LANXESS) 2.75 parts Resin type dispersant (“EFKA4300” manufactured by BASF) 4.90 parts 83.40 parts propylene glycol monomethyl ether acetate

[Preparation of Blue Pigment Dispersion (P-3)]
A blue pigment dispersion P-3 was prepared in the same manner as the green pigment dispersion (P-1) using a mixture having the following composition.
Blue pigment: C.I. I. Pigment Blue 15: 6
("Heliogen Blue L-6700F" manufactured by BASF) 12.90 parts Resin-type dispersant ("EFKA4300" manufactured by BASF) 7.40 parts 79.70 parts propylene glycol monomethyl ether acetate

[Examples 1-6 and Comparative Examples 1-2]
(Preparation of photosensitive coloring composition)
Each material was mixed and stirred at the formulation ratio shown in Table 3, and filtered through a 1 μm filter to obtain a photosensitive colored composition of each color.

Abbreviations in Table 3 are shown below.
Photoinitiator Y1: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one
("Irgacure 907" manufactured by BASF)
Photopolymerization initiator Y2: 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone
("Irgacure 379" manufactured by BASF)
Photopolymerization initiator Y3: ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime)
(BASF "Irgacure OXE02")
Sensitizer E1: 2,4-Diethylthioxanthone
(“Kayacure DETX-S” manufactured by Nippon Kayaku Co., Ltd.)
Sensitizer E2: 4,4'-bis (diethylamino) benzophenone
("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.)
Photopolymerizable compound D1: dipentaerythritol hexaacrylate
("Aronix M-402" manufactured by Toagosei Co., Ltd.)
Photopolymerizable compound D2: General formula (11) m = 1, a = 3, b = 3
Caprolactone-modified dipentaerythritol hexaacrylate
(“KAYARAD DPCA-30” manufactured by Nippon Kayaku Co., Ltd.)
Multifunctional thiol: pentaerythritol tetrakis (3-mercaptopropionate)
(“PEMP” manufactured by Sakai Chemical Industry Co., Ltd.)
Organic solvent: Propylene glycol monomethyl ether acetate

<Evaluation of photosensitive coloring composition>
The obtained photosensitive coloring composition was evaluated by the following methods. The results are shown in Table 4.
[Filter segment pattern formation]
The obtained photosensitive coloring composition was applied to a 10 cm × 10 cm glass substrate by spin coating, and then the solvent was removed by heating in a clean oven at 70 ° C. for 15 minutes to obtain a coating film of about 2 μm. . Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask having a stripe pattern of 100 μm width (pitch 200 μm) and 25 μm width (pitch 50 μm) using an ultrahigh pressure mercury lamp. Thereafter, the substrate was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated at 230 ° C. for 30 minutes in a clean oven. The spray development was performed in the shortest time during which a pattern can be formed without any development remaining on the coating film of each photosensitive coloring composition, and this was set as an appropriate development time.
The film thickness of the coating film was measured using Dektak 3030 (manufactured by ULVAC).

[Sensitivity evaluation]
The pattern film thickness in the 100 μm photomask portion of the filter segment formed by the above method was measured, and the minimum exposure amount that was 90% or more with respect to the film thickness after coating was evaluated. The smaller the minimum exposure, the higher the sensitivity and the better the photosensitive coloring composition.
The rank of evaluation is as follows.
○: Less than 50 mJ / cm ² Δ: 50 mJ / cm ² or more and less than 100 mJ / cm ² ×: 100 mJ / cm ² or more

[Linearity evaluation]
The pattern at the 100 μm photomask portion of the filter segment formed by the above method was evaluated by observation using an optical microscope. The rank of evaluation is as follows.
○: Good linearity Δ: Partially poor linearity ×: Poor linearity

[Pattern shape evaluation]
The cross section of the pattern at the 100 μm photomask portion of the filter segment formed by the above method was evaluated by observation using an electron microscope. The pattern cross section has good forward taper. The rank of evaluation is as follows.
◎: Forward tapered shape with gentle cross section ○: Cross section with forward tapered shape ×: Cross section with reverse tapered shape

[Resolution evaluation]
The pattern in the 25 μm photomask portion of the filter segment formed by the above method was evaluated by observing with an optical microscope. The rank of evaluation is as follows. The poor resolution means that adjacent stripe patterns are connected or chipped. The rank of evaluation is as follows.
◎: Good resolution and linearity ○: Slightly inferior in linearity but good resolution △: Partially defective

[Evaluation of chemical resistance]
The filter segment formed by the above method was immersed in an N-methylpyrrolidone solution for 30 minutes, then washed with ion-exchanged water, air-dried, and the pattern on the 100 μm photomask portion was observed and evaluated using an optical microscope. The rank of evaluation is as follows.
◎: Appearance and color are good without change ○: Some wrinkles are generated, but color is good without change Δ: Slight color loss is generated ×: Peeling or color loss is generated

As shown in Table 4, the filter segments formed using the photosensitive coloring compositions of Examples 1 to 6 had good sensitivity, linearity, pattern shape, resolution, and chemical resistance, while being comparative examples. When using only a resin having no structure such as (B1) as in 1-2, or when using other oxime ester photopolymerization initiators, defects in pattern characteristics occur, No improvement was obtained.
As described above, by using a color material containing a specific structure, a resin containing a specific structure, and an oxime ester compound containing a specific structure as a photopolymerization initiator, it is highly sensitive and excellent. Filter segments having linearity, pattern shape, resolution, and chemical resistance can be formed.
Therefore, a high quality color filter can be obtained by using the photosensitive coloring composition of the present invention.

Claims (4)

A photosensitive coloring composition containing a pigment (A), a resin (B), a photopolymerization initiator (C), and a photopolymerizable compound (D),
Pigment (A) contains a phthalocyanine ring,
The resin (B) includes a resin (B1) including the following structural units (a) to (c),
The photosensitive coloring composition characterized by including a photoinitiator (C) represented by following General formula (5).
(A) Structural unit having a carboxyl group: 2 to 60% by weight
(B) Structural unit having an aromatic ring group represented by the following general formula (1) or general formula (2): 2 to 80% by weight
(C) Structural unit having an aliphatic ring group represented by the following general formula (3) or general formula (4): 2 to 40% by weight
General formula (1):
General formula (2):
[In General Formulas (1) and (2), R ₁ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. ]

General formula (3):
General formula (4):
General formula (5)
(In the formula (5), R ₁ represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl, Oxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted Or an unsubstituted arylsulfinyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted amino group, Substituted or unsubstituted phosphinoyl groups, substituted or It represents an unsubstituted carbamoyl group or a substituted or unsubstituted sulfamoyl group,.
R ₂ represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted A heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group Represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted acyloxy group, or a substituted or unsubstituted amino group.
R _{3 to} R ₅ are each independently a hydrogen atom, halogen atom, cyano group, nitro group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or Unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl Represents a group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group.
R _{6 to} R ₉ are each independently a hydrogen atom, halogen atom, cyano group, haloalkyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or Unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl Group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted amino group, or the following general formula The substituent which is (6) is represented.
General formula (6)
(In Formula (6), R _{1 ′} and R _{2 ′} have the same meanings as R ₁ and R _2. )
R _{10 to} R ₁₄ each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a haloalkyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkyl It represents a sulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group, and at least one of R _{10 to} R ₁₄ is a nitro group or the following general formula (7). )

General formula (7)
(In formula (7), R _{15 to} R ₁₉ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, Substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl Represents a sulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group.))   Resin (B1) is photosensitive resin, The photosensitive coloring composition of Claim 1 characterized by the above-mentioned. Resin (B1) is an epoxy group-containing copolymer obtained by polymerizing a precursor of the structural unit (b), a precursor of the structural unit (c), and an ethylenically unsaturated monomer having an epoxy group ( Next, the epoxy group-containing copolymer (i1-1) obtained is reacted with the carboxyl group of the monocarboxyl group-containing ethylenically unsaturated monomer to obtain a hydroxyl group-containing copolymer. A resin obtained by reacting the hydroxyl group of the obtained hydroxyl group-containing copolymer (i1-2) with the acid anhydride group of the polybasic acid anhydride, after obtaining the polymer (i1-2),
Alternatively, the precursor of the structural unit (a), the precursor of the structural unit (b), and the precursor of the structural unit (c) are polymerized to obtain a carboxyl group-containing copolymer (i2-1), Next, a resin obtained by reacting a part of the carboxyl groups of the obtained carboxyl group-containing copolymer (i2-1) with an epoxy group of an ethylenically unsaturated monomer having an epoxy group,
The photosensitive coloring composition according to claim 2, wherein:   A color filter comprising a filter segment formed from the photosensitive coloring composition according to claim 1 on a transparent substrate.