JP2019133154A - Photosensitive coloring composition and color filter - Google Patents

Abstract

To provide a photosensitive composition for color filters that can form a pixel with high resolution of a coloring pattern, with reduced residues of the unexposed portion removed by development and with good yield, and a color filter formed therewith.SOLUTION: A photosensitive coloring composition contains a pigment (A), a dye derivative (B) of a specific structure, a polymer having a hydroxy group in at least one terminal, a resin dispersant (C) that is a reactant with a tricarboxylic acid anhydride or a tetracarboxylic acid dianhydride, a polymerizable compound (D), a photopolymerization initiator (E), a resin binder (F), and solvent (G).SELECTED DRAWING: None

Description

  The present invention relates to a color composition used for manufacturing a color filter used in a color liquid crystal display device, a color solid-state imaging device, an organic EL display device, a quantum dot display device, and electronic paper, and a photosensitive coloring composition. The present invention also relates to a color filter including a filter segment formed using the same.

The color filter is formed by arranging two or more kinds of fine band-like filter segments having different hues on a transparent substrate such as a glass substrate so as to be parallel to each other (in a stripe shape) or cross each other, or Two or more kinds of fine filter segments having different values are arranged so as to be sequentially arranged in each of the vertical direction and the horizontal direction. The filter segments have small dimensions of several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.

At present, as a method for producing a color filter, a method called a pigment dispersion method in which a pigment having excellent various resistances such as light resistance and heat resistance is used as a colorant has become the mainstream. In the pigment dispersion method, a color filter is manufactured by the following method. First, a photosensitive coloring composition (pigment resist) obtained by dispersing a pigment in a photosensitive transparent resin solution is applied to a transparent substrate such as glass. After removing the solvent from the coating by drying, the coating is exposed with a pattern corresponding to a filter segment of a certain color. Subsequently, the unexposed part of this coating film is removed by development, and then a treatment such as heating is performed as necessary. Thereby, a filter segment pattern of the first color is obtained. Then, by performing the same operation as this, filter segment patterns of other colors are formed, and the color filter is completed.

In recent years, high color reproduction of displays has become an important trend. Although high color reproduction of a display is mainly focused on improving the color reproducibility of the backlight, it is necessary to use a very dark color for the color filter in order to improve the color reproducibility. In such a case, in the exposure process for forming the color filter pattern, the amount of light reaching the bottom of the coating film becomes weak, so photocuring tends to be insufficient, and a pattern with a desired shape cannot be obtained. To do.

Specifically, the photosensitive coloring composition is required to have dimensional stability that can be accommodated by variation within a certain degree when the pattern size obtained in the color filter manufacturing process varies the exposure amount in the exposure process. In the photosensitive coloring composition that realizes high color reproduction, such dimensional stability tends to deteriorate. Similarly, in the photosensitive coloring composition that realizes high color reproduction, the linearity of the pattern tends to deteriorate.

Various methods have been studied so far to solve these problems. For example, in Patent Document 1, dimensional stability is ensured by adding a polymer having a specific structure to the photosensitive composition. In Patent Document 2, the pattern shape and dimensional stability are realized by providing an anchor layer on a substrate. In patent document 3, the stability of the pattern dimension in the low exposure amount is implement | achieved by adding the polymer of a specific structure to a photosensitive composition. In Patent Document 4, dimensional stability is achieved by using a polymerization initiator having a specific structure. In patent document 5, the dimensional stability with respect to image development is ensured by using a thiol type compound. However, the high dimensional stability and linearity required for color filters today are not fully achieved, and further improvements are needed.

JP 2013-254047 A JP 2013-073115 A JP 2012-108227 A JP 2011-002796 A JP 2010-039475 A

An object of the present invention is to provide a photosensitive composition for a color filter which can form a pixel with high resolution of a colored pattern and a small yield of unexposed portions removed by development and a good yield, and the use thereof. Another object is to provide a color filter.

The photosensitive coloring composition of the present invention comprises a pigment (A), a dye derivative (B) having a specific structure, a polymer having a hydroxyl group at at least one terminal, and a reaction between a tricarboxylic acid anhydride or a tetracarboxylic acid dianhydride. Reaction of polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a hydroxyl group of a product and / or a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride or tetracarboxylic dianhydride The product includes a resin-type dispersant (C), a polymerizable compound (D), a photopolymerization initiator (E), a resin binder (F), and a solvent (G).

By using the photosensitive coloring composition of the present invention, each color filter segment having few unexposed portions removed by development and having excellent linearity, pattern shape, resolution, development resistance and chemical resistance is formed. can do. Therefore, a high quality color filter can be obtained by using the photosensitive coloring composition of the present invention.

The photosensitive coloring composition of the present invention comprises a pigment (A), a dye derivative (B) represented by any one of the following general formula (1), a polymer having a hydroxyl group at at least one terminal, and a tricarboxylic acid anhydride Or in the presence of a reaction product of a reaction product with a tetracarboxylic dianhydride and / or a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride or a tetracarboxylic dianhydride. A resin-type dispersant (C), a polymerizable compound (D), a photopolymerization initiator (E), a resin binder (F), and a solvent (G), which are reaction products for polymerizing a polymerizable unsaturated monomer It is characterized by that.
Below, each structural component of the photosensitive coloring composition of this invention is demonstrated.
In the present application, when “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” is particularly described, Unless otherwise indicated, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. It shall represent.
Further, “CI” in this specification means a color index (CI).

<Colorant>
<Pigment (A)>
The photosensitive coloring composition of this invention contains a pigment (A) as a coloring agent.
As the pigment, organic or inorganic pigments can be used alone or in admixture of two or more. The pigment is preferably a pigment having a high color developability and a high heat resistance, particularly a pigment having a high heat decomposition resistance, and an organic pigment is usually used. Below, the specific example of the organic pigment which can be used for the coloring composition for color filters is shown by a color index number.

Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 4
1, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 2 4, 216, 220, 221,224, 230, 231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256, 257,258,259,260,262,263,264,265,266,267,268,269,270,271,272,273,274,275,276,277,278,279,280,281,282, 283, 284, 285, 286, 287, 291; diketopyrrolopyrrole pigment described in JP 2011-523433 A, or azo pigment described in JP 2014-112527 A, described in JP 2013-161026 A An azo pigment etc. can be mentioned. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Red 48: 1, 122, 177, 224, 242, 254, 291 and more preferably C.I. I. Pigment red 177, 254, and 291.

The red coloring composition includes C.I. I. You may use together orange pigments, such as pigment orange 36, 38, 43, 51, 55, 59, 61, 71, or 73, and / or the yellow pigment mentioned later.

Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, and more preferably C.I. I. Pigment Blue 15: 6. Moreover, it is also preferable to use an aluminum phthalocyanine pigment, and the aluminum phthalocyanine pigment described in JP-A No. 2004-333817, Japanese Patent No. 4893859 and the like can also be used.
Moreover, you may use together the below-mentioned purple pigment in a blue coloring composition.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

Examples of the green pigment include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, zinc phthalocyanine pigments described in JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, etc., aluminum phthalocyanine pigments described in JP 4893859 A, and the like. However, it is not particularly limited to these. Among these, from the viewpoint of transmittance, C.I. I. Pigment Green 36 or 58.
Further, the yellow pigment described later may be used in combination with the green coloring composition.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 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, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82,185,187,188,192,193,194,196,198,199,213,214, although quinophthalone compounds are described in Japanese Open No. 2012-226110 and the like, not particularly limited thereto. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, examples of yellow pigments include C.I. I. Pigment Yellow 138, 139, 150, 185 and at least one selected from quinophthalone pigments described in JP 2012-226110 A are preferable. More preferably, C.I. I. Pigment yellow 139, 150, and 185.

Examples of the quinophthalone pigment described in JP 2012-226110 A include quinophthalone compounds (a) to (r) shown below, but are not limited thereto.

Examples of the cyan coloring composition for forming the cyan filter segment include C.I. I. Blue pigments such as CI Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, and 81 can be used alone or in combination.

Examples of magenta colored compositions for forming magenta color filter segments include C.I. I. Pigment violet 1, 19, C.I. I. Purple and red pigments such as CI Pigment Red 144, 146, 177, 169, and 81 can be used alone or in combination. A yellow pigment can be used in combination with the magenta composition.

Inorganic pigments include titanium oxide, 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 And synthetic iron black. 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.

<Other colorants>
The photosensitive composition of the present invention can contain a colorant such as a dye other than the pigment (A).
<Dye>
As the dye, any of acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes and the like can be used. Moreover, it may be in the form of lake pigments obtained by rake-forming these derivatives or dyes.

Furthermore, in the case of an acid dye having an acid group such as sulfonic acid or carboxylic acid, or in the form of a direct dye, an inorganic salt of an acid dye, an acid dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, Alternatively, use a salt-forming compound with a nitrogen-containing compound such as a primary amine compound, or salt formation using a resin component having these functional groups, or use as a salt-forming compound after sulfonamidation. Therefore, it is possible to obtain a colored composition having excellent fastness, which is preferable.
A salt-forming compound of an acid dye and a compound having an onium base is also preferable because of excellent fastness. More preferably, the compound having an onium base is a resin having a cationic group in the side chain.

  In the case of a basic dye, it can be used after salt formation using an organic acid, perchloric acid or a metal salt thereof. Among them, a salt forming compound of a basic dye is preferable because of its resistance and excellent compatibility with pigments, and further, a basic dye and organic sulfonic acid, organic sulfuric acid, fluorine group-containing phosphorus, which are counter components that function as counter ions. It is possible to use a salt-forming compound obtained by salting an anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or an acidic dye. It is more preferable.

  Moreover, when it has a polymerizable unsaturated group in a pigment | dye frame | skeleton, it can be set as the dye excellent in tolerance, and it is preferable.

  Examples of the chemical structure of the dye include azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinones) Dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azines Dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes Mention may be made of pigment structures derived from dyes selected from perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof. .

Among these pigment structures, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium from the viewpoint of color characteristics such as hue, color separation, and color unevenness Preferred are dye structures derived from dyes selected from dyes, quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, phthalocyanine A pigment structure derived from a pigment selected from the system dyes is more preferable. For specific pigment compounds that can form a pigment structure, “New Edition Dye Handbook” (edited by the Society of Synthetic Organic Chemistry; Maruzen, 1970), “Color Index” (The Society of Dyers and Colorists), “Dye Handbook” (Okawara et al.) Ed; Kodansha, 1986).

<Miniaturization of pigment>
When the colorant used in the photosensitive coloring composition of the present invention is a pigment, it is preferably used after being refined. There are no particular limitations on the method of miniaturization. For example, any of wet grinding, dry grinding, and dissolution precipitation can be used. As exemplified in the present invention, salt milling treatment by a kneader method, which is one type of wet grinding. Etc. can be made finer. It is preferable that the average primary particle diameter calculated | required by TEM (transmission electron microscope) of a pigment is the range of 5-90 nm. When the thickness is smaller than 5 nm, dispersion in an organic solvent becomes difficult, and when the thickness is larger than 90 nm, a sufficient contrast ratio may not be obtained. For these reasons, a more preferable average primary particle size is in the range of 10 to 70 nm.

  Salt milling is a batch or continuous type of mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent, such as a kneader, 2-roll mill, 3-roll mill, ball mill, attritor, sand mill, planetary mixer, etc. In this process, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water after mechanically kneading while heating using a kneader. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

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

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

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

<Dye derivative>
<Dye derivative (B)>
The photosensitive composition of this invention contains the pigment derivative (B) represented by following General formula (1). The pigment derivative (B) is adsorbed on the pigment surface, and the primary particles of the pigment can be further refined.

General formula (1)

[In General Formula (1), R _{115 to} R ₁₁₇ each independently have a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. An optionally substituted phthalimidoalkyl group, an optionally substituted acyl group, an amino group, a sulfo group, a carboxyl group, a phosphoric acid group, a halogen group, general formulas (150) to (155), (158), or ( 159). ]

General formula (155)

[In the general formulas (150) to (155), X ₁ represents a direct bond, —SO ₂ —, —CO—, —C
_{H 2 -, - CH 2 NHCOCH} 2 -, - CONHC 6 H 4 CO-, or -CONHC ₆ H ₄ - represents a. Y ₁ is a direct bond, —NR ₁₇₀ SO ₂ —, —SO ₂ NR ₁₇₀ —, —CONR ₁₇₀ —, —NR ₁₇₀ CO—, or —CH ₂ NR ₁₇₀ COCH ₂ NR ₁₇₀ —.
Represents. Y ₂ represents a direct bond, an arylene group which may have a substituent, or a heteroaromatic ring which may have a substituent, and these groups are represented by —NR ₁₇₀ —, —O—, —SO _2. -Or CO
They may be bonded to each other through a divalent linking group selected from-. Y ₃ represents a direct bond, —NR ₁₇₀ — or —O—. o represents an integer of 0 to 20. M ₂ represents a hydrogen atom, a calcium atom, a barium atom, a strontium atom, a manganese atom or an aluminum atom. i represents the valence of _{M 2.}
R ₁₅₀ and R ₁₅₁ are each independently an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a phenyl group which may have a substituent, or R ₁₅₀ and R ₁₅₁ , And a heterocyclic ring optionally having a substituent containing a nitrogen, oxygen or sulfur atom. R _{152 to} R ₁₅₆ and R _{159 to} R ₁₆₂ are each independently a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a phenyl that may have a substituent. Represents a group or a polyoxyalkylene group. R ₁₅₇ and R ₁₅₈ are each independently a group represented by the following general formula (156) or (157), —O— (CH ₂ ) _o —R ₁₇₁ , —OR ₁₇₂ , —NR ₁₇₃ R ₁₇₄ , —Cl , —F or Y ₃ —Y ₂ —Y ₁ —Q, and _{one of} R ₁₅₇ and R ₁₅₈ is a group represented by the following general formula (156) or (157), —O— (CH ₂ ) _O -R ₁₇₁ , -OR ₁₇₂ , or NR ₁₇₃ R ₁₇₄ .
R ₁₇₀ represents a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a phenyl group that may have a substituent. R ₁₇₁ represents a heterocyclic residue which may have a substituent, and R _{172 to} R ₁₇₄ may each independently have a hydrogen atom, an alkyl group which may have a substituent, or a substituent. It represents a phenyl group which may have a good alkenyl group or substituent, and Q represents an organic dye residue. ]

General formula (156)

[In General Formula (156), Z ₁ represents —NR ₁₇₀ —, —CONH— or —O—, and Z ₂ represents an alkylene group which may have a substituent, or an alkenylene which may have a substituent. Group, an arylene group which may have a substituent, and these groups are represented by —NR ₁₇₀ —, —O—, —SO _2.
They may be bonded to each other by a divalent linking group selected from-or CO-. R ₁₇₀ represents a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a phenyl group that may have a substituent. R ₁₅₀ and R ₁₅₁ are each independently an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a phenyl group which may have a substituent, or R ₁₅₀ and R ₁₅₁ , And a heterocyclic ring optionally having a substituent containing a nitrogen, oxygen or sulfur atom. ]

Formula (157)

[In General Formula (157), Z ₃ represents a single bond connecting a triazine ring and a nitrogen atom, —NR ₁₇₅ —, —NR ₁₇₅ —Z ₄ —CO—, —NR ₁₇₅ —Z ₄ —CONR ₁₇₆ —, —NR _17
5- Z ₄ —SO ₂ —, —NR ₁₇₅ —Z ₄ —SO ₂ NR ₁₇₆ —, —O—Z ₄ —CO—
_{, -O-Z 4 -CONR 175 -} , - O-Z 4 -SO 2 -, or _{O-Z 4 -SO 2 NR 175} - _represent, respectively the R 152 _{to R 156} independently represents a hydrogen atom, a substituent Represents an alkyl group that may have a substituent, an alkenyl group that may have a substituent, a phenyl group that may have a substituent, or a polyoxyalkylene group.
R ₁₇₅ and R ₁₇₆ each independently represent a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a phenyl group that may have a substituent; ₄
Represents an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent.

[In the general formula _(159), X _{2 is, -SO 2 -, - CO -} , - NH -, - SO 2 NH -, - NHSO 2 -, - represents CONH- or _{NHCO-, R} 163 ~R ₁₆₇ Are each independently a hydrogen atom, an alkoxyl group, an amino group, a sulfo group, a carboxy group, a phosphoric acid group or a group represented by general formulas (150) to (155). ]

In general formulas (1) and (150) to (159),
In the alkyl group which may have a substituent, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, and the substituent which may have a hydrogen or halogen group is preferable.
In the phthalimidoalkyl group which may have a substituent, the alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, and the substituent which may have a hydrogen or halogen group is preferable.
In the acyl group which may have a substituent, the alkyl group is preferably an acyl group having 1 to 10 carbon atoms, and the substituent which may have a hydrogen or halogen group is preferable.
In the alkoxy group which may have a substituent, the alkyl group is preferably a linear alkoxy group having 1 to 5 carbon atoms, and the substituent which may have a hydrogen or halogen group is preferable. The alkenyl group or alkenylene group that may have a substituent is preferably hydrogen or a linear alkyl group having 1 to 10 carbon atoms as the substituent that may have.
The phenyl group which may have a substituent is preferably a hydrogen, a halogen group, a linear alkyl group having 1 to 10 carbon atoms, or an alkoxy group as the optionally substituted substituent.
The arylene group which may have a substituent is preferably a hydrogen, a halogen group, a linear alkyl group having 1 to 10 carbon atoms, or an alkoxy group as the optionally substituted substituent.
The heterocyclic ring which may have a substituent is preferably azacyclobutane, pyrrolidine, piperidine, tetrahydrofuran, tetrahydropyran, tetrahydrothiophene or tetrahydrothiopyran as the heterocyclic ring, and the substituent which may have a hydrogen or halogen group A linear alkyl group having 1 to 10 carbon atoms and an alkoxy group are preferable.
The heteroaromatic ring which may have a substituent is preferably pyrrole, pyridine, furan or thiophene as the heteroaromatic ring, and as a substituent which may have a hydrogen, a halogen group or a straight chain having 1 to 10 carbon atoms. An alkyl group and an alkoxy group are preferred.

  By adding the pigment derivative (B) to the pigment and performing pigmentation treatment such as acid pasting, acid slurry, dry milling, salt milling, and solvent salt milling, the pigment derivative (B) is adsorbed on the pigment surface, and the pigment Compared to the case where the derivative (B) is not added, the primary particles of the pigment can be further refined.

Further, in the present invention, the dye derivative (B) represented by the general formula (1) is strongly adsorbed to the pigment and mediates with a dispersant, a resin, and other polymerizable compounds. As a result, the pigment surface has polarity and the adsorption of the dispersing agent is promoted, the compatibility with the pigment, the dye derivative (B), the dispersing agent, the solvent, and other polymerizable compounds is improved, and the coloring composition and the coloring curable composition are improved. This has the effect of improving the dispersion stability of the product.
In addition, because the compatibility is improved, the distribution of the polymerizable compound inside the coating film becomes uniform when the photosensitive coloring composition is applied to glass, and unevenness in curability due to exposure is reduced. The stability and resolution of the are improved.
Further, by using a resin type dispersant (C) obtained by reacting a polymer having a hydroxyl group at at least one end with a tricarboxylic acid anhydride or tetracarboxylic dianhydride, adsorption of the pigment and the dispersing agent is achieved. It seems to be stronger. Moreover, the combined use of the resin-type dispersant (C) improves the permeability of the alkaline developer into the coating film, and has the effect of suppressing development time variations and development residues.

  The pigment derivative (B) is preferably 0.1 to 40% by mass, and 1 to 30% by mass when the total amount of the red pigment (A) and the pigment derivative (B) is 100 parts by mass. More preferred.

<Other pigment derivatives>
The photosensitive coloring composition of the present invention may contain other dye derivatives in addition to the dye derivative (B). Although it does not specifically limit as another pigment derivative, The well-known pigment derivative which has an acidic group, a basic group, a neutral group etc. in an organic pigment | dye residue can be used. For example, compounds having acidic substituents such as sulfo group, carboxy group and phosphoric acid group and amine salts thereof, compounds having basic substituents such as sulfonamide group and tertiary amino group at the terminal, phenyl group and phthalimide Examples thereof include compounds having a neutral substituent such as an alkyl group.
Examples of organic dyes include indole pigments such as anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, and benzoisoindoles. And isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, selenium pigments, metal complex pigments, azo pigments such as azo, disazo, and polyazo.
Specific examples of the diketopyrrolopyrrole dye derivative include JP2001-220520, WO2009 / 081930, WO2011 / 052617, WO2012 / 102399, JP2017-156397, phthalocyanine. JP-A-2007-226161, WO2016 / 163351, JP-A-2017-165820, JP-A-575266, and anthraquinone-based dye derivatives include JP-A-63-264673, JP 09-272812 A, JP 10-245501 A, JP 10-265697 A, JP 2007-079094 A, WO 2009/025325 pamphlet, Kina Examples of the redone-based dye derivatives include JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383, and examples of the dioxazine-based dye derivatives include JP-A-2011-162661 and thiazine indigo. JP-A-2007-314785 as a dye derivative, JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-314621 as triazine dye derivatives. No. 168208, JP-A No. 2004-217842, JP-A No. 2007-314682, JP-A 2009-57478 as a benzoisoindole dye derivative, and JP-A No. 2003-167112 as a quinophthalone dye derivative. Publication, JP 2006-291194 A JP-A-2008-31281, JP-A-2012-226110, JP-A-2012-208329, JP-A-2014-5439 as naphthol dye derivatives, and JP-A-2001 as azo dye derivatives. No. 172520, JP 2012-172092 A, acidic substituents as JP 2004-307854, basic substituents as JP 2002-201377, JP 2003-171594, Known pigment derivatives described in JP-A-2005-181383, JP-A-2005-213404 and the like can be mentioned. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound. However, the above organic dye residue has an acidic group, basic group, medium A compound having a substituent such as a functional group is synonymous with a pigment derivative.
These pigment derivatives can be used alone or in combination of two or more.

More specifically, the following pigment derivatives are preferable.

[Diketopyrrolopyrrole pigment derivatives]

[Dioxazine dye derivatives]
Upper general formula (109) and lower general formula (110)

[Benzoisoindole dye derivatives]

[Specific examples of quinophthalone derivatives]

[Azo derivatives]

In general formulas (101) to (103), (108) to (128), and (130) to (133), R _{101 to} R ₁₀₇ , R _{118 to} R ₁₃₀ , and R _{141 to} R ₁₄₅ are represented by the above general formula ( 1) As in R _{108 to} R ₁₁₀ described in (2), each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. A phthalimidoalkyl group which may have a substituent, an acyl group which may have a substituent, an amino group, a sulfo group, a carboxyl group, a phosphoric acid group, a halogen group, general formulas (150) to (155), (158) Or a group represented by (159). m and n represent a positive integer. However, when one molecule has a plurality of substituents, one or more is a substituent other than a hydrogen atom. Moreover, when there is only one substituent in one molecule, it is a substituent other than a hydrogen atom.
General formulas (150) to (155), (158), or (159) are as described in general formula (1) above.

<Resin type dispersant>
The photosensitive composition of this invention contains the resin type dispersing agent (C) which is a reaction product of the polymer which has a hydroxyl group at an at least 1 terminal, and a tricarboxylic acid anhydride or a tetracarboxylic dianhydride. The following (S1) or (S2) is mentioned as a carboxylic acid-type resin type dispersant dispersant. (S1) A resin-type dispersant that is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride and / or a tetracarboxylic dianhydride.
(S2) A polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride and / or a tetracarboxylic dianhydride. A resinous dispersant that is a coalescence.

[Resin type dispersant (S1)]
The resin-type dispersant (S1) can be produced by a known method such as WO2008 / 007776, JP2008-029901A, or JP2009-155406A. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at the terminal. For example, the ethylenically unsaturated monomer (r) is polymerized in the presence of the compound (q) having a hydroxyl group. It can be obtained as a polymer. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Since it is preferable that there are a plurality of terminal hydroxyl groups, a compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

That is, a polymer having two hydroxyl groups at one end, which is a more preferable example, includes the monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in the molecule. It can obtain as a polymer (p1) which polymerized the ethylenically unsaturated monomer (r) containing. The hydroxyl group of the polymer (p) having a hydroxyl group reacts with the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride to form an ester bond, while the anhydride ring is opened, and the carboxylic acid Produce.

[Resin type dispersant (S2)]
The resin-type dispersant (S2) can be produced by a known method such as JP2009-155406A, JP2010-185934A, JP2011-157416A, for example, a compound having a hydroxyl group By polymerizing the ethylenically unsaturated monomer (r) in the presence of a reaction product of the hydroxyl group of (q) and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride. can get. In particular, in the presence of a reaction product of the hydroxyl group of the compound (q1) having two hydroxyl groups and one thiol group in the molecule and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride. And a polymer obtained by polymerizing the ethylenically unsaturated monomer (r) containing the monomer (r1).

The difference between (S1) and (S2) is whether the polymer site obtained by polymerizing the ethylenically unsaturated monomer (r) is introduced first or later. The molecular weight and the like may be slightly different depending on various conditions, but theoretically the same can be obtained if the raw materials and reaction conditions are the same.

The resin-type dispersant (C) is preferably used in an amount of about 5 to 200% by mass relative to the total amount of the colorant, and more preferably about 10 to 100% by mass from the viewpoint of film formability. Furthermore, since it is excellent in the favorable lithography (resolution) in a image development process, about 10-40 mass% is the most preferable.

Two or more types of resin type dispersants (C) may be contained, including the following other resin type dispersants. In that case, the total amount is preferably within the above range.

The weight average molecular weight Mw of the resin-type dispersant (C) is preferably 5,000 or more and 30,000 or less from the viewpoint of developability. More preferably, it is 5,000 or more and 20,000 or less, and most preferably 5,000 or more and 10,000 or less. The acid value is preferably 10 or more and 150 or less, more preferably 40 or more and 120 or less, from the viewpoint of a balance between developability and dispersibility.

<Other dispersants>
The photosensitive coloring composition of this invention can contain other dispersing agents other than a resin type dispersing agent (C).
The resin-type dispersant has a colorant-affinity part that has the property of adsorbing to the added colorant and a part that is compatible with the colorant carrier, and is adsorbed to the added colorant and dispersed in the colorant carrier. It works to stabilize. Other resin-type dispersants are not particularly limited as long as they are resin-type dispersants other than the above-described resin-type dispersant (C), and known resin-type dispersants can be used.

Specifically, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, polysiloxane, long Oil-based dispersants such as chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly (lower alkyleneimines) and polyesters having free carboxyl groups, and salts thereof , (Meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, and other water-soluble resins and water-soluble resins Polymer compound, polyester, modified polyacrylate, Alkylene oxide / propylene oxide adduct, used phosphoric acid ester and the like, they may be used alone or in combination, is not necessarily limited thereto.

In addition to the above, other dispersants include a polymer dispersant having a basic functional group, a nitrogen atom-containing graft copolymer, a tertiary amino group in the side chain, a quaternary ammonium base, and a nitrogen-containing complex. A nitrogen atom-containing acrylic block copolymer having a functional group containing a ring and the like, a urethane polymer dispersant, and the like can be included.

The other resin-type dispersant is preferably used in an amount of about 5 to 200% by mass relative to the total amount of the colorant, and more preferably about 10 to 100% by mass from the viewpoint of film formability.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, manufactured by Big Chemi Japan. 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or LACTIMON, LACTIMON-WS, BYKUMEN, etc., SOLPERSE-3000, 9000, 1300 manufactured by Nippon Lubrizol , 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095 EFKA-46, 47, 48, 452, 4008, 4060, 4406, 4408, 450, 451, 453, 4540, 4800, 5070, 7500, 7554, 1101, 120, manufactured by BASF, etc., 55000, 56000, 76500, etc. 150, 1502, EfkaPU 4009, 4010, 4015, 4020, 4046, 4047, 4050, 4055, 4061, 4063, 4080, E ka PA 4400, 4401, 4402, 4403, 4414, 4450, EfkaPX 4300, 4310, 4320, 4330, 4340, 4350, 4700, 4701, 4731, 4732, Efka FA4610, 4665, 4666, DispexUltra PA 4501, 4503, 4550 4560, 4580, 4590, etc., Ajinomoto PAIN111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine Techno Co., Ltd. are preferable.

<Polymerizable compound (D)>
The photosensitive coloring composition of the present invention contains a polymerizable compound (D). The polymerizable compound (D) includes a monomer or oligomer that is cured by ultraviolet rays or heat to generate a transparent resin.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, trimethylolpropane tri (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, trimethylol Ropan PO modified tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, isocyanuric acid EO modified di (meth) acrylate, isocyanuric acid EO modified tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate , Ester acrylate, methylolated melamine (meth) acrylic acid ester, epoxy (meth) acrylate, urethane acrylate and other acrylic acid esters and methacrylic acid esters, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, Examples include, but are not necessarily limited to, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

As these commercially available products, KAYARAD R-128H, KAYARAD R526, KAYARAD PEG400DA, KAYARAD MAND, KAYA manufactured by Nippon Kayaku Co., Ltd.
RD NPGDA, KAYARAD R-167, KAYARAD HX-220, KAYARAD R-551, KAYARAD R712, KAYARADR-604, KAY
ARAD R-684, KAYARAD GPO-303, KAYARAD TMPTA,
KAYARAD DPHA, KAYARAD DPEA-12, KAYARAD DPHA
-2C, KAYARAD D-310, KAYARAD D-330, KAYARAD D
PCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, and M-303, M-305, M-30 manufactured by Toa Gosei Co., Ltd.
6, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, OSAKA ORGANIC BISCOAT # 310HP, BISCOAT # 335HP, BISCOAT # 700, BISCOAT # 295, BISCOAT # 330, biscoat # 360, biscoat #GPT, biscoat # 400, biscoat # 405, A-9300 manufactured by Shin-Nakamura Chemical Co., etc. can be suitably used.

The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by mass based on the total weight of the colorant (100 parts by mass), and 10 to 300 parts by mass from the viewpoint of photocurability and developability. It is more preferable that

(Polymerizable compound having an acid group)
The photopolymerizable monomer in the present invention may contain a photopolymerizable monomer having an acid group. Examples of the acid group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.

Examples of the photopolymerizable monomer having an acid group include esterified products of free hydroxyl group-containing poly (meth) acrylates of polyhydric alcohol and (meth) acrylic acid and dicarboxylic acids; Examples include esterified products with monohydroxyalkyl (meth) acrylates. Specific examples include monohydroxy oligoacrylates or monohydroxy oligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, etc. And a monoesterified product of free carboxyl group with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4 -Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid And monohydroxy monoacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, or monohydroxy monomethacrylates containing free carboxyl group-containing oligoesters and the like. However, the effects of the present invention are not limited to these.

As these commercially available products, Biscoat # 2500P manufactured by Osaka Organic Chemical Co., Ltd., M-5300, M-5400, M-5700, M-510, M-520 manufactured by Toa Gosei Co., Ltd., and the like can be suitably used.

  These photopolymerizable monomers having an acid group can be used singly or in combination of two or more at any ratio as required.

(Polymerizable compound having urethane bond)
The photopolymerizable monomer in the present invention may contain a photopolymerizable monomer containing at least one ethylenically unsaturated bond and one urethane bond. For example, a polyfunctional urethane acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, or a polyfunctional urethane obtained by reacting a polyfunctional isocyanate with an alcohol and further reacting a (meth) acrylate having a hydroxyl group. Examples thereof include urethane acrylate.

As the (meth) acrylate having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth)
Acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol ethylene oxide modified penta (meth) acrylate, dipentaerythritol propylene oxide modified penta (meth) Acrylate, dipentaerythritol caprolactone-modified penta (meth) acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction product of epoxy group-containing compound and carboxy (meth) acrylate, hydroxyl group-containing polyol polyacrylate Etc.

Moreover, as polyfunctional isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate,
Polyisocyanate etc. are mentioned.

Moreover, although there is no restriction | limiting in the structure of alcohol, when a polyhydric alcohol is used, since the crosslinking degree of a cured coating film becomes high and coating-film resistance goes up, it is preferable. Examples of the polyhydric alcohol include propylene glycol, ethylene glycol, glycerin, trimethylolpropane, and pentaerythritol.

As these commercial products, AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167, manufactured by Kyoeisha Chemical Co., Ltd., manufactured by Shin-Nakamura Chemical Co., Ltd. UA-160TM, UV-4108F manufactured by Osaka Organic Chemical Industry Co., Ltd., UV-4117F, and the like can be suitably used.

  These photopolymerizable monomers having a urethane bond can be used singly or in combination of two or more at any ratio as required.

<Photopolymerization initiator (E)>
The photosensitive composition of the present invention contains a photopolymerization initiator (E). By including the photopolymerization initiator (E), the composition can be cured by ultraviolet irradiation, and a filter segment can be formed by a photolithography method. It is preferable to prepare it in the form of a solvent development type or alkali development type photosensitive composition by adding a photopolymerization initiator (E).

As photopolymerization initiator (E), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl Acetophenone compounds such as 1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Or benzoin compounds such as benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 Benzophenone compounds such as', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4- Thioxanthone compounds such as diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-me Xylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoy Oxime)], or oxime ester compounds such as ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); Phosphine compounds such as 2,4,6-trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone A borate compound; a carbazole compound; an imidazole compound; or a titanocene compound.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

Commercially available acetophenone compounds are all manufactured by BASF Corporation, “IRGACURE 907” (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one), “IRGACURE 369”. (2- (dimethylamino) -2-
[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone), “IRGACURE 379” 2-benzyl-2-dimethylamino-1-
As (4-morpholinophenyl) -butan-1-one and phosphine compounds, all manufactured by BASF "IRGACURE 819" (bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide), "IRGACURE TPO" (2,4,6-trimethylbenzoyldiphenylphosphine oxide), and the like.

  In this invention, it is preferable to contain an oxime ester type compound among these.

(Oxime ester compounds)
The oxime ester-based compound absorbs ultraviolet rays to cleave the N—O bond of the oxime to generate an iminyl radical and an alkyloxy radical. Since these radicals are further decomposed to generate radicals with high activity, a pattern can be formed with a small exposure amount. When the concentration of the colorant in the photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may be low and the curing degree of the coating film may be low. However, the oxime ester compound is preferably used because of its high quantum efficiency. The More preferred is an oxime ester photopolymerization initiator represented by the general formula (5).

(Oxime ester photopolymerization initiator represented by the general formula (5))
General formula (5)

In general formula (5),
Y ¹ is a hydrogen atom or an optionally substituted alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group An alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group,
Y ² is a hydrogen atom or an optionally substituted alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group , An alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group.
Z is a direct bond or a -CO- group,
Y ³ is a monovalent organic group including a carbazole group which may have a substituent, a Ph-S-Ph- group (Ph represents a phenyl group or a phenylene group which may have a substituent). Etc.

Examples of the alkenyl group which may have a substituent in Y ¹ include a linear, branched, monocyclic or condensed polycyclic alkenyl group having 1 to 18 carbon atoms, and these include a plurality of carbon atoms in the structure. -It may have a carbon double bond, and specific examples include vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group. 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1 , 3-butadienyl group, cyclohexadienyl group, cyclopentadienyl group and the like, but are not limited thereto.

The alkyl group which may have a substituent in Y 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 1 Examples include linear, branched, monocyclic or condensed polycyclic alkyl groups interrupted by one or more —O—. Specific examples of linear, branched, monocyclic or condensed polycyclic alkyl groups 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 —. _{CH 3 -, - CH 2 -CH-} (OCH 3) but ₂ and the like, but is not limited thereto.

  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 alkyloxy group which may have a substituent in Y ¹ is a linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms. Examples include linear, branched, monocyclic or condensed polycyclic alkyloxy groups optionally 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, boronyl Alkoxy group, may be mentioned 4-decyl cyclohexyl 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 aryl group that may have a substituent in Y ¹ include a monocyclic or condensed polycyclic aryl group having 6 to 24 carbon atoms, and specific examples thereof include a phenyl group, a 1-naphthyl group, and 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 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-bromophenyl 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 aryloxy group which may have a substituent for Y ¹ include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms. Specific examples include a phenoxy group, a 1-naphthyloxy group, 2- Naphtyloxy group, 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group , 9-fluorenyloxy group and the like, but are not limited thereto.

Examples of the heterocyclic group which may have a substituent for Y 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. 2-thienyl group, 2-benzothienyl group, naphtho [2,3-b] thienyl group, 3-thianthrenyl 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 Lyl 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 4-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 heterocyclic oxy group that may have a substituent for Y 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. Specific examples include 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyl. Examples thereof include, but are not limited to, a ruoxy group, a 3-carbazolyloxy group, a 4-carbazolyloxy group, and a 9-acridinyloxy group.

Examples of the alkylsulfanyl group which may have a substituent in Y ¹ include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms. Specific examples include a methylthio group. , 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 arylsulfanyl group which may have a substituent for Y ¹ include a monocyclic or condensed polycyclic arylthio group having 6 to 18 carbon atoms, and specific examples thereof include a phenylthio group, a 1-naphthylthio group, 2- A naphthylthio group, a 9-anthrylthio group, a 9-phenanthrylthio group and the like are exemplified, but the invention is not limited thereto.

The alkylsulfinyl group which may have a substituent in Y ¹ is preferably an alkylsulfinyl group having 1 to 20 carbon atoms, and specific examples thereof include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, Butylsulfinyl group, hexylsulfinyl group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methyloxymethylsulfinyl group, etc. Although it is mentioned, it is not limited to these.

The arylsulfinyl group which may have a substituent in Y ¹ is preferably an arylsulfinyl group having 6 to 30 carbon atoms, and specific examples thereof include a phenylsulfinyl group, a 1-naphthylsulfinyl group, a 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methyloxyphenylsulfinyl group, 2-butyloxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methyloxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4- Examples thereof include, but are not limited to, a phenylsulfanylphenylsulfinyl group and a 4-dimethylaminophenylsulfinyl group.

The alkylsulfonyl group which may have a substituent in Y 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, Butylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methyloxymethylsulfonyl group, etc. Although it is mentioned, it is not limited to these.

The arylsulfonyl group which may have a substituent for Y 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, 2-chlorophenylsulfonyl 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 Examples thereof include, but are not limited to, a nyl group and a 4-dimethylaminophenylsulfonyl group.

Examples of the acyl group that may have a substituent in Y 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. A carbonyl group substituted by an alkyloxy group having 2 to 20 carbon atoms, a carbonyl group to which a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms is bonded, or a monocyclic or condensed polycyclic aryloxy group having 6 to 18 carbon atoms. Examples include a substituted carbonyl group, a carbonyl group having a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include formyl Group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, Thearoyl 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, butyloxycarbonyl Group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, trifluoromethyloxycarbonyl group, benzoyl group, toluoyl group, 1-naphthoyl group, 2-naphthoyl group, 9-anthrylcarbonyl Group, phenyloxycarbonyl group, 4-methylphenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-dimethylaminophenyloxy group Carbonyl group, 2-methylsulfanylphenyloxycarbonyl group, 1-naphthoyloxycarbonyl group, 2-naphthoyloxycarbonyl group, 9-anthrylyloxycarbonyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, isonicotinoyl Although groups etc. can be mentioned, it is not limited to these.

Examples of the acyloxy group which may have a substituent in Y ¹ include an acyloxy group having 2 to 20 carbon atoms, and specific examples include an acetyloxy group, a propanoyloxy group, a butanoyloxy group, and a pentanoyloxy group. Group, trifluoromethylcarbonyloxy group, benzoyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group and the like.

Examples of the amino group which may have a substituent in Y 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. Can be mentioned.

  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 group includes 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 phosphinoyl group which may have a substituent in Y ¹ include phosphinoyl groups having 2 to 50 carbon atoms, and specific examples thereof include dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group. Group, diphenylphosphinoyl group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group, etc. Is not to be done.

Examples of the carbamoyl group which may have a substituent for Y ¹ include carbamoyl groups having 1 to 30 carbon atoms, and specific examples thereof include an N-methylcarbamoyl group, an N-ethylcarbamoyl group, and an 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 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-cyanoph Enylcarbamoyl 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 sulfamoyl group which may have a substituent in Y ¹ include a sulfamoyl group having 0 to 30 carbon atoms, and specific examples thereof include a sulfamoyl group, an N-alkylsulfamoyl group, and an N-arylsulfamoyl group. Group, 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.

Y ² may have a substituent, an alkenyl group, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, As the arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, and amino group, the aforementioned alkenyl group that may have a substituent in R1, an alkyl group that may have a substituent, and a substituent An alkyloxy group that may have, an aryl group that may have a substituent, an aryloxy group that may have a substituent, a heterocyclic group that may have a substituent, and a substituent A good heterocyclic oxy group, an optionally substituted alkylsulfanyl group, an optionally substituted arylsulfanyl group, and a substituent. Alkylsulfinyl group which may have, arylsulfinyl group which may have substituent, alkylsulfonyl group which may have substituent, arylsulfonyl group which may have substituent, and substituent It is synonymous with the acyloxy group which may be sufficient, and the amino group which may have a substituent.

Examples of these substituents in Y ¹ and Y ² 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, phenoxy group and p-tolyloxy. Aryloxy groups such as methoxycarbonyl groups, butoxycarbonyl groups, alkoxycarbonyl groups such as phenoxycarbonyl groups, acyloxy groups such as acetoxy groups, propionyloxy groups, benzoyloxy groups, acetyl groups, benzoyl groups, isobutyryl groups, acryloyl groups , Acyl groups such as methacryloyl group and methoxalyl group, alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group, arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group, methylamino group Alkylamino group such as cyclohexylamino group, dialkylamino group such as dimethylamino group, diethylamino group, morpholino group, piperidino group, arylamino group such as phenylamino group, p-tolylamino group, methyl group, ethyl group, tert-butyl Group, dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctadecyl group and other alkyl groups, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group In addition to aryl groups such as anthryl group and phenanthryl group, heterocyclic groups such as furyl group and thienyl group, etc., hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group Group, nitro group, cyano group, trif Examples thereof include a fluoromethyl group, a trichloromethyl group, a trimethylsilyl group, a phosphinico group, a phosphono group, a trimethylammoniumyl group, a dimethylsulfoniumum group, and a triphenylphenacylphosphoniumyl group.
One or more kinds of these substituents may be present, and the hydrogen atom of these substituents may be further substituted with other substituents.

  Among the oxime ester photopolymerization initiators represented by the general formula (5), the oxime ester photopolymerization initiator represented by the following general formula (6) or (7) is excellent in sensitivity and more preferable. is there.

[Oxime ester photopolymerization initiator represented by general formula (6)]
General formula (6)

The general formula (6) corresponds to the case where Z in the general formula (5) is a —CO— group and Y ³ is a Ph—S—Ph— group, and Y ⁴ to Y ⁶ represent a hydrogen atom or a substituent. An alkyl group or an aryl group which may be contained is preferable. The alkyl group that may have a substituent or the aryl group that may have a substituent in Y ^{4 to} Y ⁶ has the same meaning as the alkyl group or the aryl group in Y ¹ and Y ² .

Further, Y ¹ may be an aryl group that may have a substituent, Y ² may be an optionally substituted alkyl group having 1 to 20 carbon atoms, and Y ⁴ and Y ⁶ may further be a hydrogen atom. Y ⁵ is more preferably a hydrogen atom or a Y ⁷ —CO— group.

As Y ⁷ , for example, 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, aryloxy groups such as phenoxy group and p-tolyloxy group, Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, etc., acyloxy groups such as acetoxy group, propionyloxy group, benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, methoxalyl group, etc. An acylsulfanyl group such as an acyl group, a methylsulfanyl group, and a tert-butylsulfanyl group; an arylsulfanyl group such as a phenylsulfanyl group and a p-tolylsulfanyl group; a methylamino group and a cyclohexylamino group; Killamino, dimethylamino, diethylamino, morpholino, piperidino and other dialkylamino groups, phenylamino, p-tolylamino and other arylamino groups, methyl, ethyl, tert-butyl, dodecyl, etc. In addition to aryl groups such as alkyl groups, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, and benzofuranyl groups, heterocyclic groups such as furyl groups and thienyl groups, hydroxy groups, 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 Mill group, dimethylsulfonyl group, And a rephenylphenacylphosphoniumyl group.

More preferable examples of the substituent for Y ² include cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclooctadecyl group.

  Specific examples of the oxime ester photopolymerization initiator represented by the general formula (6) include a photopolymerization initiator represented by the following chemical formula (6-1) or (6-2). A photopolymerization initiator represented by the chemical formula (6-3) or (6-4) as a similar structure is also preferred.

The general formula (7) corresponds to the case where Y ³ in the general formula (5) is a monovalent organic group including a carbazole group which may have a substituent, and Y ⁷ to Y ¹⁴ are Y ¹ and Y It is synonymous with the substituent in ² .

Furthermore, the alkyl group having 1 to 20 carbon atoms which may have a substituent as Y ¹ may have an alkyl group having 1 to 20 carbon atoms which may have a substituent as Y ² or a substituent. A good aryl group is preferably a hydrogen atom as Y ^{7 to} Y ¹⁴ , an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent.

  When Z in the general formula (7) is a direct bond, an oxime ester photopolymerization initiator represented by the following general formula (7a) is preferable.

"Oxime ester photopolymerization initiator represented by general formula (7a)"
General formula (7a)

The general formula (7a) corresponds to the case where Z in the general formula (7) is a direct bond and Y ³ is a monovalent organic group including a carbazole group which may have a substituent. Y < ⁷ > -Y < ¹⁰ > and Y < ¹² > -Y < ¹³ > are hydrogen atoms.
Y ¹¹ is preferably a Y ¹⁵ —CO— group or a nitro group. Y ¹⁵ is ^{Y 1}
And an aryl group which is synonymous with the substituent in Y ² and may have a substituent. The Y ¹⁵ —CO— group is preferably an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, or a methoxalyl group, which may further have a substituent. More preferably, it is a benzoyl group or nitro group which may have a substituent. Y ¹⁴ is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent.

Moreover, as a substituent in the benzoyl group which may have a substituent, a C1-C20 alkyl group or an alkyloxy group is preferable. Further, the alkyl group is preferably a methyl group or an ethyl group, and among the alkyloxy groups, a linear or branched chain having 2 to 18 carbon atoms and optionally interrupted by one or more —O— Monocyclic or condensed polycyclic alkyloxy groups are preferred, linear, branched, monocyclic or condensed polycyclic having 2 to 18 carbon atoms in Y ¹ and optionally interrupted by one or more —O— Synonymous with alkyloxy group.

Y ² is preferably an alkyl group having 1 to 20 carbon atoms that may have a substituent, and the substituent is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, A cycloalkyl group such as a cyclooctadecyl group; In addition, an aryl group which may have a substituent is preferable, and as the substituent, an alkyl group having 1 to 20 carbon atoms which may further have a substituent, a methoxy group, an ethoxy group, or a tert-butoxy group Etc. are preferred.

  Specific examples of the oxime ester photopolymerization initiator represented by the general formula (7a) include photopolymerization initiators represented by the following chemical formulas (7a-1) to (7a-6).

"Oxime ester photopolymerization initiator represented by the general formula (7b)"
When Z in the general formula (7) is a -CO- group, an oxime ester photopolymerization initiator represented by the following general formula (7b) is preferable.

General formula (7b)

General formula (7b) corresponds to the case where Z in the general formula (7) is a -CO- group and Y ³ is a monovalent organic group including a carbazole group which may have a substituent. Is an oxime ester photopolymerization initiator. Y ^{7 to} Y ¹³ are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and Y ¹⁴ may have a substituent. A good aryl group is preferred. As the substituent of the aryl group which may have a substituent, an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group and a methoxalyl group is preferable, and a benzoyl group is more preferable.

  Specific examples of the oxime ester photopolymerization initiator represented by the general formula (7b) include photopolymerization initiators represented by the following chemical formulas (7b-1) to (7b-4).

Commercially available products of these oxime ester compounds include 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (IR from BASF
GACURE OXE-01), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (IRGACURE OXE 02), N- 1919 (made by ADEKA), TRONLYTR-P
BG-304, TRONLY TR-PBG-305, TRONLY TR-PBG-309 (all of which are manufactured by Changzhou Strong New Materials Co., Ltd.) are commercially available. In addition to these, oximes described in JP2007-210991A, JP2009-179619A, JP2010-037223A, JP2010-215575A, JP2011-020998A, and the like. It is also possible to use an ester photopolymerization initiator.

  The content of the oxime ester-based compound is preferably 2 to 50 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 2 to 30 parts by mass from the viewpoint of photocurability and developability. When the amount is less than 2 parts by mass, the adhesion of the formed pattern to the substrate is deteriorated, and when it exceeds 50 parts by mass, there may be a problem in developability or a decrease in brightness after heat treatment at 230 ° C.

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

  Among the sensitizers, sensitizers that can be sensitized particularly preferably 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.

These sensitizers can be used singly or in combination of two or more at any ratio as required.
Examples of commercially available products include “KAYACURE DETX-S” (2,3-diethylthioxanthone manufactured by Nippon Kayaku Co., Ltd.) and “EAB-F” (4,4′-bis (diethylamino) benzophenone manufactured by Hodogaya Chemical Co., Ltd.). It is done.

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

Content when using a sensitizer is radical photopolymerization initiator 100 contained in a coloring composition.
It is preferable that it is 3-60 mass parts with respect to a mass part, and it is more preferable that it is 5-50 mass parts from a viewpoint of photocurability and developability.

<Resin binder (F)>
The photosensitive composition of the present invention contains a resin binder (F). The resin binder (F) is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm. The resin binder (F) is classified into its main curing method, and includes thermoplastic resin, thermosetting resin, active energy ray curable resin having an ethylenically unsaturated double bond, etc., and active energy ray curable resin. May be a thermoplastic resin or may have a thermosetting function, and is preferably an alkali-soluble resin from the viewpoint of developability. Further, it may contain a thermoplastic resin that is not active energy ray curable, and it is preferable that this is also alkali-soluble. These can be used alone or in admixture of two or more.

The content of the resin binder (F) in the photosensitive composition of the present invention is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, based on the total weight of the colorant (100 parts by mass). is there. It is preferably used in an amount of 20 parts by mass or more because the film formability and various resistances are good, and it is preferably used in an amount of 400 parts by mass or less because the colorant concentration is high and good color characteristics can be expressed. .

<Thermoplastic resin>
Examples of the thermoplastic resin that can be used as the resin binder (F) include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, and vinyl chloride-vinyl acetate. Polymer, polyvinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and A polyimide resin etc. are mentioned.
The thermoplastic resin is preferably alkali-soluble, and examples thereof include resins having acidic groups such as carboxyl groups and sulfone groups. Specific examples of the resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or isobutylene / And (anhydrous) maleic acid copolymer. Among them, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an alkali-soluble resin having an acidic group and / or a hydroxyl group, has developability, heat resistance, and transparency. Since it is high, it is preferably used.

<Alkali-soluble resin>
It is preferable that the photosensitive resin composition of this invention contains alkali-soluble resin from the point of developability, heat resistance, and transparency. This is for imparting development solubility in the alkali development step when producing the color filter, and has an acid group and / or a hydroxyl group. In order to further improve the photosensitivity, it is more preferable to use a resin having an ethylenically unsaturated double bond.

<Alkali-soluble resin having an ethylenically unsaturated double bond>
The alkali-soluble resin contained in the photosensitive resin composition of the present invention preferably has an ethylenically unsaturated double bond. In particular, by using a resin into which an ethylenically unsaturated double bond is introduced by the following methods (i) and (ii), the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. As a result, the crosslink density is increased and the chemical resistance is improved.

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

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4-epoxybutyl (meth) acrylate. And 3,4-epoxycyclohexyl (meth) acrylate, which may be used alone or in combination of two or more. 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 polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. 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. Further, when tetrahydrophthalic 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 side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers. There is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of a carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and an unsaturated monobasic acid monomer having another carboxyl group or another 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 methacrylates such as mono (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 hydroxyalkyl (meth) acrylate, polyγ-valerolactone, polyε-caprolactone, and / or Polyester mono (meth) acrylate added with poly-12-hydroxystearic acid or the like can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl methacrylate or glycerol mono (meth) acrylate is preferable. From the viewpoint of sensitivity, it is preferable to use one having 2 to 6 hydroxyl groups. Glycerol mono (meth) acrylate is more preferable.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloylethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [methacryloyloxy] ethyl isocyanate, and the like. However, two or more types can be used in combination without being limited to these.

The following are mentioned as a monomer which comprises alkali-soluble resin. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) Acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypolyethylene Glycol (meth) acrylate of (meth) acrylates,
Alternatively, (meth) acrylamide (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine, etc. Acrylamide styrene, styrene such as α-methylstyrene, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, vinyl ethers such as isobutyl vinyl ether, fatty acid vinyls such as vinyl acetate, or vinyl propionate Etc.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimide ethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4′-bismaleimide diphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N′-1,3-phenylenedimaleimide, N, N′-1,4- Phenylene dimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succin Midyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N- [4- (2-benzimidazolyl) phenyl N-substituted maleimides such as maleimide and 9-maleimide acridine,
Compounds represented by the following general formula (8), specifically EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, phenol ethylene oxide (EO) modified (meth) acrylate EO or propylene oxide (PO) modified (meth) acrylate of paracumylphenol, EO modified (meth) acrylate of nonylphenol, PO modified (meth) acrylate of nonylphenol, and the like.

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.)

A carboxyl group-containing ethylenically unsaturated monomer can also be used. Examples of the carboxyl group-containing ethylenically unsaturated monomer include acrylic acid, methacrylic acid, ε-caprolactone-added acrylic acid, ε-caprolactone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

Moreover, a hydroxyl-containing ethylenically unsaturated monomer can also be used. Examples of the hydroxyl group-containing ethylenically unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, or cyclohexane. And hydroxyalkyl (meth) acrylates such as dimethanol mono (meth) acrylate. Polyether mono (meth) acrylates 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) ester mono (meth) acrylate added with (poly) 12-hydroxystearic acid and the like.

A phosphoric ester group-containing ethylenically unsaturated monomer can also be used. As the phosphoric ester group-containing ethylenically unsaturated monomer, for example, a monomer that can be obtained by reacting the hydroxyl group of the hydroxyl group-containing ethylenically unsaturated monomer with a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid. Is mentioned.

<Alkali-soluble resin having no ethylenically unsaturated double bond>
The photosensitive resin composition of the present invention can contain an alkali-soluble resin having no ethylenically unsaturated double bond in order to adjust the degree of curing of the coating film. By synthesizing at least one kind of carboxyl group-containing ethylenically unsaturated monomer and one or more other ethylenically unsaturated monomers, and by not giving an ethylenically unsaturated bond to the side chain, It is possible to obtain an alkali-soluble resin that does not have an unsaturated double bond.

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

The weight average molecular weight (Mw) of the alkali-soluble resin in the present invention is from 2,000 to 40,000, preferably from 3,000 to 30,000, preferably 4,000, in order to impart alkali development solubility. More preferable is 20,000 or less. Moreover, it is preferable that the value of Mw / Mn is 10 or less. When the weight average molecular weight (Mw) is less than 2,000, the adhesion to the substrate is lowered, and the exposed pattern is less likely to remain. If it exceeds 40,000, the alkali development solubility is lowered, a residue is generated, and the linearity of the pattern is deteriorated.
The acid value of the alkali-soluble resin in the present invention is from 50 to 200 (KOHmg / g) in order to impart alkali development solubility, preferably in the range from 70 to 180, more preferably from 90 to 170. It is a range. When the acid value is less than 50, the alkali development solubility is lowered, a residue is generated, and the linearity of the pattern is deteriorated. If it exceeds 200, the adhesion to the substrate is lowered, and the exposure pattern is less likely to remain.
<Solvent (G)>
In the photosensitive coloring composition of the present invention, the coloring agent is sufficiently dispersed and permeated in the coloring agent carrier, and applied to a glass substrate or the like so that the dry film thickness is 0.2 to 5 μm. In order to facilitate the formation of the film, it is essential to contain the solvent (G). The solvent (G) is selected in consideration of good applicability of the photosensitive composition, solubility of each component of the photosensitive composition, and safety.

Examples of the solvent (G) include 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate. 1,4-butanediol diacetate, 1,4-
Dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3 -Methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene , M-diethylbenzene, 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, -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 monohexyl ether, ethylene glycol monomethyl ether, 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 Ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene 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 acetate, propyl acetate, dibasic acid ester, etc. Is mentioned.
These solvents can be used alone or in admixture of two or more at any ratio as required.

  Among them, the dispersibility of the colorant, the penetrability, and the coating property of the photosensitive composition are good, so that ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol diacetate, ethylene glycol monomethyl ether Acetates such as acetate, ethylene glycol monoethyl ether acetate, 1,3-butylene glycol diacetate, cyclohexanol acetate, 1,4-butanediol diacetate, butanediol diacetate, benzyl alcohol, diacetone alcohol, 1-methoxy It is preferable to use alcohols such as 2-propanol and 3-methoxybutanol, ketones such as cyclohexanone, ethyl 3-ethoxypropionate, and the like.

  In addition, the solvent (G) adjusts the photosensitive composition to an appropriate viscosity and can form a desired colored film having a uniform film thickness. Therefore, the amount of the solvent (G) is 500 to 4000 parts by mass with respect to 100 parts by mass of the colorant. It is preferable to use in.

<Epoxy compound>
It is preferable to add an epoxy compound to the photosensitive coloring composition of the present invention. As an epoxy compound to be used, a known compound having an epoxy group can be used without particular limitation.

Epoxy compounds include phenol novolac type epoxy resin, cresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, biphenol type epoxy. Examples thereof include resins, bisphenol-A novolac type epoxy resins, naphthalene skeleton-containing epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins.
Among these, it is preferable that the epoxy compound is an alicyclic epoxy resin from the viewpoint of improvement of water spots or heat resistance and chemical resistance.

  Specific examples of the phenol novolac type epoxy resin include, for example, Epicron N-740, Epicron N-770, Epicron N-775 manufactured by DIC Corporation, and D.C. E. N438, Nippon Kayaku Co., Ltd. RE-306, Mitsubishi Chemical Corporation jER152, jER154, etc. are mentioned.

  Specific examples of the cresol novolac type epoxy resin include Epicron N-660, Epicron N-665, Epicron N-670, Epicron N-673, Epicron N-680, Epicron N-695, and Epicron N-665 manufactured by DIC Corporation. EXP, Epicron N-672-EXP, Nippon Kayaku Co., Ltd. EOCN-102S, EOCN-103S, EOCN-104S, Union Carbide Corporation UVR-6650, Sumitomo Chemical Co., Ltd. ESCN-195 etc. are mentioned.

Specific examples of the trishydroxyphenylmethane type epoxy resin include Nippon Kayaku Co., Ltd. EPPN-503, EPPN-502H, EPPN-501H, Dow Chemical Co., Ltd. TACTIX-742, Mitsubishi Chemical Co., Ltd. jERE1032H60, and the like. It is done.

Specific examples of the dicyclopentadiene phenol type epoxy resin include Epicron EXA-7200 manufactured by DIC Corporation, TACTIX-556 manufactured by Dow Chemical Corporation, and the like.

  Specific examples of the bisphenol type epoxy resin include jER828 and jER1001 manufactured by Mitsubishi Chemical Corporation, UVR-6410 manufactured by Union Carbide Corporation, and D.C. E. Bisphenol-A type epoxy resin such as R-331, YC-8125 manufactured by Nippon Kayaku Manufacturing Co., Ltd., UVR-6490 manufactured by Union Carbide Co., Ltd., YDF-8170 manufactured by Nippon Kayaku Epoxy Manufacturing Co., Ltd. An epoxy resin etc. are mentioned.

Specific examples of the biphenol type epoxy resin include biphenol type epoxy resins such as NC-3000 and NC-3000H manufactured by Nippon Kayaku Co., Ltd., jERY manufactured by Mitsubishi Chemical Corporation.
Examples thereof include xylenol type epoxy resins such as X-4000 and jER YL-6121.

  Specific examples of the bisphenol A novolac type epoxy resin include Epicron N-880 manufactured by DIC Corporation, jER E157S75 manufactured by Mitsubishi Chemical Corporation, and the like.

  Specific examples of the naphthalene skeleton-containing epoxy resin include NC-7000 and NC-7300 manufactured by Nippon Kayaku Co., Ltd., EXA-4750 manufactured by DIC Corporation, and the like.

  Specific examples of the alicyclic epoxy resin include Seikeside 2021P, 2081, 2000, Epolide PB3600, PB4700, GT401, EHPE-3150, and Cyclomer M100 manufactured by Daicel Corporation.

  Specific examples of the heterocyclic epoxy resin include TEPIC-L, TEPIC-H, and TEPIC-S manufactured by Nissan Chemical Industries, Ltd.

  These epoxy compounds can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  Content of the epoxy compound used for the coloring composition of this invention is 0.5-50 mass% normally in 100 mass% of solid content of a coloring composition, Preferably it is 1-40 mass%. When the content of the epoxy compound is in the above range, heat resistance is high and an excellent coating film is obtained, which is preferable.

<Oxetane compound>
It is preferable to add an oxetane compound to the photosensitive coloring composition of the present invention. As the oxetane compound, a known compound having an oxetane group is not particularly limited and can be used. Examples of the oxetane compound include those in which the oxetane group is monofunctional, those in which the oxetane group is bifunctional, and those in which the oxetane group is bifunctional or more.

Examples of the monofunctional oxetane group include (3-ethyloxetane-3-yl) methyl acrylate, (3-ethyloxetane-3-yl) methyl methacrylate, and 3-ethyl-3.
-Hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-methacryloxymethyl) oxetane, 3- And ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane.
Specific examples include OXE-10 manufactured by Osaka Organic Chemical Industry Co., Ltd., OXE-30 manufactured by Toagosei Co., Ltd., OXT-101, 212, and the like.

Examples of the bifunctional oxetane group include 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl), 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl]. Benzene, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di [1-ethyl (3-oxetanyl)] methyl ether, di [1-ethyl (3-oxetanyl)] methyl Ether-3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (2-phenoxymethyl) oxetane, 3,7-bis (3- Oxetanyl) -5-oxa-nonane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3- Til-3-oxetanylmethoxy) methyl] propane, ethyleneglycose bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethyleneglycolbis (3-ethyl) -3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl) -3-Oxetanylmethoxy) hexane, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bis Enol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ) Ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether, and the like.
Specific examples include Ube Industries, Ltd., OXBP, OXTP, Toagosei Co., Ltd., OXT-121, OXT-221, and the like.

As an oxetane group having 3 or more functional groups,
Pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol penta Kis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified di Pentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, oxy Resin (e.g., Patent No. 3,783,462 No. oxetane-modified phenol novolak resin according) containing Tan group or above, such as OXE-30 (meth) polymers obtained by the acrylic monomer by radical polymerization. Such a polymer can be obtained using a known polymerization method.

  Content of the oxetane compound used for the photosensitive coloring composition of this invention is 0.5-50 mass% normally in 100 mass% of solid content of a coloring composition, Preferably it is 1-40 mass%. It is preferable for the content of the oxetane compound to be in the above range since an excellent coating film having good water spots and high chemical resistance can be obtained.

<Thiol chain transfer agent>
The photosensitive coloring composition of the present invention preferably contains a thiol chain transfer agent as the chain transfer agent. By using a thiol together with a photopolymerization initiator, a thiyl radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated in the radical polymerization process after light irradiation, so that the resulting colored composition has high sensitivity. .

Further, a polyfunctional aliphatic thiol bonded to an aliphatic group such as methylene or ethylene group having two or more SH groups is preferable. More preferably, it is a polyfunctional aliphatic thiol having 4 or more SH groups. By increasing the number of functional groups, the polymerization initiation function is improved, and the pattern can be cured from the surface to the vicinity of the substrate.

Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropioate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibu Tilamino) -4,6-dimercapto-s-triazine and the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate.

  These thiol chain transfer agents can be used singly or in combination of two or more.

Moreover, it is preferable that content of a thiol type | system | group chain transfer agent is 1 to 10% in the total solid of a coloring composition, More preferably, it is 2.0 to 8.0%. In this range, the effect of the chain transfer agent is increased, and the sensitivity, taper shape, wrinkle, film shrinkage ratio and the like are improved.

<Ultraviolet absorber>
The photosensitive coloring composition of the invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorbing function, and examples thereof include benzotriazole organic compounds, triazine organic compounds, benzophenone organic compounds, cyanoacrylate organic compounds, and salicylate organic compounds. .

As for content of a ultraviolet absorber, 5-70 mass% is preferable in a total of 100 mass% of a photoinitiator and a ultraviolet absorber. When the content of the UV absorber is less than the above, the effect of the UV absorber is small and the resolution cannot be ensured. When the content is more than the above, the sensitivity is lowered and the pixel peeling or the hole diameter becomes larger than the design value. May cause problems.

At this time, when the photosensitive coloring composition contains a sensitizer, the content of the sensitizer is included in the content of the photopolymerization initiator.

Further, the total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass in 100% by mass of the solid content of the photosensitive coloring composition. If the total content of the photopolymerization initiator and the ultraviolet absorber is less than the above, the adhesion is weakened and pixel peeling occurs, and if it is more than the above, the sensitivity may be too high and the resolution may deteriorate.

At this time, when the photosensitive coloring composition contains a sensitizer, the content of the sensitizer is included in the content of the photopolymerization initiator.

Examples of the benzotriazole-based organic compound include 2- (5 methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, and octyl-3 [3-tert-butyl. -4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H) -Benzotriazol-2-yl) phenyl] propionate, 2- [2-hydroxy-
3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (
3-tbutyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy- 5'-t-octylphenyl) benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3- (2H-benzotriazol-2-yl)-(1,1-dimethyl) Ethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester compounds, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) pheno Le, and the like.

More specifically, “TINUVIN P”, “TINUVIN PS”, “TINUVIN 109”, “TINUVIN 234”, “TINUVIN 326” manufactured by BASF,
"TINUVIN 328", "TINUVIN 329", "TINUVIN 360"
, “TINUVIN 384-2”, “TINUVIN 900”, “TINUVIN 9”
28 "," TINUVIN 99-2 "," TINUVIN 1130 "," ADEKA STAB LA-29 "manufactured by ADEKA," RUNA-93 "manufactured by Otsuka Chemical and the like.

Examples of triazine organic compounds include 2- [4,6-di (2,4-xylyl) -1,3,5-triazin-2-yl] -5-octyloxyphenol, 2- [4,6-bis. (2,4-Dimethylphenyl) -1,3,5-triazin-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxyphenyl)- Reaction product of 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl-glycidic acid ester, 2,4-bis “2-hydroxy-4-butoxyphenyl” And -6- (2,4-dibutoxyphenyl) -1,3-5-triazine.

More specifically, “KEMISORB 102” manufactured by Chemipro Kasei Co., Ltd. and “T” manufactured by BASF Corp.
INUVIN 400 "," TINUVIN 405 "," TINUVIN 460 ","
“TINUVIN 477-DW”, “TINUVIN 479”, “TINUVIN 15”
77 ”,“ ADEKA STAB LA-46 ”manufactured by ADEKA,“ ADEKA STAB LA-F70 ”,“ CYASORB UV-1164 ”manufactured by Sun Chemical Co., Ltd., and the like.

Examples of benzophenone-based organic compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3 water temperature, 2-hydroxy-4-n- Examples include octoxybenzophenone and 2,2-di-hydroxy-4-methoxybenzophenone.

More specifically, “KEMISORB 10”, “KEMISORB 11”, “KEMISORB 11S”, “KEMISORB 12”, “KEMISORB 111”, and “SEESORB 101” and “SEESORB 107” manufactured by Sipro Kasei Co., Ltd.
And “ADEKA STAB 1413” manufactured by ADEKA.

<Polymerization inhibitor>
The photosensitive coloring composition of the present invention can contain a polymerization inhibitor in order to prevent exposure by the diffracted light of the mask during exposure. By adding a polymerization inhibitor, it is possible to obtain an effect of preventing the curing from proceeding to the outside of a desired pattern by photopolymerization chain polymerization.

As polymerization inhibitors, catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert- Alkyl catechol compounds such as butyl catechol and 3,5-di-tert-butyl catechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresor Alkyl resorcinol compounds such as sinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, Alkylhydroquinone compounds such as 2,5-di-tert-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, trioctylphosphine oxide, triphenylphosphine oxide, etc. Phosphites such as phosphine oxide compounds, triphenyl phosphite, trisnonylphenyl phosphite Compounds, pyrogallol, and the like phloroglucinol. As for content of a polymerization inhibitor, 0.01-0.4 mass part is preferable with respect to 100 mass parts of weight except the solvent of the coloring composition. In this range, the effect of the polymerization inhibitor is increased, and the taper linearity, the wrinkle of the coating film, the pattern resolution, etc. are improved.

<Antioxidant>
The photosensitive coloring composition of the present invention can contain an antioxidant. The antioxidant prevents the photopolymerization initiator and thermosetting compound contained in the photosensitive coloring composition from oxidizing and yellowing due to the thermal process during thermal curing and ITO annealing. Can be high. In particular, when the colorant concentration of the coloring composition is high, the amount of coating crosslinking component decreases, so the use of a highly sensitive crosslinking component and the increase in the amount of photopolymerization initiator are taken into account. Is seen. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

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

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

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

  Specific examples include ADEKA Corporation's ADK STAB AO-20, AO-30, AO-40, AO50, AO60, AO80, AO320, Chemipro Corporation's KEMINOX 101, 179, 76, 9425, BASF Corporation IRGANOX1010, 1035. 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, Sun Chemical Co., Ltd. Syanox CY-1790, CY-2777, and the like.

Examples of hindered amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4 -Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3, 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidyl ) Imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2, 2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomer type having a hindered amine structure And poly Mer type compounds can also be used.
Specific examples include Adeka Stab LA-52, LA-57, LA-63 manufactured by ADEKA Corporation.
P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, LA-502XP, KAMISTAB 29, 62, 77, 29 manufactured by Chemipro Kasei Co., Ltd. 94, Tinuvin 249, TINUVIN111FDL, 123, 144, 292, 5100 manufactured by BASF Corporation, Siasorb UV-3346, UV-3529, UV-3385 manufactured by Sun Chemical Co., Ltd., and the like.

Phosphorous antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 ′ isopropylidenediphenol phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2 , 4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidenebis (3-methyl-) 6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxyphosphonoxy) -ben Zen, ethylbisphosphite (2,4-ditert-butyl-6-methylphenyl), and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.
Specific examples include Adeka Stab PEP-36, PEP-8, and HP-1 manufactured by ADEKA Corporation.
0, ADK STAB 2112, 1178, 1500, C, 3013, TPP, IRGAFOS168 manufactured by BASF Corporation, HostanoxP-EPQ manufactured by Clariant Chemicals Corporation, and the like.

As sulfur-based antioxidants, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol, 2,2-bis {[3- (dodecylthio) -1-oxopropoxy] methyl} propane-1,3-diylbis [3- (Dodecylthio) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and the like. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.
Specific examples include Adeka Stub AO-412S and AO-503 manufactured by ADEKA Corporation, and KEMINOXPLS manufactured by Chemipro Kasei Corporation.

As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.
Specific examples include Adeka Stab LA-29, LA-31RG, LA- manufactured by ADEKA Corporation.
32, LA-36, -412S, Chemipro Chemical Co., Ltd. KEMISORB 71, 73, 74, 79, 279, BASF Corporation TINUVIN PS, 99-2, 384-2, 900, 928, 1130 and the like.

Examples of the benzophenone antioxidant include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4 -Octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4 -Methoxy-5 sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.
Specific examples include Adeka Stub 1413 manufactured by ADEKA Co., Ltd., K manufactured by Chemipro Kasei Co., Ltd.
EMISORB10, 11, 11S, 12, 111, Sun Chemical Co., Ltd. UV-12, UV-329, etc. are mentioned.

Examples of the triazine antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.
Specific examples include Adeka Stab LA-46 and F70 manufactured by ADEKA Co., Ltd., KEMISORB102 manufactured by Chemipro Kasei Co., Ltd., TINUVIN400, 405, 460, 477 and 479 manufactured by BASF Co., Ltd., and Siasorb UV-1164 manufactured by Sun Chemical Co., Ltd. .

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

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

  Further, the content of the antioxidant is more preferably 0.5 to 5.0% by mass in 100% by mass of the solid content of the coloring composition because the transmittance, spectral characteristics, and sensitivity are good.

<Adhesion improver>
The photosensitive coloring composition of the present invention can contain an adhesion improving agent such as a silane coupling agent in order to enhance the adhesion to the substrate. By improving the adhesion with the adhesion improver, the reproducibility of fine lines is improved and the resolution is improved.

Examples of the adhesion improver include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3- (Meth) acrylsilanes such as methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3- Epoxysilanes such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylme Rudimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3- Aminosilanes such as dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-mercaptopropyl Mercaptos such as methyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureides such as 3-ureidopropyltriethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, etc. Sulfides Silane coupling agent of isocyanates such as 3-isocyanate propyl triethoxysilane and the like. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the colorant in the coloring composition. Within this range, the effect becomes large, and the balance between adhesion, resolution, and sensitivity is good, which is more preferable.

<Leveling agent>
A leveling agent is preferably added to the photosensitive coloring composition of the present invention for the purpose of improving the coating property of the composition on the transparent substrate and the drying property of the colored film. As the leveling agent, various surfactants such as silicone surfactants, fluorine surfactants, nonionic surfactants, and cationic surfactants (surfactants and anionic surfactants) can be used.

Examples of silicone surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups are introduced into side chains and terminals.
Specific examples include BYK-300, BYK-306, BYK-310, BYK-313, BYK-315N, BYK-320, BYK-322, BYK-323, BYK-330, BYK-331, BYK-manufactured by BYK-Chemie. 333, BYK-342, BYK-345 / 346, BYK-347, BYK-348, BYK-349, BYK-370, BYK-377, BYK-378, BYK-3455, BYK-UV3510, BYK-3570, Toray Dow Corning, FZ-7001, FZ-7002, FZ-2110, FZ-2122, FZ-2123], FZ-2191, FZ-5609, Shin-Etsu Chemical Co., Ltd. X-22-4952, X-22 -4272, X-22-6266, KF-351A, K354L, KF- 55A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, etc. KF-6004 and the like.

Examples of the fluorine-based surfactant include agents having a fluorocarbon chain (surfactant or leveling).
Specific examples include Surflon S-242 and S-243 manufactured by AGC Seimi Chemical Co., Ltd.
S-420, S-611, S-651, S-386, DIC Corporation MegaFuck F-253, F-477, F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, DS-21, Sumitomo 3M Limited FC-4430, FC-4432, Mitsubishi Materials Electronics Chemical Co., Ltd. Examples thereof include EF-PP31N09, EF-PP33G1, EF-PP32C1, and Neos Corporation's Footgent 602A.

Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristol ether, polyoxyethylene octyldodecyl Ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl Ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, sol Tan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan monolaurate, sorbitan esquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, Polyoxyethylene orbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbite tetraoleate, glycerol monostearate, glycerol monooleate Ate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol di Teareto, polyethylene glycol monomethyl oleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl amines, alkyl alkanol amides, alkyl betaine such as alkyl imidazoline and alkyl dimethyl amino acetic acid betaine.

Specific examples include Emulgen 103, Emulgen 104P, Emulgen 106, Emulgen 108, Emulgen 109P, Emulgen 120, Emulgen 123P, Emulgen 130K, Emulgen 147, Emulgen 150, Emulgen 210P, Emulgen 220P, Emulgen 306P, Emulgen 320P, manufactured by Kao Corporation. , Emulgen 350, Emulgen 404, Emulgen 408, Emulgen 409 PV, Emulgen 420, Emulgen 430, Emulgen 705, Emulgen 707, Emulgen 709, Emulgen 1108, Emulgen 1118S-70, Emulgen 1135S-70, Emulgen 1150S-
60, Emulgen 2020G-HA, Emulgen 2025G, Emulgen LS-106, Emulgen LS-110, Emulgen LS-114, Emulgen MS-110, Emulgen A-60, Emulgen A-90, Emulgen B-66, Emulgen PP-290, Latemul PD-420, Lateml PD-430, Latemul PD-430S, Latemul PD450, Rheodor SP-L10, Rheodor SP-P10, Rheodor SP-S10V, Rheodor SP-S20, Rheodor SP-S30V, Rheodor SP-O10V, Rheodor SP -O30V, Rheodor Super SP-L1, Rheodor AS-10V, Rheodor AO-10V, Rheodor AO-15V, Rheodor TW-L120, Rheodor TW-L106, Rheodor T -P120, Rheodor TW-S120V, Rheodor TW-L106V, Rheodor TW-S320V, Rheodor TW-O120V, Rheodor TW-O106V, Rheodor TW-IS399C, Rheodor Super TW-L120, Rheodor 430V, Rheodor 440V, Rheodor 460V MS-50, Rheidol MS-60, Rheidol MO-60, Rheodor MS-165V, Emanon 1112, Emanon 3199V, Emanon 3299V, Emanon 3299RV, Emanon 4110, Emanon CH-25, Emanon CH-40, Emanon CH-60 (K ), Amite 102, Amite 105, Amite 105A, Amite 302, Amite 320, Aminone PK-02S, Aminone -02, homogenol L-95, ADEKA Corporation Adeka Pluronic L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, Adeka Pluronic TR-701, 702, 704, 913R, etc. Can be mentioned.

Examples of cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, and their ethylene oxide adducts.
As specific examples, Acetamine 24, 26, Cotamin 24P, 86P Conch manufactured by Kao Corporation, KP341 manufactured by Shin-Etsu Chemical Co., Ltd., (meth) acrylic acid (co) polymer polyflow No. manufactured by Kyoeisha Chemical Co., Ltd. 75, no. 90, no. 95 etc. are mentioned.

  Anionic surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine , Lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate, and the like.

  Specific examples include Neos Inc.'s Footgent 100, 150, Adeka Corporation Adeka Hope YES-25, Adeka Coal TS-230E, PS-440E, EC-8600, and the like.

When the photosensitive coloring composition of the present invention contains a surfactant, the addition amount of the surfactant is preferably 0.001 to 2.0% by mass with respect to the total solid content of the composition of the present invention. More preferably, it is 0.005-1.0 mass%. By being in this range, the balance between the coating property of the colored composition, the pattern adhesion, and the transmittance is improved.
The photosensitive coloring composition of the present invention may contain only one type of surfactant or two or more types of surfactant. When two or more types are included, the total amount is preferably within the above range.

<Method for producing photosensitive composition>
The photosensitive coloring composition included in the present invention comprises a coloring agent in a coloring agent carrier such as a dispersant, a binder resin, and / or a solvent, preferably together with a dispersing aid (a pigment derivative or a surfactant). It can be manufactured by finely dispersing using various dispersing means such as a kneader, 2-roll mill, 3-roll mill, ball mill, horizontal sand mill, vertical sand mill, annular bead mill, or attritor (colorant dispersion). . At this time, two or more kinds of colorants or the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. When the solubility of the colorant such as a dye is high, specifically, it is highly soluble in the solvent to be used, and if it is dissolved and no foreign matter is confirmed by stirring, it is finely dispersed as described above. There is no need.

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

<Dispersing aid>
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a dispersant, or a surfactant can be appropriately contained. Since the dispersion aid has a great effect of preventing re-aggregation of the colorant after dispersion, the color composition formed by dispersing the colorant in the colorant carrier using the dispersion aid has brightness, contrast, and storage stability. Good. The pigment derivative and the dispersant are as described above.

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

  When adding a surfactant, it is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass with respect to 100 parts by mass of the colorant. When the blending amount of the surfactant is less than 0.1 parts by mass, it is difficult to obtain the added effect. When the content is more than 55 parts by mass, the dispersion may be affected by an excessive dispersant. .

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

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention includes a red filter segment, a green filter segment, and a blue filter segment. The color filter may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment.

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

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

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

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

A black matrix can be formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

The color filter of the present invention is bonded to a counter substrate using a sealant, and after injecting liquid crystal from an injection port provided in a seal portion, the injection port is sealed, and a polarizing film or a retardation film is formed on the substrate as necessary. A color liquid crystal display device is manufactured by pasting to the outside. This color liquid crystal display device includes Twisted Nematic (TN), Super Twisted Nematic (STN), In-Plane Switching (IPS), Vertical Alignment (VA), Optically Convencend Bend (OCB). ) Etc., and can be used in a liquid crystal display mode in which colorization is performed.

  The color filter of the present invention can also be used for the production of color solid-state imaging devices, organic EL display devices, quantum dot display devices, electronic paper, and the like in addition to color liquid crystal display devices.

  Hereinafter, the present invention will be described by way of examples. In the examples, “parts” and “%” represent “parts by mass” and “% by mass”, respectively. “PGMEA” means propylene glycol monomethyl ether acetate.

  Prior to the examples, the calculation method of the measurement method of the weight average molecular weight of the resin and the acid value of the resin will be described.

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

(Resin acid value)
80 ml of acetone and 10 ml of water are added to 0.5 to 1 g of the resin solution and stirred to dissolve uniformly, and an automatic titrator (“COM-555” manufactured by Hiranuma Sangyo Co., Ltd.) is used with a 0.1 mol / L KOH aqueous solution as a titrant. ), And the acid value (mgKOH / g) 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.

  Then, the manufacturing method of the dispersing agent, resin binder solution, processing pigment, and coloring agent dispersion which were used by the Example and the comparative example is demonstrated.

<Production of Resin Type Dispersant Dispersant (C)>
[Production Example 1]
(Resin type dispersant (C-1) solution)
A reaction vessel equipped with a gas inlet tube, temperature, condenser and stirrer is charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate and 50 parts of propylene glycol monomethyl ether acetate, and nitrogen gas Replaced with.
The reaction vessel was heated and stirred at 50 ° C., and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90 ° C., and the reaction was carried out for 7 hours while adding a solution obtained by adding 0.1 part of 2,2′-azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate. It was confirmed that 95% had reacted by solid content measurement.
19 parts of pyromellitic anhydride, 50 parts of propylene glycol monomethyl ether acetate, 50 parts of cyclohexanone and 0.4 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added at 100 ° C. The reaction was performed for 7 hours. The acid value was measured to confirm that 98% or more of the acid anhydride had been half-esterified, the reaction was terminated, and propylene glycol monomethyl ether acetate was added and diluted so that the solid content would be 40% solids. A solution of a carboxylic acid resin dispersant C-1 having a valence of 77 and a weight average molecular weight of 8,500 was obtained.

[Production Examples 2 to 10]
(Resin type dispersant (C-2 to 10) solution)
The synthesis was performed in the same manner as in Production Example 1 except that the raw materials and preparation amounts shown in Table 1 were used, and solutions of resin-type dispersants C-2 to C-10 were obtained.

[Production Example 11]
(Resin type dispersant (C2-11) solution)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer, 6 parts 3-mercapto-1,2-propanediol, 9.7 parts pyromellitic dianhydride, 23.5 parts cyclohexanone, 0.01 parts of mono-n-butyltin (IV) oxide was charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 100 ° C. and reacted for 7 hours. After confirming that 97% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70 ° C., and 80 parts of methyl methacrylate and 20 parts of hydroxyethyl methacrylate were charged. A solution prepared by dissolving 0.1 part of 2′-azobisisobutyronitrile in 26.2 parts of cyclohexanone was added and reacted for 10 hours. The solid content measurement confirmed that the polymerization had progressed 95%, and the reaction was completed. After completion of the reaction, the nonvolatile content was adjusted to 40% with propylene glycol monomethyl ether acetate to obtain a solution of resin type dispersant C2-11 having a weight average molecular weight of 9,500.

  The raw materials used in the production examples are listed below.

[Tetracarboxylic acid anhydride]
・ Pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.)

[Esterification reaction catalyst]
・ Mono-n-butyltin (IV) oxide

[Ethylenically unsaturated monomer having a hydroxyl group]
・ HEMA: Hydroxyethyl methacrylate

[Ethylenically unsaturated monomer having no hydroxyl group]
-MMA: Methyl methacrylate-MAA: Methacrylic acid-N-MAM: N-Methylolacrylamide ("N-MAM" manufactured by Yushi Corporation)
-NBM: Nn-butoxymethylacrylamide ("Amide NBM" manufactured by Yushi Co., Ltd.)
MOI-BM: 2-[(1′-methylpropylideneamino) carboxyamino] ethyl methacrylate (“Karenz MOI-BM” manufactured by Showa Denko)

[Compound with two hydroxyl groups and one thiol group in the molecule]
・ 3-Mercapto-1,2-propanediol

[Radical polymerization initiator]
AIBN: 2,2′-azobisisobutyronitrile

〔Organic solvent〕
・ Cyclohexanone ・ Propylene glycol monomethyl ether acetate

[Production Examples 12 to 16]
(Resin type dispersant (C2-12-16) solution)
The synthesis was performed in the same manner as in Production Example 11 except that the raw materials and preparation amounts shown in Table 1-2 were used, and solutions of resin-type dispersants C2-12 to C2-16 were obtained.

[Production Example 21]
(Resin type dispersant (C2-21) solution)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 160 parts of n-butyl acrylate, 40 parts of Karenz MOI-BM (manufactured by Showa Denko), 50 parts of propylene glycol monomethyl ether acetate, 50 parts of cyclohexanone are prepared. Replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and 12 parts of 3-mercapto-1,2-propanediol was added and reacted for 12 hours. It was confirmed that 95% had reacted by solid content measurement. Next, 19 parts of pyromellitic dianhydride, 231 parts of cyclohexanone, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 100 ° C. for 7 hours. It was. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. The solid content was adjusted to 40% with propylene glycol monomethyl ether acetate to obtain a solution of a resin type dispersant C2-21 having an acid value of 42 mgKOH / g and a weight average molecular weight of 9000.

[Production Examples 22, 25 to 28]
(Resin type dispersant (C2-22, 25-28) solution)
Synthesis was carried out in the same manner as in Production Example 21 except that the raw materials and preparation amounts described in Table 1-3 were used, and solutions of resin type dispersants C2-22, C2-25 to C2-28 were obtained.

[Production Example 23]
(Resin type dispersant (C2-23) solution)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, 100 parts of n-butyl acrylate, 60 parts of methyl methacrylate, 40 parts of Karenz MOI-BM (made by Showa Denko), 50 parts of propylene glycol monomethyl ether acetate, cyclohexanone 50 parts were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a solution in which 0.1 part of 2,2′-azobisisobutyronitrile was dissolved in 12 parts of 3-mercapto-1,2-propanediol was added. Reacted for hours. It was confirmed that 95% had reacted by solid content measurement. Next, 26 parts of BPDA [3,3 ′, 4,4′-biphenyltetracarboxylic anhydride (manufactured by Mitsubishi Chemical Corporation)], 11 parts of neopentyl glycol, 238 parts of cyclohexanone, 1,8-diazabicyclo- as a catalyst [5.4.0] -7-Undecene (0.40 part) was added, and the mixture was reacted at 100 ° C. for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. The solid content was adjusted to 40% with propylene glycol monomethyl ether acetate to obtain a solution of a resin type dispersant C2-23 having an acid value of 40 mgKOH / g and a weight average molecular weight of 9100.

[Production Example 24]
(Resin type dispersant (C2-24) solution)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer, 80 parts of n-butyl acrylate, 60 parts of methyl methacrylate, 20 parts of methacrylic acid, 20 parts of Karenz MOI-BM (manufactured by Showa Denko), ETERNACOLL OXMA (Ube) 20 parts by Kosan) and 100 parts of propylene glycol monomethyl ether acetate were charged and replaced with nitrogen gas. Heat the reaction vessel to 80 ° C. and add a solution of 0.1 part of 2,2′-azobisisobutyronitrile to 14 parts of 2-mercapto-2-methyl-1,3-propanediol. And reacted for 10 hours. It was confirmed that 95% had reacted by solid content measurement. Next, BPAF: 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Co., Ltd.) 39 parts, C-1015N (bifunctional polycarbonate polyol, trade name Kuraray polyol C-1015N) (Hydroxyl value 112 mg KOH / g, manufactured by Kuraray Co., Ltd.)) 106 parts, trimellitic anhydride 33 parts, cyclohexanone 392 parts, 1,8-diazabicyclo- [5.4.0] -7-undecene 0.40 as a catalyst Part was added and reacted at 100 ° C. for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. The solid content was adjusted to 40% with propylene glycol monomethyl ether acetate to obtain a solution of a resin type dispersant C2-24 having an acid value of 94 mgKOH / g and a weight average molecular weight of 7000.

[Production Example 29]
(Resin type dispersant (C2-29) solution)
Synthesis was carried out in the same manner as in Production Example 24 except that the raw materials and preparation amounts described in Table 1-3 were used, and a resin type dispersant C2-29 solution was obtained.

[Production Example 30]
(Resin type dispersant (C2-30) solution)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 25 parts of 3-mercapto-1,2-propanediol, 40 parts of pyromellitic dianhydride, 66 parts of cyclohexanone, and monobutyltin oxide 0. 06 parts were added and reacted at 100 ° C. for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride was half-esterified. Next, 80 parts of n-butyl acrylate, 60 parts of methyl methacrylate, 20 parts of 2-hydroxypropyl methacrylate, and 40 parts of Karenz MOI-BM (manufactured by Showa Denko) were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and 200 parts of a cyclohexanone solution in which 0.5 part of 2,2′-azobisisobutyronitrile was dissolved was added and reacted for 10 hours. The solid content measurement confirmed that 95% had reacted, and the process was completed. The solid content was adjusted to 40% with propylene glycol monomethyl ether acetate to obtain a solution of a resin type dispersant C2-30 having an acid value of 77 mgKOH / g and a weight average molecular weight of 8200.

[Production Examples 31-34]
(Resin type dispersant (C2-31 to 34) solution)
The synthesis was performed in the same manner as in Production Example 30 except that the raw materials and preparation amounts described in Table 1-4 were used, and solutions of resin-type dispersants C2-31 to C2-34 were obtained.

Karenz MOI-BM: 2-([1′-methylpropylideneamino] carboxyamino) ethyl methacrylate, (Showa Denko)
ETERNACOLL OXMA: (methacrylic acid (3-ethyloxetane-3-yl) methyl, manufactured by Ube Industries)
t-BMA: t-butyl methacrylate PMA: pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.)
BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic acid anhydride (manufactured by Mitsubishi Chemical Corporation)
BPAF: 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, (manufactured by JFE Chemical Co., Ltd.)
C-1015N: bifunctional polycarbonate polyol, trade name Kuraray polyol C-1015N, (hydroxyl value 112 mg KOH / g, manufactured by Kuraray Co., Ltd.)
DBU: 1,8-diazabicyclo- [5.4.0] -7-undecene (manufactured by San Apro Co., Ltd.)

[Production Example 41]
(Resin type dispersant (C2-41) solution)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 108 parts of 3-mercapto-1,2-propanediol, 174 parts of pyromellitic dianhydride, 650 parts of propylene glycol monomethyl ether acetate, After charging 0.2 parts of butyltin oxide and replacing with nitrogen gas, the reaction was carried out at 120 ° C. for 5 hours (first step). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl methacrylate Part, 50 parts of methacrylic acid and 663 parts of propylene glycol monomethyl ether acetate, the reaction vessel was heated to 80 ° C., and 1.2 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was added. , Reacted for 12 hours (second step). It was confirmed that 95% had reacted by solid content measurement. Finally, 500 parts of a 50% propylene glycol monomethyl ether acetate solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 part of hydroquinone were charged, and the isocyanate was measured by IR. The reaction was carried out until the disappearance of the peak at 2270 cm-1 based on the group was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the solid content was adjusted with propylene glycol monomethyl ether acetate to obtain a solution of resin-type dispersant C2-41 having a solid content of 40%. The obtained dispersant had an acid value of 68, an unsaturated double bond equivalent of 1593, and a weight average molecular weight of 13,000.

[Production Examples 42 to 50]
(Resin type dispersant (C2-42-50) solution)
The synthesis was performed in the same manner as in Production Example 41 except that the raw materials and preparation amounts shown in Table 1-5 were used, and solutions of resin-type dispersants C2-42 to C2-50 having a solid content of 40% were obtained.

1,6-HD: 1,6-hexanediol PMA: pyromellitic dianhydride BTA: 1,2,3,4-butanetetracarboxylic dianhydride BPDA: 3,3 ′, 4,4′-biphenyl Tricarboxylic acid anhydride TMEG: Ethylene glycol ditrimellitic anhydride ester (manufactured by Shin Nippon Rika Co., Ltd .: Ricacid TMEG-100)
BTDA: 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride DSDA: 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride BPAF: 9,9-bis (3,4 -Dicarboxyphenyl) fluorene dianhydride TMA: trimellitic anhydride HEMA: 2-hydroxyethyl methacrylate 2HPMA: 2-hydroxypropyl methacrylate 4HBA: 2-hydroxybutyl acrylate FM-3: terminal hydroxyl group polycaprolactone modified methacrylate ( Daicel Chemical Industries: Plaxel FM-3)
EA: ethyl acrylate t-BA: t-butyl acrylate 2MTA: 2-methoxyethyl acrylate MMA: methyl methacrylate BMA: n-butyl methacrylate BzMA: benzyl methacrylate St: styrene MAA: methacrylic acid MOI: 2-methacryloyloxyethyl isocyanate (Showa (Denko: Karenz MOI)
AOI: 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko: Karenz AOI)
BEI: 1,1-bis (acryloyloxymethyl) ethyl isocyanate (manufactured by Showa Denko: Karenz BEI)
MOI-EG: 2-methacryloyloxyethoxyethyl isocyanate (manufactured by Showa Denko: Karenz MOI-EG)

<Manufacture of resin binder (F)>
(Resin binder (F-1) solution)
196 parts of cyclohexanone was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device in a separable four-necked flask, and the temperature was raised to 80 ° C. From the tube, 20.0 parts of benzyl methacrylate, 17.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (manufactured by Toagosei Co., Ltd. Aronix M110 ") 20.7 parts and a mixture of 2,2'-azobisisobutyronitrile 1.1 parts were added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain an acrylic resin solution.
After cooling to room temperature, sample about 2 parts of the resin solution, heat dry at 180 ° C for 20 minutes, measure the nonvolatile content, and add PGMAC to the previously synthesized resin solution so that the nonvolatile content is 20% by mass Thus, a resin binder (F-1) solution was prepared. The weight average molecular weight (Mw) was 26,000.

(Resin binder (F-2) solution)
207 parts of cyclohexanone was placed in a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. From the tube, 20 parts of methacrylic acid, 20 parts of benzyl methacrylate, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 25 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2, A mixture of 1.33 parts of 2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour to obtain an acrylic resin solution. After cooling to room temperature, sample 2 parts of the resin solution, heat dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20% by mass. Thus, a resin binder (F-2) solution was prepared. The weight average molecular weight (Mw) was 18,000.

(Resin binder (F-3) solution)
After introducing 182 g of propylene glycol monomethyl ether acetate into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and changing the atmosphere in the flask from air to nitrogen, the temperature was raised to 100 ° C., 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) ) And propylene glycol monomethyl ether acetate (136 g) in a solution obtained by adding 3.6 g of azobisisobutyronitrile to the flask over 2 hours from the dropping funnel and further stirring at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol, 0.5%. 9 g and 0.145 g of hydroquinone were put into the flask, and the reaction was continued at 110 ° C. for 6 hours. About 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the synthesized resin solution so that the nonvolatile content was 20% by mass to obtain a resin binder (F-3) solution. The weight average molecular weight was 13,000, the molecular weight distribution (Mw / Mn) was 2.1, and the solid content acid value was 79 mgKOH / g.

(Resin binder (F-4) solution)
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, and 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. The reaction was terminated when the value reached 0.8, and a resin solution having a weight average molecular weight of about 12,000 (measured by GPC) was obtained.
Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine were added and reacted at 120 ° C. for 4 hours. Propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 20%, and resin binder (F-4) was added. A solution was prepared.

<Structure of dye derivative>
Below, it shows about the pigment derivative used in the Example.

<Manufacture of treated pigment>
(Red treated pigment A: PR177)
Anthraquinone red pigment C.I. I. 135 parts of Pigment Red 177 (Sinix “Sinilex Red SR3C”), 15 parts of pigment derivative 2, 1500 parts of sodium chloride, and 330 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 80 ° C. For 8 hours. Next, this kneaded material is put into 6000 parts of water, stirred for 2 hours to form a slurry, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, dried at 85 ° C. overnight, pulverized, and 145 parts. Of red processed pigment A was obtained.

(Red treated pigment B: PR177)
A red-treated pigment B was obtained in the same manner as in the production of the red-treated pigment A, except that the dye derivative 6 was used instead of the pigment derivative 2 used in the production of the red-treated pigment A.

(Red treated pigment C: PR254)
Diketopyrrolopyrrole red pigment C.I. I. 135 parts of Pigment Red 254 ("IRGAPHOR REDS3610CF" manufactured by BASF), 15 parts of pigment derivative 4, 1500 parts of sodium chloride, and 330 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 80 ° C. Kneaded for 8 hours. Next, the kneaded product is put into 6000 parts of water, stirred for 2 hours to form a slurry, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, dried at 85 ° C. overnight, pulverized, and 145 Part of red-treated pigment C was obtained.

(Red treated pigment D: PR177)
Anthraquinone red pigment C.I. I. 135 parts of Pigment Red 177 (Sinix “Sinilex Red SR3C”), 1500 parts of sodium chloride, and 330 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 8 hours. Next, this kneaded material is put into 6000 parts of water, stirred for 2 hours to form a slurry, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, dried at 85 ° C. overnight, pulverized, and 145 parts. Of red-treated pigment D was obtained.

(Yellow treatment pigment A: PY150)
Nickel complex yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 15 parts of pigment derivative 8, 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) at 6 ° C. Kneaded for hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A nickel complex-based yellow-treated pigment A was obtained.

(Yellow treatment pigment B: PY139)
C. used in the production of yellow-treated pigment A I. Instead of CI Pigment Yellow 150, C.I. I. A yellow-treated pigment B was obtained in the same manner as in the production of yellow-treated pigment A except that CI Pigment Yellow 139 was used.

(Yellow treatment pigment C: PY138)
C. used in the production of yellow-treated pigment A I. Instead of CI Pigment Yellow 150, C.I. I. A yellow-treated pigment C was obtained in the same manner as in the production of yellow-treated pigment A except that CI Pigment Yellow 138 was used.

(Yellow-treated pigment D: PY185)
C. used in the production of yellow-treated pigment A I. Instead of CI Pigment Yellow 150, C.I. I. A yellow-treated pigment D was obtained in the same manner as in the production of yellow-treated pigment A except that CI Pigment Yellow 185 was used.

(Yellow-treated pigment E: quinophthalone compound (b))
C. used in the production of yellow-treated pigment A I. A yellow-treated pigment E was obtained in the same manner as in the production of the yellow-treated pigment A except that the quinophthalone compound (b) was used instead of Pigment Yellow 150.

(Yellow treated pigment F: PY150)
Nickel complex yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A nickel complex-based yellow-treated pigment F was obtained.

(Green treatment pigment A: PG36)
C. used in the production of red processed pigment A I. In place of Pigment Red 177, C.I. I. Except for using CI Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Color Co., Ltd.), the same operation as in the production of red treated pigment A was performed to obtain green treated pigment A.

(Green treatment pigment B: PG36)
A green-treated pigment B was obtained in the same manner as in the production of the green-treated pigment A, except that the dye derivative 6 was used instead of the dye derivative 2 used in the production of the green-treated pigment A.

(Green treated pigment C: PG58)
Phthalocyanine green pigment C.I. I. Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation) 200 parts, 15 parts of pigment derivative 2, 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 80 ° C. Kneaded for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A green-treated pigment C was obtained.

(Green treated pigment D: PG36)
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A green-treated pigment D was obtained.

(Blue treatment pigment A: PB15: 6)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyocolor Co., Ltd., specific surface area 60 m ² / g) 200 parts, pigment derivative 2 15 parts, sodium chloride 1400 parts and diethylene glycol 360 parts 1 gallon kneader made of stainless steel ( Prepared by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A blue-treated pigment A was obtained.

(Blue treatment pigment B: PB15: 6)
A blue-treated pigment B was obtained in the same manner as in the production of the blue-treated pigment A except that the dye derivative 6 was used instead of the dye derivative 2 used in the production of the blue-treated pigment A.

(Blue treatment pigment C: PB15: 6)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (Toyocolor Co., Ltd. “LIONOL BLUE ES”, specific surface area 60 m ² / g) 200 parts, sodium chloride 1400 parts and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho). It knead | mixed at 80 degreeC for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A blue-treated pigment C was obtained.

(Manufacture of purple processed pigment A: PV-23)
Dioxazine-based purple pigment C.I. I. Pigment Violet 23 (Toyocolor Co., Ltd. “LIONOGEN VIOLET RL”) 200 parts, pigment derivative 2 15 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) at 80 ° C. For 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A purple-treated violet pigment A was obtained.

(Manufacture of purple processed pigment B: PV-23)
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A purple-treated purple pigment B was obtained.

<Method for producing colorant dispersion>
(Colorant dispersion (DR-1))
After the following mixture was stirred and mixed so as to be uniform, it was dispersed for 5 hours with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm It filtered with the filter and produced the coloring agent dispersion (DR-1).
Red treated pigment A: 12.0 parts Dye derivative 1: 1.0 part Resin type dispersant (C-1) solution: 5.0 parts Solvent Propylene glycol monomethyl ether acetate (PGMEA)
: 52.0 parts

(Colorant dispersion (DR-2 to 26, DG-1 to 26, DB-1 to 25, DY-1 to 28, DV-1 to 24))
Dispersing the colorant in the same manner as the colorant dispersion (DR-1), except that the treated pigment, the dye derivative, and the resin-type dispersant solution were changed to the types shown in Table 3-1, Table 3-2, and 4. The bodies (DR-2 to 26, DG-1 to 26, DB-1 to 25, DY-1 to 28, DV-1 to 24) were prepared.

Abbreviations in the table are shown below.
EFKA4300: “EfkaPX 4300” manufactured by BASF (acrylic polymer dispersant)

(Colorant dispersion (DR-27 to 36), (DG-27 to 36), (DB-26 to 35), (DY-29 to 38))
The colored dispersion (DR-1) was treated in the same manner as the colorant dispersion (DR-1) except that the treated pigment, dye derivative, and resin-type dispersant solution were changed to the types shown in Tables 4-2 and 4-3. -27 to 36), (DG-27 to 36), (DB-26 to 35), and (DY-29 to 38) were produced.

<Production of photosensitive coloring composition>
The following adjustments were made in the production of the photosensitive coloring composition.
Resin binder solution A: A mixed solution prepared by mixing the resin binder (F-1) to (F-4) solutions at 1: 1: 1: 1.
Polymerizable compound A: Aronix M402, Aronix M520 manufactured by Toa Gosei Co., Ltd., KAYARAD DPCA-30 manufactured by Nippon Kayaku Co., Ltd., UA-510H manufactured by Kyoeisha Chemical Co., Ltd. 1: 1: 1
1: A mixture / photopolymerization initiator A prepared by mixing at 1: 1 part of IRGACURE 907, 1 part of IRGACURE 369, 1 part of IRGACURE 819 was dissolved in 100 parts of propylene glycol monomethyl ether acetate (PGMEA).
Photopolymerization initiator B: 1 part of the oxime ester photopolymerization initiator of the chemical formula (6-1), 1 part of the oxime ester photopolymerization initiator of the chemical formula (6-3), and the oxime of the chemical formula (7a-1) A mixed solution in which 1 part of an ester photopolymerization initiator is dissolved in 100 parts of propylene glycol monomethyl ether acetate (PGMEA).
Sensitizer A: A mixed solution in which 1 part of “KAYACURE DETX-S” and 1 part of “EAB-F” are dissolved in 100 parts of propylene glycol monomethyl ether acetate (PGMEA).
Epoxy compound A: a mixture prepared by mixing jER E157S75, EHPE-3150, and TEPIC-S at 1: 1: 1.
Oxetane compound A: OXT-221 manufactured by Toa Gosei Co., Ltd.
UV absorber A: 1 part of “TINUVIN P” manufactured by BASF, “TINUVIN 405”
A mixed solution in which 1 part, 1 part of “KEMISORB 10” manufactured by Chemipro Kasei Co., Ltd. was dissolved in 100 parts of propylene glycol monomethyl ether acetate (PGMEA).
Polymerization inhibitor A: A mixed solution in which 1 part of “3-methylcatechol”, 1 part of “methylhydroquinone” and 1 part of “tert-butylhydroquinone” are dissolved in 100 parts of propylene glycol monomethyl ether acetate (PGMEA).
Antioxidant A: 1 part of “IRGANOX1010” manufactured by BASF, 1 part of “ADK STAB LA-52” manufactured by ADEKA, 1 part of “ADEKA STAB PEP-36” manufactured by ADEKA, 1 part of “ADK STAB AO-412S” manufactured by ADEKA Is a mixed solution in which 100 parts of propylene glycol monomethyl ether acetate (PGMEA) is dissolved.
Thiol chain transfer agent A: pentaerythritol tetrakisthiopropionate Silane coupling agent A: Shin-Etsu Silicone KBM-403, KBM-5103,
A mixture prepared by mixing KBM-1003, KBM-573, and KBM-803 at 1: 1: 1: 1: 1.
Leveling agent A: 1 part of “BYK-330” manufactured by Big Chemie Co., 1 part of “MegaFuck F-551” manufactured by DIC Corporation, and 1 part of “Emulgen 103” manufactured by Kao Corporation 100% of propylene glycol monomethyl ether acetate (PGMEA) Mixed solution dissolved in part.
Solvent A: propylene glycol monomethyl ether acetate, cyclohexanone,
A mixed solution prepared by mixing ethyl 3-ethoxypropionate and 1,3-butylene glycol diacetate in a ratio of 3: 1: 1: 1.

[Example 1]
(Photosensitive coloring composition (R-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a photosensitive coloring composition (R-1).
Colorant dispersion (DR-1): 30.0 parts Colorant dispersion (DY-1): 10.0 parts Resin binder solution A: 6.0 parts Polymerizable compound A: 1.0 part Photopolymerization initiator A: 8.0 parts sensitizer A: 1.0 part epoxy compound A: 1.0 part oxetane compound A: 1.0 part UV absorber A: 1.0 part polymerization inhibitor A: 1.0 part oxidation Inhibitor A: 1.0 part Thiol chain transfer agent A: 1.0 part Silane coupling agent A: 1.0 part Leveling agent A: 1.0 part Solvent A: 36.0 parts

[Examples 2 to 154, Comparative Examples 1 to 12]
(Photosensitive coloring composition (R-2 to 166))
The mixture was stirred and mixed to be uniform in the same manner as the photosensitive coloring composition (R-1) except that the colorant dispersion and the photopolymerization initiator were changed to the compositions shown in Tables 5 to 7. Then, it filtered with a 1 micrometer filter and obtained the photosensitive coloring composition (R-2 to 166).

[Example 155]
(Photosensitive coloring composition (R-167))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a photosensitive colored composition (R-167).
Colorant dispersion (DR-27): 28.0 parts Colorant dispersion (DR-2): 6.0 parts Colorant dispersion (DY-1): 6.0 parts Resin binder solution A: 6.0 Partially polymerizable compound A: 1.0 part Photopolymerization initiator B: 8.0 parts Sensitizer A: 1.0 part Epoxy compound A: 1.0 part Oxetane compound A: 1.0 part UV absorber A: 1.0 part polymerization inhibitor A: 1.0 part antioxidant A: 1.0 part thiol chain transfer agent A: 1.0 part silane coupling agent A: 1.0 part leveling agent A: 1.0 Part solvent A: 36.0 parts

[Examples 156 to 188]
(Photosensitive coloring composition (R-168-200))
Except for changing the colorant dispersion to the compositions shown in Tables 8 to 9, the mixture was stirred and mixed to be uniform in the same manner as the photosensitive coloring composition (R-155), and then a 1 μm filter. To obtain a photosensitive coloring composition (R-168 to 200).

[Examples 189 to 198]
(Photosensitive composition (R-201 to 210))
Except for changing the colorant dispersion and the photopolymerization initiator to the compositions shown in Table 10, in the same manner as the photosensitive coloring composition (R-1), the mixture was stirred and mixed to be uniform, It filtered with a 1 micrometer filter and obtained the photosensitive coloring composition (R-201-210).

<Evaluation of photosensitive composition>
The obtained photosensitive coloring compositions (R-1 to R-166) and (R-167 to R-210) were evaluated by the following methods. The results are shown in Tables 5-7 and Tables 8-10.

[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 5 minutes to obtain a coating film of about 2 μm. . Next, the substrate was cooled to room temperature, and then exposed using an ultra-high pressure mercury lamp through a photomask having a stripe pattern of 100 μm width (pitch 200 μm) and 25 μm width (pitch 50 μm) at 50 mJ / cm ² . Thereafter, this 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 20 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 determined using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).

[Resolution evaluation (pattern resolution)]
About the pattern in the 25 micrometer photomask part of the filter segment formed by the said method, resolution was evaluated visually using the optical microscope, and the following reference | standard evaluated. The poor resolution means that adjacent stripe patterns are connected or chipped. X is an unusable level.
◯: Stripe pattern is completely independent and no residue is observed between lines. Δ: Adjacent stripe pattern is partially connected. X: Adjacent stripe pattern is connected.

[Development residue evaluation]
The photosensitive coloring composition was applied onto a 10 × 10 cm silicone wafer substrate and dried by heating at 80 ° C. for 1 minute to form a coating film having a thickness of 2 microns. The coating film was exposed at 50 mJ / cm ² with a high-pressure mercury lamp using a pattern mask having a line width of 50 microns, spray-developed with a 0.05% potassium hydroxide aqueous solution maintained at 25 ° C. for 60 seconds, An evaluation coating film was obtained by thoroughly washing with replacement water and drying with clean air. On the substrate from which the coating film was removed by development, the presence or absence of a residue was observed with a 50 × optical microscope. The case where no residue was confirmed at all was marked as ◯, the case where residues were confirmed at a number of 1 or more and less than 10 was evaluated as Δ, and the case where 10 or more residues were confirmed was marked as x. X is an unusable level.

As shown in the above table, when the photosensitive coloring composition of the present invention was evaluated as a cured film, favorable results were obtained in pattern resolution and development residue. Further, when the same evaluation was performed on the color filter produced using the cured film, a favorable result was obtained with respect to pattern resolution and development residue, and production with a high yield could be performed. As a result, the liquid crystal display device, the solid-state imaging device, and the organic EL display device using the color filter can be suitably used.

Claims (10)

A reaction product of a pigment (A), a dye derivative (B) represented by the following general formula (1), a polymer having a hydroxyl group at at least one terminal, and a tricarboxylic acid anhydride or tetracarboxylic acid dianhydride; A reaction product for polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride or tetracarboxylic dianhydride Photosensitive coloring composition containing a certain resin type dispersing agent (C), polymeric compound (D), photoinitiator (E), resin binder (F), and solvent (G).
General formula (1)



[In General Formula (1), R _{115 to} R ₁₁₇ each independently have a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. An optionally substituted phthalimidoalkyl group, an optionally substituted acyl group, an amino group, a sulfo group, a carboxyl group, a phosphoric acid group, a halogen group, general formulas (150) to (155), (158), or ( 159). ]


[In the general formulas (150) to (155), X ₁ represents a direct bond, —SO ₂ —, —CO—, —C
_{H 2 -, - CH 2 NHCOCH} 2 -, - CONHC 6 H 4 CO-, or -CONHC ₆ H ₄ - represents a. Y ₁ is a direct bond, —NR ₁₇₀ SO ₂ —, —SO ₂ NR ₁₇₀ —, —CONR ₁₇₀ —, —NR ₁₇₀ CO—, or —CH ₂ NR ₁₇₀ COCH ₂ NR ₁₇₀ —.
Represents. Y ₂ represents a direct bond, an arylene group which may have a substituent, or a heteroaromatic ring which may have a substituent, and these groups are represented by —NR ₁₇₀ −, —O— and —SO _2. -Or CO
They may be bonded to each other through a divalent linking group selected from-. Y ₃ represents a direct bond, —NR ₁₇₀ — or —O—. o represents an integer of 0 to 20. M ₂ represents a hydrogen atom, a calcium atom, a barium atom, a strontium atom, a manganese atom or an aluminum atom. i represents the valence of _{M 2.}
R ₁₅₀ and R ₁₅₁ are each independently an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a phenyl group which may have a substituent, or R ₁₅₀ and R ₁₅₁ , And a heterocyclic ring optionally having a substituent containing a nitrogen, oxygen or sulfur atom. R _{152 to} R ₁₅₆ and R _{159 to} R ₁₆₂ are each independently a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a phenyl that may have a substituent. Represents a group or a polyoxyalkylene group. R ₁₅₇ and R ₁₅₈ are each independently a group represented by the following general formula (156) or (157), —O— (CH ₂ ) _o —R ₁₇₁ , —OR ₁₇₂ , —NR ₁₇₃ R ₁₇₄ , —Cl , —F or Y ₃ —Y ₂ —Y ₁ —Q, and _{one of} R ₁₅₇ and R ₁₅₈ is a group represented by the following general formula (156) or (157), —O— (CH ₂ ) _O -R ₁₇₁ , -OR ₁₇₂ , or NR ₁₇₃ R ₁₇₄ .
R ₁₇₀ represents a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a phenyl group that may have a substituent. R ₁₇₁ represents a heterocyclic residue which may have a substituent, and R _{172 to} R ₁₇₄ may each independently have a hydrogen atom, an alkyl group which may have a substituent, or a substituent. It represents a phenyl group which may have a good alkenyl group or substituent, and Q represents an organic dye residue. ]
General formula (156)


[In General Formula (156), Z ₁ represents —NR ₁₇₀ —, —CONH— or —O—, and Z ₂ represents an alkylene group which may have a substituent, or an alkenylene which may have a substituent. Group, an arylene group which may have a substituent, and these groups are represented by —NR ₁₇₀ —, —O—, —SO _2.
They may be bonded to each other by a divalent linking group selected from-or CO-. R ₁₇₀ represents a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a phenyl group that may have a substituent. R ₁₅₀ and R ₁₅₁ are each independently an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a phenyl group which may have a substituent, or R ₁₅₀ and R ₁₅₁ , And a heterocyclic ring optionally having a substituent containing a nitrogen, oxygen or sulfur atom. ]
General formula (157)



[In General Formula (157), Z ₃ represents a single bond connecting a triazine ring and a nitrogen atom, —NR ₁₇₅ —, —NR ₁₇₅ —Z ₄ —CO—, —NR ₁₇₅ —Z ₄ —CONR ₁₇₆ —, —NR _17
5- Z ₄ —SO ₂ —, —NR ₁₇₅ —Z ₄ —SO ₂ NR ₁₇₆ —, —O—Z ₄ —CO—
_{, -O-Z 4 -CONR 175 -} , - O-Z 4 -SO 2 -, or _{O-Z 4 -SO 2 NR 175} - _represent, respectively the R 152 _{to R 156} independently represents a hydrogen atom, a substituent Represents an alkyl group that may have a substituent, an alkenyl group that may have a substituent, a phenyl group that may have a substituent, or a polyoxyalkylene group.
R ₁₇₅ and R ₁₇₆ each independently represent a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a phenyl group that may have a substituent; ₄ represents an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent. ]
General formula (158)


General formula (159)


[In the general formula _(159), X _{2 is, -SO 2 -, - CO -} , - NH -, - SO 2 NH -, - NHSO 2 -, - represents CONH- or _{NHCO-, R} 163 ~R ₁₆₇ Are each independently a hydrogen atom, an alkoxyl group, an amino group, a sulfo group, a carboxy group, a phosphoric acid group or a group represented by general formulas (150) to (155). ] The pigment (A) is C.I. I. Pigment green 7, 36, 58, 59, 62, 63, C.I. I. The photosensitive coloring composition of Claim 1 containing at least 1 sort (s) chosen from pigment yellow 138, 139, 150, and 185. The photosensitive coloring composition of Claim 1 or 2 in which the resin binder (F) contains the alkali-soluble resin which has an ethylenically unsaturated double bond. The photosensitive coloring composition of any one of Claims 1-3 in which a photoinitiator (E) contains an oxime ester system initiator. Furthermore, the photosensitive coloring composition of any one of Claims 1-4 containing an epoxy compound or an oxetane compound. The cured film formed by hardening | curing the photosensitive coloring composition of any one of Claims 1-5. A color filter having the cured film according to claim 6. A liquid crystal display device comprising the color filter according to claim 7. A solid-state imaging device comprising the color filter according to claim 7. An organic EL display device comprising the color filter according to claim 7.