JP7592979B2 - Photosensitive green composition, color filter and liquid crystal display device - Google Patents

Description

The present invention relates to a photosensitive green composition used in the manufacture of color filters used in color liquid crystal displays, color solid-state imaging devices, organic EL displays, quantum dot displays, electronic paper, etc., and to a color filter having filter segments formed using the same.

A color filter is formed by arranging two or more fine band-shaped filter segments of different hues on a transparent substrate such as a glass substrate in parallel (stripes) or crossing each other, or by arranging two or more fine filter segments of different hues in order in both the vertical and horizontal directions. The filter segments have small dimensions of several microns to several hundreds of microns, and are regularly arranged in a predetermined array for each hue.
Currently, the main method for manufacturing color filters is a pigment dispersion method, which uses a pigment having excellent resistance to various factors such as light resistance and heat resistance as a coloring material. 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 film by drying, the coating film is exposed to light in a pattern corresponding to a filter segment of a certain color. Next, the unexposed parts of the coating film are removed by development, and then a treatment such as heating is performed as necessary. This results in a filter segment pattern of the first color. Then, the same operation is performed to form filter segment patterns of other colors, completing a color filter.

Furthermore, on the color filter, a transparent electrode for driving the liquid crystal is generally formed by deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed on top of that. In order to obtain sufficient performance from these transparent electrodes and alignment films, the formation process is generally carried out at a high temperature of 200° C. or higher. In the manufacturing process of such color filters,
This causes a decrease in the brightness of the coating film during the formation of the transparent electrode and the heating process, and an improvement in this area is required.

In addition, in order to improve the color reproduction characteristics of the color filter, it is necessary to increase the content of the colorant in the photosensitive coloring composition or to increase the film thickness. In the method of increasing the content of the colorant, problems such as deterioration of developability, deterioration of pattern shape, and deterioration of coating film resistance occur due to a decrease in the resin and photopolymerizable compound, which are the curing materials. In addition, in the method of increasing the film thickness, problems such as poor pattern shape due to the irradiation light not reaching the bottom of the film tend to occur. Furthermore, since there is an increasing demand for thinner color display devices and there is a tendency to reduce the film thickness, a technology using a multifunctional thiol or an antioxidant is disclosed in Patent Document 1 for a photosensitive coloring composition containing a high concentration of colorant. However, the photocuring of the coating surface is promoted by the multifunctional thiol, and the pattern shape after post-baking becomes overhanging. In addition, Patent Document 2 discloses a technology that is effective for pattern shape and remaining film rate by using a specific oxime ester compound as a photopolymerization initiator. However, there is an issue with water stains, and there is a need to develop technology that satisfies all of the requirements for film remaining rate, water stains, and pattern shape.

JP 2018-173470 A JP 2011-209710 A

The present invention aims to achieve the following objects.
That is, an object of the present invention is to provide a photosensitive composition for color filters which has a high film remaining rate of a colored pattern and is capable of forming pixels which are excellent in terms of water stain resistance and pattern shape, and a color filter formed using the same.

As a result of extensive research, the inventors have discovered that it is possible to provide a photosensitive green composition with a high film retention rate, as well as a color filter and color liquid crystal display device that have excellent pattern shape and are suppressed from causing water stains.

That is, the present invention provides a photosensitive green composition comprising an organic pigment (A), a resin-type dispersant (B), a binder resin (C), a polymerizable compound (D), and a photopolymerization initiator (E),
The organic pigment (A) includes one or more pigments selected from an aluminum phthalocyanine pigment (A1), a halogenated zinc phthalocyanine pigment (A2), and a halogenated copper phthalocyanine pigment (A3), and a yellow pigment (A4), and
The photosensitive green composition is characterized in that the photopolymerization initiator (E) contains an oxime ester-based photopolymerization initiator (E1) represented by the following general formula (1):

General formula (1)

[In general formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ² represents a hydrocarbon group having 1 to 20 carbon atoms, n represents 0 or 1, at least one of R ³ to R ⁵ is substituted with a substituent represented by the following general formula (2), and the remaining represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group, and each alkyl group and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom and an alkoxyl group having 1 to 12 carbon atoms.]

General formula (2)

[In the general formula (2), * represents a bond to the benzene ring. X represents a direct bond, an oxygen atom, or a carbonyl group. ^R6 represents a direct bond or a hydrocarbon group having 1 to 12 carbon atoms. ^R7 represents a hydroxyl group or a carboxyl group.]

The present invention also relates to the above photosensitive green composition, wherein the binder resin (C) contains an alkali-soluble resin having a carboxy group and a polymerizable unsaturated group in a side chain selected from the following (I) and (II):
(I) An alkali-soluble resin obtained by reacting a product of an epoxy group in a polymer having an epoxy group and a carboxy group in a carboxy group-containing monomer with a polybasic acid or a polybasic acid anhydride. (II) An alkali-soluble resin which is a reaction product of a carboxy group in a polymer having a carboxy group and an epoxy group in an epoxy group-containing monomer.

The present invention also relates to the photosensitive green composition, which further contains a polymerization inhibitor (F).

The present invention also relates to the above photosensitive green composition, characterized in that the resin-type dispersant (B) contains a resin-type dispersant having an acidic functional group and a resin-type dispersant having a basic functional group.

The present invention also relates to the above photosensitive green composition, which further contains two or more types of silicone-based leveling agents or fluorine-based leveling agents (G).

The present invention also relates to the photosensitive green composition, further characterized in that the polymerizable compound (D) contains one or more types of ethylene oxide (EO)-modified (meth)acrylate or propylene oxide (PO)-modified (meth)acrylate.

The present invention also relates to the above photosensitive green composition, further characterized in that the photopolymerization initiator (E) contains two or more types of oxime ester photopolymerization initiators.

The present invention also relates to a color filter having a substrate and filter segments formed from the above-mentioned photosensitive green composition.

The present invention also relates to a liquid crystal display device comprising the above-mentioned color filter.

The present invention provides a photosensitive green composition with a high film retention rate, as well as a color filter and color liquid crystal display device with excellent pattern shape and reduced water stains.

FIG. 1 is a schematic cross-sectional view of a liquid crystal display device.

Each of the components of the photosensitive green composition of the present invention will be described below.
In this application, unless otherwise specified, the terms "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" respectively mean "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide".
In addition, "C.I." in this specification means Color Index (C.I.).

<Organic pigment (A)>
The organic pigment (A) contains one or more pigments selected from the group consisting of aluminum phthalocyanine pigments (A1), halogenated zinc phthalocyanine pigments (A2) and halogenated copper phthalocyanine pigments (A3), and a yellow pigment (A4) described below. In order to obtain good optical properties, the photosensitive green composition of the present invention can be used in combination with other organic pigments, inorganic pigments, dyes, etc.

(Aluminum Phthalocyanine Pigment (A1))
The aluminum phthalocyanine pigment (A1) is a phthalocyanine pigment having an aluminum atom as a central metal. The aluminum phthalocyanine pigment (A1) is preferably, for example, a pigment described in JP-A-2017-111398.

(Halogenated zinc phthalocyanine pigment (A2))
The halogenated zinc phthalocyanine pigment (A2) is a phthalocyanine pigment having a zinc atom as a central metal and a halogen atom as a substituent. The halogenated zinc phthalocyanine pigment (A2) is, for example, preferably a halogenated zinc phthalocyanine having an average of 10 to 14 halogen atoms in the molecule, and the halogen atoms are preferably a halogenated zinc phthalocyanine having an average of 8 to 12 bromine atoms and an average of 2 to 5 chlorine atoms. In order to obtain high-level color reproduction, the halogen atoms are preferably an average of 11 to 13 halogen atoms in the molecule, and more preferably an average of 8 to 11 bromine atoms and an average of 2 to 3 chlorine atoms. The halogenated zinc phthalocyanine pigment is a pigment composition having a halogen distribution, and the average composition is determined by fluorescent X-ray analysis.

(Halogenated copper phthalocyanine pigment (A3))
The halogenated copper phthalocyanine pigment (A3) is a halogenated phthalocyanine pigment having a copper atom as a central metal. For example, C.I. Pigment Green 7, 36, 37, etc. can be mentioned. Among these, C.I. Pigment Green 36 is preferable from the viewpoint of transmittance.

(Yellow Pigment (A4))
Yellow pigments include, for example, C.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, 1 27, 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, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, and the like described in JP-A-2012-226110. Pigment Yellow 138, 139, 150, 185, 231, 233, and pigments described in JP-A-2012-226110.

(Other organic pigments)
In the present invention, organic pigments other than the aluminum phthalocyanine pigment (A1), the halogenated zinc phthalocyanine pigment (A2), the halogenated copper phthalocyanine pigment (A3), and the yellow pigment (A4) can be used as long as the effects of the present invention are not impaired.
Examples of red pigments include C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 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, 1 14, 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, 214, 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, 26 2, 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, 295, 296, pigments described in JP-A-2014-134712, and pigments described in Japanese Patent No. 6368844. Among these, from the viewpoints of heat resistance, light resistance, and transmittance of the filter segment, C.I. Pigment Red 48:1, 122, 177, 224, 242, 269, 254, 291, 295, 296, pigments described in JP-A-2014-134712, and pigments described in Japanese Patent No. 6368844, and more preferably C.I. Pigment Red 177, 254, 291, 295, 296, pigments described in JP-A-2014-134712, and pigments described in Japanese Patent No. 6368844.

Examples of blue pigments include C.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, and 79.

Examples of purple pigments include C.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, and 50.

Examples of green pigments include C.I. Pigment Green 1, 2, 4, 8, 10, 13, 14, 15, 17, 18, 19, 26, 37, 45, 48, 50, 51, 54, and 55.

(Inorganic pigments)
In the present invention, inorganic pigments may be used as long as the effects of the present invention are not impaired.
Examples of inorganic pigments include titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, amber, and synthetic iron black.

(dye)
In the present invention, dyes may be used as long as they do not impair the effects of the present invention.
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, etc. may be used. In addition, the dye may be in the form of a derivative of these dyes or a lake pigment obtained by making the dye into a lake.

Furthermore, in the case of an acid dye having an acidic group such as sulfonic acid or carboxylic acid, or in the form of a direct dye, it is preferable to use the acid dye as a salt-forming compound by forming a salt using an inorganic salt of the acid dye, or a salt-forming compound of the acid dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound, or a resin component having these functional groups, or to use the acid dye as a sulfonamide compound by sulfonamidation, which results in a photosensitive green composition having excellent fastness, which can be excellent in resistance.
Further, a salt-forming compound of an acid dye and a compound having an onium salt group is also preferred because it has excellent fastness, and more preferably, the compound having an onium salt group is a resin having a cationic group in the side chain.

In the case of a basic dye, it can be used after being salted with an organic acid, perchloric acid or a metal salt thereof. Among these, a salt-forming compound of a basic dye is preferred because of its excellent resistance and compatibility with pigments, and it is even more preferred to use a salt-forming compound obtained by salting a basic dye with a counter component acting as a counter ion, such as an organic sulfonic acid, an organic sulfuric acid, a fluorine-containing phosphorus anion compound, a fluorine-containing boron anion compound, a cyano-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or an acid dye.

In addition, when the dye skeleton has a polymerizable unsaturated group, the dye has excellent resistance, which is preferable.

The chemical structure of dyes includes, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine Examples of the dye structure include dyes derived from dyes selected from the group consisting of polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof.

Among these dye structures, from the viewpoint of color characteristics such as hue, color separation, and color unevenness, dye structures derived from dyes selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred, and dye structures derived from dyes selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferred. Specific dye compounds that can form dye structures are described in "New Dye Handbook" (edited by the Society of Organic Synthesis Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and Colourists), "Dye Handbook" (edited by Okawara et al.; Kodansha, 1986), etc.

<Minification of pigment>
When the colorant used in the photosensitive green composition of the present invention is a pigment, it is preferable to use it after it has been finely divided. The method of finely dividing is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution precipitation methods can be used. As exemplified in the present invention, finely dividing can be performed by salt milling treatment using a kneader method, which is a type of wet grinding. The average primary particle size of the pigment determined by TEM (transmission electron microscope) is preferably in the range of 5 to 90 nm. If it is smaller than 5 nm, it becomes difficult to disperse it in an organic solvent, and if it is larger than 90 nm, a sufficient contrast ratio may not be obtained. For these reasons, the average primary particle size is more preferably in the range of 10 to 70 nm.

Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt, and water-soluble organic solvent is mechanically kneaded while being heated using a batch or continuous mixer such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, or planetary mixer, and then the water-soluble inorganic salt and water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment with a very fine primary particle size, a narrow distribution range, and a sharp particle size distribution.

Sodium chloride, potassium chloride, sodium sulfate, etc. can be used as the water-soluble inorganic salt, but sodium chloride (table salt) is preferred from the viewpoint of cost. From the viewpoints of both processing efficiency and production efficiency, it is preferable to use 50 to 2000 parts by mass of the water-soluble inorganic salt per 100 parts by mass of the pigment, and it is most preferable to use 300 to 1000 parts by mass.

The water-soluble organic solvent is not particularly limited as long as it functions to wet the pigment and the water-soluble inorganic salt, and dissolves (is miscible with) water, and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent becomes prone to evaporate, a high-boiling point solvent with a boiling point of 120°C or higher is preferred from the standpoint of safety. 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, etc. may be used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, per 100 parts by weight of the pigment.

When the pigment is subjected to salt milling, a resin may be added as necessary. There are no particular limitations on the type of resin used, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc. may be used. The resin used is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in the organic solvents mentioned above. The amount of resin used is preferably in the range of 5 to 200 parts by mass per 100 parts by mass of the pigment.

<Resin-type dispersant (B)>
The photosensitive green composition of the present invention contains a resin-type dispersant (B), and a known resin-type dispersant can be used. The resin-type dispersant may be any dispersant that has a colorant affinity site that has the property of adsorbing to an added colorant and a site that is compatible with the colorant carrier, and that functions to adsorb to the added colorant and stabilize the dispersion in the colorant carrier. Specifically, urethane-based dispersants such as polyurethane, polycarboxylates such as polyacrylates, unsaturated polyamides, polycarboxylates, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylates, and modified products thereof. Examples of the dispersants that can be used include oil-based dispersants such as amides formed by the reaction of poly(lower alkylene imine) with a polyester having a free carboxyl group and salts thereof, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyester-based compounds, modified polyacrylate-based compounds, ethylene oxide/propylene oxide adducts, and phosphate-based compounds, and these can be used alone or in combination of two or more kinds.

The photosensitive green composition of the present invention preferably contains a resin-type dispersant having an acidic functional group and a resin-type dispersant having a basic functional group.

(Resin-type dispersant with acidic functional groups)
Preferred examples of resin-type dispersants having an acidic functional group include resin-type dispersants having an aromatic carboxylic acid structure, which can be produced by known methods such as those described in WO2008/007776, JP2008-029901A, JP2009-155406A, JP2010-185934A, JP2011-157416A, JP2009-251481A, JP2007-23195A, and JP1996-143651A.

(Resin-type dispersant with basic functional groups)
Preferred examples of the resin-type dispersant having a basic functional group include nitrogen-atom-containing graft copolymers, and nitrogen-atom-containing acrylic block copolymers and urethane-based polymer dispersants having functional groups including tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc. in the side chains.

An example of a resin-type dispersant having an acidic functional group and a resin-type dispersant having a basic functional group is the combined use of a resin-type dispersant having an aromatic carboxyl group and a vinyl resin having a tertiary amino group (which functions as a resin-type dispersant), as disclosed in JP 2009-185277 A.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, and 2095 manufactured by BYK Japan Co., Ltd. 2150, 2155, 2163, 2164, Anti-Terra-U, 203, 204, BYK-P104, P104S, 220S, Lactimon, Lactimon-WS, Bykumen, etc. manufactured by Lubrizol Japan Co., Ltd. SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26 000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 44 01, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajisper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Ltd.

The resin-type dispersant (B) is preferably used in an amount of about 3 to 200% by mass relative to the organic pigment (A), and from the viewpoint of dispersion stability, it is more preferable to use about 5 to 100% by mass.

<Dye derivative (b0)>
If necessary, a dye derivative (b0) can be added to the photosensitive green composition used in the present invention.

The dye derivative used in the present invention may be a known dye derivative having an acidic group, a basic group, a neutral group, etc. in the organic dye residue. Examples of such a dye derivative include compounds having an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group, and their amine salts, compounds having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal, and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group.
Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, azo pigments such as azo, disazo, and polyazo, and the like.

Specifically, diketopyrrolopyrrole dye derivatives are described in JP 2001-220520 A, WO 2009/081930 pamphlet, WO 2011/052617 pamphlet, WO 2012/102399 pamphlet, and JP 2017-156397 A, phthalocyanine dye derivatives are described in JP 2007-226161 A, WO 2016/163351 A, JP 2017-165820 A, and Japanese Patent No. 5753266 A, and anthraquinone dye derivatives are described in JP-A-63-264674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009/025325 pamphlet; quinacridone dye derivatives are shown in JP-A-48-54128, JP-A-03-9961, and JP-A-2000-273383; dioxazine dye derivatives are shown in JP-A-2011-162662; thiazine indigo dye derivatives are shown in JP-A-2007-314785 As triazine-based dye derivatives, see JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, and JP-A-2007-314681; as benzoisoindole-based dye derivatives, see JP-A-2009-57478; as quinophthalone-based dye derivatives, see JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, and JP-A-2012-2 Examples of naphthol-based dye derivatives include those described in JP-A-2012-208329 and JP-A-2014-5439; examples of azo-based dye derivatives include those described in JP-A-2001-172520 and JP-A-2012-172092; examples of acidic substituents include those described in JP-A-2004-307854; and examples of basic substituents include those described in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, and JP-A-2005-213404. In these documents, the dye derivatives are sometimes referred to as derivatives, pigment derivatives, dispersants, pigment dispersants, or simply compounds, but the compounds having substituents such as acidic groups, basic groups, and neutral groups in the organic dye residues are synonymous with dye derivatives.

<Binder Resin (C)>
The photosensitive green composition of the present invention contains a binder resin (C). The binder resin (C) is preferably a resin having a transmittance of 80% or more, more preferably 95% or more, in the entire wavelength range of 400 to 700 nm. Binder resins are classified according to their main curing method, and include thermoplastic resins, thermosetting resins, and active energy ray curable resins having ethylenically unsaturated double bonds, etc., and the active energy ray curable resin may be a thermoplastic resin or may also have a thermosetting function, and is preferably an alkali-soluble resin from the viewpoint of developability. In addition, a thermoplastic resin that is not active energy ray curable may be included, and it is also preferably alkali-soluble. These may be used alone or in combination of two or more.

The binder resin (C) preferably contains an alkali-soluble resin having a carboxy group and a polymerizable unsaturated group on the side chain selected from the following (I) and (II).
(I) An alkali-soluble resin obtained by reacting a product of an epoxy group in a polymer having an epoxy group and a carboxy group in a carboxy group-containing monomer with a polybasic acid or a polybasic acid anhydride. (II) An alkali-soluble resin which is a reaction product of a carboxy group in a polymer having a carboxy group and an epoxy group in an epoxy group-containing monomer.

The content of the binder resin in the photosensitive green composition of the present invention is preferably 20 to 400 parts by mass, and more preferably 50 to 250 parts by mass, based on the total mass of the colorant (100 parts by mass). It is preferable to use an amount of 20 parts by mass or more because it has good film-forming properties and various resistances, and it is preferable to use 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 thermoplastic resins that can be used as the binder resin include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.
The thermoplastic resin is preferably alkali-soluble, and examples thereof include resins having an acidic group such as a carboxyl group or a sulfonic group. Specific examples of the resin include an acrylic resin having an acidic group, an α-olefin/maleic acid (anhydride) copolymer, a styrene/styrene sulfonic acid copolymer, an ethylene/(meth)acrylic acid copolymer, or an isobutylene/maleic acid (anhydride) copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene/styrene sulfonic acid copolymer, particularly an alkali-soluble resin having an acidic group and/or a hydroxyl group, is preferably used because of its high developability, heat resistance, and transparency.

(Alkali-soluble resin)
The photosensitive green composition of the present invention preferably contains an alkali-soluble resin in terms of developability, heat resistance, and transparency. The resin is for imparting development solubility in the alkali development step during the preparation of a color filter, and has an acid group and/or a hydroxyl group. In order to further improve 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 green 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 has been 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, thereby increasing the crosslink density and improving chemical resistance.

[Method (i)]
An example of the method (i) is a method in which a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond (a carboxyl group-containing monomer) is subjected to an addition reaction with a side-chain epoxy group of a copolymer (a polymer having an epoxy group) obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with one or more other monomers, and further, a polybasic acid or a polybasic acid anhydride is reacted with the generated hydroxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

Examples of ethylenically unsaturated monomers having an epoxy group include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate, which may be used alone or in combination of two or more. Glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with the unsaturated monobasic acid in the next step.

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

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., which may be used alone or in combination of two or more. If necessary, for example, to increase the number of carboxyl groups, it is also possible to use a tricarboxylic acid anhydride such as trimellitic anhydride, or a tetracarboxylic acid dianhydride such as pyromellitic dianhydride to hydrolyze the remaining anhydride groups. In addition, if tetrahydrophthalic anhydride or maleic anhydride, which has an ethylenically unsaturated double bond, is used as the polybasic acid anhydride, the number of ethylenically unsaturated double bonds can be further increased.

As a method similar to method (i), for example, there is a method in which an ethylenically unsaturated monomer having an epoxy group (epoxy group-containing monomer) is added to some of the side chain carboxyl groups of a copolymer (polymer having a carboxyl group) obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with one or more other monomers, thereby introducing an ethylenically unsaturated double bond and a carboxyl group.

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

Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate,
Examples of the hydroxyalkyl methacrylates include hydroxyalkyl methacrylates such as 1- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate, and these may be used alone or in combination of two or more. In addition, polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to the above-mentioned hydroxyalkyl (meth)acrylates, and polyester mono(meth)acrylates obtained by addition of poly(γ-valerolactone), poly(ε-caprolactone, and/or poly(12-hydroxystearic acid) can also be used. From the viewpoint of suppressing foreign matter in the coating, 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferred, and from the viewpoint of sensitivity, it is preferred to use one having 2 to 6 hydroxyl groups, with glycerol mono(meth)acrylate being more preferred.

Examples of ethylenically unsaturated monomers having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate, but are not limited to these, and two or more types can be used in combination.

Examples of monomers constituting the alkali-soluble resin include the following: (meth)acrylates such as 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, and ethoxypolyethylene glycol (meth)acrylate;
Alternatively, examples of the vinyl monomer include (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine; styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acid vinyls such as vinyl acetate and vinyl propionate.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide Examples of such compounds include N-substituted maleimides such as imidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine, EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

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

Hydroxyl-containing ethylenically unsaturated monomers can also be used. Examples of hydroxyl-containing ethylenically unsaturated monomers include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. Examples of the hydroxyalkyl (meth)acrylate include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to the above-mentioned hydroxyalkyl (meth)acrylates, and (poly)ester mono(meth)acrylates obtained by addition of (poly)γ-valerolactone, (poly)ε-caprolactone, and/or (poly)12-hydroxystearic acid.

Phosphate-containing ethylenically unsaturated monomers can also be used. Examples of phosphate-containing ethylenically unsaturated monomers include monomers that can be obtained by reacting the hydroxyl group of the hydroxyl-containing ethylenically unsaturated monomer with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

(Alkali-soluble resin having no ethylenically unsaturated double bond)
The photosensitive green composition of the present invention may contain an alkali-soluble resin having no ethylenically unsaturated double bond in order to adjust the degree of hardening of the coating film. By synthesizing the composition using at least one carboxyl group-containing ethylenically unsaturated monomer and one or more of the other ethylenically unsaturated monomers, and not providing an ethylenically unsaturated bond to the side chain, an alkali-soluble resin having no ethylenically unsaturated double bond can be obtained.

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

In the present invention, the weight average molecular weight (Mw) of the alkali-soluble resin is 2,000 to 40,000, preferably 3,000 to 300,000, more preferably 4,000 to 20,000, in order to provide alkali development solubility. The value of Mw/Mn is preferably 10 or less. If the weight average molecular weight (Mw) is less than 2,000, the adhesion to the substrate decreases, and the exposed pattern is less likely to remain. If it exceeds 40,000, the alkali development solubility decreases, residue is generated, and the linearity of the pattern deteriorates.
The acid value of the alkali-soluble resin in the present invention is from 50 to 200 (KOH mg/g) in order to impart solubility in alkaline development, preferably from 70 to 180, and more preferably from 90 to 170. If the acid value is less than 50, the solubility in alkaline development decreases, residues are generated, and linearity of the pattern deteriorates. If the acid value exceeds 200, adhesion to the substrate decreases, making it difficult to leave an exposed pattern.

(Thermosetting compound (CE))
In the present invention, a thermosetting compound (CE) can be contained as a binder resin. When a color filter is produced using the photosensitive green composition of the present invention, the inclusion of a thermosetting compound can improve the properties of the filter segment. When the filter segment is baked, the crosslinking density of the coating film increases, improving the heat resistance of the filter segment, suppressing pigment aggregation during baking of the filter segment, and improving the contrast ratio.

The thermosetting compound may be a low molecular weight compound or a high molecular weight compound such as a resin.
Examples of the thermosetting compound include, but are not limited to, epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. In the photosensitive green composition of the present invention, epoxy compounds and oxetane compounds are preferably used.

(Epoxy compound (CE-1))
The epoxy compound may be a low molecular weight compound or a high molecular weight compound such as a resin.
Examples of such epoxy compounds include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), polycondensates of phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropyl ether, polystyrene, polystyrene-based copolymers ... Examples of the epoxy resin include polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzene dimethanol, α,α,α',α'-benzene dimethanol, biphenyl dimethanol, α,α,α',α'-biphenyl dimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethyl biphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidyl amine epoxy resins, and glycidyl ester epoxy resins, but are not limited to these, so long as they are commonly used epoxy compounds. These may be used alone, or two or more of them may be used.

Commercially available products include, for example, Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (all trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004, Epicoat 1256 (all trade names; manufactured by Japan Epoxy Resins Co., Ltd.), TECHMORE VG3101L (trade name; manufactured by Mitsui Chemicals, Inc.), EPPN-501H, 502H (trade names; manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60 (trade name; manufactured by Japan Epoxy Resins Co., Ltd.), JER 157S65, 157S70 (product names; manufactured by Japan Epoxy Resins Co., Ltd.), EPPN-201 (product name; manufactured by Nippon Kayaku Co., Ltd.), JER152, JER154 (all of the above are product names; manufactured by Japan Epoxy Resins Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (all of the above are product names; manufactured by Nippon Kayaku Co., Ltd.), Celoxide 2021, EHPE- 3150 (all trade names; manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 (all trade names; manufactured by Nagase ChemteX Corporation), TEPIC-L, TEPIC-H, TEPIC-S (manufactured by Nissan Chemical Industries, Ltd.), and the like.
These include, but are not limited to, the following:

The amount of epoxy compound blended is preferably 0.5 to 300 parts by weight, and more preferably 1.0 to 50 parts by weight, per 100 parts by weight of colorant. If it is less than 0.5 parts by weight, the effect of improving the contrast ratio and heat resistance is small, and if it is more than 300 parts by weight, problems may occur when forming filter segments by photolithography.

(Oxetane Compound (CE-2))
It is preferable to add an oxetane compound to the photosensitive green composition of the present invention. As the oxetane compound, any known compound having an oxetane group can be used without any particular limitation. 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 higher.

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

Examples of compounds having a 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, and 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-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycose bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl -3-oxetanylmethyl) ether, triethylene glycol bis(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 Examples of such bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether include bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, propylene oxide (PO)-modified bisphenol 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, and EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl)ether.
Specific examples include OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd.

Examples of the oxetane group having two or more functional groups include
Pentaerythritol tris(3-ethyl-3-oxetanylmethyl)ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether, caprolactone-modified dipentaerythritol hexa Examples of such polymers include (3-ethyl-3-oxetanylmethyl)ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl)ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl)ether, resins containing an oxetane group (e.g., the oxetane-modified phenol novolak resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the above-mentioned OXE-30. Such polymers can be obtained by using known polymerization methods.

The content of the oxetane compound used in the photosensitive green composition of the present invention is usually 0.5 to 50% by mass, preferably 1 to 40% by mass, based on 100% by mass of the solid content of the photosensitive green composition. When the content of the oxetane compound is within the above range, it is preferable because an excellent coating film with good resistance to water spots and high chemical resistance can be obtained.

(Melamine compounds)
The melamine compound in the present invention refers to a compound having a melamine ring structure. The melamine compound may be a low molecular weight compound or a high molecular weight compound such as a resin. In the present invention, a melamine compound having a methylol type or an ether type, and an average number of methylol groups and/or ether groups per melamine ring of 5.0 or more is preferred. If the average number of methylol groups and/or ether groups per melamine ring is less than 5.0, there are few reaction sites, and the crosslinked structure during curing is not sufficiently dense, so that the effect of suppressing the decrease in contrast ratio due to the heat treatment process and improving NMP resistance may be reduced.

Commercially available products include, for example, Nikalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, and MX-410 (manufactured by Sanwa Chemical Co., Ltd.), and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, and 370 (manufactured by Nippon Cytec Industries Co., Ltd.), but are not limited to these.

Among these, Nikarak MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MX-45 (manufactured by Sanwa Chemical Co., Ltd.) and Cymel 232, 235, 236, 238, 300, 301, 303, 350 (manufactured by Nippon Cytec Industries Co., Ltd.) are preferred because they have an average of 5.0 or more methylol groups and/or ether groups per melamine ring, and they provide a dense crosslinked structure.

(Hardening agent)
The photosensitive green composition of the present invention may contain a curing agent (curing accelerator) or the like, if necessary, to assist the curing of the thermosetting compound. As the curing agent, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, a sulfonic acid compound, and the like are effective, but are not particularly limited thereto, and any curing agent may be used as long as it can react with the thermosetting compound. As the curing agent, for example, an amine compound (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), a quaternary ammonium salt compound (e.g., triethylbenzylammonium chloride, etc.), a blocked isocyanate compound (e.g., dimethylamine, etc.), an imidazole derivative, a bicyclic amidine compound and its salt (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-methyl ... -phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by mass relative to 100 parts by mass of the thermosetting compound.

<Polymerizable compound (D)>
The photosensitive green composition of the present invention is characterized by comprising an organic pigment (A), a resin-type dispersant (B), a binder resin (C), a polymerizable compound (D), and a photopolymerization initiator (E). The polymerizable compound (D) includes a monomer or oligomer that is cured by exposure to ultraviolet light, heat, or the like to form a transparent resin.

The polymerizable compound (D) may be a monomer or oligomer that is cured by ultraviolet light or heat to produce a transparent resin. Among them, a polymerizable compound having an acid group, a polymerizable compound having a urethane bond, or an ethylene oxide (EO)- or propylene oxide (PO)-modified polymerizable compound is preferred, and an ethylene oxide (EO)- or propylene oxide (PO)-modified polymerizable compound is particularly preferred.

(Polymerizable compound having an acid group)
The polymerizable compound in the present invention may contain a polymerizable compound having an acid group, such as a sulfonic acid group, a carboxyl group, or a phosphoric acid group.

Examples of polymerizable compounds having an acid group include esters of dicarboxylic acids and free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid; esters of polycarboxylic acids and monohydroxyalkyl(meth)acrylates. Specific examples include free carboxyl group-containing monoesters of monohydroxy oligoacrylates or monohydroxy oligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, and dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid); Examples include free carboxyl group-containing oligoesters of tricarboxylic acids such as butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid, and monohydroxymonoacrylates or monohydroxymonomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate, but the effects of the present invention are not limited to these.

As commercially available products, Viscoat #2500P manufactured by Osaka Organic Industries, and Aronix M-5300, M-5400, M-5700, M-510, M-520 manufactured by Toagosei Co., Ltd. can be suitably used.

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

Examples of (meth)acrylates having a hydroxyl group include 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 an epoxy group-containing compound and carboxy(meth)acrylate, and hydroxyl group-containing polyol polyacrylate.

Examples of polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate, etc.

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

The above polymerizable compounds can be used alone or in a mixture of two or more in any ratio as required.

The photosensitive green composition of the present invention preferably contains one or more ethylene oxide (EO) modified (meth)acrylates or propylene oxide (PO) modified (meth)acrylates as the polymerizable compound (D). When the composition has an (EO) modified unit or a (PO) modified unit, such as an ethylene oxide (EO) modified (meth)acrylate or a propylene oxide (PO) modified (meth)acrylate, a hydrogen bond is formed with the oxime ester photopolymerization initiator (E1) used in the present application, and the radical generation site and the reaction site can be brought into close proximity to each other, which is thought to have the effect of promoting more efficient photocuring. As a result, water spots can be suppressed and a high residual film rate can be achieved.

As examples of these, the photopolymerizable compound preferably contains at least one (meth)acrylate compound selected from the group consisting of (meth)acrylate compounds having a trimethylolpropane skeleton, (meth)acrylate compounds having a ditrimethylolpropane skeleton, (meth)acrylate compounds having a pentaerythritol skeleton, (meth)acrylate compounds having a dipentaerythritol skeleton, (meth)acrylate compounds having a glycerin skeleton, (meth)acrylate compounds having a diglycerin skeleton, and alkylene oxide modified compounds thereof. The (meth)acrylate compound is preferably a bifunctional or higher (meth)acrylate compound having two or more (meth)acryloyl groups, and more preferably a trifunctional or higher (meth)acrylate compound having three or more (meth)acryloyl groups.

Here, the (meth)acrylate compound having a skeleton derived from ditrimethylolpropane can be obtained, for example, by a method of esterifying ditrimethylolpropane with (meth)acrylic acid, or by a transesterification method using a neutral catalyst. Such compounds also include compounds modified with alkyleneoxy groups. The above compounds preferably have two or more ester bonds in one molecule, and may be mixed with compounds having two to four ester bonds.

In addition, (meth)acrylate compounds having a diglycerin-derived skeleton can be obtained, for example, by a method of esterifying diglycerin with (meth)acrylic acid, or by a transesterification method using a neutral catalyst. Such compounds also include compounds modified with alkyleneoxy groups. The above compounds preferably have two or more ester bonds in one molecule, and may be mixed with compounds having two to four ester bonds.

The above-mentioned (meth)acrylate compound having a skeleton derived from ditrimethylolpropane and (meth)acrylate compound having a skeleton derived from diglycerin preferably contains at least one compound selected from alkylene oxide-modified ditrimethylolpropane di(meth)acrylate compounds, alkylene oxide-modified ditrimethylolpropane tri(meth)acrylate compounds, alkylene oxide-modified ditrimethylolpropane tetra(meth)acrylate compounds, alkylene oxide-modified diglycerin di(meth)acrylate compounds, alkylene oxide-modified diglycerin tri(meth)acrylate compounds, and alkylene oxide-modified diglycerin tetra(meth)acrylate compounds, and more preferably contains at least one compound selected from alkylene oxide-modified ditrimethylolpropane tetra(meth)acrylate compounds and alkylene oxide-modified diglycerin tetra(meth)acrylate compounds.

Examples of (meth)acrylates having a dipentaerythritol-derived skeleton include dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and alkylene oxide-modified compounds thereof. Of these, dipentaerythritol hexa(meth)acrylate and alkylene oxide-modified dipentaerythritol hexa(meth)acrylate are preferred.

Examples of (meth)acrylate compounds having a skeleton derived from trimethylolpropane include trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and alkylene oxide modified compounds thereof. Among these, trimethylolpropane tri(meth)acrylate and alkylene oxide modified trimethylolpropane tri(meth)acrylate are preferred.
Examples of (meth)acrylate compounds having a skeleton derived from pentaerythritol include pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and alkylene oxide modified compounds thereof. Among these, pentaerythritol tetra(meth)acrylate and alkylene oxide modified pentaerythritol tetra(meth)acrylate are preferred.
Examples of (meth)acrylate compounds having a glycerin-derived skeleton include glycerin di(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide-modified compounds thereof. Among these, glycerin tri(meth)acrylate and alkylene oxide-modified glycerin tri(meth)acrylate are preferred.

(Other polymerizable compounds)
Other polymerizable compounds include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, (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, (meth)acrylic acid ester of methylolated melamine, epoxy (meth)acrylate, methacrylic acid ester, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinyl formamide, acrylonitrile, and the like.

The amount of the polymerizable compound is preferably 1 to 50 parts by mass based on the total solids content of the photosensitive green composition (100 parts by mass), and more preferably 2 to 40 parts by mass from the viewpoints of photocurability and developability.

<Photopolymerization initiator (E)>
The photosensitive green composition of the present invention contains, as the photopolymerization initiator (E), an oxime ester photopolymerization initiator (E1) having a structure represented by the following general formula (1): By containing the oxime ester photopolymerization initiator (E1), it is possible to suppress the occurrence of water spots, and to obtain a high residual film rate and an excellent pattern shape in the process of producing a color filter segment using the composition.

(Oxime Ester Photopolymerization Initiator (E1))
General formula (1)

[In general formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ² represents a hydrocarbon group having 1 to 20 carbon atoms, n represents 0 or 1, one or more of R ³ to R ⁵ are substituted with a substituent represented by the following general formula (2), and the remaining represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group, and each alkyl group and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom and an alkoxyl group having 1 to 12 carbon atoms.]

Specific examples of ^R1 and ^R2 include a hydrogen atom, a methyl group, an ethyl group, a phenyl group, a benzyl group, etc. The hydrocarbon group may be linear or cyclic, and may or may not be branched.
At least one of R ³ to R ⁵ is a substituent having a hydroxyl group at its terminal, represented by the following general formula (2).

General formula (2)

* represents a bond to the benzene ring. X represents a direct bond, an oxygen atom, or a carbonyl group. ^R6 is a hydrocarbon group having 1 to 12 carbon atoms, specific examples of which include a methyl group, an ethyl group, a phenyl group, and a benzyl group. The hydrocarbon group may be linear or cyclic, and may or may not be branched. ^R7 represents a hydroxyl group or a carboxyl group.
Among ^R3 to ^R5 , those which are not the substituents represented by general formula (2) represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group, and each alkyl group and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom and an alkoxyl group having 1 to 12 carbon atoms.

Preferred examples of the compounds represented by the above general formula (1) include the compounds represented by the following chemical formulas (3) to (6). These compounds can be produced by known methods such as those described in JP 2011-132215 A.

Chemical formula (3)

Chemical formula (4)

Chemical formula (5)

Chemical formula (6)

These compounds with hydroxyl groups at the end form hydrogen bonds with the binder resin or photopolymerizable monomer, bringing the radical generation site and the reaction site closer together, which is thought to promote more efficient photocuring. As a result, water stains can be suppressed and a high residual film rate can be achieved. In addition, improved compatibility with the binder resin and photopolymerizable monomer provides appropriate thermal flow properties during post-baking, which is thought to result in an appropriate pattern shape.

<Other Photopolymerization Initiators (E2)>
Other photopolymerization initiators include acetophenone-based compounds such as 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)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzoin, benzoin methyl ether, benzo benzoin compounds such as benzoin ethyl ether, benzoin isopropyl ether, or benzil dimethyl ketal; benzophenone compounds such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine , 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(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-(4'-methoxystyryl)-6-triazine. triazine-based compounds such as azine; oxime ester-based compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, or 1-(O-acetyloxime); phosphine-based compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone-based compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate-based compounds; carbazole-based compounds; imidazole-based compounds; or titanocene-based compounds.
These photopolymerization initiators may be used alone or in combination of two or more kinds in any ratio as required.

Commercially available products include acetophenone compounds, all manufactured by IGM Resins, such as "Omnirad 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one), "Omnirad 369E" (2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone), and "Omnirad 379EG" (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone), and phosphine compounds, all manufactured by IGM Resins, such as "Omnirad 819" (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide), "Omnirad "TPO" (diphenyl-2,4,6-trimethylbenzoylphosphine oxide), etc.

The content of the photopolymerization initiator (E) is preferably 0.5 to 20 parts by mass relative to 100 parts by mass of the photosensitive green composition excluding the solvent, and more preferably 1 to 10 parts by mass from the viewpoints of photocurability and developability. If it is less than 0.5 parts by mass, the adhesion of the formed pattern to the substrate is deteriorated, and if it exceeds 20 parts by mass, problems with developability may occur, and a decrease in brightness after heat treatment at 230°C may occur.
The content of the photopolymerization initiator (E1) in the photopolymerization initiator (E) is preferably 50 to 100 parts by mass, and more preferably 80 to 100 parts by mass, per 100 parts by mass of the photopolymerization initiator (E).

The photopolymerization initiator (E) preferably contains two or more types of oxime ester photopolymerization initiators. In this case, it may contain two or more types of oxime ester photopolymerization initiators (E1) represented by general formula (1), or it may contain an oxime ester photopolymerization initiator (E1) represented by general formula (1) and an oxime ester photopolymerization initiator other than general formula (1).

<Polymerization inhibitor (F)>
The photosensitive green composition of the present invention preferably contains a polymerization inhibitor in order to further enhance the water stain suppression effect of the present invention.
For example, alkyl catechol compounds such as 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-t-butylcatechol, 3-t-butylcatechol, 4-t-butylcatechol, and 3,5-di-t-butylcatechol; 2-methylresorcinol, 4-methylresorcinol, and the like. resorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, 4-t-butylresorcinol and other alkylresorcinol compounds; methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone and other alkylhydroquinone compounds; tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenyl ... Examples of the polymerization inhibitor include phosphine compounds such as benzylphosphine, phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide, phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite, pyrogallol, and phloroglucin. Preferred examples include hindered phenol-based polymerization inhibitors, such as 2,6-di-tert-butyl-p-cresol, 2,5-bis(1,1,3,3-tetramethylbutyl)hydroquinone, 2,5-bis(1,1-dimethylbutyl)hydroquinone, pentaerythritol tetrakis bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 4,4',4"-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol, 6,6'-di-tert-butyl-4,4'-butylidene-di-m-cresol, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 2,2'-thiodiethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], isooctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, calcium bis[3,5-di(tert-butyl)-4-hydroxybenzyl(ethoxy)phosphinate], bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylene bis(oxyethylene)](, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2,6-di-tert-butylphenol.

The content of the polymerization inhibitor is preferably 0.01 to 0.5 parts by mass per 100 parts by mass of the photosensitive green composition excluding the solvent. In this range, the effect of the polymerization inhibitor becomes greater, and the linearity of the taper, wrinkles in the coating film, pattern resolution, etc. are improved.

<Leveling Agent (G)>
It is preferable to add a leveling agent to the photosensitive green composition of the present invention in order to improve the coating properties of the composition on a transparent substrate and the drying properties of the colored coating. As the leveling agent, various surfactants such as fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants can be used.

When the photosensitive green composition of the present invention contains a surfactant, the amount of the surfactant added is preferably 0.001 to 2.5 mass % based on the total solid content of the composition of the present invention, and more preferably 0.005 to 2.0 mass %. Within this range, the photosensitive green composition has a good balance between the coatability, pattern adhesion, and transmittance.

The photosensitive green composition of the present invention may contain only one type of surfactant, or may contain two or more types. When two or more types are contained, it is preferable that the total amount is within the above range. In addition, the type of leveling agent is preferably a fluorine-based leveling agent or a silicone-based leveling agent.

The photosensitive green composition of the present invention preferably contains two or more types of silicone-based leveling agents or fluorine-based leveling agents (G), and in particular, it is preferable to contain two types of fluorine-based leveling agents, since this reduces water spots.

Fluorine-based leveling agents include surfactants or leveling agents that have a fluorocarbon chain.

Commercially available products include Surflon S-242, S-243, S-420, S-611, S-651, and S-386 manufactured by AGC Seimi Chemical Co., Ltd., Megafac F-253, F-477, F-551, F-552, F-554, F-555, F-558, F-560, F-563, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, and DS-21 manufactured by DIC Corporation, FC-4430 and FC-4432 manufactured by Sumitomo 3M Limited, EF-PP31N09, EF-PP33G1, and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., and Ftergent 602A manufactured by NEOS Corporation.

Silicone surfactants include linear polymers consisting of siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or ends.

More specifically, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345/346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 manufactured by BYK-Chemie Co., Ltd., and FZ-7002, 2110 manufactured by Dow Corning Toray Co., Ltd. , 2122, 2123, 2191, 5609, Shin-Etsu Chemical Co., Ltd.'s X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341, etc.

Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, Examples of such sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkyl imidazoline, etc.

More specifically, Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS manufactured by Kao Corporation. -106, LS-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD450, Leodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW -L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanone 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-6 0(K), Amito 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, Adeka Pluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R manufactured by ADEKA CORPORATION, (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd., etc.

Cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and their ethylene oxide adducts.

More specifically, examples include Acetamine 24, Cortamine 24P, 60W, and 86P Conc., manufactured by Kao Corporation.

Examples of anionic surfactants include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkyl naphthalene sulfonates, sodium alkyl diphenyl ether disulfonates, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, polyoxyethylene alkyl ether phosphates, etc.

More specifically, examples include Futergent 100 and 150 manufactured by Neos Corporation, and Adeka Hope YES-25, Adeka Col TS-230E, PS-440E, and EC-8600 manufactured by ADEKA Corporation.

Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyl dimethylaminoacetate betaine, and alkyl amine oxides such as lauryl dimethylamine oxide.

More specifically, examples include Anhithol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, and 20N manufactured by Kao Corporation.

<Thiol-Based Chain Transfer Agent (H)>
The photosensitive green composition may contain a chain transfer agent. The chain transfer agent is preferably a thiol-based chain transfer agent. When the thiol-based chain transfer agent is used in combination with a photopolymerization initiator, a thiyl radical that is not easily inhibited by oxygen during radical polymerization after irradiation with light is generated, improving the sensitivity of the photosensitive green composition.

The thiol chain transfer agent is preferably a polyfunctional thiol having two or more thiol groups (SH groups). It is more preferable that the thiol chain transfer agent has four or more SH groups. As the number of functional groups increases, the coating becomes easier to photocure from the surface to the deepest part.

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

Thiol-based chain transfer agents can be used alone or in combination of two or more types.

The content of the thiol chain transfer agent is preferably 1 to 10% by mass, and more preferably 2 to 8% by mass, based on 100% by mass of the non-volatile content of the photosensitive green composition. When an appropriate amount is included, the photosensitivity and taper shape are improved, and wrinkles are less likely to occur on the coating surface.

<Ultraviolet absorber (J)>
The photosensitive green composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorbing function, and examples of the ultraviolet absorber include benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, salicylic acid ester-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds.

The content of the UV absorber is preferably 5 to 70% by mass, with the total of the photopolymerization initiator and the UV absorber being 100% by mass. If the content of the UV absorber is less than the above, the effect of the UV absorber is small and resolution cannot be ensured, whereas if the content is more than the above, the sensitivity is reduced and problems such as pixel peeling and hole diameters larger than the design value may occur.

In this case, if the photosensitive green composition contains a sensitizer, the content of the sensitizer is included in the content of the photopolymerization initiator.

The total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass, based on 100% by mass of the solid content of the photosensitive green composition. If the total content of the photopolymerization initiator and the ultraviolet absorber is less than the above, adhesion may weaken and pixel peeling may occur, and if it is more than the above, the sensitivity may be too high, resulting in poor resolution.

In this case, if the photosensitive green composition contains a sensitizer, the content of the sensitizer is included in the content of the photopolymerization initiator.

Benzotriazole organic compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α, α-Dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 branched and linear alkyl ester mixture, 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)phenol, methyl Reaction products of 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6 -t-butyl-4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-t-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-t-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate. Other oligomer and polymer type compounds having a benzotriazole structure can also be used.

More specifically, examples include TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, and 1130 manufactured by BASF Corporation, ADK STAB LA-29, LA-31RG, LA-32, and LA-36 manufactured by ADEKA Corporation, KEMISORB 71, 73, 74, 79, and 279 manufactured by Chemipro Chemical Co., Ltd., and RUVA-93 manufactured by Otsuka Chemical Co., Ltd.

Triazine organic compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester. The product includes 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine, etc. In addition, oligomer and polymer type compounds having a triazine structure can also be used.

More specifically, examples include KEMISORB 102 manufactured by Chemipro Chemicals, TINUVIN 400, 405, 460, 477, 479, and 1577ED manufactured by BASF, Adeka STAB LA-46 and LA-F70 manufactured by ADEKA, and CYASORB UV-1164 manufactured by Sun Chemical.

Benzophenone-based organic compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3H2O, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. Other oligomer and polymer compounds having a benzophenone structure can also be used.

More specifically, examples include KEMISORB 10, 11, 11S, 12, and 111 manufactured by Chemipro Chemicals Co., Ltd., SEESORB 101 and 107 manufactured by Shipro Chemicals Co., Ltd., Adeka STAB 1413 manufactured by ADEKA Corporation, and UV-12 manufactured by Sun Chemical Co., Ltd.

Examples of salicylic acid ester organic compounds include phenyl salicylate, p-octylphenyl salicylate, and t-butylphenyl salicylate. Other oligomer and polymer type compounds having a salicylic acid ester structure can also be used.

<Antioxidant (K)>
The photosensitive green composition of the present invention may contain an antioxidant. The antioxidant prevents the photopolymerization initiator or thermosetting compound contained in the photosensitive green composition from being oxidized and yellowed by the thermal process during thermal curing or ITO annealing, and therefore can increase the transmittance of the coating film. In particular, when the colorant concentration of the photosensitive green composition is high, the amount of the coating film crosslinking component is reduced, and therefore a phenomenon in which yellowing during the thermal process is intensified due to the use of a highly sensitive crosslinking component or an increase in the amount of the photopolymerization initiator is taken. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a high transmittance of the coating film can be obtained.

The "antioxidant" in the present invention may be any compound that has a radical scavenging function or a peroxide decomposition function. Specific examples of the antioxidant include hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds, and known antioxidants can be used. In addition, the antioxidant used in the present invention is preferably one that does not contain a halogen atom.

Among these antioxidants, from the viewpoint of achieving both the transmittance and sensitivity of the coating film, preferred ones include hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.

Hindered amine antioxidants include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2 ,6,6-tetramethyl-4-piperidyl methacrylate, polycondensation product of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], ester of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3,5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis(tetramethylbutyl)amino, Bis[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, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)ester, reaction products of 1,1-dimethylethyl hydroperoxide with octane, bis(1,2,2,6,6-pentamethyl-4-pyridyl)[[3,5-bis(1,1dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate methyl 1,2,2,6,6-pentamethyl-4-pyridylsebake ester, poly[[6-morpholino-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid ester, 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, etc. In addition, oligomer type and polymer type compounds having a hindered amine structure can also be used.

More specifically, examples of such compounds include ADK STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, and LA-502XP manufactured by ADEKA CORPORATION, KAMISTAB 29, 62, 77, and 94 manufactured by Chemipro Chemical Co., Ltd., Tinuvin 249, TINUVIN 111FDL, 123, 144, 292, and 5100 manufactured by BASF Corporation, and Cyasorb UV-3346, UV-3529, and UV-3853 manufactured by Sun Chemical Co., Ltd.

Phosphorus-based antioxidants include di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl)2-ethylhexyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, diphenyl mono( 2-ethylhexyl) phosphite, diphenyl isodecyl phosphite, tris(isodecyl) phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4-biphenyl diphosphonate, tris(tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl tridecyl phosphite, 4,4'-isopropylide diphenyl alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl Examples include 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(diphenoxyphosphonyloxy)-benzene, ethyl bis(2,4-di-t-butyl-6-methylphenyl) phosphite, etc. Other oligomer and polymer type compounds having a phosphite structure can also be used.

More specifically, examples include Adeka STAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, and TPP manufactured by ADEKA CORPORATION, IRGAFOS168 manufactured by BASF CORPORATION, and Hostanox P-EPQ manufactured by Clariant Chemicals K.K.

Examples of sulfur-based antioxidants include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], ditridecyl 3,3'-thiobispropionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, and 2,4-bis[(laurylthio)methyl]-o-cresol. Other oligomer and polymer type compounds having a thioether structure can also be used.

More specifically, examples include Adeka STAB AO-412S and AO-503 manufactured by ADEKA CORPORATION, and KEMINOX PLS manufactured by Chemipro Chemicals Co., Ltd.

These antioxidants can be used alone or in a mixture of two or more in any ratio as needed.

In addition, the content of the antioxidant is preferably 0.5 to 5.0% by mass based on 100% by mass of the solid content of the photosensitive green composition, since this provides good transmittance, spectral characteristics, and sensitivity.

<Storage stabilizer (L)>
The photosensitive green composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites. The storage stabilizer may be used in an amount of 0.1 to 10% by mass based on the total amount of the colorant (100% by mass).

<Adhesion improver (M)>
The photosensitive green composition of the present invention may contain an adhesion promoter such as a silane coupling agent in order to improve adhesion to the substrate. The improved adhesion due to the adhesion promoter improves the reproducibility of fine lines and improves resolution.

Adhesion improvers include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, (meth)acrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane, epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3- Examples of the silane coupling agent include aminosilanes such as aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride; mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureidos such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatepropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, per 100 parts by weight of the colorant in the photosensitive green composition. This range is more preferable because the effect is greater and the balance between adhesion, resolution, and sensitivity is good.

<Solvent (N)>
The photosensitive green composition of the present invention contains a solvent to facilitate the formation of a colored film by coating the composition on a substrate such as glass so as to give a dry film thickness of 0.2 to 5 μm. The solvent is selected in consideration of the good coatability of the photosensitive green composition, the solubility of each component of the photosensitive green composition, and safety.

Solvents that are commonly used in the field can be used, and they can be used alone or in combination as appropriate to suit the application conditions (speed, drying conditions, etc.) taking into account performance such as boiling point, SP value, evaporation rate, and viscosity.

Examples of solvents that can be used include ester solvents (solvents that contain -COO- in the molecule but do not contain -O-), ether solvents (solvents that contain -O- in the molecule but do not contain -COO-), ether ester solvents (solvents that contain -COO- and -O- in the molecule), ketone solvents (solvents that contain -CO- in the molecule but do not contain -COO-), alcohol solvents (solvents that contain OH in the molecule but do not contain -O-, -CO- or -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc.

Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and gamma-butyrolactone.

Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, anisole, phenetole, and methyl anisole.

Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Examples include methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, and dipropylene glycol diacetate.

Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, 1,3-butylene glycol, and glycerin.

Aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.
These solvents may be used alone or in combination of two or more kinds.

Among the above solvents, from the viewpoint of coatability and drying property, it is preferable to use an organic solvent having a boiling point of 120°C or more and 180°C or less at 1 atm. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, etc. are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. are more preferable.

<Method of producing colored composition>
The photosensitive green composition of the present invention can be prepared by previously finely dispersing the pigment in a dispersant, binder resin and/or solvent, preferably together with a dispersion aid (dye derivative or surfactant), using various dispersing means such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, an attritor, etc. At this time, two or more types of pigments may be simultaneously dispersed in a colorant carrier (binder resin and/or solvent), or the pigments may be separately dispersed in colorant carriers and then mixed.

<Dispersed Pigment Particle Diameter>
The average dispersed particle diameter of the pigment in the coloring composition is preferably in the range of 30 to 200 nm, and more preferably in the range of 40 to 120 nm. Within this range, the viscosity and dispersion stability are high, and when this coloring composition is used alone or in mixture, and a polymerizable compound (D) and a photopolymerization initiator (E) are further added, a photosensitive green composition can be obtained that not only has high viscosity and dispersion stability, but also has high sensitivity and a fast development speed, and when a color filter is produced using this, a high-quality color filter can be obtained.

The method for measuring the dispersed particle size of pigments is to use Nikkiso's Microtrac UPA-EX150, which employs dynamic light scattering (FFT power spectrum method), with particle permeability set to absorption mode, particle shape set to non-spherical, and D50 set to the average diameter. The dilution solvent used for the measurement is the same as that used for the dispersion, and it is preferable to measure samples treated with ultrasound immediately after sample preparation, as this tends to give results with less variation.

<Method for producing photosensitive green composition>
The photosensitive green composition can be prepared as a solvent-developable or alkali-developable coloring composition. The solvent-developable or alkali-developable coloring composition can be prepared by mixing the coloring composition, the photopolymerizable monomer and/or the photopolymerization initiator, and, if necessary, a solvent, other dispersing aids, and additives. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

<Removal of large particles>
The photosensitive green composition of the present invention is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably coarse particles of 0.5 μm or more, and mixed dust, by means of centrifugation, filtration with a sintered filter or membrane filter, etc. In this way, it is preferable that the photosensitive green composition does not substantially contain particles of 0.5 μm or more, and more preferably 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 comprises a red filter segment, a green filter segment, and a blue filter segment, and may further comprise a magenta filter segment, a cyan filter segment, and a yellow filter segment.

<Manufacturing method of color filter>
The color filter can be manufactured by a printing method or a photolithography method.
The formation of filter segments by the printing method can be patterned simply by repeatedly printing and drying a photosensitive green composition prepared as a printing ink, and is therefore a low-cost and mass-productive method for producing color filters. Furthermore, the development of printing technology has made it possible to print fine patterns with high dimensional accuracy and smoothness. In order to print, it is preferable to use a composition that does not allow the ink to dry or solidify on the printing plate or blanket. In addition, control of the fluidity of the ink on the printing machine is also important, and the ink viscosity can be adjusted by using a dispersant or an extender pigment.

When forming filter segments by photolithography, the photosensitive green composition prepared as the above-mentioned solvent-developable or alkali-developable colored resist material is applied to a transparent substrate by a coating method such as spray coating, spin coating, slit coating, or roll coating so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed (irradiated with radiation) through a mask having a predetermined pattern that is provided in contact with or not in contact with the film. Thereafter, the uncured parts are removed by immersing the film in a solvent or alkali developing solution or spraying the developing solution with a spray or the like to form a desired pattern, and the same operation is repeated for other colors to produce a color filter. Furthermore, heating can be performed as necessary to promote polymerization of the colored resist material. According to the photolithography method, a color filter with higher accuracy than the above-mentioned printing method can be produced.

In the development, an aqueous solution of sodium carbonate, sodium hydroxide, etc. is used as an alkaline developer, and an organic alkali such as dimethylbenzylamine, triethanolamine, etc. can also be used. In addition, a defoaming agent or a surfactant can also be added to the developer.
In order to increase the exposure sensitivity, after the colored resist is applied and dried, a water-soluble or alkaline water-soluble resin, such as polyvinyl alcohol or a water-soluble acrylic resin, may be applied and dried to form a film for preventing polymerization inhibition due to oxygen, and then exposure may be performed.

The color filter of the present invention can be manufactured by the above-mentioned method, as well as by the electrodeposition method, transfer method, inkjet method, etc., and the photosensitive green composition of the present invention can be used in any of these methods. The electrodeposition method is a method of manufacturing a color filter by using a transparent conductive film formed on a substrate to electrodeposit each color filter segment onto the transparent conductive film by electrophoresis of colloidal particles. The transfer method is a method in which filter segments are formed in advance on the surface of a peelable transfer base sheet, and the filter segments are then transferred to the desired substrate.

Before forming each color filter segment on the transparent substrate or reflective substrate, a black matrix can be formed in advance. Examples of the black matrix include, but are not limited to, a multilayer film of chromium or chromium/chromium oxide, an inorganic film such as titanium nitride, or a resin film with a light-shielding agent dispersed therein. Thin film transistors (TFTs) can also be formed in advance on the transparent substrate or reflective substrate, and then each color filter segment can be formed. In addition, an overcoat film, a transparent conductive film, etc. can be formed on the color filter of the present invention as necessary.

The color filter of the present invention is laminated to an opposing substrate using a sealant, liquid crystal is injected through an injection port provided in the sealing portion, the injection port is sealed, and a polarizing film or retardation film is laminated to the outside of the substrate as necessary, thereby manufacturing a color liquid crystal display device. This color liquid crystal display device can be used in liquid crystal display modes that use color filters such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically concave bend (OCB).

In addition to color liquid crystal displays, the color filters of the present invention can also be used to manufacture color solid-state imaging devices, organic EL displays, quantum dot displays, electronic paper, and the like.

<Liquid Crystal Display Device>
A liquid crystal display device equipped with the color filter of the present invention will now be described.
The liquid crystal display device of the present invention comprises the color filter of the present invention and a light source. Examples of the light source include a cold cathode fluorescent lamp (CCFL) and a white LED, but in the present invention, it is preferable to use a white LED because it widens the red reproduction range. Fig. 1 is a schematic cross-sectional view of a liquid crystal display device 10 equipped with the color filter of the present invention. The device 10 shown in Fig. 1 comprises a pair of transparent substrates 11 and 21 arranged to face each other at a distance, and a liquid crystal LC is sealed between them.

A TFT (thin film transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. A polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

On the other hand, the color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. The red, green, and blue filter segments that make up the color filter 22 are separated by a black matrix (not shown).

A transparent protective film (not shown) is formed as necessary to cover the color filter 22, and a transparent electrode layer 23 made of, for example, ITO is formed on top of the protective film, and an alignment layer 24 is provided to cover the transparent electrode layer 23.

In addition, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. In addition, a backlight unit 30 is provided below the polarizing plate 15.

The liquid crystal LC is aligned according to the driving mode, such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane switching), VA (Vertical Alignment), OCB (Optically Compensated Birefringence), etc. A TFT (thin film transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. A polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

On the other hand, the color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. The red, green, and blue filter segments that make up the color filter 22 are separated by a black matrix (not shown).

A transparent protective film (not shown) is formed as necessary to cover the color filter 22, and a transparent electrode layer 23 made of, for example, ITO is formed on top of the protective film, and an alignment layer 24 is provided to cover the transparent electrode layer 23.

A polarizing plate 25 is formed on the outer surface of the transparent substrate 21. A backlight unit 30 is provided below the polarizing plate 15.

White LED light sources include those in which a fluorescent filter is formed on the surface of a blue LED, and those in which a phosphor is contained in the resin package of a blue LED, and have a wavelength (λ3) in the range of 430 nm to 485 nm at which the emission intensity is maximized, a wavelength (λ4) in the range of 530 nm to 580 nm at which the emission intensity is maximized, and a wavelength (λ5) in the range of 600 nm to 650 nm at which the emission intensity is maximized, and the ratio (I4/I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less. , a white LED light source (LED1) having spectral characteristics in which the ratio (I5/I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 is 0.1 or more and 1.3 or less, a white LED light source (LED2) having a wavelength (λ1) at which the emission intensity is maximum within the range of 430 nm to 485 nm, a peak wavelength (λ2) of the second emission intensity within the range of 530 nm to 580 nm, and a ratio (I2/I1) of the emission intensity I1 at wavelength λ1 to the emission intensity I2 at wavelength λ2 is 0.2 or more and 0.7 or less is preferable.

Specific examples of LED1 include NSSW306D-HG-V1 (manufactured by Nichia Chemicals), NSSW304D-HG-V1 (manufactured by Nichia Chemicals), etc.

Specific examples of the LED 2 include NSSW440 (manufactured by Nichia Chemical Industries, Ltd.) and NSSW304D (manufactured by Nichia Chemical Industries, Ltd.).

The present invention will be explained below with reference to the following examples. In the examples, "parts" and "%" refer to "parts by mass" and "% by mass", respectively.

Before going into the examples, we will explain each measurement method.

The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mg KOH/g), and amine value (mg KOH/g) of the resin are as follows:

(Average molecular weight of resin)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the binder resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. The apparatus used was an HLC-8220GPC (manufactured by Tosoh Corporation), two separation columns were connected in series, and both packings were "TSK-GEL SUPER HZM-N" connected in series. The oven temperature was 40°C, a THF solution was used as the eluent, and the flow rate was 0.35 ml/min.
The sample was dissolved in a solvent containing 1 wt % of the above eluent, and 20 microliters was injected. The molecular weights are all polystyrene equivalent values.

(Acid value of resin (mgKOH/g))
80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of the resin solution, and the solution was stirred to dissolve uniformly, and titrated with an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) using a 0.1 mol/L KOH aqueous solution as a titrant to measure the acid value (mg KOH/g) of the resin solution. 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.

(Fine Phthalocyanine Pigment A1-1)
Equation (7)

(Fine Phthalocyanine Pigment A1-2)
Equation (8)

(Fine Phthalocyanine Pigment A1-3)
Equation (9)

(Fine Phthalocyanine Pigment A1-4)
Equation (10)

(Fine Phthalocyanine Pigment A1-5)
Equation (11)

(Fine Phthalocyanine Pigment (A2-1))
100 parts of phthalocyanine pigment C.I. Pigment Green 58 (DIC Corporation "FASTGEN GREEN A110"), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 70 ° C. This kneaded product was added to 3000 parts of warm water, heated to 70 ° C. and stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for a day and night to obtain 97 parts of fine phthalocyanine pigment (A2-1).

(Fine Phthalocyanine Pigments (A1-1/A2-1))
The finely divided phthalocyanine pigment (A1-1) and the finely divided phthalocyanine pigment (A2-1) were mixed in equal amounts to obtain a finely divided phthalocyanine pigment (A1-1/A2-1).

(Fine Phthalocyanine Pigment (A2-2))
In a 300 mL flask, 91 parts of sulfuryl chloride, 109 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 74 parts of bromine were charged. The mixture was heated to 130°C over 40 hours, taken out in water, and filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged in a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was taken out in 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a fine phthalocyanine pigment (A2-2). The resulting finely divided phthalocyanine pigment (A2-2) was found to be a zinc phthalocyanine halide pigment having an average of 13.97 halogen atoms per molecule, including an average of 11.46 bromine atoms and an average of 2.51 chlorine atoms, as determined by fluorescent X-ray analysis using a Rigaku ZSX100E.

(Fine Phthalocyanine Pigment (A2-3))
In a 300 mL flask, 91 parts of sulfuryl chloride, 109 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 59 parts of bromine were charged. The mixture was heated to 130°C over 40 hours, taken out in water, and then filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged in a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was taken out in 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a fine phthalocyanine pigment (A2-3). The obtained fine phthalocyanine pigment (A2-3) was found to have an average of 12.71 halogen atoms per molecule from fluorescent X-ray analysis, of which the average number of bromine atoms was 10.22 and the average number of chlorine atoms was 2.49, making it a halogenated zinc phthalocyanine pigment.

(Fine Phthalocyanine Pigment (A2-4))
In a 300 mL flask, 91 parts of sulfuryl chloride, 109 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 44 parts of bromine were charged. The mixture was heated to 130°C over 40 hours, taken out in water, and then filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged in a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was taken out in 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a fine phthalocyanine pigment (A2-4). The obtained fine phthalocyanine pigment (A2-4) was found to have an average of 11.98 halogen atoms per molecule from fluorescent X-ray analysis, of which the average number of bromine atoms was 9.00 and the average number of chlorine atoms was 2.98, making it a halogenated zinc phthalocyanine pigment.

(Fine Phthalocyanine Pigment (A2-5))
In a 300 mL flask, 109 parts of sulfuryl chloride, 131 parts of aluminum chloride, 18 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 52 parts of bromine were charged. The mixture was heated to 130°C over 40 hours, taken out in water, and then filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged in a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was taken out in 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a fine phthalocyanine pigment (A2-5). The obtained fine phthalocyanine pigment (A2-5) was found to have an average of 12.69 halogen atoms per molecule from fluorescent X-ray analysis, of which the average number of bromine atoms was 8.54 and the average number of chlorine atoms was 4.16, making it a halogenated zinc phthalocyanine pigment.

(Fine Phthalocyanine Pigment (A2-6))
In a 300 mL flask, 91 parts of sulfuryl chloride, 72 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 29 parts of bromine were charged. The mixture was heated to 130°C over 40 hours, taken out in water, and then filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged in a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was taken out in 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a fine phthalocyanine pigment (A2-6). The obtained fine phthalocyanine pigment (A2-6) was found to have an average of 8.88 halogen atoms per molecule from fluorescent X-ray analysis, of which the average number of bromine atoms was 6.90 and the average number of chlorine atoms was 1.98, making it a halogenated zinc phthalocyanine pigment.

(Fine Phthalocyanine Pigment (A3))
200 parts of phthalocyanine pigment C.I. Pigment Green 36, 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 6 hours at 80° C. Next, this kneaded product was put into 8 liters of warm water, heated to 80° C. and stirred for 2 hours to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85° C. for 24 hours to obtain 190 parts of fine phthalocyanine pigment (A3).

<Production of Finely Divided Yellow Pigment>
(Fine Yellow Pigments (A4-1 to A4-3))
According to the examples of JP 2012-226110 A, fine phthalocyanine pigments (A4-1 to A4-3) of quinophthalone pigments of the following formulas (12) to (14) were prepared. The structures are shown below.

(Fine Yellow Pigment A4-1)
Equation (12)

(Fine Yellow Pigment A4-2)
Equation (13)

(Fine Yellow Pigment A4-3)
Equation (14)

(Fine Yellow Pigment (A4-4))
100 parts of C.I. Pigment Yellow 138 (PY138) (BASF "Paliotol Yellow K0960-HD"), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho) and kneaded for 6 hours at 80 ° C. This mixture was added to 2000 parts of hot water, heated to 80 ° C. and stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C. for 24 hours to obtain 95 parts of finely divided yellow pigment (A4-4).

(Fine Yellow Pigment (A4-5))
100 parts of isoindoline yellow pigment C.I. Pigment Yellow 139 ("Irgaphor Yellow 2R-CF" manufactured by Ciba Japan Co., Ltd.), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader and kneaded for 10 hours at 60 ° C. Next, this mixture was put into 3 liters of warm water, heated to about 80 ° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and the solvent, and then dried at 80 ° C. for one day and night to obtain a finely divided yellow pigment (A4-5).

(Fine Yellow Pigment (A4-6))
100 parts of a metal complex yellow pigment (C.I. pigment yellow 150, Lanxess "Yellow Pigment E4GN"), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 10 hours. Next, this mixture was added to 3 liters of warm water, heated to about 80°C and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and the solvent, and then dried at 80°C for 1 day and night to obtain a fine yellow pigment (A4-6). The average primary particle size was 36.6 nm.

(Fine Yellow Pigment (A4-7))
Yellow pigment C.I. Pigment Yellow 185 (Ciba Japan Co., Ltd. "Paliotol Yellow D1155"): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a stainless steel 1 gallon kneader and kneaded for 8 hours at 120 ° C. Next, this kneaded product was put into 5 liters of warm water, heated to 70 ° C. and stirred for 1 hour to make a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for a day and night to obtain a fine yellow pigment (A4-7).

RMAT
Pcは、フタロシアニン骨格を表す。 <Dye derivative (b0)>
The following dye derivatives were used:
Dye derivative (b0-1)

RMAT
Pc represents a phthalocyanine skeleton.

Dye derivative (b0-2)

The following abbreviations have the following meanings:
HEMA: 2-hydroxyethyl methacrylate EHMA: 2-ethylhexyl methacrylate BMA: n-butyl methacrylate BzMA: benzyl methacrylate MMA: methyl methacrylate DMAPMA: dimethylaminopropyl methacrylamide DMAEMA: dimethylaminoethyl methacrylamide PGMAc: propylene glycol monomethyl ether acetate

<Preparation of Resin-Type Dispersant (B) Solution>
(Preparation of Resin-Type Dispersant (B-1) Solution)
In a 500 mL round-bottomed 4-neck separable flask equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of tetrahydrofuran (THF) and 5.81 parts by mass of dimethylketene methyltrimethylsilyl acetal as an initiator were added through the addition funnel, and sufficient nitrogen replacement was performed. 0.5 parts by mass of a 1 mol/L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst was injected using a syringe, and 19.7 parts by mass of HEMA, 7.5 parts by mass of EHMA, 12.9 parts by mass of BMA, 10.7 parts by mass of BzMA, and 30.9 parts by mass of MMA, which are block monomers having solvent affinity, were dropped using the addition funnel over 60 minutes. The temperature was kept below 40° C. by cooling the reaction flask in an ice bath. After 1 hour, 18.3 parts by mass of DMAPMA, which is a monomer for colorant adsorption functional blocks, was dropped over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to stop the reaction. The resulting block copolymer THF solution was reprecipitated in hexane, filtered, and purified by vacuum drying to obtain a compound (B1) containing a colorant-adsorbing functional block containing a structural unit represented by general formula (1) and a block having solvent affinity. Further, PGMAc was added to adjust the solid content to 20% by mass to obtain a resin-type dispersant (B-1) solution.

(Preparation of Resin-Type Dispersant (B-2) Solution)
In a 100 mL round-bottom flask, 10.0 parts by mass of compound (B1) was dissolved in 40.6 parts by mass of PGMAc, and 0.75 parts by mass of phenylphosphinic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.50 mol of phenylphosphinic acid per 1.0 mol of DMAPMA unit of compound (B1)) was added, and the mixture was stirred at a reaction temperature of 30° C. for 20 hours. PGMAc was added to adjust the solid content to 20% by mass, thereby obtaining a resin-type dispersant (B-2) solution.

(Preparation of Resin-Type Dispersant (B-3) Solution)
A reaction vessel equipped with a gas inlet tube, a temperature control, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 100 parts of MMA, 70 parts of i-butyl methacrylate, 20 parts of BzMA, and 50 parts of PGMAc, and substituted with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile added to 90 parts of PGMAc was added and reacted for 7 hours. It was confirmed that 95% had reacted by solid content measurement. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out 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, and the reaction solution was diluted with PGMAc so that the solid content was 20% by measuring the solid content, thereby obtaining a resin-type dispersant (B-3) solution having an acid value of 70 mgKOH/g and a weight average molecular weight of 8,500.

(Preparation of Resin-Type Dispersant (B-4) Solution)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 parts of monobutyltin (IV) oxide as a catalyst were charged, and the mixture was replaced with nitrogen gas, and then heated and stirred at 120 ° C. for 4 hours. After confirming that 98% had reacted by solid content measurement, 73.3 parts of pyromellitic anhydride were added and reacted at 120 ° C. for 2 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by acid value measurement. A resin-type dispersant (B-4) solution with a solid content of 20% was obtained by adjusting the solid content with PGMAc. The obtained dispersant was a white solid at room temperature, and the acid value was 49 mg KOH / g.

<Production Example of Binder Resin (C)>
(Preparation of binder resin (C-1) liquid)
A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer to prepare a reaction vessel. 196 parts of cyclohexanone were charged, and the temperature was raised to 80 ° C., and the inside of the reaction vessel was replaced with nitrogen. From the dropping tube, a mixture of 37.2 parts of BMA, 12.9 parts of HEMA, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), and 1.1 parts of 2,2'-azobisisobutyronitrile was dropped over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and PGMAc was added to the resin solution synthesized earlier so that the nonvolatile content was 20% to prepare a binder resin (C-1) liquid. The weight average molecular weight (Mw) was 26,000.

(Preparation of binder resin (C-2) liquid)
A separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer was charged with 370 parts of cyclohexanone, and the temperature was raised to 80°C. After replacing the atmosphere in the flask with nitrogen, a mixture of 18 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of BzMA, 18.2 parts of glycidyl methacrylate, 25 parts of MMA and 2.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours from the dropping tube. After the dropwise addition, the mixture was further reacted at 100°C for 3 hours, and then a solution of 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was continued at 100°C for 1 hour. Next, the inside of the vessel was replaced with air, and 9.3 parts of acrylic acid (100% of glycidyl groups), 0.5 parts of trisdimethylaminophenol, and 0.1 parts of hydroquinone were added to the vessel, and the reaction was continued for 6 hours at 120° C., and the reaction was terminated when the solid acid value reached 0.5, to obtain an acrylic resin solution. Furthermore, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added, and the reaction was continued for 3.5 hours at 120° C. to obtain an acrylic resin solution.
After cooling to room temperature, about 2 g of the resin solution was sampled and dried at 180 ° C for 20 minutes to measure the non-volatile content, and PGMAc was added to the previously synthesized resin solution so that the non-volatile content was 20 mass % to prepare a binder resin (C-2) liquid. The weight average molecular weight (Mw) was 19,000.

(Preparation of binder resin (C-3) liquid)
Into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube, 182 g of propylene glycol monomethyl ether acetate was introduced, and the atmosphere in the flask was changed from air to nitrogen. After that, the temperature was raised to 100°C, and then a solution of 3.6 g of azobisisobutyronitrile added to a mixture consisting of 70.5 g (0.40 mol) of BzMA, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of a monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) and 136 g of propylene glycol monomethyl ether acetate was dropped from the dropping funnel into the flask over 2 hours, and stirring was continued at 100°C for another 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate [0.25 moles, (50 moles relative to the carboxyl group of the methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued for 6 hours at 110 ° C. to obtain a photosensitive transparent resin solution with an acid value of 79 mg KOH / g. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAc was added to the photosensitive transparent resin solution synthesized earlier so that the non-volatile content was 20 mass% to prepare a binder resin (C-3) solution. The mass average molecular weight (Mw) was 13,000.

(Preparation of binder resin (C-4) liquid)
A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer. 207 parts of cyclohexanone was charged into the reaction vessel, which was then heated to 80°C and substituted with nitrogen in the reaction vessel. From the dropping tube, a mixture of 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of HEMA and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the total amount of the copolymer solution obtained was stirred while stopping the nitrogen gas and injecting dry air for 1 hour, and then cooled to room temperature, and a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko K.K.), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was dropped at 70 ° C. for 3 hours. After the dropwise addition, the reaction was continued for another 1 hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone was added to the resin solution previously synthesized so that the non-volatile content was 20% to prepare a binder resin (C-4). The weight average molecular weight (Mw) was 18,000.

(Preparation of binder resin (C-5) liquid)
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, a thoroughly stirred mixture of 40 parts of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 40 parts of methacrylic acid, 120 parts of MMA, 4 parts of t-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fats), and 40 parts of PGMAc was prepared as a monomer dropping vessel. A thoroughly stirred mixture of 8 parts of n-dodecanethiol and 32 parts of PGMAc was prepared as a chain transfer agent dropping vessel.
395 parts of PGMAc was charged into the reaction vessel, and after replacing with nitrogen, the temperature of the reaction vessel was raised to 90 ° C. by heating in an oil bath while stirring. After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel. Dropping was carried out over 135 minutes while maintaining the temperature at 90 ° C. 60 minutes after the end of dropping, the temperature was raised to 110 ° C. After maintaining 110 ° C. for 3 hours, a gas inlet tube was attached to the separable flask, and bubbling of a mixed gas of oxygen / nitrogen = 5 / 95 (volume ratio) was started. Next, 70 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 parts of triethylamine were charged into the reaction vessel, and the reaction was carried out at 110 ° C. for 12 hours. Then, 150 parts of PGMAc was added and cooled to room temperature, and about 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content, and PGMAc was added to the previously synthesized resin solution so that the non-volatile content was 20% by mass to obtain a binder resin (C-5) solution. The weight average molecular weight of the resin was 18,000, and the acid value per solid content was 2 mgKOH/g.

(Preparation of binder resin (C-M) liquid)
The binder resins (C-2) to (C-5) were mixed in equal amounts to prepare a binder resin (CM) liquid.

<Method for producing colored composition (single color)>
[Production Example 1]
(Preparation of Colored Composition (R-1))
The mixture below was stirred and mixed to be homogeneous, and then dispersed for 3 hours in an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm. The mixture was then filtered through a filter having a pore size of 5.0 μm to prepare a colored composition (R-1) having a non-volatile content of 25% by mass.
Pigment (A1-1): 20 parts Resin type dispersant liquid 1 (B-1: 20% non-volatile liquid): 3 parts Resin type dispersant liquid 2 (B-3: 20% non-volatile liquid): 2 parts Binder resin (C-1: 20% non-volatile liquid): 20 parts Solvent (N): 55 parts

[Production Examples 2 to 36]
(Preparation of Colored Compositions (R-2 to R-36))
Colored compositions (R-2 to R-36) were prepared in the same manner as in Production Example 1, except that the material types and masses were changed as shown in Table 1.

<Method for producing photosensitive green composition>
[Example 1]
(Photosensitive green composition (X-1))
The following raw materials were mixed and stirred, and then filtered through a filter having a pore size of 1.0 μm to obtain a photosensitive green composition (X-1).
Green composition (R-1: non-volatile content 25%): 35.0 parts Colored composition (R-25: non-volatile content 25%): 15.0 parts Binder resin (CM: non-volatile content 20%): 12.6 parts Thermosetting compound (CE-1): 1.0 parts Thermosetting compound (CE-2): 1.0 parts Photopolymerizable monomer (D-1): 5.5 parts Photopolymerization initiator (E1-3): 1.45 parts Polymerization inhibitor (F-1): 0.05 parts Leveling agent (G-1: non-volatile content 3%): 1.0 parts Thiol chain transfer agent (H): 0.5 parts Ultraviolet absorber (J): 0.1 parts Antioxidant (K): 0.1 parts Storage stabilizer (L): 0.1 parts Adhesion improver (M): 0.2 parts Solvent (N): 25.95 parts

[Examples 2 to 66, Comparative Examples 1 to 5]
(Preparation of Photosensitive Green Compositions (X-2 to 71))
Photosensitive green compositions (X-2 to 71) were prepared in the same manner as in Example 1, except that the material types and masses of the photosensitive green composition in Example 1 were changed as shown in Table 2. The raw materials for each were as follows. In this specification, Examples 1 to 55 and 58 to 66 are reference examples.

<Thermosetting compound (CE)>
Epoxy compound (CE-1)
(CE-1-1) 1,2- of 2,2'-bis(hydroxymethyl)-1-butanol
Epoxy-4-(2-oxiranyl)cyclohexane adduct
[EHPE-3150 (manufactured by Daicel)],
(CE-1-2) Glycidyl etherified epoxy compounds of sorbitol
[Denacol EX611 (manufactured by Nagase ChemteX Corporation)],
(CE-1-3) Triglycidyl isocyanurate (CE-1-1) to (CE-1-3) were mixed in equal amounts to prepare an epoxy compound (CE-1).
Oxetane compound (CE-2):
3-Ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane
[Aron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]

<Polymerizable compound (D)>
(D-1) Trimethylolpropane triacrylate
[Aronix M309 (manufactured by Toagosei Co., Ltd.)]
(D-2) Trimethylolpropane ethylene oxide (EO) modified triacrylate
[Aronix M350 (manufactured by Toagosei Co., Ltd.)]
(D-3) Trimethylolpropane propylene oxide (PO) modified triacrylate
[Aronix M310 (manufactured by Toagosei Co., Ltd.)]
(DM) The following (D-4) to (D-9) were mixed in equal amounts to prepare a photopolymerizable monomer (DM).
(D-4) Dipentaerythritol penta- and hexaacrylate
[Aronix M402 (manufactured by Toagosei Co., Ltd.)]
(D-5) Polybasic acidic acrylic oligomer
[Aronix M520 (manufactured by Toagosei Co., Ltd.)]
(D-6) Caprolactone-modified dipentaerythritol hexaacrylate
[KAYARAD DPCA-30 (manufactured by Nippon Kayaku)]

(D-7) Polyfunctional urethane acrylate prepared as follows: Pentaerythritol triacrylate (432 g) and hexamethylene diisocyanate (84 g) were charged into a 1-liter five-necked reaction vessel and reacted at 60° C. for 8 hours to obtain a product containing a polyfunctional urethane acrylate (D-7) having a (meth)acryloyl group. The proportion of the polyfunctional urethane acrylate (D-7) in the product was 70 mass%, with the remainder being other photopolymerizable monomers. It was confirmed by IR analysis that no isocyanate groups were present in the reaction product.

(D-8) Difunctional bisphenol A type (meth)acrylate
[ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)]
(D-9) Ethoxylated isocyanuric acid triacrylate
[A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)]

<Photopolymerization initiator (E)>
(E1-1) Compound represented by chemical formula (3) (E1-2) Compound represented by chemical formula (4) (E1-3) Compound represented by chemical formula (5) (E1-4) Compound represented by chemical formula (6) (E2-5) 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)]
[Irgacure OXE01 (manufactured by BASF Japan)]
(E2-6) Compound represented by formula (17)

Chemical formula (17)

(E2-7) Compound represented by chemical formula (18)

(E2-8) Ethan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetyloxime)
[Irgacure OXE02 (manufactured by BASF Japan)]
(E2-M) The following (E2-9) to (E2-15) were mixed in equal amounts to prepare a photopolymerization initiator (E2-M).
(E2-9) 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one
[Irgacure 907 (manufactured by BASF Japan)]
(E2-10) 2-(Dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone
[Irgacure 379 (manufactured by BASF Japan)]
(E2-11) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
[Lucirin TPO (manufactured by Ciba Japan)]
(E2-12) 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole
[Biimidazole (Kurokane Chemicals)]
(E2-13) p-Dimethylaminoacetophenone
[DMA (manufactured by Daikifine)]
(E2-14) 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one
[Irgacure 2959 (manufactured by BASF Japan)]
(E2-15) Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide
[Irgacure 819 (manufactured by BASF Japan)]

(E1-1/E1-3): Equal amounts of (E1-1) and (E1-3) were mixed.
(E1-2/E1-3): Equal amounts of (E1-2) and (E1-3) were mixed.
(E1-3/E1-4): Equal amounts of (E1-3) and (E1-4) were mixed.
(E1-3/E2-5): Equal amounts of (E1-3) and (E2-5) were mixed.
(E1-3/E2-6): Equal amounts of (E1-3) and (E2-6) were mixed.
(E1-3/E2-7): Equal amounts of (E1-3) and (E2-7) were mixed.
(E1-3/E2-8): Equal amounts of (E1-3) and (E2-8) were mixed.
(E1-3/E2-M): Equal amounts of (E1-3) and (E2-M) were mixed.

<Polymerization inhibitor (F)>
(F-1) 2,6-di-tert-butyl-p-cresol (F-2) methylhydroquinone (FM) The following (F-3) and (F-4) were mixed in equal amounts to prepare a photopolymerization initiator (FM).
(F-3) 3-Methylcatechol (F-4) t-Butylhydroquinone

<Leveling Agent (G)>
(G-1) A solution obtained by mixing 3 parts of "Megafac F-575" manufactured by DIC Corporation with 97 parts of PGMAc. (G-2) A solution obtained by mixing 3 parts of "BYK-330" manufactured by BYK-Chemie with 97 parts of PGMAc. (G-3) A solution obtained by mixing 3 parts of "Emulgen 103" manufactured by Kao Corporation with 97 parts of PGMAc. (G-4) A solution obtained by mixing 3 parts of "Megafac F-563" manufactured by DIC Corporation with 97 parts of PGMAc. (G-5) A solution obtained by mixing 3 parts of "BYK-323" manufactured by BYK-Chemie with 97 parts of PGMAc. (G-1/G-2) Equal amounts of (G-1) and (G-2) were mixed to obtain (G-1/G-2).
(G-1/G-3) Equal amounts of (G-1) and (G-3) were mixed to prepare (G-1/G-3).
(G-1/G-4) Equal amounts of (G-1) and (G-4) were mixed to prepare (G-1/G-4).
(G-2/G-3) Equal amounts of (G-2) and (G-3) were mixed to prepare (G-2/G-3).
(G-2/G-5) Equal amounts of (G-2) and (G-5) were mixed to prepare (G-2/G-5).
<Thiol-Based Chain Transfer Agent (H)>
(H-1) Trimethylolethane tris(3-mercaptobutyrate)
[TEMB (Showa Denko)]
(H-2) Trimethylolpropane tris(3-mercaptobutyrate)
[TPMB (Showa Denko)]
(H-3) Pentaerythritol tetrakis(3-mercaptopropionate)
[PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(H-4) Trimethylolpropane tris(3-mercaptopropionate)
[TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(H-5) Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate
[TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)]
The above (H-1) to (H-5) were mixed in equal amounts to prepare a thiol-based chain transfer agent (H).

<Ultraviolet absorber (J)>
(J-1) 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
[TINUVIN 400 (manufactured by BASF Japan)]
(J-2) 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol
[TINUVIN900 (manufactured by BASF Japan)]
The above (J-1) and (J-2) were mixed in equal amounts to prepare an ultraviolet absorber (J).

<Antioxidant (K)>
(K-1) pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (K-2) dioctadecyl 3,3'-thiodipropanoate (K-3) tris[2,4-di-(t)-butylphenyl]phosphine (K-4) bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate (K-5) p-octylphenyl salicylate The above (K-1) to (K-5) were mixed in equal amounts to give antioxidant (K).

<Storage stabilizer (L)>
Triphenylphosphine ("TPP" manufactured by Hokko Chemical Industry Co., Ltd.)

<Adhesion improver (M)>
(M-1) 3-glycidoxypropyltriethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(M-2) 3-Methacryloxypropyltriethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(M-3) N-2-(aminoethyl)-3-aminopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(M-4) 3-mercaptopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
The above (M-1) to (M-4) were mixed in equal amounts to prepare an adhesion improver (M).

<Solvent (N)>
(N-1) PGMAc 60 parts (N-2) Ethyl 3-ethoxypropionate 10 parts (N-3) Propylene glycol monomethyl ether 10 parts (N-4) Cyclohexanol acetate 10 parts (N-5) Dipropylene glycol methyl ether acetate 10 parts The above (N-1) to (N-5) were mixed in the above parts by mass to obtain solvent (N).

<Evaluation of Photosensitive Green Composition>
The tests were carried out as follows. The test results are shown in Table 3.
The meaning of the evaluation rank is as follows:
◎: Very good ○: Good △: Practical ×: Not suitable for practical use

<Evaluation of film remaining rate>
The obtained photosensitive green composition was applied to a 100 mm x 100 mm, 0.7 mm glass substrate to a film thickness of 3.4 μm, and exposed to ultraviolet light at 40 mJ/cm ² through a mask having a stripe pattern with a width of 100 μm. Thereafter, the composition was developed by immersing the composition in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23° C. for 40 seconds, and washed with pure water to obtain a pattern. The obtained coating film was subjected to a heat treatment (post-baking) in an oven at 230° C. for 20 minutes, and the change in film thickness (residual film ratio) before and after the post-baking was calculated from the following formula.
Remaining film ratio=film thickness after post-bake/film thickness before post-bake×100
The evaluation criteria are as follows:
◎: 85% or more ○: 80% or more but less than 85% △: 75% or more but less than 80% ×: Less than 75%

<Water stain evaluation>
The obtained photosensitive green composition was applied to a 100 mm x 100 mm, 0.7 mm glass substrate to a film thickness of 3.4 μm, and exposed to ultraviolet light at 40 mJ/cm ^2. The substrate was then immersed in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23° C. for 40 seconds, and washed with pure water to obtain a solid-coated substrate, and water stains were observed with a magnifying glass. The evaluation criteria are as follows:
: No water stains.
A: Water stains were less than 10% of the solid area.
Δ: Water stains were 10% or more but less than 30% of the solid portion.
x: Water stains were present in 30% or more of the solid portion.

<Pattern shape evaluation>
The obtained photosensitive green composition was applied to a 100 mm x 100 mm, 0.7 mm glass substrate to a film thickness of 3.4 μm, and exposed to ultraviolet light at 40 mJ/cm ² through a mask having a 100 μm wide stripe pattern. Thereafter, the composition was developed by immersing the composition in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23 ° C. for 40 seconds, and washed with pure water to obtain a pattern. The obtained coating film was subjected to a heat treatment (post-baking) in an oven at 230 ° C. for 20 minutes, and the pattern shape was confirmed with a scanning electron microscope (Hitachi High-Tech Corporation "S-3000H"). The evaluation was performed by capturing an SEM image of the cross section of a 100 μm wide stripe pattern, and the taper angle between the substrate and the end of the pattern cross section was evaluated as follows using a protractor.
◎: Taper angle is 40 degrees or more and less than 50 degrees ○: Taper angle is 30 degrees or more and less than 40 degrees or 50 degrees or more and less than 60 degrees △: Taper angle is less than 30 degrees or 60 degrees or more and less than 70 degrees ×: Taper angle is 70 degrees or more

REFERENCE SIGNS LIST 10 Liquid crystal display device 11 Transparent substrate 12 TFT array 13 Transparent electrode layer 14 Alignment layer 15 Polarizing plate 21 Transparent substrate 22 Color filter 23 Transparent electrode layer 24 Alignment layer 25 Polarizing plate 30 Backlight unit 31 White LED light source LC Liquid crystal

Claims (8)

A photosensitive green composition comprising an organic pigment (A), a resin-type dispersant (B), a binder resin (C), a polymerizable compound (D), and a photopolymerization initiator (E),
the organic pigment (A) contains one or more pigments selected from an aluminum phthalocyanine pigment (A1), a halogenated zinc phthalocyanine pigment (A2), and a halogenated copper phthalocyanine pigment (A3), and a yellow pigment (A4);
The polymerizable compound (D) contains one or more compounds selected from the group consisting of trimethylolpropane ethylene oxide (EO)-modified triacrylate and trimethylolpropane propylene oxide (PO)-modified triacrylate, and
The photosensitive green composition, wherein the photopolymerization initiator (E) contains an oxime ester-based photopolymerization initiator (E1) represented by the following general formula (1):
General formula (1)

[In general formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ² represents a hydrocarbon group having 1 to 20 carbon atoms, n represents 0 or 1, one or more of R ³ to R ⁵ are substituted with a substituent represented by the following general formula (2), and the remaining represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group, and each alkyl group and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom and an alkoxyl group having 1 to 12 carbon atoms.]
General formula (2)

[In the general formula (2), * represents a bond to the benzene ring. X represents a direct bond, an oxygen atom, or a carbonyl group. ^R6 represents a direct bond or a hydrocarbon group having 1 to 12 carbon atoms. ^R7 represents a hydroxyl group or a carboxy group.] 2. The photosensitive green composition according to claim 1, wherein the binder resin (C) contains an alkali-soluble resin having a carboxy group and a polymerizable unsaturated group in a side chain selected from the following (I) and (II):
(I) An alkali-soluble resin obtained by reacting a product of an epoxy group in a polymer having an epoxy group and a carboxy group in a carboxy group-containing monomer with a polybasic acid or a polybasic acid anhydride. (II) An alkali-soluble resin which is a reaction product of a carboxy group in a polymer having a carboxy group and an epoxy group in an epoxy group-containing monomer. The photosensitive green composition according to claim 1 or 2, further comprising a polymerization inhibitor (F). The photosensitive green composition according to any one of claims 1 to 3, characterized in that the resin-type dispersant (B) contains a resin-type dispersant having an acidic functional group and a resin-type dispersant having a basic functional group. The photosensitive green composition according to any one of claims 1 to 4, further comprising two or more types of silicone-based leveling agents or fluorine-based leveling agents (G). The photosensitive green composition according to any one of claims 1 to 5, characterized in that the photopolymerization initiator (E) contains two or more types of oxime ester photopolymerization initiators. A color filter having a substrate and filter segments formed from the photosensitive green composition according to any one of claims 1 to 6. A liquid crystal display device comprising the color filter according to claim 7.

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