JP2021170089A - Photosensitive green composition, color filters and liquid crystal displays - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition for a color filter capable of forming pixels having a high residual film ratio of a colored pattern and good water stain and pattern shape, and a color filter formed by using the photosensitive composition.
A photosensitive green composition containing 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) is one or more pigments selected from aluminum phthalocyanine pigment (A1), zinc halide phthalocyanine pigment (A2) and copper halide phthalocyanine pigment (A3), and a yellow pigment (A4). ), And the photopolymerization initiator (E) contains an oxime ester-based photopolymerization initiator (E1).
[Selection diagram] Fig. 1

Description

The present invention uses a photosensitive green composition used for producing a color filter used for a color liquid crystal display device, a color solid-state imaging device, an organic EL display device, a quantum dot display device, electronic paper, and the like, and the photosensitive green composition using the same. It relates to a color filter having a formed filter segment.

The color filter is formed by arranging two or more kinds of fine band-shaped filter segments having different hues on a transparent substrate such as a glass substrate so as to be parallel (striped) or intersect with each other, or the hue. Two or more kinds of fine filter segments having different values are arranged so as to be arranged in order in each of the vertical direction and the horizontal direction. The filter segments have small dimensions of a few microns to a few hundreds of microns and are neatly arranged in a predetermined arrangement for each hue.
Currently, as a method for manufacturing a color filter, a method called a pigment dispersion method, which uses a pigment having excellent resistances such as light resistance and heat resistance as a coloring material, is the mainstream. In the pigment dispersion method, a color filter is manufactured by the following method. First, a photosensitive coloring composition (pigment resist) obtained by dispersing a pigment in a photosensitive transparent resin solution is applied to a transparent substrate such as glass. After removing the solvent from the coating by drying, the coating is exposed in a pattern corresponding to a filter segment of a certain color. Next, the unexposed portion of the coating film is removed by development, and then heat treatment or the like is performed as necessary. As a result, the filter segment pattern of the first color is obtained. Then, by performing the same operation as this, a filter segment pattern of another color is formed, and the color filter is completed.

Further, a transparent electrode for driving the liquid crystal is generally formed on the color filter by vapor deposition or sputtering, and an alignment film for orienting the liquid crystal in a certain direction is further formed on the transparent electrode. In order to obtain sufficient performance of these transparent electrodes and alignment films, the forming step is generally performed at a high temperature of 200 ° C. or higher. In the manufacturing process of such color filters
In the process of forming the transparent electrode and the heating process, it causes a decrease in the brightness of the coating film, and improvement thereof is required.

Further, 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 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 or photopolymerizable compound as a curing material. Further, in the method of increasing the film thickness, the irradiation light does not reach the bottom of the film, and problems such as a poor pattern shape are likely to occur. Furthermore, there is an increasing demand for thinning of color display devices, and there is a tendency to reduce the film thickness. Therefore, in a photosensitive coloring composition containing a coloring agent at a high concentration, a polyfunctional thiol or an antioxidant is used. The technique used is disclosed in Patent Document 1. However, the polyfunctional thiol promotes photocuring of the coating film surface, resulting in an overhang of the pattern shape after post-baking. Further, Patent Document 2 discloses a technique effective for pattern shape and residual film ratio by using a specific oxime ester compound as a photopolymerization initiator. However, there is a problem that water stains occur, and it is required to acquire a technique that satisfies all of the residual film ratio, water stains, and pattern shape.

JP-A-2018-173470 Japanese Unexamined Patent Publication No. 2011-209710

An object of the present invention is to achieve the following object.
That is, an object of the present invention is to provide a photosensitive composition for a color filter capable of forming pixels having a high residual film ratio of a colored pattern and a good water stain and pattern shape, and a color filter formed by using the photosensitive composition. To do.

As a result of diligent studies, the present inventors can provide a photosensitive green composition having a high residual film ratio, a color filter having an excellent pattern shape and suppressing water stains, and a color liquid crystal display device. I found.

That is, the present invention is a photosensitive green color containing an organic pigment (A), a resin-type dispersant (B), a binder resin (C), a polymerizable compound (D), and a photopolymerization initiator (E). It ’s a composition,
The organic pigment (A) contains one or more pigments selected from an aluminum phthalocyanine pigment (A1), a zinc halide phthalocyanine pigment (A2) and a copper halide phthalocyanine pigment (A3), and a yellow pigment (A4). ,And,
The present invention relates to a 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 the general formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and 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 rest represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group, and each of them shows. The alkyl group and the 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 with a benzene ring. X represents a direct bond or an oxygen atom or a carbonyl group. R ⁶ represents a direct bond or a hydrocarbon group having 1 to 12 carbon atoms. R ⁷ represents a hydroxyl group or a carboxy group. ]

Further, the present invention is characterized in that the binder resin (C) contains an alkali-soluble resin having a carboxy group and a polymerizable unsaturated group in the side chain selected from the following (I) and (II). Regarding sex green compositions.
(I) An alkali-soluble resin (II) obtained by reacting a product of an epoxy group in a polymer having an epoxy group with a carboxy group of a carboxy group-containing monomer with a polybasic acid or a polybasic acid anhydride. An alkali-soluble resin which is a reaction product of a carboxy group in a polymer having a carboxy group and an epoxy group of an epoxy group-containing monomer.

The present invention further relates to the above-mentioned photosensitive green composition, which further comprises a polymerization inhibitor (F).

The present invention also relates to the above-mentioned photosensitive green composition, wherein 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 further relates to the above-mentioned photosensitive green composition, which further comprises two or more kinds of silicone-based leveling agent or fluorine-based leveling agent (G).

Further, the present invention is further characterized in that the polymerizable compound (D) contains one or more kinds of ethylene oxide (EO) modified (meth) acrylate or propylene oxide (PO) modified (meth) acrylate. Regarding green composition.

The present invention further relates to the above-mentioned photosensitive green composition, wherein the photopolymerization initiator (E) contains two or more kinds of oxime ester-based photopolymerization initiators.

The present invention also relates to a color filter having a substrate and a filter segment formed of the photosensitive green composition.

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

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a photosensitive green composition having a high residual film ratio, a color filter having an excellent pattern shape and suppressing water stains, and a color liquid crystal display device.

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

Hereinafter, each component of the photosensitive green composition of the present invention will be described.
In addition, in this application, when it is described as "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide", it is particularly described. "Acryloyl and / or methacrylic acid", "acrylic and / or methacrylic acid", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide", respectively, unless It shall be represented.
Further, "CI" mentioned in the present specification means a color index (CI).

<Organic pigment (A)>
The organic pigment (A) is one or more pigments selected from the group consisting of an aluminum phthalocyanine pigment (A1), a zinc halide phthalocyanine pigment (A2) and a copper halide phthalocyanine pigment (A3), and a yellow pigment (A4) described later. ) And. 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 and the like.

(Aluminum phthalocyanine pigment (A1))
The aluminum phthalocyanine pigment (A1) is a phthalocyanine pigment having an aluminum atom in the central metal. As the aluminum phthalocyanine pigment (A1), for example, the pigment described in JP-A-2017-1111398 is preferable.

(Halogenated zinc phthalocyanine pigment (A2))
The halogenated zinc phthalocyanine pigment (A2) is a phthalocyanine pigment having a zinc atom in the central metal and a halogen atom in the substituent. The halogenated zinc phthalocyanine pigment (A2) preferably has, for example, an average of 10 to 14 halogen atoms in the molecule, and the halogen atoms have an average of 8 to 12 bromine atoms and an average of 2 to 5 chlorine atoms. Halogenated zinc phthalocyanines are preferred. In order to obtain high color reproduction, the number of halogen atoms in the molecule is preferably 11 to 13 on average, and the halogen atoms are more preferably 8 to 11 bromine atoms on average and 2 to 3 chlorine atoms on average. .. 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 in the central metal. For example, C.I. I. Pigment Green 7, 36, 37 and the like. Among these, from the viewpoint of transmittance, C.I. I. Pigment Green 36.

(Yellow pigment (A4))
For yellow pigments, for example, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, Examples thereof include pigments described in 192, 193, 194, 196, 198, 199, 213, 214, 231 and 233, and Japanese Patent Application Laid-Open No. 2012-226110. Preferably C.I. I. Pigment Yellow 138, 139, 150, 185, 231, 233, the pigment described in JP-A-2012-226110.

(Other organic pigments)
In the present invention, organic pigments other than aluminum phthalocyanine pigment (A1), zinc halide phthalocyanine pigment (A2), copper halide phthalocyanine pigment (A3), and yellow pigment (A4) are used as long as the effects of the present invention are not impaired. Can be used.
Examples of the red pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 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, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 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, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, Examples thereof include pigments described in 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, Japanese Patent Application Laid-Open No. 2014-134712, and pigments described in Japanese Patent No. 6368844. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Red 48: 1, 122, 177, 224, 242, 269, 254, 291, 295, 296, the pigment described in JP-A-2014-134712, and the pigment described in Japanese Patent No. 6368844. More preferably, C.I. I. Pigment Red 177, 254, 291, 295, 296, the pigment described in JP-A-2014-134712, and the pigment described in Japanese Patent No. 6368844.

The blue pigment is, for example, C.I. I. Pigment Bull-1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33 , 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like.

Purple pigments include, for example, C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, Examples thereof include 37, 39, 42, 44, 47, 49 and 50.

The green pigment is, for example, C.I. I. Pigment greens 1, 2, 4, 8, 10, 13, 14, 15, 17, 18, 19, 26, 37, 45, 48, 50, 51, 54, 55 and the like.

(Inorganic pigment)
In the present invention, an inorganic pigment may be used as long as the effect of the present invention is not impaired.
Inorganic pigments include, for example, titanium oxide, barium sulfate, zinc flower, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt green, and amber. , Synthetic iron black and the like.

(dye)
In the present invention, dyes may be used as long as the effects of the present invention are not impaired.
As the dye, any of acidic dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, medium dyes, construction dyes, sulfide dyes and the like can be used. Further, these derivatives or a lake pigment obtained by rake-forming the dye may be used.

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

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

Further, when the dye skeleton has a polymerizable unsaturated group, the dye can be a dye having excellent resistance, which is preferable.

The chemical structure of the dye includes, for example, azo dye, disuazo dye, azomethin dye (indoaniline dye, indophenol dye, etc.), dipyrromethene dye, quinone dye (benzoquinone dye, naphthoquinone dye, anthraquinone). Carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acrydin dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes Dyes, polymethine dyes (oxonol dyes, merocyanine dyes, allylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone Examples thereof include dye structures derived from dyes selected from based dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and their metal complex dyes.

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

<Pigment miniaturization>
When the colorant used in the photosensitive green composition of the present invention is a pigment, it is preferable to use it in a finely divided form. The miniaturization method is not particularly limited, and for example, wet grinding, dry grinding, and dissolution precipitation method can be used, and as illustrated in the present invention, salt milling treatment by the kneader method, which is a kind of wet grinding, can be used. And so on, it can be miniaturized. The average primary particle size determined by the TEM (transmission electron microscope) of the pigment 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 this reason, the more preferable average primary particle size is in the range of 10 to 70 nm.

The salt milling treatment is a batch type or continuous type of a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent, such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, a sand mill, and a planetary mixer. This is a treatment in which a water-soluble inorganic salt and a water-soluble organic solvent are removed by washing with water after mechanically kneading while heating using a kneader. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

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

The water-soluble organic solvent has a function of wetting the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint 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 and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by mass, and most preferably 50 to 500 parts by mass with respect to 100 parts by mass of the pigment.

When the pigment is salt-milled, a resin may be added if necessary. The type of resin used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin used is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by mass with respect to 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 has a colorant-affinitive moiety having a property of adsorbing to the additive colorant and a moiety compatible with the colorant carrier, and is adsorbed on the additive colorant and dispersed in the colorant carrier. Anything that works to stabilize Salts, ammonium polycarboxylic acid salts, alkylamine polycarboxylic acid salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters and their modifications, poly (lower alkyleneimine) and free carboxyl groups Oily dispersants such as amides and salts thereof formed by reaction with polyesters having (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-malein. Water-soluble resins such as acid copolymers, polyvinyl alcohols, and polyvinylpyrrolidones, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide addition compounds, phosphoric acid esters, etc. are used. Can be used alone or in combination of two or more.

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 having an acidic functional group)
Preferred examples of the resin-type dispersant having an acidic functional group include resin-type dispersants having an aromatic carboxylic acid structure, which are WO2008 / 007776, JP-A-2008-029901 and JP-A-2009-. Manufactured by known methods such as JP-A-155406, JP-A-2010-185934, JP-A-2011-157416, JP-A-2009-251481, JP-A-2007-23195, JP-A-1996-143651, etc. can do.

(Resin-type dispersant having a basic functional group)
Preferred examples of the resin-type dispersant having a basic functional group include a nitrogen atom-containing graft copolymer and a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocycle and the like in the side chain. Examples thereof include a nitrogen atom-containing acrylic block copolymer and a urethane-based polymer dispersant.

As an example including a resin-type dispersant having an acidic functional group and a resin-type dispersant having a basic functional group, as disclosed in Japanese Patent Application Laid-Open No. 2009-185277, a resin-type dispersion having an aromatic carboxyl group Examples thereof include the combined use of the agent and a vinyl-based resin having a tertiary amino group (having a function of a resin-type dispersant).

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167 manufactured by Big Chemie Japan. 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti -Terra-U, 203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS or Bykuman, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, manufactured by Japan Lubrizol. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 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., manufactured by Ajinomoto Fine Techno Co., Ltd. Examples thereof include azisper PA111, PB711, PB821, PB822, PB824 and the like.

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

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

As the dye derivative used in the present invention, a known dye derivative having an acidic group, a basic group, a neutral group or the like in the organic dye residue can be used. For example, a compound having an acidic substituent such as a sulfo group, a carboxy group or a phosphoric acid group, an amine salt thereof, a compound having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal, a phenyl group or a phthalimide. Examples thereof include compounds having a neutral substituent such as an alkyl group.
Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, and benzo. Indole pigments such as isoindole, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, slene pigments, metal complex pigments, azo pigments such as azo, disazo, polyazo, etc. Be done.

Specifically, as the diketopyrrolopyrrole dye derivative, JP-A-2001-220520, WO2009 / 081930 pamphlet, WO2011 / 052617 pamphlet, WO2012 / 102399 pamphlet, JP-A-2017-156397, phthalocyanine. Examples of the dye derivative are JP-A-2007-226161, WO2016 / 163351, JP-A-2017-165820, and Patent No. 5735266. Japanese Patent Application Laid-Open No. 09-272812, Japanese Patent Application Laid-Open No. 10-245501, Japanese Patent Application Laid-Open No. 10-265697, Japanese Patent Application Laid-Open No. 2007-079094, WO2009 / 025325 pamphlet, as a quinacridone-based dye derivative, JP-A-48- 54128, 03-9961 and 2000-273383, the dioxazine dye derivative is 2011-162662, and the thiazineindigo dye derivative is 2007-314785. Examples of JP, Triazine-based dye derivatives include JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, and JP-A-2004-217842. JP-A-2007-314681, JP-A-2009-57478 as a benzoisoindole-based dye derivative, JP-A-2003-167112, JP-A-2006-291194, and JP-A as quinophthalone-based dye derivatives. 2008-31281, 2012-226110, naphthol dye derivatives are 2012-208329, 2014-5439, and azo dye derivatives are 2001-172520. Japanese Unexamined Patent Publication No. 2012-172092, JP-A-2004-307854 as acidic substituents, JP-A-2002-201377, JP-A-2003-171594, JP-A-2005 as basic substituents. Examples thereof include known dye derivatives described in Japanese Patent Application Laid-Open No. -181383, Japanese Patent Application Laid-Open No. 2005-213404, and the like. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound, but the above-mentioned organic dye residue includes an acidic group, a basic group, and the like. A compound having a substituent such as a sex group is synonymous with a dye derivative.

<Binder resin (C)>
The photosensitive green composition of the present invention contains a binder resin (C). As the binder resin (C), a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm is used. Binder resins include thermoplastic resins, thermosetting resins, active energy ray-curable resins having ethylenically unsaturated double bonds, etc. when classified according to their main curing methods, and active energy ray-curable resins are thermoplastic. It may be a resin or one having a thermosetting function, and is preferably an alkali-soluble resin from the viewpoint of developability. In addition, a thermoplastic resin that is not inactive energy ray-curable may be contained, and this is also preferably alkali-soluble. These can 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 in the side chain selected from the following (I) and (II).
(I) An alkali-soluble resin (II) obtained by reacting a product of an epoxy group in a polymer having an epoxy group with a carboxy group of a carboxy group-containing monomer with a polybasic acid or a polybasic acid anhydride. An alkali-soluble resin which is a reaction product of a carboxy group in a polymer having a carboxy group and an epoxy group of 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, 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 it in an amount of 20 parts by mass or more because of its good film forming property and various resistances, and it is preferable to use it in an amount of 400 parts by mass or less because it has a high colorant concentration and can exhibit good color characteristics. ..

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

(Alkali-soluble resin)
The photosensitive green composition of the present invention preferably contains an alkali-soluble resin from the viewpoint of developability, heat resistance and transparency. It is for imparting development solubility in the alkaline development step at the time of producing a color filter, and has an acid group and / or a hydroxyl group. Further, in order to further improve the photosensitivity, it is more preferable to use a resin having an ethylenically unsaturated double bond.

(Alkali-soluble resin with 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 having an ethylenically unsaturated double bond introduced by the methods (i) and (ii) shown below, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. As a result, the crosslink density is increased and the chemical resistance is improved.

[Method (i)]
As the method (i), for example, a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with one or more other monomers (weight having an epoxy group). A carboxyl group of an unsaturated monobasic acid (carboxy group-containing monomer) having an ethylenically unsaturated double bond is added to the side chain epoxy group of (coalescence), and the generated hydroxyl group is further subjected to polybasic acid or There is a method of reacting a polybasic acid anhydride to introduce an ethylenically unsaturated double bond and a carboxyl group.

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

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

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, and these may be used alone or in combination of two or more. It doesn't matter. If necessary, such as by increasing the number of carboxyl groups, a tricarboxylic acid anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride may be used to obtain the remaining anhydride. It is also possible to hydrolyze the group. Further, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bond can be further increased.

As a method similar to the method (i), for example, a copolymer (carboxy group) obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with one or more other monomers. An ethylenically unsaturated monomer (epoxide group-containing monomer) having an epoxy group is added to a part of the side chain carboxyl groups of the polymer (polymer having) to form an ethylenically unsaturated double bond and a carboxyl group. There is a way to introduce it.

[Method (ii)]
As the method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and by copolymerizing with an unsaturated monobasic acid monomer having another carboxyl group or another monomer. There is a method of reacting the side chain hydroxyl group of the obtained copolymer with the 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
-Or 4-hydroxyalkyl methacrylates such as 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, or cyclohexanedimethanol mono (meth) acrylate can be mentioned, and these may be used alone or in combination of two or more. May be used in combination. Further, a polyether mono (meth) acrylate obtained by superpolymerizing the above hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, and / or butylene oxide, poly γ-valerolactone, poly ε-caprolactone, and / or Polyester mono (meth) acrylate to which poly 12-hydroxystearic acid or the like is added can also be used. 2-Hydroxyethyl methacrylate or glycerol mono (meth) acrylate is preferable from the viewpoint of suppressing foreign matter in the coating film, and from the viewpoint of sensitivity, it is preferable to use one having 2 or more and 6 or less hydroxyl groups. Therefore, glycerol mono (meth) acrylate is more preferable.

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

Examples of the monomers constituting the alkali-soluble resin include the following. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-Ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) (Meta) acrylates such as acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypolyethylene glycol (meth) acrylate,
Alternatively, (meth) such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholin. Acrylamides styrene or styrenes such as α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, vinyl acetate, or fatty acid vinyls such as vinyl propionate. And so on.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimide propionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide. Kumarin, 4,4'-bismaleimidediphenylmethane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3-phenylenedimaleimide, N, N'-1,4- Phenylened maleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-Bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide Hexanoart, N- [4- (2-benzoimidazolyl) phenyl] maleimide, N-substituted maleimides such as 9-maleimideacrinedin, EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl Ethyloxide (EO) -modified (meth) acrylate of 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, PO-modified (meth) acrylate of nonylphenol, etc. Can be mentioned.

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

Further, a hydroxyl group-containing ethylenically unsaturated monomer can also be used. Examples of the hydroxyl group-containing ethylenically unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, or cyclohexane. Examples thereof include hydroxyalkyl (meth) acrylates such as dimethanol mono (meth) acrylate. Further, a polyether mono (meth) acrylate obtained by superpolymerizing the above hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, and / or butylene oxide, (poly) γ-valerolactone, and (poly) ε-caprolactone. , And / or (poly) ester mono (meth) acrylate to which (poly) 12-hydroxystearic acid or the like is added.

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

(Alkali-soluble resin without 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 curing of the coating film. Ethylene is synthesized by synthesizing at least one carboxyl group-containing ethylenically unsaturated monomer and one or more of the other ethylenically unsaturated monomers, and not imparting an ethylenically unsaturated bond to the side chain. An alkali-soluble resin having no sex-unsaturated double bond can be obtained.

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

The weight average molecular weight (Mw) of the alkali-soluble resin in the present invention is 2,000 or more and 40,000 or less, preferably 3,000 or more and 3,000 or less, preferably 4,000, in order to impart alkali development solubility. More than 20,000 or less is more preferable. Further, 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 is lowered and the exposure pattern is less likely to remain. If it exceeds 40,000, the alkali development solubility is lowered, a residue is generated, and the linearity of the pattern is deteriorated.
The acid value of the alkali-soluble resin in the present invention is 50 or more and 200 or less (KOHmg / g) in order to impart alkali development solubility, preferably in the range of 70 or more and 180 or less, and more preferably 90 or more and 170 or less. The range. If the acid value is less than 50, the alkali development solubility is lowered, a residue is generated, and the linearity of the pattern is deteriorated. If it exceeds 200, the adhesion to the substrate is lowered and the exposure pattern is less likely to remain.

(Thermosetting compound (CE))
In the present invention, the binder resin may contain a thermosetting compound (CE). When a color filter is produced using the photosensitive green composition of the present invention, the inclusion of a thermosetting compound causes a reaction during firing of the filter segment to increase the crosslink density of the coating film, thereby improving the heat resistance of the filter segment. However, the effect of suppressing pigment aggregation during firing of the filter segment and improving the contrast ratio can be obtained.

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 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. It is not something that is done. Epoxy compounds and oxetane compounds are preferably used in the photosensitive green composition of the present invention.

(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.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxy). Weight of benzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaaldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Condensates, phenols and polymers of various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadien, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenol Polycondensate of class and ketones (acetone, methylethyl ketone, methylisobutylketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α, α, α', α'-benzenedimethanol , Biphenyldimethanol, α, α, α', α'-biphenyldimethanol, etc.) and phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.) Polycondensate, bisphenol and various aldehyde polycondensates, glycidyl ether-based epoxy resin obtained by glycidylizing alcohols, alicyclic epoxy resin, heterocyclic epoxy resin, aliphatic epoxy resin, glycidylamine-based epoxy resin , Glysidyl ester-based epoxy resin and the like, but are not limited to these as long as they are commonly used epoxy compounds. These may be used alone or two or more kinds may be used.

Examples of commercially available products include Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004, Epicoat 1256 (or more). Is a product name; manufactured by Japan Epoxy Resin Co., Ltd., TECHMORE VG3101L (trade name: manufactured by Mitsui Chemicals Co., Ltd.), EPPN-501H, 502H (trade name: manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60 (trade name). ; Japan Epoxy Resin Co., Ltd.), JER 157S65, 157S70 (trade name: Japan Epoxy Resin Co., Ltd.), EPPN-201 (trade name: Nippon Kayaku Co., Ltd.), JER152, JER154 (the above are products) Name: Japan Epoxy Resin Co., Ltd., EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (the above are product names; manufactured by Nippon Kayaku Co., Ltd.), Serokiside 2021, EHPE-3150 (the above products) Name: Daicel Chemical Industry Co., Ltd., Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721, (and above) Is a trade name; Nagase ChemteX Corporation), TEPIC-L, TEPIC-H, TEPIC-S (manufactured by Nissan Chemical Industry Co., Ltd.) and the like.
However, it is not limited to these.

The blending amount of the epoxy compound is preferably 0.5 to 300 parts by mass, and more preferably 1.0 to 50 parts by mass with respect to 100 parts by mass of the colorant. If it is less than 0.5 parts by mass, the contrast ratio and heat resistance improving effect are small, and if it is more than 300 parts by mass, a problem may occur when forming a filter segment 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, a known compound having an oxetane group can be used without 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 monofunctional oxetane groups include (3-ethyloxetane-3-yl) methyl acrylate, (3-ethyloxetane-3-yl) methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, and 3-ethyl-. 3- (2-Ethylhexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-methacryloxymethyl) oxetane, 3-ethyl-3-{[3-( Triethoxysilyl) propoxy] methyl} oxetane and the like.
Specific examples include OXE-10 and OXE-30 manufactured by Osaka Organic Chemical Industry Co., Ltd., OXT-101 and OXT-212 manufactured by Toagosei Co., Ltd.

Examples of bifunctional oxetane groups include 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl) and 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl]. Benzene, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di [1-ethyl (3-oxetanyl)] methyl ether, di [1-ethyl (3-oxetanyl)] methyl Ether-3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (2-phenoxymethyl) oxetane, 3,7-bis (3-bis) Oxetanyl) -5-oxa-nonane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene Glycose bis (3-ethyl-3-oxetanyl methyl) ether, dicyclopentenyl bis (3-ethyl-3-oxetanyl methyl) ether, triethylene glycol bis (3-ethyl-3-oxetanyl methyl) 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-oxetanylmethoxy) 3-Ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) -modified 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, EO-modified bisphenol F (3-ethyl-3) -Oxetanyl methyl) ether and the like can be mentioned.
Specific examples include OXBP and OXTP manufactured by Ube Industries, Ltd., OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd.

If the oxetane group is bifunctional or higher,
Pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol penta Kiss (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified di Pentaerythritol Pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropantetrax (3-ethyl-3-oxetanylmethyl) ether, resin containing an oxetane group (for example, oxetane-modified phenol according to Patent No. 3783462). Examples thereof include a polymer obtained by radically polymerizing a (meth) acrylic monomer such as (Novolak resin or the like) or the above-mentioned OXE-30. Such a polymer can be obtained by using a known polymerization method.

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 having good water stains and high chemical resistance can be obtained.

(Melamine compound)
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. Preferred in the present invention are methylol-type and ether-type melamine compounds having an average number of methylol groups and / or ether groups of 5.0 or more per melamine ring. If the average number of methylol groups and / or ether groups per melamine ring is less than 5.0, the number of reaction sites is small and the crosslinked structure at the time of curing is not sufficiently dense, so that the contrast ratio reduction due to the heat treatment step is suppressed and NMP resistance is achieved. The effect of improvement may be small.

Commercially available products include, for example, Nikarac 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, MX-410 (Manufactured by Sanwa Chemical Co., Ltd.), Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, 370 (manufactured by Nippon Cytec Industries, Ltd.) and the like, but are not limited thereto.

Among them, the number of methylol groups and / or ether groups per melamine ring is 5.0 or more on average. -22, MS-21, MS-11, MW-24X, MX-45 (manufactured by Sanwa Chemical Co., Ltd.) Cymel 232, 235, 236, 238, 300, 301, 303, 350 (manufactured by Nippon Cytec Industries), etc. , It is preferable in that a dense crosslinked structure can be obtained.

(Hardener)
Further, the photosensitive green composition of the present invention may contain a curing agent (curing accelerator) or the like, if necessary, in order to assist the curing of the thermosetting compound. As the curing agent, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but the curing agent is not particularly limited thereto and can react with a thermosetting compound. Any curing agent may be used as long as it is used. Examples of the curing agent include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N). , N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidin compounds and salts thereof (eg, imidazole, etc.) 2-Methyl imidazole, 2-ethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 4-phenyl imidazole, 1-cyanoethyl-2-phenyl imidazole, 1- (2-cyanoethyl) -2-ethyl- 4-Methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), S-triazine derivatives (eg, 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 done. 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 with respect to 100 parts by mass of the thermosetting compound.

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

Examples of the polymerizable compound (D) include monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin. Among them, a polymerizable compound having an acid group, a polymerizable compound having a urethane bond, and ethylene oxide ( EO) -modified or propylene oxide (PO) -modified polymerizable compounds are preferable, and ethylene oxide (EO) -modified or propylene oxide (PO) -modified polymerizable compounds are particularly preferable.

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

Examples of the polymerizable compound having an acid group include an esterified product of a free hydroxyl group-containing poly (meth) acrylate of a polyhydric alcohol and (meth) acrylic acid and a dicarboxylic acid; a polyvalent carboxylic acid and a monohydroxyalkyl. Examples thereof include esterified products with (meth) acrylates. Specific examples include monohydroxyoligoacrylates such as trimethylolpropane diacrylate, trimethylolpropanedimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, or monohydroxyoligomethacrylates. Free carboxyl group-containing monoesteride with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; propane-1,2,3-tricarboxylic acid (tricarboxylic acid), butane-1,2,4 -Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, and 2-hydroxyethyl acrylate, 2- Examples thereof include monohydroxymonoacrylates such as hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, and oligoesterides containing a free carboxyl group with monohydroxymonomethacrylates, but the effects of the present invention are limited thereto. It is not something that is done.

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

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

Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropandi (meth) acrylate, pentaerythritol tri (meth) acrylate, and ditrimethylol propanetri (meth). Meta) 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 Examples thereof include methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and carboxy (meth) acrylate, and a hydroxyl group-containing polyol polyacrylate.

Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

These commercially available products include AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167, manufactured by Kyoeisha Chemical Co., Ltd. UA-160TM, UV-4108F, UV-4117F manufactured by Osaka Organic Chemical Industry Co., Ltd. and the like can be preferably used.

The above-mentioned polymerizable compounds may be used alone or in admixture of two or more at any ratio as required.

The photosensitive green composition of the present invention preferably contains at least one type of ethylene oxide (EO) modified (meth) acrylate or propylene oxide (PO) modified (meth) acrylate as the polymerizable compound (D). Having an (EO) -modified unit or a (PO) -modified unit, such as ethylene oxide (EO) -modified (meth) acrylate or propylene oxide (PO) -modified (meth) acrylate, initiates the oxime ester-based photopolymerization used in the present application. By forming a hydrogen bond with the agent (E1), the radical generation site and the reaction site can be brought close to each other, which is considered to have an effect of promoting more efficient photocuring. As a result, it is possible to suppress water stains and achieve a high residual film ratio.

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

Here, the (meth) acrylate compound having a skeleton derived from ditrimethylolpropane can be obtained, for example, by a method of esterifying ditrimethylolpropane and (meth) acrylic acid, or a method of transesterification using a neutral catalyst. Can be done. The compound also includes a compound modified with an alkyleneoxy group. The above compound preferably has 2 or more ester bonds in one molecule, and a compound having 2 to 4 ester bonds may be mixed.

Further, the (meth) acrylate compound having a skeleton derived from diglycerin can be obtained, for example, by a method of esterifying diglycerin and (meth) acrylic acid, or a method of transesterification using a neutral catalyst. The compound also includes a compound modified with an alkyleneoxy group. The above compound preferably has 2 or more ester bonds in one molecule, and a compound having 2 to 4 ester bonds may be mixed.

The (meth) acrylate compound having a skeleton derived from ditrimethylolpropane and the (meth) acrylate compound having a skeleton derived from diglycerin are modified with an alkylene oxide from the viewpoint of further improving the ability to suppress electrode corrosion and the ease of development. Ditrimethylol propanedi (meth) acrylate compound, alkylene oxide modified ditrimethylol propanetri (meth) acrylate compound, alkylene oxide modified ditrimethylol propanetetra (meth) acrylate compound, alkylene oxide modified diglycerin di (meth) acrylate compound, alkylene oxide modified di It is preferable to contain at least one compound selected from a glycerin tri (meth) acrylate compound and an alkylene oxide-modified diglycerin tetra (meth) acrylate compound, and an alkylene oxide-modified ditrimethylol propanetetra (meth) acrylate compound and an alkylene oxide. It is more preferable to contain at least one compound selected from the modified diglycerin tetra (meth) acrylate compound.

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

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

(Other polymerizable compounds)
Examples of other polymerizable compounds include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and β-carboxyethyl. (Meta) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethyl propantri (meth) acrylate , Phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol Diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, Tricyclodecanyl (meth) acrylate, (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, Examples thereof include pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile.

The blending amount of the polymerizable compound is preferably 1 to 50 parts by mass based on the total solid content of the photosensitive green composition (100 parts by mass), and 2 to 40 parts by mass from the viewpoint of photocurability and developability. It is more preferable that it is a part.

<Photopolymerization initiator (E)>
The photosensitive green composition of the present invention contains an oxime ester-based photopolymerization initiator (E1) having a structure represented by the following general formula (1) as the photopolymerization initiator (E). By including the oxime ester-based photopolymerization initiator (E1), in the process of producing a color filter segment using the composition, the generation of water stains can be suppressed, and a high residual film ratio and an excellent pattern shape can be obtained. Can be done.

(Oxime ester-based photopolymerization initiator (E1))
General formula (1)

[In the general formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and 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 rest represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group, and each of them shows. The alkyl group and the 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 R ¹ and R ² include a hydrogen atom, a methyl group, an ethyl group, a phenyl group, a benzyl group and the like. The hydrocarbon group may be chain-like or cyclic, and may or may not have a branch.
One or more of R ^{3 to} R ⁵ are substituents having a hydroxyl group at the terminal represented by the following general formula (2).

General formula (2)

* Represents a bond with a benzene ring. X represents a direct bond or an oxygen atom or a carbonyl group. R ⁶ is a hydrocarbon group having 1 to 12 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a phenyl group, and a benzyl group. The hydrocarbon group may be chain-like or cyclic, and may or may not have a branch. R ⁷ represents a hydroxyl group or a carboxy group.
Of R ^{3 to} R ⁵ , those which are not substituents represented by the 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 is a halogen atom. , It may be substituted with a substituent selected from the group consisting of an alkoxyl group having 1 to 12 carbon atoms.

Among the compounds represented by the general formula (1), preferable examples include compounds of the following chemical formulas (3) to (6). These compounds can be produced by a known method such as JP-A-2011-132215.

Chemical formula (3)

Chemical formula (4)

Chemical formula (5)

Chemical formula (6)

These compounds having a hydroxyl group at the terminal form a hydrogen bond with a binder resin or a photopolymerizable monomer, so that the radical generation site and the reaction site can be close to each other, and more efficient photocuring is promoted. It can be considered to be effective. As a result, it is possible to suppress water stains and achieve a high residual film ratio. In addition, it is considered that an appropriate pattern shape was obtained because the compatibility with the binder resin and the photopolymerizable monomer was also improved to provide an appropriate heat flow property in post-baking.

<Other photopolymerization initiator (E2)>
Other photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-Hydroxycyclohexylphenylketone, 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, etc. Acetphenone compounds; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicization Benzophenone compounds such as benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, or 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methyl Thioxanthone compounds such as thioxanthone, 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- (naphtho-1-yl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6 Triazine compounds such as −triazine, or 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio) phenyl- , 2- (O-benzoyloxime)], or etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), etc. Oxym ester compounds; phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; 9,10-phenanthrene quinone, camphorquinone , Ethylanthraquinone and other quinone compounds; borate compounds; carbazole compounds; imidazole compounds; or titanosen compounds.
These photopolymerization initiators can be used alone or in admixture of two or more at any ratio as required.

As commercially available products, the acetophenone compounds are all manufactured by IGM Resins, Inc., "Omnirad 907" (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one), "Omnirad". 369E "(2- (dimethylamino) -1- [4- (4-morpholino) phenyl] -2- (phenylmethyl) -1-butanone)," Omnirad 379EG "(2- (dimethylamino) -2-[ (4-Methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone), as phosphine compounds, all manufactured by IGM Resins, "Omnirad 819" (bis (2,4) 6-trimethylbenzoyl) -phenylphosphine oxide), "Omnirad TPO" (diphenyl-2,4,6-trimethylbenzoylphosphine oxide), and the like.

The content of the photopolymerization initiator (E) is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass by mass of the photosensitive green composition excluding the solvent, and is photocurable and developable. From the viewpoint, it is more preferably 1 to 10 parts by mass. If it is less than 0.5 parts by mass, the adhesion of the formed pattern to the substrate may be deteriorated, and if it exceeds 20 parts by mass, a problem may occur in developability or 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, preferably 80 to 100 parts by mass, based on 100 parts by mass of the photopolymerization initiator (E). It is more preferably by mass.

The photopolymerization initiator (E) preferably contains two or more types of oxime ester-based photopolymerization initiators. In this case, even if two or more kinds of the oxime ester-based photopolymerization initiator (E1) represented by the general formula (1) are contained, the oxime ester-based photopolymerization initiator (E1) represented by the general formula (1) is generally used. It may contain an oxime ester-based photopolymerization initiator other than the 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 suppressing effect of the present invention.
For example, catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propyl Catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-t-butyl catechol, 3-t-butyl catechol, 4-t-butyl catechol, 3 , 5-Di-t-butyl catechol and other alkyl catechol compounds, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n- Alkyl resorcinol compounds such as butyl resorcinol, 4-n-butyl resorcinol, 2-t-butyl resorcinol, 4-t-butyl resorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, 2,5-di- Alkyl hydroquinone compounds such as t-butyl hydroquinone, phosphine compounds such as tributyl phosphine, trioctyl phosphine, tricyclohexyl phosphine, triphenyl phosphine, tribenzyl phosphine, phosphine oxide compounds such as trioctyl phosphine oxide, triphenyl phosphine oxide, tri Phosphite compounds such as phenylphosphite and trisnonylphenylphosphite, pyrogallol, fluoroglucin, and preferred examples include hindered phenolic polymerization bans, 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 [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-methylpropanol-3-iriden) Tris (6-tert) -Butyl-m-cresol, 6,6'-di-tert-butyl-4,4'-butylidendi-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] [ethylenebis (oxyethylene)] (1 , 6-Hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], and 4- [[4,6-bis (octylthio) -1,3,5-triazine- 2-Il] amino] -2,6-di-tert-butylphenol and the like can be mentioned.

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

<Leveling agent (G)>
It is preferable to add a leveling agent to the photosensitive green composition of the present invention for the purpose of improving the coatability of the composition on the transparent substrate and the drying property of the colored film. As the leveling agent, various surfactants such as a fluorine-based surfactant, a silicone-based surfactant, a nonionic surfactant, a cationic surfactant, and an anionic surfactant 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% by mass with respect to the total solid content of the composition of the present invention. More preferably, it is 0.005 to 2.0% by mass. Within this range, the balance between the coatability of the photosensitive green composition, the pattern adhesion, and the transmittance is good.

The photosensitive green composition of the present invention may contain only one type of surfactant, or may contain two or more types of surfactants. When two or more types are included, the total amount is preferably in the above range. 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 agent or fluorine-based leveling agent (G), and among them, when two types of fluorine-based leveling agent are contained, water stains are reduced. preferable.

Examples of the fluorine-based leveling agent include a surfactant having a fluorocarbon chain or a leveling agent.

Commercially available products include Surflon S-242, S-243, S-420, S-611, S-651, S-386 manufactured by AGC Seimi Chemical Co., Ltd., Megafuck F-253 and F-477 manufactured by DIC Co., Ltd. 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, DS-21, FC-4430, FC-4432, Sumitomo 3M Co., Ltd., EF-PP31N09, EF-PP33G1, EF-PP32C1, Neos Co., Ltd. Can be mentioned.

Examples of the silicone-based surfactant include a linear polymer composed of a siloxane bond and a modified siloxane polymer in which an organic group is introduced into a side chain or a terminal.

More specifically, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345/346, 347, 348, 349, 370, 377, 378 manufactured by Big Chemie. , 3455, UV3510, 3570, FZ-7002, 2110, 2122, 2123, 2191, 5609, manufactured by Toray Dow Corning Co., Ltd., X-22-4952, X-22-2272, X-22, manufactured by Shin-Etsu Chemical Co., Ltd. 6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341 and the like.

Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristel ether, and polyoxyethylene octyldodecyl. Ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrene phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl Ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate Rate, Polyoxyethylene sorbitan monopalmitate, Polyoxyethylene sorbitan monostearate, Polyoxyethylene sorbitan tristearate, Polyoxyethylene sorbitan monooleate, Polyoxyethylene sorbitan triisostearate, Polyoxyethylene sorbit tetraoleate , Glykolmonone stearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanol Examples thereof include amide and alkyl imidazoline.

More specifically, Emargen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430 manufactured by Kao Corporation. , 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90 , B-66, PP-290, Polymer 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, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH- 60 (K), Amit 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA CORPORATION ADEKA PLRONIC® L-23, 31, 44, 61 , 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, manufactured by Kyoeisha Chemical Co., Ltd. (meth) acrylic acid-based (co) polymer Polyflow No. 75, No. 90, No. 95 and the like can be mentioned.

Examples of the cationic surfactant include alkylquaternary ammonium salts such as alkylamine salts, lauryltrimethylammonium chlorides, stearyltrimethylammonium chlorides, and cetyltrimethylammonium chlorides, and ethylene oxide adducts thereof.

More specifically, Kao Corporation's Acetamine 24, Coatamine 24P, 60W, 86P Conch and the like can be mentioned.

Examples of anionic surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, and monoethanolamine lauryl sulfate. , Triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate and the like.

More specific examples thereof include Footgent 100 and 150 manufactured by Neos Co., Ltd., Adeka Hope YES-25 manufactured by ADEKA Corporation, Adeka Call TS-230E, PS-440E, EC-8600 and the like.

Examples of the amphoteric tenside include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine and alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide.

More specifically, Kao Corporation's Anchor 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, 20N and the like can be mentioned.

<Thiol chain transfer agent (H)>
The photosensitive green composition can contain a chain transfer agent. The chain transfer agent is preferably a thiol-based chain transfer agent. When the thiol chain transfer agent is used in combination with a photopolymerization initiator, chiyl radicals that are less susceptible to polymerization inhibition by oxygen are generated during radical polymerization after light irradiation, and the sensitivity of the photosensitive green composition is improved.

The thiol-based chain transfer agent is preferably a polyfunctional thiol having two or more thiol groups (SH groups). The thiol chain transfer agent more preferably has 4 or more SH groups. As the number of functional groups increases, photocuring from the surface of the film to the deepest part becomes easier.

Polyfunctional thiols include, for example, hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate. , Trimethylol Propanetristhioglycolate, Trimethylol Propanetristhiopropionate, Trimethylol Propantris (3-mercaptobutyrate), Pentaerythritol Tetrakissthioglycolate, Pentaerythritol Tetraxthiopropionate, Tris Trimercaptopropionate (2-Hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine And the like, preferably ethylene glycol bisthiopropionate, trimethylolpropanthrithiopropionate, pentaerythritol tetrakisthiopropionate and the like.

The thiol chain transfer agent can be used alone or in combination of two or more.

The content of the thiol-based chain transfer agent is preferably 1 to 10% by mass, 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 contained, the light sensitivity and the tapered shape are improved, and wrinkles are less likely to occur on the film 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 is a benzotriazole-based organic compound, a triazine-based organic compound, a benzophenone-based organic compound, a salicylate ester-based organic compound, a cyanoacrylate-based organic compound, and a salicylate-based compound. Examples include organic compounds.

The content of the ultraviolet absorber is preferably 5 to 70% by mass based on 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. If the content of the ultraviolet absorber is less than the above, the effect of the ultraviolet absorber is small and the resolution cannot be ensured, and if it is more than the above, the sensitivity becomes low and the pixel peeling and the hole diameter become larger than the design value. Problems such as spilling may occur.

At this time, when the photosensitive green composition contains a sensitizer, the content of the photopolymerization initiator includes the content of the sensitizer.

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, the adhesion is weakened and pixel peeling occurs, and if it is more than the above, the sensitivity may be too high and the resolution may be deteriorated.

At this time, when the photosensitive green composition contains a sensitizer, the content of the photopolymerization initiator includes the content of the sensitizer.

Examples of benzotriazole-based 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-benzotriazole-2-yl)-(1,1) -Dimethylethyl) -4-hydroxy, C7-9 side chain and mixture of linear alkyl esters, 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) Phenol, 2- (2H-benzotriazole-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, methyl 3- (3) -(2H-benzotriazole-2-yl) -5-t-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction product, 2- (2H-benzotriazole-2-yl) -4- (1) , 1,3,3-tetramethylbutyl) phenol, 2,2'-methylenebis [6- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] , 2- (2H-benzotriazole-2-yl) -p-cresol, 2- (5-chloro-2H-benzotriazole-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- [3- t-Butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole-2-yl) phenyl] propionate, 2-ethylhexyl-3- [3-t-butyl-4-hydroxy-5- (5-) Chloro-2H-benzotriazole-2-yl) phenyl] propionate can be mentioned. In addition, oligomer-type and polymer-type compounds having a benzotriazole structure can also be used.

More specifically, TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130 manufactured by BASF Corporation, ADEKA STAB LA-29, LA-31RG, LA manufactured by ADEKA Corporation. −32, LA-36, KEMISORB71, 73, 74, 79, 279 manufactured by Chemipro Kasei Co., Ltd., RUVA-93 manufactured by Otsuka Chemical Co., Ltd., and the like.

Examples of the triazine-based organic compound 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, 2- (2,4-dihydroxy) Phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidate ester reaction product, 2,4-bis "2-hydroxy-4" -Butoxyphenyl "-6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-( Hexyloxy) phenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] phenol, 2,4,6- Examples thereof include tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

More specifically, CHEMIPROB 102 manufactured by Chemipro Kasei Co., Ltd., TINUVIN 400, 405, 460, 477, 479, 1577ED manufactured by BASF, ADEKA Adecaster LA-46, LA-F70 manufactured by ADEKA, CYASORB UV-1164 manufactured by Sun Chemical Co., Ltd., etc. Can be mentioned.

Examples of benzophenone-based organic compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3 water temperature, and 2-hydroxy-4-n-. Octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadesiloxybenzophenone , 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like. In addition, oligomer-type and polymer-type compounds having a benzophenone structure can also be used.

More specifically, KEMIPROB 10, 11, 11S, 12, 111 manufactured by Chemipro Kasei Co., Ltd., SEESORB 101, 107 manufactured by Cipro Kasei Co., Ltd., ADEKA STAB 1413 manufactured by ADEKA Co., Ltd., UV-12 manufactured by Sun Chemical Co., Ltd., etc. Can be mentioned.

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

<Antioxidant (K)>
The photosensitive green composition of the present invention may contain an antioxidant. The antioxidant is used to reduce the transmittance of the coating film in order to prevent the photopolymerization initiator and thermosetting compound contained in the photosensitive green composition from being oxidized and yellowed by the thermal process during heat curing or ITO annealing. Can be high. In particular, when the colorant concentration of the photosensitive green composition is high, the amount of the cross-linking component of the coating film is small, so the yellowing of the thermal process is strong due to the use of a highly sensitive cross-linking component and the increase in the amount of the photopolymerization initiator. The phenomenon is seen. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high transmittance of the coating film can be obtained.

The "antioxidant" in the present invention may be a compound having a radical capture function or a peroxide decomposition function, and specifically, as an antioxidant, a hindered amine type, a phosphorus type, a sulfur type, and a hydroxylamine. Examples thereof include known compounds, and known antioxidants can be used. Further, the antioxidant used in the present invention preferably does not contain a halogen atom.

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

Examples of hindered amine antioxidants include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate and tetrakis (2,2,6,6-). Tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 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, polycondensate 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]], 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol and 3,5 , 5-trimethylhexanoic acid ester, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino } -1,3,5-triazin-2-yl] -4,7-diazadecan-1,10-diamine, bisdecanediate (2,2,6,6-tetramethyl-1- (octyloxy)- 4-piperidinyl) ester, reaction product of 1,1-dimethylethylhydroperoxide and octane, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1) Dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 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. Can be mentioned. In addition, oligomer-type and polymer-type compounds having a hindered amine structure can also be used.

More specifically, Adecastab LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87 manufactured by ADEKA Co., Ltd. , LA-402F, LA-502XP, KAMISTAB29, 62, 77, 94 manufactured by Chemipro Kasei Co., Ltd., Tinuvin249 manufactured by BASF Co., Ltd., TINUVIN111FDL, 123, 144, 292, 5100, Siasorb UV-3346 manufactured by Sun Chemical Co., Ltd., UV- 3529, UV-3853 and the like can be mentioned.

As phosphorus-based antioxidants, di (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis (4,6-methylenebis) Di-t-butylphenyl) 2-ethylhexyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tetra (C12-C15 alkyl) -4,4'- Isopropyridene diphenyldiphosphite, diphenylmono (2-ethylhexyl) phosphite, diphenylisodecylphosphite, tris (isodecyl) phosphite, triphenylphosphite, tetrakis (2,4-di-t-butylphenyl) -4 , 4-biphenyldiphoshonito, tris (tridecyl) phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenyltridecylphosphite, 4,4' -Isopropyridene diphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (biphenyl) phosphite, di (2,4-di-t-butylphenyl) pentaerythritol diphosphite, di ( Nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis (3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-Methyl-4-hydroxy-5-t-butylphenyl) butanetriphosphenyl, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodiumbis (4-t-butylphenyl) phosphite , Sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3-bis (diphenoxyphosphonyloxy) -benzene, ethylbis phosphite (2,4-) Dit-butyl-6-methylphenyl) and the like. In addition, oligomer-type and polymer-type compounds having a phosphite structure can also be used.

More specifically, ADEKA Co., Ltd. Adecaster PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP, BASF Co., Ltd. IRGAFOS168, Clariant Chemicals Co., Ltd. HostanoxP- EPQ and the like can be mentioned.

Sulfur-based antioxidants include 2,2-bis {[3- (dodecylthio) -1-oxopropoxy] methyl} propane-1,3-diylbis [3- (dodecylthio) propionate], 3,3'-thio. Ditridecyl bispropionate, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl] -o-cresol , 2,4-Bis [(laurylthio) methyl] -o-cresol and the like. In addition, oligomer-type and polymer-type compounds having a thioether structure can also be used.

More specifically, ADEKA Stab AO-412S and AO-503 manufactured by ADEKA Corporation, KEMINOXPLS manufactured by Chemipro Kasei Co., Ltd., and the like can be mentioned.

These antioxidants may be used alone or in admixture of two or more at any ratio as required.

The content of the antioxidant is more preferably 0.5 to 5.0% by mass based on 100% by mass of the solid content of the photosensitive green composition because the transmittance, spectral characteristics and sensitivity are good.

<Storage stabilizer (L)>
The photosensitive green composition of the present invention may contain a storage stabilizer to stabilize the viscosity of the composition over time. Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and phosphorous acid and their methyl ethers, and organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenyl. , Phosphate and the like. The storage stabilizer can 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 improver such as a silane coupling agent in order to enhance the adhesion to the substrate. By improving the adhesion by the adhesion improver, the reproducibility of fine lines is improved and the resolution is improved.

Adhesion improvers include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-. (Meta) acrylic silanes such as methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Epoxysilanes such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxy Silane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-) Aminosilanes such as butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-mercaptopropylmethyldimethoxy Silane, mercaptos such as 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureids such as 3-ureidopropyltriethoxysilane, sulfides such as bis (triethoxysilylpropyl) tetrasulfide , 3-Silane Coupling agents such as isocyanates such as propyltriethoxysilane and silane. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the colorant in the photosensitive green composition. It is more preferable because the effect is large within this range and the balance between adhesion, resolution and sensitivity is good.

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

As the solvent, a solvent usually used in the art can be used, and in consideration of performance such as boiling point, SP value, evaporation rate, viscosity, etc., it may be used alone or as appropriate according to the coating conditions (speed, drying conditions, etc.). Used as a mixture.

Examples of the solvent used include an ester solvent (a solvent containing -COO- in the molecule and not containing -O-) and an ether solvent (a solvent containing -O- in the molecule and not containing -COO-). , Ether ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (OH in the molecule) Included, -O-, -CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.

Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, 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, γ-butyrolactone and the like.

Examples of the ether solvent 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, and propylene glycol monoethyl ether. , Propropylene 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 Examples thereof include ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, anisole, phenetol, methylanisole and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy. Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-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 Examples thereof include 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. And so on.

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

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.

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

Among the above solvents, it is preferable to include an organic solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm from the viewpoint of coatability and drying property. 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 and the like are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and the like are more preferable.

<Manufacturing method of coloring composition>
In the photosensitive green composition of the present invention, a pigment is previously placed in a dispersant, a binder resin and / or a solvent, preferably together with a dispersion aid (dye derivative or surfactant), in a kneader, a two-roll mill, and the like. A colored composition can be obtained by finely dispersing using various dispersion means such as a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annual bead mill, or an attritor. At this time, two or more kinds of pigments may be dispersed in the colorant carrier (binder resin and / or solvent) at the same time, or separately dispersed pigments in the colorant carrier may be mixed.

<Dispersed particle size of pigment>
The average dispersed particle size of the pigment in the coloring composition is preferably in the range of 30 to 200 nm. More preferably, it is 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 mixed, and the polymerizable compound (D) and the photopolymerization initiator (E) are further added, only the viscosity and dispersion stability can be obtained. Instead, a photosensitive green composition having high sensitivity and high development speed can be obtained, and when a color filter is produced using the photosensitive green composition, a high-quality color filter can be obtained.

As a method for measuring the dispersed particle size of the pigment, Nikkiso's Microtrack UPA-EX150, which adopted the dynamic light scattering method (FFT power spectrum method), was used, the particle permeability was set to the absorption mode, and the particle shape was set to non-spherical. It can be mentioned that D50 is used as the average diameter. It is preferable to use the solvent used for the dispersion as the diluting solvent for the measurement, and to measure the sample treated by ultrasonic waves immediately after the sample preparation because it is easy to obtain a result with little variation.

<Manufacturing method of photosensitive green composition>
Further, the photosensitive green composition can be prepared as a solvent-developed type or an alkali-developed type coloring composition. The solvent-developed or alkaline-developed coloring composition includes the coloring composition, a photopolymerizable monomer and / or a photopolymerization initiator, and if necessary, a solvent, other dispersion aids, additives and the like. Can be mixed and adjusted. 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 coarse particles>
The photosensitive green composition of the present invention has coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably 0.5 μm or more by means such as centrifugation, filtration with a sintering filter or a membrane filter. It is preferable to remove particles and mixed dust. As described above, it is preferable that the photosensitive green composition does not substantially contain particles having a size of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention includes a red filter segment, a green filter segment, and a blue filter segment. Further, the color filter may further include a magenta color filter segment, a cyan color 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 repeating printing and drying of the photosensitive green composition prepared as a printing ink, so it is excellent in mass productivity at low cost as a manufacturing method of color filters. .. Further, with the development of printing technology, it is possible to print a fine pattern having high dimensional accuracy and smoothness. In order to perform printing, it is preferable that the composition is such that the ink does not dry or solidify on the printing plate or on the blanket. It is also important to control the fluidity of the ink on the printing machine, and the viscosity of the ink can be adjusted with a dispersant or an extender pigment.

When forming a filter segment by a photolithography method, a photosensitive green composition prepared as the solvent-developed or alkali-developed colored resist material is applied onto a transparent substrate by spray coating, spin coating, slit coating, roll coating, or the like. According to the coating method of, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed (irradiation) through a mask having a predetermined pattern provided in contact with or without contact with the film. Then, after immersing in a solvent or an alkaline developer or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to manufacture a color filter. be able to. Further, in order to promote the polymerization of the colored resist material, heating can be applied as needed. According to the photolithography method, a color filter having higher accuracy than the above printing method can be manufactured.

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

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an inkjet method or the like in addition to the above methods, but the photosensitive green composition of the present invention can be used in any of the methods. The electrodeposition method is a method of manufacturing a color filter by electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles using the transparent conductive film formed on the substrate. .. Further, the transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and the filter segment is transferred to a desired substrate.

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

In the color filter of the present invention, a sealing agent is used to bond the liquid crystal display to the opposing substrate, liquid crystal is injected from the injection port provided in the sealing portion, the injection port is sealed, and a polarizing film or a retardation film is attached to the substrate as necessary. A color liquid crystal display device is manufactured by sticking it on the outside of the surface. This color liquid crystal display device is twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), optical convencend bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as).

In addition to the color liquid crystal display device, the color filter of the present invention can also be used for manufacturing a color solid-state imaging device, an organic EL display device, a quantum dot display device, electronic paper, and the like.

<Liquid crystal display>
A liquid crystal display device including the color filter of the present invention will be described.
The liquid crystal display device of the present invention includes 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 the red reproduction region is widened. FIG. 1 is a schematic cross-sectional view of a liquid crystal display device 10 provided with the color filter of the present invention. The device 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 arranged so as to be separated from each other, and a liquid crystal LC is enclosed 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 on the TFT (thin film transistor) array 12. An alignment layer 14 is provided on the transparent electrode layer 13. Further, 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 over the color filter 22 as needed, and a transparent electrode layer 23 made of, for example, ITO is formed on the transparent protective film (not shown), and the alignment layer 24 covers the transparent electrode layer 23. Is provided.

Further, 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.

The liquid crystal LC is oriented according to a drive mode such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane switching), VA (Vertical Alignment), OCB (Optically Compensated Birefringence). 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 on the TFT (thin film transistor) array 12. An alignment layer 14 is provided on the transparent electrode layer 13. Further, 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 over the color filter 22 as needed, and a transparent electrode layer 23 made of, for example, ITO is formed on the transparent protective film (not shown), and the alignment layer 24 covers the transparent electrode layer 23. Is provided.

Further, 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 a resin package of a blue LED. It has λ3), has a wavelength (λ4) that maximizes the emission intensity in the range of 530 nm to 580 nm, has a wavelength (λ5) that maximizes the emission intensity in the range of 600 nm to 650 nm, and has a wavelength. The ratio (I4 / I3) of the emission intensity I3 at the wavelength λ3 and the emission intensity I4 at the wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio of the emission intensity I3 at the wavelength λ3 and the emission intensity I5 at the wavelength λ5 (I5 / I3). ) Is 0.1 or more and 1.3 or less, and has a white LED light source (LED1) and a wavelength (λ1) that maximizes emission intensity in the range of 430 nm to 485 nm, and is in the range of 530 nm to 580 nm. Spectral characteristics having a second emission intensity peak wavelength (λ2) inside, and the ratio (I2 / I1) of the emission intensity I1 at the wavelength λ1 to the emission intensity I2 at the wavelength λ2 is 0.2 or more and 0.7 or less. A white LED light source (LED2) having a wavelength is preferable.

Specific examples of the LED1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation) and NSSW304D-HG-V1 (manufactured by Nichia Corporation).

Specific examples of the LED2 include NSSW440 (manufactured by Nichia Corporation) and NSSW304D (manufactured by Nichia Corporation).

Hereinafter, the present invention will be described with reference to examples. The "parts" and "%" in the examples represent "parts by mass" and "% by mass", respectively.

Prior to the embodiment, each measurement method will be described.

The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), and amine value (mgKOH / 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. Using HLC-8220GPC (manufactured by Tosoh Corporation) as an apparatus, two separation columns are connected in series, and "TSK-GEL SUPER HZM-N" is connected in two for both fillers, and the oven temperature is 40. The measurement was carried out at a flow rate of 0.35 ml / min using a THF solution as an eluent at ° C.
The sample was dissolved in a solvent consisting of 1 wt% of the above eluent and injected in 20 microliters. All molecular weights are polystyrene-equivalent values.

(Acid value of resin (mgKOH / g))
80 ml of acetone and 10 ml of water are added to 0.5 to 1 g of the resin solution and stirred to uniformly dissolve the solution. Using a 0.1 mol / L KOH aqueous solution as a titrator, an automatic titrator (“COM-555” manufactured by Hiranuma Sangyo) ) Was titrated, and the acid value (mgKOH / g) of the resin solution was measured. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

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

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

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

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

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

(Miniaturized phthalocyanine pigment (A2-1))
Phthalocyanine pigment C.I. I. Pigment Green 58 (“FASTGEN GREEN A110” manufactured by DIC Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. This kneaded product is put into 3000 parts of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours to make fine particles. 97 parts of the phthalocyanine pigment (A2-1) was obtained.

(Miniaturized phthalocyanine pigment (A1-1 / A2-1))
The same amount of the refined phthalocyanine pigment (A1-1) and the refined phthalocyanine pigment (A2-1) were mixed to obtain a refined phthalocyanine pigment (A1-1 / A2-1).

(Miniaturized phthalocyanine pigment (A2-2))
A 300 mL flask was charged with 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. The temperature was raised to 130 ° C. over 40 hours, taken out into water, and then filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of crushed sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged into a 1 L dual-arm kneader and kneaded at 100 ° C. for 6 hours. After kneading, the mixture was taken out into 2 kg of water at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a finely divided phthalocyanine pigment (A2-2). The obtained finely divided phthalocyanine pigment (A2-2) has an average of 13.97 halogen atoms in one molecule from fluorescence X-ray analysis using ZSX100E manufactured by Rigaku Co., Ltd., of which an average of 11.46 bromine atoms. It was a halogenated zinc phthalocyanine pigment having an average number of chlorine atoms of 2.51.

(Miniaturized phthalocyanine pigment (A2-3))
A 300 mL flask was charged with 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. The temperature was raised to 130 ° C. over 40 hours, taken out into water, and then filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of crushed sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged into a 1 L dual-arm kneader and kneaded at 100 ° C. for 6 hours. After kneading, the mixture was taken out into 2 kg of water at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a finely divided phthalocyanine pigment (A2-3). The obtained finely divided phthalocyanine pigment (A2-3) has an average of 12.71 halogen atoms in one molecule from fluorescent X-ray analysis, of which an average of 10.22 bromine atoms and chlorine atoms. Was an average of 2.49 zinc halide phthalocyanine pigments.

(Miniaturized phthalocyanine pigment (A2-4))
A 300 mL flask was charged with 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. The temperature was raised to 130 ° C. over 40 hours, taken out into water, and then filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of crushed sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged into a 1 L dual-arm kneader and kneaded at 100 ° C. for 6 hours. After kneading, the mixture was taken out into 2 kg of water at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a finely divided phthalocyanine pigment (A2-4). The obtained finely divided phthalocyanine pigment (A2-4) has an average number of halogen atoms in one molecule of 11.98 from fluorescent X-ray analysis, of which an average number of bromine atoms is 9.00 and the number of chlorine atoms is 9.00. Was an average of 2.98 zinc halide phthalocyanine pigments.

(Miniaturized phthalocyanine pigment (A2-5))
A 300 mL flask was charged with 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. The temperature was raised to 130 ° C. over 40 hours, taken out into water, and then filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of crushed sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged into a 1 L dual-arm kneader and kneaded at 100 ° C. for 6 hours. After kneading, the mixture was taken out into 2 kg of water at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a finely divided phthalocyanine pigment (A2-5). The obtained finely divided phthalocyanine pigment (A2-5) has an average of 12.69 halogen atoms in one molecule from fluorescent X-ray analysis, of which an average of 8.54 bromine atoms and chlorine atoms. Was an average of 4.16 halogenated zinc phthalocyanine pigments.

(Miniaturized phthalocyanine pigment (A2-6))
A 300 mL flask was charged with 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. The temperature was raised to 130 ° C. over 40 hours, taken out into water, and then filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of crushed sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged into a 1 L dual-arm kneader and kneaded at 100 ° C. for 6 hours. After kneading, the mixture was taken out into 2 kg of water at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a finely divided phthalocyanine pigment (A2-6). The obtained finely divided phthalocyanine pigment (A2-6) has an average number of halogen atoms in one molecule of 8.88 from fluorescent X-ray analysis, of which an average number of bromine atoms is 6.90 and the number of chlorine atoms is 6. Was an average of 1.98 zinc halide phthalocyanine pigments.

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

<Manufacturing of finely divided yellow pigment>
(Miniaturized yellow pigment (A4-1-3))
Miniaturized phthalocyanine pigments (A4-1 to 3) of the quinophthalone pigments of the following formulas (12) to (14) were prepared according to the examples of JP2012-226110A. The structure is shown below.

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

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

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

(Miniaturized yellow pigment (A4-4))
C. I. 100 parts of Pigment Yellow 138 (PY138) (BASF's "Pariotor Yellow K0960-HD"), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) for 6 hours at 80 ° C. Kneaded. This mixture was poured into 2000 parts of warm water, stirred for 1 hour while heating at 80 ° C. 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 make 95 parts fine. A yellow pigment (A4-4) was obtained.

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

(Miniaturized yellow pigment (A4-6))
100 parts of metal complex yellow pigment (CI pigment yellow 150, "Yellow Pigment E4GN" manufactured by LANXESS), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho). It was kneaded at 60 ° C. for 10 hours. Next, this mixture was put into 3 liters of warm water, stirred with a high-speed mixer for about 1 hour while heating at about 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and solvent, and then 80. The mixture was dried at ° C. for one day and night to obtain a finely divided yellow pigment (A4-6). The average primary particle size was 36.6 nm.

(Miniaturized yellow pigment (A4-7))
Yellow pigment C.I. I. Pigment Yellow 185 (“Pariotol Yellow D1155” manufactured by Ciba Japan): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged in a stainless steel 1-gallon kneader and kneaded at 120 ° C. for 8 hours. Next, this kneaded product was put into 5 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , A finely divided yellow pigment (A4-7) was obtained.

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 the phthalocyanine skeleton.

Dye derivative (b0-2)

The meanings of the abbreviations shown below are as follows.
HEMA: 2-Hydroxyethyl methacrylate EHMA: 2-ethylhexyl methacrylate BMA: n-butyl methacrylate BzMA: Benzyl methacrylate MMA: Methyl methacrylate DMAPMA: Dimethylaminopropylmethacrylamide DMAEMA: Dimethylaminoethylmethacrylamide PGMAC: Propylglycol Monomethyl ether acetate

<Manufacturing of resin type dispersant (B) solution>
(Manufacturing of resin type dispersant (B-1) solution)
In a 500 mL round bottom 4-port separable flask equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, 250 parts by mass of tetrahydrofuran (THF) and the initiator dimethylketenemethyltrimethylsilylacetal 5.81 A mass portion was added via the addition funnel and sufficient nitrogen substitution was performed. 0.5 parts by mass of 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 and 7.5 parts by mass of EHMA of a solvent-based blocking monomer were injected. , BMA 12.9 parts by mass, BzMA 10.7 parts by mass, and MMA 30.9 parts by mass were added dropwise over 60 minutes using an addition funnel. 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 the color material adsorption function block, was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to stop the reaction. The obtained block copolymer THF solution is reprecipitated in hexane, filtered, and purified by vacuum drying, and has a solvent-like property with a color material adsorption function block containing a structural unit represented by the general formula (1). A compound (B1) containing a block was obtained. Further, PGMAc was added to 20% by mass of the solid content to prepare a resin-type dispersant (B-1) solution.

(Manufacturing of resin type dispersant (B-2) solution)
10.0 parts by mass of compound (B1) was dissolved in 40.6 parts by mass of PGMAc in a 100 mL round bottom flask, and 0.75 parts by mass of phenylphosphinic acid (manufactured by Tokyo Kasei) (DMAPMA unit 1.0 of compound (B1)). (0.50 mol) of phenylphosphinic acid was added to the molar, and the mixture was stirred at a reaction temperature of 30 ° C. for 20 hours, and PGMAc was added to 20% by mass of the solid content to prepare a resin-type dispersant (B-2) solution. Obtained.

(Manufacturing of resin type dispersant (B-3) solution)
In a reaction vessel equipped with a gas introduction tube, a temperature, a condenser, and a stirrer, 10 parts of methacrylic acid, 100 parts of MMA, 70 parts of i-butyl methacrylate, 20 parts of BzMA, and 50 parts of PGMAc were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50 ° C., and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90 ° C., and the reaction was carried out for 7 hours while adding a solution in which 0.1 part of 2,2'-azobisisobutyronitrile was added to 90 parts of PGMAc. It was confirmed by solid content measurement that 95% had reacted. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 part of 1,8-diazabicyclo- [5.4.0] -7-undecene were added as a catalyst, and the mixture was reacted at 100 ° C. for 7 hours. .. It was confirmed by measuring the acid value that 98% or more of the acid anhydride was half-esterified, the reaction was terminated, and PGMAc was added and diluted so that the solid content was 20% by measuring the solid content, and the acid value was 70 mgKOH / g. , A resin-type dispersant (B-3) solution having a weight average molecular weight of 8500 was obtained.

(Manufacturing of resin type dispersant (B-4) solution)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst were charged, and nitrogen gas was charged. After replacement with, the mixture was heated at 120 ° C. for 4 hours and stirred. After confirming that 98% had reacted by solid content measurement, 73.3 parts of pyromellitic anhydride was added, and the reaction was carried out at 120 ° C. for 2 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. By adjusting the solid content with PGMAc, a resin-type dispersant (B-4) solution having a solid content of 20% was obtained. The obtained dispersant was a white solid at room temperature and had an acid value of 49 mgKOH / g.

<Production example of binder resin (C)>
(Preparation of binder resin (C-1) liquid)
196 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped. From the tube, 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 Toa Synthetic Co., Ltd.), 2,2'-azobis A mixture of 1.1 parts of isobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of acrylic resin. 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 PGMAc was added to the previously synthesized resin solution so that the non-volatile content was 20%. A binder resin (C-1) solution was prepared. The weight average molecular weight (Mw) was 26000.

(Preparation of binder resin (C-2) liquid)
370 parts of cyclohexanone was placed in a separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, the temperature was raised to 80 ° C. 2 parts of a mixture of 18 parts of milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.), 10 parts of BzMA, 18.2 parts of glycidyl methacrylate, 25 parts of MMA, and 2.0 parts of 2,2'-azobisisobutyronitrile. Dropped over time. After the dropwise addition, the mixture was further reacted at 100 ° C. for 3 hours, 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container was replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100% of glycidyl group) in the above container at 120 ° C. The reaction was continued for 6 hours, and when the solid content acid value reached 0.5, the reaction was terminated to obtain a solution of acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 part of triethylamine were subsequently added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution.
After cooling to room temperature, 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. A binder resin (C-2) solution was prepared. The weight average molecular weight (Mw) was 19000.

(Preparation of binder resin (C-3) liquid)
182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, the atmosphere inside the flask was changed from air to nitrogen, and then the temperature was raised to 100 ° C. BzMA 70.5 g (0.40 mol), methacrylic acid 43.0 g (0.5 mol), tricyclodecane skeleton monomethacrylate (Hitachi Kasei FA-513M) 22.0 g (0.10 mol) and propylene glycol A solution prepared by adding 3.6 g of azobisisobutyronitrile to a mixture consisting of 136 g of monomethyl ether acetate was added dropwise to the flask from the dropping funnel over 2 hours, and the mixture was further stirred at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol 0. 9 g and 0.145 g of hydroquinone were put into a flask, and the reaction was continued at 110 ° C. for 6 hours to obtain a photosensitive transparent resin solution having an acid value of 79 mgKOH / g. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and the non-volatile content becomes 20% by mass in the previously synthesized photosensitive transparent resin solution. As described above, PGMAc was added to prepare a binder resin (C-3) solution. The mass average molecular weight (Mw) was 13,000.

(Preparation of binder resin (C-4) liquid)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of HEMA, and 2,2'-azobisisobutyronitrile 1 The mixture of .33 parts 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, for the entire amount of the obtained copolymer solution, nitrogen gas was stopped, dry air was injected for 1 hour, and the mixture was stirred, cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Showa Denko's Karenz). A mixture of 6.5 parts of MOI), 0.08 parts of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropping, the reaction was continued for another 1 hour to obtain a solution of acrylic resin. 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 previously synthesized resin solution so that the non-volatile content was 20%. Binder resin (C-4) was prepared. The weight average molecular weight (Mw) was 18,000.

(Preparation of binder resin (C-5) liquid)
A separable flask with a cooling tube was prepared as a reaction tank, while 40 parts of dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, 40 parts of methacrylic acid, and 120 parts of MMA were prepared as a monomer dropping tank. , T-Butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by Nippon Oil & Fats Co., Ltd.) and 40 parts of PGMAc are well mixed and mixed, and 8 parts of n-dodecanethiol are prepared as a chain transfer agent dropping tank. , PGMAc 32 parts were well stirred and mixed to prepare.
395 parts of PGMAc was charged into the reaction vessel, replaced with nitrogen, and then heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel became stable at 90 ° C., the dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was carried out over 135 minutes while keeping the temperature at 90 ° C. 60 minutes after the dropping was completed, the temperature was raised to 110 ° C. After maintaining 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 5/95 (volume ratio) mixed gas was started. Next, 70 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 part of triethylamine were charged in the reaction vessel, and the mixture was allowed to react at 110 ° C. for 12 hours. rice field. After that, 150 parts of PGMAc is added and cooled to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and the non-volatile content becomes 20% by mass in the previously synthesized resin solution. As described above, PGMAc was added 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 (CM) liquid)
The same amounts of the binder resin (C-2) to (C-5) solutions were mixed to obtain a binder resin (CM) solution.

<Manufacturing method of coloring composition (single color)>
[Manufacturing Example 1]
(Preparation of Coloring Composition (R-1))
The following mixture is stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm for 3 hours, and then the pore diameter is 5. The mixture was filtered through a 0 μm filter to prepare a colored composition (R-1) having a non-volatile component of 25% by mass.
Pigment (A1-1): 20 parts Resin-type dispersant liquid 1 (B-1: Non-volatile content 20% liquid): 3 parts Resin-type dispersant liquid 2 (B-3: Non-volatile content 20% liquid): 2 parts Binder Resin (C-1: 20% non-volatile liquid): 20 parts Solvent (N): 55 parts

[Manufacturing Examples 2-36]
(Preparation of Coloring Compositions (R-2 to 36))
Coloring compositions (R-2 to 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.

<Manufacturing method of photosensitive green composition>
[Example 1]
(Photosensitive green composition (X-1))
The following raw materials were mixed and stirred, and filtered through a filter having a pore size of 1.0 μm to obtain a photosensitive green composition (X-1).
Green composition (R-1: 25% non-volatile content): 35.0 parts Colored composition (R-25: 25% non-volatile content): 15.0 parts Binder resin (CM: 20% non-volatile content): 12 .6 parts Thermocurable compound (CE-1): 1.0 part Thermocurable compound (CE-2): 1.0 part Photopolymerizable monomer (D-1): 5.5 parts Photopolymerization started Agent (E1-3): 1.45 parts Polymerization inhibitor (F-1): 0.05 parts Leveling agent (G-1: Non-volatile content 3%): 1.0 parts Thiol-based chain transfer agent (H): 0.5 part UV absorber (J): 0.1 part Antioxidant (K): 0.1 part Storage stabilizer (L): 0.1 part Adhesion improver (M): 0.2 part Solvent ( N): 25.95 copies

[Examples 2-66, Comparative Examples 1-5]
(Preparation of photosensitive green composition (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 type and mass of the photosensitive green composition of Example 1 were changed as shown in Table 2. .. The raw materials are as follows.

<Thermosetting compound (CE)>
-Epoxy compound (CE-1)
(CE-1-1) 1,2'-bis (hydroxymethyl) -1-butanol 1,2-
Epoxy-4- (2-oxylanyl) cyclohexane adduct
[EHPE-3150 (manufactured by Daicel)],
(CE-1-2) Glycidyl etherified epoxy compound 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-ethyloxetane-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 the same amount to obtain 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 Co., Ltd.)]

(D-7) Polyfunctional urethane acrylate according to the following. Pentaerythritol triacrylate (432 g, hexamethylene diisocyanate 84 g) was charged into a reaction vessel having a content of 1 liter and 5 mouths, and reacted at 60 ° C. for 8 hours to form a (meth) acryloyl group. A product containing the polyfunctional urethane acrylate (D-7) having the above was obtained. The proportion of the polyfunctional urethane acrylate (D-7) in the product was 70% by mass, and the balance was other photopolymerizable. It is occupied by monomer. It was confirmed by IR analysis that the isocyanate group was not present in the reaction product.

(D-8) Bifunctional 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) Chemical formula (6) ) In the compound (E2-5) 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)]
[Irgacure OXE01 (manufactured by BASF Japan Ltd.)]
(E2-6) Compound represented by chemical formula (17)

Chemical formula (17)

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

(E2-8) Ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl], 1- (O-acetyloxime)
[Irgacure OXE02 (manufactured by BASF Japan Ltd.)]
(E2-M) The following (E2-9) to (E2-15) were mixed in equal amounts to obtain a photopolymerization initiator (E2-M).
(E2-9) 2-Methyl-1- [4- (Methylthio) Phenyl] -2-morpholinopropan-1-one
[Irgacure 907 (manufactured by BASF Japan Ltd.)]
(E2-10) 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone
[Irgacure 379 (manufactured by BASF Japan Ltd.)]
(E2-11) 2,4,6-trimethylbenzoyludiphenyl-phosphine oxide
[Lucillin TPO (manufactured by Ciba Japan)]
(E2-12) 2,2'-bis (o-chlorophenyl) -4,5,4', 5'-tetraphenyl-1,2'-biimidazole
[Biimidazole (manufactured by Kurokin Kasei Co., Ltd.)]
(E2-13) p-dimethylaminoacetophenone
[DMA (manufactured by Daiki Fine)]
(E2-14) 1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one
[Irgacure 2959 (manufactured by BASF Japan Ltd.)]
(E2-15) Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
[Irgacure 819 (manufactured by BASF Japan Ltd.)]

(E1-1 / E1-3): (E1-1) and (E1-3) were mixed in the same amount.
(E1-2 / E1-3): (E1-2) and (E1-3) were mixed in the same amount.
(E1-3 / E1-4): (E1-3) and (E1-4) were mixed in the same amount.
(E1-3 / E2-5): (E1-3) and (E2-5) were mixed in the same amount.
(E1-3 / E2-6): (E1-3) and (E2-6) were mixed in the same amount.
(E1-3 / E2-7): (E1-3) and (E2-7) were mixed in the same amount.
(E1-3 / E2-8): (E1-3) and (E2-8) were mixed in the same amount.
(E1-3 / E2-M): (E1-3) and (E2-M) were mixed in equal amounts.

<Polymerization inhibitor (F)>
(F-1) 2,6-Di-tert-butyl-p-cresol (F-2) Methylhydroquinone (FM) The following (F-3) and (F-4) are mixed in equal amounts. Then, it was used as a photopolymerization initiator (FM).
(F-3) 3-Methylcatechol (F-4) t-butylhydroquinone

<Leveling agent (G)>
(G-1) Solution of 3 parts of "Mega Fvck F-575" manufactured by DIC Corporation mixed with 97 parts of PGM Ac (G-2) Solution of 3 parts of "BYK-330" manufactured by BIC Chemie mixed with 97 parts of PGM Ac (G-) 3) Solution of 3 parts of "Emargen 103" manufactured by Kao Corporation mixed with 97 parts of PGMAc (G-4) Solution of 3 parts of "Megafuck F-563" manufactured by DIC Corporation mixed with 97 parts of PGMAc (G-5) Big Chemie A solution (G-1 / G-2) (G-1) and (G-2) in which 3 parts of "BYK-323" manufactured by the same company were mixed with 97 parts of PGMAc were mixed in the same amount, and (G-1 / G-2). ).
(G-1 / G-3) (G-1) and (G-3) were mixed in the same amount to obtain (G-1 / G-3).
(G-1 / G-4) (G-1) and (G-4) were mixed in the same amount to obtain (G-1 / G-4).
(G-2 / G-3) (G-2) and (G-3) were mixed in the same amount to obtain (G-2 / G-3).
(G-2 / G-5) (G-2) and (G-5) were mixed in the same amount to obtain (G-2 / G-5).
<Thiol chain transfer agent (H)>
(H-1) Trimethylolethane ethanetris (3-mercaptobutyrate)
[TEMB (manufactured by Showa Denko)]
(H-2) Trimethylolpropane Tris (3-mercaptobutyrate)
[TPMB (manufactured by Showa Denko)]
(H-3) Pentaerythritol tetrakis (3-mercaptopropionate)
[PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(H-4) Trimethylolpropanetris (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.)]
As described above, (H-1) to (H-5) were mixed in the same amount 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
[TINUVIN400 (manufactured by BASF Japan Ltd.)]
(J-2) 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol
[TINUVIN900 (manufactured by BASF Japan)]
As described 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) 3,3'-dioctadecylthiodipropanoate (K-3) tris [2] , 4-Di- (t) -Butylphenyl] Phosphine (K-4) Bis (2,2,6,6-Tetramethyl-4-piperidyl) Sevacate (K-5) P-Octylphenyl salicylate or higher, (K) -1) to (K-5) were mixed in the same amount to prepare an antioxidant (K).

<Storage stabilizer (L)>
Triphenylphosphine ("TPP" manufactured by Hokuko 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.)]
As described above, (M-1) to (M-4) were mixed in the same amount to prepare the 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) Diproprene glycol 10 parts or more of methyl ether acetate and (N-1) to (N-5) were mixed by the above mass parts to prepare a solvent (N).

<Evaluation of photosensitive green composition>
Each test was performed by the following method. The test results are shown in Table 3.
The meaning of the evaluation rank is as follows.
⊚: Extremely good ○: Good △: Practical use ×: Not suitable for practical use

<Evaluation of residual film rate>
The obtained photosensitive green composition was applied onto a glass substrate of 100 mm × 100 mm and 0.7 mm so as to have a film thickness of 3.4 μm, and passed through a mask having a stripe pattern having a width of 100 μm under the condition of ^{40 mJ / cm 2.} UV exposure was performed at. Then, a pattern is obtained by immersing in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 40 seconds for development, and washing with pure water. rice field. The obtained coating film was heat-treated (post-baked) in an oven at 230 ° C. for 20 minutes, and the change in film thickness (residual film ratio) before and after post-baking was calculated from the following formula.
Residual film thickness = film thickness after post-baking / film thickness before post-baking x 100
The evaluation criteria are as follows.
⊚: 85% or more ○: 80% or more and less than 85% Δ: 75% or more and less than 80% ×: less than 75%

<Water stain evaluation>
The obtained photosensitive green composition was applied onto a glass substrate of 100 mm × 100 mm and 0.7 mm so as to have a film thickness of 3.4 μm, and was exposed to ultraviolet rays under the condition of ^{40 mJ / cm 2.} Then, it is immersed in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 40 seconds and washed with pure water to obtain a solid coated substrate. Then, the water stain was observed with a magnifying glass. The evaluation criteria are as follows.
⊚: There was no water stain.
◯: Water stain was less than 10% of the solid part.
Δ: Water stain was 10% or more and less than 30% of the solid portion.
X: Water stain was 30% or more of the solid portion.

<Pattern shape evaluation>
The obtained photosensitive green composition was applied onto a glass substrate of 100 mm × 100 mm and 0.7 mm so as to have a film thickness of 3.4 μm, and passed through a mask having a stripe pattern having a width of 100 μm under the condition of ^{40 mJ / cm 2.} UV exposure was performed at. Then, a pattern is obtained by immersing in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 40 seconds for development, and washing with pure water. rice field. The obtained coating film was heat-treated (post-baked) in an oven at 230 ° C. for 20 minutes, and the pattern shape was confirmed with a scanning electron microscope (“S-3000H” manufactured by Hitachi High-Tech Co., Ltd.). For the evaluation, an SEM image of a cross section of a striped pattern having a width of 100 μm was taken in, and the taper angle between the base material and the end of the pattern cross section was evaluated using a protractor as follows.
⊚: Taper angle 40 degrees or more and less than 50 degrees ○: Taper angle 30 degrees or more and less than 40 degrees or 50 degrees or more and less than 60 degrees Δ: Taper angle less than 30 degrees or 60 degrees or more and less than 70 degrees ×: Taper angle 70 degrees or more

10 Liquid crystal display 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 Orientation layer 25 Plate plate 30 Backlight unit 31 White LED light source LC Liquid crystal

Claims (9)

A photosensitive green composition containing 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 zinc halide phthalocyanine pigment (A2) and a copper halide phthalocyanine pigment (A3), and a yellow pigment (A4). ,And,
A 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 the general formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and 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 rest represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group, and each of them shows. The alkyl group and the 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 with a benzene ring. X represents a direct bond or an oxygen atom or a carbonyl group. R ⁶ represents a direct bond or a hydrocarbon group having 1 to 12 carbon atoms. R ⁷ represents a hydroxyl group or a carboxy group. ] The photosensitive green color according to claim 1, wherein the binder resin (C) contains an alkali-soluble resin having a carboxy group and a polymerizable unsaturated group in the side chain selected from the following (I) and (II). Composition.
(I) An alkali-soluble resin (II) obtained by reacting a product of an epoxy group in a polymer having an epoxy group with a carboxy group of a carboxy group-containing monomer with a polybasic acid or a polybasic acid anhydride. An alkali-soluble resin which is a reaction product of a carboxy group in a polymer having a carboxy group and an epoxy group of an epoxy group-containing monomer. The photosensitive green composition according to claim 1 or 2, further comprising a polymerization inhibitor (F). The photosensitive green color according to any one of claims 1 to 3, wherein 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. Composition. The photosensitive green composition according to any one of claims 1 to 4, further comprising two or more types of a silicone-based leveling agent or a fluorine-based leveling agent (G). Further, the present invention according to any one of claims 1 to 5, wherein the polymerizable compound (D) contains one or more kinds of ethylene oxide (EO) modified (meth) acrylate or propylene oxide (PO) modified (meth) acrylate. Photosensitive green composition. The photosensitive green composition according to any one of claims 1 to 6, wherein the photopolymerization initiator (E) contains two or more kinds of oxime ester-based photopolymerization initiators. A color filter having a base material and a filter segment formed from the photosensitive green composition according to any one of claims 1 to 7. A liquid crystal display device comprising the color filter according to claim 8.

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