JP2020071252A - Photosensitive colored composition, red filter segment, color filter and color liquid crystal display device - Google Patents

Abstract

To provide a photosensitive colored composition excellent in solvent resistance, a high-quality color filter having free of defects in a pattern figure when a filter segment (pixel) is formed by using the above composition, and a color liquid crystal display device.SOLUTION: The photosensitive colored composition comprises a pigment (A), a dispersant (B), a binder resin (C), a polymerizable compound (D), a photopolymerization initiator (E) and a leveling agent (F). The pigment (A) comprises a brominated diketopyrrolopyrrole pigment; and the leveling agent (F) is made of a copolymer (FD) of an ethylenically unsaturated monomer (FD1) containing a fluorinated alkyl group and/or a poly(perfluoroalkylene ether) chain and another ethylenically unsaturated monomer (FD2).SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive coloring composition used for producing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter using the same.

  For color filters that compose liquid crystal displays (LCD), color image pickup tube devices (CCD), etc., a coating solution (coloring composition) is applied on a transparent substrate and dried to form a coating film having a thickness of about 1 to 3 μm. It is manufactured by

  In the red filter segment, which is one of the three primary colors (red, green, blue; RGB) of the color filter substrate, pigments such as diketopyrrolopyrrole pigment, anthraquinone pigment, perylene pigment or disazo pigment are used as colorants. It is generally used alone or in combination. Patent Document 1 discloses a brominated diketopyrrolopyrrole pigment having high contrast.

  In recent years, in order to realize high brightness and high contrast of a color filter, a pigment contained in a filter segment is often used after being miniaturized. However, various pigments (which are called crudes having a particle size of 10 to 100 μm produced by a chemical reaction and made into a mixture of primary particles and secondary particles obtained by aggregating them by a pigmentation treatment) are variously used. Even when miniaturized by a refining treatment method, pigments in which primary particles or secondary particles have been refined are generally easily aggregated, and if the refinement is too advanced, a huge lumpy pigment solid is formed. I will end up. Further, the finely-divided pigment is dispersed in a pigment carrier containing a resin or the like, and even if an attempt is made to stabilize the secondary particles of the pigment again as close to the primary particles as possible, a stable colored composition is obtained. Things are very difficult.

  Therefore, for example, a pigment composition containing a pigment composed of fine particles often exhibits a high viscosity, which not only makes it difficult to take out or transport the product from the disperser, but also causes gelation during storage in a bad case. It may even wake up and become difficult to use. Therefore, by using a structure-controlled one having a block structure or a comb structure, or a resin-type dispersant such as a polyester dispersant having a specific structure (Patent Document 2), etc., excellent dispersibility, storage stability, and high contrast can be obtained. Studies have been made on colored compositions having ratios.

  Further, in Patent Document 3, by using a polymer having an oxetanyl group and a polymerizable unsaturated bond, a pixel having sufficient development resistance even at a low exposure amount and having excellent solvent resistance and A radiation-sensitive composition for forming a colored layer capable of forming a black matrix is disclosed.

JP, 2013-14750, A International Publication No. 2008/007776 Pamphlet JP, 2010-44365, A

  Provided are a photosensitive coloring composition having an excellent pattern shape and solvent resistance, a high-quality color filter having no defect in the pattern shape when a filter segment (pixel) is formed using the same, and a color liquid crystal display device. The purpose is to

  That is, the present invention is a photosensitive coloring composition containing a pigment (A), a dispersant (B), a binder resin (C), a polymerizable compound (D), a photopolymerization initiator (E) and a leveling agent (F). Wherein the pigment (A) contains a brominated diketopyrrolopyrrole pigment represented by the following chemical formula (1), and the leveling agent (F) contains a fluorinated alkyl group and / or poly (per) (Fluoroalkylene ether) chain-containing ethylenically unsaturated monomer (FD1) and another ethylenically unsaturated monomer (FD2), comprising a copolymer (FD) It relates to a coloring composition.

  The present invention also relates to the above-mentioned photosensitive coloring composition, which further contains a diketopyrrolopyrrole pigment represented by the following general formula (2).

[In the general formula (2), X represents a chlorine atom or a bromine atom, and A and B are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, or a carbon number of 1 12 alkyl group, an optionally substituted phenyl ^{_{group, -CF 3, -OR 1, -SR}} 2, -N (R 3) R 4, -COOR 5, -CONH 2, -CONHR 6, ^{-CON (R 7) R 8,} -SO 2 NH 2, -SO 2 NHR 9, or a ^{_{-SO 2 N (R 10) R}} 11, R 1 ~R 11 are each independently, carbon atoms 1 to 12 alkyl group, a phenyl group which may have a substituent, or an aralkyl group which may have a substituent. However, A and B do not become hydrogen atoms at the same time. Further, A is X and B is not a hydrogen atom, and B is X and A is not a hydrogen atom. ]

  In the invention, the diketopyrrolopyrrole pigment represented by the general formula (2) has the following general formula (2-1), general formula (2-2), and general formula (2-3), And the said photosensitive coloring composition containing one or more types of pigments selected from the group which consists of following General formula (2-4).

[In general formula (2-1), general formula (2-2), general formula (2-3), and general formula (2-4), X represents a chlorine atom or a bromine atom. Moreover, in General formula (2-3) and General formula (2-4), R < ¹² > -R < ¹⁴ > is respectively independently the C1-C12 alkyl group, or the phenyl which may have a substituent. It is a base. R ¹³ and R ¹⁴ may together form a ring. ]

  The present invention also relates to the above-mentioned photosensitive coloring composition, wherein the other ethylenically unsaturated monomer (FD2) contains a monomer having an adamantyl group.

  The present invention also relates to a red filter segment formed using the above photosensitive coloring composition.

  The present invention also relates to a color filter having a substrate and at least a filter segment other than red in addition to the above red filter segment.

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

  INDUSTRIAL APPLICABILITY Since the present invention is a photosensitive coloring composition having an excellent pattern shape and solvent resistance, it is possible to provide a high-quality color filter having no defect in the shape of a pixel formed using the same, and a color liquid crystal display device. ..

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

Below, each component of the photosensitive coloring composition of this invention is demonstrated.
In addition, in this application, when it describes with "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide", it demonstrates especially. Unless otherwise specified, "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide", respectively. Shall be represented.
Further, “C.I.” mentioned in this specification means a color index (C.I.).

<Pigment (A)>
(Brominated diketopyrrolopyrrole pigment (Aa) represented by the chemical formula (1))
In the photosensitive coloring composition for a color filter of the present invention, the pigment (A) contains a brominated diketopyrrolopyrrole pigment represented by the following chemical formula (1).

(Diketopyrrolopyrrole pigment (Ab) represented by the general formula (2))
The photosensitive coloring composition for a color filter of the present invention preferably further contains a diketopyrrolopyrrole pigment represented by the general formula (2).

[In the general formula (2), X represents a chlorine atom or a bromine atom, and A and B are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, or a carbon number of 1 12 alkyl group, an optionally substituted phenyl ^{_{group, -CF 3, -OR 1, -SR}} 2, -N (R 3) R 4, -COOR 5, -CONH 2, -CONHR 6, ^{-CON (R 7) R 8,} -SO 2 NH 2, -SO 2 NHR 9, or a ^{_{-SO 2 N (R 10) R}} 11, R 1 ~R 11 are each independently, carbon atoms 1 to 12 alkyl group, a phenyl group which may have a substituent, or an aralkyl group which may have a substituent. However, A and B do not become hydrogen atoms at the same time. Further, A is X and B is not a hydrogen atom, and B is X and A is not a hydrogen atom. ]

  The alkyl group having 1 to 12 carbon atoms may be linear or branched, and is specifically a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl. Group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, 1,5-dimethylhexyl group, 1,6-dimethylheptyl group, 2-ethylhexyl group, and the like, but are not limited to these. Absent.

  Examples of the phenyl group which may have a substituent include an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a halogen atom, a nitro group, a cyano group, a carbamoyl group, a sulfamoyl group and an alkoxyl having 1 to 4 carbon atoms. Examples thereof include a phenyl group having a substituent such as a group. More specifically, phenyl group, p-methylphenyl group, 4-tert-butylphenyl group, p-nitrophenyl group, p-methoxyphenyl group, p-chlorophenyl group, 2,4-dichlorophenyl group, 3-carbamoyl Examples thereof include phenyl group and the like, but are not limited thereto.

  Specific examples of the aralkyl group which may have a substituent include benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group and 2,4- Examples thereof include, but are not limited to, a dichlorobenzyl group.

In the present invention, the diketopyrrolopyrrole pigment represented by the general formula (2) has the following general formula (2-1), the following general formula (2-2), the following general formula (2-3), and the following. The pigment is preferably at least one selected from the group consisting of general formula (2-4). This further improves the brightness, the contrast, and the effect of suppressing crystal precipitation. Further, in R ^{12 to} R ¹⁴ of the general formulas (2-3) and (2-4), an alkyl group having a carbon number of 4 or more, or a phenyl group which may have a substituent is used for contrast and crystal precipitation. It is preferable from the viewpoint of suppressing effect. The reason why they are effective in increasing the contrast and suppressing the precipitation of crystals is that the pigment is due to the steric hindrance effect due to the bulky substituents such as a carboxamide group having an alkyl group having 4 or more carbon atoms, a phenyl group and a t-butyl group. It is thought that this is because the aggregation of the is suppressed. Further, the specific heterodiketopyrrolopyrrole pigment having a carboxamide group, a phenyl group, and a t-butyl group is also excellent in color characteristics, and thus is superior to the brominated diketopyrrolopyrrole pigment represented by the chemical formula (1). There is no loss of brightness.

[In general formula (2-1), general formula (2-2), general formula (2-3), and general formula (2-4), X represents a chlorine atom or a bromine atom. Moreover, in General formula (2-3) and General formula (2-4), R < ¹² > -R < ¹⁴ > is respectively independently the C1-C12 alkyl group, or the phenyl which may have a substituent. It is a base. R ¹³ and R ¹⁴ may together form a ring]

  Specific examples of the specific heterodiketopyrrolopyrrole pigment represented by the general formula (2) that can be used in the present invention are shown below, but the invention is not limited thereto.

(Other diketopyrrolopyrrole pigments (A-c))
The photosensitive coloring composition for a color filter of the present invention comprises, as the pigment (A), a diketopyrrolopyrrole pigment (A-a) and a diketopyrrolopyrrole pigment (A-b) as long as the effects of the present invention are not impaired. Other than the above), a diketopyrrolopyrrole pigment (A-c) may be used in combination. Specifically, C.I. I. Pigment Red 254, 255, 264, 270, 272, 283, C.I. I. Pigment Orange 71, 73, 81 and the like, but are not limited to the diketopyrrolopyrrole pigments. Examples of diketopyrrolopyrrole pigments that can be used in combination include C.I. I. Pigment Red 254 is preferable. C. I. Pigment Red 254 is preferable because it is less likely to adversely affect the excellent brightness of the brominated diketopyrrolopyrrole pigment represented by the chemical formula (1).

(Method for producing diketopyrrolopyrrole pigment)
The brominated diketopyrrolopyrrole pigment represented by the chemical formula (1) can be produced by a succinic acid diester synthesis method. That is, 2 mol of 4-bromobenzonitrile with respect to 1 mol of succinic acid diester in an inert organic solvent such as tert-amyl alcohol in the presence of an alkali metal or an alkali metal alkoxide at a high temperature of 80 to 110 ° C. A condensation reaction is performed to generate an alkali metal salt of a diketopyrrolopyrrole compound, and subsequently, with respect to the alkali metal salt of the diketopyrrolopyrrole compound, water, an alcohol, by protonation using an acid or the like, Brominated diketopyrrolopyrrole pigments can be obtained. At this time, the size of the obtained primary particle diameter can be controlled by the temperature in the protonation, the kind, ratio and amount of water, alcohol or acid. The method for producing the brominated diketopyrrolopyrrole pigment represented by the chemical formula (1) is not limited to this method.

  The specific heterodiketopyrrolopyrrole pigment represented by the general formula (2) is described in, for example, the literature Synth. Commun. , 1988, 18, 1213 and Tetrahedron, 58 (2002) 5547-5565.

  Further, the specific heterodiketopyrrolopyrrole pigment represented by the general formula (2) is C.I. I. Pigment Red 254 or C.I. I. It can also be synthesized as a mixture with Pigment Red 291. This can be achieved by utilizing a method of using at least two structurally different benzonitrile compounds in the succinic acid diester synthesis method (hereinafter, referred to as “succinic acid diester co-synthesis method”). Specifically, in the method described in WO2009 / 081930, a plurality of benzonitrile compounds used are 4-chlorobenzonitrile or 4-bromobenzonitrile and benzonitrile represented by the following chemical formula (3). By selecting from the compounds, the specific heterodiketopyrrolopyrrole pigment of the general formula (2) can be used as C.I. I. Pigment Red 254 or C.I. I. Pigment Red 291 and can be manufactured as a mixture.

化学式（３）

Chemical formula (3)

[In the chemical formula (3), A and B each independently have a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, and a substituent. also a phenyl ^{_{group, -CF 3, -OR 1, -SR}} 2, -N (R 3) R 4, -COOR 5, -CONH 2, -CONHR 6, -CON (R 7) R 8, -SO 2 NH _2, or -SO ₂ NHR ^9,, an ^{_{-SO 2 N (R 10) R}} 11, R 1 ~R 11 each independently have an alkyl group, a substituted group of 1 to 12 carbon atoms It is an optionally substituted phenyl group or an optionally substituted aralkyl group. However, A and B do not become hydrogen atoms at the same time. ]

  The diketopyrrolopyrrole pigment of the present invention is produced by separately producing a brominated diketopyrrolopyrrole pigment represented by the chemical formula (1) and a specific heterodiketopyrrolopyrrole pigment represented by the general formula (2). The materials can be mixed and used. Further, a specific heterodiketopyrrolopyrrole pigment synthesized by a succinic acid diester co-synthesis method and C.I. I. The mixture of Pigment Red 254 may be further mixed with a brominated diketopyrrolopyrrole pigment represented by the chemical formula (1) and used. In these cases, the pigments may be simply mixed before being dispersed, or may be ground and mixed by a salt milling treatment.

  In the diketopyrrolopyrrole pigment of the present invention, the mass ratio of the brominated diketopyrrolopyrrole pigment represented by the chemical formula (1) and the specific heterodiketopyrrolopyrrole pigment represented by the general formula (2) is It can be analyzed using TOF-MASS, FD-MASS, LC-MASS or NMR. Alternatively, as disclosed in JP-A-08-199085, a composition having a diketopyrrolopyrrole pigment is stirred at room temperature with di-tert-butyldicarbonate and 4-dimethylaminopyridine in tetrahydrofuran. After conversion into a soluble diketopyrrolopyrrole compound obtained by the above, analysis using NMR, MASS, LC-MASS or the like may be performed. Alternatively, the hydrogen of the NH group of the pyrrolopyrrole ring may be substituted with an alkyl group using an alkyl halide or the like to convert into a soluble diketopyrrolopyrrole, and then the above analysis may be performed.

(Other colorants (AS))
The photosensitive coloring composition for a color filter of the present invention comprises, as other coloring agents, diketopyrrolopyrrole pigments (A-a), (A-b) and (A-c) as long as the effects of the present invention are not impaired. A colorant (AS) other than the above) may be used in combination. These colorants can be used alone or as a mixture of two or more kinds at an arbitrary ratio as needed.

  Examples of other coloring agents (AS) include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 242, 246, 269, 273, 274, 276, 277, 278, 279, 280, 281, 282, Red pigments such as 284, 285, 286, 287. Further, azo pigments described in JP-A-2014-112527, azo pigments described in JP-A-2013-161026 and the like can be mentioned.

  Also, C.I. I. Pigment Orange 43 and / or 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, Examples include yellow pigments such as 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221 or 231. Further, quinophthalone-based pigments described in Japanese Patent No. 4993026 and the like can be mentioned.

  Preferable pigments to be used in combination include azo, naphtholazo, anthraquinone, quinophthalone, and perylene pigments from the viewpoint of fastness such as heat resistance and light resistance and a chromaticity region. Specifically, C.I. I. Pigment Red 177, 269, C.I. I. Pigment Yellow 138, 139, 150, 185, 231.

  Further, any of an acid dye, a direct dye, a basic dye, a salt-forming dye, an oil-soluble dye, a disperse dye, a reactive dye, a mordant dye, a vat dye, a sulfur dye and the like can be used. It may be in the form of a derivative thereof or a lake pigment in which a dye is laked.

Furthermore, acidic dyes having acidic groups such as sulfonic acid and carboxylic acid, in the case of direct dyes, inorganic salts of acidic dyes, acidic dyes and quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, Alternatively, a salt-forming compound with a nitrogen-containing compound such as a primary amine compound, or salt-forming using a resin component having these functional groups to be used as a salt-forming compound, or sulfonamide-forming to be used as a sulfonic acid amide compound It is preferable that the coloring composition has excellent fastness because it has excellent durability.
Further, a salt-forming compound of an acid dye and a compound having an onium base is also preferable because it is excellent in fastness, and more preferably, a compound having an onium base is a resin having a cationic group in its side chain.

  In the case of a basic dye, it can be used by salification using an organic acid, perchloric acid or a metal salt thereof. Among them, a salt forming compound of a basic dye is preferable because it is resistant and excellent in combination with a pigment, and further, a basic dye and an organic sulfonic acid, an organic sulfuric acid, or a fluorine group-containing phosphorus that is a counter component that acts as a counter ion. 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 a salt-forming compound prepared by salting with an acid dye may be used. It is more preferable.

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

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

  Among these pigment structures, from the viewpoint of color characteristics such as hue, color separation, and color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium. -Based dyes, quinophthalone-based dyes, phthalocyanine-based dyes, sub-phthalocyanine-based dyes preferably have a dye structure derived from a dye, and xanthene-based dyes, cyanine-based dyes, triphenylmethane-based dyes, anthraquinone-based dyes, dipyrromethene-based dyes, phthalocyanines A dye structure derived from a dye selected from the group-based dyes is more preferable. Specific dye compounds capable of forming a dye structure are described in "New Edition Dye Handbook" (edited by The Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and colors), "Dye Handbook" (Okawara et al.). Ed .; Kodansha, 1986) and the like.

(Red photosensitive coloring composition for red filter segment)
The red photosensitive coloring composition for forming the red filter segment includes the above-mentioned pigment (A), a dispersant (B), a binder resin (C), a polymerizable compound (D), and a photopolymerization described below. It is prepared by mixing the initiator (E) and the leveling agent (F) with other components as necessary.

<Refinement of pigment>
The method for micronizing the pigment used in the photosensitive coloring composition of the present invention is not particularly limited, and for example, wet grinding, dry grinding, dissolution precipitation method can all be used, and as shown in the present invention, wet method It is possible to make finer by performing a salt milling treatment by a kneader method, which is one type of grinding. The average primary particle diameter of the pigment determined by TEM (transmission electron microscope) is preferably in the range of 10 to 80 nm. If it is smaller than 10 nm, it becomes difficult to disperse it in an organic solvent, and if it is larger than 80 nm, it may not be possible to obtain a sufficient contrast ratio. For this reason, the more preferable average primary particle diameter is in the range of 15 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 two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, 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 with heating using a kneading machine. The water-soluble inorganic salt functions 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 diameter, a narrow distribution range, and a sharp particle size distribution.

  As the water-soluble inorganic salt, sodium chloride, potassium chloride, sodium sulfate or the like can be used, but it is preferable to use sodium chloride (salt) from the viewpoint of cost. 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, per 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, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety, because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by mass, and most preferably 50 to 500 parts by mass, based on 100 parts by mass of the pigment.

  When the salt is subjected to the salt milling treatment, a resin may be added if necessary. The type of resin used is not particularly limited, and natural resin, modified natural resin, synthetic resin, synthetic resin modified with natural resin, and the like can be used. The resin used is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in the above 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.

<Dispersant (B)>
A dispersant (B) such as a dye derivative or a resin type dispersant is added to the photosensitive coloring composition used in the present invention.

<Resin type dispersant>
A known resin type dispersant can be used in the photosensitive coloring composition of the present invention. The resin-type dispersant has a colorant-affinity site that has the property of adsorbing to the added colorant and a site that is compatible with the colorant carrier, and is adsorbed to the added colorant and dispersed in the colorant carrier. As long as it has a function of stabilizing, specifically, urethane dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine. Salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters and modified products thereof, poly (lower alkyleneimine) and free carboxyl groups Dispersants such as amides and salts thereof formed by reaction with polyesters containing (meth) acrylic acid-styrene copolymer , (Meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc., water-soluble resin or water-soluble polymer compound, polyester-based, modified polyacrylate A system, an ethylene oxide / propylene oxide addition compound, a phosphoric acid ester system, etc. are used, and these can be used alone or in combination of two or more.
As the polymer dispersant having a basic functional group, a nitrogen atom-containing graft copolymer or a nitrogen atom-containing graft copolymer having a functional group containing a tertiary amino group, a quaternary ammonium salt group, or a nitrogen-containing heterocycle in its side chain is used. Examples thereof include acrylic block copolymers and urethane polymer dispersants.

  Examples of commercially available resin type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, manufactured by Big Chemie Japan. 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, LPN6919, LPN21116, LPN21324 or Lactimon, Lactimon-WS, or Bykumen, etc., manufactured by Nippon Le Brisol. OLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500 etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400 made by BASF. , 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 53, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503 and the like, Ajiza-PA111, PB711, PB821, PB822 manufactured by Ajinomoto Fine-Techno Inc. , PB824 and the like.

<Dye derivative (b)>
As the dye derivative (b) 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 and a phosphoric acid group and an amine salt thereof, a compound having a basic substituent such as a sulfonamide group or a tertiary amino group at the end, a phenyl group and a phthalimide Examples thereof include compounds having a neutral substituent such as an alkyl group. Since the resin-type dispersant used in combination has an acidic group, a dye derivative having a basic group is preferable.
Examples of organic dyes 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, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, slene pigments, metal complex pigments, azo pigments such as azo, disazo, polyazo, and the like. Be done.

  Specifically, as the diketopyrrolopyrrole dye derivative, JP 2001-220520 A, WO 2009/081930 Pamphlet, WO 2011/052617 Pamphlet, WO 2012/102399 Pamphlet, JP 2017-156397 A, Phthalocyanine As the system dye derivative, JP 2007-226161 A, WO 2016/163351 pamphlet, JP 2017-165820 A, JP 575266 B, and as the anthraquinone dye derivative, JP 63-264674 A, JP-A 09-272812, JP-A 10-245501, JP-A 10-265697, JP-A 2007-079094, WO 2009/025325 pamphlet, KINA Examples of the redone-based dye derivative are JP-A-48-54128, JP-A-03-9961 and JP-A-2000-273383, and examples of the dioxazine-based dye derivative are JP-A-2011-162662 and thiazineindigo. Japanese Patent Application Laid-Open No. 2007-314785 discloses trie-based dye derivatives, and Japanese Patent Application Laid-Open No. 61-246261, Japanese Patent Application Laid-Open No. 11-199796, Japanese Patent Application Laid-Open No. 2003-165922, and Japanese Patent Application Laid-Open No. 2003-2003. No. 168208, JP-A 2004-217842, JP-A 2007-314681, JP-A No. 2009-57478 as a benzoisoindole dye derivative, and JP-A No. 2003-167112 as a quinophthalone dye derivative. Publication, JP 2006-291194 A JP-A-2008-31281, JP-A-2012-226110, JP-A-2012-208329 and JP-A-2014-5439 for naphthol dye derivatives, and JP-A-2001 for azo dye derivatives. -172520, JP 2012-172092A, JP-A 2004-307854 as an acidic substituent, JP-A 2002-201377, JP-A 2003-171594 as a basic substituent, Known dye derivatives described in JP-A-2005-181383, JP-A-2005-213404, etc. may be mentioned. In these references, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound. The compound having a substituent such as a functional group has the same meaning as a dye derivative.

These dye derivatives can be used alone or in combination of two or more.
More specifically, the following dye derivatives are preferable.

[Diketopyrrolopyrrole dye derivative]

[Phthalocyanine dye derivative]

[Anthraquinone dye derivative]

[Quinacridone dye derivative]

[Dioxazine dye derivative]

[Thiazine indigo dye derivative]

[Triazine dye derivative]

[Benzoisoindole dye derivative]

[Quinophthalone dye derivative]

[Naphthol dye derivative]

[Azo dye derivative]

In general formulas (101) to (112), (114) to (128), and (130) to (133),
R _{101 to} R ₁₁₇ , R ₁₂₉ , R ₁₃₀ , and R _{141 to} R ₁₄₅ are each independently a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. Phthalimidoalkyl group which may have a group, acyl group which may have a substituent, amino group, sulfo group, carboxyl group, phosphoric acid group, halogen group, general formulas (150) to (155), (158) ) Or a group represented by (159). m and n each independently represent a positive integer. However, when one molecule has a plurality of substituents, at least one is a substituent other than a hydrogen atom. Further, when only one substituent is present in one molecule, it is a substituent other than a hydrogen atom.

In general formula (113), R ₁₁₈ is a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an alkoxy group, an aryloxy group, —SO ₂ R ₁₇₇ , or —NR ₁₇₈ R ₁₇₉ . However, R ₁₇₇ is a hydrogen atom, an alkyl group which may have a substituent, a phenyl group which may have a substituent, or a halogen atom, and R ₁₇₈ and R ₁₇₉ are each independently a hydrogen atom. , A C 1-12 alkyl group, or R ₁₇₈ and R ₁₇₉ together represent a heterocycle which may further contain a nitrogen, oxygen or sulfur atom.
R ₁₁₉ represents a hydrogen atom, an alkyl group which may have a substituent, or an acyl group which may have a substituent.
R ₁₂₀ , R ₁₂₁ , and R _{123 to} R ₁₂₈ are each independently a hydrogen atom, an alkyl group which may have a substituent, a phenyl group which may have a substituent, a halogen atom, a cyano group, or a substituent. Or an NR ₁₈₀ R ₁₈₁ . However, R ₁₈₀ and R ₁₈₁ may independently of each other be a hydrogen atom, an alkyl group which may have a substituent, or R ₁₈₀ and R ₁₈₁ may be combined together to include a further nitrogen, oxygen or sulfur atom. Represents a good heterocycle.
R ₁₂₂ represents a hydrogen atom, an alkyl group which may have a substituent, an acyl group which may have a substituent, or a group represented by any of the general formulas (150) to (155).

In the general formula (129), R _{131 to} R ₁₄₀ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a perfluoroalkyl group, an alkoxyl group or a general formula (150), (153) or (159). Represents a group represented by Adjacent groups of R _{131 to} R ₁₄₀ may combine with each other by a —NHCONH— group to form a benzimidazolone ring. At least one of R _{131 to} R ₁₄₀ is a group represented by the general formula (150), (153) or (159).

In the general formulas (150) to (155),
X ₁ is a direct bond, -SO2 -, - CO -, - CH2 -, - CH2NHCOCH2 -, - CONHC 6 H 4 CO-, or -CONHC ₆ H ₄ - represents a.
Y ₁ is a direct _{bond, -NR 170 SO 2 -, -} SO 2 NR 170 -, - CONR 170 -, - NR 170 CO-, or _{-CH 2 NR 170 COCH 2 NR 170} - represents a.
Y ₂ is a direct bond, an arylene group which may have a substituent, or represents an aromatic heterocycle having a substituent, these _{groups, -NR 170 -, -O -,} - SO 2 They may be bonded to each other with a divalent linking group selected from --or CO--.
Y ₃ is a direct bond, -NR ₁₇₀ - represents a or -O-.
o represents an integer of 0 to 20.
M ₁ represents a hydrogen atom, a copper atom, a zinc atom, a manganese atom, a nickel atom, a cobalt atom, or an iron atom.
M ₂ represents a hydrogen atom, a calcium atom, a barium atom, a strontium atom, a manganese atom or an aluminum atom.
i represents the valence of M ₂ .
R ₁₅₀ and R ₁₅₁ each independently represent an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a phenyl group which may have a substituent, or R ₁₅₀ and R ₁₅₁ . Together they represent an optionally substituted heterocycle containing further nitrogen, oxygen or sulfur atoms.
R _{152 to} R ₁₅₆ and R _{159 to} R ₁₆₂ may each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. It represents a phenyl group or a polyoxyalkylene group.
R ₁₅₇ and R ₁₅₈ each independently represent a group represented by the following general formula (156) or (157), —O— (CH ₂ ) _o —R ₁₇₁ , —OR ₁₇₂ , —NR ₁₇₃ R ₁₇₄ , — Cl, —F or Y ₃ —Y ₂ —Y ₁ —Q, and _{one of} R ₁₅₇ and R ₁₅₈ is a group represented by general formula (156) or (157) below, —O— (CH ₂ ) _o —R ₁₇₁ , —OR ₁₇₂ , or NR ₁₇₃ R ₁₇₄ .
R ₁₇₀ represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a phenyl group which may have a substituent.
R ₁₇₁ represents a heterocyclic residue which may have a substituent, and R _{172 to} R ₁₇₄ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a substituent which may have a substituent. Represents a good alkenyl group or a phenyl group which may have a substituent, and Q represents an organic dye residue.

In formula (156), Z ₁ represents —NR ₁₇₀ —, —CONH— or —O—, and Z ₂ is an alkylene group which may have a substituent or an alkenylene group which may have a substituent. Represents an arylene group which may have a substituent, and these groups are mutually bonded by a divalent linking group selected from —NR ₁₇₀ —, —O—, —SO ₂ — or CO—. Good. However, R ₁₇₀ has the same meaning as R ₁₇₀ in formula (150) - (155).
R ₁₅₀ and R ₁₅₁ are each independently an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a phenyl group which may have a substituent, or R ₁₅₀ and R ₁₅₁ Together represent a heterocycle which may further have a substituent and which contains a further nitrogen, oxygen or sulfur atom.

In formula (157), Z ₃ represents a single bond connecting a triazine ring and a nitrogen atom, —NR ₁₇₅ —, —NR ₁₇₅ —Z ₄ —CO—, —NR ₁₇₅ —Z ₄ —CONR ₁₇₆ —, and —NR _{175. -Z 4 -SO 2 -, - NR} 175 -Z 4 - SO 2 NR 176 -, - O-Z 4 -CO -, - O-Z 4 -CONR 175 -, - O-Z 4 -SO 2 -, or _{O-Z 4 -SO 2 NR 175} - represents, R ₁₇₅ and R ₁₇₆ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or Represents a phenyl group which may have a substituent, Z ₄ represents an alkylene group which may have a substituent, an alkenylene group which may have a substituent or an arylene group which may have a substituent. Represent
R _{152 to} R ₁₅₆ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a phenyl group which may have a substituent or a polyoxyalkylene. Represents a group.

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

The alkyl group which may have a substituent is preferably a linear alkyl group having 1 to 20 carbon atoms, and the substituent which may have a hydrogen or halogen group.
The phthalimidoalkyl group which may have a substituent is preferably an alkyl group having 1 to 3 carbon atoms as the alkyl group, and the substituent which may have a hydrogen or halogen group is preferable.
The acyl group which may have a substituent is preferably an acyl group having 1 to 10 carbon atoms as the alkyl group, and the substituent which may have a hydrogen or halogen group is preferable.
The alkoxy group which may have a substituent is preferably a straight-chain alkoxy group having 1 to 5 carbon atoms as the alkyl group, and the substituent which may have a hydrogen or halogen group is preferable.
The alkenyl group or alkenylene group which may have a substituent is preferably hydrogen or a linear alkyl group having 1 to 10 carbon atoms as the substituent which may have a substituent.
The phenyl group which may have a substituent is preferably hydrogen, a halogen group, a linear alkyl group having 1 to 10 carbon atoms, or an alkoxy group as the substituent which may have a substituent.
The arylene group which may have a substituent is preferably hydrogen, a halogen group, a linear alkyl group having 1 to 10 carbon atoms or an alkoxy group as the substituent which may have a substituent.
The heterocycle which may have a substituent is preferably azacyclobutane, pyrrolidine, piperidine, tetrahydrofuran, tetrahydropyran, tetrahydrothiophene or tetrahydrothiopyran as the heterocycle, and the substituent which may have hydrogen or a halogen group. A linear alkyl group having 1 to 10 carbon atoms or an alkoxy group is preferable.
The heteroaromatic ring which may have a substituent is preferably pyrrole, pyridine, furan or thiophene as the heteroaromatic ring, and the substituent which may have a hydrogen, a halogen group or a straight chain having 1 to 10 carbon atoms. An alkyl group and an alkoxy group are preferable.

  Particularly, the diketopyrrolopyrrole dye derivatives represented by the general formulas (101) and (102), which have a substituent represented by the general formulas (150), (151) and (155), are preferable.

  The dye derivative is preferably added in an amount of 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, and further preferably 5 to 50 parts by mass, relative to 100 parts by mass of the pigment.

  By adding a pigment derivative to the pigment and performing pigmentation treatment such as acid pasting, acid slurry, dry milling, salt milling, and solvent salt milling, the pigment derivative is adsorbed on the pigment surface and the pigment derivative is not added. In comparison, the primary particles of the pigment can be made finer.

  The pigment derivative is adsorbed on the pigment surface and the pigment surface is polar and the resin type dispersant is adsorbed by adding the pigment derivative to the pigment and performing a dispersion treatment such as two-roll, three-roll, and wet dispersion using beads. Is promoted, the compatibility with pigments, dye derivatives, resin-type dispersants, solvents, and other additives is improved, and dispersion stability and viscosity stability with time when used as a photosensitive coloring composition or a colored curable composition are improved. Is improved. Further, since the compatibility is improved, the stability of the coating film over time when the colored curable composition is applied to a glass substrate or the like is excellent, and the waiting time from the application of the colored curable composition to the exposure (PCD: Post Coating) is improved. The stability and characteristic dependence of the pattern shape and the line width sensitivity stability with respect to the (Delay) and the waiting time (PED: Post Exposure Delay) from the exposure to the heat treatment are improved. Further, since the pigment surface is adsorbed and coated with the dye derivative and the resin-type dispersant, it is possible to suppress the precipitation of crystals due to the aggregation or sublimation of the pigment when the coating film is heated and baked. Further, variations in development time and development residues are suppressed.

<Binder resin (C)>
The photosensitive coloring 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 by the main curing method. Active energy ray curable resins are thermoplastic resins. It may be a resin or one having a thermosetting function, and is preferably an alkali-soluble resin from the viewpoint of developability. Further, a thermoplastic resin that is not curable by active energy rays may be contained, and it is preferable that this also be alkali-soluble. These may be used alone or in combination of two or more.

  The content of the binder resin in the photosensitive coloring 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 preferably used in an amount of 20 parts by mass or more because the film-forming property and various resistances are good, and it is preferably used in an amount of 400 parts by mass or less because the colorant concentration is high and good color characteristics can be exhibited. ..

<Thermoplastic resin>
The thermoplastic resin that can be used as the binder resin, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, 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. Is mentioned.

<Alkali-soluble resin>
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. Specific examples of the resin include acrylic resin having an acid group, α-olefin / (anhydrous) maleic acid copolymer, styrene / styrene sulfonic acid copolymer, ethylene / (meth) acrylic acid copolymer, or isobutylene / (Anhydrous) maleic acid copolymer etc. are 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 has developability, heat resistance, and transparency. Since it is expensive, it is preferably used.
The photosensitive coloring composition of the present invention preferably contains an alkali-soluble resin as the binder resin (B) from the viewpoints of developability, heat resistance and transparency. It is for imparting developing solubility in an alkali developing step at the time of producing a color filter, and has an acid group and / or a hydroxyl group. Examples of the alkali-soluble resin include an alkali-soluble resin having no ethylenically unsaturated double bond (C1) and an alkali-soluble resin having an ethylenically unsaturated double bond (C2) which improves the photosensitivity of the composition. They are used alone or in combination.

  The alkali-soluble resin in the present invention is preferably a resin having a spectral transmittance of 80% or more, and 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 30,000 or less, and 4,000 in order to impart alkali developing solubility. More preferably, it is 20,000 or less. Further, the value of Mw / Mn is preferably 10 or less. When 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. When it exceeds 40,000, the alkali developing 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 to 200 or less (KOHmg / g) in order to impart alkali developing solubility, preferably 70 or more and 180 or less, more preferably 90 or more and 170 or less. It is a range. When the acid value is less than 50, the alkali developing solubility is lowered, a residue is generated and the linearity of the pattern is deteriorated. When it exceeds 200, the adhesion to the substrate is deteriorated and the exposure pattern is less likely to remain.

<Alkali-soluble resin having no ethylenically unsaturated double bond (C1)>
The photosensitive coloring composition of the present invention may contain an alkali-soluble resin (C1) having no ethylenically unsaturated double bond in order to adjust the degree of curing of the coating film. By synthesizing at least one kind of carboxyl group-containing ethylenically unsaturated monomer and one or more kinds of the other ethylenically unsaturated monomers mentioned above, and by not giving an ethylenically unsaturated bond to the side chain, ethylene can be obtained. An alkali-soluble resin having no unsaturated double bond can be obtained.

<Alkali-soluble resin having ethylenically unsaturated double bond (C2)>
The alkali-soluble resin contained in the photosensitive coloring 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 method (i) or (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 side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers , An unsaturated monobasic acid carboxyl group having an ethylenically unsaturated double bond is subjected to an addition reaction, and the generated hydroxyl group is reacted with a polybasic acid anhydride to form an ethylenically unsaturated double bond and a carboxyl group. There is a way to introduce.

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4-epoxybutyl (meth) acrylate. , And 3,4-epoxycyclohexyl (meth) acrylate, which may be used alone or in combination of two or more kinds. From the viewpoint of reactivity with the 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 compounds. Examples thereof include monocarboxylic acids, and these may be used alone or in combination of two or more kinds.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like. These may be used alone or in combination of two or more kinds. I don't care. If necessary, such as increasing the number of carboxyl groups, use a tricarboxylic acid anhydride such as trimellitic anhydride, or use a tetracarboxylic acid dianhydride such as pyromellitic dianhydride to leave the remaining anhydride. It is also possible to hydrolyze the group. 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 side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers There is a method of adding an ethylenically unsaturated monomer having an epoxy group to a part of the carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and an unsaturated monobasic acid monomer having another carboxyl group is copolymerized with another monomer. There is a method of reacting the side chain hydroxyl group of the obtained copolymer with the isocyanate group of the 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 hydroxyalkyl methacrylates such as 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, or cyclohexanedimethanol mono (meth) acrylate. These may be used alone or two or more kinds. You may use together. Further, a polyether mono (meth) acrylate obtained by addition-polymerizing ethylene oxide, propylene oxide, and / or butylene oxide to the hydroxyalkyl (meth) acrylate, polyγ-valerolactone, polyε-caprolactone, and / or Polyester mono (meth) acrylate added with poly-12-hydroxystearic acid or the like can also be used. 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 to 6 hydroxyl groups. Are preferred, and glycerol mono (meth) acrylate is more preferred.

  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, without being limited to these, two or more kinds can be used in combination.

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

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4'-bismaleimidodiphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N'-1,3-phenylenedimaleimide, N, N'-1,4- Phenylene dimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succin Midyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N- [4- (2-benzimidazolyl) phenyl ] N-substituted maleimides such as maleimide and 9-maleimide acridine,
A compound represented by the following general formula (12), specifically EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, and ethylene oxide (EO) -modified (meth) acrylate of phenol. , EO or propylene oxide (PO) -modified (meth) acrylate of paracumylphenol, EO-modified (meth) acrylate of nonylphenol, and PO-modified (meth) acrylate of nonylphenol.

General formula (12)

(In the general formula (12), R ₆ is a hydrogen atom or a methyl group, R ₇ is an alkylene group having 2 or 3 carbon atoms, and R ₈ is a carbon which may have a benzene ring. It is an alkyl group of 1 to 20, and n is an integer of 1 to 15.)

  It is also possible to use a carboxyl group-containing ethylenically unsaturated monomer. 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 addition-polymerizing ethylene oxide, propylene oxide, and / or butylene oxide, etc. to the hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) ester mono (meth) acrylate added with (poly) 12-hydroxystearic acid.

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

<Thermosetting compound (C3)>
In the present invention, a thermosetting compound (C3) can be further contained in combination with the thermoplastic resin. When a color filter is produced using the photosensitive coloring composition for a color filter of the present invention, by containing a thermosetting compound, it reacts during firing of the filter segment to increase the crosslink density of the coating film, and thus the heat resistance of the filter segment. The properties are improved, the pigment agglomeration during the firing of the filter segment is suppressed, and the contrast ratio is improved.

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 an epoxy compound, an oxetane compound, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, and a phenol compound, but the present invention is not limited thereto. It is not something that will be done. Epoxy compounds and oxetane compounds are preferably used in the photosensitive coloring composition for color filters of the present invention.

(Epoxy compound (C3-1))
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). Benzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) Condensates, phenols and various diene compounds (dicyclopentadiene, terpenes, Polymers of nylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc., phenols and ketones (acetone, methylethylketone, methylisobutylketone, acetophenone, benzophenone, etc.) ), Polycondensates with phenols and aromatic dimethanols (benzenedimethanol, α, α, α ', α'-benzenedimethanol, biphenyldimethanol, α, α, α', α'-biphenyldim Polycondensate with methanol, etc., Polycondensate with phenol and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.), Polycondensate of bisphenol with various aldehydes, alcohols Glycidyl Examples of the glycidyl ether-based epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, aliphatic epoxy resin, glycidyl amine-based epoxy resin, glycidyl ester-based epoxy resin, etc. It is not limited. These may be used alone or in combination of two or more.

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

  The compounding 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 effect of improving the contrast ratio and heat resistance is small, and if it is more than 300 parts by mass, problems may occur when the filter segment is formed by photolithography.

(Oxetane compound (C3-2))
It is preferable to add an oxetane compound to the photosensitive coloring composition of the present invention. As the oxetane compound, a known compound having an oxetane group can be used without particular limitation. Examples of the oxetane compound include those having a monofunctional oxetane group, those having a bifunctional oxetane group, and those having a bifunctional or more oxetane group.

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

Examples of the bifunctional oxetane group 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- Oxetanyl) -5-oxa-nonane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-e Tyl-3-oxetanylmethoxy) methyl] propane, ethyleneglycose bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl) -3-Oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl) -3-Oxetanylmethoxy) hexane, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bis Enol A bis (3-ethyl-3-oxetanylmethyl) ether, EO modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ) Ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether, and the like.
Specific examples thereof include OXBP, OXTP manufactured by Ube Industries, Ltd., and OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd.

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

  The content of the oxetane compound used in the photosensitive coloring composition of the present invention is 0.5 to 50% by mass, preferably 1 to 40% by mass based on 100 parts by mass of the colorant. When the content of the oxetane compound is within the above range, an excellent coating film having high solvent resistance can be obtained, which is preferable.

(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. In the present invention, a melamine compound having a methylol type or an ether type and having an average number of methylol groups and / or ether groups per melamine ring of 5.0 or more is preferred. When the number of methylol groups and / or ether groups per melamine ring is less than 5.0 on average, the number of reaction points is small and the cross-linking structure at the time of curing does not become sufficiently dense, so that the contrast ratio is suppressed and NMP resistance is reduced by the heat treatment process. The effect of improvement may be reduced.

  Examples of commercially available products include Nicarac 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 Co., 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, Nicarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW. -22, MS-21, MS-11, MW-24X, MX-45 (manufactured by Sanwa Chemical Co., Ltd.) Cymel 232, 235, 236, 238, 300, 301, 303, 350 (manufactured by Nippon Cytec Industries Co., Ltd.) and the like. It is preferable in that a dense crosslinked structure can be obtained.

(Curing agent)
Further, the photosensitive coloring composition for a color filter 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, etc. are effective, but are not particularly limited to these and may react with thermosetting compounds. Any curing agent may be used as long as it is one. Examples of the curing agent include amine compounds (eg, 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 amidine compounds and salts thereof (eg imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl- Four 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 used. .. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting compound.

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

  Examples of the monomer or oligomer that is cured by ultraviolet rays or heat to produce a transparent resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polypropylene glycol di (meth ) Acrylate, trimethylolpropane tri (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, trimethylol Lopan PO modified tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, isocyanuric acid EO modified di (meth) acrylate, isocyanuric acid EO modified tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth ) Acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate (Meth) acrylic acid ester of methylolated melamine, epoxy (meth) acrylate, urethane acrylate, and various acrylic acid esters and methacrylic acid esters, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol diester Examples thereof include vinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile, but are not necessarily limited thereto.

  These commercially available products include KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, and GPO- manufactured by Nippon Kayaku Co., Ltd. 303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, and Aronix M-303, M manufactured by Toagosei. -305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403. , M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, screws manufactured by Osaka Organic Co., Ltd. Over preparative # 310HP, # 335HP, # 700, # 295, # 330, # 360, # GPT, # 400, # 405, can be preferably used by Shin-Nakamura Chemical Co., Ltd. NK Ester A-9300 and the like.

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

  Examples of the polymerizable compound having an acid group include esterification products of poly (meth) acrylates containing a free hydroxyl group of polyhydric alcohol and (meth) acrylic acid, and dicarboxylic acids; polyvalent carboxylic acids, and monohydroxyalkyl. Examples thereof include esterified products with (meth) acrylates. Specific examples include trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, and other monohydroxyoligoacrylates or monohydroxyoligomethacrylates. And a free carboxyl group-containing monoester of dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic 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 Examples include monohydroxy monoacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate, and free carboxyl group-containing oligoester compounds with monohydroxy monomethacrylates. The effect of the present invention is not limited to these.

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

(Polyfunctional urethane acrylate)
The polymerizable compound in the invention preferably contains a polymerizable compound containing at least one ethylenically unsaturated bond and one urethane bond. For example, a polyfunctional urethane acrylate obtained by reacting a polyfunctional isocyanate with a (meth) acrylate having a hydroxyl group, or a polyfunctional urethane obtained by reacting a polyfunctional isocyanate with an alcohol and further reacting a (meth) acrylate having a hydroxyl group. Urethane acrylate etc. are mentioned. Further, it is more preferable that the polymerizable compound having a urethane bond further has an acid group.

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

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

These commercially available products include Kyoeisha Chemical Co., Ltd. AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167, Shin-Nakamura Chemical Co., Ltd. UA-160TM, UV-4108F, UV-4117F manufactured by Osaka Organic Chemical Industry Co., Ltd. can be preferably used.
The above-mentioned polymerizable compounds can be used alone or in a mixture of two or more at an arbitrary ratio, if necessary.

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

<Photopolymerization initiator (E)>
The photosensitive composition of the present invention contains a photopolymerization initiator (E). By containing the photopolymerization initiator (E), the composition can be cured by irradiation with ultraviolet rays and a filter segment can be formed by a photolithography method. It is preferred to add a photopolymerization initiator (E) to prepare a solvent-developable or alkali-developable photosensitive composition.

As the photopolymerization initiator (E), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one , 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -1- [4- (4-morpholino) Phenyl] -2- (phenylmethyl) -1-butanone or 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone Acetophenone compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoinyl Benzoin compounds such as propyl ether or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3, Benzophenone compounds such as 3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4 Thioxanthone compounds such as diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4 , 6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -S-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2 , 4-trichloromethyl- (4'-methoxystyryl) -6-triazine and other triazine compounds; 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2, (O-benzoyl oxime) or oxime ester compounds such as ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) A phosphine compound such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, etc. Quinone compounds; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds.
These photopolymerization initiators can be used singly or as a mixture of two or more kinds at an arbitrary ratio as needed.

  As commercially available products, as acetophenone compounds, all are IGM Resins' "Omnirad 907" (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one), "Omnirad. 369E "(2- (dimethylamino) -1- [4- (4-morpholino) phenyl] -2- (phenylmethyl) -1-butanone)," Omnirad 379EG "(2- (dimethylamino) -2- [ (4-Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone) and phosphine compounds are all "Imnirad 819" (bis (2,4,4, manufactured by IGM Resins). 6-trimethylbenzoyl) -phenylphosphine oxide), "Omnirad TPO" (diff Sulfonyl-2,4,6-trimethyl benzoyl phosphine oxide), and the like. In the present invention, among these, it is preferable to contain an oxime ester compound.

(Oxime ester compound)
The oxime ester-based compound cleaves the N—O bond of the oxime by absorbing ultraviolet rays to generate an iminyl radical and an alkyloxy radical. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small exposure amount. When the concentration of the coloring agent in the photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may be low and the curing degree of the coating film may be low, but oxime ester compounds are preferably used because they have high quantum efficiency. It

  Commercially available products of these oxime ester compounds include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime) (IRGACURE OXE01), ethanone, 1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (IRGACURE OXE02) (both manufactured by BASF), N-1919 (manufactured by ADEKA), TRONLY TR-PBG-304, TRONLY TR-PBG-305, TRONLY TR-PBG-309 (all manufactured by Changzhou Strong New Materials Co., Ltd.) and the like are commercially available. In addition to these, oximes described in JP2007-210991A, JP2009-179619A, JP2010-0372223A, JP2010-215575A, JP2011-020998A, and the like. It is also possible to use an ester photopolymerization initiator.

  The content of the photopolymerization initiator (E) is preferably 0.1 to 20 parts by mass, based on the total solid content of the photosensitive coloring composition (100 parts by mass), and the content of the photocurability and the developability is From the viewpoint, it is more preferably 0.5 to 10 parts by mass. If the amount is less than 0.1 parts by mass, the adhesion of the formed pattern to the base material may be poor, and if the amount is more than 20 parts by mass, the developability may be deteriorated or the brightness may be lowered after the heat treatment at 230 ° C. ..

<Leveling agent (F)>
The leveling agent (F) of the present invention comprises an ethylenically unsaturated monomer (FD1) containing a fluorinated alkyl group and / or a poly (perfluoroalkylene ether) chain, and another ethylenically unsaturated monomer ( It is characterized by containing a copolymer (FD) of FD2). By using the leveling agent, it is possible to obtain a photosensitive coloring composition comprising a diketopyrrolopyrrole pigment having excellent solvent resistance, which is used on a transparent substrate when forming a filter segment (pixel) using the same. It is possible to obtain a filter segment (pixel) having no defect in the shape, which is effective in improving the coatability of the composition in 1. and the drying property of the colored film.
Further, the other ethylenically unsaturated monomer (FD2) preferably has an adamantyl group.

  Examples of the method of producing the copolymer (FD) include a method of polymerizing in an organic solvent using a polymerization initiator. As the organic solvent used here, ketones, esters, amides, sulfoxides, ethers, hydrocarbons are preferable, and specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like can be mentioned. These are appropriately selected in consideration of boiling point, compatibility, and polymerizability. Examples of the polymerization initiator include peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile. Further, if necessary, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid and octylthioglycolic acid can be used.

As the ethylenically unsaturated monomer (FD1) containing a fluorinated alkyl group that constitutes the compound (FD), for example, those represented by the following general formula (L1) can be preferably exemplified.
General formula (L1)

[In the above general formula (L1), R represents a hydrogen atom or a methyl group, L represents any one of the following formulas (L-1) to (L-10), and Rf represents the following formula (Rf -1) to (Rf-7). ]

(N in the above formulas (L-1) and (L-3) to (L-7) represents an integer of 1 to 8. m in the above formulas (L-8) to (L-10) is 1. Represents an integer of 8 and n represents an integer of 0-8.
Rf ″ in the above formulas (L-6) and (L-7) represents any one of the following formulas (Rf-1) to (Rf-7). )

N in the above formulas (Rf-1) to (Rf-4) is, for example, an integer of 1 to 6, and preferably an integer of 4 to 6. In the formula (Rf-5), m is, for example, an integer of 1 to 18, n is an integer of 0 to 5, and the sum of m and n is 1 to 23. Preferably, m is an integer of 1-5, n is an integer of 0-4, and the sum of m and n is 4-5. In the formula (Rf-6), m is, for example, an integer of 1 to 6, n is an integer of 1 to 3, l is an integer of 1 to 20, p is an integer of 0 to 5, And the sum of the products of m, p, and n and l is 2 to 71. Preferably, m is an integer of 1-3, n is an integer of 1-3, l is an integer of 1-6, p is an integer of 0-2, and m, p and n The sum of the products of and 1 is 2-23.

  Among the ethylenically unsaturated monomers (FD1) containing a fluorinated alkyl group, a fluorine-containing thermally decomposable resin exhibiting excellent smoothness can be obtained, so that a fluorine atom directly bonded to a carbon atom A monomer having a fluorinated alkyl group of 1 to 6 is preferable, and a monomer having a fluorinated alkyl group of 4 to 6 carbon atoms to which a fluorine atom is directly bonded is more preferable.

The ethylenically unsaturated monomer (FD1) containing a poly (perfluoroalkylene ether) chain that constitutes the compound (FD) includes a divalent fluorocarbon group having 1 to 3 carbon atoms and an oxygen atom. Examples thereof include those having a structure in which they are alternately connected. The divalent fluorocarbon group having 1 to 3 carbon atoms may be one kind or may be a mixture of plural kinds. Specifically, one represented by the following structural formula (A1) is Can be mentioned.

(In the above structural formula (A1), X is the following structural formulas (A1-1) to (A1-5), and all Xs in the structural formula (A1) may have the same structure, In addition, a plurality of structures may be present randomly or in a block form, and n is an integer of 1 or more that represents a repeating unit.)

Among these, the perfluoromethylene structure represented by the structural formula (A1-1) and the above-described structure are particularly preferable in that the coating film surface has good wiping-off property for stains and a coating film excellent in antifouling property can be obtained. Those in which a perfluoroethylene structure represented by the formula (A1-2) coexists are particularly preferable. The value of n in the structural formula (A1) is preferably in the range of 3 to 100, more preferably in the range of 6 to 70, and even more preferably in the range of 12 to 50.

Further, the other ethylenically unsaturated monomer (FD2) constituting the compound (FD) is preferably a monomer having an adamantyl group, and more appropriate water content control can be expected.
The ethylenically unsaturated monomer having an adamantyl group is a compound having an adamantane structure represented by the following general formula (B1) and a (meth) acryloyl group. The (meth) acryloyl group may be bonded to any carbon atom in the adamantane structure. Further, a part or all of the hydrogen atoms bonded to the carbon atoms constituting the adamantane structure may be substituted with a hydroxyl group, a fluorine atom, an alkyl group or the like.

(In general formula (B1), R represents a hydrogen atom, a methyl group, or CF _3. )

  Specific examples include Surflon S-242, S-243, S-420, S-611, S-651, S-386 manufactured by AGC Seimi Chemical Co., Ltd., Megafac F-253, F-477 manufactured by DIC Corporation, F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, DS- 21, FC-4430 and FC-4432 manufactured by Sumitomo 3M Limited, EF-PP31N09, EF-PP33G1, EF-PP32C1 manufactured by Mitsubishi Materials Electronics Co., Ltd., and Futgent 602A manufactured by Neos Co., Ltd. may be mentioned.

[Other leveling agents]
Other leveling agents that can be used in combination include silicone-based surfactants or, depending on another classification, various surfactants such as nonionic surfactants and cationic (surfactants, anionic surfactants, etc.).

Examples of the silicone-based surfactant include a linear polymer having a siloxane bond and a modified siloxane polymer having an organic group introduced into a side chain or a terminal.
As a specific example, BYK-300, BYK-306, BYK-310, BYK-313, BYK-315N, BYK-320, BYK-322, BYK-323, BYK-330, BYK-331, BYK- manufactured by Big Chemie. 333, BYK-342, BYK-345 / 346, BYK-347, BYK-348, BYK-349, BYK-370, BYK-377, BYK-378, BYK-3455, BYK-UV3510, BYK-3570, Toray. FZ-7001, FZ-7002, FZ-2110, FZ-2122, FZ-2123], FZ-2191, FZ-5609, Shin-Etsu Chemical Co., Ltd. X-22-4952, X-22. -4272, X-22-6266, KF-351A, K354L, KF- 55A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, etc. KF-6004 and the like.

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

  Specific examples include Emulgen 103, Emulgen 104P, Emulgen 106, Emulgen 108, Emulgen 109P, Emulgen 120, Emulgen 123P, Emulgen 130K, Emulgen 147, Emulgen 150, Emulgen 210P, Emulgen 220, Emulgen 306P, and Emulgen 320P manufactured by Kao Corporation. , Emulgen 350, Emulgen 404, Emulgen 408, Emulgen 409PV, Emulgen 420, Emulgen 430, Emulgen 705, Emulgen 707, Emulgen 709, Emulgen 1108, Emulgen 1118S-70, Emulgen 1135S-70, Emulgen 1150S-60, Emulgen 2020G-HA. , Emulgen 2025G, Emulgen LS-106, Emulgen LS-110, Rugen LS-114, Emulgen MS-110, Emulgen A-60, Emulgen A-90, Emulgen B-66, Emulgen PP-290, Latemulu PD-420, Latemulu PD-430, Latemulu PD-430S, Latemulu PD450, Leodol SP. -L10, Rheodor SP-P10, Rheodor SP-S10V, Rheodor SP-S20, Rheodor SP-S30V, Rheodor SP-O10V, Rheodor SP-O30V, Rheodor Super SP-L1, Rheodor AS-10V, Rheodor AO-10V, Leodol AO-15V, Leodol TW-L120, Leodol TW-L106, Leodol TW-P120, Leodol TW-S120V, Leodol TW-L106V, Leodol TW-S320V, Leodol TW-O120V, Leodol TW-O106V, Leodol TW-IS399C, Leodol Super TW-L120, Leodol 430V, Leodol 440V, Leodol 460V, Leodol MS-50, Leodol MS-60, Leodol MO-60, Leodol MS-165V, Emanone 1112, Emanone 3199V, Emanone 3299V, Emanone 3299RV, Emanone 4110, Emanone CH-25, Emanone CH-40, Emanone CH-60 (K), Amate 102, Amate 105, Amate 105A, Amit 302, Amit 320, Aminone PK. -02S, Aminone L-02, Homogenol L-95, ADEKA Pluronic L-23, 31, 44, 61, 62, 6 manufactured by ADEKA Corporation. 4, 71, 72, 101, 121, ADEKA Pluronic TR-701, 702, 704, 913R and the like.

Examples of the cationic surfactant include alkyl amine salts, alkyl quaternary ammonium salts such as lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride and cetyl trimethyl ammonium chloride, and ethylene oxide adducts thereof.
Specific examples include Acetamine 24 and 26 manufactured by Kao Corporation, Coatamine 24P and 86P Conc, KP341 manufactured by Shin-Etsu Chemical Co., Ltd., and (meth) acrylic acid (co) polymer Polyflow No. manufactured by Kyoeisha Chemical Co., Ltd. 75, No. 90, No. 95 and the like.

  Examples of the anionic surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalene sulfonate, sodium alkyl diphenyl 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 ester and the like.

  Specific examples thereof include Neos Co., Ltd. Futgent 100 and 150, ADEKA Co., Ltd. ADEKA HOPE YES-25, ADEKA COL TS-230E, PS-440E, EC-8600 and the like.

The addition amount of the leveling agent in the photosensitive coloring composition of the present invention is preferably 0.001 to 2.0 mass% with respect to the total solid content of the composition of the present invention, and more preferably 0.005 to 1. It is 0 mass%. Within this range, the object of the present invention can be achieved more preferably.
The photosensitive coloring composition of the present invention may include only one type of surfactant, or may include two or more types of surfactant. When two or more kinds are contained, the total amount is preferably within the above range.

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

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

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

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

Further, the content of the thiol chain transfer agent is preferably 0.05 to 10% by mass, and more preferably 0.1 to 8.0% by mass, based on the total solid content of the photosensitive coloring composition. Within this range, the effect of the chain transfer agent becomes large, and the sensitivity, taper shape, wrinkles, and film shrinkage ratio become good.

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

  As the polymerization inhibitor, catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol. , 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert- Alkylcatechol compounds such as butylcatechol, 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresor Alkylresorcinol compounds such as cinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, Alkylhydroquinone compounds such as 2,5-di-tert-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, trioctylphosphine oxide, triphenylphosphine oxide, etc. Phosphine oxide compounds, triphenyl phosphite, trisnonyl phenyl phosphite and other phosphite compounds , Pyrogallol, and the like phloroglucinol. The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass with respect to 100 parts by mass of the photosensitive coloring composition excluding the solvent. Within this range, the effect of the polymerization inhibitor becomes large, and the linearity of the taper, the wrinkles of the coating film, the pattern resolution and the like are improved.

<Sensitizer>
Further, the photosensitive coloring composition of the present invention may contain a sensitizer.
Examples of the sensitizer include chalcone derivatives, unsaturated ketones represented by dibenzalacetone, etc., 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives. , Polymethine dyes such as xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonole derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, Trapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, anulene derivative, spiropyran derivative, spirooxazine Derivative, thiospiropyran derivative, metal arene complex, organic ruthenium complex, or Michler's ketone derivative, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzophenone , 4,4′-bis (diethylamino) benzophenone and the like.

  Among the above sensitizers, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are particularly preferable as the sensitizers that can be sensitized. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis. (Dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.

These sensitizers may be used alone or in a mixture of two or more at an arbitrary ratio, if necessary.
Examples of commercially available products include "KAYACURE DETX-S" (2,4-diethylthioxanthone manufactured by Nippon Kayaku Co., Ltd.) and "CHEMARK DEABP"(4,4'-bis (diethylamino) benzophenone manufactured by Chemchemical Chemical).

  More specifically, Nobu Okawara et al., "Dye Handbook" (1986, Kodansha), Nobu Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Tadaburo Ikemori et al. Examples of the sensitizer include those described in "Special Functional Material" (1986, CMC), but are not limited thereto. In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region may be contained.

  The content when the sensitizer is used is preferably 3 to 60 parts by mass with respect to 100 parts by mass of the radical photopolymerization initiator contained in the photosensitive coloring composition, and the content of photocurability and developability is From the viewpoint, it is more preferably 5 to 50 parts by mass.

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

  The content of the ultraviolet absorber is preferably 5 to 70% by mass in the total 100% by mass 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, the resolution cannot be secured, 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. There may be a problem such as an accident.

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

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

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

  Examples of the benzotriazole-based organic compound are 2- (5methyl-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-tbutyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy -5'-t-octylphenyl) benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3- (2H-benzotriazol-2-yl)-(1,1- Dimethylethyl) -4-hydroxy, a mixture of C7-9 side chain and straight chain alkyl esters, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1 , 3,3-Tetramethylbutyl) phenol, methyl 3- (3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction product, 2 -(2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4 -(1,1,3,3-Tetramethylbutyl) phenol], 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (5-chloro-2H-benzo Lyazol-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-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate, 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate may be mentioned. In addition, oligomer type and polymer type compounds having a benzotriazole structure can also be used.

  More specifically, BASF Corporation TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130, ADEKA Corporation ADEKA STAB LA-29, LA-31RG, LA. -32, LA-36, Kemipro Chemicals Co., Ltd. KEMISORB71, 73, 74, 79, 279, Otsuka Chemical Co., Ltd. RUVA-93, etc. are mentioned.

  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-triazin-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) -glycidic acid 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-triazin-2-yl) -5- ( Hexyloxy) Nol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] phenol, 2,4,6-tris (2 -Hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine and the like. In addition, oligomer type and polymer type compounds having a triazine structure can also be used.

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

  Examples of the benzophenone-based organic compound 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'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octade Examples thereof include siloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

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

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

<Antioxidant>
The photosensitive coloring composition of the present invention may contain an antioxidant. The antioxidant is used to prevent the photopolymerization initiator and thermosetting compound contained in the photosensitive coloring composition from being oxidized and yellowing due to a heat step during heat curing or ITO annealing, and thus the transmittance of the coating film is reduced. Can be higher. Especially when the colorant concentration of the coloring composition is high, the amount of coating film cross-linking component decreases, so that the use of high-sensitivity cross-linking component and the increase in the amount of photopolymerization initiator, the phenomenon that the yellowing of the thermal process becomes strong Can be seen. Therefore, by containing 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 scavenging function or a peroxide decomposing function, and specifically, as a antioxidant, a hindered phenol type, a hindered amine type, a phosphorus type, or a sulfur type. System and hydroxylamine 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, from the viewpoint of compatibility of the transmittance and the sensitivity of the coating film, preferred are hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants or sulfur antioxidants. Agents.

  As the hindered phenol-based antioxidant, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,1,3-tris- (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -butane, 4,4′-butylidene-bis- (2-t -Butyl-5-methylphenol), 3- (3,5-di-t-butyl-4-hydroxyphenyl) stearyl propionate, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-) Hydroxyphenyl) propionate, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8, 1 -Tetraoxaspiro [5.5] undecane, 1,3,5-tris (3,5-di-t-butyl-4-hydroxyphenylmethyl) -2,4,6-trimethylbenzene, 1,3,5 -Tris (3-hydroxy-4-t-butyl-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,2'-methylenebis (6-t-butyl-4-ethylphenol), 2,2'thiodiethylbis- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, N, N-hexamethylenebis (3,3) 5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,6-bis (dodecylthiomethyl) ) -O -Cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis (octylthiomethyl) -o-cresol, bis [3- (3-methyl- 4-hydroxy-5-t-butylphenyl) propionic acid] ethylene bisoxybisethylene, 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2, 4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,2'-thio-bis- (6-t- Butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis- (4. -Dimethyl-phenol), 2,2'-methylene-bis- (6- (1-methyl-cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, etc. Can be mentioned. In addition, oligomer type and polymer type compounds having a hindered phenol structure can also be used.

  More specifically, ADEKA CORPORATION ADEKA STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330, Kemipro Corporation KEMINOX 101, 179, 76, 9425, IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, manufactured by BASF Corporation, Cyanox CY-1790, CY-2777, etc. manufactured by Sun Chemical Co., Ltd. Is mentioned.

  Examples of the hindered amine-based antioxidant include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate and tetrakis (2,2,6,6-tetramethyl). Methyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetra Methyl-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, dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2 Polycondensate with 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, An ester of 6-tetramethyl-1-piperidineethanol and 3,5,5-trimethylhexanoic acid, N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 2,6,6-Pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, decanedioic acid bis (2,2,6) , 6-Tetramethyl-1- (octyloxy)- -Piperidinyl) ester, the reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis (1,2,2,6,6-pentamethyl-4-pyrididyl) [[3,5-bis (1,1dimethyl Ethyl) -4-hydroxyphenyl] methyl] butyl malonate methyl 1,2,2,6,6-pentamethyl-4-pyridyridyl 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 esters, 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, ADEKA CORPORATION ADEKA STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87. , LA-402F, LA-502XP, Kamipro Kasei Co., Ltd. KAMISTAB29, 62, 77, 94, BASF Corporation Tinuvin249, TINUVIN111FDL, 123, 144, 292, 5100, Sun Chemical Co., Ltd. Siasorb UV-3346, UV-. 3529, UV-3853 and the like.

  Examples of phosphorus-based antioxidants include di (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, and 2,2'-methylenebis (4,6- Di-t-butylphenyl) 2-ethylhexylphosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tetra (C12-C15alkyl) -4,4'- Isopropylidene diphenyl diphosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl isodecyl phosphite, tris (isodecyl) phosphite, triphenyl phosphite, tetrakis (2,4-di-t-butylphenyl) -4 , 4-biphenyl diphosphonite Tris (tridecyl) phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenyltridecylphosphite, 4,4'isopropylidenediphenolalkylphosphite, 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'-butylidene bis (3-methyl-6-t-butylphenol) Phosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphite Diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3-bis (diphenoxyphosphoni Roxy) -benzene, ethyl bisphosphite (2,4-ditert-butyl-6-methylphenyl) and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  More specifically, ADEKA Corporation ADEKA STAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP, BASF Corporation IRGAFOS 168, Clariant Chemicals Corporation Hostanox P-. EPQ etc. are mentioned.

  Examples of 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 CORPORATION ADEKA STAB AO-412S, AO-503, Kemipro Chemical Co., Ltd. KEMINOX PLS, etc. are mentioned.

  These antioxidants can be used singly or as a mixture of two or more kinds at an arbitrary ratio according to need.

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

<Storage stabilizer>
The photosensitive coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. Examples thereof include organic phosphine and phosphite. 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>
The photosensitive coloring composition of the present invention may contain an adhesion improver such as a silane coupling agent in order to improve 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.

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

<Solvent>
The photosensitive coloring composition of the present invention contains a solvent in order to easily form a colored film by coating it on a substrate such as glass so as to have a dry film thickness of 0.2 to 5 μm. The solvent is selected in consideration of good coatability of the photosensitive coloring composition, solubility of each component of the photosensitive coloring composition, and safety.

As the solvent, a solvent usually used in this field can be used, and in consideration of performance such as boiling point, SP value, evaporation rate, viscosity, etc., it may be used alone or in accordance with coating conditions (speed, drying conditions, etc.). Used as a mixture.
Examples of the solvent used include ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-). , An ether ester solvent (a solvent containing -COO- and -O- in the molecule), a ketone solvent (a solvent containing -CO- in the molecule and not containing -COO-), an alcohol solvent (OH in the molecule). And a solvent containing no —O—, —CO— and —COO—), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide and the like.

  As the ester solvent, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate. , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

  As the ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl -n- propyl ether, anisole, phenetole, and the like methyl anisole.

  Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and 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 ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol diacetate.

  As the ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, isophorone And so on.

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

  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.

  Of the above solvents, it is preferable to include an organic solvent having a boiling point of 120 ° C. or more and 180 ° C. or less at 1 atm from the viewpoints of coating properties and drying properties. 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.

<Method for producing photosensitive coloring composition>
The photosensitive coloring composition included in the present invention comprises a pigment, a kneader, a two-roll mill, a three-roll mill, and a ball mill in a dispersant, a binder resin and / or a solvent, preferably together with a dye derivative or a surfactant. , A horizontal sand mill, a vertical sand mill, an annular bead mill, an attritor, or other various dispersing means can be used for fine dispersion. At this time, two or more kinds of pigments may be simultaneously dispersed in the color carrier, or the pigment carriers may be separately dispersed and mixed.

  Further, the photosensitive coloring composition can be prepared by mixing a photopolymerizable monomer and / or a photopolymerization initiator with a solvent, another dispersion aid, an additive, etc., if necessary. .. The photopolymerization initiator may be added at the stage of preparing the photosensitive coloring composition, or may be added later to the prepared photosensitive coloring composition.

<Removal of coarse particles>
The photosensitive coloring composition of the present invention has a coarse particle of 5 μm or more, preferably a coarse particle of 1 μm or more, more preferably a coarse particle of 0.5 μm or more, by means such as centrifugation, filtration with a sintering filter or a membrane filter. It is preferred to remove particles and entrained dust. As described above, it is preferable that the photosensitive coloring composition does not substantially contain particles of 0.5 μm or more. It is more preferably 0.3 μm or less.

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

<Colorant used for filter segment>
The photosensitive coloring composition of the present invention is used to form a red filter segment.
As the pigment used in the filter segments other than the green filter segment, organic or inorganic pigments can be used alone or in combination of two or more. The pigment is preferably a pigment having high color development and high heat resistance, particularly a pigment having high thermal decomposition resistance, and an organic pigment is usually used. Specific examples of usable organic pigments are shown below by color index numbers.

(Green filter segment)
Examples of the green pigment used in the green photosensitive coloring composition for forming the green filter segment include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, and the like, but are not particularly limited thereto. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Green 7, 36, 58, 59, 62, 63.

Examples of the yellow pigment used in combination with the green pigment include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82,185,187,188,192,193,194,196,198,199,213,214,231, also can be mentioned pigments described in JP-A-2012-226110. Preferably C.I. I. Pigment Yellow 138, 139, 150, 185, 231.

(Blue filter segment)
Examples of the blue pigment used in the blue photosensitive coloring composition for forming the blue filter segment include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, and more preferably C.I. I. Pigment Blue 15: 6. Further, a purple pigment or dye (a) described below may be used in combination with the blue photosensitive coloring composition.

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

  The cyan photosensitive coloring composition for forming the cyan filter segment includes, for example, C.I. I. Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81 and the like can be used alone or in combination.

  The magenta color photosensitive coloring composition for forming the magenta color filter segment includes, for example, C.I. I. Pigment Violet 1, 19, C.I. I. Pigment Red 144, 146, 177, 169, 81 and other violet pigments and red pigments may be used alone or in combination. A yellow pigment can be used in combination with the magenta color composition.

Further, as inorganic pigments, titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine blue, navy blue, chromium oxide green, cobalt green, amber , Synthetic iron black and the like. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability, etc., while maintaining a balance between saturation and lightness.

<Other colorants>
The photosensitive coloring composition of the present invention may contain a coloring agent such as a dye other than the pigment (A).

<Dye (a)>
As the dye, any of an acid dye, a direct dye, a basic dye, a salt-forming dye, an oil-soluble dye, a disperse dye, a reactive dye, a mordant dye, a vat dye, a sulfur dye and the like can be used. Further, it may be in the form of a derivative thereof or a lake pigment in which a dye is laked.

Furthermore, acidic dyes having acidic groups such as sulfonic acid and carboxylic acid, in the case of direct dyes, inorganic salts of acidic dyes, acidic dyes and quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, Alternatively, a salt-forming compound with a nitrogen-containing compound such as a primary amine compound, or salt-forming using a resin component having these functional groups to be used as a salt-forming compound, or sulfonamide-forming to be used as a sulfonic acid amide compound It is preferable that the photosensitive coloring composition has excellent fastness because it has excellent durability.
Further, a salt-forming compound of an acid dye and a compound having an onium base is also preferable because it is excellent in fastness, and more preferably, a compound having an onium base is a resin having a cationic group in its side chain.

  In the case of a basic dye, it can be used by salification using an organic acid, perchloric acid or a metal salt thereof. Among them, a salt forming compound of a basic dye is preferable because it is resistant and excellent in combination with a pigment, and further, a basic dye and an organic sulfonic acid, an organic sulfuric acid, or a fluorine group-containing phosphorus that is a counter component that acts as a counter ion. 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 a salt-forming compound prepared by salting with an acid dye may be used. It is more preferable.

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

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

  Among these pigment structures, from the viewpoint of color characteristics such as hue, color separation, and color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium. -Based dyes, quinophthalone-based dyes, phthalocyanine-based dyes, sub-phthalocyanine-based dyes preferably have a dye structure derived from a dye, and xanthene-based dyes, cyanine-based dyes, triphenylmethane-based dyes, anthraquinone-based dyes, dipyrromethene-based dyes, phthalocyanines A dye structure derived from a dye selected from the group-based dyes is more preferable. Specific dye compounds capable of forming a dye structure are described in "New Edition Dye Handbook" (edited by The Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and colors), "Dye Handbook" (Okawara et al.). Ed .; Kodansha, 1986) and the like.

<Method of manufacturing color filter>
The color filter can be manufactured by a printing method or a photolithography method.
Since the formation of the filter segment by the printing method can be patterned by simply printing and drying the photosensitive coloring composition prepared as the printing ink, the method for producing the color filter is low cost and excellent in mass productivity. .. Furthermore, the development of printing technology enables printing of fine patterns having high dimensional accuracy and smoothness. For printing, it is preferable that the composition is such that the ink does not dry and solidify on the printing plate or on the blanket. In addition, it is 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 the filter segment is formed by the photolithography method, the photosensitive coloring composition prepared as the solvent-developing or alkali-developing colored resist material is spray-coated, spin-coated, slit-coated or roll-coated on a transparent substrate. The coating method is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed (irradiated with radiation) through a mask having a predetermined pattern which is provided in contact with or not in contact with the film. After that, after immersing in a solvent or an alkali developing solution or spraying a developing solution 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 produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, it is possible to heat it if necessary. According to the photolithography method, it is possible to manufacture a color filter with higher accuracy than the above printing method.

Upon development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as an 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 exposure sensitivity, after coating and drying the above-mentioned colored resist, a water-soluble or alkali water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is coated 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, etc. in addition to the above methods, and the photosensitive coloring composition of the present invention can be used in any method. The electrodeposition method is a method of producing a color filter by utilizing a transparent conductive film formed on a substrate to form each color filter segment on the transparent conductive film by electrophoretic deposition of colloidal particles. . The transfer method is a method in which a filter segment is previously formed 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 forming each color filter segment on the transparent substrate or the reflective substrate. As the black matrix, chromium, a chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed is used, but the black matrix is not limited thereto. It is also possible to previously form a thin film transistor (TFT) on the transparent substrate or the reflective substrate, and then form each color filter segment. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as needed.

  The color filter of the present invention is laminated with a counter substrate using a sealing agent, and after injecting liquid crystal from an injection port provided in the sealing portion, the injection port is sealed, and if necessary, a polarizing film or a retardation film is provided on the substrate. A color liquid crystal display device is manufactured by sticking it to the outside of the. This color liquid crystal display device includes Twisted Nematic (TN), Super Twisted Nematic (STN), In-Plane Switching (IPS), Vertically Alignment (VA), Optically Convenient Bend (OCB). ) And the like can be used for a liquid crystal display mode in which colorization is performed using a color filter.

  Further, the color filter of the present invention can be used for manufacturing a color solid-state image pickup device, an organic EL display device, a quantum dot display device, electronic paper, etc., in addition to the color liquid crystal display device.

<Liquid crystal display>
A liquid crystal display device including the color filter of the present invention will be described.
A 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. In the present invention, it is preferable to use the white LED because the red reproduction area is widened. FIG. 1 is a schematic sectional view of a liquid crystal display device 10 including a color filter of the present invention. The device 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 arranged facing each other with a space therebetween, and a liquid crystal LC is sealed between them.

  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 thereon. An alignment layer 14 is provided on the transparent electrode layer 13. A polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

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

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

  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.

  As the white LED light source, there are one in which a fluorescent filter is formed on the surface of a blue LED and one in which a fluorescent substance is contained in a resin package of the blue LED, and there are wavelengths at which the emission intensity becomes maximum in the range of 430 nm to 485 nm ( λ3), has a wavelength (λ4) that maximizes the emission intensity within the range of 530 nm to 580 nm, has a wavelength (λ5) that maximizes the emission intensity within the range of 600 nm to 650 nm, and has a wavelength The ratio (I4 / I3) of the emission intensity I3 at λ3 and the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio of the emission intensity I3 at wavelength λ3 and the emission intensity I5 at wavelength λ5 (I5 / I3 ) Is 0.1 or more and 1.3 or less and has a white LED light source (LED1) having a spectral characteristic, or a wavelength (λ1) having the maximum emission intensity within the range of 430 nm to 485 nm. Has a peak wavelength (λ2) of the second emission intensity in the range of 530 nm to 580 nm, and the ratio (I2 / I1) of the emission intensity I1 at the wavelength λ1 and the emission intensity I2 at the wavelength λ2 is 0.2 or more 0. A white LED light source (LED2) having a spectral characteristic of 0.7 or less is preferable.

  Specific examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nichia) and NSSW304D-HG-V1 (manufactured by Nichia).

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

  The present invention will be described below with reference to examples. In addition, "part" and "%" in an Example represent a "mass part" and "mass%", respectively.

  Weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), amine value (mgKOH / g), ammonium salt relating to resins such as binder resins, resin-type dispersants, and resins for forming dye salts The values (mgKOH / g) are as follows.

<Weight average molecular weight (Mw), number average molecular weight (Mn),>
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as a device, two separation columns were connected in series, and "TSK-GEL SUPER HZM-N" was used in a double connection for both packings, and an oven temperature of 40 Measurement was carried out at a flow rate of 0.35 ml / min using a THF solution as an eluent at ℃. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent and injected in an amount of 20 microliters. All molecular weights are polystyrene equivalent values.

<Acid value (mgKOH / g)>
To 0.5 to 1 g of the resin solution, 80 ml of acetone and 10 ml of water were added and stirred to be uniformly dissolved, and a 0.1 mol / L KOH aqueous solution was used as a titration liquid to prepare an automatic titrator (“COM-555” manufactured by Hiranuma Sangyo Co., Ltd.). ) Was used to measure the acid value (mgKOH / g) of the resin solution. 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.

<Amine value (mgKOH / g)>
The amine value is a value obtained by converting the measured total amine value (mgKOH / g) into solid content according to the method of ASTM D 2074.

<Ammonium salt value (mgKOH / g)>
The ammonium salt value is a value obtained by titrating with an aqueous solution of 0.1 N silver nitrate using a 5% potassium chromate aqueous solution as an indicator, and then converted into the equivalent of potassium hydroxide, and represents the ammonium salt value of the nonvolatile content.

<Synthesis of Pigment (A)>
<Synthesis of Diketopyrrolopyrrole Pigment (A-a)>
To a stainless steel reaction vessel equipped with a reflux tube, under a nitrogen atmosphere, 200 parts of tert-amyl alcohol dehydrated with molecular sieves and 140 parts of sodium-tert-amyl alkoxide were added, and the mixture was heated to 100 ° C. with stirring to give an alcoholate solution. Prepared. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and heated to 90 ° C. with stirring to dissolve them to prepare a solution of these mixtures. The heated solution of this mixture was slowly added dropwise to the above alcoholate solution heated to 100 ° C. at a constant rate over 2 hours with vigorous stirring. After completion of the dropping, heating and stirring were continued at 90 ° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Further, 600 parts of methanol, 600 parts of water and 304 parts of acetic acid were added to a reaction container with a glass jacket and cooled to -10 ° C. This cooled mixture was cooled to 75 ° C. while rotating a share disk having a diameter of 8 cm at 4000 rpm by using a high-speed stirring disperser, and the alkali metal salt of the diketopyrrolopyrrole compound thus obtained The solution was added in small portions. At this time, the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C. while cooling so that the temperature of the mixture of methanol, acetic acid, and water always maintained at −5 ° C. or lower. Was added in small portions over approximately 120 minutes. After the addition of the alkali metal salt, red crystals were precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 ° C. and then filtered to obtain a red paste. This paste was redispersed in 3500 parts of methanol cooled to 0 ° C. to prepare a suspension having a methanol concentration of about 90%, stirred at 5 ° C. for 3 hours, and subjected to particle sizing accompanied by crystal transition and washing. Subsequently, the mixture was filtered with an ultrafilter, and the obtained water paste of the diketopyrrolopyrrole compound was dried at 80 ° C. for 24 hours and pulverized to diketopyrrolopyrrole pigment (A-a) 150. .8 parts were obtained.

<Synthesis of Diketopyrrolopyrrole Pigment (Ab)>
(Diketopyrrolopyrrole pigment (A-b_1))
While 220 parts of tert-amyl alcohol was put in the reaction vessel 1 and 32 parts of 60% NaH was added while cooling with a water bath, the mixture was heated and stirred at 90 ° C. Next, 100 parts of tert-amyl alcohol, 85.0 parts of the compound of the following chemical formula (8) synthesized by the method of Tetrahedron, 58 (2002) 5547-5565, and 60.9 parts of 4-cyanobiphenyl were heated in a reaction vessel 2. It was made to melt | dissolve and this was dripped at the reaction container 1 over 2 hours. After reacting at 120 ° C. for 10 hours, the mixture was cooled to 60 ° C., 400 parts of methanol and 50 parts of acetic acid were added, followed by filtration and washing with methanol, and diketopyrrolopyrrole pigment (A-b_1) 88. I got one copy.

(Diketopyrrolopyrrole pigment (A-b_2))
Diketopyrrolopyrrole pigment was prepared in the same manner as the diketopyrrolopyrrole pigment (Ab_1), except that 60.9 parts of 4-cyanobiphenyl was changed to 54.1 parts of 4-tert-butylbenzonitrile. 83.9 parts of (Ab_2) was obtained.

(Diketopyrrolopyrrole pigment (A-b_3))
Diketopyrrolopyrrole pigment was prepared in the same manner as the diketopyrrolopyrrole pigment (Ab_1) except that 60.9 parts of 4-cyanobiphenyl was changed to 68.7 parts of N-butyl-4-cyanobenzamide. 87.0 parts of pigment (A-b_3) was obtained.

(Diketopyrrolopyrrole pigment (A-b_4))
Diketopyrrolopyrrole pigment was prepared in the same manner as the diketopyrrolopyrrole pigment (Ab_1) except that 60.9 parts of 4-cyanobiphenyl was changed to 75.5 parts of N-phenyl-4-cyanobenzamide. 86.9 parts of pigment (A-b_4) was obtained.

(Diketopyrrolopyrrole pigment (A-b_5))
Diketopyrrolopyrrole pigment (Ab_1) was prepared in the same manner as in diketopyrrolopyrrole pigment (Ab_1) except that 60.9 parts of 4-cyanobiphenyl was changed to 87.8 parts of N, N-dibutyl-4-cyanobenzamide. 87.1 parts of a pyrrole pigment (Ab_5) was obtained.

(Diketopyrrolopyrrole pigment (A-b_6))
While 220 parts of tert-amyl alcohol was put in the reaction vessel 1 and 32 parts of 60% NaH was added while cooling with a water bath, the mixture was heated and stirred at 90 ° C. Then, 100 parts of tert-amyl alcohol, 99.2 parts of the compound of the following chemical formula (9) synthesized by the method of Tetrahedron, 58 (2002) 5547-5565, and 60.9 parts of 4-cyanobiphenyl were heated in a reaction vessel 2. It was made to melt | dissolve and this was dripped at the reaction container 1 over 2 hours. After reacting at 120 ° C. for 10 hours, the mixture was cooled to 60 ° C., 400 parts of methanol and 50 parts of acetic acid were added, followed by filtration and washing with methanol, and diketopyrrolopyrrole pigment (Ab_6) 87. 8 parts were obtained.

(Diketopyrrolopyrrole pigment (A-b_7))
Diketopyrrolopyrrole pigment (Ab_6) was prepared in the same manner as in the diketopyrrolopyrrole pigment (Ab_6) except that 60.9 parts of 4-cyanobiphenyl was changed to 87.8 parts of N, N-dibutyl-4-cyanobenzamide. 87.1 parts of a pyrrole pigment (Ab_7) was obtained.

<Diketopyrrolopyrrole Pigment (A-c)>
C. I. Pigment Red 254 (“Irgafore Red B-CF” manufactured by BASF) was used as the pigment (A-c).

<Miniaturization of diketopyrrolopyrrole pigment>
The diketopyrrolopyrrole pigment produced as described above was micronized as described below, and P-1 to 10 shown in Tables 1-1 to 3 were obtained.

(Micronized diketopyrrolopyrrole pigment (P-1))
100 parts of diketopyrrolopyrrole pigment (A-a), 1000 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 60 ° C. for 10 hours. Next, the kneaded mixture is poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed with water to remove salt and diethylene glycol, and then dried at 80 ° C. for one day and pulverized. As a result, 96.9 parts of finely divided diketopyrrolopyrrole pigment (P-1) was obtained.

(Micronized diketopyrrolopyrrole pigment (P-2 to 10))
Hereinafter, as shown in Tables 1-1 to 3, except that the composition and the blending amount were changed, the micronized diketopyrrolopyrrole pigment (P-1) was prepared in the same manner as the micronized diketopyrrolopyrrole pigment (P-2). 10) was obtained.

<Method for producing other coloring agent (AS)>
(Colorant (AS-1))
C. I. Pigment Red 177 ("Chlomophthal Red A2B" manufactured by BAS-F): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kept at 120 ° C for 8 hours. Kneaded 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 repeatedly with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. Then, a colorant (AS-1) was obtained.

(Colorant (AS-2))
C. I. Pigment Red 269 (“Toner Magenta F8B” manufactured by Clariant), 800 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 5 hours. This mixture was poured into 4000 parts of warm water and stirred at a high speed mixer for about 1 hour while heating to about 80 ° C to form a slurry, which was repeatedly filtered and washed with water to remove salt and solvent, and then at 80 ° C for 24 hours. It dried and the coloring agent (AS-2) was obtained.

(Colorant (AS-3))
A colorant (AS-3) represented by the following chemical formula (10) was obtained by the same production method as the red colorant 1 (R-1) described in the example of Japanese Patent No. 6350885.

(Colorant (AS-4))
C. I. Pigment Yellow 138 (manufactured by BAS-F "Paritor Yellow K0961HD") 100 parts, crushed salt 800 parts, and diethylene glycol 180 parts were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C for 4 hours. .. This mixture was poured into 3000 parts of warm water and stirred at a high speed mixer for about 1 hour while heating at about 80 ° C to form a slurry, which was repeatedly filtered and washed with water to remove salt and solvent, and then at 80 ° C for 24 hours. It dried and obtained the coloring agent (AS-4).

(Colorant (AS-5))
A colorant (AS-5) represented by the following chemical formula (11) was obtained by the same production method as the yellow colorant 8 (Y-8) described in the example of Japanese Patent No. 4993026.

(Colorant (AS-6)
According to the synthetic method described in JP 2012-226110 A, a compound represented by the following chemical formula (12) was obtained. 40 parts of the chemical formula (12) and 22 parts of N-bromosuccinimide were added to 300 parts of N, N-dimethylformamide, and the mixture was stirred at 80 ° C for an hour. The reaction mixture was poured into a stirred mixed solvent of 300 parts of methanol / 700 parts of water and stirred at room temperature for 1 hour. The produced precipitate was filtered, washed with water, washed with methanol and washed with water in this order, and dried to obtain 48 parts of Intermediate (a-1). The obtained Intermediate (a-1) (45 parts), tetrachlorophthalic anhydride (37 parts) and benzoic acid (35 parts) were added to methyl benzoate (100 parts), and the mixture was heated with stirring at 160 ° C. for 4 hours. After cooling to room temperature, the reaction mixture was added to 1000 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol and dried to obtain 65 parts of a quinophthalone compound. 100 parts of the quinophthalone compound, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, this kneaded product was poured into warm water and stirred for 1 hour while heating to about 70 ° C. to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for one day and night. A colorant (AS-6) represented by the following chemical formula (13) was obtained.

(Colorant (AS-7))
To 1200 parts of 98% sulfuric acid, 150 parts of 2,3-naphthalenedicarboxylic acid anhydride and 230 parts of trichloroisocyanuric acid were added and reacted at 80 ° C. for 4 hours. The reaction solution was poured into 9000 parts of stirred ice water, and the generated precipitate was filtered, washed with water, washed with a 1% sodium hydroxide aqueous solution and washed with water in this order, and dried to obtain an intermediate (a-2). 220 parts were obtained. 105 parts of the compound represented by the chemical formula (12), 150 parts of intermediate (a-2) and 100 parts of benzoic acid were added, and the mixture was heated to 180 ° C. and stirred for 4 hours. Further, after cooling to room temperature, the reaction mixture was put into 5000 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol, and dried to obtain 183 parts of a quinophthalone compound. 100 parts of the quinophthalone compound, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, this kneaded product was poured into warm water and stirred for 1 hour while heating to about 70 ° C. to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for one day and night. A colorant (AS-7) represented by the following chemical formula (14) was obtained.

(Colorant (AS-8))
In the synthesis of the intermediate (a-2), an intermediate (a-3) was obtained by a similar method except that 350 parts of trichloroisocyanuric acid was changed to 244 parts of N-bromosuccinimide. When the number of bromine substituents was calculated for the intermediate (a-3), it was 1.5 on average.
To 200 parts of methyl benzoate, 50 parts of 8-aminoquinaldine, 115 parts of the intermediate (a-2) and 140 parts of benzoic acid were added, and the mixture was stirred at 120 ° C. for 4 hours. Then, 143 parts of Intermediate (a-3) was further added to the reaction mixture, heated to 180 ° C., and stirred for 4 hours while distilling water off. After cooling to room temperature, the reaction mixture was added to 2000 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol and dried to obtain a quinophthalone compound. 100 parts of the quinophthalone compound, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, this kneaded product was poured into warm water and stirred for 1 hour while heating to about 70 ° C. to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for one day and night. A colorant (AS-8) represented by the following chemical formula (15) was obtained.

(Colorant (AS-9))
C. I. 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) and kneaded at 60 ° C. for 10 hours. Next, this mixture was poured into 3 liters of warm water, stirred with a high speed mixer for about 1 hour while heating to about 80 ° C. to form a slurry, and filtration and washing with water were repeated to remove sodium chloride and the solvent. It was dried at ℃ for 1 day to obtain a colorant (AS-9).

(Colorant (AS-10))
C. I. Pigment Yellow 139 (“Irgafore Yellow 2R-CF” manufactured by BAS-F), 1600 parts of sodium chloride, and 190 parts of diethylene glycol are charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and the temperature is 60 ° C. for 10 hours. Kneaded Next, this mixture was poured into 3 liters of warm water, stirred with a high speed mixer for about 1 hour while heating to about 80 ° C. to form a slurry, and filtration and washing with water were repeated to remove sodium chloride and the solvent. It was dried at ℃ for 1 day to obtain a coloring agent (AS-10).

(Colorant (AS-11))
C. I. Pigment Yellow 185 (BAS-F "Paritor Yellow D1155") 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C for 8 hours. did. Next, the kneaded product was poured 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. overnight. , And a colorant (AS-11) was obtained.

<Other Coloring Agents: Method for Producing Dye Resin Salt (AS-12-14)>
Resin 1 having a cationic group in the following side chain and each dye were used to produce resin salt-forming products (AS-12 to 14) of the dye.
(Resin 1 having a cationic group in the side chain)
A 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser was charged with 67.3 parts of methyl ethyl ketone and heated to 75 ° C. under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2'-azobis (2,4-dimethylvaleronitrile). (6) and 25.1 parts of methyl ethyl ketone were homogenized, then charged into a dropping funnel, attached to a 4-neck separable flask, and added dropwise over 2 hours. Two hours after the completion of the dropping, it was confirmed that the polymerization yield was 98% or more based on the nonvolatile content, and the weight average molecular weight (Mw) was 6830, and the mixture was cooled to 50 ° C. Methyl chloride (3.2 parts) and ethanol (22.0 parts) were added thereto, reacted at 50 ° C for 2 hours, heated to 80 ° C over 1 hour, and further reacted for 2 hours. In this way, Resin 1 having a cationic group in the side chain having a resin component of 47 mass% was obtained. The ammonium salt value of the obtained resin was 34 mgKOH / g.

(Other colorants (AS-12))
To 2000 parts of water, 30 parts of the side chain having a cationic group as a non-volatile component was added, and the resin 1 was sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, 90 parts of water to 10 parts of C.I. I. An aqueous solution in which Acid Red 52 was dissolved was prepared and added dropwise to the above resin solution little by little. After the dropping, the mixture was stirred at 60 ° C. for 120 minutes to carry out a sufficient reaction. To confirm the end point of the reaction, it was determined that the salt-forming compound was obtained by dripping the reaction solution onto a filter paper and observing the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing water with a drier, and C.I. I. A colorant (AS-12), which is a salt-forming compound of Acid Red 52 and Resin 1 having a cationic group in its side chain, was obtained. At this time, C.I. in the colorant (AS-12) was used. I. The content of the effective pigment component derived from Acid Red 52 was 25% by mass.

(Other colorants (AS-13))
C. I. Acid Red 52 to C.I. I. Acid Red 289, except that the colorant (AS-12) was produced in the same manner as C.I. I. A colorant (AS-13) which is a salt-forming compound of Acid Red 289 and Resin 1 having a cationic group in its side chain was obtained. At this time, C.I. in the coloring agent (AS-13) was used. I. The content of the effective pigment component derived from Acid Red 289 was 27% by mass.

(Other colorants (AS-14))
In a 1 L stainless steel reaction vessel equipped with a reflux tube, under a nitrogen atmosphere, C.I. I. Basic Violet 10 (BV10: manufactured by Taoka Chemical Co., Ltd .: Rodamine B) 5.0 parts and hydroxyethyl methacrylate (HEMA) 1.6 parts were dissolved in 40 ml of dichloromethane to prepare 1- (3-dimethylaminopropyl) -3-ethyl. 2.2 parts of carbodiimide hydrochloride and 0.25 parts of dimethylaminopyridine were added, and the mixture was stirred at room temperature for 24 hours. The obtained dichloromethane solution was washed with water, dried under reduced pressure, and purified with a silica gel column to obtain a coloring agent (AS-14).

(Production of resin type dispersant (B))
In a reaction tank equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, trimellitic anhydride 3 parts, 3-mercapto-1,2-propanediol 1 part, propylene glycol monomethyl ether acetate 50 parts, dimethylbenzylamine 0.1 part was charged. After purging with nitrogen gas, the inside of the reaction vessel was heated to 120 ° C. and reacted for 4 hours, and then reacted at 80 ° C. for 2 hours. Furthermore, 30 parts of tertiary butyl acrylate, 20 parts of oxetane methacrylate, 5 parts of methacrylic acid, 40 parts of ethyl acrylate, and 10 parts of propylene glycol monomethyl ether acetate were charged, and 2,2'-azobisisosine was maintained while maintaining the reaction vessel at 80 ° C. 0.2 parts of butyronitrile was added in 15 batches every 30 minutes. One hour after the final addition, the solid content was measured to confirm that 95% of the monomers had reacted. Resin type dispersant (B) liquid having an acid value per solid content of 51 mgKOH / g and a number average molecular weight (Mn) of 8,000, which is diluted by adding propylene glycol monomethyl ether acetate so that the solid content is 40%. Got

<Dye derivative>
The following pigment derivatives were used.

(Derivative 1)

(Derivative 2)

<Production Example of Binder Resin (C1: Non-Photosensitive Resin)>
(Preparation of Binder Resin (C1-1) Solution)
Charge 196 parts of propylene glycol monomethyl ether acetate into a reaction vessel equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirrer in a separable 4-neck flask, raise the temperature to 80 ° C., and replace the inside of the reaction vessel with nitrogen. After that, from a dropping pipe, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) ) A mixture of 20.7 parts and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content, and the propylene glycol monomethyl ether was added to the resin solution synthesized above so that the nonvolatile content was 20%. A binder resin (C1-1) solution was prepared by adding acetate. The weight average molecular weight (Mw) was 26000.

(Preparation of Binder Resin (C1-2) Solution)
A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was filled with a nitrogen atmosphere, 210 parts of propylene glycol monomethyl ether acetate was added, and the temperature was raised to 100 ° C. with stirring. Next, 106 parts of benzyl methacrylate, 22 parts of acrylic acid and 22 parts of dicyclopentanyl methacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were dissolved in 215 parts of propylene glycol monomethyl ether acetate, and 2,2′-azobis was further added. A solution prepared by dissolving 3.6 parts of isobutyronitrile was dropped into the flask, and stirring was continued at 100 ° C. for 5 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content, and the propylene glycol monomethyl ether was added to the resin solution synthesized above so that the nonvolatile content was 20%. A binder resin was prepared by adding acetate to obtain a resin (C1-2) solution having a weight average molecular weight (Mw) of 10,000.

(Preparation of binder resin (C1-M) liquid)
The binder resin (C1-1) liquid and the binder resin (C1-2) liquid were mixed and stirred in the same amount to prepare a binder resin (C1-M) liquid.

<Production Example of Binder Resin (C2: Photosensitive Resin)>
(Preparation of Binder Resin (C2-1) Solution)
A separable 4-neck flask was charged with 207 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a thermometer, a cooling pipe, a nitrogen gas introducing pipe, a dropping pipe and a stirring device, heated to 80 ° C., and the inside of the reaction container was replaced with nitrogen. Then, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2 from a dropping pipe. A mixture of 1.33 parts of'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, with respect to the total amount of the obtained copolymer solution, nitrogen gas was stopped, and after stirring while injecting dry air for 1 hour, after cooling to room temperature, 2-methacryloyloxyethyl isocyanate (Karenzu manufactured by Showa Denko KK) A mixture of 6.5 parts of MOI), 0.08 part of dibutyltin laurate and 26 parts of propylene glycol monomethyl ether acetate was added dropwise at 70 ° C. over 3 hours. After the dropping was completed, the reaction was continued for another hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content, and the propylene glycol monomethyl ether was added to the resin solution synthesized above so that the nonvolatile content was 20%. A binder resin (C2-1) was prepared by adding acetate. The weight average molecular weight (Mw) was 18,000.

(Preparation of Binder Resin (C2-2) Solution)
In a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, 333 g of propylene glycol monomethyl ether acetate was introduced, and the atmosphere in the flask was changed from air to nitrogen, and then heated to 100 ° C., 70.5 g (0.40 mol) of benzyl methacrylate, 71.1 g (0.50 mol) of glycidyl methacrylate, and 22.0 g (0.10 mol of FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton monomethacrylate. ) And a mixture of 164 g of propylene glycol monomethyl ether acetate and 3.6 g of azobisisobutyronitrile were added dropwise to the flask through 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 43.0 g of methacrylic acid [0.5 mol, (100 mol% with respect to the glycidyl group of glycidyl methacrylate used in this reaction)], trisdimethylaminomethylphenol. 9 g and 0.145 g of hydroquinone were put into the flask, the reaction was continued at 110 ° C. for 6 hours, and the reaction was terminated when the acid value of solid content became 1 mgKOH / g. Next, 60.9 g (0.40 mol) of tetrahydrophthalic anhydride and 0.8 g of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a photosensitive transparent resin solution having an acid value of 80 mgKOH / g. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content, and the nonvolatile content of the photosensitive transparent resin solution synthesized above was 20% by mass. Thus, propylene glycol monomethyl ether acetate was added to prepare a binder resin (C2-2) solution. The weight average molecular weight (Mw) was 12,000.

(Adjustment of binder resin (C2-3) liquid)
A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 182 g of propylene glycol monomethyl ether acetate, the atmosphere in the flask was changed from air to nitrogen, and the temperature was raised to 100 ° C. 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, and 22.0 g (0.10 mol of FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton monomethacrylate. ) And 136 g of propylene glycol monomethyl ether acetate, and a solution of 3.6 g of azobisisobutyronitrile added thereto was added dropwise from the dropping funnel to the flask 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. 9 g and 0.145 g of hydroquinone were put into the 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 was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content, and the nonvolatile content of the photosensitive transparent resin solution synthesized above was 20% by mass. Thus, propylene glycol monomethyl ether acetate was added to prepare a binder resin (C2-3) solution. The weight average molecular weight (Mw) was 13,000.

(Preparation of Binder Resin (C2-4) Solution)
A separable flask equipped 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 methacrylic acid were used as a monomer dropping tank. A mixture of 120 parts of methyl, 4 parts of t-butyl peroxy-2-ethylhexanoate (“Perbutyl O 2” manufactured by NOF CORPORATION), and 40 parts of propylene glycol monomethyl ether acetate was thoroughly stirred and prepared, and a chain transfer agent dropping tank was prepared. As a mixture, 8 parts of n-dodecanethiol and 32 parts of propylene glycol monomethyl ether acetate were thoroughly stirred and mixed.
After 395 parts of propylene glycol monomethyl ether acetate was charged into the reaction tank and the atmosphere was replaced with nitrogen, the temperature of the reaction tank was raised to 90 ° C. by stirring in an oil bath. After the temperature of the reaction tank became stable at 90 ° C., dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was carried out for 135 minutes while maintaining the temperature at 90 ° C. 60 minutes after the dropping was completed, the temperature was raised to 110 ° C. in the reaction tank. After maintaining the temperature at 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of a mixed gas of oxygen / nitrogen = 5/95 (volume ratio) was started. Next, 70 parts of glycidyl methacrylate, 0.4 part of 2,2′-methylenebis (4-methyl-6-t-butylphenol) and 0.8 part of triethylamine were charged into a reaction tank and allowed to react at 110 ° C. for 12 hours. It was Then, 150 parts of propylene glycol monomethyl ether acetate was added and cooled 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 nonvolatile content. Propylene glycol monomethyl ether acetate was added to 20% by mass to obtain a binder resin (D-4) liquid. 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 (C2-M) Liquid)
The binder resins (C2-1) to (C2-4) liquids were mixed and stirred in the same amount to prepare a binder resin (C2-M) liquid.

(Adjustment of Polymerizable Compound (DM))
(D-1) Trimethylolpropane triacrylate
[Aronix M309 (manufactured by Toagosei Co., Ltd.)]
(D-2) Dipentaerythritol penta and hexaacrylate (E-2)
[Aronix M402 (manufactured by Toagosei Co., Ltd.)]
(D-3) Polybasic acidic acrylic oligomer
[Aronix M520 (manufactured by Toagosei Co., Ltd.)]
(D-4) Caprolactone-modified dipentaerythritol hexaacrylate
[KAYARAD DPCA-30 (Nippon Kayaku Co., Ltd.)]

(D-5) Polyfunctional urethane acrylate according to the following: Pentaerythritol triacrylate (432 g, hexamethylene diisocyanate 84 g) was charged into a 5-neck reaction vessel having an internal capacity of 1 liter and reacted at 60 ° C. for 8 hours to give a (meth) acryloyl group. A product containing a polyfunctional urethane acrylate (D-5) having a polyfunctional urethane acrylate (D-5) was obtained, the proportion of the polyfunctional urethane acrylate (D-5) in the product was 70% by mass, and the balance was other photopolymerizable It was occupied by the monomer, and it was confirmed by IR analysis that there were no isocyanate groups in the reaction product.

(D-6) Bifunctional bisphenol A type (meth) acrylate
[ABE-300 (Shin Nakamura Chemical Co., Ltd.)]
(D-7) Ethoxylated isocyanuric acid triacrylate
[A-9300 (Shin Nakamura Chemical Co., Ltd.)]
As described above, (D-1) to (D-7) were mixed in equal amounts to give a photopolymerizable monomer (DM).

<Production of Leveling Agent (F) Liquid>
(Production of Leveling Agent (FD-1-1) Solution)
In a reaction vessel purged with nitrogen, 117 parts by mass of methyl ethyl ketone, 50 parts by mass of 2-propanol, 4.69 parts by mass of 2,2′-bipyridyl and 1.49 parts by mass of cuprous chloride were charged and stirred at 20 ° C. for 30 minutes. .. Then, 78.1 parts by mass of 2-hydroxyethyl methacrylate and 2.93 parts by mass of ethyl 2-bromoisobutyrate were added, and the mixture was reacted at 20 ° C. for 16 hours under a nitrogen stream. Then, 45.8 parts by mass of methyl ethyl ketone, 19.5 parts by mass of 2-propanol, and 40 parts by mass of 2- (nonafluorobutyl) ethyl methacrylate represented by the following formula are added, and the temperature is raised to 60 ° C. to react for 8 hours. It was Further, 91.6 parts by mass of methyl ethyl ketone, 39 parts by mass of 2-propanol, and 80 parts by mass of 2- (nonafluorobutyl) ethyl methacrylate were added and reacted for 26 hours. This reaction mixture was dissolved in methanol and reprecipitated and purified with water / methanol to obtain a block polymer. 60 parts by mass of this block polymer is dissolved in 80 parts by mass of methyl ethyl ketone, 10 parts by mass of a tin 2-ethylhexanoate solution (0.2% by mass of methyl ethyl ketone solution), and 0.1 parts by mass of a polymerization inhibitor (p-methoxyphenol). Parts were added and the temperature was raised to 60 ° C. While introducing dry air into the liquid, 44.1 parts by mass of a 50% by mass solution of 2-acryloyloxyethyl isocyanate in methyl ethyl ketone was added dropwise, reacted for 1 hour, further reacted at 80 ° C. for 3 hours, and had a fluorine content of 20 mass. %, A solution of a fluorine-containing radical-polymerizable copolymer that is a block copolymer was obtained. Further, propylene glycol monomethyl ether acetate was added to the obtained polymer solution to obtain a solution containing 20% by mass of the fluorine radical-polymerizable copolymer.

(Production of Leveling Agent (FD-2-1 to 12) Solution)
Polymerization on the side chain or poly (perfluoroalkylene ether) chain having a fluorinated alkyl group shown in Table 2 and its terminal using methyl isobutyl ketone as a solvent and t-butylperoxy-2-ethylhexarate as a polymerization initiator. Polymerization reaction was carried out using a compound having a polymerizable unsaturated group and a polymerizable unsaturated monomer having an adamantyl group having a reactive functional group to obtain a fluororesin solution.
After cooling to room temperature, about 2 g of the fluororesin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether was added so that the non-volatile content was 20% by mass in the fluororesin solution. Acetate was added to obtain FD-2-1 to 12-12 shown in Table 2.

FD1 and FD2 in Table 2 are shown below.

下記式中の「−ＰＦＰＥ−」は、ポリ（パーフルオロアルキレンエーテル）鎖を示す。

"-PFPE-" in the following formula represents a poly (perfluoroalkylene ether) chain.

<Method for producing colored composition>
[Production Example 1]
(Preparation of colored composition (R-1))
The following mixture was 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.) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then the pore size was 5. The mixture was filtered through a 0 μm filter to prepare a colored composition (R-1) having a nonvolatile content of 20% by mass.
Pigment (P-1): 15.6 parts Resin type dispersant (B): Non-volatile content 40% liquid): 3.0 parts Binder resin (C1-M: Non-volatile content 20% liquid): 16.0 parts Solvent ( N): 65.4 parts

(Solvent (N))
However, the solvent (N) is a mixture of the following (N-1) to (N-6) in respective parts by mass.
(N-1) Propylene glycol monomethyl ether acetate 30 parts (N-2) Cyclohexanone 30 parts (N-3) Ethyl 3-ethoxypropionate 10 parts (N-4) Propylene glycol monomethyl ether 10 parts (N-5) cyclo Hexanol acetate 10 parts (N-6) dipropylene glycol methyl ether acetate 10 parts

[Production Examples 2 to 13]
(Preparation of colored composition (R-2 to 23))
Colored compositions (R-2 to 23) were produced in the same manner as in Production Example 1 except that the material types and the masses as described in Table 3 were changed.

[Production Example 101]
(Preparation of Colored Composition (X-1))
The following raw materials were mixed, stirred, and filtered with a filter having a pore size of 1.0 μm to obtain a colored composition (X-1).
Coloring composition (R-1: 20% non-volatile content liquid): 56 parts Binder resin (C1-M: 20% non-volatile content liquid): 32 parts Solvent (N: as described above): 12 parts

[Production Examples 102 to 129]
(Production of Colored Compositions (X-2 to 29))
Coloring compositions (X-2 to 29) were prepared in the same manner as in Production Example 101, except that the material types and parts by mass as shown in Table 4 were changed.

<Method for producing photosensitive coloring composition>
[Example 1]
(Photosensitive coloring composition (Y-1))
The following raw materials were mixed, stirred, and filtered with a filter having a pore size of 1.0 μm to obtain a photosensitive coloring composition (Y-1).
Coloring composition (X-1: non-volatile content 17.6%): 50.0 parts Binder resin (C2-M: non-volatile content 20%): 15.0 parts Thermosetting compound (C3-1): 1.0 Parts Thermosetting compound (C3-2): 1.0 part Polymerizable compound (D-1): 3.0 parts Photopolymerization initiator (E): 1.8 parts Sensitizer (I): 0.2 Part Thiol chain transfer agent (G-1): 0.4 part Polymerization inhibitor (H-1): 0.1 part Ultraviolet absorber (J): 0.1 part Antioxidant (K): 0.1 Parts leveling agent (FD-2-1: non-volatile content 3%): 1.0 part storage stabilizer (L): 0.1 part silane coupling agent (M): 0.2 part solvent (N): 26. Copy 0

[Examples 2 to 50, Comparative Examples 1 and 2]
(Preparation of Photosensitive Coloring Compositions (Y-2 to 52))
Photosensitive coloring compositions (Y-2 to 52) were prepared in the same manner as in Example 1 except that the types of the photosensitive coloring composition and the binder resin solution in Example 1 were changed as shown in Table 5. did.
The respective raw materials are as follows.

<Thermosetting compound (C3)>
・ Epoxy compound (C3-1)
1,2-Epoxy-4- (2-oxiranyl) cyclohexane adduct of (C3-1-1) 2,2'-bis (hydroxymethyl) -1-butanol
[EHPE-3150 (manufactured by Daicel)],
(C3-1-2) Glycidyl etherified epoxy compound of sorbitol
[Denacol EX611 (manufactured by Nagase Chemtex Corporation)],
(C3-1-3) Triglycidyl isocyanurate (C3-1-1) to (C3-1-3) were mixed in the same amount to obtain an epoxy compound (C3-1).
-Oxetane compound (C3-2):
3-Ethyl-3-[(3-ethyloxetane-3-yl) methoxymethyl] oxetane
[Aron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]

<Photopolymerization initiator (E)>
(E-1) 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one
[Irgacure 907 (manufactured by BASF Japan)]
(E-2) 2- (Dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone
[Irgacure 379 (manufactured by BASF Japan)]
(E-3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
[Lucirin TPO (Ciba Japan)]
(E-4) 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole
[Biimidazole (manufactured by Kurogane Kasei)]
(E-5) p-dimethylaminoacetophenone
[DMA (manufactured by Daiki Fine)]
(E-6) Ethan-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime)
[Irgacure OXE02 (manufactured by BASF Japan)]
(E-7) 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one
[Irgacure 2959 (manufactured by BASF Japan)]
(E-8) Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
[Irgacure 819 (manufactured by BASF Japan)]
As described above, (E-1) to (E-8) were mixed in the same amount to obtain a photopolymerization initiator (E).

<Sensitizer (I)>
(I-1) 2,4-diethylthioxanthone
[Kayakyu DETX-S (Nippon Kayaku Co., Ltd.)]
(I-2) 4,4'-bis (diethylamino) benzophenone
[CHEMARK DEABP (Chemmark Chemical Co.)]
As described above, (I-1) and (I-2) were mixed in the same amount to prepare a sensitizer (I).

<Thiol chain transfer agent (G)>
(G-1) trimethylolethane tris (3-mercaptobutyrate)
[TEMB (Showa Denko)]
(G-2) Trimethylolpropane tris (3-mercaptobutyrate)
[TPMB (Showa Denko)]
(G-3) Pentaerythritol tetrakis (3-mercaptopropionate)
[PEMP (made by Sakai Chemical Industry)]
(G-4) Trimethylolpropane tris (3-mercaptopropionate)
[TMMP (made by Sakai Chemical Industry)]
(G-5) Tris [(3-mercaptopropionyloxy) -ethyl] -isocyanurate
[TEMPIC (made by Sakai Chemical Industry)]

<Polymerization inhibitor (H)>
(H-1) 3-methylcatechol (H-2) methylhydroquinone (H-3) tert-butylhydroquinone

<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)]
(J-2) 2- (2H-benzotriazol-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 the same amount to obtain an ultraviolet absorber (J).

<Antioxidant (K)>
(K-1) pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (K-2) 3,3′-dioctadecyl thiodipropanoate (K-3) tris [2 , 4-di- (tert) -butylphenyl] phosphine (K-4) bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (K-5) p-octylphenyl salicylate or higher, (K -1) to (K-5) were mixed in the same amount to obtain an antioxidant (K).

<Other leveling agents (FM)>
"BYK-330: Polyether-modified polydimethylsiloxane" manufactured by BYK Chemie, 1 part,
A mixed solution prepared by dissolving 1 part of "Emulgen 103: polyoxyethylene lauryl ether" manufactured by Kao Corporation in 98 parts of propylene glycol monomethyl ether acetate.

<Storage stabilizer (L)>
(L-1) 2,6-bis (1,1-dimethylethyl) -4-methylphenol ("BHT" manufactured by Honshu Chemical Industry Co., Ltd.)
(L-2) Triphenylphosphine ("TPP" manufactured by Kitako Chemical Co., Ltd.)
As described above, (L-1) and (L-2) were mixed in the same amount to obtain a storage stabilizer (L).

<Silane coupling agent (M)>
(M-1) 3-glycidoxypropyltriethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-403 (Shin-Etsu Chemical Co., Ltd.)]
(M-2) 3-methacryloxypropyltriethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBE-503 (Shin-Etsu Chemical Co., Ltd.)]
(M-3) N-2- (aminoethyl) -3-aminopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-603 (Shin-Etsu Chemical Co., Ltd.)]
(M-4) 3-mercaptopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-803 (Shin-Etsu Chemical Co., Ltd.)]
As described above, (M-1) to (M-4) were mixed in the same amount to obtain a silane coupling agent (M).

<Evaluation of photosensitive coloring composition>
Each test was conducted by the following method. The test results are shown in Table 6.
[Pattern formation of filter segment]
The obtained photosensitive coloring composition was applied on a glass substrate of 10 cm × 10 cm by spin coating, and then heated in a clean oven at 70 ° C. for 15 minutes to remove the solvent, and a coating film of about 2 μm was obtained. .. Next, this substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask having a stripe pattern of 100 μm width (pitch 200 μm) and 25 μm width (pitch 50 μm) using an ultrahigh pressure mercury lamp. Then, this substrate was spray-developed with an aqueous sodium carbonate solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated in a clean oven at 230 ° C. for 30 minutes. The spray development was carried out for the coating film of each photosensitive coloring composition in the shortest time that pattern formation could be performed without development residue, and this was taken as the proper development time.
The film thickness of the coating film was measured using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).

[Pattern shape: linearity (pixel loss) evaluation]
The pattern of the 100 μm photomask portion of the filter segment formed by the above method was observed and evaluated using an optical microscope. The evaluation ranks are as follows.
◯: Good linearity: Good △: Poor linearity due to very few pixels missing: Practical range ×: Poor linearity due to missing pixels ： Not suitable for practical use

[Pattern shape: sectional evaluation]
The cross section of the pattern in the 100 μm photomask portion of the filter segment formed by the above method was observed and evaluated using an electron microscope. The pattern cross section has a good forward taper. The evaluation ranks are as follows.
◯: Forward tapered shape with gentle cross section: Good △: Forward tapered shape with cross section: Practical range ×: Reverse tapered shape with cross section: Not suitable for practical use

[Evaluation of solvent resistance]
The filter segment formed by the above method was immersed in an N-methylpyrrolidone solution for 30 minutes, washed with ion-exchanged water, air-dried, and evaluated by observing the pattern at the 100 μm photomask portion using an optical microscope. The evaluation ranks are as follows.
◯: Good with no change in appearance and color: Good △: Good with some wrinkles, but with no change in color ： Practical range ×: Peeling or discoloration occurred: Not suitable for practical use

10 Liquid Crystal Display Device 11 Transparent Substrate 12 TFT Array 13 Transparent Electrode Layer 14 Alignment Layer 15 Polarizing Plate 21 Transparent Substrate 22 Color Filter 23 Transparent Electrode Layer 24 Alignment Layer 25 Polarizing Plate 30 Backlight Unit 31 White LED Light Source LC Liquid Crystal

Claims (7)

A photosensitive coloring composition comprising a pigment (A), a dispersant (B), a binder resin (C), a polymerizable compound (D), a photopolymerization initiator (E) and a leveling agent (F), wherein the pigment (A) contains a brominated diketopyrrolopyrrole pigment represented by the following chemical formula (1), and the leveling agent (F) contains a fluorinated alkyl group and / or a poly (perfluoroalkylene ether) chain. A photosensitive coloring composition comprising a copolymer (FD) of the contained ethylenically unsaturated monomer (FD1) and another ethylenically unsaturated monomer (FD2).

Chemical formula (1)

The photosensitive coloring composition according to claim 1, further comprising a diketopyrrolopyrrole pigment represented by the following general formula (2).

General formula (2)


[In the general formula (2), X represents a chlorine atom or a bromine atom, and A and B are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, or a carbon number of 1 12 alkyl group, an optionally substituted phenyl ^{_{group, -CF 3, -OR 1, -SR}} 2, -N (R 3) R 4, -COOR 5, -CONH 2, -CONHR 6, ^{-CON (R 7) R 8,} -SO 2 NH 2, -SO 2 NHR 9, or a ^{_{-SO 2 N (R 10) R}} 11, R 1 ~R 11 are each independently, carbon atoms 1 to 12 alkyl group, a phenyl group which may have a substituent, or an aralkyl group which may have a substituent. However, A and B do not become hydrogen atoms at the same time. Further, A is X and B is not a hydrogen atom, and B is X and A is not a hydrogen atom. ] The diketopyrrolopyrrole pigment represented by the general formula (2) has the following general formula (2-1), the following general formula (2-2), the following general formula (2-3), and the following general formula (2). The photosensitive coloring composition according to claim 2, comprising at least one pigment selected from the group consisting of -4).

[In general formula (2-1), general formula (2-2), general formula (2-3), and general formula (2-4), X represents a chlorine atom or a bromine atom. Moreover, in General formula (2-3) and General formula (2-4), R < ¹² > -R < ¹⁴ > is respectively independently the C1-C12 alkyl group, or the phenyl which may have a substituent. It is a base. Together, R ¹³ and R ¹⁴ may form a ring. ]

  The said other ethylenically unsaturated monomer (FD2) contains the monomer which has an adamantyl group, The photosensitive coloring composition in any one of Claims 1-3 characterized by the above-mentioned.   A red filter segment formed by using the photosensitive coloring composition according to claim 1.   A color filter comprising a substrate and at least a filter segment other than red in addition to the red filter segment according to claim 5.   A liquid crystal display device comprising the color filter according to claim 6.

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