KR20220126231A - Colored resin composition and compound - Google Patents

Abstract

The present invention relates to a colored resin composition and a compound capable of forming a color filter having excellent heat resistance. The colored resin composition comprises: a colorant; and an alkali-soluble resin, wherein the colorant contains a compound represented by formula (I). In the formula (1), R^1 to R^8 represent, independently of each other, a hydrogen atom, -R^(a1), -OR^(a1), a halogen atom, a hydroxyl group, a carboxy group, -CO-O-R^(a1), -O-CO-R^(a1), -CO-R^(a1), or a nitro group, and R^7 and R^8 may combine with each other to form a ring. R^(a1) represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. L^1 represents an n-valent linking group. n represents an integer of 2 to 6.

Description

A colored resin composition and a compound {COLORED RESIN COMPOSITION AND COMPOUND}

The present invention relates to a colored resin composition and a compound.

The color filter used for display apparatuses, such as a liquid crystal display device, an electroluminescent display device, and a plasma display, and solid-state imaging elements, such as a CCD and CMOS sensor, is manufactured from a colored resin composition. As a colored resin composition for the said color filter formation, various coloring agents are used.

For example, it is known that the perylene compound represented by the following formula (x) can be used as a coloring agent (Non-Patent Document 1).

BASF's notation (Lumogen (registered trademark) F), BASF, November 1997, 2-6

However, the said perylene compound may not fully satisfy heat resistance when it is set as a colored resin composition. Then, this invention makes it a subject to provide the colored resin composition and compound which can form the color filter excellent in heat resistance.

The gist of the present invention is as follows.

[1] A colored resin composition containing a colorant and an alkali-soluble resin, and the colorant comprising a compound represented by formula (I).

[In formula (I),

R ¹ to R ⁸ are, independently of each other, a hydrogen atom, -R ^a1 , -OR ^a1 , a halogen atom, a hydroxy group, a carboxy group, -CO-OR ^a1 , -O-CO-R ^a1 , -CO-R ^a1 , or It represents a nitro group, and R ⁷ and R ⁸ may combine with each other to form a ring.

R ^a1 represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

L ¹ represents an n-valent linking group.

n represents an integer of 2 to 6.]

[2] The colored resin composition according to [1], further comprising a polymerizable compound and a polymerization initiator.

[3] A color filter formed from the colored resin composition according to [1] or [2].

[4] A display device including the color filter according to [3].

[5] A compound represented by formula (I-a).

[In formula (I-a),

R ¹ to R ⁸ are, independently of each other, a hydrogen atom, -R ^a1 , -OR ^a1 , a halogen atom, a hydroxy group, a carboxy group, -CO-OR ^a1 , -O-CO-R ^a1 , -CO-R ^a1 , or It represents a nitro group, and R ⁷ and R ⁸ may combine with each other to form a ring.

R ^a1 represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

N ^x represents a nitrogen atom.

L ² represents an n-valent linking group containing an aromatic ring, and a carbon atom constituting the aromatic ring is directly bonded to N ^x .

n represents an integer of 2 to 6.]

ADVANTAGE OF THE INVENTION According to this invention, the colored resin composition and compound which can form the color filter excellent in heat resistance can be provided.

The colored resin composition of the present invention contains a colorant (hereinafter, sometimes referred to as a colorant (A)) and an alkali-soluble resin (hereinafter, may be referred to as a resin (B)), and the colorant is represented by formula (I) compounds represented.

The colored resin composition of the present invention may further contain a polymerizable compound (hereinafter, may be referred to as a polymerizable compound (C)) and a polymerization initiator (hereinafter may be referred to as a polymerization initiator (D)). .

The colored resin composition of this invention may contain the solvent (Hereinafter, it may call a solvent (E)) further.

The colored resin composition of the present invention may further contain a polymerization initiation assistant (hereinafter, sometimes referred to as polymerization initiation assistant (D1)).

The colored resin composition of this invention may contain the leveling agent (Hereinafter, it may call a leveling agent (F)) further.

In addition, in this specification, the compound illustrated as each component can be used individually or in combination of multiple types, unless otherwise indicated.

< Colorant (A) >

A coloring agent (A) contains the compound (Hereinafter, it may be called compound (I)) represented by Formula (I). The colored resin composition containing compound (I) as a coloring agent is excellent in heat resistance.

<< Compound (I) >>

[In formula (I),

R ¹ to R ⁸ are, independently of each other, a hydrogen atom, -R ^a1 , -OR ^a1 , a halogen atom, a hydroxy group, a carboxy group, -CO-OR ^a1 , -O-CO-R ^a1 , -CO-R ^a1 , or It represents a nitro group, and R ⁷ and R ⁸ may combine with each other to form a ring.

R ^a1 represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

L ¹ represents an n-valent linking group.

n represents an integer of 2 to 6.]

Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ^a1 include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be saturated or unsaturated, and may be linear or alicyclic.

Examples of the saturated or unsaturated chain hydrocarbon group represented by R ^a1 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, and a tridecyl group. straight-chain alkyl groups such as , tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and icosyl group; isopropyl group, (1-ethyl)propyl group, isobutyl group, sec-butyl group, tert-butyl group, (1-ethyl)butyl group, (2-ethyl)butyl group, (1-propyl)butyl group, Isopentyl group, neopentyl group, tert-pentyl group, (2-methyl)pentyl group, (1-ethyl)pentyl group, (3-ethyl)pentyl group, (1-propyl)pentyl group, (1-butyl) Pentyl group, isohexyl group, (2-methyl)hexyl group, (5-methyl)hexyl group, (2-ethyl)hexyl group, (1-butyl)hexyl group, (1-pentyl)hexyl group, (2- Methyl) heptyl group, (2-ethyl) heptyl group, (3-ethyl) heptyl group, (1-hexyl) heptyl group, (2-methyl) octyl group, (2-ethyl) octyl group, (1-heptyl) branched alkyl groups such as octyl group, (2-ethyl)nonyl group, and (1-octyl)nonyl group; Vinyl group, 1-propenyl group, 2-propenyl group (allyl group), (1-methyl)ethenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, (1-(2-pro alkenyl groups such as phenyl))ethenyl, (1,2-dimethyl)propenyl, and 2-pentenyl; and the like. As for carbon number of a saturated chain hydrocarbon group, 1-18 are preferable, More preferably, it is 2-15, More preferably, it is 3-12. Moreover, as for carbon number of an unsaturated chain hydrocarbon group, 2-18 are preferable, More preferably, it is 2-15, More preferably, it is 3-12.

Examples of the saturated or unsaturated alicyclic hydrocarbon group represented by R ^a1 include a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; Cycloalkenyl groups, such as a cyclohexenyl group (For example, cyclohexa-2-ene, cyclohexa-3-ene), a cycloheptenyl group, and a cyclooctenyl group; a norbornyl group, an adamantyl group, a bicyclo[2.2.2]octyl group, etc. are mentioned. As for carbon number of a saturated or unsaturated alicyclic hydrocarbon group, 3-15 are preferable, More preferably, it is 3-12.

Examples of the aromatic hydrocarbon group represented by R ^a1 include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a phenanthryl group, an anthryl group, and a pyrenyl group. 6-15 are preferable and, as for carbon number of an aromatic hydrocarbon group, 6-12 are more preferable.

As long as the upper limit of carbon number is 20, the hydrocarbon group represented by R ^a1 may also contribute the combination of two or more of the above-mentioned chain hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group. Such a group may, for example, be a contribution obtained by combining at least one of an aromatic hydrocarbon group, a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group, and in the hydrocarbon group by the combination, a chain hydrocarbon group, You may combine as a bivalent group (for example, alkanediyl group). Examples of the hydrocarbon group by the above combination include benzyl group, (2,4,5-trimethylphenyl)methyl group, phenethyl group, 1-methyl-1-phenylethyl group, (2,4,5-triethylphenyl)ethyl group, etc. aralkyl group; arylalkenyl groups such as a phenylethenyl group (phenylvinyl group); Aryl alkynyl groups, such as a phenylethynyl group; o-tolyl group, m-tolyl group, p-tolyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group , 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,3,5,6,-tetramethylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-iso Propylphenyl group, 2,3-diisopropylphenyl group, 2,4-diisopropylphenyl group, 2,5-diisopropylphenyl group, 2,6-diisopropylphenyl group, 2,4,6-triisopropylphenyl group, 4-butylphenyl group, o-tert-butylphenyl group, m-tert-butylphenyl group, p-tert-butylphenyl group, 2,6-di(tert-butyl)phenyl group, 3,5-di(tert-butyl)phenyl group, 3,6-di(tert-butyl)phenyl group, 4-tert-butyl-2,6-dimethylphenyl group, 4-pentylphenyl group, 4-octylphenyl group, 4-(2,4,4-trimethyl-2-pentyl) alkylaryl groups such as a phenyl group, a 2-dodecylphenyl group, a 3-dodecylphenyl group, and a 4-dodecylphenyl group; alkenylaryl groups such as 4-vinylphenyl group; 2,3-dihydro-4-indenyl group, 1,2,3,5,6,7-hexahydro-4-s-indacenyl group, 8-methyl-1,2,3,5,6,7 -hexahydro-4-s-indacenyl group, 5,6,7,8-tetrahydro-1-naphthyl group, 5,6,7,8-tetrahydro-2-naphthyl group, 3-methyl-5, Aryl to which an alkanediyl group such as 6,7,8-tetrahydro-2-naphthyl group or 3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl group is bonded energy; an aryl group to which one or more aryl groups such as a biphenyl group and a terphenylyl group are bonded; A cyclohexylmethylphenyl group, a benzylphenyl group, (dimethyl(phenyl)methyl)phenyl group, etc. are mentioned. The hydrocarbon group may be, for example, a hydrocarbon group formed by a combination of a chain hydrocarbon group and an alicyclic hydrocarbon group, and examples thereof include 1-methylcyclopropyl group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 3 -Methylcyclohexyl group, 4-methylcyclohexyl group, 1,2-dimethylcyclohexyl group, 1,3-dimethylcyclohexyl group, 1,4-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2 ,4-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,2-dimethylcyclo Hexyl group, 3,3-dimethylcyclohexyl group, 4,4-dimethylcyclohexyl group, 2,4,6-trimethylcyclohexyl group, 2,2,6,6-tetramethylcyclohexyl group, 3,3, an alicyclic hydrocarbon group to which one or more alkyl groups or alicyclic hydrocarbon groups such as 5,5-tetramethylcyclohexyl group, 4-pentylcyclohexyl group, 4-octylcyclohexyl group and 4-cyclohexylcyclohexyl group are bonded; One or more alicyclic hydrocarbons such as cyclopropylmethyl group, cyclopropylethyl group, cyclobutylmethyl group, cyclobutylethyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclohexylmethyl group, 2-methylcyclohexylmethyl group, cyclohexylethyl group, and adamantylmethyl group The alkyl group etc. which the group couple|bonded are mentioned. 6-18 are preferable and, as for carbon number of group which combined two or more of a chain|strand-shaped hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, 6-15 are more preferable.

Examples of the substituent which the hydrocarbon group having 1 to 20 carbon atoms represented by R ^a1 may have include a halogen atom; nitrile group; nitro group; amino group; hydroxyl group; an alkoxy group having 1 to 20 carbon atoms such as a methoxy group and an ethoxy group; C6-C20 aryloxy groups, such as a phenyloxy group, 1-naphthyloxy group, and 2-naphthyloxy group; thiol group; C1-C20 alkylthio groups, such as a methylthio group and an ethylthio group; allylthio group; C6-C20 arylthio groups, such as a phenylthio group, 1-naphthylthio group, and 2-naphthylthio group; sulfoxy group; an alkylsulfoxy group having 1 to 20 carbon atoms, such as a methylsulfoxy group and an ethylsulfoxy group; an arylsulfoxy group having 6 to 20 carbon atoms, such as a phenylsulfoxy group, a 1-naphthylsulfoxy group, and a 2-naphthylsulfoxy group; silyl group; Boryl group; C1-C20 alkylamino groups, such as a monomethylamino group, a dimethylamino group, a trimethylamino group, a monoethylamino group, a diethylamino group, and a triethylamino group; C6-C20 arylamino groups, such as a monophenylamino group, a diphenylamino group, and a triphenylamino group; an aralkylamino group having 7 to 20 carbon atoms, such as a benzylamino group; carboxyl group; carbamoyl group; an alkylcarbonyl group having 2 to 20 carbon atoms, such as an acetyl group and a propionyl group; an arylcarbonyl group having 7 to 20 carbon atoms, such as a benzoyl group, a 1-naphthylcarbonyl group, and a 2-naphthylcarbonyl group; an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group and an ethoxycarbonyl group; an aryloxycarbonyl group having 7 to 20 carbon atoms, such as a phenyloxycarbonyl group, a 1-naphthyloxycarbonyl group, and a 2-naphthyloxycarbonyl group; and the like.

As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned. From the viewpoint of synthesis, a chlorine atom and a bromine atom are preferable.

Examples of R ^a1 include groups represented by the following formulas (D-1) to (D-47) and (G-1) to (G-22). * indicates a bond.

Examples of -OR ^a1 represented by R ¹ to R ⁸ include an oxy group having R ^a1 described above, and an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and the like. Specific examples of -OR ^a1 include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a phenoxy group, and a naphthyloxy group.

Examples of the halogen atom as R ¹ to R ⁸ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. From the viewpoint of synthesis, a chlorine atom and a bromine atom are preferable.

Examples of -CO-OR ^a1 represented by R ¹ to R ⁸ include an oxycarbonyl group having R ^a1 described above, an alkoxycarbonyl group having 2 to 21 carbon atoms, and an aryloxycarbonyl group having 7 to 21 carbon atoms. . R ^a1 of -CO-OR ^a1 is preferably a saturated chain hydrocarbon group, a saturated alicyclic hydrocarbon group, a group combining an alicyclic hydrocarbon group and a chain hydrocarbon group, an aromatic hydrocarbon group, or a group combining an aromatic hydrocarbon group and a chain hydrocarbon group. , a saturated chain hydrocarbon group having 1 to 20 carbon atoms, a saturated alicyclic hydrocarbon group having 3 to 15 carbon atoms, a group combining an alicyclic hydrocarbon group having 4 to 15 carbon atoms and a chain hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or 7 carbon atoms It is more preferable that the group is a combination of an aromatic hydrocarbon group having ∼20 and a chain hydrocarbon group, a saturated chain hydrocarbon group having 3 to 18 carbon atoms, a group combining an alicyclic hydrocarbon group having 4 to 10 carbon atoms and a chain hydrocarbon group, or an aromatic group having 7 to 15 carbon atoms. It is more preferable that it is a group in which a hydrocarbon group and a chain hydrocarbon group are combined. Specific examples of -CO-OR ^a1 include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, and a (1-ethyl)pentyloxycarbonyl group. , Hexyloxycarbonyl group, (2-ethyl)hexyloxycarbonyl group, heptyloxycarbonyl group, (1-butyl)heptyloxycarbonyl group, octyloxycarbonyl group, (1-heptyl)octyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, undecyl group Oxycarbonyl group, dodecyloxycarbonyl group, tridecyloxycarbonyl group, tetradecyloxycarbonyl group, pentadecyloxycarbonyl group, hexadecyloxycarbonyl group, heptadecyloxycarbonyl group, octadecyloxycarbonyl group, phenyloxycarbonyl group, benzyloxycarbonyl group, cyclohexyloxycarbonyl group , a cyclohexyl methoxycarbonyl group, an icosyloxycarbonyl group, and the like.

Examples of -O-CO-R ^a1 represented by R ¹ to R ⁸ include a carbonyloxy group having R ^a1 described above, an alkylcarbonyloxy group having 2 to 21 carbon atoms, and an arylcar group having 7 to 21 carbon atoms. A bornyloxy group etc. are mentioned. Specific examples of -O-CO-R ^a1 include methylcarbonyloxy group, ethylcarbonyloxy group, propylcarbonyloxy group, butylcarbonyloxy group, pentylcarbonyloxy group, hexylcarbonyloxy group, (2 -ethyl) hexylcarbonyloxy group, phenylcarbonyloxy group, cyclohexylcarbonyloxy group, etc. are mentioned.

Examples of -CO-R ^a1 represented by R ¹ to R ⁸ include a carbonyl group having the above R ^a1 , an alkylcarbonyl group having 2 to 21 carbon atoms, an arylcarbonyl group having 7 to 21 carbon atoms, and the like. Specific examples of -CO-R ^a1 include an acetyl group, a propionyl group, a butyroyl group, a pentanoyl group, a hexanoyl group, a cyclohexanoyl group, and a benzoyl group.

Examples of the ring formed by bonding R ⁷ and R ⁸ to each other include groups represented by the following formulas (H-1) to (H-4).

[In formulas (H-1) to (H-4),

R ¹² to R ²⁴ are each independently a hydrogen atom, -R ^a2 , -OR ^a2 , a halogen atom, a hydroxy group, a carboxy group, -CO-OR ^a2 , -O-CO-R ^a2 , -CO-R ^a2 , or A nitro group is represented, and R ^a2 represents a C1-C20 hydrocarbon group which may have a substituent.

* indicates a bond possessed by R ⁷ , ** indicates a bond possessed by R ⁸ ]

Examples of the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent represented by R ^a2 include the same groups as the groups described as the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent represented by R ^a1 , and preferred embodiments thereof are also the same. to be.

Examples of the halogen atom as R ¹² to R ²⁴ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. From the viewpoint of synthesis, a chlorine atom and a bromine atom are preferable.

As -OR ^a2 , -CO-OR ^a2 , -O-CO-R ^a2 , and -CO-R ^a2 as R ¹² to R ²⁴ , -OR ^a1 , -CO-OR ^a1 represented by R ¹ to R ⁸ , The groups described as -O-CO-R ^a1 and -CO-R ^a1 are exemplified.

R ¹² to R ²⁴ are each independently preferably a hydrogen atom, -R ^a2 , a halogen atom or a hydroxy group, and more preferably a hydrogen atom.

In formula (I), n pieces of R ¹ may be the same or different, but preferably the same, n pieces of R ² may be the same or different, but preferably the same, and n pieces of R ³ may be the same or different, but the same Preferably, n R ⁴ may be the same or different, but preferably the same, n R ⁵ may be the same or different, but preferably the same, n R ⁶ may be the same or different, but preferably the same and, although n pieces of R ⁷ may be the same or different, the same is preferable, and although n pieces of R ⁸ may be the same or different, the same is preferable.

The n-valent linking group represented by L ¹ is preferably an n-valent organic group, and more preferably an n-valent hydrocarbon group which may have a substituent. The n-valent hydrocarbon group is a group in which n hydrogen atoms constituting the hydrocarbon are substituted with a bond. It is preferable that n bonds exist at different carbon atoms, respectively. In addition, in the n-valent hydrocarbon group, the methylene group constituting the hydrocarbon may be substituted with -O-, -C(=O)-, etc., and the methylene group having a bond is -O-, -C(=O). )-, etc. may be substituted. It is preferable that carbon number of the said hydrocarbon is 1-20.

Examples of the n-valent hydrocarbon group include an n-valent chain hydrocarbon group, an n-valent alicyclic hydrocarbon group, an n-valent aromatic hydrocarbon group, and an n-valent group combining two or more of a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. .

Examples of the n-valent chain hydrocarbon group include a group in which n-1 hydrogen atoms in the monovalent saturated or unsaturated chain hydrocarbon group represented by R ^a1 described above are substituted with a bond. As for carbon number of n-valent saturated chain hydrocarbon group, 1-15 are preferable, More preferably, it is 1-10, More preferably, it is 1-8. Moreover, as for carbon number of an n-valent unsaturated chain hydrocarbon group, 2-15 are preferable, More preferably, it is 2-10, More preferably, it is 2-8.

The n-valent chain hydrocarbon group is preferably an n-valent saturated chain hydrocarbon group, methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane- Alkanediyl groups, such as a 1, 5- diyl group and a hexane-1, 6- diyl group, are more preferable.

Examples of the n-valent alicyclic hydrocarbon group include a group in which n-1 hydrogen atoms in the monovalent saturated or unsaturated alicyclic hydrocarbon group represented by R ^a1 described above are substituted with a bond. As for carbon number of an n-valent alicyclic hydrocarbon group, 3-15 are preferable, More preferably, it is 3-12, More preferably, it is 3-8.

As the n-valent alicyclic hydrocarbon group, an n-valent saturated alicyclic hydrocarbon group is preferable, and a divalent saturated alicyclic hydrocarbon group such as a cyclohexyl-1,2-diyl group and a cyclohexyl-1,4-diyl group is more preferable.

Examples of the n-valent aromatic hydrocarbon group include groups in which n-1 hydrogen atoms of the monovalent aromatic hydrocarbon group represented by R ^a1 are substituted with bonds. As for carbon number of an n-valent aromatic hydrocarbon group, 6-15 are preferable, More preferably, it is 6-12.

As the n-valent aromatic hydrocarbon group, n-valent benzene such as a 1,2-phenylene group, a 1,4-phenylene group and a benzene-1,2,4,5-tetrayl group is preferable, and a phenylene group is more preferable.

As the n-valent group combining two or more of a chain hydrocarbon group, an alicyclic hydrocarbon group, and two or more aromatic hydrocarbon groups, the above-mentioned R ^a1 , a chain hydrocarbon group, an alicyclic hydrocarbon group, and a group combining two or more aromatic hydrocarbon groups and a group in which n-1 hydrogen atoms are substituted with a bond. 7-18 are preferable and, as for carbon number of the n-valent group which combined two or more of a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, 7-15 are more preferable.

As an n-valent group combining two or more chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, at least one of an aromatic hydrocarbon group, a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group is combined. It is preferably an n-valent group, and more preferably an n-valent group in which an aromatic hydrocarbon group and a chain hydrocarbon group are combined, or an n-valent group in which an aromatic hydrocarbon group and an aromatic hydrocarbon group are combined. Specific examples of the n-valent group obtained by combining two or more chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups include groups represented by the following formulas.

[In the above formula,

R ^p11 to R ^p14 , R ^p21 to R ^p22 , R ^p41 to R ^p44 , R ^p51 to R ^p52 , R ^q11 to R ^q14 , R ^q21 to R ^q28 , and R ^q31 to R ^q38 are each independently a hydrogen atom or -R ^a3 . However, at least one of R ^q11 to R ^q14 represents -R ^a3 .

R ^a3 represents a hydrocarbon group having 1 to 20 carbon atoms, and the methylene group constituting the hydrocarbon group may be substituted with -O- or -C(=O)-.

* indicates a bond with a nitrogen atom.]

Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ^a3 include groups similar to those described as the hydrocarbon group having 1 to 20 carbon atoms represented by R ^a1 . R ^a3 is preferably a linear or branched alkyl group, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, still more preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 4 carbon atoms. It is more preferable that it is a -4 linear alkyl group.

Examples of the group in which the methylene group constituting the hydrocarbon group is substituted with -O- or -C(=O)- include groups represented by the following formulas. In the following formula, * represents a bond.

As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned. From the viewpoint of synthesis, a chlorine atom and a bromine atom are preferable.

R ^p11 to R ^p14 , R ^p21 to R ^p22 , R ^p41 to R ^p44 , R ^p51 to R ^p52 , R ^q11 to R ^q14 , R ^q21 to R ^q28 , and R ^q31 to R ^q38 are each independently a hydrogen atom Or it is preferable that it is an alkyl group, and it is more preferable that it is a hydrogen atom or a C1-C4 linear alkyl group.

Examples of the substituent which the n-valent hydrocarbon group may have include a halogen atom; nitrile group; nitro group; amino group; C1-C20 alkylamino groups, such as a monomethylamino group, a dimethylamino group, a trimethylamino group, a monoethylamino group, a diethylamino group, and a triethylamino group; C6-C20 arylamino groups, such as a monophenylamino group, a diphenylamino group, and a triphenylamino group; an aralkylamino group having 7 to 20 carbon atoms, such as a benzylamino group; and the like.

In formula (I), as R< ¹ > and R< ² >, mutually independently, the saturated chain hydrocarbon group which may have a substituent; aromatic hydrocarbon group which may have a substituent; Or it is preferable that it is the group which combined the aromatic hydrocarbon group which may have a substituent and a chain hydrocarbon group. From the viewpoint of improving the solubility of compound (I) in a solvent, the saturated chain hydrocarbon group is preferably a saturated branched hydrocarbon group. 1-15 are preferable and, as for carbon number of the said saturated chain hydrocarbon group (preferably saturated branched hydrocarbon group), 3-15 are more preferable. The aromatic hydrocarbon group is preferably a phenyl group. The group combining the aromatic hydrocarbon group and the chain hydrocarbon group is preferably a phenyl group to which a chain hydrocarbon group having 1 to 12 carbon atoms (preferably 1 to 10) is bonded, and a phenyl group to which 2-3 chain hydrocarbon groups having 1 to 4 carbon atoms are bonded. It is more preferable that it is a phenyl group which the C1-C4 chain hydrocarbon group couple|bonded at two ortho positions. Among them, it is more preferable that R ¹ and R ² each independently represent a group represented by the formulas (D-4) to (D-14) or (G-5) to (G-22). and, independently of each other, formula (D-4) to formula (D-14), formula (G-5), formula (G-7), formula (G-8), formula (G-11) to formula ( It is more preferably a group represented by any of G-13), formula (G-15), formula (G-16), formula (G-19), formula (G-21), or formula (G-22), , independently of each other, formula (D-4) to formula (D-14), formula (G-7), formula (G-11), formula (G-13), formula (G-15) or formula (G) A group represented by any of -16) is particularly preferable.

Moreover, it is preferable that it is the same group as R< ¹ > and R< ² >.

In the formula (I), R ³ to R ⁸ are each independently preferably a hydrogen atom, a halogen atom or a hydroxyl group, and more preferably a hydrogen atom.

In formula (I), L ¹ is an alkanediyl group which may have a substituent, an n-valent saturated alicyclic hydrocarbon group which may have a substituent, n-valent benzene which may have a substituent, and the formula (Lp) which may have a substituent. Any of the groups represented by -1) to formula (Lp-6), or any of the groups represented by formulas (Lq-1) to (Lq-3) which may have a substituent is preferable. L ¹ is more preferably a group containing at least an aromatic ring, n-valent benzene which may have a substituent, and any of the groups represented by the above formulas (Lp-1) to (Lp-6) which may have a substituent. or any of the groups represented by the formulas (Lq-1) to (Lq-3) which may have a substituent is more preferable.

Among them, L ¹ is an n-valent linking group containing an aromatic ring, and it is preferable that carbon atoms constituting the aromatic ring have a bond, that is, L ¹ is an n-valent linking group containing an aromatic ring, It is preferable that the carbon atom which comprises the said aromatic ring is a group which couple|bonds directly with the nitrogen atom. Examples of the n-valent linking group containing an aromatic ring in which a carbon atom constituting the aromatic ring is directly bonded to a nitrogen atom include n-valent benzene which may have a substituent; in the alkylaryl group which may have a substituent, among hydrogen atoms bonded to carbon atoms constituting the aromatic ring, n-1 hydrogen atoms are separated to form a bond; Or the n-valent biphenyl which may have a substituent is preferable. Specific examples of the n-valent linking group containing an aromatic ring in which a carbon atom constituting the aromatic ring is directly bonded to a nitrogen atom include groups represented by the following formulas (Lr-1) to (Lr-6). , the group represented by the formula (Lr-1), the formula (Lr-3), the formula (Lr-4), or the formula (Lr-5) is preferable, and the group represented by the formula (Lr-1) is more desirable.

[wherein, R ^r11 to R ^r14 , R ^r21 to R ^r23 , R ^r31 to R ^r32 , R ^r41 to R ^r48 , R ^r51 to R ^r58 , and R ^r61 to R ^r66 are each independently a hydrogen atom; -R ^a4 , a halogen atom, or a nitro group.

R ^a4 represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and the methylene group constituting the hydrocarbon group may be substituted with -O- or -C(=O)-.

* indicates a bond with a nitrogen atom.]

Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ^a4 include the same groups as those described as the hydrocarbon group having 1 to 20 carbon atoms represented by R ^a3 , and the preferred aspect thereof is also the same.

As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned. From the viewpoint of synthesis, a chlorine atom and a bromine atom are preferable.

R ^r11 to R ^r14 , R ^r21 to R ^r23 , R ^r31 to R ^r32 , R ^r41 to R ^r48 , R ^r51 to R ^r58 , and R ^r61 to R ^r66 are each independently a hydrogen atom, -R ^a4 , or A halogen atom is preferable, a hydrogen atom or -R ^a4 is more preferable, and it is still more preferable that it is a hydrogen atom or a C1-C4 linear alkyl group.

In formula (I), as n, it is preferable that it is an integer of 2-4, and it is more preferable that it is 2 or 4.

The compound (I) is preferably a compound represented by the following formula (I-a) (hereinafter sometimes referred to as compound (I-a)). Further, compound (I-a) is also encompassed by the present invention.

[In formula (I-a),

R ¹ to R ⁸ , and n have the same meanings as described above.

N ^x represents a nitrogen atom.

L ² represents an n-valent linking group including an aromatic ring, and a carbon atom constituting the aromatic ring is directly bonded to N ^x .]

Examples of L ² include the n-valent linking group containing an aromatic ring in L ¹ described above, and the group described as a group in which a carbon atom constituting the aromatic ring is directly bonded to a nitrogen atom, and its preferred embodiment is also the same .

Specific examples of compound (I) include compounds (I-1) to (I-24) shown in Table 1 below.

In Table 1, H represents a hydrogen atom.

D-6, D-13, and G-7 mean groups represented by the above formulas (D-6), (D-13) and (G-7), respectively.

L-1 to L-8 each mean a group represented by the following formulas (L-1) to (L-8). In the following formula, * represents a bond with a nitrogen atom.

As the compound (I), compounds (I-17) to (I-24) are preferable, and compounds (I-17) to (I-19) are more preferable.

Compound (I) is, for example, by reacting a compound represented by the following formula (pt1) with maleic anhydride in the presence of a dehydrogenating agent to prepare a compound represented by formula (pt2), and represented by the obtained formula (pt2) The compound represented by the formula (MA1) is reacted with the compound represented by the formula (MA1), the compound represented by the formula (pt3) is prepared, and then the compound represented by the obtained formula (pt3) and the compound represented by the formula (pt2') are reacted It can be manufactured by

[Wherein, R ¹ to R ⁸ , L ¹ , and n are the same as defined above.]

Examples of the compound represented by the formula (pt1) include N ¹ ,N ² -bis(2,6-diisopropylphenyl)perylene-3,4,9,10-tetracarboxylic acid diimide, N ¹ . ,N ² -bis(5-nonyl)perylene-3,4,9,10-tetracarboxylic diimide, N ¹ ,N ² -bis(6-undecyl)perylene-3,4,9,10 -tetracarboxylic acid diimide, N ¹ ,N ² -bis(7-tridecyl)perylene-3,4,9,10-tetracarboxylic acid diimide, etc. are mentioned.

The amount of maleic anhydride used is usually 1 mol or more and 1,000 mol or less, preferably 1 mol or more and 800 mol or less, more preferably 1 mol or more and 600 mol or less with respect to 1 mol of the compound represented by formula (pt1). and more preferably 1 mole or more and 400 moles or less.

The dehydrogenating agent is used to dehydrogenate and aromaticize the 6-membered ring compound. Examples of the dehydrogenating agent include chloranyl, p-benzoquinone, 2,5-dichloro-p-quinone, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, tetramethyl-p-quinone, 2, 5-diphenyl-p-quinone and bromanyl are preferable, and chloranyl and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone are more preferable.

The usage-amount of a dehydrogenator is 1 mol or more and 10 mol or less normally with respect to 1 mol of the compound represented by Formula (pt1), Preferably they are 1 mol or more and 5 mol or less.

The reaction temperature at the time of making the compound represented by Formula (pt1) and maleic anhydride react is -100 degreeC or more and 300 degrees C or less, for example.

The compound represented by the formula (pt3) can be produced by reacting the compound represented by the formula (pt2) with the compound represented by the formula (MA1). The compound represented by formula (MA1) is a compound in which an amino group is bonded to n bonding hands of L ¹ , for example, 1,4-phenylenediamine, 2,3,5,6-tetramethyl-1, 4-phenylenediamine etc. are mentioned.

The amount of the compound represented by the formula (pt2) to be used may be appropriately adjusted according to n, but it is usually 0.1 mol or more and 10 mol or less, preferably 0.2 mol or more and 5 mol with respect to 1 mol of the compound represented by the formula (MA1). is below.

The reaction between the compound represented by the formula (pt2) and the compound represented by the formula (MA1) is preferably performed in the presence of an acid catalyst. As the acid catalyst, carboxylic acids such as acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid and heptanoic acid are preferable.

The amount of the acid catalyst used is usually 1 mol or more and 1,000 mol or less, preferably 1 mol or more and 800 mol or less, more preferably 1 mol or more and 600 mol or less with respect to 1 mol of the compound represented by formula (MA1). , more preferably 1 mole or more and 400 moles or less.

The reaction temperature at the time of making the compound represented by Formula (pt2) and the compound represented by Formula (MA1) react is -100 degreeC or more and 300 degrees C or less, for example.

Compound (I) can be produced by reacting the compound represented by the formula (pt3) with the compound represented by the formula (pt2'). The compound represented by the formula (pt2') may be manufactured by the same method as the compound represented by the formula (pt2) described above. In addition, R< ¹ > in a formula (pt2') and R< ¹ > in a formula (pt3) may be same or different. Similarly, R ² to R ⁸ in the formula (pt2') may be the same as or different from R ² to R ⁸ in the formula (pt3).

The amount of the compound represented by the formula (pt2') to be used may be appropriately adjusted according to n, but it is usually 1 mol or more and 20 mol or less, and preferably 1 mol or more and 10 mol with respect to 1 mol of the compound represented by the formula (pt3). mol or less, More preferably 1 mol or more and 5 mol or less.

The reaction between the compound represented by the formula (pt3) and the compound represented by the formula (pt2') is preferably performed in the presence of an acid catalyst. As the acid catalyst, carboxylic acids such as acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid and heptanoic acid are preferable.

The amount of the acid catalyst used is usually 1 mol or more and 1,000 mol or less, preferably 1 mol or more and 800 mol or less, more preferably 1 mol or more and 600 mol or less with respect to 1 mol of the compound represented by formula (pt3). , more preferably 1 mole or more and 400 moles or less.

The reaction temperature at the time of making the compound represented by Formula (pt3) and the compound represented by Formula (pt2') react is -100 degreeC or more and 300 degrees C or less, for example.

The method for taking out compound (I) after completion|finish of reaction is not specifically limited, It can take out by well-known various methods. After taking out, you may refine|purify the obtained residue by column chromatography, recrystallization, etc. The chemical structure of the obtained compound can be analyzed by a well-known analysis method and its conditions. Although it does not specifically limit as such an analysis method, For example, X-ray crystal structure analysis method, mass spectrometry (LC), NMR analysis method, elemental analysis method, etc. are mentioned.

The content rate of compound (I) is preferably 0.1 mass % or more and 50 mass % or less, more preferably 0.5 mass % or more and 40 mass % or less, further preferably 1 to the total amount of solid content of the colored resin composition. mass % or more and 30 mass % or less.

Here, the "total amount of solid content" in this specification means the quantity remove|excluding content of the solvent from the total amount of a colored resin composition. The total amount of solid content and content of each component with respect to this can be measured by well-known analytical means, such as liquid chromatography or gas chromatography, for example.

<< Colorant (A1) >>

The colored resin composition of the present invention is a colorant (A) as a dye other than the compound (I) (hereinafter sometimes referred to as dye (A1-1)) and/or pigment (hereinafter referred to as pigment (A1-2) may be included). Hereinafter, the dye (A1-1) and the pigment (A1-2) may be collectively referred to as a coloring agent (A1). These may be used independently and may be used in combination of 2 or more type.

The dye (A1-1) is not particularly limited as long as it does not contain the compound (I), and a known dye can be used. Examples of the dye (A1-1) include solvent dyes, acid dyes, direct dyes, mordant dyes, and the like. . As a dye, the compound classified as a dye by the color index (published by The Society of Dyers and Colorists), and the well-known dye described in the dyeing notebook (Skisensha) are mentioned, for example. Moreover, according to the chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine and dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, and phthalocyanine dyes. Among these, organic solvent-soluble dyes are preferable.

As the dye (A1-1), specifically,

C. I. Solvent Yellow 4, 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 117, 162, 163, 167, 189;

C. I. Solvent Red 24, 45, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172 , 175, 181, 207, 218, 222, 227, 230, 245, 247;

C. I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 77, 86, 99;

C. I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

C. I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 38, 44, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94 , 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;

C. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35; C. I. solvent dyes such as;

C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 , 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76 , 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172 , 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281 , 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;

C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;

C. I. Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;

C. I. Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45 , 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1 , 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147 , 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236 , 242, 243, 249, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, 340;

C. I. Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80 , 104, 105, 106, 109; C. I. acid dyes such as

C. I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102 , 108, 109, 129, 132, 136, 138, 141;

C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C. I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

C. I. Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84 , 85, 86, 87, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150 , 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195 , 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245 , 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

C. I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, 82; C. I. direct dyes such as;

C. I. Disperse Yellow 51, 54, 76;

C. I. Disperse Violet 26, 27;

C. I. Disperse Blue 1, 14, 56, 60; C. I. dispers dyes such as;

C. I. Basic Red 1, 10;

C. I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66 , 67, 68, 81, 83, 88, 89;

C. I. Basic Violet 2;

C. I. Basic Red 9;

C. I. Basic Green 1; C. I. basic dyes such as

C. I. Reactive Yellow 2, 76, 116;

C. I. Reactive Orange 16;

C. I. Reactive Red 36; C. I. reactive dyes such as

C. I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

C. I. Mordant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;

C. I. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

C. I. Mordant Violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58;

C. I. Mordant Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;

C. I. Mordant Greens 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53; C. I. mordant dyes such as;

C. I. Bat Green 1; and dyes with color index (C.I.) numbers, such as C.I. vat dyes.

As the pigment (A1-2), as long as it does not contain compound (I), it does not specifically limit and a well-known pigment can be used, For example, it is classified as a pigment by the color index (published by The Society of Dyers and Colorists). pigments can be mentioned.

As a pigment classified as a pigment, For example, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109 , 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, 231 yellow pigments;

C. I. Orange pigments such as pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

C. I. Pigment Red 9, 97, 105, 122, 144, 166, 168, 176, 177, 180, 190, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, red pigments such as 269 and 273;

C. I. Blue pigments such as Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60;

C. I. Violet pigments such as Pigment Violet 1, 19, 23, 32, 36, 38;

Green pigments such as C. I. Pigment Green 7, 36, 58, 59, 62, 63;

C. I. Brown pigments such as Pigment Brown 23 and 25;

C. I. Black pigments such as Pigment Black 1 and 7; can be heard

As the colorant (A1), yellow, red or green dyes and pigments are preferred.

The colorant (A1) is, if necessary, a rosin treatment, a surface treatment using a derivative into which an acidic group or a basic group is introduced, a graft treatment to the surface of the colorant (A1) with a polymer compound, etc., atomization treatment by a sulfuric acid atomization method, etc.; Washing treatment with an organic solvent, water, etc. for removing impurities, removal treatment of ionic impurities by an ion exchange method, etc. may be performed. It is preferable that the particle diameter of a coloring agent (A1) is substantially uniform.

When the colorant (A) further contains the colorant (A1), the content of the compound (I) is, for example, 1 mass% or more, preferably 2 mass% or more, based on the total amount of the colorant (A). and more preferably 10 mass % or more, still more preferably 25 mass % or more, and particularly preferably 50 mass % or more. Moreover, when a coloring agent (A) further contains a coloring agent (A1), the content rate of compound (I) is less than 100 mass % with respect to the total amount of coloring agent (A), for example.

When the colored resin composition contains the solvent (E), a colorant-containing liquid (sometimes referred to as a coloring composition) containing the colorant (A) and the solvent (E) is prepared in advance, and then using the colorant-containing liquid You may prepare a colored resin composition. In the case where the colorant (A) does not dissolve in the solvent (E), for example, when the colorant (A) contains the pigment (A1-2), the colorant-containing liquid is prepared by adding the colorant (A) to the solvent (E). It can be prepared by dispersing and mixing. The coloring agent containing liquid may contain a part or all of the solvent (E) contained in a colored resin composition.

The content rate of the solid content in the colorant-containing liquid is preferably 0.01 mass% or more and 99.99 mass% or less, more preferably 0.1 mass% or more and 99.9 mass% or less, further preferably 0.1 mass% or more with respect to the total amount of the colorant-containing liquid. 99 mass % or less, More preferably, it is 0.5 mass % or more and 90 mass % or less, Especially preferably, it is 1 mass % or more and 50 mass % or less.

The coloring agent (A) is good also as a state in which the coloring agent (A) disperse|distributed uniformly in the solution by making it contain a dispersing agent and performing a dispersion process. When using in combination of 2 or more type as a coloring agent (A), each may be individually dispersed, and multiple types may be mixed and a dispersion-processed may be carried out.

As a dispersing agent, surfactant etc. are mentioned, for example, Cationic, anionic, nonionic, and amphoteric any surfactant may be sufficient. Specifically, surfactants, such as a polyester type, a polyamine type, and an acryl type, etc. are mentioned. You may use these dispersing agents individually or in combination of 2 or more types. As a dispersing agent, if expressed by a brand name, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Florene (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), EFKA (registered trademark) ( BASF Corporation), Azispa (registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.) and Disperbyk (registered trademark) (manufactured by Big Chemi Co., Ltd.), BYK (registered trademark) (manufactured by Big Chemi Co., Ltd.), etc. can As a dispersing agent, you may use resin (B) mentioned later.

When using a dispersing agent, the usage-amount of the said dispersing agent (solid content) is 1 mass part or more and 10000 mass parts or less normally with respect to 100 mass parts of coloring agents (A), Preferably it is 5 mass parts or more and 5000 mass parts or less, More preferably Preferably, they are 10 mass parts or more and 1000 mass parts or less, More preferably, they are 15 mass parts or more and 800 mass parts or less. When the usage-amount of the said dispersing agent exists in the said range, there exists a tendency for the colorant containing liquid in a more uniformly dispersed state to be obtained.

The content rate of the colorant (A) is preferably 0.1 mass % or more and 50 mass % or less, more preferably 0.5 mass % or more and 40 mass % or less, further preferably 1 to the total amount of solid content of the colored resin composition. mass % or more and 30 mass % or less. When the content of the colorant (A) is within the above range, the color density when the color filter is used is sufficient, and the resin (B) can be contained in the required amount in the composition, so that a pattern having sufficient mechanical strength can be formed. desirable.

< Resin (B) >

Resin (B) is alkali-soluble resin, and it is preferable that it is alkali-soluble resin which has carboxylic acid. The colored resin composition in which alkali-soluble resin was used as resin (B) can be used suitably as a photoresist use.

Examples of the resin (B) include the following resins [K1] to [K6].

resin [K1]; A structural unit derived from at least one (a) (hereinafter sometimes referred to as “(a)”) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, a cyclic ether structure having 2 to 4 carbon atoms, and ethylene a copolymer having a structural unit derived from a monomer (b) having a sexually unsaturated bond (hereinafter sometimes referred to as “(b)”);

resin [K2]; The structural unit derived from (a), the structural unit derived from (b), and the monomer (c) copolymerizable with (a) (however, it is different from (a) and (b).) (hereinafter "(c)" copolymers having a structural unit derived from );

resin [K3]; a copolymer having a structural unit derived from (a) and a structural unit derived from (c);

resin [K4]; a copolymer having a structural unit derived from (c) and a structural unit obtained by adding (b) to the structural unit derived from (a);

resin [K5]; a copolymer having a structural unit derived from (a) added to the structural unit derived from (b) and a structural unit derived from (c);

resin [K6]; A copolymer having a structural unit derived from (c) and a structural unit obtained by adding (a) to the structural unit derived from (b) and further adding carboxylic acid anhydride.

As a monomer (a), For example, unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid, a crotonic acid, and o-, m-, p-vinyl benzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene , 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] a bicyclo unsaturated compound containing a carboxy group such as hept-2-ene;

carboxylic acid anhydrides such as anhydrides of the above unsaturated dicarboxylic acids other than fumaric acid and mesaconic acid;

Unsaturated mono[(meth)acryloyloxyalkyl] of polyhydric carboxylic acid having more than divalence, such as succinic acid mono[2-(meth)acryloyloxyethyl] and phthalic acid mono[2-(meth)acryloyloxyethyl] esters;

unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid; and the like.

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable from the point of copolymerization reactivity and the solubility point to the aqueous alkali solution of resin obtained.

In addition, in this specification, "(meth)acrylic acid" shows at least 1 sort(s) chosen from the group which consists of acrylic acid and methacrylic acid. Notations, such as "(meth)acryloyl" and "(meth)acrylate", also have the same meaning.

The monomer (b) has a cyclic ether structure having 2 to 4 carbon atoms (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring (oxolane ring)) and an ethylenically unsaturated bond. refers to a polymerizable compound having It is preferable that a monomer (b) is a monomer which has a C2-C4 cyclic ether and a (meth)acryloyloxy group.

As the monomer (b), for example, a monomer having an oxiranyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (b1)"), a monomer having an oxetanyl group and an ethylenically unsaturated bond (hereinafter, "monomer (b2)" may be referred to), a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter, may be referred to as "monomer (b3)"), and the like.

As the monomer (b1), for example, a monomer having a structure in which an unsaturated aliphatic hydrocarbon is epoxidized (hereinafter sometimes referred to as "monomer (b1-1)"), a structure in which an unsaturated alicyclic hydrocarbon is epoxidized A monomer (Hereinafter, it may be called "monomer (b1-2)") is mentioned.

As the monomer (b1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferable. Specific examples of the monomer (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzylglycidyl ether dilether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis( Glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxy) Methyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) Styrene etc. are mentioned.

As the monomer (b1-2), vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide (registered trademark) 2000; manufactured by Daicel Corporation), 3,4-epoxy Cyclohexylmethyl (meth) acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, cyclomer ( registered trademark) M100 (manufactured by Daicel Corporation), the compound represented by the formula (BI), the compound represented by the formula (BII), and the like.

[In formulas (BI) and (BII), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group, there may be

X ^a and X ^b each independently represent a single bond, *-R ^c -, *-R ^c -O-, *-R ^c -S- or *-R ^c -NH-.

R ^c represents an alkanediyl group having 1 to 6 carbon atoms.

* indicates a bond with O.]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.

Examples of the alkyl group in which a hydrogen atom is substituted by a hydroxy group include a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, and 3-hydroxypropyl group. , 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. can be heard

R ^a and R ^b preferably include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group. , a hexane-1,6-diyl group, and the like.

As X ^a and X ^b , Preferably, a single bond, a methylene group, an ethylene group, *-CH ₂ -O- (* represents a bond with O) group, and *-CH ₂ CH ₂ -O- group are mentioned. and more preferably a single bond and *-CH ₂ CH ₂ -O- group (* represents a bond with O).

Examples of the compound represented by the formula (BI) include compounds represented by any of formulas (BI-1) to (BI-15). Among them, formula (BI-1), formula (BI-3), formula (BI-5), formula (BI-7), formula (BI-9) and formula (BI-11) to formula (BI-15) The compound represented by is preferable, and the compound represented by a formula (BI-1), a formula (BI-7), a formula (BI-9), and a formula (BI-15) is more preferable.

Examples of the compound represented by formula (BII) include compounds represented by any of formulas (BII-1) to (BII-15), and among them, formulas (BII-1) and (BII-3) , compounds represented by formulas (BII-5), formula (BII-7), formula (BII-9) and formulas (BII-11) to formula (BII-15) are preferred, and formula (BII-1), The compounds represented by the formulas (BII-7), (BII-9) and (BII-15) are more preferable.

The compound represented by the formula (BI) and the compound represented by the formula (BII) may be used alone, respectively, or the compound represented by the formula (BI) and the compound represented by the formula (BII) may be used in combination. When these are used together, the content ratio of the compound represented by the formula (BI) and the compound represented by the formula (BII) is, on a molar basis, preferably 5:95 to 95:5, more preferably 10:90 to It is 90:10, More preferably, it is 20:80-80:20.

As a monomer (b2) which has an oxetanyl group and an ethylenically unsaturated bond, the monomer which has an oxetanyl group and a (meth)acryloyloxy group is more preferable. As the monomer (b2), for example, 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, 3-methyl-3- (meth)acryloyloxyethyloxetane, 3-ethyl-3-(meth)acryloyloxyethyloxetane, etc. are mentioned.

As the monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable. As a monomer (b3), tetrahydrofurfuryl acrylate (For example, Viscoat V#150, Osaka Organic Chemical Co., Ltd. product), tetrahydrofurfuryl methacrylate etc. are mentioned, for example.

As the monomer (c), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate , 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in the technical field, as a common name, "dicyclopentanyl (meth) acrylate" Also called "tricyclodecyl (meth)acrylate" in some cases), tricyclo[5.2.1.0 ^2,6 ]decan-9-yl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decene-8-yl (meth)acrylate (in the technical field, commonly referred to as "dicyclopentenyl (meth)acrylate"), tricyclo[5.2.1.0 ^2,6 ]decene- 9-yl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) ) (meth)acrylic acid esters such as acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate and benzyl (meth)acrylate;

hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid;

Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybi Cyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2 -ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept -2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept- 2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methyl Bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxy Cycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene and 5,6-bis(cyclohexylox) bicyclo unsaturated compounds such as cycarbonyl)bicyclo[2.2.1]hept-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutylate, N-succinimidyl dicarbonylimide derivatives such as -6-maleimide caproate, N-succinimidyl-3-maleimide propionate and N-(9-acridinyl)maleimide;

vinyl group-containing aromatic compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene and p-methoxystyrene; vinyl group-containing nitriles such as (meth)acrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; vinyl group-containing amides such as (meth)acrylamide; esters such as vinyl acetate; dienes such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene; and the like.

Among these, from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyltoluene, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate, and tricyclo[5.2.1.0 ^2,6 ]decane-9 -yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decen-9-yl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, benzyl (meth)acrylate and the like are preferable.

In the resin [K1], the ratio of the structural units derived from each of the total structural units constituting the resin [K1],

a structural unit derived from (a); 2-60 mol%

a structural unit derived from (b); 40-98 mol%

It is preferable that

a structural unit derived from (a); 10-50 mol%

a structural unit derived from (b); 50-90 mol%

It is more preferable that

When the ratio of the structural unit of resin [K1] exists in the said range, there exists a tendency excellent in the storage stability of a colored resin composition, the developability at the time of forming a colored pattern, and the solvent resistance of the color filter obtained.

Resin [K1] is, for example, the method described in the document "Experimental Methods for Polymer Synthesis" (published by Takayuki Otsu, Chemical Dongin, 1st Edition, 1st Edition, March 1, 1972) and citations described in the document It can be prepared with reference to the literature.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, etc. are placed in a reaction vessel, for example, by replacing oxygen with nitrogen, to create a deoxidized atmosphere, and heating and keeping warm while stirring. method can be found. In addition, the polymerization initiator, solvent, etc. used here are not specifically limited, What is normally used in the said field|area can be used. For example, as a polymerization initiator, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or an organic peroxide (benzoyl peroxide etc.) These are mentioned, What is necessary is just to melt|dissolve each monomer as a solvent, The solvent etc. which are mentioned later as a solvent (E) of the colored resin composition of this invention are mentioned.

In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was taken out as a solid (powder) by methods, such as reprecipitation. In particular, by using the solvent contained in the colored resin composition of the present invention as a solvent at the time of this polymerization, the solution after the reaction can be used as it is for preparation of the colored resin composition of the present invention, so production of the colored resin composition of the present invention The process can be simplified.

In the resin [K2], the ratio of the structural units derived from each of the total structural units constituting the resin [K2],

a structural unit derived from (a); 2-45 mol%

a structural unit derived from (b); 2-95 mol%

a structural unit derived from (c); 1-65 mol%

It is preferable that

a structural unit derived from (a); 5-40 mol%

a structural unit derived from (b); 5-80 mol%

a structural unit derived from (c); 5-60 mol%

It is more preferable that

When the ratio of the structural units of the resin [K2] is within the above range, the storage stability of the colored resin composition, the developability when forming a colored pattern, and the solvent resistance, heat resistance and mechanical strength of the obtained color filter tend to be excellent. have.

The resin [K2] can be produced, for example, in the same manner as described as the method for producing the resin [K1].

In the resin [K3], the ratio of the structural units derived from each of the total structural units constituting the resin [K3],

a structural unit derived from (a); 2-60 mol%

a structural unit derived from (c); 40-98 mol%

It is preferable that

a structural unit derived from (a); 10-50 mol%

a structural unit derived from (c); 50-90 mol%

It is more preferable that

The resin [K3] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].

Resin [K4] can be prepared by obtaining the copolymer of (a) and (c), and adding the cyclic ether having 2 to 4 carbon atoms of (b) to the carboxylic acid and/or carboxylic acid anhydride of (a). can

First, the copolymer of (a) and (c) is produced in the same manner as described as the method for producing the resin [K1]. In this case, it is preferable that the ratio of the structural unit derived from each is the same ratio as that given in the resin [K3].

Next, the C2-C4 cyclic ether which (b) has is made to react with a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the said copolymer.

Continuing with the preparation of the copolymer of (a) and (c), the atmosphere in the flask is substituted with air from nitrogen, and (b), a reaction catalyst between carboxylic acid or carboxylic acid anhydride and a cyclic ether (e.g., tris ( dimethylaminomethyl)phenol) and a polymerization inhibitor (such as hydroquinone) are placed in a flask and reacted at, for example, 60 to 130° C. for 1 to 10 hours to produce resin [K4]. have.

As for the usage-amount of (b), 5-80 mol is preferable with respect to (a) 100 mol, More preferably, it is 10-75 mol. By setting it as this range, there exists a tendency for the balance of the storage stability of a colored resin composition, the developability at the time of pattern formation, and solvent resistance, heat resistance, mechanical strength, and a sensitivity of the pattern obtained to become favorable. Since the reactivity of a cyclic ether is high and unreacted (b) hardly remains, as (b) used for resin [K4], (b1) is preferable and (b1-1) is more preferable.

As for the usage-amount of the said reaction catalyst, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (b), and (c). As for the usage-amount of the said polymerization inhibitor, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (b), and (c).

Reaction conditions, such as an introduction method, reaction temperature, and time, can be suitably adjusted in consideration of manufacturing equipment, the amount of heat generated by polymerization, and the like. In addition, similarly to polymerization conditions, the introduction method and reaction temperature can be adjusted suitably in consideration of manufacturing equipment, the calorific value by polymerization, etc.

The resin [K5] is the first step, in the same manner as in the above-described method for producing the resin [K1], to obtain a copolymer of (b) and (c). Similarly to the above, the obtained copolymer may use the solution after reaction as it is, may use a concentrated or diluted solution, and may use what was taken out as a solid (powder) by methods, such as reprecipitation.

The ratio of the structural units derived from (b) and (c) is, respectively, with respect to the total number of moles of all the structural units constituting the copolymer,

a structural unit derived from (b); 5-95 mol%

a structural unit derived from (c); 5-95 mol%

It is preferable that

a structural unit derived from (b); 10-90 mol%

a structural unit derived from (c); 10-90 mol%

It is more preferable that

Further, the carboxylic acid or carboxylic acid anhydride of (a) is reacted with the cyclic ether derived from (b) which the copolymer of (b) and (c) has under the same conditions as in the production method of the resin [K4]. By doing this, resin [K5] can be obtained.

As for the usage-amount of (a) made to react with said copolymer, 5-80 mol is preferable with respect to 100 mol of (b). Since the reactivity of a cyclic ether is high and unreacted (b) hardly remains, as (b) used for resin [K5], (b1) is preferable and (b1-1) is more preferable.

Resin [K6] is resin in which resin [K5] was further made to react with carboxylic acid anhydride. A carboxylic acid anhydride is made to react with the hydroxyl group which generate|occur|produces by reaction of a cyclic ether and carboxylic acid or carboxylic acid anhydride.

Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, and the like. As for the usage-amount of carboxylic acid anhydride, 0.5-1 mol is preferable with respect to 1 mol of usage-amounts of (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decylacrylate/(meth)acrylic acid resins such as copolymer [K1]; Glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2 .1.0 ^2,6 ]decylacrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decylacrylate/(meth)acrylic acid/N- Resin [K2], such as a cyclohexyl maleimide/2-hydroxyethyl (meth)acrylate copolymer and 3-methyl-3- (meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer; resins [K3] such as benzyl (meth)acrylate/(meth)acrylic acid copolymer and styrene/(meth)acrylic acid copolymer; A resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate/(meth) acrylic acid copolymer, and glycidyl (meth) to a tricyclodecyl (meth) acrylate/styrene/(meth)acrylic acid copolymer ) Resin to which acrylate was added, resin [K4], such as a resin which added glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer; A resin obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate, tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate resin [K5] such as a resin obtained by reacting (meth)acrylic acid with a copolymer; and resin [K6] such as a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid and further reacting with tetrahydrophthalic anhydride. have.

The resin (B) is more preferably a resin [K1] and a resin [K2], and particularly preferably a resin [K1].

The weight average molecular weight (Mw) in terms of polystyrene of the resin (B) is preferably 1,000 or more and 100,000 or less, more preferably 2,000 or more and 50,000 or less, and still more preferably 3,000 or more and 30,000 or less. When a weight average molecular weight exists in said range, the solubility with respect to the developing solution of an unexposed part is high, and there exists a tendency for the residual film rate and hardness of the pattern obtained also to be high.

The degree of dispersion [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1 or more and 6 or less, more preferably 1.001 or more and 4 or less, and still more preferably 1.01 or more and 4 or less. to be.

The acid value (in terms of solid content) of the resin (B) is preferably 10 mg-KOH/g or more and 300 mg-KOH/g or less, more preferably 20 mg-KOH/g or more and 250 mg-KOH/g or less, , more preferably 25 mg-KOH/g or more and 200 mg-KOH/g or less, even more preferably 30 mg-KOH/g or more and 150 mg-KOH/g or less, particularly preferably 60 mg-KOH/g or less. /g or more and 135 mg-KOH/g or less. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.

In 100 mass % of solid content of a colored resin composition, content rate of resin (B) becomes like this. Preferably it is 5-50 mass %, More preferably, it is 10-40 mass %, More preferably, it is 15-30 mass %. When content of resin (B) exists in said range, there exists a tendency for the solubility with respect to the developing solution of an unexposed part to be high.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized with an active radical and/or an acid generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, preferably Preferably, it is a (meth)acrylic acid ester compound.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, and 2-hydroxy Ethyl acrylate, N-vinylpyrrolidone, etc., and the above-mentioned monomer (a), monomer (b), and monomer (c) are mentioned.

Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tri Ethylene glycol di(meth)acrylate, the bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc. are mentioned.

It is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol penta(meth)acrylate. Pentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth) ) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate, preferably Dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are mentioned.

The weight average molecular weight of the polymerizable compound (C) is preferably 50 or more and 4,000 or less, more preferably 70 or more and 3,500 or less, still more preferably 100 or more and 3,000 or less, still more preferably 150 or more and 2,900 or less. and particularly preferably 250 or more and 1,500 or less.

The content rate of the polymerizable compound (C) may be, for example, 1 mass % or more and 99 mass % or less, preferably 5 mass % or more and 90 mass % or less, with respect to the total amount of solid content of the colored resin composition, more preferably is 10 mass% or more and 80 mass% or less, and more preferably 20 mass% or more and 70 mass% or less.

< Polymerization initiator (D) >

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating an active radical, an acid, etc. under the action of light or heat, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include an O-acyloxime compound, an alkylphenone compound, a biimidazole compound, a triazine compound, and an acylphosphine oxide compound.

As the O-acyloxime compound, for example, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl) ) Octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-(4 -Phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine , N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6 -{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1 -[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine and N-benzoyloxy-1-[9-ethyl-6-( 2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Moreover, you may use commercial items, such as Irgacure (trademark) OXE01, OXE02 (above, BASF Corporation make), and N-1919 (made by ADEKA Corporation) as an O-acyl oxime compound. Among them, as the O-acyloxime compound, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane- At least one selected from the group consisting of 1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine is preferable, and N -benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine is more preferable.

Examples of the alkylphenone compound include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane. -1-one and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one; and the like. As an alkylphenone compound, you may use commercial items, such as Irgacure (trademark) 369, 907, 379 (above, BASF Corporation make).

Examples of the alkylphenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one. one, 1-hydroxycyclohexylphenylketone, oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone and benzyldimethylketal can also be heard.

As the biimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3- Dichlorophenyl) -4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Application Laid-Open No. 6-75372, Japanese Patent Application Laid-Open No. 6-75373, etc.), 2 ,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5 ,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (e.g. , Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.) and biimi in which the phenyl group at the 4,4',5,5'-position is substituted with a carboalkoxy group Dazole compounds (for example, refer to Unexamined-Japanese-Patent No. 7-10913 etc.) etc. are mentioned.

Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4- Methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl) )-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl ]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4 -bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine and 2,4-bis(trichloromethyl)-6- [2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine etc. are mentioned.

2,4,6-trimethylbenzoyldiphenylphosphine oxide etc. are mentioned as an acylphosphine oxide compound. You may use commercial items, such as Irgacure (trademark) 819 (made by BASF).

Moreover, as a polymerization initiator (D), Benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, o-benzoyl methylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone and benzophenone compounds such as 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, and the like.

It is preferable to use these in combination with the polymerization initiation auxiliary|assistant (D1) (particularly an amine compound) mentioned later.

The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a biimidazole compound, More preferably, it is a polymerization initiator containing an O- acyl oxime compound.

The content of the polymerization initiator (D) is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) contained in the colored resin composition. is 1 mass part or more and 20 mass parts or less. When content of a polymerization initiator (D) exists in said range, since there exists a tendency for an exposure time to become highly sensitive and to shorten, productivity of a color filter improves.

< Auxiliary for polymerization initiation (D1) >

The polymerization initiation auxiliary (D1) is a compound or sensitizer used to promote polymerization of the polymerizable compound (C) whose polymerization is initiated by the polymerization initiator (D). When the polymerization initiator auxiliary (D1) is included, it is usually used in combination with the polymerization initiator (D).

Examples of the polymerization initiation auxiliary (D1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminomethylbenzoate, 4-dimethylaminobenzoate ethyl, 4-dimethylaminobenzoate isoamyl, benzoate 2-dimethylaminoethyl, 4-dimethylaminobenzoic acid 2 -Ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone and 4,4'- Bis(ethylmethylamino)benzophenone etc. are mentioned, Preferably 4,4'-bis(diethylamino)benzophenone is mentioned. Moreover, you may use commercial items, such as EAB-F (made by Hodogaya Chemical Industry Co., Ltd.), as an amine compound.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy. anthracene and 2-ethyl-9,10-dibutoxyanthracene; and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythiok. Santon etc. are mentioned.

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, and chlorophenylsulfanylacetic acid. Panylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

When using these polymerization initiation auxiliary|assistant (D1), the content becomes like this with respect to 100 mass parts of total amounts of resin (B) and polymeric compound (C) contained in a colored resin composition, Preferably 0.1 mass part or more and 30 mass parts. Hereinafter, more preferably, they are 1 mass part or more and 20 mass parts or less.

< Solvent (E) >

The solvent (E) is not specifically limited, The solvent normally used in this field|area can be used.

The solvent (E) is, for example, an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (containing -O- in the molecule and not containing -COO-). solvent), ether ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (solvent containing -COO- in the molecule) solvents containing OH and not containing -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like. These solvents may use 2 or more types together.

As an ester solvent, methyl lactate, ethyl lactate, butyl lactate, 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyric acid butyl, 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, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol and methyl anisole, etc. can be heard

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methyl Methyl propionate, 2-ethoxy-2-methyl ethyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl and ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol methyl ether acetate.

As a ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentane on, cyclohexanone, isophorone, and the like.

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

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

Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.

It is preferable that it is a solvent containing at least 1 sort(s) chosen from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and cyclohexanone as a solvent (E).

The content rate of the solvent (E) is 99.99 mass % or less normally with respect to the total amount of the colored resin composition, Preferably it is 40 mass % or more and 99 mass % or less, More preferably, it is 50 mass % or more and 95 mass % or less, More preferably, they are 70 mass % or more and 95 mass % or less, More preferably, they are 75 mass % or more and 90 mass % or less. In other words, the total amount of solid content of the colored resin composition is usually 0.01 mass % or more, preferably 1 mass % or more and 60 mass % or less, more preferably 5 mass % or more and 50 mass % or less, further preferably They are 5 mass % or more and 30 mass % or less, More preferably, they are 10 mass % or more and 25 mass % or less. When the content rate of the solvent (E) is within the above range, flatness at the time of application becomes favorable, and since color density does not run short when a color filter is formed, there exists a tendency for a display characteristic to become favorable.

< Leveling agent (F) >

As a leveling agent (F), a silicone type surfactant, a fluorine type surfactant, the silicone type surfactant which has a fluorine atom, etc. are mentioned. These may have a polymerizable group in a side chain.

As a silicone type surfactant, the surfactant etc. which have a siloxane bond in a molecule|numerator are mentioned. Specifically, Toray Silicon DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan Joint Stock Company), etc. can

As a fluorochemical surfactant, the surfactant etc. which have a fluorocarbon chain in a molecule|numerator are mentioned. Specifically, Florad (registered trademark) FC430, dong FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapac (registered trademark) F142D, dong F171, dong F172, dong F173, dong F177, dong F183, dong F554, dong R30 , RS-718-K (manufactured by DIC Co., Ltd.), EFTO (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Material Electric Chemical Co., Ltd.), Surflon (registered trademark) S381, Copper S382, copper SC101, copper SC105 (manufactured by AGC Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Institute), etc. are mentioned.

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include Megapac (registered trademark) R08, copper BL20, copper F475, copper F477, and copper F443 (manufactured by DIC Corporation).

When containing a leveling agent (F), the content rate of a leveling agent (F) with respect to the total amount of a colored resin composition, Preferably they are 0.0005 mass % or more and 1 mass % or less, More preferably, they are 0.001 mass % or more and 0.5 mass % or less, more preferably 0.005 mass% or more and 0.1 mass% or less. In addition, content of said dispersing agent is not contained in this content. When the content rate of a leveling agent (F) exists in said range, the flatness of a color filter can be made favorable.

< Other ingredients >

The colored resin composition may contain additives known in the art, such as fillers, other high molecular compounds, adhesion promoters, quenchers, antioxidants, light stabilizers, and chain transfer agents, as needed.

<Method for producing colored resin composition>

The colored resin composition comprises a colorant (A), a resin (B), and optionally a polymerizable compound (C), a polymerization initiator (D), a polymerization initiation aid (D1), a solvent (E), and a leveling agent (F). ) and other components can be mixed. Mixing can be performed by a well-known or customary apparatus and conditions.

The colorant (A) may be used in a state in which it is mixed with a part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle diameter is about 0.2 µm or less, or in a dispersed state It is preferable to use in At this time, you may mix|blend a part or all of the said dispersing agent and resin (B) as needed. Moreover, you may use the coloring agent (A) in the state previously melt|dissolved in a part or all of a solvent (E). The color resin composition made into the objective can be prepared by mixing the remaining component with the coloring agent containing liquid obtained in this way so that it may become predetermined density|concentration.

< Manufacturing method of color filter >

From the colored resin composition of this invention, the color filter which may be a color conversion layer can be formed. A photolithographic method, an inkjet method, a printing method, etc. are mentioned as a method of forming a coloring pattern. Among them, the photolithography method is preferable. The photolithography method is a method of apply|coating the said colored resin composition to a board|substrate, drying it, forming a colored resin composition layer, exposing the said colored resin composition layer through a photomask, and developing. The photolithographic method WHEREIN: The colored coating film which is hardened|cured material of the said colored resin composition layer can be formed by not using a photomask at the time of exposure and/or not developing. The colored pattern and colored coating film thus formed are the color filters of the present invention.

The film thickness of the color filter to be produced is not particularly limited, and can be appropriately adjusted according to the purpose or use, for example, 0.1 µm or more and 30 µm or less, preferably 0.1 µm or more and 20 µm or less, more preferably is 0.5 µm or more and 6 µm or less.

Examples of the substrate include a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass coated with silica, a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, aluminum on the substrate, What formed a silver, silver/copper/palladium alloy thin film etc. is used. On these board|substrates, another color filter layer, a resin layer, a transistor, a circuit, etc. may be formed.

Formation of each color pixel by the photolithographic method can be performed with a well-known or customary apparatus and conditions. For example, it can be produced as follows.

First, a colored resin composition is apply|coated on a board|substrate, volatile components, such as a solvent, are removed and dried by heat-drying (pre-baking) and/or drying under reduced pressure, and a smooth colored resin composition layer is obtained.

Examples of the coating method include a spin coating method, a slit coating method, and a slit-and-spin coating method.

30 degreeC or more and 120 degrees C or less are preferable and, as for the temperature in the case of heat-drying, 50 degreeC or more and 110 degrees C or less are more preferable. Moreover, as a heating time, it is preferable that they are 10 second or more and 60 minutes or less, and it is more preferable that they are 30 second or more and 30 minutes or less.

When performing reduced-pressure drying, it is preferable to carry out in the temperature range of 20 degreeC or more and 25 degrees C or less under the pressure of 50 Pa or more and 150 Pa or less.

The film thickness of a colored resin composition layer is not specifically limited, What is necessary is just to select suitably according to the film thickness of the target color filter.

Next, the colored resin composition layer is exposed through a photomask for forming a target colored pattern. The pattern on the said photomask is not specifically limited, The pattern according to the intended use is used. In addition, it is preferable to use an exposure apparatus such as a mask aligner and a stepper, since it is possible to uniformly irradiate parallel rays to the entire exposure surface and to accurately align the photomask and the substrate on which the colored resin composition layer is formed. do. What is necessary is just to expose without using a photomask, when forming a colored coating film.

As a light source used for exposure, the light source which generate|occur|produces the light of the wavelength of 250 nm or more and 450 nm or less is preferable. For example, light of less than 350 nm is cut using a filter that cuts this wavelength region, or a bandpass filter that extracts light in the vicinity of 436 nm, 408 nm, and 365 nm in these wavelength ranges is used. Thus, it may be selectively taken out or may be taken out. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

A colored pattern is formed on a board|substrate by making a developing solution contact and developing the colored resin composition layer after exposure. By image development, the unexposed part of a colored resin composition layer melt|dissolves in a developing solution, and is removed. As a developing solution, the aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, and tetramethylammonium hydroxide, is preferable, for example. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 mass% or more and 10 mass% or less, and more preferably 0.03 mass% or more and 5 mass% or less. Moreover, the developing solution may contain surfactant.

The developing method may be any of a paddle method, a dipping method, and a spray method. In addition, you may incline a board|substrate at an arbitrary angle at the time of development.

The substrate after development is preferably washed with water.

Moreover, it is preferable to post-baking to the obtained coloring pattern or colored coating film. 150 degreeC or more and 250 degrees C or less are preferable, and, as for post-baking temperature, 160 degreeC or more and 240 degrees C or less are more preferable. 1 minute or more and 120 minutes or less are preferable, and, as for post-baking time, 10 minutes or more and 60 minutes or less are more preferable.

< Display device >

The color filter is useful as a color filter used for a display device (for example, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor, and especially as a color filter used for an organic EL device.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples from the beginning, and it is also carried out with appropriate changes within the range that can be suitable for the purpose of the preceding and latter period. Of course, it is possible, and all of them are included in the technical scope of the present invention. In addition, in the following, unless otherwise indicated, "part" means "mass part" and "%" means "mass %".

In the following examples, the structure of the compound was confirmed by mass spectrometry (LC; Agilent Model 1200, MASS; Agilent Model LC/MSD6130).

The polystyrene conversion weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by GPC method under the following conditions.

Device: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG2000HXL

Column temperature: 40°C

Solvent: tetrahydrofuran

Flow rate: 1.0 mL/min

Solid content concentration of analysis sample: 0.001 to 0.01 mass %

Injection volume: 50 μL

Detector: RI

Calibration standards: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio (Mw/Mn) of the weight average molecular weight and the number average molecular weight in terms of polystyrene obtained above was referred to as the degree of dispersion.

[Synthesis Example 1]

<Preparation of compound I-18-1>

N ¹ ,N ² -bis(2,6-diisopropylphenyl)perylene-3,4,9,10-tetracarboxylic acid diimide (manufactured by Tokyo Chemical Industry Co., Ltd.) 20 parts, maleic anhydride ( 788 parts of Tokyo Chemical Industry Co., Ltd.) and 12 parts of p-chloranyl (Tokyo Chemical Industry Co., Ltd. product) were mixed, and it stirred at 170 degreeC for 25 hours. While maintaining the obtained mixture at 70°C or lower, 800 parts of previously prepared 1 mol/L hydrochloric acid (manufactured by Kanto Chemical Co., Ltd.) and 300 parts of acetone (manufactured by Kanto Chemical Co., Ltd.) were added, and a yellow precipitate was formed. The mixture containing this yellow precipitate was filtered, and the residue after filtration was wash|cleaned with 400 parts of water and 200 parts of methanol. The obtained residue was dried under reduced pressure at 60°C, and N ¹ ,N ² -bis(2,6-diisopropylphenyl)benzo[ghi]perylene-2,3,8 represented by the formula (I-18-1) 15 parts of 9,11,12-hexanecarboxylic acid-2,3,8,9-bisimide-11,12-acid anhydride (hereinafter sometimes referred to as compound (I-18-1)) were obtained ( yield 75%).

<Identification of compound I-18-1>

(Mass spectrometry) Ionization mode = ESI +: m/z = [M + H] ⁺ 821

Exact Mass: 820

[Synthesis Example 2]

<Preparation of compound (I-18-2)>

4.0 parts of the compound (I-18-1) obtained in Synthesis Example 1, 2,3,5,6-tetramethyl-1,4-phenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.0 parts, and propionic acid ( 240 parts of Tokyo Chemical Industry Co., Ltd. product) were mixed, and it stirred at 140 degreeC for 6 hours. The obtained mixture was concentrated, and when 5 parts of methanol was added, yellow precipitate arose. The mixture containing this yellow precipitate was filtered, and the residue after filtration was washed with 2 parts of methanol. The obtained residue was dried under reduced pressure at 60° C. and purified by silica gel column (solvent: chloroform). N ¹ ,N ² -bis(2,6-diisopropylphenyl)- represented by the formula (I-18-2)- N ³ -(4-amino-2,3,5,6-tetramethylphenyl)-benzo[ghi]perylene-2,3,8,9,11,12-hexanecarboxylic acid triimide (hereinafter compound (I) -18-2)) was obtained (yield 77%).

<Identification of compound I-18-2>

(Mass spectrometry) Ionization mode = ESI +: m/z = [M + H] ⁺ 951

Exact Mass: 950

[Synthesis Example 3]

<Preparation of compound (I-18)>

2.0 parts of the compound (I-18-1) obtained in Synthesis Example 1, 2.4 parts of the compound (I-18-2) obtained in Synthesis Example 2, and 120 parts of heptanoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added; The mixture was stirred at 220°C for 14 hours. The obtained mixture was concentrated, and when 5 parts of methanol was added, yellow precipitate arose. The mixture containing this yellow precipitate was filtered, and the residue after filtration was washed with 2 parts of methanol. The obtained residue was dried under reduced pressure at 60° C. and purified by silica gel column (solvent: chloroform). N ¹ ,N ² -bis(2,6-diisopropylphenyl)-N ³ represented by the formula (I-18) -(4-amino-2,3,5,6-tetramethylphenyl)-benzo[ghi]perylene-2,3,8,9,11,12-hexanecarboxylic acid triimide (hereinafter compound (I-18) )) was obtained (yield 22%).

<Identification of compound I-18>

(Mass spectrometry) Ionization mode = ESI +: m/z = [M + H] ⁺ 1738

Exact Mass: 1737

Lumogen (registered trademark) F Yellow083 represented by the following formula (x) was synthesized according to the description of Japanese Patent Application Laid-Open No. 60-203650.

[Synthesis Example 4]

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was flowed into the flask, replaced with a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was placed, and the mixture was heated to 80°C while stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-ylacrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-9-ylacrylic A mixed solution of 289 parts of a mixture (content ratio of 1:1) and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a solution obtained by dissolving 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was held at 80°C for 4 hours, cooled to room temperature, and a copolymer (resin B1) solution having a solid content of 35.1% and a viscosity of 125 mPa·s measured with a B-type viscometer (23°C) was obtained. . The resulting copolymer had a weight average molecular weight Mw of 9.2×10 ³ , a dispersion degree of 2.08, and an acid value in terms of solid content of 77 mg-KOH/g. Resin B1 has the following structural units.

< Example 1 >

(1) Preparation of colored resin composition

Each component was mixed in the following ratios, and colored resin composition 1' was obtained.

(A) Colorant: a compound represented by the formula (I-18) Part 2.6

(B) Resin: Resin B1 solution 54 copies

(E) Solvent: propylene glycol monomethyl ether acetate 420 copies

(2) Preparation of colored resin composition

Next, each component was mixed in the following ratios, and the colored resin composition 1 was obtained.

Colored resin composition 1' 478 copies

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayarad (registered trademark) DPHA; manufactured by Nihon Kayaku Co., Ltd.) 40 copies

(D) Polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) part 2

(F) Leveling agent: polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.15 parts

(3) Preparation of colored coating film

On a 5 cm wide glass substrate (Eagle XG; manufactured by Corning), the colored resin composition 1 was applied by spin coating so that the post-baked film thickness was 1.7 to 2 µm, and then pre-baked at 100°C for 3 minutes. Thus, a colored resin composition layer was formed. After standing to cool, the colored resin composition layer formed on the substrate was exposed to light using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) at an exposure dose of 80 mJ/cm 2 (based on 365 nm) in an atmospheric atmosphere. investigated. After light irradiation, in oven, it post-baked at 230 degreeC for 30 minute(s), and obtained the colored coating film.

(4) Measurement of λ _max

The absorbance of the obtained colored coating film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). The wavelength at which the absorbance at 380 to 780 nm is highest was calculated as the maximum absorption wavelength (λ _max ).

(5) Heat resistance test

The obtained colored coating film was heated at 230 degreeC for 120 minute(s) in air atmosphere in oven. Color difference ΔE ^* ab was calculated by the method described in JIS Z 8730:2009 (7. Calculation method of color difference) from the xy chromaticity coordinates (x, y) and Y measurement values before and after the test. The color difference ΔE ^* ab means that the color change is smaller as the value is smaller, and when ΔE ^* ab is 5 or less, it can be said that the colored coating film has practically no problem as a color filter. Moreover, if the heat resistance of a colored coating film is favorable, it can be said that heat resistance is favorable also for the coloring pattern produced from the same colored resin composition. A result is shown in Table 2.

< Comparative Example 1 >

Instead of 2.6 parts of compound (I-18), except having used 2.6 parts of Lumogen (trademark) F Yellow083, it carried out similarly to Example 1, and obtained the colored resin composition. A result is shown in Table 2.

Claims (5)

A colored resin composition comprising a colorant and an alkali-soluble resin, wherein the colorant contains a compound represented by formula (I).

[In formula (I),
R ¹ to R ⁸ are, independently of each other, a hydrogen atom, -R ^a1 , -OR ^a1 , a halogen atom, a hydroxy group, a carboxy group, -CO-OR ^a1 , -O-CO-R ^a1 , -CO-R ^a1 , or It represents a nitro group, and R ⁷ and R ⁸ may combine with each other to form a ring.
R ^a1 represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
L ¹ represents an n-valent linking group.
n represents an integer of 2 to 6.] The method of claim 1,
A colored resin composition further comprising a polymerizable compound and a polymerization initiator. The color filter formed from the colored resin composition of Claim 1 or 2. A display device comprising the color filter according to claim 3 . A compound represented by formula (Ia).

[In formula (Ia),
R ¹ to R ⁸ are, independently of each other, a hydrogen atom, -R ^a1 , -OR ^a1 , a halogen atom, a hydroxy group, a carboxy group, -CO-OR ^a1 , -O-CO-R ^a1 , -CO-R ^a1 , or It represents a nitro group, and R ⁷ and R ⁸ may combine with each other to form a ring.
R ^a1 represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
N ^x represents a nitrogen atom.
L ² represents an n-valent linking group containing an aromatic ring, and a carbon atom constituting the aromatic ring is directly bonded to N ^x .
n represents an integer of 2 to 6.]