KR20220121204A - Colored resin composition - Google Patents

Abstract

The present invention is to provide a colored resin composition capable of forming a color filter having excellent heat resistance. The colored resin composition includes a colorant and a resin, wherein the colorant contains a compound represented by formula (I). In the formula (I), R^1 to R^11 independently represent a hydrogen atom, -R^(a1), -OR^(a1), a halogen atom, a hydroxyl group, a carboxyl 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. E represents C-H, C-R^(a1), or N. R^(a1) represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

Description

Colored resin composition {COLORED RESIN COMPOSITION}

The present invention relates to a colored resin composition.

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, the example which used the compound represented by following formula (x) for a coloring composition is known (patent document 1).

Japanese Patent Laid-Open No. 2020-79396

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 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 a resin, and the colorant comprising a compound represented by formula (I).

[In formula (I),

R ¹ to R ¹¹ 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 nitro group, and R ⁷ and R ⁸ may combine with each other to form a ring.

E represents CH, CR ^a1 or N.

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

[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].

ADVANTAGE OF THE INVENTION According to this invention, the colored resin composition 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, may be referred to as a colorant (A)) and a resin (hereinafter may be referred to as a resin (B)), and the colorant is represented by formula (I) compounds.

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, Preferably it is excellent also in light resistance.

<< Compound (I) >>

[In formula (I),

R ¹ to R ¹¹ 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 nitro group, and R ⁷ and R ⁸ may combine with each other to form a ring.

E represents CH, CR ^a1 or N.

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

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 an aralkyl group such as a benzyl group, a phenethyl group, and a 1-methyl-1-phenylethyl 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, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl 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)phenyl group, 2-dodecylphenyl group, 3-dodecylphenyl group , an alkylaryl group such as 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 biphenylyl group and a terphenylyl group are bonded; A cyclohexylmethylphenyl group, a benzylphenyl group, (dimethyl(phenyl)methyl)phenyl group, etc. are mentioned. Further, 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 the 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 ¹¹ 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 ¹¹ 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 ¹¹ 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 ¹¹ 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 ¹¹ include a carbonyl group having R ^a1 described above, 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, independently of each other, 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 nitro group, and R ^a2 represents a hydrocarbon group having 1 to 20 carbon atoms 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 as R ¹ to R ¹¹ , -CO-OR ^a1 , -O The groups described as -CO-R ^a1 and -CO-R ^a1 are exemplified.

In E, CH denotes a carbon atom to which a hydrogen atom is bonded, CR ^a1 denotes a carbon atom to which R ^a1 is bonded, and N denotes a nitrogen atom.

R ¹ and R ² are preferably, independently of each other, a saturated chain hydrocarbon group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, or a group in which an aromatic hydrocarbon group which may have a substituent and a chain hydrocarbon group are combined. 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 couple|bonded with the C1-C4 chain hydrocarbon group at two ortho positions. Among them, R ¹ and R ² are each independently more preferably a group represented by the formulas (D-4) to (D-14) or (G-5) to (G-22). , 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 (G) -13), a group represented by any of formula (G-15), formula (G-16), formula (G-19), formula (G-21), or formula (G-22) is more preferable, 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- It is especially preferable that it is a group represented by any of 16).

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

R ³ to R ⁶ are each independently preferably a hydrogen atom, a halogen atom, or a hydroxy group, and more preferably a hydrogen atom.

R ⁷ and R ⁸ are preferably, independently of each other, a hydrogen atom, a halogen atom, or a hydroxyl group, or those which are bonded to each other to form a ring;

It is more preferable that R ⁷ and R ⁸ are hydrogen atoms, or R ⁷ and R ⁸ combine with each other to form any of the groups represented by the above formulas (H-1) to (H-3),

It is more preferable that R ⁷ and R ⁸ are hydrogen atoms, or R ⁷ and R ⁸ combine with each other to form the above formula (H-1) or (H-2).

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.

R ⁹ to R ¹¹ are each independently preferably a hydrogen atom, -R ^a1 , a halogen atom or a hydroxyl group, and more preferably a hydrogen atom.

As E, it is preferable that it is C-H or N.

Specific examples of the compound (I) include compounds (I-1) to (I-30) shown in Table 1 below.

In Table 1, H represents a hydrogen atom, and N represents a nitrogen atom.

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

C-H means a carbon atom to which a hydrogen atom is bonded.

H-1-1, H-2-1, H-3-1, and H-4-1, R ⁷ and R ⁸ are bonded to each other, the following formula (H-1-1), formula (H-2 -1), formula (H-3-1), means an embodiment in which the group represented by the formula (H-4-1) is respectively formed. In the following formula, * represents a bond possessed by R ⁷ , and ** represents a bond possessed by R ⁸ .

As the compound (I), compounds (I-17) to (I-24) are preferable, and compounds (I-17) to (I-22) are more preferable.

Compound (I) can be prepared according to route 1 or route 2, for example.

Route 1 is a step (i) of reacting a compound represented by the following formula (pt-1) with X ₂ to obtain a compound represented by the formula (pt-2), a compound represented by the formula (pt-2), and It consists of the process (ii) of making the compound represented by Formula (MA-1) react, and obtaining compound (I).

Route 2 is a step (iii), formula (pt-) of reacting a compound represented by the following formula (pt-2) with a compound represented by the formula (MA-2) to obtain a compound represented by the formula (pt-3) It consists of step (iv) of converting the compound represented by 3) to obtain compound (I).

In the formulas (pt-1) to (pt-3), R ¹ to R ¹¹ and E have the same meanings as above. In formulas (MA-1) and (MA-2), R ^B1 is each independently a hydrogen atom, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, 2,2-dimethylpropyl-1,3-diyl group formed with two R ^B1 rings, 2,3-dimethylbutyl-2,3-diyl group, 2-methylpentyl-2,4- A diyl group or a 1,2-phenylene group is shown.

X in X ₂ used in the process (i) of route 1 represents a halogen atom, and a chlorine atom and a bromine atom are preferable. The compound represented by the formula (pt-2) can be produced by reacting the compound represented by the formula (pt-1) with X ₂ in a solvent.

Examples of the compound represented by the formula (pt-1) include N,N'-bis(2,6-diisopropylphenyl)-3,4,9,10-perylenetetracarboxylic acid diimide. can be heard

Examples of the solvent include water; nitrile solvents such as acetonitrile; Alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, 1-octanol, and phenol ; ether solvents such as diethyl ether and tetrahydrofuran; ketone solvents such as acetone and methyl isobutyl ketone; ester solvents such as ethyl acetate; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene; halogenated hydrocarbon solvents such as methylene chloride, chloroform, and 1,2-dichlorobenzene; amide solvents such as N,N-dimethylformamide and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; carboxylic acid solvents, such as acetic acid, propionic acid, and butyric acid, are mentioned, Methylene chloride and chloroform are more preferable.

The amount of X ₂ used is usually 1 mol or more and 5 mol or less, more preferably 1 mol or more and 2.5 mol or less, further preferably 1 mol or more and 1.25 mol with respect to 1 mol of the compound represented by the formula (pt-1). less than moles.

The usage-amount of a solvent is 1-1000 mass parts normally with respect to 1 mass part of the compound represented by Formula (pt-1).

Reaction temperature is -100 degreeC or more and 300 degrees C or less normally.

Compound (I) in step (ii) is prepared by mixing a compound represented by formula (pt-2) (sometimes referred to as compound (pt-2)) and a compound represented by formula (MA-1) in a solvent. , a catalyst, a phosphine ligand, and can be prepared by reacting in the presence of a base.

Examples of the catalyst include tris(dibenzylideneacetone)dipalladium(0), bis(dibenzylideneacetone)palladium(0), palladium(II) acetate, palladium(II) chloride, sodium tetrachloropalladium(II)ate, palladium. (II) (π-cinnamyl) chloride (dimer), allyl palladium (II) chloride dimer, bis (benzonitrile) palladium (II) dichloride, bis (acetonitrile) palladium (II) dichloride; , palladium (II) acetate and bis (dibenzylideneacetone) palladium (0) are more preferable.

Examples of the phosphine ligand include tributylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, triphenylphosphine, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine, tri(p -Tolyl) phosphine, tris (3-methoxyphenyl) phosphine, tris [3,5-bis (trifluoromethyl) phenyl] phosphine, ethyldiphenylphosphine, tris (2,6-dimethoxyphenyl) ) phosphine, tris (4-fluorophenyl), diphenylpropylphosphine, di-tert-butylphenylphosphine, tri (2-furyl) phosphine, tri (2-thienyl) phosphine, tris (4 -Methoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, methyldiphenylphosphine, 1-[2-(di-tert-butylphosphino)phenyl]-3,5-diphenyl-1H -Pyrazole, (4-dimethylaminophenyl)di-tert-butylphosphine, 2-(di-tert-butylphosphino)biphenyl, di-tert-butyl (1,1-diphenyl-1-propene) -2-yl) phosphine, isopropyl diphenyl phosphine, 2- (dicyclohexyl phosphino) -2'- (dimethylamino) biphenyl, 2- (dicyclohexyl phosphino) biphenyl, 2- ( Diphenylphosphino) biphenyl, 2-dicyclohexylphosphino-2'-methylbiphenyl, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, 2-dicyclohexylphos Pino-2',6'-dimethoxybiphenyl, dicyclohexyl (1-methyl-2,2-diphenylcyclopropyl)phosphine, di-tert-butyl (2',4',6'-triiso Propyl-3,6-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2 -diphenylphosphino-2'-(N,N-dimethylamino)biphenyl, 2-di-tert-butylphosphino-2',4',6'-triisopropylbiphenyl, dicyclohexyl (2 ',4',6'-triisopropyl-3,6-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine, dicyclohexyl (1,1-diphenyl-1-prop Monodentate phosphine ligands such as phen-2-yl)phosphine, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphine) Pino)propane, 1,4-bis(diphenylphosphino)butane, 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, 4,5-bis(dicyclohexylphosphino) )-9,9-dimethylxanthene, 1,2,3,4,5- Pentaphenyl-1'-(di-tert-butylphosphino)ferrocene, 1',2'-bis[bis(3,5-dimethylphenyl)phosphino]-1,1'-biphenyl, 4,5- Bis(diphenylphosphino)-9,9-dimethylxanthene, 1,3-bis(diphenylphosphino)propane, 1,1'-bis(di-tert-butylphosphino)ferrocene, bis[2- bidentate phosphine ligands such as (diphenylphosphino)phenyl]ether, 1,1'-bis(diisopropylphosphino)ferrocene, and 1,1'-bis(diphenylphosphino)ferrocene and preferably a monodentate phosphine ligand, more preferably triphenylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, and most preferably triphenylphosphine.

Examples of the base include inorganic bases and organic bases.

Examples of the inorganic base include hydroxides, carbonates, hydrogencarbonates, phosphates, carboxylates, and alkoxides of alkali metals or alkaline earth metals. Here, as a form of the base used here, an anhydride form may be sufficient, and a hydrate form may be sufficient as it.

The inorganic base preferably includes hydroxides, carbonates, hydrogencarbonates, phosphates and carboxylates of alkali metals or alkaline earth metals, and carbonates and phosphates of alkali metals or alkaline earth metals are more preferable. As salts of alkali metals or alkaline earth metals, carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate and barium carbonate, and phosphates such as lithium phosphate, sodium phosphate and potassium phosphate are preferable, and sodium carbonate, potassium carbonate, Potassium phosphate is more preferable.

Examples of the organic base include triethylamine, 4-(N,N-dimethylamino)pyridine, pyridine, piperidine, N,N-diisopropylethylamine, 1,4-diazabicyclo[2.2.2]octane, 1 ,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, and the like, and 1,8-diazabicyclo[5.4.0 ]-7-undecene is more preferable.

As the base, hydroxides, carbonates, hydrogencarbonates, phosphates, and carboxylates of alkali metals or alkaline earth metals, and organic bases are preferable, and carbonates and phosphates of alkali metals or alkaline earth metals, and organic bases are more preferable.

Examples of the solvent include water; nitrile solvents such as acetonitrile; Alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, 1-octanol, and phenol ; ether solvents such as diethyl ether and tetrahydrofuran; ketone solvents such as acetone and methyl isobutyl ketone; ester solvents such as ethyl acetate; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene; halogenated hydrocarbon solvents such as methylene chloride, chloroform, and 1,2-dichlorobenzene; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; carboxylic acid solvents, such as acetic acid, propionic acid, and butyric acid, etc. are mentioned, N,N- dimethylformamide, N,N- dimethylacetamide, and toluene are preferable.

The amount of the catalyst used is usually 0.01 mol or more and 1 mol or less, more preferably 0.01 mol or more and 0.5 mol or less, and still more preferably 0.01 mol or more and 0.25 mol or less with respect to 1 mol of compound (pt-2).

The amount of the phosphine ligand to be used is usually 0.01 mol or more and 3 mol or less, more preferably 0.02 mol or more and 1 mol or less, and still more preferably 0.02 mol or more and 0.5 mol or less with respect to 1 mol of compound (pt-2). .

The amount of the base used is usually 1 mol or more and 50 mol or less, more preferably 1 mol or more and 25 mol or less, and still more preferably 1 mol or more and 15 mol or less with respect to 1 mol of compound (pt-2).

The amount of the compound represented by the formula (MA-1) to be used is usually 1 mol or more and 10 mol or less, more preferably 1 mol or more and 5 mol or less, still more preferably with respect to 1 mol of the compound (pt-2). is 1 mole or more and 2 moles or less.

The usage-amount of a solvent is 1-1000 mass parts normally with respect to 1 mass part of compound (pt-2).

Reaction temperature is -100 degreeC or more and 300 degrees C or less normally.

The compound represented by the formula (pt-3) in the step (iii) of the route 2 (sometimes referred to as the compound (pt-3)) is represented by the compound (pt-2) and the formula (MA-2), It can be produced by reacting the compound in a solvent in the presence of a catalyst, a phosphine ligand, and a base. In addition, compound (pt-2) can be manufactured by the above-mentioned process (i), for example.

Examples of the catalyst include tris(dibenzylideneacetone)dipalladium(0), bis(dibenzylideneacetone)palladium(0), palladium(II) acetate, palladium(II) chloride, sodium tetrachloropalladium(II)ate, palladium. (II) (π-cinnamyl) chloride (dimer), allyl palladium (II) chloride dimer, bis (benzonitrile) palladium (II) dichloride, bis (acetonitrile) palladium (II) dichloride; , palladium (II) acetate and bis (dibenzylideneacetone) palladium (0) are more preferable.

Examples of the phosphine ligand include tributylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, triphenylphosphine, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine, tri(p -Tolyl) phosphine, tris (3-methoxyphenyl) phosphine, tris [3,5-bis (trifluoromethyl) phenyl] phosphine, ethyldiphenylphosphine, tris (2,6-dimethoxyphenyl) ) phosphine, tris (4-fluorophenyl), diphenylpropylphosphine, di-tert-butylphenylphosphine, tri (2-furyl) phosphine, tri (2-thienyl) phosphine, tris (4 -Methoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, methyldiphenylphosphine, 1-[2-(di-tert-butylphosphino)phenyl]-3,5-diphenyl-1H -Pyrazole, (4-dimethylaminophenyl)di-tert-butylphosphine, 2-(di-tert-butylphosphino)biphenyl, di-tert-butyl (1,1-diphenyl-1-propene) -2-yl) phosphine, isopropyl diphenyl phosphine, 2- (dicyclohexyl phosphino) -2'- (dimethylamino) biphenyl, 2- (dicyclohexyl phosphino) biphenyl, 2- ( Diphenylphosphino) biphenyl, 2-dicyclohexylphosphino-2'-methylbiphenyl, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, 2-dicyclohexylphos Pino-2',6'-dimethoxybiphenyl, dicyclohexyl (1-methyl-2,2-diphenylcyclopropyl)phosphine, di-tert-butyl (2',4',6'-triiso Propyl-3,6-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2 -diphenylphosphino-2'-(N,N-dimethylamino)biphenyl, 2-di-tert-butylphosphino-2',4',6'-triisopropylbiphenyl, dicyclohexyl (2 ',4',6'-triisopropyl-3,6-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine, dicyclohexyl (1,1-diphenyl-1-prop monodentate phosphine ligands such as phen-2-yl)phosphine, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, 4,5-bis(dicyclohexylphosphino)-9, 9-dimethylxanthene, 1,2,3,4,5-pentaphenyl -1'-(di-tert-butylphosphino)ferrocene, 1',2'-bis[bis(3,5-dimethylphenyl)phosphino]-1,1'-biphenyl, 4,5-bis( Diphenylphosphino)-9,9-dimethylxanthene, 1,3-bis(diphenylphosphino)propane, 1,1'-bis(di-tert-butylphosphino)ferrocene, bis[2-(di bidentate phosphine ligands such as phenylphosphino)phenyl]ether, 1,1'-bis(diisopropylphosphino)ferrocene, and 1,1'-bis(diphenylphosphino)ferrocene, preferably It is a monodentate phosphine ligand.

Examples of the base include hydroxides, carbonates, hydrogen carbonates, phosphates, carboxylates, and alkoxides of alkali metals or alkaline earth metals that are inorganic bases. Here, as a form of the base used here, an anhydride form or a hydrate form may be sufficient as it. Preferably, hydroxides, carbonates, hydrogen carbonates, phosphates, and carboxylates of alkali metals or alkaline earth metals are mentioned, and carbonates and phosphates of alkali metals or alkaline earth metals are more preferable. As the alkali metal or alkaline earth metal salt, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, barium carbonate, lithium phosphate, sodium phosphate, and potassium phosphate are preferable, and sodium carbonate, potassium carbonate, and potassium phosphate are more preferable.

Examples of the solvent include water; nitrile solvents such as acetonitrile; Alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, 1-octanol, and phenol ; ether solvents such as diethyl ether and tetrahydrofuran; ketone solvents such as acetone and methyl isobutyl ketone; ester solvents such as ethyl acetate; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene; halogenated hydrocarbon solvents such as methylene chloride, chloroform, and 1,2-dichlorobenzene; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; carboxylic acid solvents, such as acetic acid, propionic acid, and butyric acid, etc. are mentioned, Toluene, xylene, and tetrahydrofuran are preferable.

The amount of the catalyst used is usually 0.01 mol or more and 1 mol or less, more preferably 0.01 mol or more and 0.5 mol or less, and still more preferably 0.01 mol or more and 0.25 mol or less with respect to 1 mol of compound (pt-2).

The amount of the phosphine ligand to be used is usually 0.01 mol or more and 3 mol or less, more preferably 0.02 mol or more and 1 mol or less, and still more preferably 0.02 mol or more and 0.5 mol or less with respect to 1 mol of compound (pt-2). .

The amount of the base used is usually 1 mol or more and 50 mol or less, more preferably 1 mol or more and 25 mol or less, and still more preferably 1 mol or more and 15 mol or less with respect to 1 mol of compound (pt-2).

The amount of the compound represented by the formula (MA-2) to be used is usually 1 mol or more and 10 mol or less, more preferably 1 mol or more and 5 mol or less, still more preferably with respect to 1 mol of the compound (pt-2). is 1 mole or more and 2 moles or less.

The usage-amount of a solvent is 1-1000 mass parts normally with respect to 1 mass part of compound (pt-2).

Reaction temperature is -100 degreeC or more and 300 degrees C or less normally.

Compound (I) in step (iv) of route 2 can be produced by reacting the compound represented by formula (pt-3) (sometimes referred to as compound (pt-3)) in a solvent with light irradiation. have.

Examples of the solvent include water; nitrile solvents such as acetonitrile; Alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, 1-octanol, and phenol ; ether solvents such as diethyl ether and tetrahydrofuran; ketone solvents such as acetone and methyl isobutyl ketone; ester solvents such as ethyl acetate; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene; halogenated hydrocarbon solvents such as methylene chloride, chloroform, and 1,2-dichlorobenzene; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; carboxylic acid solvents, such as acetic acid, propionic acid, and butyric acid, etc. are mentioned, Dichloromethane and chloroform are preferable.

The light source used for light irradiation is not limited, For example, sunlight, a xenon lamp, a fluorescent lamp, a light emitting diode (LED), a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned.

The usage-amount of a solvent is 1-1000 mass parts normally with respect to 1 mass part of compound (pt-3).

Reaction temperature is -100 degreeC or more and 300 degrees C or less normally.

Further, compound (I) in step (iv) can also be produced by reacting compound (pt-3) with compound (MA-3) in a solvent.

As compound (MA-3), a metal chloride is mentioned, Iron (III) chloride, zinc chloride, and aluminum chloride are preferable.

The usage-amount of compound (MA-3) is 0.01 mol or more and 10 mol or less normally with respect to 1 mol of compound (pt-3), More preferably, it is 0.1 mol or more and 5 mol or less.

Examples of the solvent include water; nitrile solvents such as acetonitrile; Alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, 1-octanol, and phenol ; ether solvents such as diethyl ether and tetrahydrofuran; ketone solvents such as acetone and methyl isobutyl ketone; ester solvents such as ethyl acetate; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene; halogenated hydrocarbon solvents such as methylene chloride, chloroform, and 1,2-dichlorobenzene; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; carboxylic acid solvents, such as acetic acid, propionic acid, and butyric acid, nitro solvents, such as nitromethane and nitrobenzene, etc. are mentioned, Dichloromethane, chloroform, and nitromethane are preferable.

The usage-amount of a solvent is 1-1000 mass parts normally with respect to 1 mass part of compound (pt-3).

Reaction temperature is -100 degreeC or more and 300 degrees C or less normally.

<< 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, and mordant dyes. . 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, 6; C. I. dispers dyes such as 0;

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, etc. are mentioned.

As the pigment (A1-2), as long as it does not contain compound (I), it does not specifically limit, 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 type. As a dispersing agent, if it shows by a brand name, KP (Shin-Etsu Chemical Co., Ltd. product), Florene (Kyoeisha Chemical Co., Ltd. product), Solsperse (trademark) (Zeneca Co., Ltd. product), EFKA (registered trademark) (manufactured by BASF), 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 be heard 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.

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.

< Resin (B) >

Although resin (B) is not specifically limited, It is preferable that it is resin used for formation of a photoresist unlike a thermoplastic resin. Especially, as resin (B), it is more preferable that it is alkali-soluble resin, and it is more 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 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 unit of the resin [K2] is within the above range, the storage stability of the colored resin composition, the developability at the time of forming a colored pattern, and the tendency for the solvent resistance, heat resistance and mechanical strength of the obtained color filter to be excellent There is this.

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) does not remain|survive easily, 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) does not remain easily, 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 weights (Mw) in terms of polystyrene of the resin (B) are 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 of the resin (B) [weight average molecular weight (Mw)/number average molecular weight (Mn)] is preferably 1 or more and 6 or less, more preferably 1.001 or more and 4 or less, still more preferably 1.01 or more and 4 is below.

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, and more preferably 20 mg-KOH/g or more and 250 mg-KOH/g or less. and 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. KOH/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 comprising 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 it to become highly sensitive and exposure time 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.

Examples of the ester solvent include 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 be heard

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);

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 initiator auxiliary (D1), a solvent (E), a leveling agent (F) And it can be prepared by mixing other components. Mixing can be performed by a well-known or customary apparatus and conditions.

The colorant (A) may be mixed with a part or all of the solvent (E) in advance and used in a dispersed state using a bead mill or the like until the average particle diameter becomes 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 drying under reduced pressure, 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. Moreover, you may incline a board|substrate at an arbitrary angle at the time of development.

It is preferable that the board|substrate after image development is 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 type 1200, MASS; Agilent type 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-19>

Compound (I-19) was synthesized according to the description of Chemical Communications 2005, 4045-4046.

<Identification of compound I-19>

(Mass spectrometry) Ionization mode = ESI +: m/z = [M + H] ⁺ 875

Exact Mass: 874

[Synthesis Example 2]

<Preparation of compound I-17>

Compound (I-17) was synthesized according to the description of European Journal of Organic Chemistry, 2014, 5178-5195.

<Identification of compound I-17>

(Mass spectrometry) Ionization mode = ESI +: m/z = [M + H] ⁺ 801

Exact Mass: 800

[Synthesis Example 3]

<Preparation of compound I-22>

Compound (I-22) was synthesized according to the description of Organic Letters, 2010, Vol. 12, 228-231.

<Identification of compound I-22>

(Mass spectrometry) Ionization mode = ESI +: m/z = [M + H] ⁺ 877

Exact Mass: 876

[Synthesis Example 4]

<Preparation of compound I-18>

Compound (I-18) was synthesized according to the description of Organic Letters, 2010, Vol. 12, 228-231.

<Identification of compound I-18>

(Mass spectrometry) Ionization mode = ESI +: m/z = [M + H] ⁺ 802

Exact Mass: 801

Lumogen (registered trademark) F Orange240 (compound represented by the following formula (x)) was obtained from Tokyo Chemical Industry Co., Ltd.

[Synthesis Example 5]

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 the colored resin composition 1 was obtained.

(A) Colorant: a compound represented by the formula (I-19) Part 2.6

(B) Resin: Resin B1 solution 54 copies

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

(2) Preparation of colored curable resin composition

Next, each component was mixed in the following ratio, and the colored curable 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) Production of colored coating film (color filter)

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

It was 2 micrometers when the film thickness of the obtained colored coating film was measured using DEKTAK3 (made by Nippon Vacuum Technology Co., Ltd.).

Chromaticity evaluation of the colored coating film is measured spectroscopy using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and xy chromaticity coordinates (x, y) and the stimulus value Y were measured.

(4) 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 small 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 curable resin composition. A result is shown in Table 2.

(5) light fastness test

An ultraviolet cut filter (COLORED OPTICAL GLASS L38; manufactured by Hoya Corporation; which cuts light of 380 nm or less) is placed on the obtained colored coating film, and a xenon lamp light is irradiated with a light resistance tester (SUNTEST CPS+: manufactured by Toyo Seiki Corporation) for 48 hours. did. 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. In addition, the color difference ΔE ^* ab means that the color change is small 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 light resistance of a colored coating film is favorable, it can be said that the light resistance is favorable also for the colored pattern produced from the same colored curable resin composition. A result is shown in Table 2.

< Examples 2 to 4 and Comparative Example 1 >

Instead of 2.6 parts of compound (I-19),

2.6 parts of compound (I-17) (Example 2),

2.6 parts of compound (I-22) (Example 3),

2.6 parts of compound (I-18) (Example 4), or

Except having used 2.6 parts of Lumogen (trademark) F Orange240 (comparative example 1) as a coloring agent, it carried out similarly to Example 1, and obtained colored curable resin composition. Moreover, it carried out similarly to Example 1, the colored coating film was produced, and the said heat resistance test and the light resistance test were done. A result is shown in Table 2.

Claims (4)

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

[In formula (I),
R ¹ to R ¹¹ 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 nitro group, and R ⁷ and R ⁸ may combine with each other to form a ring.
E represents CH, CR ^a1 or N.
R ^a1 represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.] 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 .