KR101695048B1

KR101695048B1 - Display device

Info

Publication number: KR101695048B1
Application number: KR1020127006321A
Authority: KR
Inventors: 다카키요 데라카와
Original assignee: 스미또모 가가꾸 가부시키가이샤
Priority date: 2009-08-12
Filing date: 2010-07-30
Publication date: 2017-01-10
Also published as: WO2011018987A1; CN102472849B; CN102472849A; JP5614155B2; TWI516840B; TW201207501A; JP2011059673A; KR20120048678A

Abstract

The present invention relates to a color filter comprising a color filter and a white LED light source including a dye, wherein light emitted from a white LED light source has a wavelength lambda ₁ at which light emission intensity is maximum within a wavelength range of 430 to 485 nm, And has a wavelength lambda ₂ within a range of from 5 nm to 580 nm and a lambda ₃ at a maximum within a range of from 590 nm to 680 nm.

Description

Display device {DISPLAY DEVICE}

The present invention relates to a display device.

In a color liquid crystal display device or the like, color (image) display is performed using a color filter.

The color filter is generally manufactured by forming colored transparent fine patterns (called pixels) of three colors on transparent substrates such as glass or opaque substrates such as silicon. As the three colors, three primary colors of red (R), green (G) and blue (B) are often employed.

For example, Patent Document 1 describes a display device including a color filter including a pigment as a coloring agent and a backlight on which a white LED light source is mounted as a light source.

Japanese Patent Application Laid-Open No. 2008-96471

In a conventional display device, there are cases where the luminance and the contrast are not always satisfied.

That is, the present invention provides the following inventions 1 to 11.

1. A color filter comprising a dye and a white LED light source,

The light emitted from the white LED light source has a wavelength? ₁ at which the light emission intensity is maximum within the range of 430 to 485 nm and a wavelength? ₂ at which the light emission intensity is maximized within the wavelength range of 500 to 580 nm , And has a wavelength? ₃ at which the light emission intensity is maximized within a wavelength range of 590 nm to 680 nm.

2. A display device according to claim 1, wherein the white LED light source is a light source including a blue LED light source and a phosphor.

3. The display device according to 1 or 2, wherein the white LED light source is a light source including a blue LED light source, a red light-emitting fluorescent substance and a green light-emitting fluorescent substance.

4. Color filters are color filters including dyes and pigments. To the display device.

5. A dye comprising at least one dye selected from the group consisting of a dye having a group derived from an azo dye and a dye having a group derived from a xanthene dye. To the display device.

6. The dye according to any one of claims 1 to 5, wherein the dye is a dye represented by the following formula (1). To the display device.

(In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ or -SO ₂ NR < ⁸ > R < ⁹ >

R ⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ ,

m represents an integer of 0 to 5, and when m is an integer of 2 or more, plural R ^{5 s} may be the same or different,

X represents a halogen atom, a represents an integer of 0 or 1,

R ⁶ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, and -CH ₂ - included in the saturated hydrocarbon group may be replaced by -O-, -NR < ⁷ > -,

R ⁷ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom or an alkoxy group having 1 to 10 carbon atoms,

R ⁸ and R ⁹ each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q, or R ⁸ and R ⁹ are bonded to each other to form a heterocyclic ring having 1 to 10 carbon atoms However,

Q is a monovalent aromatic hydrocarbon group or a monovalent aromatic heterocyclic group having a carbon number of 3 to 10 carbon atoms of 6 to 10, the hydrogen atoms contained in the aromatic hydrocarbon group and the aromatic heterocyclic group is -OH, -R ^6, -OR ⁶ , -NO ₂ , -CH = CH ₂ , -CH = CHR ⁶ or a halogen atom,

M represents a sodium atom or a potassium atom, the number of + charge and - charge is the same as that of the compound represented by formula (1).)

7. A color filter comprising a color filter formed from a photosensitive resin composition containing a dye, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent. To the display device.

8. The display device of claim 7, wherein the photosensitive resin composition comprises a pigment.

9. A display device according to claim 8, wherein the ratio of the content of the dye to the content of the pigment is in a mass fraction of 1:99 to 99: 1.

Wherein the pigment is selected from the group consisting of CI Pigment Blue 15: 6, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Red 177, Wherein the pigment is at least one selected from the group consisting of CI Pigment Red 242 and CI Pigment Red 254.

11. The pigment is C.I. Pigment Blue 15: 6 8. to 10. To the display device.

1 is a schematic view showing a color filter.
2 is a schematic view showing a display device.
3 is a perspective view showing a backlight unit.
Fig. 4 shows the emission spectrum of the light source 1. Fig.
Fig. 5 shows the emission spectrum of the light source 2. Fig.

A display device of the present invention includes a color filter including a dye and a white light emitting diode (LED) light source.

The color filter includes a dye.

The dyes are not particularly limited, and known dyes can be used, and examples thereof include oil dyes, acid dyes, amine salts of acid dyes and sulfonamide derivatives of acid dyes.

Examples of the dyes include dyes classified in the color index (published by The Society of Dyers and Colourists) or dyes described in the dyeing notes (dyeing yarn), and specifically, CI solvents 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162, CI Solvent 4 (hereinafter abbreviated as CI Solvent Yellow) CI Solvent Blue 1, 3, 4, 5, 7, 28, CI Solvent Blue 35, 37, 59, 29, 32, 33, 34, 35, and the like.

CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 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,

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

CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173,

CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, , 335, 340,

C.I. Acid Violet 6B, 7, 9, 17, 19,

Dyes such as C.I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106,

CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141,

CI 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 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107,

CI Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117 , 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193 , 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252 , 256, 257, 259, 260, 268, 274, 275, 293,

CI direct green 25, 27, 31, CI direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, and the like.

Further, as the C.I. modern dye, there may be mentioned C.I.Modent Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65,

CI Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95,

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

CI modern blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84,

C. I. Modern Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58,

Dyes such as C.I. Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43,

Examples of the dye include amine salts of the acidic dyes represented by the formulas (i) to (vii) and sulfonamide derivatives of the acidic dyes represented by the formula (viii) or (ix).

[In the formulas (i) to (ix), D represents a group derived from a dye.

and m represents an integer of 1 or more and 20 or less.

and n represents an integer of 1 or more and 20 or less.

e and f independently represent an integer of 1 or more and 10 or less.

Ph represents a phenyl group.

Py ⁺ represents a group represented by the following formula (I) connected to a nitrogen atom C _n H _2n _{+ 1} .

(In the formula (I), R 'represents a methyl group, and ma represents an integer of 0 or 1.)

and p represents an integer of 1 or more and 8 or less.

q represents an integer of 0 or more and 8 or less.

And L represents a hydrogen atom or a monovalent cation.

Specific examples of D include groups derived from azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes and phthalocyanine dyes.

m is preferably an integer of 1 or more and 10 or less, and more preferably an integer of 1 or more and 8 or less.

n is preferably an integer of 1 or more and 10 or less, and more preferably an integer of 1 or more and 8 or less.

e and f each independently represent an integer of preferably 1 or more and 8 or less, more preferably 1 or more and 6 or less.

Py ⁺ preferably represents a group represented by the following formula (I-1).

p is preferably an integer of 1 or more and 6 or less, more preferably an integer of 1 or more and 5 or less.

q is preferably an integer of 0 or more and 6 or less, more preferably 0 or more and 5 or less.

Examples of the monovalent cation in L include an organic ammonium ion such as lithium ion, sodium ion, potassium ion and (C ₂ H ₅ ) ₃ HN ^+, and the like, preferably sodium ion.

Examples of the azo dye include the dyes represented by the formulas (71) to (74).

[In the formula (71), R ⁷¹ represents an alkyl group having 2 to 20 carbon atoms, a cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain, an alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain, an alkoxy group having 2 to 12 carbon atoms An alkylcarbonyloxyalkyl group represented by the formula (71-1), an alkyloxycarbonylalkyl group represented by the formula (71-2), a phenyl group substituted with an alkyl group having 1 to 20 carbon atoms , Or an alkyl group having 1 to 20 carbon atoms substituted with a phenyl group.

L ¹ -CO-OL ² - (71-1)

L ³ -O-CO-L ⁴ - (71-2)

(In the formula (71-1), L ¹ represents an alkyl group having 2 to 12 carbon atoms.

L ² represents an alkylene group having ² to 12 carbon atoms.

In the formula (71-2), L ³ represents an alkyl group having 2 to 12 carbon atoms.

And L < ⁴ > represents an alkylene group having 2 to 12 carbon atoms.

R ⁷² to R ^{75 each} represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group or a halogen atom.

Examples of the alkyl group having 2 to 20 carbon atoms include an ethyl group, an n-propyl group, an isopropyl group, an n-hexyl group, an n-nonyl group, Butyl group, 1-methylbutyl group, 1,5-dimethylhexyl group and 1,1,3,3-tetramethylbutyl group.

Examples of the cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain include a cyclohexylethyl group, a 3-cyclohexylpropyl group and an 8-cyclohexyloctyl group.

Examples of the alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain include a 2-ethylcyclohexyl group, a 2-propylcyclohexyl group, and a 2- (n-butyl) cyclohexyl group.

Examples of the alkyl group having 2 to 12 carbon atoms substituted with an alkoxy group having 2 to 12 carbon atoms include a 3-ethoxypropyl group, a propoxypropyl group, a 4-propoxybutyl group, a 3-methylhexyloxyethyl group and a 3- And a propyl group).

Examples of the phenyl group substituted with an alkyl group having 1 to 20 carbon atoms include o-isopropylphenyl group and the like.

Examples of the alkyl group having 1 to 20 carbon atoms substituted with a phenyl group include a DL-1-phenylethyl group, a benzyl group and a 3-phenylbutyl group.

Examples of the alkyl group having 2 to 12 carbon atoms in L ¹ and L ³ include an ethyl group, a propyl group, an n-hexyl group, a n-nonyl group, a n-decyl group, Dimethylbutyl group, 1-methylbutyl group, 1,5-dimethylhexyl group and 1,1,3,3-tetramethylbutyl group.

Examples of the alkylene group having 2 to 12 carbon atoms in L ² and L ⁴ include a dimethylene group and a hexamethylene group.

R ⁷² to R ^{75 each} represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group or a halogen atom. Examples of R ⁷² to R ⁷⁵ include a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an n-butyl group, an isopropyl group, a sec- Butyl group, isopropyl group, sec-butyl group, tert-butyl group, fluorine atom or chlorine atom can be exemplified.

Among the dyes represented by the formula (71), preferred dyes include the dyes represented by the formula (75).

The dye having a group derived from an anthraquinone dye includes, for example, a dye represented by the formula (76).

The dye having a group derived from a triphenylmethane dye includes, for example, a dye represented by the formula (77).

Examples of the dye having a group derived from the phthalocyanine dye include dyes represented by the following formula (78).

The dye is preferably a dye containing a dye containing a carboxyl group because it tends to react with the cyclic ether structure to improve the solvent resistance.

The dye containing a carboxyl group is not particularly limited and a known material can be used. Examples thereof include dyes represented by the formulas (80) to (89).

The dye used in the display device of the present invention is preferably a dye having a group derived from a xanthene dye and a dye having a group derived from an azo dye.

As the dye having a group derived from a xanthene dye, a dye represented by the following formula (1) is preferable.

(In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ or -SO ₂ NR < ⁸ > R < ^{9 &} gt ;.

R ⁵ is -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ Or it represents a -SO ₂ NR ⁸ R ^9.

m represents an integer of 0 to 5; When m is an integer of 2 or more, plural R ^{5 s} may be the same or different.

X represents a halogen atom. a represents an integer of 0 or 1;

R ⁶ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, -CH ₂ - included in the saturated hydrocarbon group may be replaced by -O-, -CO - or -NR ⁷ -.

R ⁷ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom or an alkoxy group having 1 to 10 carbon atoms.

R ⁸ and R ⁹ each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q. Or R ⁸ and R ⁹ may combine with each other to form a heterocyclic ring having 1 to 10 carbon atoms.

Q is a monovalent aromatic hydrocarbon group or a monovalent aromatic heterocyclic group having a carbon number of 3 to 10 carbon atoms of 6 to 10, the hydrogen atoms contained in the aromatic hydrocarbon group and the aromatic heterocyclic group, -OH, -R ^6, - OR ⁶ , -NO ₂ , -CH = CH ₂ , -CH = CHR ⁶ or a halogen atom.

M represents a sodium atom or a potassium atom.

However, the + and - charge numbers of the compound represented by the formula (1) are the same.)

R ^{6 is preferably a} methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, , An unsubstituted saturated hydrocarbon group such as an octyl group, a 2-ethylhexyl group, a cyclooctyl group, a nonyl group, a decyl group and a tricyclodecyl group; A methoxypropyl group, an ethoxypropyl group, a hexyloxypropyl group, a 2-ethylhexyloxypropyl group, a methoxyhexyl group, and a saturated hydrocarbon group substituted with an alkoxy group of an ethoxypropyl group.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group.

Examples of the substituent of the above-mentioned monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include fluorine, chlorine, bromine and the like.

Examples of -SO ₃ R ⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, a hexyloxysulfonyl group, and a decyloxysulfonyl group.

Examples of -CO ₂ R ⁶ include methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, isobutyloxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, cyclopentyloxycarbonyl , A cyclohexyloxycarbonyl group, a cyclohexyloxycarbonyl group, a heptyloxycarbonyl group, a cycloheptyloxycarbonyl group, an octyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, a cyclooctyloxycarbonyl group, a nonyloxycarbonyl group, a decyloxycarbonyl group, a tricyclodecyloxycarbonyl group, An ethoxypropyloxycarbonyl group, a hexyloxypropyloxycarbonyl group, a 2-ethylhexyloxypropyloxycarbonyl group, a methoxyhexyloxycarbonyl group and the like can be given.

Examples of -SO ₂ NHR ⁸ include sulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl, N-butylsulfamoyl, An n-pentylsulfamoyl group, an n-pentylsulfamoyl group, an N-isopentylsulfamoyl group, an N-neopentylsulfamoyl group, an N-cyclopentylsulfamoyl group, (2-ethylhexyl) sulfamoyl group, an N- (1,5-dimethylhexyl) sulfamoyl group, an N-heptylsulfamoyl group, an N-heptylsulfamoyl group, (Methoxypropyl) sulfamoyl group, an N- (ethoxypropyl) sulfamoyl group, an N-aminosulfamoyl group, an N-decylsulfamoyl group, , N- (propoxypropyl) sulfamoyl group, N- (isopropoxypropyl) sulfamoyl group, N- (hexyloxypropyl) sulfamoyl group, N- (Methoxyhexyl) sulfamoyl group, N- (3-phenyl-1-methylpropyl) sulfa It can be a diary, etc.

In _{^{-SO 2 NR 8 R 9, R}} 8 And R < ⁹ > may form a ring having 1 to 10 carbon atoms and may or may not be aromatic.

As the aromatic heterocyclic group,

And the like, and as the heterocyclic ring having no aromaticity,

And the like. In addition, the above-mentioned heterocyclic ring is bonded to a sulfur atom at the position shown in the figure.

As the monovalent aromatic heterocyclic group having 3 to 10 carbon atoms in Q,

And the like. In addition, the number of bonds can be arbitrary.

Examples of -SO ₂ NHR ⁸ and -SO ₂ NR ⁸ R ^9, also include groups represented by the following formula.

In the formula, X ¹ represents a halogen atom. Examples of the halogen atom in X ¹ include a fluorine atom, a chlorine atom and a bromine atom.

In the formula, X ³ represents an alkyl group having 1 to ³ carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and the hydrogen atom of the alkyl group and the alkoxy group may be substituted with a halogen atom.

Examples of the alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom include methyl, ethyl, propyl, isopropyl, trifluoromethyl and the like.

Examples of the alkoxy group having 1 to 3 carbon atoms which may be substituted with a halogen atom include methoxy, ethoxy, propoxy and the like.

In the formula, X ² represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a halogen atom or a nitro group, and the hydrogen atom of the alkyl group and the alkoxy group may be substituted with a halogen atom.

Examples of the halogen atom in X ² include a fluorine atom, a chlorine atom and a bromine atom.

Wherein X ² has the same meaning as defined above.

Wherein X ³ has the same meaning as defined above.

Examples of R ⁸ and R ⁹ contained in -SO ₂ NR ⁸ R ⁹ include a branched alkyl group having 6 to 8 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an allyl group, a phenyl group, an aralkyl group having 8 to 10 carbon atoms, Containing alkyl group and aryl group, or an alkoxy group-containing alkyl group or aryl group having 2 to 8 carbon atoms, and particularly preferably a 2-ethylhexyl group.

The substituent of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in Q is preferably an ethyl group, a propyl group, a phenyl group, a dimethylphenyl group, -SO ₃ R ⁶ or -SO ₂ NHR ⁸ .

Examples of the substituent-containing monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in Q include a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a hexylphenyl group, a decylphenyl group, a fluorophenyl group, a chlorophenyl group, a bromophenyl group, , A methoxyphenyl group, a dimethoxyphenyl group, an ethoxyphenyl group, a hexyloxyphenyl group, a decyloxyphenyl group, and a trifluoromethylphenyl group.

It is preferable that at least one of R ¹ and R ² or at least one of R ³ and R ⁴ is an alkyl group having 1 to 4 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted.

At least one of R ¹ and R ² and at least one of R ³ and R ⁴ is preferably an alkyl group having 1 to 4 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted.

At least one of R ¹ and R ² and at least one of R ³ and R ⁴ is more preferably a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms.

R ⁵ represents a carboxyl group, an ethyloxycarbonyl group, a sulfo group, N- (2-ethylhexyloxypropyl) sulfamoyl group, N- (1,5-dimethylhexyl) sulfamoyl group, N- Propyl) sulfamoyl group, and N- (isopropoxypropyl) sulfamoyl group.

It is preferable that the dye represented by the formula (1) is a dye represented by the following formula (1-1).

(In the formula (1-1), R ¹¹ to R ¹⁴ each independently represent a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be a halogen atom ^{, -R 6, -OH, -OR 6} , -SO 3 -, -SO 3 H, -SO 3 Na, -CO 2 N, -CO 2 R 6, -SO 3 R 6, -SO 2 NHR 8 or -SO ₂ NR ⁸ R ⁹ .

R ¹⁵ represents a hydrogen atom, -SO ₃ ^- , -SO ₃ H, -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ .

R ¹⁶ represents -SO ₃ ^- , -SO ₃ H, -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ .

R ⁶ , R ⁸ , R ⁹ , m, X and a have the same meanings as defined above.

However, the number of + charge and - charge in the compound represented by formula (1-1) is the same.)

It is preferable that the dye represented by the formula (1) is a dye represented by the following formula (1-2).

(In the formula (1-2), R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be a halogen atom, -R ²⁶ , -OH, -OR ²⁶ , -SO ₃ ^- , -SO ₃ Na, -CO ₂ H, -CO ₂ R ²⁶ , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁸ .

R ²⁵ represents -SO ₃ ^- , -SO ₃ Na, -CO ₂ H, -CO ₂ R ²⁶ , -SO ₃ H or SO ₂ NHR ²⁸ .

R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with -OR ²⁷ or a halogen atom.

R ²⁷ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms.

R ²⁸ represents a hydrogen atom, -R ²⁶ , -CO ₂ R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with -R ²⁶ or -OR ²⁶ .

m, X and a have the same meanings as defined above.

However, the number of + electric charges and the number of electric charges of the compound represented by formula (1-2) are the same.)

It is preferable that the dye represented by the formula (1) is a dye represented by the following formula (1-3).

(In the formula (1-3), R ³¹ and R ³² each independently represent a phenyl group, and the hydrogen atom contained in the phenyl group is a halogen atom, -R ²⁶ , -OR ²⁶ , -CO ₂ R ²⁶ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁸ .

R ³³ represents -SO ₃ ^- or -SO ₂ NHR ²⁸ .

R ³⁴ represents a hydrogen atom, -SO ₃ ^- or -SO ₂ NHR ²⁸ .

R ²⁶ , R ²⁸ , X and a have the same meanings as defined above.

However, the number of + electric charge and - electric charge of the compound represented by formula (1-3) is the same.)

It is preferable that the dye represented by the formula (1) is a dye represented by the following formula (1-4).

(In the formula (1-4), R ⁴¹ and R ⁴² each independently represent a phenyl group, and the hydrogen atom contained in the phenyl group may be substituted with -R ²⁶ or -SO ₂ NHR ²⁸ .

R ⁴³ represents -SO ₃ ^- or -SO ₂ NHR ²⁸ .

R ²⁶ , R ²⁸ , X and a have the same meanings as defined above.

However, the number of + charge and - charge in the compound represented by formula (1-4) is the same.)

Examples of the dye represented by the formula (1) include the dyes represented by the formulas (1a) to (1f).

(In the formula (1a), R ^b and R ^c each independently represent a hydrogen atom, -SO ₃ ^- , -CO ₂ H or -SO ₂ NHR ^a R ^a represents a 2-ethylhexyl group X And a have the same meanings as defined above, provided that the number of + electrons and the number of electrons in the compound represented by formula (1a) are the same.

(In the formula (1b), R ^b has the same meaning as described above.)

The dye represented by the formula (1b) is a tautomer of the dye represented by the following formula (1b-1).

(In the formula (1b-1), R ^b , X and a have the same meanings as defined above, provided that the number of + charge and - charge is the same as that of the compound represented by formula (1b-1)

(In the formulas (1c) and (1d), R ^d , R ^e and R ^f each independently represent -SO ₃ ^- , -SO ₃ Na or -SO ₂ NHR ^a R ^a represents 2-ethylhexy However, the number of + electric charges and the number of electric charges of the compound represented by formula (1c) are the same, and the number of + electric charges and - electric charges of the compound represented by formula (1d) are the same.)

(In the formulas (1e) and (1f), R ^g , R ^h and R ⁱ each independently represent a hydrogen atom, -SO ₃ ^- , -SO ₃ H or -SO ₂ NHR ^a R ^a represents 2 (1e) has the same number of + charge and - charge, and the compound of the formula (1f) has the same + charge number and - charge number).

The dye represented by the formula (1) can be produced by, for example, dyeing a dye or dye intermediate having -SO ₂ Cl obtained by crawling a dye or dye intermediate having -SO ₃ H by a regular method with R ⁸ -NH ₂ With the indicated amine. Also, the dye prepared by the method described in the right upper column to the lower column on page 3 of Japanese Laid-Open Patent Publication No. 3-78702 can be prepared by crawling the same as described above and then reacting with the amine.

As the dye having a group derived from an azo dye, a compound represented by the following formula (2) is preferable.

[In the formula (2), A ⁰ represents a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent.

B ⁰ represents a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a monovalent aromatic heterocyclic group having 3 to 14 carbon atoms which may have a substituent.

R ⁵¹ represents a hydrogen atom, a monovalent aliphatic hydrocarbon group of 1 to 16 carbon atoms which may have a substituent, or an acyl group of 2 to 18 carbon atoms which may have a substituent.

p1 represents 1 or 2; When p1 is 2, a plurality of A ⁰ , B ⁰ , R ⁵¹ and R ⁵² may be the same or different.

If p1 is 1, R ⁵² is a hydrogen atom or a monovalent substituent group represents a monovalent aliphatic hydrocarbon group of 1 to 16 carbon atoms good, if p1 is 2, R ⁵² which may have a substituent of 1-35 carbon atoms good -CH ₂ - included in the monovalent aliphatic hydrocarbon group and the bivalent aliphatic hydrocarbon group may be substituted with -O-, -S-, -CO-, and -NR'-.

R 'represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms.

The dye having a group derived from an azo dye is more preferably a compound represented by the following formula (2-1).

[In the formula (2-1), Z ¹ and Z ² And Z ³ each independently represent a divalent aliphatic hydrocarbon group of 1 to 16 carbon atoms which may have a substituent and Z ¹ and Z ² And -CH ₂ - included in Z ³ may be substituted with -CO- or -O.

R ⁵³ And R ⁵⁴ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, or an acyl group having 2 to 18 carbon atoms which may have a substituent.

A ¹ and A ² each independently represent a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent.

B ¹ and B ² each independently represent a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a monovalent aromatic heterocyclic group having 3 to 14 carbon atoms which may have a substituent.

Z ¹ , Z ² And Z ³ each independently represent a divalent aliphatic hydrocarbon group of 1 to 16 carbon atoms which may have a substituent. The number of carbon atoms of the substituent does not include the number of carbon atoms of the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms, and the number thereof is preferably 2 to 10, more preferably 2 to 8.

Examples of the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include an alkanediyl group having 1 to 16 carbon atoms, and examples thereof include methylene, ethylene, propane di, , An octanediyl group, a decanediyl group, a tetradecanediyl group and a hexadecanediyl group.

-CH ₂ - contained in a divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms may be substituted with -CO- or -O-. C ₁ _-16 aliphatic hydrocarbon groups include a hydrogen atom that is, it may be substituted with a halogen atom such as a fluorine atom.

Z ¹ and Z ² are preferably an alkanediyl group having 1 to 8 carbon atoms which may contain -O-, and more preferably an alkanediyl group having 5 to 7 carbon atoms which may contain -O-. A preferred group, such _{as, - (CH 2) 3 -} , - (CH 2) 2 -O- (CH 2) 2 -, - (CH 2) 2 -O- (CH 2) 2 -O- (CH 2 ) ₂ - or -CH ₂ -CH (CH ₃ ) -.

Z ³ is preferably a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may contain -C (= C) -, more preferably an unsubstituted alkanediyl group having 1 to 8 carbon atoms, more preferably 4 to 8 carbon atoms More preferably an unsubstituted alkanediyl group. Preferred examples thereof include - (CH ₂ ) ₂ -, - (CH ₂ ) ₄ - or -CH ₂ -C (= CH ₂ ) -.

The monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms representing R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ may be any of linear, branched or cyclic. The carbon number of the aliphatic hydrocarbon group does not include the carbon number of the substituent, and the number thereof is preferably from 6 to 10, more preferably from 1 to 4.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- Methylhexyl group (1,5-dimethylhexyl group and the like), ethylhexyl group (2-ethylhexyl group and the like), cyclopentyl group, cyclohexyl group, methyl A cyclohexyl group (such as a 2-methylcyclohexyl group) and a cyclohexylalkyl group.

The hydrogen atom contained in the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms may be substituted with an alkoxy group having 1 to 8 carbon atoms or a carboxy group. Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms substituted with an alkoxy group having 1 to 8 carbon atoms include a propoxypropyl group such as a 3- (isopropoxy) propyl group and an alkoxypropyl group such as 3- (2-ethylhexyloxy) And a propyl group). Examples of the aliphatic hydrocarbon group having 1 to 16 carbon atoms substituted with a carboxy group include a 2- (carboxy) ethyl group, a 3- (carboxy) propyl group and a 4- (carboxy) butyl group.

As the monovalent aliphatic hydrocarbon group of 1 to 16 carbon atoms which may have a substituent and represent R ⁵² ,

Examples of the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent represented by R ⁵² include an alkanediyl group having 1 to 35 carbon atoms and examples thereof include a methylene group, an ethylene group, a propane di A diaryl group, a diaryl group, a hexanediyl group, a heptanediyl group, an octanediyl group, a decanediyl group, a tetradecanediyl group and a hexadecanediyl group.

-CH ₂ - included in the bivalent aliphatic hydrocarbon group having 1 to 35 carbon atoms may be substituted with -O-, -S-, -CO- and -NR'-. The hydrogen atom contained in the aliphatic hydrocarbon group having 1 to 35 carbon atoms may be substituted with a halogen atom such as a fluorine atom.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms for R 'include methyl, ethyl, propyl, butyl, pentyl, hexyl and cyclohexyl.

The hydrogen atom contained in the acyl group having 2 to 18 carbon atoms representing R ⁵¹ , R ⁵³ and R ⁵⁴ may be substituted with an alkoxy group having 1 to 8 carbon atoms. The carbon number of the acyl group having 2 to 18 carbon atoms which may have a substituent is counted including the carbon number of the substituent and the number thereof is preferably 6 to 10. [ Examples of the acyl group which may have a substituent include an acetyl group, a benzoyl group, a methoxybenzoyl group (p-methoxybenzoyl group and the like) and the like.

As R ⁵³ and R ⁵⁴ , a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms, and an acyl group having 2 to 5 carbon atoms are preferable. Preferable examples thereof include a hydrogen atom, an acetyl group and a propionyl group.

Examples of the divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which represent A ⁰ , A ¹ and A ² include a phenylene group and a naphthalenediyl group, and among them, a phenylene group is preferable.

Examples of the substituent of the divalent aromatic hydrocarbon group having 6 to 14 carbon atoms include a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a nitro group, a sulfo group, a sulfamoyl group, .

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom, a chlorine atom or a bromine atom is preferable.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl. An alkyl group having 1 to 2 carbon atoms is more preferable, and a methyl group is particularly preferable.

Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert- An alkoxy group having 1 to 4 carbon atoms is preferable, an alkoxy group having 1 to 2 carbon atoms is more preferable, and a methoxy group is particularly preferable.

Examples of the N-substituted sulfamoyl group include -SO ₂ NHR ⁵⁵ and -SO ₂ N (R ⁵⁵ ) R ⁵⁶ , and specific examples include -SO ₂ NHR ⁸ in the compound represented by the formula (1) -SO ₂ N (R ⁸ ) R ⁹ includes the same groups as those mentioned above. Among them, R ⁵⁵ and R ⁵⁶ are each independently preferably an aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent or an N-substituted sulfamoyl group which is an acyl group having 2 to 18 carbon atoms which may have a substituent.

B ⁰ , B ¹ and B ² each independently represent a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a monovalent aromatic heterocyclic group having 3 to 14 carbon atoms which may have a substituent.

Examples of the monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.

Examples of the monovalent aromatic heterocyclic group having 3 to 14 carbon atoms include the groups shown below.

[R represents a hydrogen atom or a methyl group]

The monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms and the hydrogen atom contained in the monovalent aromatic heterocyclic group having 3 to 14 carbon atoms may be substituted with a hydroxyl group, an oxo group, a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms, a cyano group, - substituted amino group.

As the N-substituted amino group, -NHR ⁵⁷ group or -NR ⁵⁷ R ⁵⁸ group is preferable. R ⁵⁷ and R ⁵⁸ each independently represent a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent or a monovalent aromatic heterocyclic group having 3 to 14 carbon atoms which may have a substituent. Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms and the monovalent aromatic heterocyclic group having 3 to 14 carbon atoms include the same groups as described above.

B ⁰ , B ¹ and B ² each independently represent a group represented by the following formula (2-1a).

[In the formula (2-1a), R ⁵⁹ represents a hydrogen atom or a monovalent aliphatic hydrocarbon group of 1 to 16 carbon atoms which may have a substituent. R ⁶⁰ represents a monovalent aliphatic hydrocarbon group of 1 to 16 carbon atoms which may have a substituent.]

The pyridone ring of the group represented by the formula (2-1a) may be of a keto type or a phenol type.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include the same groups as described above. R ⁵⁹ represents a methylbutyl group (1,1,3,3-tetramethylbutyl group, etc.), a methylhexyl group (1,5- Ethylhexyl group, etc.), methylcyclohexyl group (2-methylcyclohexyl group and the like) and alkoxypropyl group (3- (2-ethylhexyloxy) propyl group and the like) Or a branched chain aliphatic hydrocarbon group.

Examples of the substituent for R ⁵⁹ and R ⁶⁰ include a hydroxyl group, a halogen atom, an alkoxy group having 1 to 8 carbon atoms, and an acyloxy group having 1 to 8 carbon atoms. Examples of the alkoxy group having 1 to 8 carbon atoms include the same ones as described above. Examples of the acyloxy group having 1 to 8 carbon atoms include an acetyloxy group, a propionyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group and a benzoyloxy group.

R ⁶⁰ is preferably a methyl group.

Examples of the compound represented by formula (2) include compounds represented by formulas (I-1) to (I-18). In the table, A ¹ , A ² , Z ^1, and Z ² represent the number of bonds on the right side closer to Z ³ .

It is more preferable that B ¹ and B ² are groups of the same kind, and more preferably A ¹ and A ² , R ⁵³ and R ⁵⁴ , and Z ¹ and Z ² are groups of the same kind. When these groups are used, the preparation of the compound represented by the formula (2-1) is easy.

The compound represented by the formula (2-1) is obtained by reacting the compound represented by the formula (IA) and the compound represented by the formula (I-A ') with the compound represented by the formula (IB) RTI ID = 0.0 > C. &Lt; / RTI >

Z ¹ , Z ² , Z ³ , R ⁵³ , R ⁵⁴ , A ¹ , A ² , B ¹ and B ² in the formulas (IA), (I-A ' It represents meaning.

R ⁶⁷ and R ⁶⁸ each independently represent -OR ⁶⁹ or a halogen atom. R ⁶⁹ represents a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms.

Examples of the compound represented by the formula (I-B) include dimethyl malonate, isobutyl succinate, dimethyl adipate and diethyl superate, malonic acid chloride, succinic acid chloride, adipic acid chloride and suberic acid chloride.

The amount of the compound represented by the formula (I-B) is preferably 0.5 to 3 moles per 1 mole of the total amount of the compound represented by the formula (I-A) and the compound represented by the formula (I-A '). When water is contained in the solvent, it is preferable to use the compound represented by the formula (I-B) in excess of the amount described above.

When R ³¹ and R ³² of the compound represented by the formula (IB) are -OR ³³ , it is preferable to add a known acid catalyst. Examples of the acid catalyst include sulfuric acid, para-toluenesulfonic acid and the like. The amount of the acid catalyst to be used is preferably 0.01 to 2 moles per 1 mole of the total amount of the compound represented by the formula (IA) and the compound represented by the formula (I-A ').

The reaction between the compound represented by the formula (I-A) and the compound represented by the formula (I-A ') and the compound represented by the formula (I-B) is carried out in a solvent. As the solvent, for example, water; Ethers such as 1,4-dioxane (especially cyclic ethers); Halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, dichloroethylene, trichlorethylene, perchlorethylene, dichloropropane, amyl chloride and 1,2-dibromoethane; Ketones such as acetone, methyl isobutyl ketone, and cyclohexanone; Carbon-based aromatic compounds such as benzene, toluene and xylene; N, N-dimethylformamide, N, N-dibutylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like are preferable and two or more solvents may be used in combination. The amount of the solvent to be used is, for example, 1 to 20 parts by mass, more preferably 2 to 10 parts by mass, relative to 1 part by mass of the total amount of the compound represented by formula (IA) and the compound represented by formula (I-A ' Mass part.

The reaction of the compound represented by the formula (IA) and the compound represented by the formula (I-A ') with the compound represented by the formula (IB) is preferably carried out under a nitrogen atmosphere or an argon atmosphere, The reaction may be carried out in dry air.

The reaction temperature is, for example, preferably 0 to 150 占 폚, more preferably 10 to 130 占 폚. The reaction time is preferably, for example, 1 to 25 hours, more preferably 3 to 15 hours.

The order of addition of the compound represented by the formula (IA), the compound represented by the formula (I-A '), the compound represented by the formula (IB) and the solvent is not particularly limited, It is preferable to add (drop) the compound represented by the formula (IB) to a solution comprising the compound represented by the formula (I-A ') and a solvent. In the case of using an acid catalyst, it is preferable to add (drop) a compound represented by the formula (IB) to a solution comprising a compound represented by the formula (IA), a compound represented by the formula (I-A '), desirable.

The method for obtaining the target compound represented by the formula (2-1) from the reaction mixture obtained as described above is not particularly limited, and various known methods can be employed. For example, the reaction mixture is dissolved in an organic solvent And the like. Further, if necessary, it may be further purified by a known method such as washing with an alkaline aqueous solution or acidic aqueous solution, recrystallization and the like.

The compound represented by the formula (2-1) can be produced by coupling the compound represented by the formula (IC) with the compound represented by the formula (ID) and the compound represented by the formula (I-D ' can do. By reacting a salt of the compound represented by the formula (IC) with a compound represented by the formula (ID) and a compound represented by the formula (I-D ') at 20 to 60 ° C in an aqueous solvent, ) Can be prepared.

(In the formulas (IC) and (ID), Z ¹ , Z ² , Z ³ , R ⁵³ , R ⁵⁴ , A ¹ , A ² , B ¹ and B ² have the same meanings as defined above.

X ^- represents an inorganic or organic anion.)

Expression as inorganic or organic anions of the compounds represented by (IC), fluoride ion, chloride ion, bromide ion, Yo de cargo ion, perchloric acid ion, hypochlorous acid ion, CH ₃ -COO ^- or the like ^-, Ph-COO And preferably chloride ion, bromide ion, CH ₃ ^- COO ^- .

The dye having a group derived from an azo dye may be a dye containing a metal complex having an azo compound as a ligand. Such a dye is preferably a dye containing a compound represented by the formula (3). The compound represented by the formula (3) is a salt of a chromium complex anion or a cobalt complex anion and a cation.

R ^a1 to R ^a18 each independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, a phenyl group, -SO ₂ NHR ^a30 , -SO ₃ ^- , ^- It represents a -COOR ^a30 or -SO ₂ R ^a30.

R ^a19 and R ^a20 each ^represents an independently represent a hydrogen atom, a methyl group, an ethyl group or an amino group.

R ^a30 each independently represent a hydrogen atom or a monovalent hydrocarbon group of 1 to 10 carbon atoms, and -CH ₂ - included in the hydrocarbon group may be substituted with -O- or -CO-.

M ¹ represents Cr or Co.

n ¹ represents an integer of ¹ to 5;

D ¹ represents a monovalent cation derived from a compound having a hydron, a monovalent metal cation or a xanthene skeleton.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ^a1 to R ^a18 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec- N-hexyl, n-heptyl, n-octyl, decyl, 1-methylbutyl, 1,1,3,3-tetramethylbutyl, 1,5-dimethylhexyl, -Dimethylheptyl group, 2-ethylhexyl group, and 1,1,5,5-tetramethylhexyl group.

As the monovalent hydrocarbon group having 1 to 10 carbon atoms representing R ^a30 , a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, And a group having 4 to 10 carbon atoms in combination. Examples of the monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms include the same groups as described above. Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include the same groups as those represented by Q of the compound represented by the formula (1) have. Examples of the monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclodecyl group.

Examples of the hydrocarbon group substituted with -CH ₂ - by -O- or -CO- include -R ^a32 -OR ^a33 , -R ^a32 -CO-OR ^a33 , -R ^a32 -O-CO-R ^a33 have. R ^a32 is a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R ^a33 is a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

Examples of the divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms representing R ^a32 include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, -1,3-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group and octane-1,8-diyl group.

^{Examples of} -R ^a32 -OR ^a33 include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a propoxyethyl group, a methoxypropyl group, an ethoxypropyl group, a propoxypropyl group, 4-methoxybutyl group, octyloxypropyl group, 3-ethoxypropyl group, 3- (2-ethylhexyloxy) propyl group and the like.

^{Examples of} -R ^a32- CO-OR ^a33 include methoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, propoxycarbonylmethyl, propoxycarbonylethyl, butoxycarbonyl Methyl group, and butoxycarbonyl ethyl group.

^{Examples of} -R ^a32 -O-CO-R ^a33 include an acetyloxymethyl group, an acetyloxyethyl group, an ethylcarbonyloxymethyl group, an ethylcarbonyloxyethyl group, a propylcarbonyloxymethyl group, a propylcarbonyloxyethyl group, a butylcarbonyloxymethyl group, Butylcarbonyloxyethyl group and the like.

Examples of -SO ₂ NHR ^a30 include a sulfamoyl group;

N-isopropylsulfamoyl group, N-methylsulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, (1, 1-dimethylpropyl) sulfamoyl group, N- (1, 2-dimethylpropyl) sulfamoyl group, N-methylpyrrolyl group, N- (2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, an N-cyclopentylsulfamoyl group, an N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) Substituted with an aliphatic hydrocarbon group such as a sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group, N- Sulfamoyl group;

(2-methoxyethyl) sulfamoyl group, N- (2-ethoxyethyl) sulfamoyl group, N- (1-methoxypropyl) sulfamoyl group, N- (3-ethoxypropyl) sulfamoyl group, N- (3-ethoxypropyl) sulfamoyl group, N- ) -S (-O-lower alkyl) sulfamoyl group such as N- (2-ethylhexyloxypropyl) sulfamoyl group, N- ^{31 a} sulfamoyl group substituted with -OR ³² ;

(Methoxycarbonylmethyl) sulfamoyl group, N- (methoxycarbonylethyl) sulfamoyl group, N- (methoxycarbonylethyl) sulfamoyl group, N- (ethoxycarbonylethyl) sulfamoyl group, N- (Propoxycarbonylmethyl) sulfamoyl group, N- (propoxycarbonylethyl) sulfamoyl group, N- (butoxycarbonylmethyl) sulfamoyl group, N- (butoxycarbonylethyl) A sulfamoyl group substituted with -R ³¹ -CO-OR ^{32 such} as a sulfamoyl group;

N- (ethylcarbonyloxymethyl) sulfamoyl group, N- (ethylcarbonyloxyethyl) sulfamoyl group, N- (acetyloxymethyl) sulfamoyl group, N- (Propylcarbonyloxymethyl) sulfamoyl group, N- (propylcarbonyloxyethyl) sulfamoyl group, N- (butylcarbonyloxymethyl) sulfamoyl group, N- (butylcarbonyloxyethyl) sulfamoyl group and the like A sulfamoyl group substituted with -R ³¹ -O-CO-R ³² ;

(2-methylcyclohexyl) sulfamoyl group, N- (3-methylcyclohexyl) sulfamoyl group, N- (4-methylcyclohexyl) sulfamoyl group, N- 4-butylcyclohexyl) sulfamoyl group, and the like; a sulfamoyl group substituted with a cyclohexyl group having a substituent;

(2-phenylethyl) sulfamoyl group, N- (3-phenylpropyl) sulfamoyl group, N- (4-phenylbutyl) sulfamoyl group, N- ) Sulfamoyl group, N- (2- (2-naphthyl) ethyl] sulfamoyl group, N- [2- (4-methylphenyl) Pamoyl group, and sulfamoyl group substituted with an aralkyl group such as N- (3-phenyl-1-methylpropyl) sulfamoyl group.

Examples of -COOR ^a30 include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a cyclohexyloxycarbonyl group, and a decyloxycarbonyl group.

Examples of -SO ₂ R ^a30 include methanesulfonyl, ethanesulfonyl, propanesulfonyl, isopropanesulfonyl, n-butanesulfonyl, sec-butanesulfonyl, tert- Methylbutane sulfonyl group, 1,1,3,3-tetramethylbutane sulfonyl group, 1,5-dimethylhexanesulfonyl group, 1,6-dimethylheptane sulfonyl group, 2-ethyl Hexanesulfonyl group, and 1,1,5,5-tetramethylhexanesulfonyl group.

It is preferable that at least one of R ^a1 to R ^a18 is a nitro group since heat resistance tends to be high.

Examples of R ^a30, monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, optionally substituted with an alkyl group having 1 to 4 carbon atoms good cyclohexyl, -R -OR ^a32 ^a33, ^a32 -R -CO-OR ^a33 and ^a32 -R - O-CO-R < ^a33 & gt ^; is preferred.

In the compound represented by the formula (3), preferred examples of the pyrazole compound to be the ligand of the complex anion include the compounds represented by the formulas (1-a1) to (1-a64).

In the compound represented by the formula (3), preferred examples of the complex anion include the anions represented by the formulas (1-b1) to (1-b60).

D ¹ is a monovalent cation derived from a compound having a hydron, a monovalent metal cation or a xanthene skeleton. Among them, a monovalent cation derived from a compound having a xanthene skeleton is preferable in that the lightness of the obtained color filter is high. Examples of the compound having a xanthene skeleton include a compound represented by the formula (1).

The compound represented by the formula (3) is preferably a compound represented by the following formula (3-1) in view of solubility in an organic solvent.

Equation (3-1) of, R ^a41 ^a58 ~R are, independently of one another, a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, a sulfo group, -SO ₂ R ^a33, or - SO ₂ NHR ^a34 .

R ^a34 represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms, -R ^a32 -OR ^a33 , -R ^a32 -CO-OR ^a33 , -R ^a32- O-CO-R ^a33 or an aralkyl group having 7 to 10 carbon atoms.

R ^a32 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

R ^a33 represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

R ^a59 and R ^a60 independently represent a hydrogen atom, a methyl group, an ethyl group or an amino group.

M ² represents Cr or Co.

R ^a21 to R ^a24 independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group of 1 to 8 carbon atoms or a monovalent aromatic hydrocarbon group of 6 to 10 carbon atoms, and the hydrogen atoms contained in the aliphatic hydrocarbon group and the aromatic hydrocarbon group a hydroxy group, -OR ^32, sulfo, -SO ₃ Na, -SO ₃ K or may be substituted with a halogen atom.

R ^a25 and R ^a26 each independently represent a hydrogen atom or a methyl group.

R ^a27 represents an ethylene group, a propane-1,3- ^diyl group or a propane-1,2- ^diyl group.

R ^a28 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

n represents an integer of 1 to 4; When n is an integer of 2 or more, a plurality of R < ²⁷ > may be the same or different.]

Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include the same groups as those shown above for R ^a1 to R ^a18 .

Examples of the divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include the same groups as those represented by R ^a32 .

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

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include aryl groups such as a phenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group and a naphthyl group; An aralkyl group such as a benzyl group, a diphenylmethyl group, a phenylethyl group and a 3-phenylpropyl group.

Examples of the cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms include a 2-methylcyclohexyl group, a 2-ethylcyclohexyl group, a 2-propylcyclohexyl group, a 2-isopropylcyclohexyl group, A 4-methylcyclohexyl group, a 4-ethylcyclohexyl group, a 4-propylcyclohexyl group, a 4-isopropylcyclohexyl group, and a 4-butylcyclohexyl group.

Since the high heat resistance tends, during ^a41 R ^a58 ~R, preferably at least one nitro group.

In addition, R ^a41 ~R at least one of the at least one ^a46 and R ^a50 in ^a45 ~R is, sulfo, -SO ₂ NHR ^a34 or -SO ₂ R ^a33 is preferably, more preferably -SO ₂ R ^a33, and more preferably, -SO ₂ CH _3.

R ^a21 to R ^a24 are preferably a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, which may have a substituent, and more preferably a hydrogen atom or an ethyl group.

As R ^a27 , an ethylene group and a propane-1,2- ^diyl group are preferable, and an ethylene group is more preferable.

As R ^{a28, a} hydrogen atom is preferable.

n is an integer of 1 to 4, preferably an integer of 2 to 4, more preferably 3 or 4, and more preferably 3.

- (R ^a27 -O) n R ^{a28 is preferably} selected from the group ^consisting of 2- (2-hydroxyethoxy) ethyl group and 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group in terms of solubility in organic solvents And more preferred is 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group.

In the compound represented by the formula (3-1), preferred examples of the cation derived from the xanthene compound include a cation represented by the formula (1-c1) to (1-c48).

Specific examples of the compound represented by the formula (3-1) include compounds represented by the formulas (3a-1) to (3a-26).

(3a-1), (3a-3) to (3a-5), and (3a-7) in terms of the solubility in organic solvent among the specific examples of the compound represented by formula (3-1) (3a-9), (3a-11) to (3a-16), 3a-18 to 3a-21 and 3a- Is preferably a compound represented by the formula (3a-1), a compound represented by the formula (3a-3) and a compound represented by the formula (3a-23)

In order to produce the compound represented by the formula (3), the chromium complex salt is formed using the compound represented by the formula (3d) and the chromium compound, or the compound represented by the formula (3d) and the cobalt compound is used to form the cobalt To form a complex salt. Thereafter, the compound represented by the formula (3) can be prepared by subjecting the salt having the D < ¹ > salt to a salt exchange reaction according to necessity.

[In the formula (3d), R ^a1 to R ^a5 , R ^a11 to R ^a14 And R ^a19 have the same meanings as in the formula (3).]

The compound represented by the formula (3d) can be produced by a method of diazo coupling of a diazonium salt and a pyrazole compound well known in the dye field.

The compound represented by the formula (3-1) is prepared by subjecting the complex salt and the xanthene compound represented by the formula (b) to a salt exchange reaction.

In the formula (b), R ^a21 to R ^a28 and n have the same meanings as in the formula (3-1). A ^- represents a monovalent anion.]

Examples of the monovalent anion include Cl ^- , Br ^- , I ^- , ClO ₄ ^- , PF ₆ ^-, or BF ₄ ^- .

The xanthene compound represented by the formula (b) can be produced by reacting the compound represented by the formula (b0) with the compound represented by the formula (b1) in an organic solvent.

[In formulas (b0) and (b1), R ^a21 to R ^a28 and n have the same meanings as in formula (2-1). A ^- has the same meaning as in formula (b).]

In the above-mentioned reaction, the reaction temperature is preferably 15 ° C to 60 ° C, and the reaction time is preferably 1 hour to 12 hours. Further, it is preferable to use an acid catalyst and / or a dehydrating agent in terms of shortening the reaction time or improving the yield.

Examples of the acid catalyst include sulfuric acid, p-toluenesulfonic acid and the like.

Examples of the dehydrating agent include carbodiimides such as dicyclohexylcarbodiimide, diisopropylcarbodiimide and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride; 1-alkyl-2-halopyridinium salts; 1,1'-carbonyldiimidazole; Bis (2-oxo-3-oxazolidinyl) phosphine acid chloride; Di-2-pyridyl carbonate, and the like. Among them, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride is preferable as the dehydrating agent since post treatment and purification are easy.

Examples of the organic solvent used in the reaction include dichloromethane, chloroform, tetrahydrofuran, toluene, acetonitrile and the like.

The compound represented by the formula (3-1) can be produced by subjecting the complex salt and the xanthene compound represented by the formula (b) to a salt exchange reaction in a solvent. It is preferable to react the cobalt complex salt with the xanthene compound (b) in a molar ratio of 1: 1 to 1: 4.

These dyes are appropriately selected in accordance with the solubility in a solvent or the light discoloration resistance and spectral spectrum when a pattern of a color filter is formed using a photosensitive resin composition containing the dye.

The content of the dye is preferably 5 to 65% by mass, more preferably 8 to 60% by mass, and still more preferably 10 to 55% by mass, based on the solid content of the photosensitive resin composition forming the color filter.

When a dye having a carboxyl group is contained in the dye, the content thereof is preferably from 1 to 100 mass%, more preferably from 5 to 100 mass%, and still more preferably from 10 to 100 mass% %to be.

Here, the solid content in the present specification refers to the total amount of the components excluding the solvent contained in the photosensitive resin composition.

In the display device of the present invention, it is preferable that the color filter is a color filter formed of a photosensitive resin composition containing a dye, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

The binder resin preferably contains a constituent unit derived from (meth) acrylic acid.

Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid. The content of the constituent unit derived from (meth) acrylic acid is preferably 16 mol% or more and 40 mol% or less, and more preferably 18 mol% or more and 38 mol% or less, of all the constituent units constituting the binder resin. When the content of the constitutional unit derived from (meth) acrylic acid is within the above-mentioned range, the solubility of the non-hydrogenated portion at the time of development tends to be good and the residue tends to remain in the non-calcined portion after development.

Examples of other monomers for deriving the constituent units of the binder resin other than the (meth) acrylic acid-derived constituent units include aromatic vinyl compounds, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, unsaturated carboxylic acid glycides Unsaturated amides, unsaturated imides, aliphatic conjugated dienes, monoacryloyl groups or mono-methacryloyl groups at the ends of the polymer molecular chain, , A structural unit represented by the formula (II), and a structural unit represented by the formula (III).

(In the formulas (II) and (III), R ⁸⁰ and R ⁸² each independently represent a hydrogen atom or an alkyl group having a carbon number of 1 to 6. R ⁸¹ and R ⁸³ each independently represent a hydrogen atom, Lt; 6 >

Specific examples of the binder resin include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate copolymer (II), R ⁸⁰ represents a methyl group, a methacrylic acid group, a methacrylic acid group, a methacrylic acid group, a styrene group, a benzyl methacrylate / N-phenylmaleimide copolymer, And R ⁸¹ represents a hydrogen atom) / benzyl methacrylate copolymer, a component represented by the formula (II) wherein R ⁸⁰ represents a methyl group and R ⁸¹ represents a hydrogen atom (III), R ⁸² represents a methyl group, and R ⁸³ represents a hydrogen atom), a benzyl methacrylate copolymer, a methacrylic acid / a structural component represented by the formula (III) / Styrene copolymer / tricyclodecanyl methacrylate Copolymer is preferred.

The binder resin having the constituent unit represented by the formula (II) is obtained by obtaining a copolymer having a constituent unit derived from at least one compound selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride , A carboxylic acid or an acid anhydride contained in the copolymer, and a compound represented by the formula (V). The binder resin having the constituent unit represented by the formula (III) can be prepared by reacting the carboxylic acid or acid anhydride contained in the copolymer with the compound represented by the formula (VI) In the same manner as in the above-mentioned method.

[Wherein R ⁸¹ and R ⁸³ have the same meanings as defined above].

For example, a methacrylic acid / a constituent component represented by the formula (II) (wherein, in the formula (II), R ⁸⁰ represents a methyl group and R ⁸¹ represents a hydrogen atom) / benzyl methacrylate copolymer, The obtained two-component polymer and the compound represented by the formula (V) (here, in the formula (V), R ⁸¹ represents a hydrogen atom) is reacted with a compound represented by the formula .

Methacrylic acid / a constituent component represented by the formula (III) (wherein, in the formula (III), R ⁸² represents a methyl group and R ⁸³ represents a hydrogen atom) / styrene copolymer / tricyclodecanyl methacrylate The late copolymer can be obtained by reacting glycidyl methacrylate with a monomethacrylate copolymer of benzyl methacrylate, methacrylic acid and tricyclodecane skeleton.

In particular, the binder resin represented by the formula (IV) is preferable from the viewpoints of curability and developability.

The copolymerization is generally carried out in a solvent using a polymerization initiator. Examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis (methyl 2-methylpropionate), peroxides such as benzoyl peroxide and -tert-butyl peroxide do. The solvent may be any solvent as long as it dissolves the respective monomers. Examples of the solvent include glycol ether esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate do. The reaction temperature may be determined in consideration of the decomposition temperature of the polymerization initiator, the boiling point of the solvent and the monomer. The side chain of the copolymer thus obtained may be modified with a compound having a polymerizable group to form a photosensitive binder resin. At this time, a catalyst for introducing a polymerizable group into the resin may be added. As the catalyst, for example, trisdimethylaminomethylphenol can be mentioned. Further, an additive for preventing side reaction may be added. As the additive, for example, hydroquinone can be mentioned.

The binder resin is a resin having alkaline solubility and includes a constituent unit derived from a compound (C0) having a carbon-carbon unsaturated double bond and a cyclic ether structure (hereinafter may be referred to as (C0)) and an unsaturated carboxylic acid , And at least one compound (C2) selected from the group consisting of unsaturated carboxylic acid anhydrides (hereinafter may be referred to as " (C2) ").

(C0) cyclic ether structure includes, for example, an epoxy (i.e., oxirane) structure, an oxetane structure, and a tetrahydrofuran structure.

Examples of the epoxy structure include an aliphatic epoxy structure (that is, a structure in which an alkene is epoxidized), an aliphatic monocyclic epoxy structure, and an aliphatic polycyclic epoxy structure (that is, a structure in which a polycyclic cycloalkane is epoxidized) Is particularly preferable.

Specific examples of the compound having a carbon-carbon unsaturated double bond and an aliphatic epoxy structure include glycidyl (meth) acrylate,? -Methyl glycidyl (meth) acrylate,? -Ethylglycidyl , Glycidyl vinyl ether, compounds represented by the following formulas described in JP-A-7-248625, and the like.

(Wherein R ⁶¹ to R ⁶³ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and m ⁶ is an integer of 1 to 5).

Examples of the compound represented by the above formula include o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether,? -Methyl-o-vinyl benzyl glycidyl ether ,? -methyl-m-vinylbenzyl glycidyl ether,? -methyl-p-vinylbenzyl glycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4- diglycidyloxymethylstyrene , 2,5-diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene , 2,3,6-triglycidyloxymethylstyrene, 3,4,5-triglycidyloxymethylstyrene, and 2,4,6-triglycidyloxymethylstyrene.

The compound having a carbon-carbon unsaturated double bond and an aliphatic monocyclic epoxy structure is a compound having a structure in which a carbon-carbon unsaturated double bond and a monocyclic cycloalkene are epoxidized. Examples of the monocyclic cycloalkene include cyclopentene, cyclohexene, cycloheptene, cyclooctene, and the like. Among them, a compound having 5 to 7 carbon atoms is preferable.

Specific examples of the compound having a carbon-carbon unsaturated double bond and an aliphatic monocyclic epoxy structure include vinylcyclohexene monoxide 1,2-epoxy-4-vinylcyclohexane (e.g., Sucoxide 2000; ), 3,4-epoxycyclohexylmethyl acrylate (e.g., Cychroma A400, manufactured by Daicel Chemical Industries Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (e.g., Cychroma M100; Manufactured by Cell Chemical Industry Co., Ltd.).

The compound (C1) having a carbon-carbon unsaturated double bond and an aliphatic polycyclic epoxy structure (hereinafter occasionally referred to as "(C1)") has a structure obtained by epoxidizing a carbon-carbon unsaturated double bond and a polycyclic cycloalkene . Examples of the above-mentioned polycyclic cycloalkene include dicyclopentene, tricyclodecene, norbornene, isononbonene, bicyclooctene, bicyclo- nonene, bicyclo- undecene, tricyclo- undecene, bicyclodecene, .

(C1-1) and the compound represented by the formula (C1-2) include, for example, 3,4-epoxycyclohexyl acrylate, 3,4-epoxy norbornyl methacrylate, , And preferably at least one compound selected from the group consisting of a compound represented by formula (C1-1) and a compound represented by formula (C1-2).

In the formulas (C1-1) and (C1-2), R ⁸⁷ and R ⁸⁸ 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 .

X ⁸⁷ and X ⁸⁸ each independently represent an alkylene group having 1 to 6 carbon atoms which may contain a single bond or a hetero atom.

Specific examples of the alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxy group include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a n-butyl group, Hydroxyethyl group, 1-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy- Hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like. Of these, methyl group, hydroxymethyl group, 1- A hydroxyethyl group, and a 2-hydroxyethyl group, more preferably a methyl group.

R is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group.

Examples of the hetero atom in the alkylene group having 1 to 6 carbon atoms which may contain a hetero atom include an oxygen atom, a sulfur atom and a nitrogen atom. Also, the number of heteroatoms is not included in the number of carbon atoms.

Examples of the alkylene group having 1 to 6 carbon atoms which may contain a hetero atom include a methylene group, an ethylene group, a propylene group, an oxymethylene group (-OCH ₂ -), an oxyethylene group (-OCH ₂ CH ₂ -), -OCH ₂ CH ₂ CH ₂ -), a thiomethylene group (-SCH ₂ -), a thioethylene group (-SCH ₂ CH ₂ -), a thiopropylene group (-SCH ₂ CH ₂ CH ₂ - (-NH-CH ₂ -), an iminoethylene group (-NH-CH ₂ CH ₂ -) and an iminopropylene group (-NH-CH ₂ CH ₂ CH ₂ -), An ethylene group, an oxymethylene group or an oxyethylene group, more preferably an oxyethylene group.

X is preferably a single bond, a methylene group, an ethylene group, an oxymethylene group or an oxyethylene group, more preferably a single bond or an oxyethylene group.

Examples of the compound represented by the formula (C1-1) include a compound represented by the formula (C1-1-1) to (C1-1-15), preferably a compound represented by the formula (C1-1-1) , (C1-1-3), (C1-1-5), (C1-1-7), (C1-1-9), (C1-1-11) (C1-1-1), (C1-1-7), (C1-1-9) or (C1-1-9), more preferably a compound represented by the formula 15). &Lt; / RTI >

Examples of the compound represented by the formula (C1-2) include a compound represented by the formula (C1-2-1) to (C1-2-15), preferably a compound represented by the formula (C1-2-1) , (C1-2-3), (C1-2-5), (C1-2-7), (C1-2-9), (C1-2-11) (C1-2-), (C1-2-9) or (C1-2-), more preferably a compound represented by the formula 15). &Lt; / RTI >

At least one kind of compound selected from the group consisting of a compound represented by the formula (C1-1) and a compound represented by the formula (C1-2) may be used alone. In addition, they can be mixed at an arbitrary ratio. In the case of mixing, the mixing ratio thereof is preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, particularly preferably in a molar ratio of formula (C1-1): formula (C1-2) 20:80 to 80:20.

Examples of the compound having a carbon-carbon unsaturated double bond and an oxetane structure include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3- Methyl-3-acryloxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-ethyl-3-methacryloxyethyl oxetane, Oxetane or 3-ethyl-3-acryloxyethyloxetane.

As the compound having a carbon-carbon unsaturated double bond and a tetrahydrofuran structure, specific examples of the monomer having a tetrahydrofuryl group include tetrahydrofurfuryl acrylate (for example, Viscot V # 150, Osaka Organic Chemical Industry Co., ), Tetrahydrofurfuryl methacrylate, and the like.

(C2) include, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid;

Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] , 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto- [2.2.1] hept-2-ene, and 5-carboxy-6-ethylbicyclo [2.2.1] hepto-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , Anhydrides of unsaturated dicarboxylic acids such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride (hymic acid anhydride);

(Meth) acryloyloxyalkyl (meth) acrylate of a divalent or higher polyvalent carboxylic acid such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- Esters;

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

Of these, acrylic acid, methacrylic acid and maleic anhydride are preferably used from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution. These are used alone or in combination.

The binder resin is a copolymer comprising a constituent unit derived from (C1) and a constituent unit derived from (C2), wherein the ratio of the constituent unit derived from (C1) to the constituent unit derived from (C2) When the molar fraction of the constituent units constituting the copolymer is within the following range, the storage stability, heat resistance and mechanical strength tend to be favorable.

(C1); 2 to 98 mol%

(C2); 2 to 98 mol%

The ratio of the above-mentioned structural units is preferably within the following range from the viewpoints of developability and solvent resistance.

(C1); 40 to 85 mol%

(C2); 15 to 60 mol%

The above-mentioned binder resin can be produced by a method described in, for example, "Experimental Method of Polymer Synthesis" (published by Otsu, Takayuki, 1st edition, 1st edition, published by Kagaku Kogyo Co., Ltd., March 1, 1972) Can be prepared by referring to the reference documents listed in the literature.

Specifically, a predetermined amount of (C1) and (C2), a polymerization initiator and a solvent are placed in a reaction vessel, and oxygen is replaced by nitrogen, thereby stirring, heating, and keeping the temperature under oxygen absence. As the obtained copolymer, the solution after the reaction may be used as it is, or a concentrated or diluted solution may be used, or it may be taken out as a solid (powder) by a method such as re-precipitation.

The binder resin is preferably a compound which can be copolymerized with (C1) and (C2) in addition to the constituent unit derived from (C1) and the constituent unit derived from (C2) ) (C3) (hereinafter may be referred to as " (C3) ").

As the above-mentioned (C3), there may be mentioned methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec- (Meth) acrylic acid alkyl esters;

Alkyl acrylates such as methyl acrylate and isopropyl acrylate; Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in the technical field, dicyclopentanyl (Meth) acrylate), dicyclopentanyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate;

Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate (referred to in the art as diclofenanyl acrylate), dicyclopenta Cyclic alkyl esters of acrylic acid such as oxyethyl acrylate and isobornyl acrylate;

(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;

Aryl acrylates such as phenyl acrylate and benzyl acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;

Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] 2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] 2.2.1] hepto-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] Ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 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- Cyclohexylbicyclo [2.2.1] hepto-2-ene, 5,6 2,6-di (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, and 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] Bicyclo-unsaturated compounds;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinic acid imidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as N-succinic acid imidyl-3-maleimidepropionate and N- (9-acridinyl) maleimide;

And examples thereof include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, But are not limited to, vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, glycidyl acrylate, glycidyl methacrylate, glycidyl α- Dicumyl acrylate, glycidyl alpha-n-butyl acrylate, 3,4-epoxybutyl acrylate, methacrylic acid-3,4-epoxybutyl acrylate, Heptyl,? -Ethyl acrylate-6,7-epoxyheptyl, O-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether. In the present specification, (meth) acrylate represents at least one kind selected from the group consisting of acrylate and methacrylate. Further, (meth) acrylic acid represents at least one kind selected from the group consisting of acrylic acid and methacrylic acid.

Of these, benzyl acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and bicyclo [2.2.1] hept-2-ene are preferred.

The above-mentioned (C3) is used alone or in combination.

(C3), it is preferable that the proportion of the constitutional unit derived from (C1) to (C3) falls within the following range as a molar fraction with respect to the total molar number of the constitutional unit constituting the copolymer.

(C1); 2 to 97 mol%

(C2); 2 to 97 mol%

(C3); 1 to 96 mol%

The binder resin containing the above-mentioned (C1) to (C3) can be produced in the same manner as described above.

The weight average molecular weight of the binder resin in terms of polystyrene is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, still more preferably from 5,000 to 35,000, particularly preferably from 6,000 to 30,000, Is 7,000 to 28,000. When the weight average molecular weight of the binder resin is within the above range, the coating property and the coating film hardness tend to be good, and furthermore, the film is hardly reduced at the time of development and the non-pixel portion (i.e., (I.e., solubility in a developer) tends to be good.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the binder resin is preferably 1.1 to 6.0, more preferably 1.2 to 4.0. When the molecular weight distribution is within the above-mentioned range, development tends to be excellent, which is preferable.

The content of the binder resin is preferably 10 to 35 mass%, more preferably 15 to 30 mass%, based on the solid content in the photosensitive resin composition. When the content of the binder resin is within the above range, solubility in a developing solution is sufficient, development residue does not easily occur on the substrate of the non-pixel portion, and film reduction of the pixel portion of the exposed portion is difficult to occur during development, The dropout of the pixel portion tends to be favorable.

The acid value of the binder resin is preferably 50 to 150 mgKOH / g, more preferably 60 to 135 mgKOH / g, particularly preferably 70 to 135 mgKOH / g. When the acid value is in the above-mentioned range, the solubility in the developer is improved, and the unexposed portion tends to dissolve, and a high sensitivity and a pattern of the exposed portion remain at the time of development to improve the residual film ratio. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the acrylic acid-based polymer, and can be generally determined by titration using an aqueous solution of potassium hydroxide.

The content of the binder resin is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass, based on the solid content of the photosensitive resin composition. When the content of the binder resin is in the above range, a pattern can be formed and the resolution and the residual film ratio tend to be improved, which is preferable.

The photopolymerizable compound is, for example, a compound having a polymerizable carbon-carbon unsaturated bond, which can be polymerized by an active radical or acid generated from a photopolymerization initiator upon irradiation with light.

The photopolymerizable compound is preferably a multifunctional photopolymerizable compound having three or more functionalities. The multifunctional photopolymerizable compound having three or more functionalities means a compound having three or more polymerizable carbon-carbon unsaturated bonds. As the group containing a polymerizable carbon-carbon unsaturated bond, a (meth) acryloyl group is preferable. Examples of multifunctional photopolymerizable compounds having trifunctional or more functional groups include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexaacrylate, di Pentaerythritol hexamethacrylate, and the like. The content of the photopolymerizable compound is preferably 7 to 65% by mass, more preferably 13 to 60% by mass based on the solid content of the photosensitive resin composition, and may be used alone or in combination of two or more. By mass, more preferably from 17 to 55% by mass. When the content of the photopolymerizable compound is in the above-mentioned range, curing is sufficiently carried out, the ratio of the film thickness before and after the development is improved, the undercut is difficult to be introduced into the pattern, and the adhesion tends to be good.

The photosensitive resin composition forming the color filter includes a photopolymerization initiator. The photopolymerization initiator is a compound capable of generating an active radical, an acid or the like upon irradiation with light and capable of initiating polymerization of the photopolymerizable compound. Among them, a compound which generates a radical by ultraviolet rays is preferable. Examples of the photopolymerization initiator include an active radical generator and an acid generator.

The active radical generator generates active radicals upon irradiation with light. Examples of the active radical generator include acetophenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, oxime compounds, and the like.

Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2- 2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone And oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one and the like, - (4-methylthiophenyl) propan-1-one.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- -Propoxyloxanthone, and the like.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4- 6,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, Bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- (2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2 -Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4- dimethoxyphenyl) ethenyl] -1,3,5 -Triazine, and the like.

Examples of the oxime-based compound include O-acyloxime compounds, and specific examples thereof include 1- (4-phenylsulfanylphenyl) -butane-1,2-dione 2-oxime- (I.e., N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-l-one-2-imine) Benzoate (i.e., N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan- 1-one-2-imine), 1- [ (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane- 1-imine), 1- [9-ethyl-6- (2-methyl-4- (3,3- dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl) -9H- Ethyl] -6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethan-1-imine).

Examples of the active radical generator other than the above examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'- Tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphaquinone, phenylglyoxylmethyl, May be used.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfate 4-acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate , And diphenyl iodonium hexafluoroantimonate, nitrobenzyl tosylates, benzoin tosylates, and the like.

Among the above-mentioned compounds as active radical generating agents, there are compounds which generate an acid at the same time as an active radical. For example, a triazine type photopolymerization initiator is also used as an acid generator.

The content of the photopolymerization initiator is preferably from 0.1 to 30 mass%, more preferably from 1 to 20 mass%, based on the total amount of the binder resin and the photopolymerizable compound. When the content of the photopolymerization initiator is within the above-mentioned range, high sensitivity is obtained and the exposure time is shortened and the productivity is improved.

The photosensitive resin composition forming the color filter may further contain a photopolymerization initiator. The photopolymerization initiator is generally used in combination with a photopolymerization initiator and is a compound or a sensitizer used for promoting the polymerization of the photopolymerizable compound initiated by the photopolymerization initiator.

Examples of the photopolymerization initiator include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and the like.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid isoamyl, benzoic acid 2-dimethylaminoethyl , 4-dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'- Phenanone, 4,4'-bis (ethylmethylamino) benzophenone, and the like, among which 4,4'-bis (diethylamino) benzophenone is preferable.

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

The photopolymerization initiator may be used alone or in combination of two or more. Commercially available photopolymerization initiators can be used. Commercially available photopolymerization initiators include, for example, trade names "EAB-F" (manufactured by Hodogaya Chemical Co., Ltd.).

Examples of the combination of the photopolymerization initiator and the photopolymerization initiator include diethoxyacetophenone / 4,4'-bis (diethylamino) benzophenone, 2-methyl-2-morpholino- Propane-1-one / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy- Phenanone, benzyldimethylketal / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan- (Diethylamino) benzophenone, 1-hydroxycyclohexyl phenyl ketone / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2- - (1-methylvinyl) phenyl] propan-1-one / 4,4'-bis (diethylamino) benzophenone, 2-benzyl- 1-on / 4,4'-bis (diethylamino) benzophenone, and preferably 2-methyl-2-morpholino-1- (4-methylthiophenyl) There may be mentioned 1-one plate / 4,4'-bis (diethylamino) benzophenone.

When these photopolymerization initiators are used, the amount thereof to be used is preferably 0.01 to 10 mol, more preferably 0.01 to 5 mol per mol of the photopolymerization initiator.

Examples of the solvent include ethers, aromatic hydrocarbons, ketones other than the above, alcohols, esters, amides, N-methylpyrrolidone, dimethylsulfoxide and the like.

Examples of the ethers include ethers such as tetrahydrofuran, tetrahydropyrane, 1,4-dioxane, 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, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl But are not limited to, ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, , Methyl anisole, etc. .

Examples of the above-mentioned aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene.

Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl- P-toluenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid, and the like.

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

Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyl butyrate, alkyl esters, Methyl lactate, methyl lactate, methyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, Ethyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, , Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, Ethyl propionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy- Propyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and? -butyrolactone.

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

Of these, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and 4-hydroxy-4-methyl-2-pentanone are preferable, and it is more preferable to use them in combination.

The above-mentioned solvents may be used singly or in combination of two or more kinds.

The content of the solvent in the photosensitive resin composition is preferably 70 to 95% by mass, and more preferably 75 to 90% by mass, based on the photosensitive resin composition. When the content of the solvent is within the above-mentioned range, flatness at the time of coating becomes good, and coloring density is not insufficient when a color filter is formed, so that display characteristics tend to be good.

The photosensitive resin composition forming the color filter may further contain a surfactant. Examples of the surfactant include at least one selected from the group consisting of a silicone surfactant, a fluorinated surfactant, and a silicon surfactant having a fluorine atom.

Examples of the silicone surfactant include surfactants having a siloxane bond. Concretely, it is possible to use a silicone resin such as Dowrene silicone DC3PA, Dowrene silicone SH7PA, Dowrene silicone DC11PA, Dowrene silicone SH21PA, Dowrene silicone SH28PA, Dowrene silicone SH29PA, Dowrene silicone SH30PA, (Manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF410, KP321, KP322, KP323, KP324, KP326, KP340, KP341 -4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan Joint-stock Company).

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain. Specific examples of the solvent include Fluoride (trade name) FC430, Fluoride FC431 (manufactured by Sumitomo 3M Ltd.), Megafac (trade name) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, (Trade names) EF301, Efopto EF303, Efopto EF351, Efopto EF352 (manufactured by Misc Bissmetall Electronic Co., Ltd.), Surflon (registered trademark) S381, (All manufactured by BM Chemie), E5844 (manufactured by Daikin Fine Chemical Research Institute, Ltd.), BM-1000 and BM-1100 (all trade names, manufactured by BM Chemie) .

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

These surfactants may be used alone or in combination of two or more.

The content of the surfactant is preferably 0.00001 to 0.1% by mass, more preferably 0.00005 to 0.01% by mass, based on the photosensitive resin composition. When the content of the surfactant is within the above-mentioned range, the flatness tends to be improved, which is preferable.

As a method of forming the pattern of the color filter, for example, a method of applying a photosensitive resin composition containing a dye onto a substrate or a separate resin layer (for example, a separate photosensitive resin composition layer previously formed on the substrate) A method of removing a volatile component to form a colored layer, a method of exposing and developing the colored layer through a photomask, and a method of using an inkjet apparatus that does not require a photolithography method.

The photosensitive resin composition preferably contains a pigment.

Specific examples of pigments include pigments classified as pigments in the color index (published by The Society of Dyers and Colourists). Specific examples thereof include CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, , 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194 and 214;

Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, Pigments;

Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60;

Violet pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38;

Green pigments such as CI Pigment Green 7, 36, 58;

Brown pigments such as CI Pigment Brown 23 and 25;

And C.I. Pigment Black 1 and Black Pigment 7 and the like.

When a color filter is produced using a photosensitive resin composition, the photosensitive resin composition is adjusted, for example, as a blue photosensitive resin composition, a green photosensitive resin composition and a red photosensitive resin composition, respectively.

As the pigment used in the blue photosensitive resin composition, a pigment containing at least one pigment selected from CI Pigment Red Violet 23, CI Pigment Blue 15: 3 and 15: 6 is preferable, and CI Pigment Blue 15: 6 is more preferable. As the pigment used in the green photosensitive resin composition, there may be mentioned C.I. Pigment Green 36, 58, C.I. Pigment Yellow 138, and 150, are preferable. As the pigment used in the red photosensitive resin composition, a pigment containing at least one kind selected from C.I. Pigment Yellow 138, 139, 150, C. I. Pigment Red 177, 242 and 254 is preferable. These pigments may be used alone or in combination of two or more kinds.

When the photosensitive resin composition contains a pigment, the content of the pigment is preferably from 2 to 98% by mass, more preferably from 5 to 95% by mass, and particularly preferably from 5 to 95% by mass with respect to the total amount of the dye and the pigment in the photosensitive resin composition By mass to 10% by mass to 95% by mass.

In the photosensitive resin composition used for manufacturing the display device of the present invention, the dye and the pigment are preferably contained in a mass ratio of dye: pigment of 1: 99 to 99: 1, preferably 1:99 to 60:40 And more preferably from 5:95 to 40:60. By making this ratio, it becomes easy to optimize the transmission spectrum, and a high coloring pattern with high contrast and high definition can be obtained, and heat resistance and chemical resistance of the obtained coloring pattern are improved.

When the photosensitive resin composition is a blue photosensitive resin composition, the mass ratio of CI Pigment Blue 15: 6 to the dye is preferably 99: 1 to 40:60, more preferably 97: 3 to 50:50, : 3 to 70: 30. In the case of a green photosensitive resin composition, the mass ratio of at least one selected from CI Pigment Green 36, CI Pigment Green 58, CI Pigment Yellow 138 and CI Pigment Green 150 to the dye is 99: 1 to 40:60 More preferably 99: 1 to 50:50, and still more preferably 95: 5 to 55:45. In the case of a red photosensitive resin composition, the mass ratio of at least one selected from CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Red 177, CI Pigment Red 242 and CI Pigment Red 254 to the dye is 99: More preferably from 99: 1 to 50:50, and even more preferably from 97: 3 to 65:35.

The pigment can be used as a pigment dispersion in which the pigment is uniformly dispersed in a solution by performing dispersion treatment in the presence of a dispersant, if necessary.

Examples of the dispersing agent include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polyester surfactants and polyamine surfactants. These surfactants may be used singly or in combination of two or more.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, polyethyleneimines (Manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-top (manufactured by Tochem Products), Megapack (manufactured by Dainippon Ink and Chemicals, Inc.) ), EFKA (manufactured by EFKA CHEMICALS), and PB821 (manufactured by Asahi Chemical Industry Co., Ltd.)), Fluoride (manufactured by Sumitomo 3M Ltd.), Asahi Guard, Surflon Manufactured by Ajinomoto Co., Ltd.).

When a dispersant is used, the amount of the dispersant to be used is preferably 0.1 to 100 mass%, more preferably 5 to 50 mass%, based on the pigment. When the amount of the dispersing agent used is within the above range, a uniform dispersion tends to be obtained, which is preferable.

The color filter is formed of the above-mentioned photosensitive resin composition. The color filter includes a red pixel including at least one color selected from the group consisting of a red dye, an orange dye and a yellow dye, a green pixel including at least one kind selected from the group consisting of a green dye and a yellow dye, And a blue pixel including at least one kind selected from the group consisting of a purple dye.

The color filter can be manufactured by forming each color pixel on a substrate by photolithography using a photosensitive resin composition of each color. Examples of the substrate include a transparent substrate such as glass and an opaque substrate such as silicon.

As the transparent substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass coated with silica on the surface, or a resin plate such as polycarbonate, polymethyl methacrylate or polyethylene terephthalate is used.

As the opaque substrate, it is possible to use silicon or a substrate formed by forming an aluminum, silver, silver / copper / palladium alloy thin film or the like on the above-mentioned transparent substrate.

When the respective color pixels are formed by the photolithography method, the photosensitive resin compositions for red, green and blue described above are used to develop each of the photosensitive resin compositions on the substrate in an arbitrary order to form a pattern to obtain a color filter . That is, the color filter included in the display device of the present invention is formed by forming each of the above-mentioned photosensitive resin compositions into a predetermined shape.

1 is a schematic view showing a color filter 1 included in a display device of the present invention. The color filter 1 includes a substrate 3, a lattice-shaped black matrix BM having a plurality of openings formed on the substrate 3, and a transparent red A photosensitive resin composition film R, a transparent green photosensitive resin composition film G, and a transparent blue photosensitive resin composition film B. The transparent red photosensitive resin composition film R is obtained by forming the red photosensitive resin composition into a desired shape, and the transparent green photosensitive resin composition film G is a green photosensitive resin composition formed into a predetermined shape, and a transparent blue photosensitive resin Composition film B is obtained by forming the blue photosensitive resin composition into a predetermined shape.

As a method of developing each photosensitive resin composition on a substrate, that is, forming the photosensitive resin composition into a predetermined shape, a publicly known method or a publicly known method can be used. For example, the film can be formed as follows.

The photosensitive resin composition is spin-coated on a substrate (usually glass), and the solvent is removed by heating and drying (prebaking) to obtain a smooth coated film. The thickness of the coating film at this time is usually about 1 to 5 mu m. The thus obtained coating film is irradiated with ultraviolet rays through a negative mask for forming a desired image to cure the exposed portion, and then the non-visible portion is dissolved in the developer to be developed. By repeating the above operation for each of the photosensitive resin compositions in the same manner, a photosensitive resin composition film of each color as a target pixel (pattern) can be formed. As a coating method, a spin coating method is used, but a slit coating method or a slit-and-spin coating method may also be used.

It is preferable to use an apparatus such as a mask aligner to uniformly irradiate a parallel light beam onto the entire exposed portion and precisely align the mask and the substrate during ultraviolet irradiation. After the development, it is also possible to post-cure (post-baking) at 150 to 230 캜 for about 10 to 60 minutes, if necessary.

As the black matrix (BM), a multilayer film of chromium, chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed is used.

Further, a thin film transistor (TFT) may be formed on the substrate in advance, and then the pixel may be formed. By forming pixels on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the brightness can be improved.

The display device of the present invention will be described. The display device includes a color filter including a dye and a white light emitting diode light source (hereinafter sometimes referred to as " white LED ").

The white LED has a fluorescent filter formed on the surface of a blue LED. A white LED includes a phosphor in a resin package of a blue LED. The white LED has a wavelength? ₁ at which the light emission intensity is maximum within a wavelength range of 430 nm to 485 nm, Has a wavelength? ₂ that maximizes the light emission intensity within the range of 500 nm to 580 nm and a wavelength? ₃ that maximizes the light emission intensity within the wavelength range of 590 nm to 680 nm.

The blue LED is an LED that emits blue light (wavelength is, for example, 470 nm) such as InGaN-based or GaN-based. The fluorescent filter containing the green light-emitting fluorescent substance or the resin package containing the green light-emitting fluorescent substance absorbs a part of the blue light emission from the blue LED and emits green light having the maximum light emission within the range of 500 nm to 580 nm, The fluorescent filter containing the red light-emitting fluorescent substance or the resin package containing the red light-emitting fluorescent substance likewise emits red light having the maximum light emission between 590 nm and 680 nm. In this type of white LED, a part of the blue light emitted by the blue LED is transmitted through the phosphor layer and the remainder is absorbed by the phosphor to be converted into green / red light. Examples of the green light emitting phosphor for converting blue light into green light include CaS: Eu crystals and the like as a red light emitting phosphor for converting blue light into red light such as CaGa ₂ S ₄ : Eu crystal. The observer perceives light mixed with three colors of blue light, green light, and red light as white light. Such white LEDs are available from Seiwa and the former manufacturer, SDPW50B0B, SDPW50H0B, SDPW3DG0B, and the like.

A green light emitting phosphor for converting blue light into green light and a red light emitting phosphor for converting blue light into red light are mixed with a transparent binder such as an epoxy resin and a silicone resin and applied to a blue LED. The mixing ratio may be appropriately changed to obtain a desired chromaticity. The green light emitting phosphor for converting blue light into green light and the red light emitting phosphor for converting blue light into red light may be separately applied to the blue LED. When the diffusing agent is added again to the transparent binder, the outgoing light can be made more uniform. As the dispersing agent, a colorless material having a mean particle size of 100 nm to several 10 탆 is preferable. Alumina, zirconia, yttrium oxide and the like are more preferable because they are stable in a practical temperature range of -60 to 120 占 폚. A higher refractive index is more preferable because the effect of the diffusing agent is enhanced. In the case of using a phosphor having a large particle size, it is preferable to use an anti-settling agent since color irregularity and color shift easily occur due to sedimentation of the phosphor. As the sedimentation inhibitor, fumed silica can be mentioned.

The white LED obtained in this way emits blue or deep blue light firstly by energization. The phosphor absorbs a part thereof, and emits green light or red light. As the light emitted from the white LED, the original blue light of the blue LED and the green light and the red light which are wavelength-converted by the phosphor are mixed to obtain a substantially white color.

For color television applications, color reproducibility is important. The color reproducibility of the color liquid crystal display device is determined by the color of light emitted from pixels of red (R), green (G), and blue (B), and the three color stimulus values of the three stimulus values of the CIE 1931 standard colorimetric system (X, Y, and Z), the chromaticity point of each pixel is represented by (Rx, Ry), (Gx, Gy), and (Bx, By) (0.67, 0.33), rust (0.21, 0.71), and blue (0.14, 0.08), respectively, of the three primary colors defined by the National Television System Committee (NTSC) (Unit:%, hereinafter referred to as NTSC ratio). NTSC ratios required for liquid crystal display devices for various purposes are, for example, about 40 to 50% in a general notebook computer, about 50 to 60% in a monitor for a desktop type personal computer, and about 72% in a liquid crystal television.

In order to increase the NTSC ratio, the color purity of each pixel must be increased. However, if the color purity is increased, the transmittance of the color filter is lowered and the utilization efficiency of the light source such as backlight (expressed by the brightness Y value ). For this reason, the power consumption of a light source such as a backlight necessary for maintaining a predetermined luminance is inevitably increased. A white LED formed by applying a phosphor on the surface of a blue LED is useful for a color filter having high color purity because the power consumption required for developing a predetermined luminance is low.

The white LED formed by applying the phosphor on the surface of the blue LED emits white light as blue light emitted by the blue LED passes through the film coated with the phosphor. The film coated with the phosphor has a function of converting part of the blue light into light having a longer wavelength. This white LED emits light mixed with blue light and long-wavelength light, and the observer perceives it as white light.

The color characteristics of the display device including the color filter and the light source are determined by the transmission spectrum of the color filter and the optical characteristics of the light source and are determined by the wavelength distribution of the product of the spectral intensity distribution of the light source and the transmission spectrum of the color filter .

On the color filter, an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed if necessary.

The color filter is bonded to the counter substrate by using a sealant. The liquid crystal is injected from the injection port formed in the seal portion, the injection port is sealed, and the polarizing film or the phase difference film is attached to the outside of the substrate, . Attachment of the polarizing film or the phase difference film may be performed before the color filter and the counter substrate are bonded.

Such a liquid crystal display panel includes a liquid crystal display panel such as a twisted nematic (TN), a super twisted nematic (STN), an in-plane switching (IPS) The present invention can be used in a liquid crystal display mode in which coloring is performed by using color filters such as vertically aligned (VA) and optically compensated bend (OCB).

2 is a schematic view showing the display device 10 of the present invention. The display device 10 is a typical example of a TFT-driven liquid crystal display device for a notebook computer. (For example, a TN or STN liquid crystal composition) LC is enclosed between the first transparent substrate 11 and the second transparent substrate 21 which are arranged so as to face each other with a gap therebetween . On the inner surface of the first transparent substrate 11, a TFT array 12 is formed, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. On the transparent electrode layer 13, an alignment layer 14 is formed. A polarizing plate 15 is formed on the outer surface of the first transparent substrate 11.

On the other hand, on the inner surface of the second transparent substrate 21, a color filter 22 is formed. Each color pixel (not shown) constituting the color filter is separated by a black matrix (not shown). A transparent electrode layer 23 made of, for example, ITO is formed to cover the color filter 22 and an orientation layer 24 is provided so as to cover the transparent electrode layer 23. [ A polarizing plate 25 is formed on the outer surface of the transparent substrate 21.

A backlight unit 30 having a light source 31 is provided in close proximity to the polarizer 15 from the outside of the first transparent substrate 11.

3 is a perspective view showing the backlight unit 30. Fig. The backlight unit 30 includes a light source 31, a light guide plate 33, and a diffusion plate 34 provided on the upper surface of the light guide plate 33. The light source 31 is provided facing the one side face 33a of the light guide plate 33 and is surrounded by the reflector 32 except the portion corresponding to the side face 33a of the light guide plate 33 have. Further, the light guide plate 33 is covered with the reflector 35 at three side surfaces and bottom surfaces other than the side surface 33a. Light from the light source 31 is guided to the light guide plate 33 by the reflector 32 and becomes plane light through the diffuser plate 34 and enters the liquid crystal layer LC from the polarizing plate 15. The reflection plate 35 directs the light incident on the light guide plate 33 to the diffusion plate 34 efficiently.

The display device of the present invention may be a liquid crystal display device having a white LED light source as a front light source, in addition to the liquid crystal display device having the white LED light source as the backlight light source described in Fig.

According to the present invention, a display device having excellent luminance and contrast can be obtained.

INDUSTRIAL APPLICABILITY The display device of the present invention is suitably used not only for a notebook computer but also for a portable information terminal, a cellular phone, a monitor, and a liquid crystal television.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. In the examples, "% " and " part " are by weight and part by weight unless otherwise specified.

Synthesis Example 1

15 parts of sulfolodamine B (Kanto Kagaku), 150 parts of chloroform and 9.8 parts of N, N-dimethylformamide were fed into a flask equipped with a stirrer, a cooling tube and a stirrer, 12.0 parts of thionyl was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 占 폚, held at the same temperature for 5 hours for reaction, and then cooled to 20 占 폚. The cooled reaction solution was added dropwise with a mixed solution of 13.9 parts of 2-ethylhexylamine and 24.5 parts of triethylamine while maintaining the temperature at 20 ° C or lower with stirring. Thereafter, the mixture was reacted at the same temperature for 5 hours with stirring. Subsequently, the solvent was distilled off using a rotary evaporator, and then a small amount of methanol was added thereto, followed by vigorous stirring. This mixture was added to a mixed solution of 375 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water and dried under reduced pressure at 60 ° C to obtain a dye (A1) (a dye represented by formula (A1-1) and a dye represented by formula Mixture).

Synthesis Example 2

15 parts of a dye (manufactured by Juga Chemical) represented by the formula (A0-2), 150 parts of chloroform and 7.1 parts of N, N-dimethylformamide were mixed in a flask equipped with a stirrer, a cooling tube and a stirrer, Deg.] C or less and 8.7 parts of thionyl chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 占 폚, held at the same temperature for 5 hours for reaction, and then cooled to 20 占 폚. After cooling, the reaction solution was added dropwise with a mixed solution of 10 parts of 2-ethylhexylamine and 17.7 parts of triethylamine while maintaining the temperature at 20 ° C or lower with stirring. Thereafter, the mixture was reacted at the same temperature for 5 hours with stirring. Subsequently, the solvent was distilled off using a rotary evaporator, and then a small amount of methanol was added thereto, followed by vigorous stirring. This mixture was added to a mixed solution of 375 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water and dried under reduced pressure at 60 ° C. to obtain 12.7 parts of a dye (A2) (a mixture of dyes represented by formulas (A2-3) to (A2-9) .

(In the formulas (A2-1) and (A2-2), R ^d , R ^e and R ^f each independently represent -SO ₃ ^- , -SO ₃ Na or -SO ₂ NHR ^a R ^a Represents 2-ethylhexyl.)

Synthesis Example 3

15 parts of a mixture of a dye represented by the formula (A0-3) and a dye represented by the formula (A0-4) (manufactured by Jujube Chemical Co., Ltd.), 150 parts of chloroform and 50 parts of N, And 8.9 parts of N, N-dimethylformamide were mixed and 10.9 parts of thionyl chloride was added dropwise while maintaining below 20 캜 with stirring. After completion of the dropwise addition, the temperature was raised to 50 占 폚, and the reaction was carried out at the same temperature for 5 hours, followed by cooling to 20 占 폚. The cooled reaction solution was added dropwise with a mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine with stirring while maintaining the temperature at 20 ° C or lower. Thereafter, the mixture was reacted at the same temperature for 5 hours with stirring. Subsequently, the solvent was distilled off using a rotary evaporator, and then a small amount of methanol was added thereto, followed by vigorous stirring. This mixture was added to a mixed solution of 375 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 11.3 parts of a dye (A3) (a mixture of dyes represented by formulas (A3-3) to (A3-10) .

(In the formulas (A3-1) and (A3-2), R ^g , R ^h and R ⁱ each independently represent a hydrogen atom, -SO ₃ ^- , -SO ₃ H or -SO ₂ NHR ^a R ^a represents a 2-ethylhexyl group.)

Resin Synthesis Example 1

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping rod, and a nitrogen inlet tube, and the atmosphere in the flask was changed from nitrogen to nitrogen. 22.0 g (0.10 mol) of 70.5 g (0.40 mol) of methacrylate, 43.0 g (0.5 mol) of methacrylic acid and monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Kasei Corporation) And 136 g of methyl ether acetate, to which 3.6 g of 2,2'-azobisisobutyronitrile had been added was added dropwise, and stirring was further continued at 100 ° C. Next, 35.5 g (0.25 mol) of glycidyl methacrylate (50 mol% with respect to the carboxyl group of methacrylic acid used in the present reaction) of 0.9 g of trisdimethylaminomethylphenol And 0.145 g of hydroquinone were charged into a flask, and the reaction was continued at 110 캜 to obtain a resin solution B1 (solid content: 35%) having a solid dispersion value of 79 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 3.0 x 10 ⁴ .

The measurement of the polystyrene reduced weight average molecular weight of the above resin was carried out by the GPC method under the following conditions.

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

column ; TSK-GELG2000HXL

Column temperature; 40 ℃

Solvent; THF

Flow rate; 1.0 mL / min

Solid concentration of the test solution; 0.001 to 0.01 mass%

Dose; 50 μL

Detector; RI

Calibration standards; TSK STANDARD POLYSTYRENEF-40, F-4, F-1, A-2500, A-500 (manufactured by TOSOH CORPORATION)

Example 1

[Preparation of photosensitive resin composition 1]

Pigment: C.I. Pigment Blue 15: 6 24.0 parts

Acrylic pigment dispersant 9.4 parts

Propylene glycol monomethyl ether acetate 192.7 parts

And the pigment was thoroughly dispersed using a bead mill. Subsequently,

Dye: Dye A1 36.0 parts

Binder resin: Resin solution B1 99.6 parts

Photopolymerizable compound: dipentaerythritol hexaacrylate

(Manufactured by Nippon Kayaku Co., Ltd., 34.9 parts

Photopolymerization initiator: OXE-01 (manufactured by Chiba Specialty Chemicals Co., Ltd.) 13.3 parts

Solvent: 4-hydroxy-4-methyl-2-pentanone 590.0 parts

Surfactant: SH-8400 0.1 part

(Manufactured by Dow Corning Toray Co., Ltd.) were mixed to obtain photosensitive resin composition 1.

[Formation of pattern]

The photosensitive resin composition 1 was applied by spin coating onto a glass substrate (Eagle 2000; Corning) of 2 inch square, and then prebaked at 100 占 폚 for 3 minutes. After cooling, the space between the substrate coated with this photosensitive resin composition and a quartz glass photomask having a pattern was set to 100 mu m and an exposure apparatus (TME-150 RSK; manufactured by Topcon Co., Ltd.) mJ / cm < 2 > (based on 365 nm). After the light irradiation, the coating film was immersed in an aqueous developing solution containing 0.04% of potassium hydroxide at a concentration of 0.12% of a nonionic surfactant for 80 seconds at 23 캜. After washing with water, post baking was carried out in an oven at 220 캜 for 20 minutes Respectively. After cooling, the film thickness of the obtained cured pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nihon Vacuum Technology Co., Ltd.), and found to be 2.2 탆.

〔evaluation〕

Spectroscopy was measured using a colorimeter (OSP-SP-200, manufactured by Olympus Corporation) with respect to the obtained coating film on the glass substrate, and the xy chromaticity coordinates (Bx, By) in the XYZ color system of CIE using the light source 1 were measured. . Further, the contrast value was measured with a contrast meter (CT-1; manufactured by Tsubosaka Kogyo Co., Ltd.) with a blank value of 10,000. The results are shown in Table 1.

Fig. 4 shows the emission spectrum of the light source 1. Fig. The ordinate indicates relative emission intensity, and the abscissa indicates wavelength (nm). Relative light emission intensity refers to the relative light emission intensity of each wavelength when the light emission intensity at the wavelength? ₁ of the light emission spectrum is 1. Measurement of the emission spectrum of the light source 1 and calculation of the emission peak wavelength and relative emission intensity can be performed by using a 150 W xenon lamp as an excitation light source and a multi-channel CCD detector C7041 (manufactured by Hamamatsu Photonics Co., Ltd.) (Manufactured by Nippon Bunko K.K.). The luminescence spectrum was measured at a temperature of 25 캜.

Examples 2 to 5

The photosensitive resin compositions 2 to 5 and the coated film were obtained in the same manner as in Example 1 except that the dye A1 was changed to the dyes shown in Table 1. [ The results are shown in Table 1.

Example 6

[Preparation of photosensitive resin composition 1]

Pigment: C.I. Pigment Blue 15: 6 38.2 parts

Acrylic pigment dispersant 15.0 parts

306.7 parts of propylene glycol monomethyl ether acetate

And the pigment was thoroughly dispersed using a bead mill. Subsequently,

Dye: Dye A1 3.8 parts

Binder resin: Resin solution B1 111.6 parts

Photopolymerizable compound: dipentaerythritol hexaacrylate

(Manufactured by Nippon Kayaku Co., Ltd.) 31.2 parts

Photopolymerization initiator: OXE-01 (manufactured by Chiba Specialty Chemicals Co., Ltd.) 11.9 parts

Solvent: 4-hydroxy-4-methyl-2-pentanone 481.5 parts

Surfactant: SH-8400 0.1 part

(Dow Corning Co., Ltd.) were mixed to obtain photosensitive resin composition 6.

The obtained photosensitive resin composition 6 was subjected to pattern formation and evaluation in the same manner as in Example 1. The results are shown in Table 1.

Examples 7 to 10

The photosensitive resin compositions 7 to 10 and the coated film were obtained in the same manner as in Example 6 except that the dye A1 was changed to the dyes shown in Table 1. [ The results are shown in Table 1.

Examples 11 to 20

The coating films formed from the compositions of Examples 1 to 10 were measured in the same manner as in Example 1 except that the light source 1 was changed to the light source 2.

Fig. 5 shows the emission spectrum of the light source 2. Fig. The emission spectrum of the light source 2 was measured in the same manner as the emission spectrum of the light source 1.

* Dye A4: Rhodamine B (manufactured by Daoka Chemical Co., Ltd.)

* Dye A5: Rhodamine B base (manufactured by Aldrich)

Synthesis Example 4

&Lt; Synthesis of dye A6 >

To 65 parts of water was added 7.5 parts of 2-amino-4-methylsulfonyl-6-nitrophenol (CAS No.101861-04-5), and 1.3 parts of sodium hydroxide was added to dissolve. Under ice cooling, 6.1 parts of 35% aqueous sodium nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and then 19.4 parts of 35% hydrochloric acid was added little by little and stirred for 2 hours to obtain a suspension containing the diazonium salt. Subsequently, an aqueous solution prepared by dissolving 5.6 parts of amide sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) in 26 parts of water was slowly added thereto, and excess sodium nitrite was quenched.

Subsequently, 5.6 parts of 3-methyl-1-phenyl-5-pyrazolone (manufactured by Wako Pure Chemical Industries, Ltd.) was suspended in 70 parts of water, and the pH was adjusted to 8.0 with sodium hydroxide. The suspension containing the above diazonium salt was added dropwise for 15 minutes while appropriately adding 10% sodium hydroxide solution so that the pH ranged from 7 to 7.5. After completion of the dropwise addition, stirring was continued for another 30 minutes to obtain a yellow suspension. And stirred for 1 hour. The yellow solid obtained by filtration was dried at 60 캜 under reduced pressure to obtain 11.7 parts (yield: 87%) of a compound represented by the formula (p-1).

10 parts of the compound of the formula (p-2) were dissolved in 100 parts of dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 3.1 parts of ammonium chloride (III) chloride sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) 1.1 parts of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was heated to reflux for 4 hours and a half. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% saline, and the resulting red colored solid obtained after filtration was dried at 60 캜 to obtain 13.6 parts (63%) of the compound represented by the formula (z-1).

Identification of the compound represented by the formula (z-1)

(Mass spectrometry) Ionization mode = ESI-: m / z = 882.1 [M-Na ⁺ ] ^-

Exact Mass: 905.1

, 170 parts of anhydrous chloroform (manufactured by KANTO CHEMICAL Co., Ltd.), 1.0 part of camphorsulfonic acid (manufactured by Aldrich), 4.0 parts of 4- (N, N-dimethylamino) , 1.4 parts of pyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 18 parts of triethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was stirred for about 30 minutes. Thereafter, a solution prepared by adding 47 parts of anhydrous chloroform to 10.5 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added slowly, And stirred for 2 hours. The separation operation was carried out twice with 150 parts of 1N hydrochloric acid aqueous solution, and then the organic layer was washed twice with 150 parts of 10% saline. Subsequently, 43 parts of anhydrous magnesium sulfate was added and the mixture was stirred for about 30 minutes. The drying agent was filtered and the solvent was distilled off to obtain 20.6 parts (yield: 90%) of a compound represented by the formula (g-1).

Identification of the compound represented by the formula (g-1)

(Mass Spec.) Ionization mode = ESI +: m / z = 575.3 [M-Cl -] +

Exact Mass: 610.3

To 253 parts of the compound represented by the formula (z-1), 4030 parts of methanol was added to adjust the solution (s3). To 153 parts of the compound represented by the formula (g-1), 1080 parts of methanol was added to adjust the solution (t3). Thereafter, the solutions (s3) and (t3) were mixed at room temperature and stirred for about 1 hour. The resulting red solid was dried under reduced pressure at 60 占 폚, washed with 3500 parts of water, filtered and dried under reduced pressure at 60 占 폚 to obtain 263 parts (yield 65%) of a compound represented by the formula (3a-23) .

The structure of the compound represented by the formula (3a-23) was determined by elemental analysis. An ICP emission spectrometer (ICPS-8100; manufactured by Shimadzu Corporation) was used as the analyzer.

C 55.6 H 5.1 N 11.9 Cr 3.71

Synthesis Example 5

&Lt; Synthesis of dye A7 >

After adding 200 parts of water to 10.0 parts of m-toluidine-4-sulfonic acid represented by the formula (a-2), the mixture was adjusted to pH 7 to 8 with 30% aqueous sodium hydroxide solution under ice-cooling. The following operation was performed under ice-cooling. 11.1 parts of sodium nitrite was added, and the mixture was stirred for 30 minutes. 39.0 parts of 35% hydrochloric acid was added in small portions to make a brown solution, which was then stirred for 2 hours. And 10.1 parts of amide sulfuric acid in 101 parts of water was added to the reaction solution and stirred to obtain a suspension containing the diazonium salt.

To 14.0 parts of 1- (2-ethylhexyl) -3-cyano-4-methyl-6-hydroxypyrido-2-one represented by the formula (c-2), 125 parts of water, , And the mixture was adjusted to pH 8 to 9 with 30% aqueous sodium hydroxide solution under ice-cooling.

The following operation was performed under ice-cooling. The pyridine aqueous solution was stirred to give a colorless solution, and the suspension containing the diazonium salt was added dropwise by a pump for 2 hours while adjusting the pH to 8 to 9 with 30% sodium hydroxide aqueous solution. After completion of the dropwise addition, stirring was continued for another 2 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 캜 under reduced pressure to obtain 21.4 parts (yield: 87%) of the compound represented by the formula (d-3).

0.35 g of the compound (d-3) was dissolved in N, N-dimethylformamide to make a volume of 250 cm 3, and 2 cm 3 of the solution was diluted with water to make a volume of 100 cm 3 (concentration: 0.028 g / The absorption spectrum was measured using a photometer (quartz cell, cell length: 1 cm). This compound exhibited? Max = 433 nm and an absorbance of 2.9 (arbitrary unit).

5.0 parts of the compound (d-3), 35 parts of acetonitrile and 1.6 parts of N, N-dimethylformamide were fed into a flask equipped with a stirrer, a cooling tube and a stirrer. Thionyl chloride 2.4 parts was added dropwise. After completion of the dropwise addition, the temperature was raised to 40 占 폚 and maintained at the same temperature for 2 hours to react, and then cooled to 20 占 폚. The cooled reaction solution was poured into 150 parts of ice water while stirring, and then stirred for 30 minutes. The precipitated yellow crystals were separated by filtration, washed well with tap water, and dried at room temperature for 1 hour. A flask equipped with a cooling tube and a stirrer was prepared separately and 2.0 parts of 1-amino-2-propanol and 20 parts of N-methylpyrrolidone were added thereto. While keeping the temperature below 20 ° C with stirring, Was added for 1 hour. After the yellow solid was added, the temperature of the solution was raised to room temperature, and then the reaction solution was stirred for 30 minutes. Methanol (40 parts) was added to the reaction solution and stirred. Then, the mixed solution was added to a mixed solution of 29 parts of acetic acid and 300 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 3.9 parts (yield: 69%) of a compound represented by the formula (III-3).

0.35 g of the compound (III-3) was dissolved in ethyl lactate to adjust the volume to 250 cm 3, diluting 2 cm 3 with ion-exchanged water, adjusting the volume to 100 cm 3 (concentration: 0.028 g / Quartz cell, optical path length: 1 ㎝). This compound exhibited? Max = 431 nm and an absorbance of 2.3 (arbitrary unit).

The following reaction was carried out in a nitrogen atmosphere. 2.0 parts of the compound (III-3) was added 4.0 parts of N-methylpyrrolidone, and the mixture was stirred for 30 minutes to adjust the reaction solution. While stirring the reaction solution at room temperature, 0.1 part of sebacic acid chloride was added dropwise. After completion of the dropwise addition, stirring was continued for another 8 hours. After the reaction solution was poured into 300 parts of water, 80 parts of ethyl acetate was added and the mixture was stirred for 30 minutes. The organic phase was collected by using a separating rod, and then washed with 500 parts of water, 500 parts of 10% sodium carbonate aqueous solution, 500 parts of 10% acetic acid aqueous solution, and 500 parts of ion exchange water. The separated organic phase was subjected to solvent distillation to obtain 2.0 parts of the dye A7 represented by the formula (I-6). Yield 85%.

The structure of compound (I-6) was determined by mass spectrometry. JMS-700 (manufactured by Nihon Denshi Co., Ltd.) was used as the mass spectrometer.

Mass spectrometry: ionization mode = FD +: m / z = 1200

0.35 g of Compound (I-6) was dissolved in ethyl lactate to make a volume of 250 cm 3, and 2 cm 3 of the solution was diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / L) Quartz cell, optical path length: 1 ㎝).

This compound exhibited? Max = 431 nm and absorbance 2.2 (arbitrary unit).

Resin Synthesis Example 2

&Lt; Synthesis of Resin Solution B2 >

Nitrogen was flowed at 0.02 L / min in a flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping rod to make a nitrogen atmosphere, and 935 parts by mass of ethyl lactate was added and heated to 70 캜 with stirring. Subsequently, 140 parts by mass of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (the compound represented by the following formula (C1-1-1) and the compound represented by the formula Compound in a molar ratio of 50:50) and 140 parts by mass of ethyl lactate to prepare a solution. The solution was added to a flask / RTI > On the other hand, a solution prepared by dissolving 30 parts by weight of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts by weight of ethyl lactate was added dropwise to the flask over 4 hours using a separate dropping rod. After completion of the dropwise addition of the polymerization initiator solution, the solution was kept at 70 캜 for 4 hours and then cooled to room temperature. The weight average molecular weight Mw was 9.0 × 10 ³ , the solid content was 26% by mass, the solution acid value was 32 mg- lt; 2 > / g.

Resin Synthesis Example 3

&Lt; Synthesis of Resin Solution B3 >

250 parts by mass of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping rod and a gas introduction tube. Thereafter, nitrogen gas was introduced into the flask using a gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. Thereafter, the solution in the flask was heated to 100 DEG C, and then a mixture composed of 152.6 parts by mass of benzyl methacrylate, 41.7 parts by mass of methacrylic acid, 1.5 parts by mass of azobisisobutylonitrile, and 150 parts by mass of propylene glycol monomethyl ether acetate Was added dropwise to the flask for 2 hours using a dropping rod. Stirring was continued at 100 캜 for 2.5 hours again after completion of the dropwise addition. The weight average molecular weight Mw was 2.3 占 04, the solid content was 34% by mass, / g. < / RTI >

Example 21

[Preparation of photosensitive resin composition 7]

Pigment: C.I. Pigment Red 254 42.8 parts

Acrylic pigment dispersant 16.0 parts

Resin solution B3 35.4 parts

Propylene glycol monomethyl ether acetate 211.7 parts

And the pigment was thoroughly dispersed using a bead mill. Subsequently,

Dye: Dye A6 11.2 part

Binder resin: Resin solution B2 119.7 parts

Photopolymerizable compound: dipentaerythritol hexaacrylate

(Manufactured by Nippon Kayaku Co., Ltd.) 43.4 parts

Photopolymerization initiator: 13.0 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure OXE01; BASF Japan)

Solvent: Propylene glycol monomethyl ether acetate 506.6 parts

Surfactant: 0.1 part of a polyester-modified silicone oil (SH8400, manufactured by Dow Corning Toray Co., Ltd.)

Were mixed to obtain a photosensitive resin composition 7. The obtained photosensitive resin composition 6 was subjected to pattern formation and evaluation in the same manner as in Example 1. The results are shown in Table 2.

Example 22

[Preparation of photosensitive resin composition 8]

Pigment: C.I. Pigment Green 58 32.2 parts

Acrylic pigment dispersant 8.0 parts

Resin solution B3 28.4 parts

Propylene glycol monomethyl ether acetate 161.2 parts

And the pigment was thoroughly dispersed using a bead mill. Subsequently,

Dye: Dye A7 6.8 parts

Binder resin: Resin solution B2 167.1 parts

Photopolymerizable compound: dipentaerythritol hexaacrylate

(Manufactured by Nippon Kayaku Co., Ltd.) 53.4 parts

Photopolymerization initiator: 16.0 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure OXE01; BASF Japan)

Solvent: Propylene glycol monomethyl ether acetate 526.8 parts

To obtain a photosensitive resin composition 8. Table 2 shows the results of pattern formation and evaluation in the same manner as in Example 1 of the photosensitive resin composition 8 obtained.

Example 23

[Preparation of photosensitive resin composition 9]

Pigment: C.I. Pigment Green 58 42.6 parts

Acrylic pigment dispersant 10.7 parts

Resin solution B3 37.6 parts

Propylene glycol monomethyl ether acetate 213.5 parts

And the pigment was thoroughly dispersed using a bead mill. Subsequently,

Dye: Dye A7 3.8 parts

Binder resin: Resin solution B2 138.4 parts

Photopolymerizable compound: dipentaerythritol hexaacrylate

(Manufactured by Nippon Kayaku Co., Ltd.) 49.1 parts

Photopolymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure OXE01: manufactured by BASF Japan) 14.7 parts

Solvent: Propylene glycol monomethyl ether acetate 489.5 parts

To obtain a photosensitive resin composition 9. Table 2 shows the results of pattern formation and evaluation in the same manner as in Example 1 of the obtained photosensitive resin composition 9.

Examples 24 to 26

The chromaticity (x, y), brightness and contrast were measured in the same manner as in Example 1 except that the coating film formed from the compositions of Examples 21 to 23 was changed to the light source 2 for the light source 1. The results are shown in Table 23.

1: Color filter
3: substrate
R: Transparent red photosensitive resin composition film
G: Transparent green photosensitive resin composition film
B: Transparent blue photosensitive resin composition film
BM: Black Matrix
10: Color liquid crystal display
11: transparent substrate
12: TFT array
13, 23: transparent electrode layer
14, 24: orientation layer
15, 25: polarizer
21: transparent substrate
22: Color filter
LC: liquid crystal composition
30: Backlight unit
31: Light source
32: Reflector
33: light guide plate
33a: a side surface of the light guide plate 33
34: diffusion plate
35: reflector

Claims

A color filter including a dye and a pigment, and a white LED light source,
Wherein the dye is a dye represented by the following formula (1)
The light emitted from the white LED light source has a wavelength? ₁ at which the light emission intensity is maximum within the range of 430 to 485 nm and a wavelength? ₂ at which the light emission intensity is maximized within the wavelength range of 500 to 580 nm , And has a wavelength? ₃ at which the light emission intensity is maximized within a wavelength range of 590 nm to 680 nm.

(In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ or -SO ₂ NR < ⁸ > R < ⁹ >
R ⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ ,
m represents an integer of 0 to 5, and when m is an integer of 2 or more, plural R ^{5 s} may be the same or different,
X represents a halogen atom, a represents an integer of 0 or 1,
R ⁶ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, and -CH ₂ - included in the saturated hydrocarbon group may be replaced by -O-, -NR < ⁷ > -,
R ⁷ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom or an alkoxy group having 1 to 10 carbon atoms,
R ⁸ and R ⁹ each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q, or R ⁸ and R ⁹ are bonded to each other to form a heterocyclic ring having 1 to 10 carbon atoms However,
Q is a monovalent aromatic hydrocarbon group or a monovalent aromatic heterocyclic group having a carbon number of 3 to 10 carbon atoms of 6 to 10, the hydrogen atoms contained in the aromatic hydrocarbon group and the aromatic heterocyclic group is -OH, -R ^6, -OR ⁶ , -NO ₂ , -CH = CH ₂ , -CH = CHR ⁶ or a halogen atom,
M represents a sodium atom or a potassium atom, the number of + charge and - charge is the same as that of the compound represented by formula (1).)

The display device according to claim 1, wherein the white LED light source is a light source including a blue LED light source and a phosphor.

The display device according to claim 1, wherein the white LED light source is a light source including a blue LED light source, a red light emitting phosphor and a green light emitting phosphor.

delete

The display device according to claim 1, wherein the color filter is a color filter formed of a photosensitive resin composition containing a dye, a pigment, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent.

delete

The display device according to claim 7, wherein the ratio of the content of the dye to the content of the pigment is in a mass fraction of 1:99 to 99: 1.

The pigment of claim 1, wherein the pigment is selected from the group consisting of CI Pigment Blue 15: 6, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Red 177, CI Pigment Red 242, and CI Pigment Red 254.

The display device according to claim 1, wherein the pigment is CI Pigment Blue 15: 6.