JP5614155B2 - Display device - Google Patents

Description

  The present invention relates to a display device such as a liquid crystal display device.

In a color liquid crystal display device or the like, color (image) display is performed using a color filter.
A color filter is generally manufactured by forming colored transparent fine patterns (called pixels) of three colors on a transparent substrate such as glass or an opaque substrate such as silicon. As the three colors, three primary colors of red (R), green (G), and blue (B) are often adopted.
For example, Patent Document 1 describes a display device including a color filter including a pigment as a colorant and a backlight on which a white LED light source is mounted as a light source.

JP 2008-96471 A

  In the conventional display device, the luminance and contrast are not always satisfactory.

The present invention is the following inventions.
1. Including a color filter containing a dye and a white light emitting diode light source,
The light emitted from the white light emitting diode light source has a wavelength λ ₁ at which the emission intensity is maximum within a wavelength range of 430 nm to 485 nm, and a wavelength λ ₂ at which the emission intensity is maximized within a wavelength range of 500 nm to 580 nm. The display device is a light having a wavelength λ ₃ having a maximum emission intensity within a wavelength range of 590 nm to 680 nm.

2. The white light emitting diode light source is a light source including a blue light emitting diode light source and a phosphor. The display device described.

3. The white light emitting diode light source is a light source including a blue light emitting diode light source, a red light emitting phosphor, and a green light emitting phosphor. Or 2. The display device described.

4). 1. The color filter is a color filter containing a dye and a pigment. ~ 3. The display apparatus in any one of.
5. 1. The dye is a dye containing at least one 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. ~ 4. The display apparatus in any one of.

（式（１）中、Ｒ^１〜Ｒ^４は、それぞれ独立に、水素原子、−Ｒ^６又は炭素数６〜１０の１価の芳香族炭化水素基を表し、該芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、−Ｒ^６、−ＯＨ、−ＯＲ^６、−ＳＯ_３ ⁻、−ＳＯ_３Ｈ、−ＳＯ_３Ｍ、−ＣＯ_２Ｈ、−ＣＯ_２Ｒ^６、−ＳＯ_３Ｒ^６、−ＳＯ_２ＮＨＲ^８又は−ＳＯ_２ＮＲ^８Ｒ^９で置換されていてもよい。
Ｒ^５は、−ＳＯ_３ ⁻、−ＳＯ_３Ｈ、−ＳＯ_３Ｍ、−ＣＯ_２Ｈ、−ＣＯ_２Ｒ^６、−ＳＯ_３Ｒ^６、−ＳＯ_２ＮＨＲ^８又は−ＳＯ_２ＮＲ^８Ｒ^９を表す。
ｍは、０〜５の整数を表す。ｍが２以上の整数である場合、複数のＲ^５は、同一であっても異なっていてもよい。
Ｘは、ハロゲン原子を表す。ａは、０又は１の整数を表す。
Ｒ^６は、炭素数１〜１０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよく、該飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−又は−ＮＲ^７−で置き換わっていてもよい。
Ｒ^７は、炭素数１〜１０の１価の飽和炭化水素基を表す。該炭素数１〜１０の飽和炭化水素基に含まれる水素原子は、ハロゲン原子又は炭素数１〜１０のアルコキシ基で置換されていてもよい。
Ｒ^８及びＲ^９は、それぞれ独立に、炭素数１〜１０のアルキル基、炭素数３〜３０のシクロアルキル基又は−Ｑを表す。あるいはＲ^８及びＲ^９は、互いに結合して炭素数１〜１０の複素環を形成していてもよい。
Ｑは、炭素数６〜１０の１価の芳香族炭化水素基又は炭素数３〜１０の１価の芳香族複素環基を表し、該芳香族炭化水素基及び該芳香族複素環基に含まれる水素原子は、−ＯＨ、−Ｒ^６、−ＯＲ^６、−ＮＯ_２、−ＣＨ＝ＣＨ_２、−ＣＨ＝ＣＨＲ^６又はハロゲン原子で置換されていてもよい。
Ｍは、ナトリウム原子又はカリウム原子を表す。
ただし、式（１）で表される化合物の＋電荷数と−電荷数とが同一である。） 6). 1. The dye is a dye represented by the formula (1) ~ 5. The display apparatus in any one of.

(In 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 are included in the aromatic hydrocarbon group. The hydrogen atom to be generated is 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 may be substituted.
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 . Represent.
m represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R ⁵ 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 is contained in the saturated hydrocarbon group. —CH ₂ — 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 represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q. Alternatively, R ⁸ and R ⁹ may be bonded to each other to form a heterocyclic ring having 1 to 10 carbon atoms.
Q represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a monovalent aromatic heterocyclic group having 3 to 10 carbon atoms, and is included in the aromatic hydrocarbon group and the aromatic heterocyclic group. The hydrogen atom to be substituted may be substituted with —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 number of + charges and the number of −charges of the compound represented by the formula (1) are the same. )

7). 1. The color filter is a color filter formed from a photosensitive resin composition containing a dye, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. ~ 6. The display apparatus in any one of.

8). 6. The photosensitive resin composition contains a pigment. The display device described.

9. The ratio of the dye content to the pigment content is from 1:99 to 99: 1 in mass fraction. The display device described.
10. The pigment is C.I. I. Pigment blue 15: 6, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment red 177, C.I. I. Pigment red 242 and C.I. I. 7. A pigment containing at least one selected from the group consisting of CI Pigment Red 254 Or 9. The display device described.

11. The pigment is C.I. I. Pigment Blue 15:68. -10. The display apparatus in any one of.

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

It is the schematic which shows a color filter. It is the schematic which shows a display apparatus. It is a perspective view which shows a backlight unit. The emission spectrum of the light source 1 is shown. The emission spectrum of the light source 2 is shown.

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

It does not specifically limit as dye, A well-known dye can be used, For example, an oil-soluble dye, an acidic dye, the amine salt of an acidic dye, the sulfonamide derivative of an acidic dye, etc. are mentioned.
Examples of the dye include dyes classified as dyes in the Color Index (published by The Society of Dyers and Colorists) and known dyes described in dyeing notes (color dyeing companies). Includes C.I. I. Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted, and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99. 162, C.I. I. Solvent Red 45, 49, 125, 130, C.I. I. Solvent Orange 2, 7, 11, 15, 26, 56, C.I. I. Solvent Blue 35, 37, 59, 67, C.I. I. Solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 etc. are mentioned. In addition, C.I. I. As an acid dye, C.I. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251, C.I. I. 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, C.I. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173, C.I. I. Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340, C.I. I. Acid Violet 6B, 7, 9, 17, 19, C.I. I. And dyes such as Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109. In addition, C.I. I. C. as a direct dye I. 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, C.I. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250, C.I. I. Direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107, C.I. I. 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, C.I. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104, C.I. I. Examples include direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82. Furthermore, C.I. I. As a modern dye, C.I. I. Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65, C.I. I. Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95, C.I. I. Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, C.I. I. Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 44, 48, 49, 53, 61, 74, 77, 83, 84, C.I. I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58, C.I. I. Modern dyes 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and the like can be mentioned.

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

D- (SO ₃ ⁻ ) _m (C _n H _{2n + 1} N ⁺ H ₃ ) _m (i) D- (SO ₃ ⁻ ) _m {(C _n H _{2n + 1} ) ₂ N ⁺ H ₂ } _m (ii) D- ( SO ₃ ⁻ ) _m {(C _n H _{2n + 1} ) ₃ N ⁺ H} _m (iii) D− (SO ₃ ⁻ ) _m {(C _n H _{2n + 1} ) ₄ N ⁺ } _m (iv) D− (SO ₃ ⁻ _{) m (C e H 2e +} 1 OC f H 2f n + H 3) m (v) D- (SO 3 -) m {(C n H 2n + 1) (PhCH 2) 2 n + H} m (vi) D- (SO ₃ ⁻ ) _m {(C _n H _{2n + 1} ) Py ⁺ } _m (vii) D − [{SO ₂ NH (C _n H _{2n + 1} )} _p ] [(SO ₃ L) _q ] (viii) D− [ _{{SO 2 NH (C e H} 2e + 1 OC f H 2f)} p] [(SO 3 L) q] (ix

（式（Ｉ）中、Ｒ’はメチル基を表す。ｍａは、０又は１の整数を表す。）
ｐは、１以上８以下の整数を表す。
ｑは、０以上８以下の整数を表す。
Ｌは、水素原子又は一価の陽イオンを表す。］ [In formulas (i) to (ix), D represents a group derived from a pigment.
m represents an integer of 1 or more and 20 or less.
n represents an integer of 1 or more and 20 or less.
e and f each independently represents an integer of 1 or more and 10 or less.
Ph represents a phenyl group.
Py ⁺ represents a group represented by the formula (I) connected to C _n H _{2n + 1} by a nitrogen atom.

(In the formula (I), R ′ represents a methyl group. Ma represents an integer of 0 or 1.)
p represents an integer of 1 to 8.
q represents an integer of 0 or more and 8 or less.
L represents a hydrogen atom or a monovalent cation. ]

ｐは、好ましくは１以上６以下の整数、より好ましくは１以上５以下の整数を表す。
ｑは、好ましくは０以上６以下の整数、より好ましくは０以上５以下の整数を表す。
Ｌにおける一価の陽イオンとしては、例えば、リチウムイオン、ナトリウムイオン、カリウムイオン、（Ｃ_２Ｈ_５）_３ＨＮ^＋などの有機アンモニウムイオンなどが挙げられ、好ましくはナトリウムイオンが挙げられる。 Specific examples of D include groups derived from azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, and phthalocyanine dyes.
m preferably represents an integer of 1 to 10, more preferably an integer of 1 to 8.
n is preferably an integer of 1 to 10, more preferably an integer of 1 to 8.
e and f each independently preferably represent an integer of 1 to 8, more preferably an integer of 1 to 6.
Py ⁺ preferably represents a group represented by the formula (I-1).

p preferably represents an integer of 1 to 6, more preferably an integer of 1 to 5.
q preferably represents an integer of 0 to 6, more preferably an integer of 0 to 5.
Examples of the monovalent cation in L include lithium ions, sodium ions, potassium ions, organic ammonium ions such as (C ₂ H ₅ ) ₃ HN ⁺ , and preferably sodium ions.

  Examples of the azo dye include dyes represented by 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, and a carbon number. C2-C12 alkyl group substituted by 2-12 alkoxy group, Alkylcarbonyloxyalkyl group represented by Formula (71-1), Alkyloxycarbonylalkyl group represented by Formula (71-2) Represents 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 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 formula (71-2), L ³ represents an alkyl group having 2 to 12 carbon atoms.
L ⁴ represents an alkylene group having 2 to 12 carbon atoms. )
R ^{72 to} R ^{75 each} represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxy group, or a halogen atom. ]

Examples of the alkyl group having 2 to 20 carbon atoms include ethyl group, n-propyl group, isopropyl group, n-hexyl group, n-nonyl group, n-decyl group, n-dodecyl group, 2-ethylhexyl group, 1,3 -A dimethylbutyl group, 1-methylbutyl group, 1,5-dimethylhexyl group, 1,1,3,3-tetramethylbutyl group, etc. are mentioned.
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 2-ethylcyclohexyl group, 2-propylcyclohexyl group, and 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 3-ethoxypropyl group, propoxypropyl group, 4-propoxybutyl group, 3-methylhexyloxyethyl group and 3- ( And 2-ethylhexyloxy) propyl group.
Examples of the phenyl group substituted with an alkyl group having 1 to 20 carbon atoms include an o-isopropylphenyl group.
Examples of the C1-C20 alkyl group substituted with a phenyl group include DL-1-phenylethyl group, benzyl group, and 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, an n-nonyl group, an n-decyl group, an n-dodecyl group, a 2-ethylhexyl group, 1, Examples include 3-dimethylbutyl group, 1-methylbutyl group, 1,5-dimethylhexyl group, 1,1,3,3-tetramethylbutyl group and the like.
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 represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxy group, or a halogen atom. R ^{72 to} R ⁷⁵ include a hydrogen atom, methyl group, ethyl group, n-propyl group, n-butyl group, isopropyl group, sec-butyl group, tert-butyl group, carboxy group, fluorine atom, chlorine atom, bromine. An atom, an iodine atom, etc. are mentioned, Preferably a hydrogen atom, a methyl group, an ethyl group, n-propyl group, n-butyl group, isopropyl group, sec-butyl group, tert-butyl group, a fluorine atom, or a chlorine atom is mentioned. It is done.

Of the dyes represented by formula (71), a preferred dye is specifically a dye represented by formula (75).
Examples of the dye having a group derived from an anthraquinone dye include a dye represented by the formula (76).
Examples of the dye having a group derived from a triphenylmethane dye include a dye represented by the formula (77).
Examples of the dye having a group derived from a phthalocyanine dye include a dye represented by the formula (78).

As the dye, since it tends to react with the cyclic ether structure to improve the solvent resistance, a dye containing a dye containing a carboxy group is preferable.
It does not specifically limit as a dye containing a carboxy group, A well-known substance can be used, For example, the dye etc. which are represented by Formula (80)-Formula (89) are mentioned.

As the dye used in the display device of the present invention, a dye having a group derived from a xanthene dye and a dye having a group derived from an azo dye are preferable.
Moreover, as a dye which has group derived from a xanthene dye, the dye represented by Formula (1) is preferable.

(In 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 are included in the aromatic hydrocarbon group. The hydrogen atom to be generated is 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 may be substituted.
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 . Represent.
m represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R ⁵ 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 is contained in the saturated hydrocarbon group. —CH ₂ — 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 represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q. Alternatively, R ⁸ and R ⁹ may be bonded to each other to form a heterocyclic ring having 1 to 10 carbon atoms.
Q represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a monovalent aromatic heterocyclic group having 3 to 10 carbon atoms, and is included in the aromatic hydrocarbon group and the aromatic heterocyclic group. The hydrogen atom to be substituted may be substituted with —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 number of + charges and the number of −charges of the compound represented by the formula (1) are the same. )

R ⁶ is methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, cycloheptyl group, octyl group , 2-ethylhexyl group, cyclooctyl group, nonyl group, decyl group, tricyclodecyl group and other unsubstituted saturated hydrocarbon groups; methoxypropyl group, ethoxypropyl group, hexyloxypropyl group, 2-ethylhexyloxypropyl group And a saturated hydrocarbon group substituted with an alkoxy group such as a methoxyhexyl group or 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 halogen atom exemplified as the substituent of the 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.
The -CO ₂ R ^6, a methyl group, an ethyloxycarbonyl group, a propyl group, an isopropyloxycarbonyl group, butyloxycarbonyl group, isobutyloxycarbonyl group, pentyloxycarbonyl group, iso-pentyloxy group, neo Pentyloxycarbonyl group, cyclopentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, cycloheptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, cyclooctyloxycarbonyl group, nonyl Oxycarbonyl group, decyloxycarbonyl group, tricyclodecyloxycarbonyl group, methoxypropyloxycarbonyl group, Butoxy propyl oxycarbonyl group, hexyloxy propyloxy group, 2-ethylhexyloxy propyloxy carbonyl group, such as methoxy hexyloxycarbonyl group.

—SO ₂ NHR ⁸ includes sulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group. N-isobutylsulfamoyl group, N-pentylsulfamoyl group, N-isopentylsulfamoyl group, N-neopentylsulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group N-cyclohexylsulfamoyl group, N-heptylsulfamoyl group, N-cycloheptylsulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5 -Dimethylhexyl) sulfamoyl group, N-cyclooctylsulfamoyl group, N-nonylsulfur group Amoyl group, N-decylsulfamoyl group, N-tricyclodecylsulfamoyl group, N- (methoxypropyl) sulfamoyl group, N- (ethoxypropyl) sulfamoyl group, N- (propoxypropyl) sulfamoyl group, N- (Isopropoxypropyl) sulfamoyl group, N- (hexyloxypropyl) sulfamoyl, N- (2-ethylhexyloxypropyl) sulfamoyl group, N- (methoxyhexyl) sulfamoyl group, N- (3-phenyl-1-methylpropyl) ) Sulfamoyl group and the like.

等が挙げられ、芳香性を有さない複素環としては、

等が挙げられる。なお、上記の複素環は、上図に記載される位置で硫黄原子と結合する。 In —SO ₂ NR ⁸ R ⁹ , the heterocyclic ring having 1 to 10 carbon atoms which R ⁸ and R ⁹ are bonded to each other may or may not have aromaticity. May be.
As an aromatic heterocyclic group,

As the heterocyclic ring having no aromaticity,

Etc. In addition, said heterocyclic ring couple | bonds with a sulfur atom in the position described in the above figure.

等が挙げられる。なお、結合手は任意の位置とすることができる。 As the monovalent aromatic heterocyclic group having 3 to 10 carbon atoms in Q,

Etc. In addition, a joint can be made into arbitrary positions.

Examples of —SO ₂ NHR ⁸ and —SO ₂ NR ⁸ R ⁹ further include a group represented by the following formula.

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

In the above formula, X ³ represents an alkyl group or an alkoxy group having 1 to 3 carbon atoms having 1 to 3 carbon atoms, hydrogen atoms of the alkyl group and alkoxy group may be substituted with a halogen atom.
Examples of the alkyl group having 1 to 3 carbon atoms that may be substituted with a halogen atom include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a trifluoromethyl group.
Examples of the alkoxy group having 1 to 3 carbon atoms which may be substituted with a halogen atom include a methoxy group, an ethoxy group and a propoxy group.

In the above 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 is substituted with a halogen atom. It may be.
Examples of the halogen atom for X ² include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group having 1 to 3 carbon atoms that may be substituted with a halogen atom include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a trifluoromethyl group.
Examples of the alkoxy group having 1 to 3 carbon atoms which may be substituted with a halogen atom include a methoxy group, an ethoxy group and a propoxy group.

In the above formula, X ² represents the same meaning as described above.

上記式中、Ｘ^３は、上記と同じ意味を表す。

In the above formula, X ³ represents the same meaning as described above.

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, and 8 to 8 carbon atoms. 10 aralkyl groups, a C2-C8 hydroxyl group-containing alkyl group and aryl group, or a C2-C8 alkoxy group-containing alkyl group or aryl group are preferred, and a 2-ethylhexyl group is particularly preferred.

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

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

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 an optionally substituted monovalent group having 6 to 10 carbon atoms. An aromatic hydrocarbon group is preferred.
At least one of R ¹ and R ² and at least one of R ³ and R ⁴ is an alkyl group having 1 to 4 carbon atoms or an optionally substituted monovalent group having 6 to 10 carbon atoms. An aromatic hydrocarbon group is preferred.
At least one of R ¹ and R ² and at least one of R ³ and R ⁴ is an optionally substituted monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. Further preferred.
R ⁵ represents a carboxy group, an ethyloxycarbonyl group, a sulfo group, an N- (2-ethylhexyloxypropyl) sulfamoyl group, an N- (1,5-dimethylhexyl) sulfamoyl group, or N- (3-phenyl-1-methyl). Propyl) sulfamoyl group and N- (isopropoxypropyl) sulfamoyl group are preferable.

  The dye represented by formula (1) is preferably a dye represented by formula (1-1).

(In formula (1-1), R ^{11 to} R ¹⁴ each independently represents a hydrogen atom, —R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the aromatic hydrocarbon group The hydrogen atom contained in is a halogen atom, —R ⁶ , —OH, —OR ⁶ , —SO ₃ ^— , —SO ₃ H, —SO ₃ Na, —CO ₂ H, —CO ₂ R ⁶ , —SO _3. R ⁶ , —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ may be substituted.
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 meaning as described above.
However, the number of + charges and the number of −charges of the compound represented by the formula (1-1) are the same. )

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

(In formula (1-2), R ^{21 to} R ²⁴ each independently represents a hydrogen atom, —R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the aromatic hydrocarbon group hydrogen atoms are contained in 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 may be substituted.
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 a 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 is a hydrogen ^atom, -R _26, represents a monovalent aromatic hydrocarbon radical of -CO ^{2 R 26} or a C 6-10, hydrogen atom contained in the aromatic hydrocarbon group, ^{-R 26} or it may be substituted with ^{-OR 26.}
m, X, and a represent the same meaning as described above.
However, the number of + charges and the number of −charges of the compound represented by the formula (1-2) are the same. )

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

(In 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, may be substituted by _-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 represent the same meaning as described above.
However, the number of + charges and the number of −charges of the compound represented by the formula (1-3) are the same. )

  The dye represented by formula (1) is preferably a dye represented by formula (1-4).

(In Formula (1-4), R ⁴¹ and R ⁴² each independently represent a phenyl group, and a hydrogen atom contained in the phenyl group is substituted with —R ²⁶ or —SO ₂ NHR ^28. Also good.
R ⁴³ represents —SO ₃ ^— or —SO ₂ NHR ²⁸ .
R ²⁶ , R ²⁸ , X and a represent the same meaning as described above.
However, the number of + charges and the number of −charges of the compound represented by the formula (1-4) are the same. )

（式（１ａ）中、Ｒ^ｂ及びＲ^ｃは、それぞれ独立に、水素原子、−ＳＯ_３ ⁻、−ＣＯ_２Ｈ又は−ＳＯ_２ＮＨＲ^ａを表す。Ｒ^ａは、２−エチルヘキシル基を表す。Ｘ及びａは、上記と同じ意味を表す。ただし、式（１ａ）で表される化合物の＋電荷数と−電荷数とが同一である。） Examples of the dye represented by formula (1) include dyes represented by formula (1a) to formula (1f).

(In 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 meaning as described above, provided that the number of + charges and the number of −charges of the compound represented by the formula (1a) are the same.

（式（１ｂ）中、Ｒ^ｂは、上記と同じ意味を表す。）

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

（式（１ｂ−１）中、Ｒ^ｂ、Ｘ及びａは、上記と同じ意味を表す。ただし、式（１ｂ−１）で表される化合物の＋電荷数と−電荷数とが同一である。） The dye represented by the formula (1b) is a tautomer of the dye represented by the formula (1b-1).

(In formula (1b-1), R ^b , X and a represent the same meaning as described above, provided that the number of + charges and the number of −charges of the compound represented by formula (1b-1) are the same. .)

（式（１ｃ）及び式（１ｄ）中、Ｒ^ｄ、Ｒ^ｅ及びＲ^ｆは、それぞれ独立に、−ＳＯ_３ ⁻、−ＳＯ_３Ｎａ又は−ＳＯ_２ＮＨＲ^ａを表す。Ｒ^ａは、２−エチルヘキシル基を表す。ただし、式（１ｃ）表される化合物の＋電荷数と−電荷数とが同一であり、式（１ｄ）で表される化合物の＋電荷数と−電荷数とが同一である。）

(In Formula (1c) and Formula (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- Represents an ethylhexyl group, provided that the + charge number and the −charge number of the compound represented by the formula (1c) are the same, and the + charge number and the −charge number of the compound represented by the formula (1d) are the same. is there.)

（式（１ｅ）及び式（１ｆ）中、Ｒ^ｇ、Ｒ^ｈ及びＲ^ｉは、それぞれ独立に、水素原子、−ＳＯ_３ ⁻、−ＳＯ_３Ｈ又は−ＳＯ_２ＮＨＲ^ａを表す。Ｒ^ａは、２−エチルヘキシル基を表す。ただし、式（１ｅ）表される化合物の＋電荷数と−電荷数とが同一であり、式（１ｆ）で表される化合物の＋電荷数と−電荷数とが同一である。）

(In the formula (1e) and the formula ^{(1f), R g, R} h and ^{R i} each independently represent a hydrogen _atom, ^-SO 3 -, is .R ^a representative of the -SO ₃ H or _-SO 2 NHR ^a Represents a 2-ethylhexyl group, provided that the compound represented by the formula (1e) has the same + charge number and −charge number, and the compound represented by the formula (1f) has a + charge number and a −charge number; Are the same.)

The dye represented by formula (1) is obtained by, for example, chlorinating a dye or dye intermediate having —SO ₃ H by a conventional method, and converting the obtained dye or dye intermediate having —SO ₂ Cl into R ⁸ —NH. It can manufacture by making it react with the amine represented by ₂ . Moreover, it can manufacture by making the pigment | dye manufactured by the method of Unexamined-Japanese-Patent No. 3-78702 page 3 right upper column-lower left column react with an amine after chlorination like the above.

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

Wherein (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 heterocyclic group having 3 to 14 carbon atoms which may have a substituent. Represent.
R ⁵¹ represents 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. .
p1 represents 1 or 2. When p1 is 2, the plurality of A ⁰ , B ⁰ , R ⁵¹ and R ⁵² may be the same as or different from each other.
When p1 is 1, R ⁵² represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a monovalent substituent, and when p1 is 2, R ⁵² represents an optionally substituted divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, and includes the monovalent aliphatic hydrocarbon group and the divalent aliphatic hydrocarbon group. The —CH ₂ — contained may be replaced by —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 formula (2-1).

[In Formula (2-1), Z ¹ , Z ² and Z ³ each independently represent a C 1-16 divalent aliphatic hydrocarbon group which may have a substituent, and Z ¹ , —CH ₂ — contained in Z ² and Z ³ may be replaced by —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 a carbon number which may have 2 substituents. Represents an acyl group of ˜18.
A ¹ and A ² each independently represent a C 6-14 divalent aromatic hydrocarbon group which may have a substituent.
B ¹ and B ² are each independently a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a C ^{3 to} 14 carbon group which may have a substituent. Represents a monovalent heterocyclic group. ]

Z ¹ , Z ² and Z ³ each independently represent a C 1-16 divalent aliphatic hydrocarbon group which may have a substituent. Carbon number of a substituent is not contained in carbon number of a C1-C16 bivalent aliphatic hydrocarbon group, The number becomes like this. Preferably it is 2-10, More preferably, it is 2-8.
Examples of the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include alkanediyl groups having 1 to 16 carbon atoms, such as methylene group, ethylene group, propanediyl group, butanediyl group, pentanediyl group, hexanediyl group, Examples include a heptanediyl group, an octanediyl group, a decanediyl group, a tetradecanediyl group, and a hexadecanediyl group.
—CH ₂ — contained in the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms may be replaced by —CO— or —O—. The hydrogen atom contained in the C _1-16 aliphatic hydrocarbon group 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 an alkanediyl group having 5 to 7 carbon atoms which may contain —O—. More preferably. Preferable groups include, for example, — (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₎ - and the like.
Z ³ is preferably a C 1-8 divalent aliphatic hydrocarbon group which may contain —C (═C) —, and is an unsubstituted alkanediyl group having 1 to 8 carbon atoms. More preferably, it is an unsubstituted alkanediyl group having 4 to 8 carbon atoms. Preferable groups include, for example, — (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 linear, branched or cyclic. The carbon number of the aliphatic hydrocarbon group does not include the carbon number of the substituent, and the number is preferably 6 to 10, more preferably 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-butyl group, and a tert-butyl group. , Methylbutyl group (such as 1,1,3,3-tetramethylbutyl group), methylhexyl group (such as 1,5-dimethylhexyl group), ethylhexyl group (such as 2-ethylhexyl group), cyclopentyl group, cyclohexyl group, methyl Examples thereof include a cyclohexyl group (such as 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 3- (isopropoxy) propyl group) and an alkoxypropyl group (3- (2-ethylhexyloxy) propyl group, etc.). As a C1-C16 aliphatic hydrocarbon group substituted by the carboxy group, 2- (carboxy) ethyl group, 3- (carboxy) propyl group, 4- (carboxy) butyl group, etc. are mentioned.

As the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent representing R ⁵² ,
Examples of the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms that may have a substituent representing R ⁵² include an alkanediyl group having 1 to 35 carbon atoms, such as a methylene group, an ethylene group, and propane. Examples thereof include a diyl group, a butanediyl group, a pentanediyl group, a hexanediyl group, a heptanediyl group, an octanediyl group, a decanediyl group, a tetradecanediyl group, and a hexadecanediyl group.
—CH ₂ — contained in the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms may be replaced by —O—, —S—, —CO— or —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 representing R ′ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a cyclohexyl group.

A hydrogen atom contained in an 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 is preferably 6 to 10. Examples of the acyl group that may have a substituent include an acetyl group, a benzoyl group, and a methoxybenzoyl group (such as a p-methoxybenzoyl group).

R ⁵³ and R ⁵⁴ are preferably a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms, and an acyl group having 2 to 5 carbon atoms. Examples of the preferable group include a hydrogen atom, an acetyl group, and a propionyl group.

Examples of the divalent aromatic hydrocarbon group having 6 to 14 carbon atoms representing 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 for 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, and N-substituted sulfamoyl groups and the like can be mentioned.
As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, 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 group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group and hexyl group. An alkyl group having 1 to 4 carbon atoms is preferable, 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 group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group and hexyloxy group. 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.

N-substituted sulfamoyl groups include —SO ₂ NHR ⁵⁵ and —SO ₂ N (R ⁵⁵ ) R ⁵⁶ , and specifically, —SO ₂ NHR ⁸ and — in the compound represented by formula (1) Examples thereof include the same groups as those mentioned as SO ₂ N (R ⁸ ) R ⁹ . Among them, R ⁵⁵ and R ⁵⁶ are each independently an optionally substituted aliphatic hydrocarbon group having 1 to 16 carbon atoms or an optionally substituted acyl having 2 to 18 carbon atoms. The group N-substituted sulfamoyl group is preferred.

［Ｒは、水素原子又は有機基を表す。］
該有機基としては、例えば、後述のＲ^５９と同様の基が挙げられる。 B ⁰ , B ¹ and B ² are each independently a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or 3 carbon atoms which may have a substituent. Represents a monovalent heterocyclic group of -14.
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 heterocyclic group having 3 to 14 carbon atoms include the groups shown below.

[R represents a hydrogen atom or an organic group. ]
The organic group include the same groups as R ⁵⁹ described below.

The hydrogen atom contained in the monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms and the monovalent heterocyclic group having 3 to 14 carbon atoms is a hydroxy group, an oxo group, or a monovalent fatty acid having 1 to 16 carbon atoms. May be substituted with an aromatic hydrocarbon group, a cyano group, an amino group or an N-substituted amino group.
As the N-substituted amino group, —NHR ⁵⁷ group or —NR ⁵⁷ R ⁵⁸ group is preferable. However, each of R ⁵⁷ and R ⁵⁸ independently represents an optionally substituted monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms or optionally substituted 3 to 3 carbon atoms. 14 monovalent heterocyclic groups. Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms and the monovalent heterocyclic group having 3 to 14 carbon atoms include the same groups as described above.

［式（２−１ａ）中、Ｒ^５９は水素原子又は置換基を有していてもよい炭素数１〜１６の１価の脂肪族炭化水素基を表す。Ｒ^６０は、置換基を有していてもよい炭素数１〜１６の１価の脂肪族炭化水素基を表す。］
式（２−１ａ）で表される基のピリドン環は、ケト型であってもエノール型であってもよい。 B ⁰ , B ¹ and B ² are preferably each independently a group represented by the formula (2-1a).

[In Formula (2-1a), R ⁵⁹ represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent. R ⁶⁰ represents a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent. ]
The pyridone ring of the group represented by the formula (2-1a) may be keto type or enol type.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include the same ones as described above, and R ⁵⁹ represents a methylbutyl group (such as 1,1,3,3-tetramethylbutyl group) or methylhexyl. Groups (such as 1,5-dimethylhexyl group), ethylhexyl groups (such as 2-ethylhexyl group), methylcyclohexyl groups (such as 2-methylcyclohexyl group) and alkoxypropyl groups (3- (2-ethylhexyloxy)) A branched aliphatic hydrocarbon group such as a propyl group is preferable.
Examples of the substituent for R ⁵⁹ and R ⁶⁰ include a hydroxy 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 acetyloxy group, propionyloxy group, hexylcarbonyloxy group, octylcarbonyloxy group, benzoyloxy group and the like.
R ⁶⁰ is preferably a methyl group.

Examples of the compound represented by formula (2) include compounds represented by formula (I-1) to formula (I-18). A ¹ , A ² , Z ^1, and Z ² in the table represent a bond in which the right bond is closer to Z ³ .

B ¹ and B ² are preferably the same type of group, and more preferably A ¹ and A ² , R ⁵³ and R ⁵⁴ , and Z ¹ and Z ² are the same type of group, respectively. When these groups are used, the compound represented by the formula (2-1) can be easily produced.

  The compound represented by the formula (2-1) is a compound represented by the formula (IA) and a compound represented by the formula (IA ′) and a compound represented by the formula (IB) in a solvent. It can manufacture by making the represented compound react at 0-150 degreeC.

[In formula (IA), formula (IA ′) and formula (IB), Z ¹ , Z ² , Z ³ , R ⁵³ , R ⁵⁴ , A ¹ , A ² , B ¹ and B ² Represents the same meaning as above.
R ⁶⁷ and R ⁶⁸ each independently represents —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 (IB) include dimethyl malonate, isobutyl succinate, dimethyl adipate, and diethyl suberate, malonic acid chloride, succinic acid chloride, adipic acid chloride, and suberic acid chloride. .
The amount of the compound represented by the formula (IB) is 1 mol relative to the total amount of the compound represented by the formula (IA) and the compound represented by the formula (IA ′). For example, it is preferably 0.5 to 3 mol. In addition, when water is contained in the solvent, it is preferable to use the compound represented by the formula (IB) in excess of the above amount.
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 and p-toluenesulfonic acid. The usage-amount of an acid catalyst is 0.01-2 mol with respect to 1 mol of total amounts with the compound represented by the compound represented by a formula (IA), and a formula (IA '), for example. Preferably there is.

The reaction of the compound represented by the formula (IA) and the compound represented by the formula (IA ′) with the compound represented by the formula (IB) is performed in a solvent. Examples of the solvent include water; ethers such as 1,4-dioxane (particularly cyclic ethers); chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, dichloroethylene, trichloroethylene, perchloroethylene, dichloropropane, Halogenated hydrocarbons such as amyl chloride and 1,2-dibromoethane; Ketones such as acetone, methyl isobutyl ketone and cyclohexanone; Carbon-based aromatics such as benzene, toluene and xylene; N, N-dimethylformamide, N , N-dibutylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and other alkylamides are preferred, and two or more solvents may be used in combination. The amount of the solvent used is preferably, for example, 1 to 20 parts by mass with respect to 1 part by mass of the total amount of the compound represented by the formula (IA) and the compound represented by the formula (IA ′). More preferably, it is 2-10 mass parts.
The reaction between the compound represented by the formula (IA) and the compound represented by the formula (IA ′) and the compound represented by the formula (IB) is performed under a nitrogen atmosphere or an argon atmosphere. The reaction may be carried out in air dried with calcium chloride or the like.
The reaction temperature is, for example, preferably 0 to 150 ° C, more preferably 10 to 130 ° C. For example, the reaction time is preferably 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 (IA ′), the compound represented by the formula (IB), and the solvent is not particularly limited. The compound represented by the formula (IB) is preferably added (dropped) to a solution comprising the compound represented by -A), the compound represented by the formula (IA ′) and a solvent. When an acid catalyst is used, the compound represented by the formula (IB) is added to a solution comprising the compound represented by the formula (IA), the compound represented by the formula (IA ′), the acid catalyst and a solvent. The compound to be added is preferably added (dropped).
The method for obtaining the compound represented by the formula (2-1), which is the target compound, from the reaction mixture obtained as described above is not particularly limited, and various known techniques can be employed. It can be purified by extraction with an organic solvent. Moreover, you may refine | purify further by well-known methods, such as washing | cleaning by alkaline aqueous solution or acidic aqueous solution, and recrystallization as needed.

  In addition, the compound represented by the formula (2-1) is represented by the compound represented by the formula (IC), the compound represented by the formula (ID), and the formula (ID ′). The compound can be produced by a coupling reaction. The salt of the compound represented by the formula (IC), the compound represented by the formula (ID) and the compound represented by the formula (ID ′) are, for example, 20 to 60 ° C. in an aqueous solvent. By making it react by, the compound represented by Formula (2-1) can be manufactured.

(In Formula (IC) and Formula (ID), Z ¹ , Z ² , Z ³ , R ⁵³ , R ⁵⁴ , A ¹ , A ² , B ¹ and B ² represent the same meaning as described above.
X ⁻ represents an inorganic or organic anion. )
Examples of the inorganic or organic anion of the compound represented by the formula (IC) include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, CH ₃ —COO ^−. , Ph-COO ^- is like, preferably chloride, _bromide, CH 3 -COO ^- and the like.

  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.

［式（３）中、Ｒ^ａ１〜Ｒ^ａ１８は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜８の１価の脂肪族炭化水素基、ニトロ基、フェニル基、−ＳＯ_２ＮＨＲ^ａ３０、−ＳＯ_３ ^-、−ＣＯＯＲ^ａ３０又は−ＳＯ_２Ｒ^ａ３０を表す。
Ｒ^ａ１９及びＲ^ａ２０は、それぞれ独立に、水素原子、メチル基、エチル基又はアミノ基を表す。
Ｒ^ａ３０は、それぞれ独立に、水素原子、炭素数１〜１０の１価の炭化水素基を表し、該炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−で置き換わっていてもよい。
Ｍ^１は、Ｃｒ又はＣｏを表す。
ｎ^１は、１〜５の整数を表す。
Ｄ^１は、ヒドロン、１価の金属カチオン又はキサンテン骨格を有する化合物に由来する１価のカチオンを表す。］

[In the formula (3), 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, or —SO ₂ NHR ^a30. , —SO ₃ ⁻ , —COOR ^a30 or —SO ₂ R ^a30 .
R ^a19 and R ^a20 each independently represent a hydrogen atom, a methyl group, an ethyl group, or an amino group.
R ^a30 each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is replaced by —O— or —CO—. Also good.
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 hydrone, a monovalent metal cation or a xanthene skeleton. ]

Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms representing R ^{a1 to} R ^a18 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- Butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, dexyl group, 1-methylbutyl group, 1,1,3,3-tetramethylbutyl group, 1,5-dimethylhexyl Group, 1,6-dimethylheptyl group, 2-ethylhexyl group, 1,1,5,5-tetramethylhexyl group and the like.

^Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms representing R ^a30 include a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms, Examples thereof include monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms and groups having 4 to 10 carbon atoms in combination of these. Examples of the monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms include the same groups as described above, and the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms is represented by the formula (1). And the same groups as those represented by Q of the compound. 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 in which —CH ₂ — is replaced by —O— or —CO— include: —R ^a32 —O—R ^a33 , —R ^a32 —CO—O—R ^a33 , —R ^a32 —O—CO -R ^a33 is mentioned. 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, and a butane-1,4. -Diyl group, butane-1,3-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, etc. Can be mentioned.

As —R ^a32 —O—R ^a33 , methoxymethyl group, ethoxymethyl group, propoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, 2-oxo Examples include -4-methoxybutyl group, octyloxypropyl group, 3-ethoxypropyl group, 3- (2-ethylhexyloxy) propyl group, and the like.

—R ^a32 —CO—O—R ^a33 includes methoxycarbonylmethyl group, methoxycarbonylethyl group, ethoxycarbonylmethyl group, ethoxycarbonylethyl group, propoxycarbonylmethyl group, propoxycarbonylethyl group, butoxycarbonylmethyl group, butoxycarbonyl An ethyl group etc. are mentioned.

—R ^a32 —O—CO—R ^a33 includes acetyloxymethyl group, acetyloxyethyl group, ethylcarbonyloxymethyl group, ethylcarbonyloxyethyl group, propylcarbonyloxymethyl group, propylcarbonyloxyethyl group, butylcarbonyloxy Examples thereof include a methyl group and a butylcarbonyloxyethyl group.

As —SO ₂ NHR ^a30 , a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3 -Methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1 , 4-Dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group, N- (1,1,2, , 2-tetramethylbutyl) sulfamoyl group, sulfamoyl group substituted with an aliphatic hydrocarbon group such as N-allylsulfamoyl group;

N- (2-methoxyethyl) sulfamoyl group, N- (2-ethoxyethyl) sulfamoyl group, N- (1-methoxypropyl) sulfamoyl group, N- (3-methoxypropylsulfamoyl) group, N- (3- Ethoxypropyl) sulfamoyl group, N- (3-propoxypropyl) sulfamoyl group, N- (3-isopropoxypropyl) sulfamoyl group, N- (3-hexyloxypropylsulf) famoyl group, N- (2-ethylhexyloxypropyl) A sulfamoyl group substituted with —R ³¹ —O—R ³² such as a sulfamoyl group, an N- (3-tert-butoxypropyl) sulfamoyl group, an N- (4-octyloxybutyl) sulfamoyl group;
N- (methoxycarbonylmethyl) sulfamoyl group, N- (methoxycarbonylethyl) sulfamoyl group, N- (ethoxycarbonylmethyl) sulfamoyl group, N- (ethoxycarbonylethyl) sulfamoyl group, N- (propoxycarbonylmethyl) sulfamoyl group, A sulfamoyl group substituted with —R ³¹ —CO—O—R ³² such as N- (propoxycarbonylethyl) sulfamoyl group, N- (butoxycarbonylmethyl) sulfamoyl group, N- (butoxycarbonylethyl) sulfamoyl group;
N- (acetyloxymethyl) sulfamoyl group, N- (acetyloxyethyl) sulfamoyl group, N- (ethylcarbonyloxymethyl) sulfamoyl group, N- (ethylcarbonyloxyethyl) sulfamoyl group, N- (propylcarbonyloxymethyl) Substituted with —R ³¹ —O—CO—R ³² such as sulfamoyl group, N- (propylcarbonyloxyethyl) sulfamoyl group, N- (butylcarbonyloxymethyl) sulfamoyl group, N- (butylcarbonyloxyethyl) sulfamoyl group, etc. Sulfamoyl groups;

N-cyclohexylsulfamoyl group, N- (2-methylcyclohexyl) sulfamoyl group, N- (3-methylcyclohexyl) sulfamoyl group, N- (4-methylcyclohexyl) sulfamoyl group, N- (4-butylcyclohexyl) sulfamoyl A sulfamoyl group substituted with a cyclohexyl group having a substituent such as a group, etc .;
N-benzylsulfamoyl group, N- (1-phenylethyl) sulfamoyl group, N- (2-phenylethyl) sulfamoyl group, N- (3-phenylpropyl) sulfamoyl group, N- (4-phenylbutyl) sulfamoyl Group, N- [2- (2-naphthyl) ethyl] sulfamoyl group, N- [2- (4-methylphenyl) ethyl] sulfamoyl group, N- (3-phenyl-1-propyl) sulfamoyl group, N- ( And a sulfamoyl group substituted with an aralkyl group such as a 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.

As —SO ₂ R ^a30 , a methanesulfonyl group, ethanesulfonyl group, propanesulfonyl group, isopropanesulfonyl group, n-butanesulfonyl group, sec-butanesulfonyl group, tert-butanesulfonyl group, pentanesulfonyl group, hexanesulfonyl group , Heptanesulfonyl group, octanesulfonyl group, 1-methylbutanesulfonyl group, 1,1,3,3-tetramethylbutanesulfonyl group, 1,5-dimethylhexanesulfonyl group, 1,6-dimethylheptanesulfonyl group, 2- Examples thereof include an ethylhexanesulfonyl group and a 1,1,5,5-tetramethylhexanesulfonyl group.

Since it exists in the tendency for heat resistance to be high, it is preferable that it is at least 1 nitro group among R ^{< a1} > -R ^<a18> .

As R ^a30 , 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 —O—R ^a33 , —R ^a32 —CO—O—R ^a33 and —R ^a32 —O—CO—R ^a33 are preferred.

  In the compound represented by the formula (3), preferable examples of the pyrazole azo compound serving as a complex anion ligand include compounds represented by the formula (1-a1) to the formula (1-a64). .

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

D ¹ is a monovalent cation derived from a compound having hydron, a monovalent metal cation or a xanthene skeleton. Among these, 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 Formula (3) is preferably a compound represented by Formula (3-1) from the viewpoint of solubility in an organic solvent.

[In Formula (3-1), R ^{a41 to} R ^a58 are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, a sulfo group, or —SO _2. R ^a33 or —SO ₂ NHR ^a34 is represented.
R ^a34 represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, -R ^a32 -O-R ^a33 ,- R ^a32 —CO—O—R ^a33 , —R ^a32 —O—CO—R ^a33 or an aralkyl group having 7 to 10 carbon atoms is represented.
R ^a32 represents a C 1-8 divalent aliphatic hydrocarbon group.
R ^a33 represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.
R ^a59 and R ^a60 each 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 each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, The hydrogen atom contained in the hydrogen group and the aromatic hydrocarbon group may be substituted with a hydroxy group, —OR ³² , a sulfo group, —SO ₃ Na, —SO ₃ K, or 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 greater than or equal to 2, several R < ²⁷ > may mutually be same or different. ]

Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include the same groups as those described 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 described above for 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 monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms include phenyl groups, methylphenyl groups, dimethylphenyl groups, trimethylphenyl groups, ethylphenyl groups, propylphenyl groups, butylphenyl groups, and naphthyl groups. An aralkyl group such as a benzyl group, a diphenylmethyl group, a phenylethyl group or a 3-phenylpropyl group;

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

Since it exists in the tendency for heat resistance to be high, it is preferable that it is at least 1 nitro group among R ^{< a41 >} -R ^{< a58 >} .
^Further, at least one of the at least one and ^R a46 ^{to R a50} of R a41 ^{to R a45,} preferably a sulfo _group, a -SO ^{2 NHR a34} or _-SO 2 ^{R _a33,} is -SO ^{2 R a33} It is more preferable that it is —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, since the color density increases. Or it is more preferable that it is an ethyl group.

R ^a27 is preferably an ethylene group and a propane-1,2-diyl group, and more preferably an ethylene group.
R ^a28 is preferably a hydrogen atom.
n is an integer of 1 to 4, an integer of 2 to 4 is preferable, 3 or 4 is more preferable, and 3 is more preferable.
-(R ^a27 -O) n-R ^a28 is a 2- (2-hydroxyethoxy) ethyl group or a 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group in terms of solubility in an organic solvent. Is preferable, and a 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group is more preferable.

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

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

  Among the specific examples of the compound represented by the formula (3-1), in terms of solubility in an organic solvent, the formula (3a-1), the formula (3a-3) to the formula (3a-5), the formula ( 3a-7) to formula (3a-9), formula (3a-11) to formula (3a-16), formula (3a-18) to formula (3a-21), and formula (3a-23) to formula (3a) The compound represented by -26) is preferred, the compound represented by formula (3a-1), the compound represented by formula (3a-3), and the compound represented by formula (3a-23) are more preferred.

In order to produce the compound represented by the formula (3), a 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 cobalt. A cobalt complex salt is formed using the compound. Thereafter, the compound represented by the formula (3) can be produced by subjecting the complex salt and the salt having D ¹ to a salt exchange reaction as necessary.

[In formula (3d), R ^{a1 to} R ^a5 , R ^{a11 to} R ^a14 and R ^a19 represent the same meaning as in formula (3). ]
The compound represented by the formula (3d) can be produced by a diazo coupling method of a diazonium salt and a pyrazole compound, which is well known in the dye field.

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

[In formula (b), R ^{a21 to} R ^a28 and n represent the same meaning as in formula (3-1). A ⁻ represents a monovalent anion. ]
Examples of the monovalent anion include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , PF ₆ ^{− and} BF ₄ ⁻ .

［式（ｂ０）及び式（ｂ１）中、Ｒ^ａ２１〜Ｒ^ａ２８及びｎは、式（２−１）におけるものと同じ意味を表す。Ａ⁻は、式（ｂ）におけるものと同じ意味を表す。］
前記反応において、反応温度は１５℃〜６０℃が好ましく、反応時間は１時間〜１２時間が好ましい。また、反応時間短縮や収率向上の点で、酸触媒及び／又は脱水剤を用いることが好ましい。
酸触媒としては、硫酸、ｐ−トルエンスルホン酸などが挙げられる。
脱水剤としては、ジシクロヘキシルカルボジイミド、ジイソプロピルカルボジイミド、1-エチル-3-（3-ジメチルアミノプロピル）カルボジイミド塩酸塩等のカルボジイミド類；１−アルキル−２−ハロピリジウム塩類；１，１’−カルボニルジイミダゾール；ビス（２−オキソ−3−オキサゾリジニル）ホスフィン酸塩化物；ジ−２−ピリジル炭酸塩などが挙げられる。中でも、脱水剤としては、後処理及び精製が容易であることから、1-エチル-3-（3-ジメチルアミノプロピル）カルボジイミド塩酸塩が好ましい。
前記反応に用いられる有機溶媒としては、ジクロロメタン、クロロホルム、テトラヒドロフラン、トルエン、アセトニトリルなどが挙げられる。 The xanthene compound represented by the formula (b) can be produced by reacting the compound represented by the formula (b0) and the compound represented by the formula (b1) in an organic solvent.

[In formula (b0) and formula (b1), R ^{a21 to} R ^a28 and n represent the same meaning as in formula (2-1). A ⁻ represents the same meaning as in formula (b). ]
In the above reaction, the reaction temperature is preferably 15 ° C. to 60 ° C., and the reaction time is preferably 1 hour to 12 hours. Moreover, it is preferable to use an acid catalyst and / or a dehydrating agent in terms of shortening the reaction time and improving the yield.
Examples of the acid catalyst include sulfuric acid and p-toluenesulfonic acid.
Examples of the dehydrating agent include carbodiimides such as dicyclohexylcarbodiimide, diisopropylcarbodiimide, 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 can be mentioned. Among these, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride is preferable as the dehydrating agent because of easy post-treatment and purification.
Examples of the organic solvent used in the reaction include dichloromethane, chloroform, tetrahydrofuran, toluene, and acetonitrile.

  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. The cobalt complex salt and the xanthene compound (b) are preferably reacted at a molar ratio of 1: 1 to 1: 4.

  These dyes are appropriately selected according to the solubility in a solvent, the light fading resistance when a color filter pattern is formed using a photosensitive resin composition containing the dye, and the spectral spectrum.

  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 with respect to the solid content of the photosensitive resin composition forming the color filter. .

Moreover, when it contains the dye which has a carboxy group in dye, the content becomes with respect to a dye, Preferably it is 1-100 mass%, More preferably, it is 5-100 mass%, More preferably, it is 10 ˜100 mass%.
Here, solid content in this specification means the total amount of the components except the solvent contained in the photosensitive resin composition.

<Photosensitive resin composition>
In the display device of the present invention, the color filter is preferably a color filter formed from 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 structural unit derived from (meth) acrylic acid.
Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid. The content of the structural unit derived from the (meth) acrylic acid is preferably 16 mol% or more and 40 mol% or less, more preferably 18 mol% or more and 38 mol% or less in all the structural units constituting the binder resin. is there. When the content of the structural unit derived from (meth) acrylic acid is in the above range, the solubility of the non-pixel portion is good during development, and the residue tends not to remain in the non-pixel portion after development. is there.

  Examples of the other monomer for deriving the structural unit of the binder resin other than the structural unit derived from (meth) acrylic acid include, for example, aromatic vinyl compounds, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, and unsaturated compounds. Carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, vinyl cyanide compounds, unsaturated amides, unsaturated imides, aliphatic conjugated dienes, monoacryloyl group or mono at the end of the polymer molecular chain Examples thereof include macromonomers having a methacryloyl group, a structural unit represented by the formula (II), and a structural unit represented by the formula (III).

(In Formula (II) and Formula (III), R ⁸⁰ and R ⁸² each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ⁸¹ and R ⁸³ each independently represent a hydrogen atom. Or represents a C1-C6 alkyl group.)

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, and methacrylic acid / styrene. / benzyl methacrylate / N- phenylmaleimide copolymer, component represented by methacrylic acid / formula (II) (However, in this case, in formula ^{(II), R 80} represents a methyl ^{group, R 81} represents a hydrogen atom / Benzyl methacrylate copolymer, a constituent represented by the formula (II) (in the formula (II), R ⁸⁰ represents a methyl group and R ⁸¹ represents a hydrogen atom). / Benzyl methacrylate copolymer, methacrylic acid / constituent component represented by formula (III) In the formula (III), R ⁸² represents a methyl group and R ⁸³ represents a hydrogen atom.) / Styrene copolymer / Tricyclodecanyl methacrylate copolymer and the like are preferable.

  The binder resin having a structural unit represented by the formula (II) is a copolymer having a structural unit derived from at least one compound selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, which will be described later. It can be obtained by obtaining a coalescence and reacting the carboxylic acid or acid anhydride contained in the copolymer with the compound represented by the formula (V). The binder resin having the structural unit represented by the formula (III) is a carboxylic acid or acid anhydride contained in the copolymer, and a compound represented by the formula (VI), for example, JP-A-2005-189574. It can obtain by making it react like the method as described in gazette.

[In Formula (V) and Formula (VI), R ⁸¹ and R ⁸³ represent the same meaning as described above. ]
For example, methacrylic acid / constituent component represented by formula (II) (wherein, in formula (II), R ⁸⁰ represents a methyl group and R ⁸¹ represents a hydrogen atom) / benzyl methacrylate copolymer Is obtained by polymerizing methacrylic acid and benzyl methacrylate to obtain a two-component polymer, and the obtained two-component polymer and a compound represented by formula (V) (in this case, in formula (V), R ⁸¹ represents a hydrogen atom.
) And can be obtained.

Methacrylic acid / constituent component represented by formula (III) (wherein, in formula (III), R ⁸² represents a methyl group and R ⁸³ represents a hydrogen atom) / styrene copolymer / tricyclo The decanyl methacrylate copolymer can be obtained by reacting benzyl methacrylate, methacrylic acid, or a monomethacrylate copolymer having a tricyclodecane skeleton with glycidyl methacrylate.
In particular, the binder resin represented by the formula (IV) is preferable in terms of curability and developability.

  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), benzoyl peroxide and tert-butyl peroxide. A peroxide such as is used. The solvent may be any solvent that dissolves each monomer, for example, glycol ether esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. Is used. The reaction temperature may be determined in consideration of the decomposition temperature of the polymerization initiator and the boiling points of the solvent and the monomer. The side chain of the copolymer thus obtained can 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. An example of the catalyst is trisdimethylaminomethylphenol. Moreover, you may add the additive for preventing a side reaction. Examples of the additive include hydroquinone.

  The binder resin has alkali solubility, a structural unit derived from a compound (C0) having a carbon-carbon unsaturated double bond and a cyclic ether structure (hereinafter sometimes referred to as “(C0)”), And a structural unit derived from at least one compound (C2) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter sometimes referred to as “(C2)”). It is preferable.

  Examples of the cyclic ether structure of (C0) include an epoxy (that is, oxirane) structure, an oxetane structure, and a tetrahydrofuran structure.

（式中、Ｒ^６１〜Ｒ^６３は、それぞれ独立に水素原子又は炭素原子数１〜１０のアルキル基であり、ｍ^６は１〜５の整数である。）。 Examples of the epoxy structure include an aliphatic epoxy structure (ie, a structure obtained by epoxidizing an alkene), an aliphatic monocyclic epoxy structure, and an aliphatic polycyclic epoxy structure (ie, a structure obtained by epoxidizing a polycyclic cycloalkene). An aliphatic polycyclic epoxy structure is particularly preferred.
Specific examples of the compound having a carbon-carbon unsaturated double bond and an aliphatic epoxy structure include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, and glycidyl vinyl ether. And compounds represented by the following formulas described in JP-A-7-248625.

(In the formula, 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-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m- Vinylbenzyl glycidyl ether, α-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-triglycidyl Oxymethylstyrene and Include 4,6-tri-glycidyloxy-methylstyrene.

The compound having a carbon-carbon unsaturated double bond and an aliphatic monocyclic epoxy structure is a compound having a structure obtained by epoxidizing a carbon-carbon unsaturated double bond and a monocyclic cycloalkene. Examples of the monocyclic cycloalkene include cyclopentene, cyclohexene, cycloheptene, cyclooctene and the like. Especially, a C5-C7 compound is preferable.
Specific examples of the compound having a carbon-carbon unsaturated double bond and an aliphatic monocyclic epoxy structure include vinylcyclohexene monooxide 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; Daicel Chemical Industries). 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; Daicel Chemical Industries, Ltd.) Etc.).

The compound (C1) (hereinafter sometimes referred to as “(C1)”) having a carbon-carbon unsaturated double bond and an aliphatic polycyclic epoxy structure is obtained by reacting a carbon-carbon unsaturated double bond and a polycyclic cycloalkene. It is a compound having an epoxidized structure. Examples of the polycyclic cycloalkene include dicyclopentene, tricyclodecene, norbornene, isonorbornene, bicyclooctene, bicyclononene, bicycloundecene, tricycloundecene, bicyclododecene, and tricyclododecene.
(C1) is represented by, for example, 3,4-epoxynorbornyl acrylate, 3,4-epoxynorbornyl methacrylate, a compound represented by formula (C1-1), and formula (C1-2). A compound, 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 Formula (C1-1) and Formula (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 It may be substituted with a hydroxy group.
X ⁸⁷ and X ⁸⁸ each independently represent a C 1-6 alkylene group that 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, an n-butyl group, and sec-butyl. Group, tert-butyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy-1-methylethyl group 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc., preferably methyl group, hydroxymethyl group, 1- A hydroxyethyl group and 2-hydroxyethyl group are mentioned, More preferably, a methyl group is mentioned.
R ⁸⁷ and R ⁸⁸ are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, more preferably a hydrogen atom and a methyl group.

  As a hetero atom in a C1-C6 alkylene group which may contain a hetero atom, an oxygen atom, a sulfur atom, and a nitrogen atom are mentioned. Note that the number of heteroatoms is not included in the number of carbon atoms.

The alkylene group having 1 to 6 carbon atoms which may contain a hetero atom, a methylene group, an ethylene group, a propylene group, oxymethylene group (-OCH ₂ -), an oxyethylene group _(-OCH 2 _CH 2 -), oxypropylene Group (—OCH ₂ CH ₂ CH ₂ —), thiomethylene group (—SCH ₂ —), thioethylene group (—SCH ₂ CH ₂ —), thiopropylene group (—SCH ₂ CH ₂ CH ₂ —), iminomethylene group ( _-NH-CH 2 -), Iminoechiren group _{(-NH-CH 2 CH 2 -} ) and imino propylene _{(-NH-CH 2 CH 2 CH} 2 -) and the like, preferably methylene group, ethylene group, An oxymethylene group or an oxyethylene group is mentioned, More preferably, an oxyethylene group is mentioned.
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 compounds represented by the formula (C1-1-1) to the formula (C1-1-15), preferably the formula (C1-1-1). ), Formula (C1-1-3), formula (C1-1-5), formula (C1-1-7), formula (C1-1-9), formula (C1-1-11) to formula (C1) -1-15), and more preferably a compound represented by formula (C1-1-1), formula (C1-1-7), formula (C1-1-9) or formula (C1-1). And a compound represented by 15).

  Examples of the compound represented by the formula (C1-2) include compounds represented by the formula (C1-2-1) to the formula (C1-2-15), preferably the formula (C1-2-1). ), Formula (C1-2-3), formula (C1-2-5), formula (C1-2-7), formula (C1-2-9), formula (C1-2-11) to formula (C1) -2-15), and more preferably a compound represented by formula (C1-2-1), formula (C1-2-7), formula (C1-2-9) or formula (C1-2). And a compound represented by 15).

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

  Examples of the compound having a carbon-carbon unsaturated double bond and an oxetane structure include 3-methyl-3-methacryloxymethyl oxetane, 3-methyl-3-acryloxymethyl oxetane, 3-ethyl-3-methacryloxymethyl oxetane, 3-ethyl-3-acryloxymethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-ethyl-3-methacryloxyethyl oxetane or 3-ethyl-3- And acryloxyethyl oxetane.

  As a compound having a carbon-carbon unsaturated double bond and a tetrahydrofuran structure, as a monomer having a tetrahydrofuryl group, specifically, tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, Osaka Organic Chemical Industry ( Co., Ltd.), tetrahydrofurfuryl methacrylate and the like.

Examples of (C2) include 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, itaconic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Anhydrides of unsaturated dicarboxylic acids such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride);
Unsaturated mono [(meth) acryloyloxy of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Alkyl] esters;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxyl group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Among these, acrylic acid, methacrylic acid, and maleic anhydride are preferably used from the viewpoint of copolymerization reactivity and solubility in an alkaline aqueous solution. These may be used alone or in combination.

The binder resin is a copolymer including a structural unit derived from (C1) and a structural unit derived from (C2), and the ratio of the structural unit derived from (C1) and the structural unit derived from (C2). However, when it is in the following range with respect to the total number of moles of the constituent units constituting the copolymer, storage stability, heat resistance and mechanical strength tend to be good, which is preferable.
Structural units derived from (C1); 2-98 mol%
Structural units derived from (C2); 2-98 mol%

Moreover, it is more preferable in the point of developability and solvent resistance that the ratio of the said structural unit is the following ranges.
Structural units derived from (C1); 40 to 85 mol%
Structural unit derived from (C2); 15 to 60 mol%

The binder resin is, for example, the method described in the document “Experimental Methods for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972) and the document. Can be produced with reference to the cited references described in 1.
Specifically, a predetermined amount of (C1) and (C2), a polymerization initiator, and a solvent are charged into a reaction vessel, and the oxygen is replaced with nitrogen, whereby stirring, heating, and heat retention are performed in the absence of oxygen. As a result, a copolymer is obtained. In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and took out as solid (powder) by methods, such as reprecipitation. Things may be used.

  In addition to the structural unit derived from (C1) and the structural unit derived from (C2), the binder resin is further a compound copolymerizable with (C1) and (C2) (however, (C1) and (C2 )).) A structural unit derived from (C3) (hereinafter sometimes referred to as “(C3)”).

Examples of (C3) include (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and tert-butyl (meth) acrylate. Alkyl esters;
Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, dicyclopenta Nyl (meth) acrylate), (meth) acrylic acid cycloalkyl esters such as dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate;
(Meth) acrylic acid aromatic esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
(Meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-di (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Chlorounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate and N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid 3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, 6,7-epoxyheptyl α-ethyl acrylate, O-vinyl Benzyl glycidyl ether, - such as vinylbenzyl glycidyl ether and p- vinylbenzyl glycidyl ether. Here, in the present specification, (meth) acrylate represents at least one selected from the group consisting of acrylate and methacrylate. (Meth) acrylic acid represents at least one selected from the group consisting of acrylic acid and methacrylic acid.
Of these, benzyl acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable.
Said (C3) is used individually or in combination.

When (C3) is included, the ratio of the structural units derived from (C1) to (C3) is in the following range in terms of mole fraction with respect to the total number of moles of the structural units constituting the copolymer. And preferred.
Structural units derived from (C1); 2-97 mol%
Structural units derived from (C2); 2-97 mol%
Structural units derived from (C3); 1 to 96 mol%

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

The polystyrene-reduced weight average molecular weight of the binder resin is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 35,000, and particularly preferably. It is 6,000 to 30,000, and particularly preferably 7,000 to 28,000. When the weight average molecular weight of the binder resin is in the above range, the coating property and the coating film hardness tend to be good, and the film is not easily reduced during development. Further, the non-pixel portion (that is, the unexposed portion) during development. ) Is preferred since it tends to be good (i.e., solubility in a developer).
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, and more preferably 1.2 to 4.0. The molecular weight distribution in the above range is preferable because it tends to be excellent in developability.
The content of the binder resin is preferably 10 to 35% by mass, more preferably 15 to 30% by mass, based on the solid content in the photosensitive resin composition. When the content of the binder resin is in the above range, the solubility in the developer is sufficient, development residue is hardly generated on the substrate of the non-pixel portion, and the film thickness of the pixel portion of the exposed portion is reduced during development. This is preferable because the non-pixel portion tends to be easily removed.

  The acid value of the binder resin is preferably 50 to 150 mgKOH / g, more preferably 60 to 135 mgKOH / g, and particularly preferably 70 to 135 mgKOH / g. When the acid value is in the above range, the solubility in the developer is improved and the unexposed area is easily dissolved, and the sensitivity is increased so that the pattern of the exposed area remains during development and the remaining film ratio tends to be improved. Is preferable. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic acid polymer, and is usually obtained by titration with an aqueous potassium hydroxide solution. it can.

  The content of the binder resin is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass with respect to 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 remaining film ratio tend to be improved, which is preferable.

  A photopolymerizable compound is a compound that can be polymerized by an active radical, an acid, or the like generated from a photopolymerization initiator when irradiated with light, such as a compound having a polymerizable carbon-carbon unsaturated bond. Can be mentioned.

  The photopolymerizable compound is preferably a trifunctional or higher polyfunctional photopolymerizable compound. A trifunctional or higher polyfunctional photopolymerizable compound refers to a compound having three or more polymerizable carbon-carbon unsaturated bonds. The group containing a polymerizable carbon-carbon unsaturated bond is preferably a (meth) acryloyl group. Examples of the trifunctional or higher polyfunctional photopolymerizable compound include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. Is mentioned. The photopolymerizable compounds may be used alone or in combination of two or more, and the content thereof is preferably 7 to 65% by mass, more preferably based on the solid content of the photosensitive resin composition. Is 13-60 mass%, More preferably, it is 17-55 mass%. When the content of the photopolymerizable compound is in the above range, curing is sufficiently performed, the film thickness ratio before and after development is improved, and the pattern is less likely to be undercut and adhesion is improved. It is preferable because of its tendency.

The photosensitive resin composition forming the color filter contains a photopolymerization initiator. The photopolymerization initiator is a compound that can generate an active radical, an acid, and the like when irradiated with light, and can initiate polymerization of the photopolymerizable compound. Among these, a compound that generates radicals by ultraviolet rays is preferable. Examples of the photopolymerization initiator include active radical generators and acid generators.
An active radical generator generates an active radical when irradiated with light. Examples of the active radical generator include acetophenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, and oxime compounds.

  Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, and 2-hydroxy-2-methyl-1-phenylpropane-1. -One, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1 -[4- (1-methylvinyl) phenyl] propan-1-one oligomers, and the like, preferably 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and the like. It is done.

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

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butyl). Peroxycarbonyl) 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-chloro-4-propoxythioxanthone, and the like.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- ( 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl ] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- Bis (trichloromethyl) ) Such -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the oxime compounds include O-acyloxime compounds, and specific examples thereof include 1- (4-phenylsulfanylphenyl) -butane-1,2-dione 2-oxime-O-benzo. Art (ie N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine), 1- (4-phenylsulfanyl-phenyl) -octane-1,2-dione-2-oxime -O-benzoate (ie N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine), 1- [9-ethyl-6- (2-methylbenzoyl) -9H- Carbazol-3-yl] ethanone 1-O-acetate (ie N-acetoxy-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-carbazol-3-yl] ethanone 1-O-acetate (ie N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4) -Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine) and the like.

  Examples of active radical generators other than those exemplified above 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, camphorquinone, methyl phenylglyoxylate, titanocene compound, etc. can also be used. .

  Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl, Onium salts such as methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate And benzoin tosylate.

  Among the compounds described above as the active radical generator, there are compounds that generate an acid simultaneously with the active radical. For example, a triazine photopolymerization initiator is also used as an acid generator.

  The content of the photopolymerization initiator is preferably 0.1 to 30% by mass and more preferably 1 to 20% by mass with respect to the total amount of the binder resin and the photopolymerizable compound. When the content of the photopolymerization initiator is within the above range, the sensitivity is increased, the exposure time is shortened, and the productivity is improved.

The photosensitive resin composition forming the color filter may further contain a photopolymerization initiation assistant. The photopolymerization initiation assistant is a compound or a sensitizer that is usually used in combination with a photopolymerization initiator and is used to promote polymerization of a photopolymerizable compound that has been polymerized by the photopolymerization initiator. .
Examples of photopolymerization initiation assistants include amine compounds, alkoxyanthracene compounds, and thioxanthone compounds.
Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylbenzoate. Aminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4, Examples thereof include 4′-bis (ethylmethylamino) benzophenone, and among these, 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, 2-ethyl-9,10-dibutoxyanthracene and the like.

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

  The photopolymerization initiation assistant may be used alone or in combination of two or more. In addition, as the photopolymerization initiation assistant, commercially available ones can be used, and examples of the commercially available photopolymerization initiation assistant include trade name “EAB-F” (manufactured by Hodogaya Chemical Co., Ltd.). Can be mentioned.

  Examples of the combination of the photopolymerization initiator and the photopolymerization initiation assistant include, for example, diethoxyacetophenone / 4,4′-bis (diethylamino) benzophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propane- 1-one / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one / 4,4′-bis (diethylamino) benzophenone, benzyldimethyl ketal / 4,4 '-Bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one / 4,4'-bis (diethylamino) benzophenone, 1-hydroxycyclohexyl Phenyl ketone / 4,4′-bis (diethylamino) benzofe , 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one oligomer / 4,4′-bis (diethylamino) benzophenone, 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone and the like, preferably 2-methyl-2-morpholino-1- (4-methylthiophenyl) propane- 1-one / 4,4′-bis (diethylamino) benzophenone.

  When using these photoinitiators, the usage-amount is 0.01-10 mol per mol of photoinitiators, More preferably, it is 0.01-5 mol.

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

  Examples of the ethers include tetrahydrofuran, tetrahydropyran, 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 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, anisole, phenetole, and the like methyl anisole.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.
Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, 4-hydroxy-4-methyl-2-pentanone, and cyclopentanone. And cyclohexanone.
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, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3 -Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2- Ethyl methyl propionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutane Examples include methyl acid, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and γ-butyrolactone.
Examples of the amides include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.
Among 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 these in combination.
Furthermore, the said solvent may be used individually or in combination of 2 or more types.

  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 with respect to the photosensitive resin composition. When the content of the solvent is within the above range, the flatness at the time of coating is good, and since the color density does not become insufficient when the color filter is formed, the display characteristics tend to be good, which is preferable.

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 fluorine surfactant, and a silicone surfactant having a fluorine atom.
Examples of the silicone surfactant include surfactants having a siloxane bond. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH29PA, SH30PA, polyether-modified silicone oil SH8400 (trade name: Torresilicone; manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials) Japan GK)).

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, Florard (trade name) FC430, FC431 (Sumitomo 3M Co., Ltd.), MegaFac (trade name) F142D, F171, F172, F173, F177, F177, F183, R30 (DIC) ), Ftop (trade name) EF301, EF303, EF351, EF351, EF352 (Mitsubishi Materials Electronic Chemicals), Surflon (tradename) S381, S382, SC101, SC105 (Asahi Glass) Co., Ltd.), E5844 (Daikin Fine Chemical Laboratory Co., Ltd.), BM-1000, BM-1100 (both trade names: manufactured by BM Chemie), and the like.
Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, MegaFuck (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation) and the like can be mentioned.
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 with respect to the photosensitive resin composition. When the content of the surfactant is in the above range, the flatness tends to be good, which is preferable.

  As a method for forming a color filter pattern, for example, a photosensitive resin composition containing a dye is used as a substrate or another resin layer (for example, another photosensitive resin composition layer previously formed on the substrate, etc. ), Removing a volatile component such as a solvent to form a colored layer, exposing the colored layer through a photomask, developing, and using an inkjet device that does not require a photolithography method. Can be mentioned.

The photosensitive resin composition preferably contains a pigment.
Specific examples of the pigment include pigments classified as pigments according to a color index (published by The Society of Dyers and Colorists). Specifically, for example, C.I. I
. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7.

When producing a color filter using the photosensitive resin composition, the photosensitive resin composition is adjusted as, for example, a blue photosensitive resin composition, a green photosensitive resin composition, and a red photosensitive resin composition, respectively. .
Examples of the pigment used in the blue photosensitive resin composition include C.I. I. Pigment red violet 23, C.I. I. Pigment Blue containing at least one pigment selected from Pigment Blue 15: 3 and 15: 6 is preferable. I. A pigment containing CI Pigment Blue 15: 6 is more preferable. Examples of the pigment used in the green photosensitive resin composition include C.I. I. Pigment green 36, 58, C.I. I. A pigment containing at least one selected from CI Pigment Yellow 138 and 150 is preferable. Examples of the pigment used in the red photosensitive resin composition include C.I. I. Pigment yellow 138, 139, 150, C.I. I. A pigment containing at least one selected from CI Pigment Red 177, 242, and 254 is preferable. These pigments may be used alone or in combination of two or more.

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

  In the photosensitive resin composition used for producing the display device of the present invention, the dye and the pigment are preferably contained in a mass ratio of dye: pigment = 1: 99 to 99: 1, and 1:99 to 60. : 40 is more preferable, and 5:95 to 40:60 is even more preferable. By setting such a ratio, the transmission spectrum can be easily optimized, a colored pattern with high contrast and high brightness can be obtained, and the resulting colored pattern has good heat resistance and chemical resistance.

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

  If necessary, the pigment can be used as a pigment dispersion in a state where the pigment is uniformly dispersed in the solution by performing a dispersion treatment in the presence of a dispersant.

  Examples of the dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine, and may be used alone or in combination of two or more.

  Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines, etc. In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), MegaFuck (manufactured by Dainippon Ink Chemical Co., Ltd.) , FLORARD (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by EFKA CHEMICALS Co., Ltd.) and PB821 (manufactured by Ajinomoto Co., Inc.) Etc.

  When using a dispersing agent, the usage-amount is with respect to a pigment, Preferably it is 0.1-100 mass%, More preferably, it is 5-50 mass%. It is preferable that the amount of the dispersant used be in the above range because a uniform dispersion tends to be obtained.

<Color filter>
The color filter is formed from the above-described photosensitive resin composition. The color filter includes a red pixel including at least one selected from the group consisting of a red dye, an orange dye and a yellow dye, a green pixel including at least one selected from the group consisting of a green dye and a yellow dye, and a blue dye and a purple color. A blue pixel including at least one selected from the group consisting of dyes is provided.
A color filter can be manufactured by forming each color pixel on a substrate by a photolithographic method 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 whose surface is coated with silica, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.
As the opaque substrate, silicon or a substrate obtained by forming an aluminum, silver, silver / copper / palladium alloy thin film on the transparent substrate is used.

When each color pixel is formed by a photolithography method, a pattern is formed by developing each photosensitive resin composition on the substrate in an arbitrary order using the above-described red, green, and blue photosensitive resin compositions. Thus, a color filter can be obtained. That is, the color filter included in the display device of the present invention is formed by forming each of the above-described photosensitive resin compositions into a predetermined shape.
FIG. 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 grid-like black matrix BM having a plurality of openings formed on the substrate 3, and a transparent red photosensitive material formed in order so as to cover each opening of the black matrix BM. It has a 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 a red photosensitive resin composition into a desired shape, and the transparent green photosensitive resin composition film G is a predetermined green photosensitive resin composition. The transparent blue photosensitive resin composition film B is formed by forming a blue photosensitive resin composition into a predetermined shape.

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

  The photosensitive resin composition is spin-coated on a substrate (usually glass) and heat-dried (pre-baked) to remove the solvent and obtain a smooth coating film. At this time, the thickness of the coating film is about 1 to 5 μm. The coated film thus obtained is irradiated with ultraviolet rays through a negative mask for forming a desired image to cure the exposed area, and then the unexposed area is dissolved in a developer and developed. By repeating the above operation in the same manner for each photosensitive resin composition, 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 can also be used.

  In the ultraviolet irradiation, it is preferable to use a device such as a mask aligner so that parallel light is uniformly irradiated on the entire exposed portion and the mask and the substrate are accurately aligned. Further, after development, post-curing (post-baking) can be performed at 150 to 230 ° C. for about 10 to 60 minutes as 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, but is not limited thereto.
In addition, a thin film transistor (TFT) is formed in advance on the substrate, and then a pixel can be formed. By forming pixels on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

<Display device>
The display device of the present invention will be described. The display device includes a color filter containing a dye and a white light-emitting diode light source (hereinafter also referred to as “white LED”).

The white LED has a wavelength λ ₁ at which the emission intensity is maximum within a wavelength range of 430 nm to 485 nm, a wavelength λ ₂ at which the emission intensity is maximized within a wavelength range of 500 nm to 580 nm, and a wavelength of 590 nm to 680 nm. In the range, the wavelength λ ₃ at which the emission intensity is maximized.
The white LED is preferably a light source including a blue LED and a phosphor. For example, a white LED having a fluorescent filter formed on the surface of the blue LED or a blue LED resin package containing the phosphor. It is done. The blue LED is an LED that emits blue light (wavelength is, for example, 470 nm) such as InGaN or GaN.

The white LED is more preferably a light source including a blue LED, a red light emitting phosphor, and a green light emitting phosphor. The red light-emitting phosphor and the green light-emitting phosphor are used by being contained in a fluorescent filter or a resin package in the same manner as described above.
A fluorescent filter containing a green light emitting phosphor or a resin package containing a green light emitting phosphor absorbs a part of blue light emission from a blue LED and emits green light having a maximum light emission between 500 nm and 580 nm, Similarly, a fluorescent filter containing a red light emitting phosphor or a resin package containing a red light emitting phosphor emits red light having a maximum light emission between 590 nm and 680 nm. In this type of white LED, part of the blue light emitted by the blue LED passes through the phosphor layer, and the rest is absorbed by the phosphor and converted into green and red light. Examples of the green light-emitting phosphor that converts blue light into green light include CaGa ₂ S ₄ : Eu crystals, and examples of the red light-emitting phosphor that converts blue light into red light include CaS: Eu crystals. An observer recognizes light in which three colors of light of blue light emission, green light emission, and red light emission are mixed as white light. Such white LEDs are available from SDPW50B0B, SDPW50H0B, SDPW3DG0B, etc. manufactured by Seiwa Electric Co., Ltd.

  A green light-emitting phosphor that converts blue light into green light and a red light-emitting phosphor that converts blue light into red light are mixed in 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 so as to obtain a desired chromaticity. Moreover, you may apply | coat to the blue LED separately the green light emission fluorescent substance which converts blue light into green light, and the red light emission fluorescent substance which converts blue light into red light. When a diffusing agent is further added to the transparent binder, the emitted light can be made more uniform. The diffusing agent is preferably a colorless substance having an average particle size of 100 nm to several tens of μm. Alumina, zirconia, yttria and the like are more preferable because they are stable in a practical temperature range of −60 to 120 ° C. A higher refractive index is more preferable because the effect of the diffusing agent is increased. Further, when a phosphor having a large particle size is used, it is preferable to use an anti-settling agent because color unevenness or color misregistration is likely to occur due to sedimentation of the phosphor. Examples of the anti-settling agent include fumed silica.

  When the white LED thus obtained is energized, the blue LED first emits blue or deep blue light. The phosphor absorbs part of it 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 that have been wavelength-converted by the phosphor are mixed to obtain approximately white light.

  In liquid crystal television applications, color reproducibility is important. The color reproducibility of a color liquid crystal display device is determined by the color of light emitted from the red (R), green (G), and blue (B) pixels, and is based on the three CIE 1931 standard colorimetric systems (CIE 1931 standard colorimetric system). On the xy chromaticity diagram, when the chromaticity points of the respective pixels derived from the stimulus values (X, Y, Z) are (Rx, Ry), (Gx, Gy), and (Bx, By), respectively. The three primary colors of the standard system defined by the US National Television System Committee (NTSC), red (0.67, 0.33), green (0.21, 0.71) and blue (0.14, 0.08) with respect to the area enclosed (unit:%, hereinafter abbreviated as NTSC ratio). The NTSC ratio required for liquid crystal display devices for various uses is, for example, about 40 to 50% for a general notebook personal computer, about 50 to 60% for a monitor for a desktop personal computer, and about 72% for a liquid crystal television.

  In order to increase the NTSC ratio, it is necessary to increase the color purity of each pixel. However, if the color purity is increased, the transmittance of the entire color filter is reduced, and the utilization efficiency of a light source such as a backlight (brightness Y) Value (represented by Y of tristimulus value)). For this reason, in order to maintain a predetermined luminance, a light source such as a backlight inevitably requires high power consumption. A white LED formed by applying a phosphor on the surface of a blue LED is particularly useful for a color filter with high color purity because it can obtain high luminance with low power.

  The white LED formed by applying a phosphor on the surface of the blue LED emits white light when the blue light emitted from the blue LED passes through the film of the applied phosphor. The coated phosphor film has a function of converting part of blue light into longer wavelength light. The light emitted from the white LED is recognized as white light by the observer by mixing the blue light emitted from the blue LED and the long wavelength light converted from the blue light.

The color characteristic of a display device including a color filter and a light source is determined by the transmission spectrum of the color filter and the light characteristic of the light source, and is 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.
An overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed on the color filter as necessary.

The color filter is bonded to the counter substrate using a sealing agent, and after injecting liquid crystal from the injection port provided in the seal portion, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by laminating. The polarizing film or the retardation film may be bonded before the color filter and the counter substrate are bonded.
Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used for a liquid crystal display mode in which colorization is performed using a color filter.

  FIG. 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 drive type liquid crystal display device for a notebook personal computer. A pair of a first transparent substrate 11 and a second transparent substrate 21 which are arranged to face each other are provided, and a liquid crystal composition (for example, a TN or STN liquid crystal composition) LC is sealed between them. . A TFT array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. A polarizing plate 15 is formed on the outer surface of the first transparent substrate 11.

On the other hand, a color filter 22 is formed on the inner surface of the second transparent substrate 21. 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 so as to cover the color filter 22, and an alignment 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 second transparent substrate 21.
A backlight unit 30 including a light source 31 is provided in close contact with the polarizing plate 15 outside the first transparent substrate 11.

  FIG. 3 is a perspective view showing the backlight unit 30. 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 so as to face one side surface 33 a of the light guide plate 33, and is surrounded by the reflector 32 over the entire length except for a portion corresponding to the side surface 33 a of the light guide plate 33. The light guide plate 33 is covered with the reflection plate 35 on the other three side surfaces and the bottom surface except the side surface 33a. Light from the light source 31 is guided to the light guide plate 33 by the reflector 32, passes through the diffusion plate 34, becomes planar light, and enters the liquid crystal layer LC from the polarizing plate 15. The reflection plate 35 efficiently directs the light incident on the light guide plate 33 toward the diffusion plate 34.

  In addition to the liquid crystal display device having the white LED light source as a backlight light source described in FIG. 2, 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.

  The display device of the present invention is suitably used not only for notebook personal computers but also for portable information terminals, mobile phones, monitors, and liquid crystal television applications.

  Hereinafter, the present invention will be described in more detail with reference to examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

Synthesis example 1
Into a flask equipped with a condenser and a stirrer, 15 parts of sulforhodamine B (manufactured by Kanto Chemical Co., Inc.), 150 parts of chloroform and 9.8 parts of N, N-dimethylformamide were added, and the temperature was maintained at 20 ° C. or lower with stirring. 12.0 parts of thionyl chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C., the reaction was continued for 5 hours at the same temperature, and then cooled to 20 ° C. While maintaining the reaction solution after cooling at 20 ° C. or lower with stirring, a mixed solution of 13.9 parts of 2-ethylhexylamine and 24.5 parts of triethylamine was added dropwise. Then, it was made to react by stirring at the same temperature for 5 hours. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixture of 375 parts of ion exchange water with stirring to precipitate crystals. The precipitated crystals are separated by filtration, washed well with ion exchange water, dried under reduced pressure at 60 ° C., and dye (A1) (the dye represented by formula (A1-1) and the formula (A1-2)). 14.7 parts).

Synthesis example 2
In a flask equipped with a condenser and a stirrer, 15 parts of a dye represented by the formula (A0-2) (manufactured by Chugai Kasei), 150 parts of chloroform and 7.1 parts of N, N-dimethylformamide are mixed and stirred. While maintaining the temperature below 20 ° C., 8.7 parts of thionyl chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C., the reaction was continued for 5 hours at the same temperature, and then cooled to 20 ° C. While maintaining the reaction solution after cooling at 20 ° C. or lower with stirring, a mixed solution of 10 parts of 2-ethylhexylamine and 17.7 parts of triethylamine was added dropwise. Then, it was made to react by stirring at the same temperature for 5 hours. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixture of 375 parts of ion exchange water with stirring to precipitate crystals. The precipitated crystals are separated by filtration, washed well with ion-exchanged water, dried under reduced pressure at 60 ° C., and dye (A2) (mixture of dyes represented by formula (A2-3) to formula (A2-9)). 12.7 parts were obtained.

（式（Ａ２−１）及び式（Ａ２−２）中、Ｒ^ｄ、Ｒ^ｅ及びＲ^ｆは、それぞれ独立に、−ＳＯ_３ ⁻、−ＳＯ_３Ｎａ又は−ＳＯ_２ＮＨＲ^ａを表す。Ｒ^ａは、２−エチルヘキシル基を表す。）

(In the formula (A2-1) and the formula ^{(A2-2), R d, R} e and ^{R f} each _{independently,} ^-SO 3 -, .R ^a representative of the _-SO 3 Na or _-SO 2 NHR ^a Represents a 2-ethylhexyl group.)

Synthesis example 3
In a flask equipped with a condenser and a stirrer, 15 parts of a mixture of the dye represented by formula (A0-3) and the dye represented by formula (A0-4) (manufactured by Chugai Kasei), 150 parts of chloroform and N , N-dimethylformamide (8.9 parts) was mixed and 10.9 parts of thionyl chloride was added dropwise while maintaining the temperature at 20 ° C. or lower with stirring. After completion of the dropwise addition, the temperature was raised to 50 ° C., the reaction was continued for 5 hours at the same temperature, and then cooled to 20 ° C. While maintaining the reaction solution after cooling at 20 ° C. or lower with stirring, a mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Then, it was made to react by stirring at the same temperature for 5 hours. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixture of 375 parts of ion exchange water with stirring to precipitate crystals. The precipitated crystals are filtered off, washed thoroughly with ion-exchanged water, dried under reduced pressure at 60 ° C., and dye (A3) (mixture of dyes represented by formula (A3-3) to formula (A3-10)). 11.3 parts were obtained.

（式（Ａ３−１）及び式（Ａ３−２）中、Ｒ^ｇ、Ｒ^ｈ及びＲ^ｉは、それぞれ独立に、水素原子、−ＳＯ_３ ⁻、−ＳＯ_３Ｈ又は−ＳＯ_２ＮＨＲ^ａを表す。Ｒ^ａは、２−エチルヘキシル基を表す。）

(In Formula (A3-1) and Formula (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
After introducing 182 g of propylene glycol monomethyl ether acetate into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and changing the atmosphere in the flask from air to nitrogen, the temperature was raised to 100 ° C., 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) ) And 136 g of propylene glycol monomethyl ether acetate, a solution obtained by adding 3.6 g of 2,2′-azobisisobutyronitrile was added dropwise, and stirring was continued at 100 ° C.
Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxy group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol 0. 9 g and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. to obtain a resin solution B1 (solid content: 35%) having a solid content acid value of 79 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 3.0 × 10 ⁴ .

About the measurement of the polystyrene conversion weight average molecular weight of said resin, it carried out on condition of the following using GPC method.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: THF
Flow rate: 1.0 mL / min
Test liquid solid concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Reference material for calibration; TSK STANDARD POLYSTYRENE
F-40, F-4, F-1, A-2500, A-500
(Made by Tosoh Corporation)

Example 1
[Preparation of photosensitive resin composition 1]
Pigment: C.I. I. Pigment Blue 15: 6 24.0 parts Acrylic pigment dispersant 9.4 parts Propylene glycol monomethyl ether acetate 192.7 parts are mixed, and the pigment is sufficiently dispersed using a bead mill.
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
(Ciba Specialty Chemicals) 13.3 parts Solvent: 4-hydroxy-4-methyl-2-pentanone 590.0 parts Surfactant: SH-8400 0.1 part (Toray Dow Corning Co., Ltd.) )
The photosensitive resin composition 1 was obtained by mixing.

[Formation of pattern]
Photosensitive resin composition 1 was applied on a 2-inch square glass substrate (Eagle 2000; manufactured by Corning) by spin coating, and then pre-baked at 100 ° C. for 3 minutes. After cooling, the distance between the substrate coated with the photosensitive resin composition and the quartz glass photomask having the pattern is set to 100 μm, and using an exposure machine (TME-150RSK; manufactured by Topcon Corporation), in an air atmosphere, Light irradiation was performed at an exposure amount of 150 mJ / cm ² (based on 365 nm). After light irradiation, the coating film was immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 80 seconds, washed with water, and 220 ° C. in an oven. And post-baked for 20 minutes. After standing to cool, the film thickness of the obtained cured pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.) and found to be 2.2 μm.

[Evaluation]
About the obtained coating film on the glass substrate, the spectrum was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the xy chromaticity in the XYZ color system of CIE was measured using the light source 1. Coordinates (Bx, By) and brightness were measured. In addition, the contrast value was measured using a contrast measuring machine (CT-1; manufactured by Aisaka Electric Co., Ltd.) with a blank value of 10,000. The results are shown in Table 22.
FIG. 4 shows an emission spectrum of the light source 1. The vertical axis represents relative emission intensity, and the horizontal axis represents wavelength (nm). The relative emission intensity refers to the relative emission intensity at each wavelength when the emission intensity at wavelength λ ₁ of the emission spectrum is 1. The measurement of the emission spectrum of the light source 1 and the calculation of the emission peak wavelength and the relative emission intensity are, for example, fluorescence provided with a 150 W xenon lamp as an excitation light source and a multichannel CCD detector C7041 (manufactured by Hamamatsu Photonics) as a spectrum measurement device. The measurement was performed using a measuring device (manufactured by JASCO Corporation). Furthermore, the emission spectrum was measured at a temperature of 25 ° C.

Examples 2-5
Except having changed dye A1 into the dye shown in Table 22, it carried out similarly to Example 1, and obtained the photosensitive resin compositions 2-5 and the coating film. The results are shown in Table 22.

Example 6
[Preparation of photosensitive resin composition 1]
Pigment: C.I. I. Pigment Blue 15: 6 38.2 parts Acrylic pigment dispersant 15.0 parts Propylene glycol monomethyl ether acetate 306.7 parts are mixed, and the pigment is sufficiently dispersed using a bead mill.
Dye: Dye A1 3.8 parts Binder resin: Resin solution B1 111.6 parts Photopolymerizable compound: Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.) 31.2 parts Photopolymerization initiator: OXE-01
(Manufactured by Ciba Specialty Chemicals) 11.9 parts Solvent: 481.5 parts 4-hydroxy-4-methyl-2-pentanone Surfactant: 0.1 part SH-8400 (manufactured by Toray Dow Corning Co., Ltd.) )
Were mixed to obtain a photosensitive resin composition 6.
Table 22 shows the results of pattern formation and evaluation of the obtained photosensitive resin composition 6 in the same manner as in Example 1.

Examples 7-10
Except having changed dye A1 into the dye shown in Table 1, it carried out similarly to Example 6, and obtained the photosensitive resin compositions 7-10 and the coating film. The results are shown in Table 22.

Examples 11-20
Table 22 shows the results obtained by measuring the coating films formed from the compositions of Examples 1 to 10 in the same manner as in Example 1 except that the light source 1 was changed to the light source 2.
FIG. 5 shows an emission spectrum of the light source 2. The emission spectrum of the light source 2 was measured in the same manner as the emission spectrum of the light source 1.

＊ 染料Ａ５：ローダミンＢベース（アルドリッチ製）

* Dye A4: Rhodamine B (manufactured by Taoka Chemical)

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

Synthesis example 4
<Synthesis of Dye A6>
After adding 65 parts of water to 7.5 parts of 2-amino-4-methylsulfonyl-6-nitrophenol (CAS No. 101861-4-5), 1.3 parts of sodium hydroxide was added and dissolved. Under ice cooling, 6.1 parts of a 35% aqueous sodium nitrite solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and then 19.4 parts of 35% hydrochloric acid was added little by little to dissolve, followed by stirring for 2 hours. A suspension containing was obtained. Subsequently, an aqueous solution in which 5.6 parts of amidosulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 26 parts of water was slowly added to quench excess sodium nitrite.
Subsequently, 5.6 parts of 3-methyl-1-phenyl-5-pyrazolone (manufactured by Wako Pure Chemical Industries, Ltd.) is suspended in 70 parts of water, and the pH is adjusted to 8.0 using sodium hydroxide. did. The suspension containing the diazonium salt was added dropwise over 15 minutes while adding a 10% sodium hydroxide solution appropriately so that the pH was in the range of 7 to 7.5. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a yellow suspension. Stir for 1 hour. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 11.7 parts (yield 87%) of the compound represented by the formula (p-1).

  10 parts of the compound of the formula (p-2) are dissolved in 100 parts of dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.) and dissolved in ammonium sulfate (III) 12 water (made by Wako Pure Chemical Industries, Ltd.) 3.1. After adding 1.1 parts of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.), the mixture was heated to reflux for 4 and a half hours. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% brine, the reddish orange solid obtained after filtration was dried at 60 ° C., and 13.6 parts of the compound represented by the formula (z-1) ( 63%).

The structure of the compound represented by the formula (z-1) was identified using a mass spectrometer JMS-700 (manufactured by JEOL Ltd.).
Identification of compound represented by formula (z-1) (mass spectrometry) ionization mode = ESI−: m / z = 882.1 [M−Na ⁺ ] ⁻
Exact Mass: 905.1

  18 parts of Rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd.), 170 parts of anhydrous chloroform (manufactured by Kanto Chemical Co., Ltd.), 1.0 part of camphorsulfonic acid (manufactured by Aldrich Co., Ltd.), 4- (N, N-dimethyl) Amino) pyridine (Tokyo Chemical Industry Co., Ltd.) 1.4 parts and triethylene glycol (Wako Pure Chemical Industries Co., Ltd.) 18 parts were added and stirred for about 30 minutes. Thereafter, 47 parts of anhydrous chloroform was added to 10.5 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.), and a solution dissolved beforehand was slowly added. Thereafter, the mixture was stirred at room temperature for about 2 hours. The liquid separation operation was performed twice with 150 parts of a 1N hydrochloric acid aqueous solution, and then the organic layer was washed twice with 150 parts of 10% saline. Next, 43 parts of anhydrous magnesium sulfate was added and stirred for about 30 minutes, and then the desiccant was filtered and the solvent was distilled off to obtain 20.6 parts (yield 90%) of the compound represented by the formula (g-1). It was.

Identification of compound represented by formula (g-1) (mass spectrometry) ionization mode = ESI +: m / z = 575.3 [M-Cl ⁻ ] ⁺
Exact Mass: 610.3

A solution (s3) was prepared by adding 4030 parts of methanol to 253 parts of the compound represented by the formula (z-1). Further, 1080 parts of methanol was added to 153 parts of the compound represented by the formula (g-1) to prepare a solution (t3). Thereafter, the solution (s3) and the solution (t3) were mixed at room temperature and stirred for about 1 hour. The resulting red solid was dried at 60 ° C. under reduced pressure, washed with 3500 parts of water, filtered, and dried under reduced pressure at 60 ° C. to obtain 263 parts (yield of the compound represented by formula (3a-23) (dye A6)). 65%) was obtained.
The structure of the compound represented by the formula (3a-23) was determined by elemental analysis. As an analytical instrument, an ICP emission analyzer (ICPS-8100; manufactured by Shimadzu Corporation) was used.
C55.6 H5.1 N11.9 Cr3.71

Synthesis example 5
<Synthesis of Dye A7>
200 parts of water was added to 10.0 parts of m-toluidine-4-sulfonic acid represented by the formula (a-2), and then adjusted to pH 7 to 8 with a 30% aqueous sodium hydroxide solution under ice cooling. The following operations were performed under ice cooling. 11.1 parts of sodium nitrite was added and stirred for 30 minutes. After adding 39.0 parts of 35% hydrochloric acid little by little to give a brown solution, the mixture was stirred for 2 hours. An aqueous solution obtained by dissolving 10.1 parts of amidosulfuric acid in 101 parts of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.

  14.0 parts of 1- (2-ethylhexyl) -3-cyano-4-methyl-6-hydroxypyrid-2-one represented by the formula (c-2), 125 parts of water and 25. N-methylpyrrolidone. After adding 0 parts, the solution was adjusted to pH 8-9 with 30% aqueous sodium hydroxide solution under ice cooling.

  The following operations were performed under ice cooling. The pyridone aqueous solution was stirred to obtain a colorless solution, and then the suspension containing the diazonium salt was added dropwise by a pump over 2 hours while adjusting the pH to 8 to 9 with a 30% aqueous sodium hydroxide solution. After completion of dropping, the mixture was further stirred for 2 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 21.4 parts (yield 87%) of the compound represented by the formula (d-3).

Compound (d-3) 0.35 g was dissolved in N, N-dimethylformamide to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with water to a volume of 100 cm ³ (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, cell length is 1 cm). This compound showed an absorbance of 2.9 (arbitrary unit) at λmax = 433 nm.

  Into a flask equipped with a condenser and a stirrer, 5.0 parts of compound (d-3), 35 parts of acetonitrile and 1.6 parts of N, N-dimethylformamide were added, while maintaining at 20 ° C. or lower with stirring. 2.4 parts of thionyl chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 40 ° C., the reaction was continued for 2 hours at the same temperature, and then cooled to 20 ° C. The cooled reaction solution was poured into 150 parts of ice water with 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. Prepare a flask equipped with a condenser and a stirrer separately, add 2.0 parts of 1-amino-2-propanol and 20 parts of N-methylpyrrolidone, and adjust in advance while maintaining at 20 ° C. or lower with stirring. The yellow crystals obtained were added over 1 hour. After adding the yellow solid, the liquid temperature was raised to room temperature, and then the reaction solution was stirred for 30 minutes. After adding 40 parts of methanol to the reaction solution and stirring, this 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 exchange water, and dried under reduced pressure at 60 ° C. to obtain 3.9 parts (yield 69%) of the compound represented by the formula (III-3).

Compound (III-3) 0.35 g was dissolved in ethyl lactate to a volume of 250 cm ³ , of which 2 cm ³ was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L). The absorption spectrum was measured using a photometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.3 (arbitrary unit) at λmax = 431 nm.

  The following reaction was performed in a nitrogen atmosphere. After adding 4.0 parts of N-methylpyrrolidone to 2.0 parts of the compound (III-3), the reaction solution was prepared by stirring for 30 minutes. While stirring the reaction solution at room temperature, 0.1 part of sebacic acid chloride was added dropwise. After completion of dropping, the mixture was further stirred for 8 hours. After pouring the reaction solution into 300 parts of water, 80 parts of ethyl acetate was added and stirred for 30 minutes. The organic phase was separated using a separatory funnel, and further washed with 500 parts of water, 500 parts of a 10% aqueous sodium carbonate solution, 500 parts of an aqueous 10% acetic acid solution, and 500 parts of ion-exchanged water. The separated organic phase was distilled off to obtain 2.0 parts of dye A7 represented by formula (I-6). Yield 85%.

The structure of compound (I-6) was determined by mass spectrometry. As the mass spectrometer, JMS-700 (manufactured by JEOL Ltd.) was used.
Mass spectrometry: ionization mode = FD +: m / z = 1200

Compound (I-6) 0.35 g was dissolved in ethyl lactate to a volume of 250 cm ³ , of which 2 cm ³ was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L). The absorption spectrum was measured using a photometer (quartz cell, optical path length: 1 cm).
This compound showed an absorbance of 2.2 (arbitrary unit) at λmax = 431 nm.

Resin synthesis example 2
<Synthesis of Resin Solution B2>
Nitrogen was allowed to flow at 0.02 L / min in a flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel to form a nitrogen atmosphere, 935 parts by mass of ethyl lactate was added, and the mixture was heated to 70 ° C. with stirring. Subsequently, 140 parts by mass of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the following formula (C1-1-1) and a formula (C1-2) The compound represented by -1) is mixed at a molar ratio of 50:50.) A solution is prepared by dissolving in 240 parts by mass and 140 parts by mass of ethyl lactate, and the solution is added using a dropping funnel. It was dripped in the flask kept at 70 degreeC over 4 hours. On the other hand, a solution prepared by dissolving 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of ethyl lactate was dropped into the flask using another dropping funnel over 4 hours. did. After completion of dropping of the polymerization initiator solution, the solution was kept at 70 ° C. 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, and the solution acid value was A resin solution B2 of 32 mg-KOH / g was obtained.

Resin synthesis example 3
<Synthesis of Resin Solution B3>
250 parts by mass of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and 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 temperature of the solution in the flask was raised to 100 ° C., then 152.6 parts by weight of benzyl methacrylate, 41.7 parts by weight of methacrylic acid, 1.5 parts by weight of azobisisobutyronitrile, and 150 parts by weight of propylene glycol monomethyl ether acetate. The mixture consisting of 1 part was dropped into the flask over 2 hours using a dropping funnel, and stirring was further continued at 100 ° C. for 2.5 hours after completion of the dropwise addition. The weight average molecular weight Mw was 2.3 × 10 ⁴ , solid. A resin solution B3 having a mass of 34% by mass and a solution acid value of 47 mg-KOH / g was obtained.

Example 21
[Preparation of photosensitive resin composition 7]
Pigment: C.I. 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 sufficiently disperse the pigment using a bead mill,
Dye: Dye A6 11.2 parts Binder resin: Resin solution B2 119.7 parts Photopolymerizable compound: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 43.4 parts Photopolymerization initiator: N-benzoyloxy -1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE01; manufactured by BASF Japan Ltd.) 13.0 parts Solvent: Propylene glycol monomethyl ether acetate 506.6 parts Surfactant: Polyether modified Photosensitive resin composition 7 was obtained by mixing 0.1 part of silicone oil (SH8400, manufactured by Toray Dow Corning Co., Ltd.). Table 23 shows the results of pattern formation and evaluation of the obtained photosensitive resin composition 6 in the same manner as in Example 1.

Example 22
[Preparation of photosensitive resin composition 8]
Pigment: C.I. 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 are mixed and the pigment is sufficiently dispersed using a bead mill.
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: N-benzoyloxy -1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE01; manufactured by BASF Japan Ltd.) 16.0 parts Solvent: Propylene glycol monomethyl ether acetate 526.8 parts Surfactant: Polyether modified Photosensitive resin composition 8 was obtained by mixing 0.1 part of silicone oil (SH8400, manufactured by Toray Dow Corning Co., Ltd.). Table 23 shows the results of pattern formation and evaluation of the obtained photosensitive resin composition 8 in the same manner as in Example 1.

Example 23
[Preparation of photosensitive resin composition 9]
Pigment: C.I. 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 are mixed, and the pigment is sufficiently dispersed using a bead mill.
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) octane-1-one-2-imine (Irgacure OXE01; manufactured by BASF Japan) 14.7 parts Solvent: Propylene glycol monomethyl ether acetate 489.5 parts Surfactant: Polyether modified Photosensitive resin composition 9 was obtained by mixing 0.1 part of silicone oil (SH8400, manufactured by Toray Dow Corning Co., Ltd.). Table 23 shows the results of pattern formation and evaluation of the obtained photosensitive resin composition 9 in the same manner as in Example 1.

Examples 24-26
Chromaticity (x, y), brightness, and contrast were measured in the same manner as in Example 1 except that the light source 1 was changed to the light source 2 for the coating films formed from the compositions of Examples 21 to 23. The results are shown in Table 23.

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

DESCRIPTION OF SYMBOLS 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 device 11 First transparent substrate 12 TFT arrays 13 and 23 Transparent electrode layers 14 and 24 Alignment layers 15 and 25 Polarizing plate 21 Second transparent substrate 22 Color filter LC Liquid crystal composition 30 Backlight unit 31 Light source 32 Reflector 33 Light guide plate 33a Side surface 34 of light guide plate 33 Diffusion Plate 35 Reflector

Claims (7)

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

(In 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 are included in the aromatic hydrocarbon group. The hydrogen atom to be generated is 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 may be substituted.
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 . Represent.
m represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R ⁵ 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 is contained in the saturated hydrocarbon group. —CH ₂ — 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 represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q. Alternatively, R ⁸ and R ⁹ may be bonded to each other to form a heterocyclic ring having 1 to 10 carbon atoms.
Q represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a monovalent aromatic heterocyclic group having 3 to 10 carbon atoms, and is included in the aromatic hydrocarbon group and the aromatic heterocyclic group. The hydrogen atom to be substituted may be substituted with —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 number of + charges and the number of −charges of the compound represented by the formula (1) are the same. )   The display device according to claim 1, wherein the white light emitting diode light source is a light source including a blue light emitting diode light source and a phosphor.   The display device according to claim 1, wherein the white light emitting diode light source is a light source including a blue light emitting diode light source, a red light emitting phosphor, and a green light emitting phosphor. Color filters, dyes, pigments, binder resin, a photopolymerizable compound, a photopolymerization initiator and a display device according to any one of claims 1 to 3 solvent is a color filter formed from the photosensitive resin composition containing . The display device according to any one of claims 1 to 4, wherein the ratio of the content of the dye and the content of the pigment is 1:99 to 99: 1 in terms of mass fraction. The pigment is C.I. I. Pigment blue 15: 6, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment red 177, C.I. I. Pigment red 242 and C.I. I. The display device according to claim 1, which is a pigment containing at least one selected from the group consisting of CI Pigment Red 254. The pigment is C.I. I. Pigment Blue 15: 6 is the display device according to any one of claims 1 to 6.

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