TWI516840B - Display device - Google Patents

Description

Display device

The present invention relates to a display device.

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

The color filter is usually produced by forming a three-color colored transparent fine pattern (referred to as a pixel) on a transparent substrate such as glass or an opaque substrate such as tantalum. As the above three colors, three primary colors of red (R), green (G), and blue (B) are often used.

For example, Patent Document 1 discloses a display device including a color filter containing a pigment as a colorant and a backlight loaded with a white LED light source as a light source.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-96471

In the prior display devices, there was a possibility that brightness and contrast were not necessarily satisfied.

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

A display device comprising a color filter containing a dye and a white LED light source, wherein the light emitted from the white LED light source is in a wavelength range of 430 nm to 485 nm and has a maximum wavelength of light λ ₁ at a wavelength In the range of 500 nm to 580 nm, the light having the maximum luminescence intensity λ ₂ and the wavelength 590 nm to 680 nm has a wavelength λ ₃ at which the luminescence intensity becomes extremely large.

2. The display device of 1, wherein the white LED light source is a light source comprising a blue LED light source and a phosphor.

3. The display device according to 1. or 2. wherein the white LED light source is a light source comprising a blue LED light source and a red light emitting phosphor and a green light emitting phosphor.

4. The display device of any of 1 to 3, wherein the color filter is a color filter comprising a dye and a pigment.

5. The display device according to any one of 1 to 4, wherein the dye is composed of a dye selected from the group consisting of a dye having a group derived from an azo dye and a group having a radical derived from a xanthene dye. a dye of at least one of the group.

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

(In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or a C 6-10 monovalent aromatic hydrocarbon group, and a hydrogen atom contained in the aromatic hydrocarbon group may pass through 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 - Substituting SO ₂ NR ⁸ R ⁹ , R ⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ or - SO ₂ NR ⁸ R ⁹ , m represents an integer of 0 to 5, and when m is an integer of 2 or more, plural R ^{5 's} may be the same or different, X represents a halogen atom, and a represents an integer of 0 or 1, R ⁶ represents a one-carbon saturated hydrocarbon group having 1 to 10 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO- or - NR ⁷ -substituted, R ⁷ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted by a halogen atom or an alkoxy group having 1 to 10 carbon atoms. R ⁸ and R ⁹ each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms or -Q, or R ⁸ and R ⁹ may be bonded to each other to form a carbon number of 1 a heterocycle of ～10, and 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 the aromatic hydrocarbon group and hydrogen contained in the aromatic heterocyclic group The atom may be substituted by -OH, -R ⁶ , -OR ⁶ , -NO ₂ , -CH=CH ₂ , -CH=CHR ⁶ or a halogen atom, and M represents a sodium atom or a potassium atom, and the compound represented by the formula (1) The number of positive charges is the same as the number of negative charges)

7. The display device according to any one of the items 1 to 6, wherein the color filter is formed of a photosensitive resin composition containing a dye, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. Color filter.

8. The display device according to 7, wherein the photosensitive resin composition contains a pigment.

9. The display device according to 8, wherein the ratio of the content of the dye to the content of the pigment is from 1:99 to 99:1 by mass fraction.

10. The display device according to 8. or 9, wherein the pigment is selected from the group consisting of CI Pigment Blue 15:6, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, A pigment of at least one of the group consisting of CI Pigment Red 177, CI Pigment Red 242, and CI Pigment Red 254.

11. The display device according to any one of items 8 to 10, wherein the pigment is C.I. Pigment Blue 15:6.

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

The color filter contains a dye.

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

Examples of the dyes include dyes classified as dyes in the dye index (published by The Society of Dyers and Colourists), and well-known dyes disclosed in the dyeing manual (color dyeing company), and specific examples thereof include CI solvent yellow 4 (Hereinafter, the description of CI solvent yellow is omitted, only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162, CI solvent red 45, 49, 125, 130, CI Solvent Orange 2, 7, 11, 15, 26, 56, CI Solvent Blue 35, 37, 59, 67, CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34 , 35, etc.

Further, examples of the CI acid dye include CI 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, CI acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426, CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173, CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51 , 62, 70, 74, 80, 83, 86, 87, 90, 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, CI Acid Violet 6B, 7, 9, 17, 19, CI Acid Green 1, 3, 5, 9 , 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109 and other dyes.

Further, as the CI direct dye, CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95 , 98, 102, 108, 109, 129, 136, 138, 141, CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176,177,179,181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246,250, CI Direct Orange 34, 39, 41 , 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107, CI Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 293, CI direct purple 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104, CI direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other dyes.

Further, as the CI mord dye, CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65, CI mordant 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, CI mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24 , 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, CI mordant blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84, CI mordant purple 1, 2, 4 , 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58, CI mord green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and other dyes.

Further, examples of the dye include an amine salt of an acid dye represented by the formulas (i) to (vii) and a sulfonamide derivative of an acid dye represented by the 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)

In the formulae (i) to (ix), D represents a group derived from a dye; m represents an integer of 1 or more and 20 or less; n represents an integer of 1 or more and 20 or less; and e and f each independently represent an integer of 1 or more and 10 or less; Ph represents a phenyl group; Py ⁺ represents a group represented by the formula (I) which is bonded to C _n H _2n+1 with 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 or more and 8 or less; q represents an integer of 0 or more and 8 or less; and L represents a hydrogen atom or a monovalent cation].

Specific examples of D include a group derived from an azo dye, an anthraquinone dye, a triphenylmethane dye, a dibenzopyran dye, and a phthalocyanine dye.

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

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

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

Py ^{+ is} preferably a group represented by the formula (I-1).

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

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

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

Examples of the azo dye include dyes represented by the formulae (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, and an alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain. An alkyl group having 2 to 12 carbon atoms substituted with an alkoxy group having 2 to 12 carbon atoms, an alkylcarbonyloxyalkyl group represented by the formula (71-1), and an alkoxy group represented by the formula (71-2) a carbonylcarbonyl group, a phenyl group substituted with an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms substituted with a phenyl group;

L ¹ -CO-OL ² - (71-1)

L ³ -O-CO-L ⁴ - (71-2)

(In the formula (71-1), L ¹ represents an alkyl group having 2 to 12 carbon atoms; L ² represents an alkylene group having 2 to 12 carbon atoms; and in the formula (71-2), L ³ represents a carbon number of 2 to 12; The alkyl group; L ⁴ represents an alkylene group having 2 to 12 carbon atoms).

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

Examples of the alkyl group having 2 to 20 carbon atoms include ethyl group, n-propyl group, isopropyl group, n-hexyl group, n-decyl group, n-decyl group, n-dodecyl group, 2-ethylhexyl group, and 1,3. - dimethylbutyl, 1-methylbutyl, 1,5-dimethylhexyl and 1,1,3,3-tetramethylbutyl and the like.

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 which are substituted by an alkoxy group having 2 to 12 carbon atoms include 3-ethoxypropyl group, propoxypropyl group, 4-propoxybutyl group, and 3-methyl group. Hexyloxyethyl and 3-(2-ethylhexyloxy)propyl and the like.

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

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

Examples of the alkyl group having 2 to 12 carbon atoms in L ¹ and L ³ include an ethyl group, a propyl group, a n-hexyl group, a n-decyl group, a n-decyl group, an n-dodecyl group, and a 2-ethylhexyl group. , 3-dimethylbutyl, 1-methylbutyl, 1,5-dimethylhexyl and 1,1,3,3-tetramethylbutyl 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 each} represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group or a halogen atom. Examples of R ⁷² to R ⁷⁵ include a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, a n-butyl group, an isopropyl group, a second butyl group, a tert-butyl group, a carboxyl group, a fluorine atom, a chlorine atom, and a bromine group. The atom, the iodine atom and the like are preferably a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, a n-butyl group, an isopropyl group, a second butyl group, a tert-butyl group, a fluorine atom or a chlorine atom.

Further, among the dyes represented by the formula (71), preferred examples of the dyes include the dyes represented by the formula (75).

As the dye having a group derived from an anthraquinone dye, for example, a dye represented by the formula (76) can be given.

As the dye having a group derived from a triphenylmethane dye, for example, a dye represented by the formula (77) can be given.

In addition, examples of the dye having a group derived from a phthalocyanine dye include a dye represented by the formula (78).

The dye has a tendency to improve solvent resistance by reacting with a cyclic ether structure, and therefore is preferably a dye containing a dye containing a carboxyl group.

The dye containing a carboxyl group is not particularly limited, and a known one can be used. For example, a dye represented by the formula (80) to the formula (89) can be used.

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

Further, as the dye having a group derived from a dibenzopyran dye, a dye represented by the formula (1) is preferred.

(In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or a C 6-10 monovalent aromatic hydrocarbon group, and a hydrogen atom contained in the aromatic hydrocarbon group may pass through 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 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 ; m represents an integer of 0 to 5; when m is an integer of 2 or more, plural R ^{5 's} may be the same or different; X represents a halogen atom; a represents an integer of 0 or 1; ⁶ represents a one-carbon saturated hydrocarbon group having 1 to 10 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO- or - NR ⁷ -substituted; R ⁷ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms; and a hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted by a halogen atom or an alkoxy group having 1 to 10 carbon atoms; R ⁸ and R ⁹ each independently represent an alkyl group having 1 to 10 carbon atoms, the carbon atoms or a cycloalkyl group of -Q 3 ~ 30; or R ⁸ and R ⁹ may be bonded to each other to form a carbon number of 1 a heterocyclic ring of 10; Q represents a one-valent aromatic hydrocarbon group having 6 to 10 carbon atoms or a monovalent aromatic heterocyclic group having 3 to 10 carbon atoms, and the aromatic hydrocarbon group and a hydrogen atom contained in the aromatic heterocyclic group It may be substituted by -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; wherein, represented by formula (1) The positive charge number of the compound is the same as the negative charge number).

Examples of R ⁶ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a neopentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, and a heptyl group. Unsubstituted saturated hydrocarbon group such as cycloheptyl, octyl, 2-ethylhexyl, cyclooctyl, decyl, decyl, tricyclodecyl; methoxypropyl, ethoxypropyl, hexyloxy An alkoxy-substituted saturated hydrocarbon group such as a propyl group, a 2-ethylhexyloxypropyl group, 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 one-valent aromatic hydrocarbon group having 6 to 10 carbon atoms include fluorine, chlorine, bromine and the like.

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

Examples of -CO ₂ R ⁶ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a pentyloxycarbonyl group, and an isopentyloxy group. Carbocarbonyl, neopentyloxycarbonyl, cyclopentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, cycloheptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl , cyclooctyloxycarbonyl, decyloxycarbonyl, decyloxycarbonyl, tricyclodecyloxycarbonyl, methoxypropoxycarbonyl, ethoxypropoxycarbonyl, hexyloxypropoxycarbonyl, 2- Ethylhexyloxypropoxycarbonyl, methoxyhexyloxycarbonyl, and the like.

As -SO ₂ NHR ⁸ , an aminesulfonyl group, an N-methylaminesulfonyl group, an N-ethylaminesulfonyl group, an N-propylaminesulfonyl group, and an N-isopropylaminesulfonate can be mentioned. , N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-pentylamine sulfonyl, N-isoamylamine sulfonyl, N-neopentylamine sulfonyl, N-cyclopentylamine sulfonyl, N-hexylamine sulfonyl, N-cyclohexylamine sulfonyl, N-heptylamine sulfonyl, N-cycloheptylamine sulfonyl, N-octyl Aminesulfonyl, N-(2-ethylhexyl)aminesulfonyl, N-(1,5-dimethylhexyl)aminesulfonyl, N-cyclooctylaminesulfonyl, N-fluorenyl Aminesulfonyl, N-decylamine sulfonyl, N-tricyclodecylamine sulfonyl, N-(methoxypropyl)amine sulfonyl, N-(ethoxypropyl)amine sulfonate Indenyl, N-(propoxypropyl)amine sulfonyl, N-(isopropoxypropyl)amine sulfonyl, N-(hexyloxypropyl)amine sulfonyl, N-(2 -ethylhexyloxypropyl)aminesulfonyl, N-(methoxyhexyl)aminesulfonyl, N-(3-phenyl-1-methylpropyl)aminesulfonyl and the like.

The heterocyclic ring having 1 to 10 carbon atoms which is formed by bonding R ⁸ and R ^{9 to} each other in -SO ₂ NR ⁸ R ⁹ may be aromatic or may not be aromatic.

Examples of the aromatic heterocyclic group include:

As the heterocyclic ring having no aromaticity, mention may be made of:

Wait. Further, the above heterocyclic ring is bonded to a sulfur atom at the position disclosed in the above figure.

Examples of the one-valent aromatic heterocyclic group having 3 to 10 carbon atoms in Q include:

Wait. Furthermore, the keying button can be any position.

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

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

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

The alkyl group having 1 to 3 carbon atoms which may be substituted by a halogen atom may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group or a trifluoromethyl group.

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

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 a hydrogen atom of the alkyl group and the alkoxy group may be substituted by a halogen atom.

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

The alkyl group having 1 to 3 carbon atoms which may be substituted by a halogen atom may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group or a trifluoromethyl group.

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

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

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 are preferably a branched alkyl group having 6 to 8 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an allyl group or a phenyl group. An aralkyl group having 8 to 10 carbon atoms, a hydroxyl group-containing alkyl group having 2 to 8 carbon atoms or an alkyl group or an aryl group having 2 to 8 carbon atoms, particularly preferably 2-ethylhexyl group .

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

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

At least one of R ¹ and R ² or at least one of R ³ and R ⁴ is preferably a C 1-4 alkyl group or a substituted C 6-10 monovalent aromatic hydrocarbon group.

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

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

R ^{5 is} preferably a carboxyl group, an ethoxycarbonyl group, a sulfo group, an N-(2-ethylhexyloxypropyl)aminesulfonyl group, or an N-(1,5-dimethylhexyl)aminesulfonyl group. N-(3-Phenyl-1-methylpropyl)amine sulfonyl, N-(isopropoxypropyl)amine sulfonyl.

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

(In the formula (1-1), R ¹¹ to R ¹⁴ each independently represent a hydrogen atom, -R ⁶ or a carbon number 6 to 10 monovalent aromatic hydrocarbon group, and the hydrogen atom contained in the aromatic hydrocarbon group may be 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 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 meanings as defined above; wherein the compound represented by the formula (1-1) The number of positive charges is the same as the number of negative charges).

The dye represented by the formula (1) is preferably a dye represented by the formula (1-2).

(In the formula (1-2), R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or a C 6-10 monovalent aromatic hydrocarbon group, and the hydrogen atom contained in the aromatic hydrocarbon group may be halogen. Atom, -R ²⁶ , -OH, -OR ²⁶ , -SO ₃ ^- , -SO ₃ N _a , -CO ₂ H, -CO ₂ R ²⁶ , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR Substituted by ²⁸ ; R ²⁵ represents -SO ₃ ^- , -SO ₃ Na, -CO ₂ H, -CO ₂ R ²⁶ , -SO ₃ H or SO ₂ NHR ²⁸ ; R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms , the hydrogen atom contained in the saturated hydrocarbon group may be substituted by -OR ²⁷ or a halogen atom; R ²⁷ represents a one-carbon saturated hydrocarbon group of 1 to 10 carbon atoms; R ²⁸ represents a hydrogen atom, -R ²⁶ , -CO ₂ R ²⁶ or a carbon number of 6 to 10 monovalent aromatic hydrocarbon group, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by -R ²⁶ or -OR ²⁶ ; m, X and a have the same meanings as above; wherein, formula (1) -2) The number of positive charges of the compound indicated is the same as the number of negative charges).

The dye represented by the formula (1) is preferably a dye represented by the formula (1-3).

(In the formula (1-3), R ³¹ and R ³² each independently represent a phenyl group, and a hydrogen atom contained in the phenyl group may pass through a halogen atom, -R ²⁶ , -OR ²⁶ , -CO ₂ R ²⁶ , - SO ₃ R ²⁶ or -SO ₂ NHR ²⁸ substituted; 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 represents the same meaning as described above; wherein the compound represented by the formula (1-3) has the same number of positive charges and the same number of negative charges).

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

(In the formula (1-4), R ⁴¹ and R ⁴² each independently represent a phenyl group, and a hydrogen atom contained in the phenyl group may be substituted with -R ²⁶ or -SO ₂ NHR ²⁸ ; and R ⁴³ represents -SO ₃ ^- Or -SO ₂ NHR ²⁸ ; R ²⁶ , R ²⁸ , X and a have the same meanings as defined above; wherein the compound represented by the formula (1-4) has the same number of positive charges as the number of negative charges).

The dye represented by the formula (1) is, for example, a dye represented by the formula (1a) to the formula (1f).

(In the formula (1a), R ^b and R ^c each independently represent a hydrogen atom, -SO ₃ ^- , -CO ₂ H or -SO ₂ NHR ^a ; R ^a represents 2-ethylhexyl; X and a represent the above The same meaning; wherein the compound represented by formula (1a) has the same number of positive charges as the number of negative charges)

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

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

(In the formula (1b-1), R ^b , X and a have the same meanings as described above; wherein the compound represented by the formula (1b-1) has the same number of positive charges as the number of negative charges).

(In the formulae (1c) and (1d), R ^d , R ^e and R ^f each independently represent -SO ₃ ^- , -SO ₃ Na or -SO ₂ NHR ^a ; R ^a represents 2-ethylhexyl; The compound represented by the formula (1c) has the same positive charge number as the negative charge number, and the compound represented by the formula (1d) has the same positive charge number as the negative charge number)

(In the formulae (1e) and (1f), R ^g , R ^h and R ⁱ each independently represent a hydrogen atom, -SO ₃ ^- , -SO ₃ H or -SO ₂ NHR ^a ; R ^a represents 2-ethyl group The hexyl group; wherein the compound represented by the formula (1e) has the same number of positive charges and the same number of negative charges, and the compound represented by the formula (1f) has the same number of positive charges as the number of negative charges).

The dye represented by the formula (1) can be obtained, for example, by chlorinating a dye or a dye intermediate having -SO ₃ H by a usual method, and the resulting dye or pigment intermediate having -SO ₂ Cl and R ⁸ -NH ₂ The amine is reacted to produce. In addition, the dye produced by the method disclosed in the method from the upper right column to the lower left column of the third page of the Japanese Patent Laid-Open No. Hei 3-78702 can be produced by reacting with an amine after chlorinating in the same manner as described above.

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

[In the formula (2), A ⁰ represents a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent; and B ⁰ represents a 6- to 14-membered monovalent aromatic hydrocarbon group which may have a substituent or may have a substitution. a monovalent aromatic heterocyclic group having 3 to 14 carbon atoms; R ⁵¹ represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, or a carbon number of 2 to 18 which may have a substituent醯 base; p1 represents 1 or 2; when p1 is 2, a plurality of A ⁰ , B ⁰ , R ⁵¹ and R ⁵² may be the same or different 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. When p1 is 2, R ⁵² represents a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent. The valent aliphatic hydrocarbon group and -CH ₂ - contained in the divalent aliphatic hydrocarbon group may be substituted by -O-, -S-, -CO- and -NR'-;R' represents a hydrogen atom or a carbon number of 1 to 6 One-valent aliphatic hydrocarbon group]

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

[In the formula (2-1), Z ¹ , Z ² and Z ³ each independently represent a divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, and are contained in Z ¹ , Z ² and Z ³ -CH ₂ - may be substituted by -CO- or -O-; R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom, a carbon number of 1 to 16 monovalent aliphatic hydrocarbon group which may have a substituent, or a carbon which may have a substituent a fluorenyl group of 2 to 18; A ¹ and A ² each independently represent a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent; and B ¹ and B ² each independently represent a carbon number which may have a substituent 6 to 14 a monovalent aromatic hydrocarbon group or a 3 to 14 carbon monovalent aromatic heterocyclic group which may have a substituent.

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

Examples of the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include an alkylene group having 1 to 16 carbon atoms, and examples thereof include a methylene group, an exoethyl group, a propylene group, a butyl group, a pentane group, and a hexane group. Base, heptadienyl, octyldiyl, decyldiyl, tetradecanediyl and hexadecanediyl.

The -CH ₂ - contained in the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms may be substituted 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-, more preferably an alkanediyl group having 5 to 7 carbon atoms which may contain -O-. Preferred examples of the group include -(CH ₂ ) ₃ -, -(CH ₂ ) ₂ -O-(CH ₂ ) ₂ -, -(CH ₂ ) ₂ -O-(CH ₂ ) ₂ -O- (CH ₂ ) ₂ - or -CH ₂ -CH(CH ₃ )-.

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

The one-carbon aliphatic hydrocarbon group having 1 to 16 carbon atoms of 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 carbon number is preferably from 6 to 10, more preferably from 1 to 4.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, and third butyl group. Butyl (1,1,3,3-tetramethylbutyl, etc.), methylhexyl (1,5-dimethylhexyl, etc.), ethylhexyl (2-ethylhexyl, etc.), cyclopentyl , cyclohexyl, methylcyclohexyl (2-methylcyclohexyl, etc.) and cyclohexylalkyl.

The hydrogen atom contained in the one-valent aliphatic hydrocarbon group having 1 to 16 carbon atoms may be substituted with an alkoxy group having 1 to 8 carbon atoms or a carboxyl group. Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which are substituted by an alkoxy group having 1 to 8 carbon atoms include propoxypropyl (3-(isopropoxy)propyl group and the like) and alkoxy group. Propyl (3-(2-ethylhexyloxy)propyl, etc.). Examples of the aliphatic hydrocarbon group having 1 to 16 carbon atoms which are substituted by a carboxyl group include 2-(carboxy)ethyl, 3-(carboxy)propyl and 4-(carboxy)butyl.

Examples of the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent of R ⁵² include an alkylene group having 1 to 35 carbon atoms, and examples thereof include a methylene group, an ethylidene group, a propylene group, and a butyl group. Dikito, pentanediyl, hexamethylene, heptadienyl, octyldiyl, decyldiyl, tetradecanediyl and hexadecandiyl.

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

Examples of the one-valent aliphatic hydrocarbon group having 1 to 6 carbon atoms of R' include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a cyclohexyl group.

The hydrogen atom contained in the fluorenyl group having 2 to 18 carbon atoms of R ⁵¹ , R ⁵³ and R ⁵⁴ may be substituted by an alkoxy group having 1 to 8 carbon atoms. The carbon number of the fluorenyl group having 2 to 18 carbon atoms which may have a substituent includes the carbon number of the substituent, and the carbon number is preferably 6 to 10. Examples of the fluorenyl group which may have a substituent include an ethenyl group, a benzamidine group, a methoxybenzylidene group (p-methoxybenzylidene group, etc.).

R ⁵³ and R ^{54 are} preferably a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms, and an anthracene group having 2 to 5 carbon atoms. Preferred examples of the group include a hydrogen atom, an ethenyl group or a propyl group.

Examples of the divalent aromatic hydrocarbon group having 6 to 14 carbon atoms of A ⁰ , A ¹ and A ² include a phenylene group and a naphthalene diyl group. Among them, a phenyl group is preferred.

Examples of the substituent of the divalent aromatic hydrocarbon group having 6 to 14 carbon atoms include a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a nitro group, a sulfo group, and an amine sulfonamide. And N-substituted amine sulfonyl groups and the like.

The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a fluorine atom, a chlorine atom or a bromine atom.

Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a third butyl group, a pentyl group and a hexyl group. It is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, and particularly preferably a methyl group.

Examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a second butoxy group, and a third butoxy group. The group, the pentyloxy group, the hexyloxy group and the like are preferably an alkoxy group having 1 to 4 carbon atoms, more preferably an alkoxy group having 1 to 2 carbon atoms, and particularly preferably a methoxy group.

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

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

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

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

[R represents a hydrogen atom or a methyl group].

The hydrogen atom contained in the one-membered aromatic hydrocarbon group having 6 to 14 carbon atoms and the one-valent aromatic heterocyclic group having 3 to 14 carbon atoms may be a hydroxyl group, a pendant oxy group, or a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms. Substituted with a cyano group, an amine group or an N-substituted amine group.

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

B ⁰ , B ¹ and B ^{2 are} preferably each independently a group represented by the formula (2-1a).

[In the 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; and R ⁶⁰ represents a one-carbon aliphatic group having 1 to 16 carbon atoms which may have a substituent; Hydrocarbyl group].

The pyridone ring represented by the formula (2-1a) may be a ketone type or an enol type.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include the same as the above, and R ^{59 is} preferably methylbutyl (1,1,3,3-tetramethylbutyl or the like) or methylhexyl ( 1,5-dimethylhexyl, etc.), ethylhexyl (2-ethylhexyl, etc.), methylcyclohexyl (2-methylcyclohexyl, etc.) and alkoxypropyl (3-(2-ethyl) a branched aliphatic hydrocarbon group such as hexyloxy)propyl or the like.

Examples of the substituent of R ⁵⁹ and R ⁶⁰ include a hydroxyl group, a halogen atom, an alkoxy group having 1 to 8 carbon atoms, and a decyloxy group having 1 to 8 carbon atoms. Examples of the alkoxy group having 1 to 8 carbon atoms are the same as those described above. Examples of the decyloxy group having 1 to 8 carbon atoms include an ethoxycarbonyl group, a propenyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group, and a benzhydryloxy group.

R ^{60 is} preferably a methyl group.

The compound represented by the formula (2) includes a compound represented by the formula (I-1) to the formula (I-18). The bonding bond on the right side of A ¹ , A ² , Z ¹ and Z ² in the table indicates a bonding bond close to Z ³ .

Preferably, B ¹ and B ² are 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 each a group of the same kind. When it is such a base, it is easy to manufacture the compound represented by Formula (2-1).

The compound represented by the formula (2-1) can be represented by the compound represented by the formula (IA) and the compound represented by the formula (I-A') and the compound represented by the formula (IB) in a solvent, in the range of 0 to The reaction was carried out at 150 ° C to produce.

[Formula (IA), Formula (I-A') and Formula (IB), Z ¹ , Z ² , Z ³ , R ⁵³ , R ⁵⁴ , A ¹ , A ² , B ¹ and B ² represent the same as above The meanings; R ⁶⁷ and R ⁶⁸ each independently represent -OR ⁶⁹ or a halogen atom; and 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, propylene dichloride, and diacetyl. Chlorine, hexamethylene chloride and octane chlorinated chlorine.

The compound represented by the formula (I-B) is preferably used in an amount of, for example, 0.5 to 3 mol based on the total amount of the compound represented by the formula (I-A) and the compound represented by the formula (I-A'). Further, in the case of containing water in a solvent, it is preferred to use a compound represented by the formula (I-B) which is excessive in comparison with the above amount.

In the case where R ³¹ and R ³² of the compound represented by the formula (IB) are -OR ^33, it is preferred to add a well-known acid catalyst. Examples of the acid catalyst include sulfuric acid and p-toluenesulfonic acid. The amount of the acid catalyst used is, for example, preferably 0.01 to 2 mol based on the total amount of the compound represented by the formula (IA) and the compound represented by the formula (I-A').

The reaction of the compound represented by the formula (IA) and the compound represented by the formula (I-A') with the compound represented by the formula (IB) is carried out in a solvent. As the solvent, for example, preferably: water; 1,4-two Ethers such as alkanes (especially cyclic ethers); chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, dichloroethylene, trichloroethylene, tetrachloroethylene, dichloropropane, chlorine Halogenated hydrocarbons such as pentane and 1,2-dibromoethane; ketones such as acetone, methyl isobutyl ketone and cyclohexanone; carbon aromatics such as benzene, toluene and xylene; N, N-di A methyl decylamine such as methyl carbamide, N,N-dibutylformamide, N,N-dimethylacetamide or N-methylpyrrolidone may be used in combination of two or more solvents. The amount of the solvent used is, for example, preferably from 1 to 20 parts by mass, more preferably from 2 to 10 parts by mass per 1 part by mass of the compound represented by the formula (IA) and the compound represented by the formula (I-A'). Share.

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

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

The order of addition of the compound represented by the formula (IA), the compound represented by the formula (I-A'), the compound represented by the formula (IB), and the solvent is not particularly limited, and is preferably represented by the inclusion formula (IA). The compound represented by the formula (IB) is added (dropwise) to the solution of the compound, the compound represented by the formula (I-A') and the solvent. In the case of using an acid catalyst, it is preferred to add (drop) to a solution containing a compound represented by the formula (IA), a compound represented by the formula (I-A'), an acid catalyst, and a solvent. (IB) The compound represented.

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

Further, the compound represented by the formula (2-1) can be produced by coupling a compound represented by the formula (IC) with a compound represented by the formula (ID) and a compound represented by the formula (I-D'). . The salt represented by the formula (IC) can be reacted with a compound represented by the formula (ID) and a compound represented by the formula (I-D') in, for example, an aqueous solvent at 20 to 60 ° C. The compound represented by the formula (2-1) was produced.

(In the formula (IC) and formula (ID), Z ¹ , Z ² , Z ³ , R ⁵³ , R ⁵⁴ , A ¹ , A ² , B ¹ and B ^{2 have} the same meanings as described above; X ^- represents 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, hypochlorous acid ion, CH ₃ -COO ^- , Ph-COO- ^, etc., preferably chloride ion, bromide ion, CH ₃ -COO ^- .

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

[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, -SO ₂ NHR ^a30 or -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 amine group; and R ^a30 independently represents a hydrogen atom, a hydrocarbon number of 1 to 10 carbon atoms; -CH ₂ - contained in the hydrocarbon group may be substituted by -O- or -CO-; M ¹ represents Cr or Co; n ¹ represents an integer of 1 to 5; D ¹ represents hydrogen (hydron), monovalent metal cation Or one of the cations of a compound having a dibenzopyran skeleton.

As represented by R ^a1 ~ R ^a18 carbon number of 1 to 8, one of monovalent aliphatic hydrocarbon group, include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl , n-pentyl, n-hexyl, n-heptyl, n-octyl, decyl, 1-methylbutyl, 1,1,3,3-tetramethylbutyl, 1,5-dimethylhexyl, 1 , 6-dimethylheptyl, 2-ethylhexyl and 1,1,5,5-tetramethylhexyl and the like.

Examples of the one-valent hydrocarbon group having 1 to 10 carbon atoms of R ^a30 include a carbon number of 1 to 10 one-valent aliphatic hydrocarbon group, a carbon number of 3 to 10 one-valent alicyclic hydrocarbon group, and a carbon number of 6 to 10. A valence aromatic hydrocarbon group, and a combination of these carbon atoms having a carbon number of 4 to 10. The monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms is the same as the above, and the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms is the same as the Q representing the compound represented by the formula (1). The basis. Examples of the one-valent alicyclic hydrocarbon group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclodecyl group.

The above hydrocarbon group substituted with -CH ₂ -O- or -CO- may, for example, be -R ^a32 -OR ^a33 , -R ^a32 -CO-OR ^a33 or -R ^a32 -O-CO-R ^a33 . 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 of R ^a32 include a methylene group, an exoethyl group, a propane-1,3-diyl group, a propionyl-1,2-diyl group, and a butyl group-1. 4-diyl, butyl-1,3-diyl, pent-1,5-diyl, hex-1,6-diyl, hept-1,7-diyl, oct-1,8-diyl, etc. .

Examples of -R ^a32 -OR ^a33 include methoxymethyl, ethoxymethyl, propoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxy. Propyl, ethoxypropyl, propoxypropyl, 2-oxo-4-methoxybutyl, octyloxypropyl, 3-ethoxypropyl, 3-(2-ethylhexyloxy) Base) propyl and the like.

Examples of -R ^a32 -CO-OR ^a33 include methoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, propoxycarbonylmethyl, and propoxy. Alkylcarbonylethyl, butoxycarbonylmethyl, butoxycarbonylethyl and the like.

Examples of -R ^a32 -O-CO-R ^a33 include ethoxymethyloxymethyl, ethoxylated ethyl, ethylcarbonyloxymethyl, ethylcarbonyloxyethyl, propylcarbonyloxy. Methyl, propylcarbonyloxyethyl, butylcarbonyloxymethyl, butylcarbonyloxyethyl and the like.

As -SO ₂ NHR ^a30 , there may be mentioned: an amine sulfonyl group; N-methylamine sulfonyl group, N-ethylamine sulfonyl group, N-propylamine sulfonyl group, N-isopropylamine sulfonate , N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-tert-butylamine sulfonyl, N-tert-butylamine sulfonyl, N-pentylamine sulfonate Base, N-(1-ethylpropyl)amine sulfonyl, N-(1,1-dimethylpropyl)amine sulfonyl, N-(1,2-dimethylpropyl)amine sulfonate Indenyl, N-(2,2-dimethylpropyl)aminesulfonyl, N-(1-methylbutyl)aminesulfonyl, N-(2-methylbutyl)aminesulfonyl , N-(3-methylbutyl)amine sulfonyl, N-cyclopentylamine sulfonyl, N-hexylamine sulfonyl, N-(1,3-dimethylbutyl)amine sulfonate , N-(3,3-dimethylbutyl)amine sulfonyl, N-heptylamine sulfonyl, N-(1-methylhexyl)amine sulfonyl, N-(1,4- Dimethylpentyl)aminesulfonyl, N-octylaminesulfonyl, N-(2-ethylhexyl)aminesulfonyl, N-(1,5-dimethyl)hexylaminesulfonyl , N-(1,1,2,2-tetramethylbutyl)amine sulfonyl, N-allylamine sulfonyl, etc., substituted with an aliphatic hydrocarbon group; N-(2-A Oxyethyl)amine sulfonyl, N-(2-ethoxyethyl Aminesulfonyl, N-(1-methoxypropyl)aminesulfonyl, N-(3-methoxypropyl)aminesulfonyl, N-(3-ethoxypropyl)amine Sulfonyl, N-(3-propoxypropyl)amine sulfonyl, N-(3-isopropoxypropyl)amine sulfonyl, N-(3-hexyloxypropyl)amine sulfonate Mercapto, N-(2-ethylhexyloxypropyl)amine sulfonyl, N-(3-tert-butoxypropyl)amine sulfonyl, N-(4-octyloxybutyl) Aminesulfonyl group substituted with -R ³¹ -OR ³² such as amidoxime; N-(methoxycarbonylmethyl)aminesulfonyl, N-(methoxycarbonylethyl)aminesulfonyl, N -(ethoxycarbonylmethyl)amine sulfonyl, N-(ethoxycarbonylethyl)amine sulfonyl, N-(propoxycarbonylmethyl)amine sulfonyl, N-(propoxy Carbonylethyl)amine sulfonyl, N-(butoxycarbonylmethyl)amine sulfonyl, N-(butoxycarbonylethyl)amine sulfonyl, etc., substituted by -R ³¹ -CO-OR ³² Aminesulfonyl; N-(ethoxymethyl)amine sulfonyl, N-(ethyloxyethyl)amine sulfonyl, N-(ethylcarbonyloxy)amine sulfonyl , N-(ethylcarbonyloxyethyl)amine sulfonyl, N-(propylcarbonyloxymethyl)amine sulfonyl, N-(propylcarbonyloxyethyl)amine sulfonyl, N -(butyl Oxymethyl) acyl amine sulfonamide, N- (butylcarbonyloxy) amine and the like by sulfo acyl -R ³¹ -O-CO-R ³² of the amine sulfonamide substituted acyl; sulfo N-cyclohexylamine Sulfhydryl, N-(2-methylcyclohexyl)amine sulfonyl, N-(3-methylcyclohexyl)amine sulfonyl, N-(4-methylcyclohexyl)amine sulfonyl, N- (4-butylcyclohexyl)amine sulfonyl sulfonyl group substituted with a cyclohexyl group having a substituent; a N-benzylamine sulfonyl group, N-(1-phenylethyl)amine sulfonyl group , N-(2-phenylethyl)amine sulfonyl, N-(3-phenylpropyl)amine sulfonyl, N-(4-phenylbutyl)amine sulfonyl, N-[2 -(2-naphthyl)ethyl]amine sulfonyl, N-[2-(4-methylphenyl)ethyl]amine sulfonyl, N-(3-phenyl-1-propyl)amine An sulfonyl group substituted with an aralkyl group such as a sulfonyl group or an N-(3-phenyl-1-methylpropyl)amine sulfonyl group.

Examples of the -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 methylsulfonyl group, an ethylsulfonyl group, a propyl sulfonyl group, an isopropyl sulfonyl group, a n-butyl sulfonyl group, a second butyl sulfonyl group, and a third butyl sulfonyl group are mentioned. , pentamsulfonyl, hexylsulfonyl, heptylsulfonyl, octylsulfonyl, 1-methylbutsulfonyl, 1,1,3,3-tetramethylbutsulfonyl, 1,5- Dimethylhexylsulfonyl, 1,6-dimethylheptylsulfonyl, 2-ethylhexylsulfonyl and 1,1,5,5-tetramethylhexulenyl.

In terms of having a tendency to have high heat resistance, at least one of R ^a1 to R ^a18 is preferably a nitro group.

R ^{a30 is} preferably 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 -OR ^a33 , -R ^a32 -CO-OR ^{a33 ,} and -R ^a32 -O-CO-R ^a33 .

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

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

D ¹ is hydrogen, a monovalent metal cation or a valent cation derived from a compound having a dibenzopyran skeleton. Among them, in view of the high brightness of the obtained color filter, a valent cation derived from a compound having a dibenzopyran skeleton is preferred. The compound represented by the formula (1) is exemplified as the compound having a dibenzopyran skeleton.

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

[In the formula (3-1), R ^a41 to R ^a58 each independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, a sulfo group, -SO ₂ R ^a33 or -SO; ₂ NHR ^a34 ; R ^a34 represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, -R ^a32 -OR ^a33 , -R ^a32 -CO- OR ^a33 , -R ^a32 -O-CO-R ^a33 or an aralkyl group having 7 to 10 carbon atoms; R ^a32 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms; and R ^a33 represents a carbon number of 1 to 8 aliphatic hydrocarbon group; R ^a59 and R ^a60 each independently represent a hydrogen atom, methyl, ethyl or amino; M ² represents Cr or Co; R ^a21 ~ R ^a24 each independently represent a hydrogen atom, a carbon number of 1 to 8 a monovalent aliphatic hydrocarbon group or a carbon number 6 to 10 monovalent aromatic hydrocarbon group, and the aliphatic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may be via a hydroxyl 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 a stretch ethyl, prop-1,3-diyl or 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; and n is 2 When the case where the integers, a plurality of R ²⁷ may be identical or different from each other].

Examples of the one-valent 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, a n-propyl group, an isopropyl group, an n-butyl group, a second butyl group, and a third butyl group.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, and a butylphenyl group. An aryl group such as a naphthyl group; 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, and 2- Butylcyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-propylcyclohexyl, 4-isopropylcyclohexyl, 4-butylcyclohexyl, and the like.

In terms of having a tendency to have high heat resistance, at least one of R ^a41 to R ^a58 is preferably a nitro group.

Further, it is preferable that at least one of R ^a41 to R ^a45 and at least one of R ^a46 to R ^a50 are a sulfo group, -SO ₂ NHR ^a34 or -SO ₂ R ^a33 , more preferably -SO ₂ R ^a33 , more Good for -SO ₂ CH ₃ .

In terms of the high color density, R ^a21 to R ^{a24 are} preferably a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, and more preferably a hydrogen atom or an ethyl group.

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

As R ^a28 , a hydrogen atom is preferred.

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

As ^{- (R a27 -O) nR a28} , for it as solubility of the organic solvent, preferred is 2- (2-hydroxyethoxy) ethyl and 2- [2- (2-hydroxyethoxy Ethyloxy]ethyl, more preferably 2-[2-(2-hydroxyethoxy)ethoxy]ethyl.

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

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

In the specific example 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) are preferred. ), 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) The compound represented by the formula (3a-26) is more preferably a compound represented by the formula (3a-1), a compound represented by the formula (3a-3), and a compound represented by the formula (3a-23).

To produce the compound represented by the formula (3), a compound represented by the formula (3d) is used to form a chromium salt with a chromium compound, or a compound represented by the formula (3d) is used to form a cobalt salt with a cobalt compound. Thereafter, as needed so that the complex salt with a salt of D ¹ having a salt exchange reaction, whereby the formula can be produced (3) a compound represented by the.

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

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

The compound represented by the formula (3-1) is produced by subjecting the above-mentioned staggered salt to a salt exchange reaction with a dibenzopyran compound represented by the formula (b).

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

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

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

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

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

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

Examples of the dehydrating agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide salt. Carboxylides such as acid salts; 1-alkyl-2-halogenated pyridinium salts; 1,1'-carbonyldiimidazole; bis(2-oxo-3- Pyrazinyl)phosphinic acid chloride; di-2-pyridine carbonate, and the like. Among them, as the dehydrating agent, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride is preferred in terms of ease of post-treatment and purification.

The organic solvent used in the above reaction may, for example, be dichloromethane, chloroform, tetrahydrofuran, toluene or acetonitrile.

The compound represented by the formula (3-1) can be produced by subjecting the above-mentioned salt to a salt exchange reaction with a dibenzopyran compound represented by the formula (b) in a solvent. Preferably, the cobalt salt is reacted with the dibenzopyran compound (b) at a molar ratio of 1:1 to 1:4.

These dyes can be appropriately selected depending on the solubility in a solvent or the light fading resistance or the spectroscopic spectrum when a pattern of a color filter is formed using the photosensitive resin composition containing the dye.

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

Further, when the dye contains a dye having a carboxyl group, the content thereof is preferably from 1 to 100% by mass, more preferably from 5 to 100% by mass, even more preferably from 10 to 100% by mass, based on the total amount of the dye.

Here, the solid content in the present specification means the total amount of components other than 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 of a photosensitive resin composition containing a dye, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

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

Here, (meth)acrylic acid means acrylic acid and/or methacrylic acid. In the total structural unit constituting the binder resin, the content of the structural unit derived from (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. . When the content of the structural unit derived from (meth)acrylic acid is within the above range, the solubility in the non-pixel portion during development is good, and the non-pixel portion after development tends to have no residue.

Examples of the other monomer which is introduced into the structural unit of the binder resin other than the structural unit derived from (meth)acrylic acid include an aromatic vinyl compound, an unsaturated carboxylic acid ester, and an unsaturated carboxylic acid aminoalkylene. Base esters, unsaturated carboxylic acid glycidyl esters, vinyl carboxylates, unsaturated ethers, vinyl cyanide compounds, unsaturated guanamines, unsaturated quinones, aliphatic conjugated dienes A macromonomer having a monopropenyl fluorenyl group or a monomethacryl fluorenyl group at the end of the polymer molecular chain, a structural unit represented by the formula (II), and a structural unit represented by the formula (III).

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

As the above binder resin, specifically, methacrylic acid/benzyl methacrylate copolymer, methacrylic acid/benzyl methacrylate/styrene copolymer, methacrylic acid/benzyl methacrylate are preferred. /isodecyl methacrylate copolymer, methacrylic acid / styrene / benzyl methacrylate / N-phenyl maleimide copolymer, methacrylic acid / composition represented by formula (II) (wherein, in the formula (II), R ⁸⁰ represents a methyl group, R ⁸¹ represents a hydrogen atom) / a benzyl methacrylate copolymer, and a constituent represented by the formula (II) (wherein, the formula (II) herein Wherein R ⁸⁰ represents a methyl group, R ⁸¹ represents a hydrogen atom) / benzyl methacrylate copolymer, and methacrylic acid / a component represented by the formula (III) (wherein, in the formula (III), R ⁸² represents Methyl group, R ⁸³ represents a hydrogen atom)/styrene copolymer/tricyclodecyl methacrylate copolymer or the like.

The binder resin having the structural unit represented by the formula (II) can be obtained by obtaining 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 anhydride, which will be described later. The carboxylic acid or acid anhydride contained in the copolymer is obtained by reacting with a compound represented by the formula (V). The binder resin having the structural unit represented by the formula (III) can be obtained by reacting a carboxylic acid or an acid anhydride contained in the above copolymer with a compound represented by the formula (VI), for example, with Japanese Patent Laid-Open No. 2005-189574. It is obtained by carrying out a reaction in the same manner as disclosed in the publication.

[In the formulae (V) and (VI), R ⁸¹ and R ⁸³ represent the same meanings as described above].

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

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

In particular, the binder resin represented by the formula (IV) is preferred in terms of hardenability and developability.

The copolymerization is usually carried out in a solvent using a polymerization initiator. As the polymerization initiator, for example, an azo compound such as 2,2'-azobisisobutyronitrile or 2,2'-azobis(methyl 2-methylpropionate) such as benzoic acid peroxide can be used. A peroxide or a peroxide of a third butyl peroxide. Further, the solvent may be one which can dissolve each monomer, and for example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate can be used. Ester glycol ether esters and the like. The reaction temperature can be determined in consideration of the decomposition temperature of the polymerization initiator or the boiling point of the solvent and the monomer. Further, the side chain of the copolymer thus obtained may be modified with a polymerizable group to produce a photosensitive binder resin. At this time, a catalyst for introducing a polymerizable group into the resin may be added. Examples of the catalyst include tris(dimethylaminomethyl)phenol. Further, an additive for preventing side reactions can be added. As an additive, hydroquinone is mentioned, for example.

The binder resin is an alkali-soluble one, and preferably contains 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 copolymer derived from a structural unit of at least one compound (C2) (hereinafter sometimes referred to as "(C2)") selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride.

Examples of the cyclic ether structure of (C0) include an epoxy (ie, ethylene oxide) structure, an oxetane structure, and a tetrahydrofuran structure.

Examples of the epoxy structure include an aliphatic epoxy structure (a structure in which an olefin is epoxidized), an aliphatic monocyclic epoxy structure, and an aliphatic polycyclic epoxy structure (that is, a polycyclic cycloolefin). Epoxidized structure), especially an aliphatic polycyclic epoxy structure.

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, and (methyl). A compound represented by the following formula disclosed in Japanese Laid-Open Patent Publication No. Hei 7-248625, and the like.

(wherein R ⁶¹ to R ⁶³ each independently represent 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-vinylbenzylepoxypropyl ether, m-vinylbenzylepoxypropyl ether, p-vinylbenzylepoxypropyl ether, and α-methyl- O-vinylbenzylepoxypropyl ether, α-methyl-m-vinylbenzylepoxypropyl ether, α-methyl-p-vinylbenzylepoxypropyl ether, 2,3-diepoxy Propyloxymethylstyrene, 2,4-diepoxypropoxymethylstyrene, 2,5-diepoxypropoxymethylstyrene, 2,6-diepoxypropoxymethyl Styrene, 2,3,4-triepoxypropoxymethylstyrene, 2,3,5-triepoxypropoxymethylstyrene, 2,3,6-triepoxypropoxy Styrene, 3,4,5-triepoxypropoxymethylstyrene and 2,4,6-triepoxypropoxymethylstyrene.

The compound having a carbon-carbon unsaturated double bond and an aliphatic monocyclic epoxy structure is a compound having a carbon-carbon unsaturated double bond and a structure obtained by epoxidizing a monocyclic cycloolefin. Examples of the monocyclic cycloolefin include cyclopentene, cyclohexene, cycloheptene, and cyclooctene. Among them, a compound having 5 to 7 carbon atoms is preferred.

Specific examples of the compound having a carbon-carbon unsaturated double bond and an aliphatic monocyclic epoxy structure include vinylidene oxide cyclohexene, that is, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide). 2000, manufactured by Daicel Chemical Industry Co., Ltd., 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclomer A400, manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexyl methacrylate Ester (for example, Cyclomer M100, manufactured by Daicel Chemical Industry Co., Ltd.), and the like.

A compound (C1) having a carbon-carbon unsaturated double bond and an aliphatic polycyclic epoxy structure (hereinafter sometimes referred to as "(C1)") has a carbon-carbon unsaturated double bond and a polycyclic cycloolefin A compound of epoxidized structure. Examples of the polycyclic cycloolefin include dicyclopentene, tricyclodecene, norbornene, isodecene, bicyclooctene, bicyclononene, bicycloundecene, tricycloundecene, and bicyclol. Decadiene, tricyclododecene, and the like.

Examples of (C1) include: 3,4-epoxynorbornyl acrylate, 3,4-epoxynorbornyl methacrylate, a compound represented by the formula (C1-1), and a formula (C1- 2) The compound to be represented is preferably at least one compound selected from the group consisting of a compound represented by the formula (C1-1) and a compound represented by the formula (C1-2).

In the formula (C1-1) and the 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 a hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. X ⁸⁷ and X ⁸⁸ each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms which may contain a hetero atom.

Specific examples of the alkyl group having 1 to 4 carbon atoms which may be substituted by a hydroxyl group include a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, and a t-butyl group. Hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1 -methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc., preferably, methyl, hydroxymethyl, 1-hydroxyethyl, 2 A hydroxyethyl group is more preferably a methyl group.

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

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

Examples of the alkylene group having 1 to 6 carbon atoms which may contain a hetero atom include a methylene group, an exoethyl group, a propyl group, an oxymethylene group (-OCH ₂ -), and an oxygen-extended ethyl group (-OCH _{2 ).} CH ₂ -), oxypropyl (-OCH ₂ CH ₂ CH ₂ -), thiomethylene (-SCH ₂ -), sulfur-extended ethyl (-SCH ₂ CH ₂ -), sulfur-extended propyl (- SCH ₂ CH ₂ CH ₂ -), iminomethylene (-NH-CH ₂ -), imidoethyl (-NH-CH ₂ CH ₂ -) and imidopropyl (-NH-CH) ₂ CH ₂ CH ₂ -) and the like, preferably, a methylene group, an ethyl group, an oxymethylene group or an oxygen-extended ethyl group, more preferably an oxygen-extended ethyl group.

As X, a single bond, a methylene group, an ethylidene group, an oxymethylene group or an oxygen-extended ethyl group is preferable, and a single bond or an oxygen-extended ethyl group is more preferable.

Examples of the compound represented by the formula (C1-1) include a compound represented by the formula (C1-1-1) to the formula (C1-1-15), and a formula (C1-1-1) is preferred. ), formula (C1-1-3), formula (C1-1-5), formula (C1-1-7), formula (C1-1-9), formula (C1-1-11) to formula (C1) The compound represented by -1-15) is more preferably a formula (C1-1-1), a formula (C1-1-7), a formula (C1-1-9) or a formula (C1-1-15). The compound represented.

Examples of the compound represented by the formula (C1-2) include a compound represented by the formula (C1-2-1) to the formula (C1-2-15), and a formula (C1-2-1) is preferred. , 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) The compound represented by the formula (C1-2-1), the formula (C1-2-7), the formula (C1-2-9) or the formula (C1-2-15) Compound.

At least one of 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. Also, these can be mixed in any ratio. In the case of mixing, the mixing ratio is in the molar ratio of the formula (C1-1): formula (C1-2), preferably 5:95 to 95:5, more preferably 10:90 to 90:10. , especially good for 20:80 ~ 80:20.

Examples of the compound having a carbon-carbon unsaturated double bond and an oxetane structure include 3-methyl-3-methylpropenyloxymethyloxetane and 3-methyl-3-. Propylene methoxymethyl oxetane, 3-ethyl-3-methylpropenyloxymethyl oxetane, 3-ethyl-3-propenyloxymethyl oxetane Alkane, 3-methyl-3-methylpropenyloxyethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methyl Acryloxyethyloxetane or 3-ethyl-3-propenyloxyethyloxetane and the like.

As a compound having a carbon-carbon unsaturated double bond and a tetrahydrofuran structure, a monomer having a tetrahydrofuran group may, for example, be tetrahydrofuran methyl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), methacrylic acid. Tetrahydrofuran methyl ester or the like.

Examples of (C2) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; maleic acid, fumaric acid, methyl maleic acid, and methyl fubutene; Unsaturated dicarboxylic acids such as diacid and methylene succinic 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[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, etc. Bicyclic unsaturated compounds; maleic anhydride, methyl maleic anhydride, methylene succinic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3, 4 , 5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2. 1] an acid anhydride of an unsaturated dicarboxylic acid such as hept-2-ene anhydride (bicycloheptylene dicarboxylic anhydride); succinic acid mono [2-(methyl) propylene methoxyethyl] ester, phthalic acid Formic acid mono [2-(methyl) propylene oxy group B An unsaturated mono[(methyl)acryloxyalkylalkyl] ester of a polyvalent carboxylic acid having 2 or more esters such as an ester; such as α-(hydroxymethyl)acrylic acid having an unsaturated group containing a hydroxyl group and a carboxyl group in the same molecule Acrylates, etc.

Among these, acrylic acid, methacrylic acid, and maleic anhydride are preferably used in terms of copolymerization reactivity and solubility in an alkaline aqueous solution. These may be used singly or in combination.

The binder resin contains a copolymer derived from the structural unit of (C1) and a structural unit derived from (C2), and is derived from (C1) in terms of a molar fraction relative to the total number of moles of structural units constituting the copolymer. When the ratio of the structural unit and the structural unit derived from (C2) is in the following range, storage stability, heat resistance, and mechanical strength tend to be good, which is preferable.

Structural unit from (C1): 2 to 98 mol%

Structural unit from (C2): 2 to 98 mol%

Moreover, when the ratio of the above structural unit is in the following range, it is more preferable in terms of developability and solvent resistance.

Structural unit from (C1): 40 to 85 mol%

Structural unit from (C2): 15 to 60 mol%

For the above-mentioned binder resin, for example, the method disclosed in the "Experimental Method for Polymer Synthesis" (Dazu Takashi, Institute of Chemicals, the first edition of the first edition, issued on March 1, 1972) can be referred to. And the references cited in this document are manufactured.

Specifically, a specific amount of (C1) and (C2), a polymerization initiator, and a solvent are put into a reaction vessel, and oxygen is replaced with nitrogen gas, thereby stirring, heating, and keeping warm in the absence of oxygen, thereby obtaining a copolymer. . Further, the obtained copolymer may be directly used as a solution after the reaction, or a solution which is concentrated or diluted, or may be used as a solid (powder) by reprecipitation or the like.

Further, the binder resin may further contain a compound derived from copolymerizable with (C1) and (C2) in addition to the structural unit derived from (C1) and the structural unit derived from (C2) (wherein (C1) and (C2) (except) (C3) (hereinafter sometimes referred to as "(C3)")).

Examples of the above (C3) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and (meth)acrylic acid. Alkyl (meth)acrylates such as tributyl ester; alkyl acrylates such as methyl acrylate and isopropyl acrylate; cyclohexyl (meth)acrylate, 2-methylcyclohexane (meth)acrylate Ester, tricyclo[5.1.02 ^2,6 ]non-8-yl ester (in the technical field, commonly known as dicyclopentyl (meth)acrylate), (meth)acrylic acid (cyclo)alkyl (meth)acrylates such as cyclopentyloxyethyl ester and isodecyl (meth)acrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclohexyl acrylate [5.2.1.0 ^2,6 ]癸-8-yl ester (in the technical field, commonly known as dicyclopentanyl acrylate), dicyclopentyloxyethyl acrylate, isodecyl acrylate and the like cyclic alkyl esters; (aryl) (meth) acrylate such as phenyl methacrylate or benzyl (meth) acrylate; aryl acrylate such as phenyl acrylate or benzyl acrylate; diethyl maleate and counter butyl Diethyl enedicarboxylate a dicarboxylic acid diester such as diethyl methylene succinate; a hydroxyalkyl ester such as 2-hydroxyethyl (meth)acrylate or 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]g 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-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxy Bicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2 - alkene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tributyl Oxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2- Alkene, 5,6-di(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(cyclohexyloxycarbonyl)bicyclo[2.2.1]heptane- a bicyclic unsaturated compound such as 2-ene; N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, 3-cis N-butylene imide benzoic acid-N-butyl succinimide ester, 4-m-butylene succinimide butyric acid-N-butyl succinimide ester, 6-m-butylene imidate hexanoic acid - N-butyl succinimide, 3-m-butyleneimine propionic acid-N-butyl succinimide, and dicarbonyl hydrazine such as N-(9-acridinyl) maleimide Imine derivatives; 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, acrylic ring Oxypropyl propyl ester, glycidyl methacrylate, α-ethyl methacrylate, propyl propyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic-3, 4- Butylene butyl carbonate, 3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl acrylate, -6,7-epoxyheptyl methacrylate , α-ethyl acrylate-6,7-epoxyheptyl ester, vinylbenzyl epoxy propyl ether, m-vinylbenzyl epoxy propyl ether and p-vinylbenzyl epoxy propyl ether. Here, in the present specification, (meth) acrylate means at least one selected from the group consisting of acrylates and methacrylates. Further, (meth)acrylic acid means at least one selected from the group consisting of acrylic acid and methacrylic acid.

Among these, preferred are: benzyl acrylate, styrene, N-phenyl maleimide, N-cyclohexylmethyleneimine, N-benzylbutylene Amine, bicyclo [2.2.1] hept-2-ene, and the like.

The above (C3) can be used singly or in combination.

In the case of containing (C3), it is preferred that the ratio of the structural units derived from (C1) to (C3) is in the following range with respect to the molar fraction of the total number of moles of the structural unit constituting the above copolymer. Inside.

Structural unit from (C1): 2 to 97 mol%

Structural unit from (C2): 2 to 97 mol%

Structural unit 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 weight average molecular weight of the binder resin in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 35,000, still more preferably 6,000 to 30,000, still more preferably 7,000 to 28,000. When the weight average molecular weight of the binder resin is within the above range, the coating property and the coating film hardness tend to be good, and the film formation is less likely to occur during development, and the non-pixel portion (that is, the unexposed portion) is developed during development. The peeling property (that is, the solubility in the developer) tends to be good, which is preferable.

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

The content of the binder resin is preferably from 10 to 35 mass%, more preferably from 15 to 30 mass%, based on the solid content in the photosensitive resin composition. When the content of the binder resin is within the above range, the solubility in the developer is sufficient, and development residue is hard to occur on the substrate having the non-pixel portion, and the pixel portion of the exposed portion is less likely to cause film reduction during development, and the non-pixel portion It is preferable because the tendency to fall off is good.

The acid value of the binder resin is preferably from 50 to 150 mgKOH/g, more preferably from 60 to 135 mgKOH/g, still more preferably from 70 to 135 mgKOH/g. When the acid value is in the above range, the solubility in the developer is improved, and the unexposed portion is easily dissolved. Further, the sensitivity is high, and the pattern of the exposed portion remains during development to increase the residual film ratio. Therefore, it is better. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can usually be determined by titration using an aqueous potassium hydroxide solution.

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

The photopolymerizable compound is a compound which is polymerized by an active radical, an acid or the like which is generated from a photopolymerization initiator by light irradiation, and examples thereof include a compound having a polymerizable carbon-carbon unsaturated bond.

The photopolymerizable compound is preferably a trifunctional or higher polyfunctional photopolymerizable compound. The polyfunctional photopolymerizable compound having three or more functional groups means a compound having three or more polymerizable carbon-carbon unsaturated bonds. The group containing a polymerizable carbon-carbon unsaturated bond is preferably a (meth) acrylonitrile group. Examples of the trifunctional or higher polyfunctional photopolymerizable compound include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol. Hexamethyl acrylate and the like. The photopolymerizable compound may be used singly or in combination of two or more kinds, and the content thereof is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, even more preferably from 13 to 60% by mass, more preferably the solid content of the photosensitive resin composition. It is 17 to 55 mass%. When the content of the photopolymerizable compound is within the above range, the curing is sufficiently performed, and the film thickness ratio before and after the development is increased, and it is difficult to cause undercut in the pattern to improve the adhesion, which is preferable.

The photosensitive resin composition which forms a color filter contains a photopolymerization initiator. The photopolymerization initiator is a compound which can generate a photopolymerizable compound by generating an active radical, an acid or the like by light irradiation. Among them, a compound which generates a radical by ultraviolet rays is preferred. Examples of the photopolymerization initiator include a living radical generator, an acid generator, and the like.

The living radical generator generates active radicals by light irradiation. Examples of the living radical generating agent include an acetophenone-based compound, a benzoin-based compound, a benzophenone-based compound, and 9-oxosulfuric acid. Compound, three A compound, an oxime compound, or the like.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-methyl-2-morpholinyl-1-(4-methylthienyl)propan-1-one, and 2-hydroxyl group. -2-methyl-1-phenylpropan-1-one, benzoin dimethyl ketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl] An oligomer of propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, etc. Preferably, 2-methyl-2-morpholinyl-1-(4-methylthienyl)propan-1-one or the like is mentioned.

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-based compound include benzophenone, methyl phthalic acid benzoate, 4-phenylbenzophenone, and 4-benzylidene-4'-methyldiphenyl. Thioether, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and the like.

As the above 9-oxygen sulfur A compound, for example, 2-isopropyl-9-oxysulfide 4-isopropyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-dichloro-9-oxosulfur 1-chloro-4-propoxy-9-oxosulfur Wait.

As the above three The compound is, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-three Wait.

The ruthenium-based compound may, for example, be an O-indenyl ruthenium compound, and specific examples thereof include 1-(4-phenylsulfanylphenyl)-butane-1,2-dione-2-肟-O-benzoate (ie N-benzylideneoxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine), 1-(4-phenyl Sulfur-phenyl)-octane-1,2-dione-2-indole-O-benzoate (ie N-benzylideneoxy-1-(4-phenylsulfanylphenyl) Octan-1-keto-2-imine), 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone-1-O-B Acid ester (ie N-acetoxy-1-[9-ethyl-6-(2-methylbenzylidenyl)-9H-indazol-3-yl]ethane-1-imine), 1-[9-ethyl-6-(2-methyl-4-(3,3-dimethyl-2,4-di) Cyclopentylmethoxy)benzylidene)-9H-indazol-3-yl]ethanone-1-O-acetate (ie N-acetoxy-1-[9-ethyl-6 -{2-Methyl-4-(3,3-dimethyl-2,4-dioxocyclopentylmethoxy)benzylidenyl}-9H-indazol-3-yl]ethane-1 -imine) and the like.

As the living radical generating agent other than the above-exemplified examples, for example, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or 2,2'-bis(o-chlorophenyl)-4 can be used. 4',5,5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylhydrazine, benzoin, 9,10-phenanthrenequinone, Camphorquinone, methyl phenylglyoxylate, titanocene compound, and the like.

Examples of the acid generator include 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethenyloxyphenyldimethylate. Base p-toluenesulfonate, 4-acetoxyphenyl ‧ methyl ‧ benzyl hexafluoroantimonate, triphenyl sulfonium p-toluene sulfonate, triphenyl sulfonium hexafluoroantimonate, two An anthracene salt such as phenylhydrazine p-toluenesulfonate or diphenylphosphonium hexafluoroantimonate; or a nitrobenzyl toluenesulfonate or a benzoin tosylate.

Further, among the above compounds as the living radical generating agent, a compound which simultaneously generates an acid with an active radical, for example, three A photopolymerization initiator can also be used as the acid generator.

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

The photosensitive resin composition forming the color filter may further contain a photopolymerization initiation aid. The photopolymerization initiation aid is usually used in combination with a photopolymerization initiator, and is a compound or a sensitizer for promoting polymerization of a photopolymerizable compound which starts polymerization by a photopolymerization initiator.

Examples of the photopolymerization initiation aid include an amine compound, an alkoxy ruthenium compound, and 9-oxosulfuric acid. A compound or the like.

Examples of the above amine-based compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4- Isoamyl dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-methyl Aniline, 4,4'-bis(dimethylamino)benzophenone (commonly known as mickleone), 4,4'-bis(diethylamino)benzophenone, 4,4'- Bis(ethylmethylamino)benzophenone or the like, among which 4,4'-bis(diethylamino)benzophenone is preferred.

Examples of the alkoxy oxime-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2- Ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

As the above 9-oxygen sulfur A compound, for example, 2-isopropyl-9-oxysulfide 4-isopropyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-dichloro-9-oxosulfur 1-chloro-4-propoxy-9-oxosulfur Wait.

The photopolymerization start-up aid may be used singly or in combination of two or more. In addition, as a photopolymerization initiation aid, a commercially available photopolymerization initiation aid may be used, and for example, the product name "EAB-F" (manufactured by Hodogaya Chemical Industry Co., Ltd.) may be mentioned. .

As a combination of a photopolymerization initiator and a photopolymerization initiation aid, for example, diethoxyacetophenone/4,4'-bis(diethylamino)benzophenone, 2-methyl group can be mentioned. -2-morpholinyl-1-(4-methylthienyl)propan-1-one/4,4'-bis(diethylamino)benzophenone, 2-hydroxy-2-methyl- 1-phenylpropan-1-one/4,4'-bis(diethylamino)benzophenone, benzoin dimethyl ketal/4,4'-bis(diethylamino) Benzophenone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one/4,4'-bis(diethylamino)di Benzophenone, 1-hydroxycyclohexyl phenyl ketone / 4,4'-bis(diethylamino)benzophenone, 2-hydroxy-2-methyl-1-[4-(1-methyl Oligomer of vinyl)phenyl]propan-1-one/4,4'-bis(diethylamino)benzophenone, 2-benzyl-2-dimethylamino-1- 4-morpholinylphenyl)butan-1-one/4,4'-bis(diethylamino)benzophenone, etc., preferably 2-methyl-2-morpholinyl-1-( 4-methylthienyl)propan-1-one / 4,4'-bis(diethylamino)benzophenone.

In the case of using such photopolymerization initiation assistants, the amount thereof is preferably 0.01 to 10 moles, more preferably 0.01 to 5 moles per 1 mole of the photopolymerization initiator.

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

Examples of the above ethers include tetrahydrofuran, tetrahydropyran, and 1,4-two. Alkane, 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 acetic acid Ester, anisole, phenethyl ether, methyl anisole, and the like.

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

Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, and 4-hydroxy-4-methyl- 2-pentanone, cyclopentanone, cyclohexanone, and the like.

Examples of the above 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, and butyric acid. Ethyl ester, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, methoxyacetic acid Ethyl ester, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3-methoxypropionic acid Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, Propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2 -ethyl ethoxypropionate, methyl 2-oxy-2-methylpropanoate, ethyl 2-oxy-2-methylpropionate, 2-methoxy-2-methylpropionic acid Ester, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl acetate Ethyl ester, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, γ-butyrolactone, etc. .

Examples of the above guanamines 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 together.

Further, the above solvents may be used singly or in combination of two or more.

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

The photosensitive resin composition which forms a color filter can further contain a surfactant. The surfactant is at least one selected from the group consisting of a polyfluorene-based surfactant, a fluorine-based surfactant, and a polyfluorene-based surfactant having a fluorine atom.

Examples of the polyfluorene-based surfactant include a surfactant having a decane bond. Specific examples include: Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Polyether Modified Emu Oil SH8400 (trade name: Toray Silicone, Toray Dow Corning) ))), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Mitto Hi-Tech) Material Japan Co., Ltd. (manufactured by Momentive Performance Materials Japan LLC) and the like.

The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain. Specific examples include Fluorad (trade name) FC430, Fluorad FC431 (manufactured by Sumitomo 3M), Megafac (trade name) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac R30 (DIC) )), Eftop (trade name) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (Mitsubishi Materials Electronic Chemicals), Surflon (trade name) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Co., Ltd.), BM-1000, BM-1100 (all trade names: manufactured by BM Chemie Co., Ltd.).

Examples of the polyfluorene-based surfactant having a fluorine atom include a surfactant having a decane bond and a fluorocarbon chain. Specific examples include Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, Megafac F443 (manufactured by DIC), and the like.

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

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

As a method of forming the pattern of the color filter, for example, a method in which a photosensitive resin composition containing a dye is applied to a substrate or another resin layer (for example, another photosensitive resin composition layer formed on the substrate first) In the above, a method of developing a coloring layer by removing a volatile component such as a solvent, exposing the colored layer via a photomask, and developing the inkjet device without using a photolithography method.

The photosensitive resin composition preferably contains a pigment.

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

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

The pigment used for the blue photosensitive resin composition is preferably a pigment containing at least one pigment selected from the group consisting of CI Pigment Violet 23, CI Pigment Blue 15:3, and 15:6, and more preferably CI Pigment Blue. 15:6 pigment. The pigment used for the green photosensitive resin composition preferably contains at least one selected from the group consisting of C.I. Pigment Green 36, 58, C.I. Pigment Yellow 138, 150. The pigment used for the red photosensitive resin composition preferably contains a pigment selected from at least one of C.I. Pigment Yellow 138, 139, 150, C.I. Pigment Red 177, 242, and 254. These pigments may be used singly or in combination of two or more.

When the photosensitive resin composition contains a pigment, the content of the pigment is preferably from 2 to 98% by mass, more preferably from 5 to 95% by mass, based on the total amount of the dye and the pigment in the photosensitive resin composition. Preferably, it is 10 to 95% by mass.

The photosensitive resin composition used in the production of the display device of the present invention preferably contains a dye and a pigment in a mass ratio of dye: pigment = 1:99 to 99:1, more preferably 1:99 to 60. : 40, more preferably 5:95 ~ 40:60. By setting the above ratio, it is easy to optimize the transmission spectrum, and a coloring pattern having high contrast and high definition can be obtained, and further, the heat resistance and chemical resistance of the obtained colored pattern are improved.

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

The pigment may be subjected to a dispersion treatment in the presence of a dispersing agent as needed, whereby it can be used as a pigment dispersion in a state in which the pigment is uniformly dispersed in a solution.

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

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, and fatty acid modified polyesters. Other than the class of tertiary amine modified polyurethanes, polyethyleneimine, and the like, the product name is KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (shared chemical) Manufacturing), Eftop (manufactured by Tohkem Products), Megafac (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), Fluorad (manufactured by Sumitomo 3M), AsahiGuard, Surflon (above manufactured by Asahi Glass), Solsperse (Zeneca) (manufacturing), EFKA (manufactured by EFKA CHEMICALS) and PB821 (manufactured by Ajinomoto).

In the case of using a dispersing agent, the amount thereof to be used is preferably from 0.1 to 100% by mass, more preferably from 5 to 50% by mass, based on the pigment. When the amount of the dispersant used is within the above range, there is a tendency to obtain a uniform dispersion, which is preferable.

<Color Filter>

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

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

As the transparent substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, or soda lime glass coated with cerium oxide or polycarbonate, polymethyl methacrylate or polyterephthalic acid can be used. Resin board such as ethylene glycol.

As the opaque substrate, aluminum, silver, a silver/copper/palladium alloy thin film or the like can be formed on the transparent substrate.

When the pixels of the respective colors are formed by the photolithography method, the photosensitive resin compositions of the red, green, and blue colors are used to develop the photosensitive resin composition on the substrate in an arbitrary order to form a pattern. Color filters can be made. In other words, the color filter included in the display device of the present invention is formed by forming each of the above-mentioned photosensitive resin compositions into a specific 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 has a substrate 3, a lattice-shaped black matrix BM having a plurality of openings formed on the substrate 3, and a transparent red photosensitive resin composition film sequentially formed to cover the openings of the black matrix BM. R, a transparent green photosensitive resin composition film G, and a transparent blue photosensitive resin composition film B. In the transparent red photosensitive resin composition film R, the red photosensitive resin composition is formed into a desired shape, and the transparent green photosensitive resin composition film G is formed into a specific film of the green photosensitive resin composition. In the shape of the transparent blue photosensitive resin composition film B, the blue photosensitive resin composition is formed into a specific shape.

As a method of developing each photosensitive resin composition on a substrate, that is, a film into a specific shape, a well-known or conventional method can be used. For example, a film can be formed in the following manner.

The photosensitive resin composition is spin-coated on a substrate (usually glass), and the solvent is removed by heat drying (prebaking) to obtain a smooth coating film. At this time, the thickness of the coating film is about 1 to 5 μm. On the coating film thus obtained, the exposed portion is cured by irradiating ultraviolet rays through a negative mask for forming a target image, and then the unexposed portion is dissolved in the developing solution to be developed. The above operation is repeated in the same manner for each photosensitive resin composition, whereby a photosensitive resin composition film of each color as a target pixel (pattern) can be formed. Further, as the coating method, a spin coating method or a slit coating method or a slit and spin coating method may be used.

Further, in the case of irradiating ultraviolet rays, in order to uniformly irradiate the parallel light to the entire exposed portion and to accurately position the mask and the substrate, it is preferable to use a device such as a photomask alignment machine. Further, after development, if necessary, it may be cured at 150 to 230 ° C for about 10 to 60 minutes (post-baking).

As the black matrix BM, a multilayer film of chromium or chromium/chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed can be used, but it is not limited thereto.

Further, a thin film transistor (TFT, Thin Film Transistor) may be formed in advance on the substrate, and thereafter a pixel may be formed. By forming a pixel on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased, and the brightness 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 sometimes referred to as "white LED").

The white LED is a fluorescent filter formed on the surface of the blue LED or includes a phosphor in the resin package of the blue LED, and has a maximum luminous intensity in a wavelength range of 430 nm to 485 nm. the wavelength λ _1, having a light emission intensity in the range of 500 nm ~ 580 nm of the wavelength was the maximum wavelength λ _2, at a wavelength of 590 nm ~ 680 nm of the range having a wavelength of maximum emission intensity is λ _3.

The blue LED is an LED that emits blue light (having a wavelength of, for example, 470 nm) such as an InGaN-based or GaN-based device. In addition, a fluorescent filter comprising a green luminescent phosphor or a resin package comprising a green luminescent phosphor is absorbed from a portion of the blue light emitted by the blue LED and emitted between 500 nm and 580 nm with great illumination. Green light, a fluorescent filter containing a red luminescent phosphor or a resin package containing a red luminescent phosphor similarly emits red light having a great luminescence between 590 nm and 680 nm. In the white LED of this mode, one of the blue light emitted by the blue LED partially penetrates the phosphor layer, and the rest is absorbed by the phosphor to be converted into green and red light. As a green light-emitting phosphor that converts blue light into green light, there is a crystal of CaGa ₂ S ₄ :Eu, etc., and a red light-emitting phosphor that converts blue light into red light, and a crystal of CaS:Eu or the like. The observer regards the light mixed with the blue light and the green light and the red light with the three colors as white light. Such a white LED can be obtained by SDPW50B0B, SDPW50H0B, SDPW3DG0B, etc. manufactured by Xinghe Electric Co., Ltd.

A green light-emitting phosphor that converts blue light into green light and a red light-emitting fluorescent system that converts blue light into red light are mixed in a transparent adhesive such as epoxy resin or polyoxyn resin, and applied to a blue LED. on. The mixing ratio can be appropriately changed in such a manner that the desired chromaticity can be obtained. Further, 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 can be applied to the blue LED, respectively. If a diffusing agent is further added to the transparent adhesive, the emitted light can be made more uniform. As the diffusing agent, a substance having an average particle diameter of from 100 nm to several 10 μm and being colorless is preferable. Alumina, zirconia, cerium oxide, and the like are more stable in a practical temperature range of -60 to 120 ° C, and thus are more preferable. Further, if the refractive index is high, the effect of the diffusing agent becomes high, so that it is more preferable. Further, in the case of using a phosphor having a large particle diameter, color unevenness or color deviation tends to occur due to precipitation of the phosphor, and therefore it is preferred to use an anti-precipitation agent. As the anti-precipitation agent, smoked mites can be mentioned.

The white LED thus obtained is energized, firstly blue or dark blue light is emitted by the blue LED. The phosphor absorbs a part of it and emits green or red light. As the light emitted from the white LED, the original blue light of the blue LED and the green light and the red light which are wavelength-converted by the phosphor are mixed to obtain substantially white light.

In the use of liquid crystal televisions, color reproducibility is valued. The color reproducibility of the color liquid crystal display device is determined by the color of the light emitted from the pixels of red (R), green (G), and blue (B), and will be the third from the CIE 1931 standard colorimetric system. When the chromaticity points of the pixels derived from the stimulus values (X, Y, Z) are respectively set to (Rx, Ry), (Gx, Gy), (Bx, By), the xy chromaticity diagrams are on the xy chromaticity diagrams. The area of the triangle surrounded by the point is evaluated as compared to the three primary colors, red (0.67, 0.33), green (0.21, 0.71) according to the standard method specified by the National Television System Committee (NTSC). The ratio of the area enclosed by blue (0.14, 0.08) (unit is %, hereinafter referred to as NTSC ratio). The NTSC ratio required for various types of liquid crystal display devices is, for example, about 40 to 50% for a general notebook computer, 50 to 60% for a desktop 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 color filter is lowered, and the utilization efficiency of the light source such as a backlight (indicated by the brightness Y value (Y of the tristimulus value)) Go low. Therefore, the power consumption of a light source such as a backlight necessary for maintaining a specific brightness is inevitably high. A white LED formed by coating a phosphor on the surface of a blue LED is low in power consumption for expressing a specific brightness, and thus is useful for a color filter having high color purity.

A white LED formed by coating a phosphor on the surface of a blue LED emits white light by passing a blue light emitted from the blue LED through a film coated with a phosphor. The film coated with the phosphor has a function of converting a part of the blue light into light having a longer wavelength. The white LED emits light in which blue light is mixed with light converted into long wavelengths, and the observer regards it as white light.

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

On the color filter, a protective film or a columnar spacer, a transparent conductive film, a liquid crystal alignment film, or the like can be formed as needed.

The color filter is bonded to the counter substrate by using a sealant, and the liquid crystal is injected from the injection port provided in the sealing portion, and then the injection port is sealed, and if necessary, a polarizing film or a retardation film is bonded to the outside of the substrate, thereby manufacturing the color filter. LCD panel. The bonding of the polarizing film or the retardation film can also be performed before the color filter and the counter substrate are bonded.

The liquid crystal display panel can be used for TN (Twisted Nematic), Super Twisted Nematic (STN), IPS (In-Plane Switching), Vertical Alignment (VA), Optical Alignment, Optical A liquid crystal display mode in which color filters are used for colorization, such as OCB (Optically Compensated Bend).

Fig. 2 is a schematic view showing a display device 10 of the present invention. The display device 10 is a typical example of a TFT-driven liquid crystal display device for a notebook computer. One of the first transparent substrate 11 and the second transparent substrate 21 is disposed to be opposed to each other, 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 containing, for example, ITO (Indium Tin Oxide) is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. Further, 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. The pixels (not shown) constituting the color filters are separated by a black matrix (not shown). The color filter 22 is covered to form a transparent electrode layer 23 containing, for example, ITO, and the transparent electrode layer 23 is covered to provide an alignment layer 24. Further, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21.

The backlight unit 30 including the light source 31 is provided in close contact with the polarizing plate 15 on the outer side of 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 on one side surface 33a of the light guide plate 33, and is surrounded by the reflector 32 except for a portion corresponding to the side surface 33a of the light guide plate 33 over its entire length. Further, the other three side faces and the bottom face of the light guide plate 33 excluding the side faces 33a are covered by the reflecting plate 35. The light emitted from the light source 31 is guided to the light guide plate 33 via the reflector 32, and becomes planar light through the diffusion plate 34, and is incident on the liquid crystal layer LC from the polarizing plate 15. The reflecting plate 35 guides the light incident on the light guiding plate 33 to the diffusing plate 34 efficiently.

In addition to the liquid crystal display device having the white LED light source as the backlight source as illustrated in FIG. 2, the display device of the present invention may also be a liquid crystal display device having a white LED light source as a front light source.

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

The display device of the present invention is not limited to a notebook computer, and can be suitably used for a personal digital assistant or a mobile phone, a monitor, or a liquid crystal television.

real Example

The invention will be described in detail below by way of examples. In the examples, "%" and "parts" mean % by weight and parts by weight unless otherwise specified.

Synthesis Example 1

In a flask equipped with a cooling tube and a stirring device, 15 parts of Sulforhodamine B (manufactured by Kanto Chemical Co., Ltd.), 150 parts of chloroform and 9.8 parts of N,N-dimethylformamide were added while stirring. While maintaining the temperature below 20 ° C, 12.0 parts of sulfite chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C, and the mixture was allowed to react at the same temperature for 5 hours, and then cooled to 20 ° C. While maintaining the cooled reaction solution at 20 ° C or lower under stirring, a mixed liquid of 13.9 parts of 2-ethylhexylamine and 24.5 parts of triethylamine was added dropwise. Thereafter, the mixture was stirred at the same temperature for 5 hours to cause a reaction. Then, after the obtained reaction mixture was distilled off by a rotary evaporator to remove the solvent, a small amount of methanol was added and vigorously stirred. This mixture was added to a mixed solution of 375 parts of ion-exchanged water while stirring to precipitate crystals. The precipitated crystals are separated by filtration, thoroughly washed with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain a dye (A1) (a dye represented by the formula (A1-1) and a dye represented by the formula (A1-2). Mixture) 14.7 parts.

Synthesis Example 2

In a flask equipped with a cooling tube and a stirring device, 15 parts of a dye (manufactured by Sino-foreign Chemical Co., Ltd.), 150 parts of chloroform and 7.1 parts of N,N-dimethylformamide were mixed while stirring. While maintaining the temperature below 20 ° C, 8.7 parts of sulfite chlorine was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C, and the mixture was allowed to react at the same temperature for 5 hours, and then cooled to 20 ° C. While maintaining the cooled reaction solution at 20 ° C or lower under stirring, a mixed liquid of 10 parts of 2-ethylhexylamine and 17.7 parts of triethylamine was added dropwise. Thereafter, the mixture was stirred at the same temperature for 5 hours to cause a reaction. Then, after the obtained reaction mixture was distilled off by a rotary evaporator to remove the solvent, a small amount of methanol was added and vigorously stirred. This mixture was added to a mixed solution of 375 parts of ion-exchanged water while stirring to precipitate crystals. The precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 12.7 parts of a dye (A2) (a mixture of the dyes represented by the formula (A2-3) to the formula (A2-9)). .

(In the formulae (A2-1) and (A2-2), R ^d , R ^e and R ^f each independently represent -SO ₃ ^- , -SO ₃ Na or -SO ₂ NHR ^a ; R ^a represents 2-B Base hexyl).

Synthesis Example 3

In a flask equipped with a cooling tube and a stirring device, a mixture of the dye represented by the formula (A0-3) and the dye represented by the formula (A0-4) (manufactured by a Chinese company) 15 parts, 150 parts of chloroform and N, N 8.9 parts of dimethylformamide, and 10.9 parts of sulfite chlorine was added dropwise while maintaining the temperature below 20 ° C under stirring. After completion of the dropwise addition, the temperature was raised to 50 ° C, and the mixture was allowed to react at the same temperature for 5 hours, and then cooled to 20 ° C. While maintaining the cooled reaction solution at 20 ° C or lower under stirring, a mixed liquid of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Thereafter, the mixture was stirred at the same temperature for 5 hours to cause a reaction. Then, after the obtained reaction mixture was distilled off by a rotary evaporator to remove the solvent, a small amount of methanol was added and vigorously stirred. This mixture was added to a mixed solution of 375 parts of ion-exchanged water while stirring to precipitate crystals. The precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 11.3 parts of a dye (A3) (a mixture of the dyes represented by the formula (A3-3) to the formula (A3-10)). .

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

Resin Synthesis Example 1

In a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube, 182 g of propylene glycol monomethyl ether acetate was introduced, and the atmosphere in the flask was converted from air to nitrogen, and then the temperature was raised to 100 ° C, and then dripped. Addition to monomethyl acrylate containing 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, and tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) A solution of 2,2'-azobisisobutyronitrile (3.6 g) was added to a mixture of 22.0 g (0.10 mol) and propylene glycol monomethyl ether acetate 136 g, and stirring was continued at 100 °C. Then, the environment inside the flask was converted from air to air, and propylene glycol methacrylate was 35.5 g [0.25 mol, (50 mol% relative to the carboxyl group of methacrylic acid used in the reaction)], three ( 0.9 g of dimethylaminomethyl)phenol and 0.145 g of hydroquinone were placed in a flask, and the reaction was continued at 110 ° C to obtain a resin solution B1 having a solid acid value of 79 mg KOH/g (solid content: 35%). . The weight average molecular weight in terms of polystyrene measured by GPC was 3.0 × 10 ⁴ .

The measurement of the weight average molecular weight in terms of polystyrene of the above resin was carried out under the following conditions using a GPC method.

Device: HLC-8120GPC (manufactured by Tosoh)

Column: TSK-GELG2000HXL

Column temperature: 40 ° C

Solvent: THF

Flow rate: 1.0 mL/min

Solid concentration of the test liquid: 0.001 to 0.01% by mass

Injection volume: 50 μL

Detector: RI

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh)

Example 1 [Preparation of Photosensitive Resin Composition 1]

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

Acrylic pigment dispersant 9.4 parts

Propylene glycol monomethyl ether acetate 192.7 parts

Mixing, using a bead mill to fully disperse the pigment, and then,

Dye: dye A1 36.0 parts

Adhesive resin: resin solution B1 99.6 parts

Photopolymerizable compound: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 34.9 parts

Photopolymerization initiator: OXE-01 (manufactured by Ciba Specialty Chemicals) 13.3 parts

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

Surfactant: SH-8400 0.1 part (manufactured by Toray Dow Corning Co., Ltd.)

The photosensitive resin composition 1 was obtained by mixing.

[Formation of patterns]

The photosensitive resin composition 1 was applied by a spin coating method on a glass substrate (Eagle 2000, manufactured by Corning Co., Ltd.) of 2 inches, and then prebaked at 100 ° C for 3 minutes. After cooling, the distance between the substrate coated with the photosensitive resin composition and the mask made of quartz glass having a pattern was set to 100 μm, and exposed to an atmosphere using an exposure machine (TME-150RSK, manufactured by Topcon). The light was irradiated with an exposure amount of 150 mJ/cm ² (based on 365 nm). After the light irradiation, the coating film was immersed and developed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C for 80 seconds, washed with water, and then subjected to an oven at 220 ° C for 20 seconds. Bake in minutes. After leaving to stand for cooling, the film thickness of the obtained hardened pattern was measured using a film thickness measuring device (DEKTAK3, manufactured by Nippon Vacuum Technology Co., Ltd.), and it was 2.2 μm.

[Evaluation]

The coating film on the obtained glass substrate was measured for spectroscopic using a colorimeter (OSP-SP-200, manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinate (Bx, By) in the XYZ color system of CIE was measured using the light source 1. With lightness. In addition, a contrast value (CT-1, manufactured by Kesaka Electric Co., Ltd.) was used, and the blank value was set to 10,000, and the contrast value was measured. The results are shown in Table 22.

Fig. 4 shows the luminescence spectrum of the light source 1. The vertical axis represents the relative luminous intensity, and the horizontal axis represents the wavelength (nm). The relative luminous intensity refers to the relative luminous intensity of each wavelength when the luminous intensity of the wavelength λ ₁ of the emission spectrum is set to 1. The measurement of the luminescence spectrum of the light source 1 and the calculation of the luminescence peak wavelength and the relative luminescence intensity are performed, for example, by using a fluorescence measuring device (manufactured by JASCO Corporation), and the fluorescence measuring device is provided with a 150 W xenon lamp as an excitation light source. A multi-channel CCD (Charge Coupled Device) detector C7041 (manufactured by Hamamatsu Photonics Co., Ltd.) was provided as a spectrometer. Further, the measurement of the luminescence spectrum was carried out at a temperature of 25 °C.

Examples 2 to 5

The photosensitive resin compositions 2 to 5 and the coating film were obtained in the same manner as in Example 1 except that the dye A1 was changed to the dye shown in Table 22. The results are shown in Table 22.

Example 6 [Preparation of Photosensitive Resin Composition 1]

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

Acrylic pigment dispersant 15.0 parts

Propylene glycol monomethyl ether acetate 306.7 parts

Mixing, using a bead mill to fully disperse the pigment, and then,

Dye: dye A1 3.8 parts

Adhesive resin: resin solution B1 111.6 parts

Photopolymerizable compound: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 31.2 parts

Photopolymerization initiator: OXE-01 (manufactured by Ciba Specialty Chemicals) 11.9 parts

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

Surfactant: SH-8400 0.1 part (manufactured by Toray Dow Corning Co., Ltd.)

The photosensitive resin composition 6 was obtained by mixing.

The obtained photosensitive resin composition 6 was patterned and evaluated in the same manner as in Example 1. The results are shown in Table 22.

Examples 7 to 10

The photosensitive resin compositions 7 to 10 and the coating film were obtained in the same manner as in Example 6 except that the dye A1 was changed to the dye shown in Table 22. The results are shown in Table 22.

Examples 11-20

The coating film formed from the compositions of Examples 1 to 10 was measured in the same manner as in Example 1 except that the light source 1 was changed to the light source 2. The results are shown in Table 22.

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

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. 101861-04-5), 1.3 parts of sodium hydroxide was added and dissolved. Under ice cooling, 6.1 parts of an aqueous solution of 35% sodium nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) was added, followed by a small amount of 19.4 parts of 35% hydrochloric acid, which was dissolved and stirred for 2 hours to obtain a diazonium containing diazonium. A suspension of salt. Then, an aqueous solution obtained by dissolving 5.6 parts of an aminosulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.) in 26 parts of water was slowly added, and the excess sodium nitrite was quenched.

Then, 5.6 parts of 3-methyl-1-phenyl-5-pyrazolone (manufactured by Wako Pure Chemical Industries, Ltd.) was suspended in 70 parts of water, and the pH was adjusted to 8.0 using sodium hydroxide. In the above, a 10% sodium hydroxide solution was appropriately added so as to control the pH in the range of 7 to 7.5, and the suspension containing the diazonium salt was added dropwise over 15 minutes. After completion of the dropwise addition, the mixture was further stirred for 30 minutes, whereby a yellow suspension was obtained. Stir for 1 hour. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 11.7 parts (yield: 87%) of the compound of formula (p-1).

Add 10 parts of the compound of the formula (p-2) to 100 parts of dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.) to dissolve it, and add chromium (III) ammonium sulfate dodecahydrate (Wako Pure Chemical Co., Ltd.) After manufacturing 3.1 parts of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.), the mixture was heated and refluxed for 4 hours and a half. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% physiological saline, and the orange-red solid obtained after filtration was dried at 60 ° C to obtain 13.6 parts (63%) of the compound represented by the formula (z-1). .

Identification of compounds represented by formula (z-1)

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

Exact Mass: 905.1

In 18 parts of Rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd.), 170 parts of anhydrous chloroform (manufactured by Kanto Chemical Co., Ltd.), camphorsulfonic acid (manufactured by Aldrich Co., Ltd.), 1.0 part, 4-(N, N-) were added. Dimethylamino)pyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.4 parts, triethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 18 parts, and stirred for about 30 minutes. Thereafter, a portion of anhydrous ethyl chloroform (47 parts) was added to 10.5 parts of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.). After pre-dissolving the solution, it was stirred at room temperature for about 2 hours. After two times of liquid separation operation with 150 parts of 1 N aqueous hydrochloric acid solution, the organic layer was washed twice with 150 parts of 10% physiological saline. Then, 43 parts of anhydrous magnesium sulfate was added, and after stirring for about 30 minutes, the desiccant was filtered, and the solvent was distilled off, whereby 20.6 parts of the compound represented by the formula (g-1) (yield 90%) was obtained.

Identification of the compound represented by formula (g-1) (mass spectrometry) ionization mode = ESI+: m/z = 575.3 [M-C1 ^- ] ⁺

To 253 parts of the compound represented by the formula (z-1), 4030 parts of methanol was added to prepare a solution (s3). 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 under reduced pressure at 60 ° C, washed with water 3500 parts, filtered, and dried under reduced pressure at 60 ° C to obtain 263 parts of the compound (dye A6) represented by formula (3a-23). (Yield 65%).

The structure of the compound represented by the formula (3a-23) is determined based on elemental analysis. The analysis equipment was an ICP (Inductively Coupled Plasma) luminescence analyzer (ICPS-8100, manufactured by Shimadzu Corporation).

C55.6 H5.1 N11.9 Cr3.71

Synthesis Example 5 <Synthesis of Dye A7>

After adding 200 parts of water to 10.0 parts of toluidine-4-sulfonic acid represented by the formula (a-2), the pH was adjusted to 7 to 8 with a 30% aqueous sodium hydroxide solution under ice cooling. The following operations were carried out under ice bath cooling. 11.1 parts of sodium nitrite was added and stirred for 30 minutes. 39.0 parts of 35% hydrochloric acid was added in small portions, and after a brown solution, it was stirred for 2 hours. An aqueous solution obtained by dissolving 10.1 parts of an aminosulfonic acid in 101 parts of water was added to the reaction solution, followed by stirring to obtain a suspension containing a diazonium salt.

Adding 125 parts of water and N-methyl group to 14.0 parts of 1-(2-ethylhexyl)-3-cyano-4-methyl-6-hydroxypyridin-2-one represented by formula (c-2) After 25.0 parts of pyrrolidone, the pH was adjusted to 8-9 with a 30% aqueous sodium hydroxide solution under ice cooling.

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

0.35 g of the compound (d-3) was dissolved in N,N-dimethylformamide to make the volume 250 cm ³ , and 2 cm ^{3 of the solution} was diluted with water to make the volume 100 cm ³ (concentration: 0.028) g/L), the absorption spectrum was measured using a spectrophotometer [quartz cell, the length of the groove was 1 cm]. The compound showed an absorbance of 2.9 (arbitrary units) at λ max = 433 nm.

In a flask equipped with a cooling tube and a stirring device, 5.0 parts of the compound (d-3), 35 parts of acetonitrile, and 1.6 parts of N,N-dimethylformamide were added, and while maintaining at 20 ° C or lower with stirring, the mixture was dropped. 2.4 parts of sulfite chloride. After completion of the dropwise addition, the temperature was raised to 40 ° C, and the mixture was allowed to react at the same temperature for 2 hours, and then cooled to 20 ° C. The cooled reaction solution was poured into 150 parts of ice water while stirring, and stirred for 30 minutes. The precipitated yellow crystals were separated by filtration, washed thoroughly with tap water, and dried at room temperature for 1 hour. In addition, a flask equipped with a cooling tube and a stirring device was prepared, and 2.0 parts of 1-amino-2-propanol and 20 parts of N-methylpyrrolidone were placed, and the mixture was kept at 20 ° C or lower with stirring, and before being charged for 1 hour. Preparation of yellow crystals. After the yellow solid was charged, the temperature of the solution was raised to room temperature, and then the reaction solution was stirred for 30 minutes. After 40 parts of methanol was added to the reaction solution and stirred, the mixed solution was added to a mixed liquid of 29 parts of acetic acid and 300 parts of ion-exchanged water while stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed thoroughly with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 3.9 parts (yield 69%) of the compound of formula (III-3).

0.35 g of the compound (III-3) was dissolved in ethyl lactate to a volume of 250 cm ³ , and 2 cm ^{3 of the solution} was diluted with ion-exchanged water to have a volume of 100 cm ³ (concentration: 0.028 g/L). The absorption spectrum was measured by a spectrophotometer (quartz cell, optical path length: 1 cm). The compound showed an absorbance of 2.3 (arbitrary units) at λ max = 431 nm.

The following reaction was carried out under a nitrogen atmosphere. After 4.0 parts of N-methylpyrrolidone was added 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 ruthenium dichloride was added dropwise. After the completion of the dropwise addition, the mixture was further stirred for 8 hours. After the reaction solution was poured into 300 parts of water, 80 parts of ethyl acetate was added, and the mixture was stirred for 30 minutes. The organic phase was separated using a separatory funnel, and further washed with 500 parts of water, 500 parts of a 10% sodium carbonate aqueous solution, 500 parts of a 10% aqueous acetic acid solution, and 500 parts of ion-exchanged water. The organic phase obtained was subjected to solvent distillation to obtain 2.0 parts of the dye A7 represented by the formula (I-6). The yield was 85%.

The structure of the compound (I-6) is determined by mass spectrometry. The mass spectrometer was JMS-700 (manufactured by JEOL Ltd.).

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

0.35 g of the compound (I-6) was dissolved in ethyl lactate to make the volume 250 cm ³ , and 2 cm ^{3 of the solution} was diluted with ion-exchanged water to have a volume of 100 cm ³ (concentration: 0.028 g/L). The absorption spectrum was measured by a spectrophotometer (quartz cell, optical path length: 1 cm).

The compound showed an absorbance of 2.2 (arbitrary units) at λ max = 431 nm.

Resin Synthesis Example 2 <Synthesis of Resin Solution B2>

Nitrogen gas was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel at 0.02 L/min to make a nitrogen atmosphere, and 935 parts by mass of ethyl lactate was added thereto, and the mixture was heated to 70 ° C while stirring. Then, it was dissolved in 140 parts by mass of acrylic acid, and the compound represented by the following formula (C1-1-1) and the formula (C1-2-1) of acrylate-3,4-epoxytricyclo[5.2.1.0 ^2.6 ] decyl ester. a compound was prepared by mixing 240 parts by mass of a molar ratio of 50:50 with 140 parts by mass of ethyl lactate, and adding the dissolved solution to a flask maintained at 70 ° C for 4 hours using a dropping funnel. . On the other hand, using another dropping funnel, 30 parts by mass of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts by mass of ethyl lactate in 4 hours. The solution was added dropwise to the flask. After completion of the dropwise addition of the solution of the polymerization initiator, it was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 9.0 × 10 ³ , a solid content of 26% by mass, and a solution acid value of 32. Mg-KOH/g resin solution B2.

Resin Synthesis Example 3 <Synthesis of Resin Solution B3>

Into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a gas introduction tube, 250 parts by mass of propylene glycol monomethyl ether acetate was introduced. Thereafter, nitrogen gas was introduced into the flask using a gas introduction tube, and the atmosphere inside the flask was replaced with nitrogen. Thereafter, the solution in the flask was heated to 100 ° C, and then 152.6 parts by mass of benzyl methacrylate, 41.7 parts by mass of methacrylic acid, and 1.5 parts by mass of azobisisobutyronitrile were placed in a dropping funnel over 2 hours. A mixture of 150 parts by mass of propylene glycol monomethyl ether acetate was added dropwise to the flask, and after completion of the dropwise addition, stirring was further continued at 100 ° C for 2.5 hours to obtain a weight average molecular weight Mw of 2.3 × 10 ⁴ and a solid content of 34 % by mass. The resin solution B3 having a solution acid value of 47 mg-KOH/g.

Example 21 [Preparation of Photosensitive Resin Composition 7]

Pigment: C.I. Pigment Red 254 42.8 parts

Acrylic pigment dispersant 16.0 parts

Resin solution B3 35.4 parts

Propylene glycol monomethyl ether acetate 211.7 parts

Mixing, using a bead mill to fully disperse the pigment, and then,

Dye: dye A6 11.2 parts

Adhesive resin: resin solution B2 119.7 parts

Photopolymerizable compound: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 43.4 parts

Photopolymerization initiator: N-benzylideneoxy-1-(4-phenylsulfanylphenyl)oct-1-one-2-imine (Irgacure OXE01, manufactured by BASF Japan) 13.0 parts

Solvent: propylene glycol monomethyl ether acetate 506.6 parts

Surfactant: Polyether modified eucalyptus oil (SH8400, manufactured by Toray Dow Corning Co., Ltd.) 0.1 parts

The photosensitive resin composition 7 was obtained by mixing. The obtained photosensitive resin composition 7 was patterned and evaluated in the same manner as in Example 1. The results are shown in Table 23.

Example 22 [Preparation of Photosensitive Resin Composition 8]

Pigment: C.I. Pigment Green 58 32.2 parts

Acrylic pigment dispersant 8.0 parts

Resin solution B3 28.4 parts

Propylene glycol monomethyl ether acetate 161.2 parts

Mixing, using a bead mill to fully disperse the pigment, and then,

Dye: dye A7 6.8 parts

Adhesive resin: resin solution B2 167.1 parts

Photopolymerizable compound: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 53.4 parts

Photopolymerization initiator: N-benzylideneoxy-1-(4-phenylsulfanylphenyl)oct-1-one-2-imine (Irgacure OXE01, manufactured by BASF Japan) 16.0 parts

Solvent: propylene glycol monomethyl ether acetate 526.8 parts

Surfactant: Polyether modified eucalyptus oil (SH8400, manufactured by Toray Dow Corning Co., Ltd.) 0.1 parts

The photosensitive resin composition 8 was obtained by mixing. The obtained photosensitive resin composition 8 was patterned and evaluated in the same manner as in Example 1. The results are shown in Table 23.

Example 23 [Preparation of Photosensitive Resin Composition 9]

Pigment: C.I. Pigment Green 58 42.6 parts

Acrylic pigment dispersant 10.7 parts

Resin solution B3 37.6 parts

Propylene glycol monomethyl ether acetate 213.5 parts

Mixing, using a bead mill to fully disperse the pigment, and then,

Dye: dye A7 3.8 parts

Adhesive resin: resin solution B2 138.4 parts

Photopolymerizable compound: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 49.1 parts

Photopolymerization initiator: N-benzylideneoxy-1-(4-phenylsulfanylphenyl)oct-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 eucalyptus oil (SH8400, manufactured by Toray Dow Corning Co., Ltd.) 0.1 parts

The photosensitive resin composition 9 was obtained by mixing. The obtained photosensitive resin composition 9 was patterned and evaluated in the same manner as in Example 1. The results are shown in Table 23.

Examples 24-26

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

Industrial availability

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

The display device of the present invention is not limited to a notebook computer, and is also suitable for use in a personal digital assistant or a mobile phone, a monitor, or a liquid crystal television.

1. . . Color filter

3. . . Substrate

10. . . Color liquid crystal display device

11. . . Transparent substrate

12. . . TFT array

13,23. . . Transparent electrode layer

14, 24. . . Alignment layer

15,25. . . Polarizer

twenty one. . . Transparent substrate

twenty two. . . Color filter

30. . . Backlight unit

31. . . light source

32. . . reflector

33. . . Light guide

33a. . . Side of the light guide plate 33

34. . . Diffuser

35. . . Reflective plate

B. . . Transparent blue photosensitive resin composition film

BM. . . Black matrix

G. . . Transparent green photosensitive resin composition film

LC. . . Liquid crystal composition

R. . . Transparent red photosensitive resin composition film

Fig. 1 is a schematic view showing a color filter.

Fig. 2 is a schematic view showing a display device.

Fig. 3 is a perspective view showing a backlight unit.

Fig. 4 shows the luminescence spectrum of the light source 1.

Fig. 5 shows the luminescence spectrum of the light source 2.

10. . . Color liquid crystal display device

11. . . Transparent substrate

12. . . TFT array

13,23. . . Transparent electrode layer

14, 24. . . Alignment layer

15,25. . . Polarizer

twenty one. . . Transparent substrate

twenty two. . . Color filter

30. . . Backlight unit

31. . . light source

LC. . . Liquid crystal composition

Claims (8)

A display device comprising a dye-containing color filter and a white LED light source, wherein the dye is a dye represented by formula (1-1), and the white LED light source is a light source comprising a blue LED light source and a phosphor, light system emits the white LED light source having a luminous intensity of the largest of the wavelength [lambda] at the wavelength 430nm ~ range 485nm of _1, having a light emission intensity at the wavelength 500nm ~ range 580nm to become, great range of the wavelength λ ₂ at a wavelength of 590nm ~ 680nm of Light having a wavelength λ ₃ whose luminous intensity becomes extremely large, In the formula (1-1), R ¹¹ to R ¹⁴ each independently represent a hydrogen atom, -R ⁶ or a carbon number 6 to 10 monovalent aromatic hydrocarbon group, and the hydrogen atom contained in the aromatic hydrocarbon group may pass through 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 is} 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 ; X represents a halogen atom; a represents an integer of 0 or 1, and R ⁶ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, which is contained in the saturated hydrocarbon group The hydrogen atom may be substituted by a halogen atom, and -CH ₂ - contained in the saturated hydrocarbon group may be substituted by -O-, -CO- or -NR ⁷ -; and 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 by a halogen atom or an alkoxy group having 1 to 10 carbon atoms; and R ⁸ and R ⁹ each independently represent an alkyl group having 1 to 10 carbon atoms and a carbon number; 3 to 30 cycloalkyl or -Q; or R ⁸ and R ⁹ may be bonded to each other to form a heterocyclic group having 1 to 10 carbon atoms; Q represents a carbon number of 6 to 10 monovalent aromatic hydrocarbon group or carbon number 3~ 10 price Hong aromatic heterocyclic group, the aromatic hydrocarbon group and aromatic heterocyclic group of the hydrogen atom contained in it may be ^{-OH, -R 6, -OR 6,} -NO 2, -CH = CH 2, -CH = CHR ⁶ or a halogen atom; wherein the compound represented by the formula (1-1) has the same number of positive charges as the number of negative charges. The display device of claim 1, wherein the white LED light source is a light source comprising a blue LED light source and a red light emitting phosphor and a green light emitting phosphor. The display device of claim 1, wherein the color filter is a color filter comprising a dye and a pigment. The display device of claim 1, wherein the color filter is a color filter formed of a photosensitive resin composition containing a dye, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The display device of claim 4, wherein the photosensitive resin composition contains a pigment. The display device of claim 5, wherein the ratio of the content of the dye to the content of the pigment is from 1:99 to 99:1 by mass fraction. The display device of claim 3, wherein the pigment is selected from the group consisting of CI Pigment Blue 15:6, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Red 177. a pigment of at least one of the group consisting of CI Pigment Red 242 and CI Pigment Red 254. The display device of claim 3, wherein the pigment is C.I. Pigment Blue 15:6.