JP5796273B2 - Colored photosensitive resin composition - Google Patents

Description

  The present invention relates to a colored photosensitive resin composition.

In the colored photosensitive resin composition forming the red pixel of the color filter, the spectral characteristics of the red pixel are adjusted by including a yellow pigment as a colorant for complementary color of the red pigment. For example, Patent Document 1 discloses C.I. as a red pigment and a yellow pigment for complementary color. I. A red pixel composed of a red photosensitive resin composition containing CI Pigment Yellow 150 is described.
In addition, it is known to use a dye as a colorant in the colored photosensitive resin composition in order to increase the contrast of the color filter. For example, Patent Document 2 describes a colored photosensitive resin composition containing VALIFAST Red 1308 as a red dye.

JP 2007-133131 A JP 2003-295427 A

  However, in the conventional colored photosensitive resin composition, the contrast of the obtained color filter may not be sufficiently satisfactory.

  The present invention includes a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (F), and the colorant (A) is represented by the formula (A- It is a colored photosensitive resin composition which is a colorant containing the compound represented by I) and a yellow dye.

[In formula (AI), R ^{1 to} R ¹⁸ each independently represents a hydrogen atom, a halogen atom, a C _1-8 aliphatic hydrocarbon group, a nitro group, a phenyl group, —SO ₂ NHR ²¹¹ , —SO ₃ ^- or an ^{-COOR 212,} at least one -SO ₃ ^- represents a.
R ¹⁹ and R ²⁰ each independently represents a hydrogen atom, a methyl group, an ethyl group or an amino group.
R ²¹¹ and R ²¹² are each independently a hydrogen atom, a C _1-8 aliphatic hydrocarbon group, a cyclohexyl group, a C _7-10 alkylcyclohexyl group, a C _2-15 alkoxyalkyl group, —R ³¹ —CO—O. ^{-R 32, -R 31 -O-CO} -R 32, or represents a C _7-10 aralkyl group.
R ³¹ represents a divalent C _1-8 aliphatic hydrocarbon group, and R ³² represents a monovalent C _1-8 aliphatic hydrocarbon group.
M represents Cr or Co.
n represents an integer of 2 to 5.
D represents a monovalent cation derived from a compound having hydron, a monovalent metal cation or a xanthene skeleton. ]

In the present invention, R ^{1 to} R ¹⁸ each independently represents a hydrogen atom, a chlorine atom, a methyl group, a nitro group, —SO ₂ NHR ²¹¹ , —SO ₃ ^—, or —COOR ²¹² , at least one of — The colored photosensitive resin composition representing SO ₃ ⁻ .

  Moreover, this invention is the said colored photosensitive resin composition whose yellow dye is a dye containing the compound which has an azo skeleton.

  Moreover, this invention is the said colored photosensitive resin composition whose yellow dye is at least 1 sort (s) chosen from the group which consists of a compound represented with Formula (I), and its salt.

Wherein (I), R ⁴¹ ~R ⁴⁴ independently represents a hydrogen atom, C _1-10 saturated aliphatic hydrocarbon group or a carboxy group.
R ^{45 to} R ⁵² each independently represents a hydrogen atom, a halogen atom, a C _1-10 saturated aliphatic hydrocarbon group, a halogenated C _1-10 saturated aliphatic hydrocarbon group, a C _1-8 alkoxy group, or a carboxy group. , A sulfo group, a sulfamoyl group, or an N-substituted sulfamoyl group.
R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom, a cyano group, a carbamoyl group, or an N-substituted carbamoyl group. ]

  Moreover, this invention is the said colored photosensitive resin composition whose binder resin (B) is resin which has a polymerizable unsaturated bond in a side chain.

  Moreover, this invention is a pattern formed from the said colored photosensitive resin composition.

  Moreover, this invention is a color filter which comprises the said pattern.

  Moreover, this invention is use of the said colored photosensitive resin composition for manufacturing a color filter.

  According to the colored photosensitive resin composition of the present invention, a high-contrast color filter can be obtained.

It is a graph which shows the transmittance | permeability of an Example.

  The colored photosensitive resin composition of the present invention contains a colorant (A), and the colorant (A) contains a compound represented by the formula (AI) and a yellow dye.

[In formula (AI), R ^{1 to} R ¹⁸ each independently represents a hydrogen atom, a halogen atom, a C _1-8 aliphatic hydrocarbon group, a nitro group, a phenyl group, —SO ₂ NHR ²¹¹ , —SO ₃ ^- or an ^{-COOR 212,} at least one -SO ₃ ^- represents a.
R ¹⁹ and R ²⁰ each independently represents a hydrogen atom, a methyl group, an ethyl group or an amino group.
R ²¹ and R ²² are each independently a hydrogen atom, a C _1-8 aliphatic hydrocarbon group, a cyclohexyl group, a C _7-10 alkylcyclohexyl group, a C _2-15 alkoxyalkyl group, —R ³¹ —CO—O. ^{-R 32, -R 31 -O-CO} -R 32, or represents a C _7-10 aralkyl group.
R ³¹ represents a divalent C _1-8 aliphatic hydrocarbon group, and R ³² represents a monovalent C _1-8 aliphatic hydrocarbon group.
M represents Cr or Co.
n represents an integer of 2 to 5.
D represents a monovalent cation derived from a compound having hydron, a monovalent metal cation or a xanthene skeleton. ]
In the present specification, C _ab means that the carbon number is a or more and b or less.

The compound represented by the formula (AI) can have both water solubility and oil solubility by having a sulfo group, a sulfamoyl group, and an N-substituted sulfamoyl group. In order to improve oil solubility, in the formula (AI), any one of R ^{5 to} R ⁹ and any one of R ^{14 to} R ¹⁸ , R ⁷ and R ¹⁶ are each independently- It is preferably SO ₂ NHR ²¹¹ or —SO ₃ ^— , and R ²¹¹ is preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms.

The compound represented by the formula (AI) can improve heat resistance by having a nitro group. Therefore, it is preferable that at least one of R ^{1 to} R ⁶ , R ^{8 to} R ¹⁵ , R ¹⁷ and R ¹⁸ is a nitro group.

Specific examples of the C _1-8 aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n- Pentyl group, n-hexyl group, n-heptyl group, n-octyl group, dexyl group, 1-methylbutyl group, 1,1,3,3-tetramethylbutyl group, 1,5-dimethylhexyl group, 1,6 -A dimethylheptyl group, 2-ethylhexyl group, and 1,1,5,5-tetramethylhexyl group are mentioned.

_{Examples of the} C _7-10 alkylcyclohexyl group include 2-methylcyclohexyl group, 2-ethylcyclohexyl group, 2-n-propylcyclohexyl group, 2-isopropylcyclohexyl group, 2-n-butylcyclohexyl group, 4-methylcyclohexyl group. 4-ethylcyclohexyl group, 4-n-propylcyclohexyl group, 4-isopropylcyclohexyl group, 4-n-butylcyclohexyl group and the like.

C _2-15 alkoxyalkyl groups include methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, methoxypentyl, 1-ethoxypropyl, 2-ethoxypropyl, 1-ethoxy-1-methylethyl Group, 2-ethoxy-1-methylethyl group, 1-isopropoxypropyl group, 2-isopropoxypropyl group, 1-isopropoxy-1-methylethyl group, 2-isopropoxy-1-methylethyl group, octyloxy A propyl group, a 3-ethoxypropyl group, a 3- (2-ethylhexyloxy) propyl group, and the like, preferably a 1-ethoxypropyl group, an octyloxypropyl group, a 3-ethoxypropyl group, and 3- (2-ethylhexyloxy). ) A propyl group is mentioned.

—R ³¹ —CO—O—R ³² and —R ³¹ —O—CO—R ³² (R ³¹ represents a divalent C _1-8 aliphatic hydrocarbon group, and R ³² represents a monovalent C _{1. -8} represents an aliphatic hydrocarbon group.) Represents an ester bond obtained by dehydration condensation between a C _2-9 aliphatic hydrocarbon group having a carboxy group and a C _1-8 aliphatic hydrocarbon having a hydroxy group. Or a group having an ester bond obtained by dehydration condensation between a C _1-8 aliphatic hydrocarbon group having a hydroxy group and a C _2-9 aliphatic hydrocarbon having a carboxy group. The number of carbon atoms in —R ³¹ —CO—O—R ³² and —R ³¹ —O—CO—R ³² is preferably 4 to 10.

Examples of the C _2-9 aliphatic hydrocarbon having a carboxy group include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, and the like. Preferably, acetic acid, propionic acid, and butyric acid are used.
Examples of the C _2-9 aliphatic hydrocarbon group having a carboxy group include those obtained by removing one hydrogen atom from the C _2-9 aliphatic hydrocarbon having a carboxy group.

Examples of the C _1-8 aliphatic hydrocarbon having a hydroxy group include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, and 1-methyl. -N-butanol, 2-methyl-n-butanol, 3-methyl-n-butanol, n-hexanol, n-heptanol, n-octanol, etc., preferably methanol, ethanol, n-propanol, isopropanol, n -Butanol, isobutanol, sec-butanol, tert-butanol.
Examples of the C _1-8 aliphatic hydrocarbon group having a hydroxy group include those obtained by removing one hydrogen atom from the C _1-8 aliphatic hydrocarbon having a hydroxy group.
As the group having 4 to 10 carbon atoms having an ester bond obtained by dehydration condensation between the C _2-9 aliphatic hydrocarbon group having a carboxy group and the C _1-8 aliphatic hydrocarbon having a hydroxy group, Propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, heptyl acetate, ethyl butyrate, isopropyl butyrate, butyl butyrate, pentyl butyrate, hexyl butyrate, heptyl butyrate, octyl butyrate Group, methyl valerate, ethyl valerate, isopropyl valerate, isobutyl valerate, pentyl valerate, hexyl valerate, heptyl valerate, methyl caproate, ethyl caproate, caproic acid Propyl, butyl caproate, hexyl caproate, methyl enanthate, ethyl enanthate, isopropyl enanthate, isoenate enanthate Tyl group, pentyl group of enanthate, methyl caprylate, ethyl caprylate, propyl caprylate, isopropyl caprylate, butyl caprylate, isobutyl caprylate, methyl pelargonate, ethyl pelargonate, pelargonic acid And propyl group, isopropyl pelargonate group, etc., preferably propyl acetate group, butyl acetate group, ethyl butyrate group, butyl butyrate group, pentyl butyrate group, hexyl acetate group, methyl valerate group, ethyl valerate group, Examples thereof include isopropyl valerate group and isobutyl valerate group.

In the C _2-9 aliphatic hydrocarbon group having a carboxy group or a C _2-9 aliphatic hydrocarbon having a carboxy group, the hydroxy group is changed by replacing the carboxy group with a —CO—Cl group. A group having 4 to 10 carbon atoms having an ester bond can also be obtained by dehydrochlorination condensation with a C _1-8 aliphatic hydrocarbon having or a C _1-8 aliphatic hydrocarbon group having a hydroxy group.

_{Examples of the} C _7-10 aralkyl group include a benzyl group, a phenethyl group, and a 1-methyl-3-phenylpropyl group.

  Examples of the monovalent metal cation represented by D include a lithium cation, a sodium cation, and a potassium cation.

  Examples of the monovalent cation derived from the compound having a xanthene skeleton represented by D include a cation represented by the formula (A-II).

[In formula (A-II), R ^{22 to} R ²⁶ each independently represents a hydrogen atom, a C _1-6 aliphatic hydrocarbon group or an optionally substituted C _6-10 aromatic hydrocarbon group. . ]

Examples of the C _1-6 aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 2 -Methylbutyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1, 2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3- And ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, etc., preferably methyl group, ethyl group, n-propyl group, isopropyl group Examples include a pill group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group.
Examples of the _optionally substituted C _6-10 aromatic hydrocarbon include phenyl group, o-toluyl group, m-toluyl group, p-toluyl group, and naphthyl group.
In formula (A-II), R ^{22 to} R ²⁶ can be arbitrarily combined, but preferably R ²² and R ²⁴ are a hydrogen atom, R ²³ and R ²⁵ are an ethyl group, and R ²⁶ is a methyl group. Combinations include a combination in which R ²² and R ²⁴ are hydrogen atoms, R ²³ and R ²⁵ are ethyl groups, and R ²⁶ is an ethyl group.

  The compound represented by the formula (AI) can improve the brightness by having a monovalent cation derived from a compound having a xanthene skeleton. Therefore, D is preferably a monovalent cation derived from a compound having a xanthene skeleton.

Preferred examples of the compound represented by the formula (AI) include compounds represented by the formulas (AI-1) to (AI-4).

  The content of the compound represented by the formula (AI) in the colorant (A) is preferably 25% to 99%, more preferably 25% to 80% with respect to the colorant (A). It is more preferable.

  When the content of the compound represented by the formula (AI) in the colorant (A) is in the above range, it is easy to optimize the transmission spectrum and good for obtaining high contrast and high brightness. Furthermore, it is preferable because it has good heat resistance and chemical resistance.

The colored photosensitive resin composition of the present invention contains a colorant (A), and the colorant (A) contains a yellow dye.
The yellow dye is preferably a dye containing a compound having an azo skeleton.

［式（Ｉ）中、Ｒ⁴¹〜Ｒ⁴⁴は、それぞれ独立に、水素原子、Ｃ_1-10飽和脂肪族炭化水素基又はカルボキシ基を表す。
Ｒ⁴⁵〜Ｒ⁵²は、それぞれ独立に、水素原子、ハロゲン原子、Ｃ_1-10飽和脂肪族炭化水素基、ハロゲン化Ｃ_1-10飽和脂肪族炭化水素基、Ｃ_1-8アルコキシ基、カルボキシ基、スルホ基、スルファモイル基、又はＮ−置換スルファモイル基を表す。
Ｒ⁵³及びＲ⁵⁴は、それぞれ独立に、水素原子、シアノ基、カルバモイル基、又はＮ−置換カルバモイル基を表す。］ Examples of yellow dyes include dyes containing at least one selected from the group consisting of compounds represented by formula (I) (hereinafter sometimes referred to as “compound (I)”) and salts thereof.

Wherein (I), R ⁴¹ ~R ⁴⁴ independently represents a hydrogen atom, C _1-10 saturated aliphatic hydrocarbon group or a carboxy group.
R ^{45 to} R ⁵² each independently represents a hydrogen atom, a halogen atom, a C _1-10 saturated aliphatic hydrocarbon group, a halogenated C _1-10 saturated aliphatic hydrocarbon group, a C _1-8 alkoxy group, or a carboxy group. , A sulfo group, a sulfamoyl group, or an N-substituted sulfamoyl group.
R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom, a cyano group, a carbamoyl group, or an N-substituted carbamoyl group. ]

The saturated aliphatic hydrocarbon group for R ^{41 to} R ⁴⁴ may be linear, branched or cyclic.
The carbon number of the saturated aliphatic hydrocarbon group does not include the carbon number of the substituent. The carbon number is 1-10, preferably 2-8, more preferably 3-6. Examples of the saturated aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

For example, in order to increase color density, at least one of R ^{41 to} R ⁴⁴ (preferably 2 or more) is a saturated aliphatic hydrocarbon group having 5 or less (preferably 3 or less) carbon atoms (for example, a methyl group). And an ethyl group) or a hydrogen atom.

The halogen atom for R ^{45 to} R ⁵² is preferably a fluorine atom, a chlorine atom or a bromine atom.

As in the case of R ^{41 to} R ⁴⁴ , the saturated aliphatic hydrocarbon group for R ^{45 to} R ⁵² may be linear, branched or cyclic, and the carbon number thereof is 1 to 10, preferably Is 2-8, more preferably 3-6. Specific examples of the saturated aliphatic hydrocarbon group for R ^{45 to} R ⁵² are the same as those for R ^{41 to} R ⁴⁴ . The saturated aliphatic hydrocarbon group of R ^{45 to} R ⁵² may be substituted with a halogen atom, preferably a fluorine atom. Specific examples of the halogenated saturated aliphatic hydrocarbon group include a trifluoromethyl group.

The number of carbon atoms of the alkoxy groups R ⁴⁵ to R ⁵² is 1-8, preferably 1-4. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, an n-propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.

The N-substituted sulfamoyl group of R ^{45 to} R ⁵² is preferably an N-1 substituted sulfamoyl group, and can be represented by —SO ₂ NHR ⁵⁵ . R ⁵⁵ is, C _1-10 saturated aliphatic hydrocarbon group, C _1-8 C _1-10 saturated aliphatic hydrocarbon group which alkoxy group is substituted, C _6-20 aryl group, C _7-20 aralkyl group Or a C _2-10 acyl group.

In order to improve oil solubility (that is, solubility in an organic solvent), at least one of R ^{45 to} R ⁵² is a branched aliphatic hydrocarbon group (preferably a tertiary group such as a tert-butyl group). A saturated aliphatic hydrocarbon group), a saturated aliphatic hydrocarbon group to which two or more halogen atoms are bonded (preferably a saturated aliphatic hydrocarbon group to which three or more halogen atoms such as a trifluoromethyl group are bonded) and N -A substituted sulfamoyl group is preferred.
Two or more of R ^{45 to} R ⁵² (for example, one or more (especially one) from R ^{45 to} R ⁴⁸ and one or more (especially one) from R ^{49 to} R ⁵² ) may be the aforementioned groups. Preferably, the substitution position of the group is more preferably a meta position or an ortho position with respect to the azo group.
When the group is bulky, stacking of the biphenyl moiety of the azo dye can be reduced, and oil solubility can be increased. Furthermore, when the substitution position is ortho to the azo group, the azo group can be protected and light resistance can be improved.

Preferably, at least one of R ^{45 to} R ⁵² is an N-substituted sulfamoyl group, more preferably at least one of R ^{45 to} R ⁴⁸ and at least one of R ^{49 to} R ⁵² is an N-substituted sulfamoyl group. It is particularly preferred that at least one of R ⁴⁵ and R ⁴⁸ and at least one of R ⁴⁹ and R ⁵² is an N-substituted sulfamoyl group.

The saturated aliphatic hydrocarbon group for R ⁵⁵ may be linear, branched or cyclic. The carbon number of the saturated aliphatic hydrocarbon group does not include the carbon number of the substituent, and the number thereof is 1 to 10, preferably 6 to 10, for example, methyl group, ethyl group, n-propyl group, isopropyl group , N-butyl group, isobutyl group, sec-butyl group, tert-butyl group, methylbutyl group (such as 1,1,3,3-tetramethylbutyl group), methylhexyl group (such as 1,5-dimethylhexyl group) , Ethylhexyl group (such as 2-ethylhexyl group), cyclopentyl group, cyclohexyl group, methylcyclohexyl group (such as 2-methylcyclohexyl group), cyclohexylalkyl group and the like. As described above, the saturated aliphatic hydrocarbon group for R ⁵⁵ may be substituted with a substituent such as a C _1-8 (preferably C _1-4 ) alkoxy group.
Examples of the substituted saturated aliphatic hydrocarbon group include a propoxypropyl group (3- (isopropoxy) propyl group and the like).

The aryl group of R ⁵⁵ may be unsubstituted or may have a substituent such as a saturated aliphatic hydrocarbon group or a hydroxy group. Carbon number of the said aryl group is counted including carbon number of a substituent, and is 6-20, Preferably it is 6-10. As the aryl group which may have these substituents, for example, unsubstituted phenyl group, hydroxyphenyl group (such as 4-hydroxyphenyl group), and trifluoromethylphenyl group (such as 4-trifluoromethylphenyl group) Or a substituted phenyl group etc. are mentioned.

The alkyl part of the aralkyl group for R ⁵⁵ may be either linear or branched.
The carbon number of the aralkyl group is 7 to 20, preferably 7 to 10. Examples of the aralkyl include phenylalkyl groups such as a benzyl group, a phenylpropyl group (such as 1-methyl-3-phenylpropyl group), and a phenylbutyl group (such as 3-amino-1-phenylbutyl group).

The acyl group for R ⁵⁵ may be unsubstituted or may be bonded to a substituent such as a saturated aliphatic hydrocarbon group or an alkoxy group. Carbon number of an acyl group is counted including carbon number of a substituent, and the number is 2-10, Preferably it is 6-10. Examples of the acyl group include an acetyl group, a benzoyl group, and a methoxybenzoyl group (such as a p-methoxybenzoyl group).

R ⁵⁵ is, for example, a methylbutyl group (1,1,3,3-tetramethylbutyl group), a methylhexyl group (1,5-dimethylhexyl group) in order to further increase the color density, oil solubility and the like. Branched chain saturation such as ethylhexyl group (such as 2-ethylhexyl group), methylcyclohexyl group (such as 2-methylcyclohexyl group), phenylbutyl group (such as 3-amino-1-phenylbutyl group) An aliphatic hydrocarbon group or an aralkyl group is preferred.

The carbamoyl group and N-substituted carbamoyl group of R ⁵³ and R ⁵⁴ are the structural formula of —CON (R ⁵⁶ ) R ⁵⁷ (wherein R ⁵⁶ and R ⁵⁷ are each independently a hydrogen atom, C _1-10 saturated) An aliphatic hydrocarbon group, a C _1-10 saturated aliphatic hydrocarbon group substituted by a C _1-8 alkoxy group, a C _6-20 aryl group, a C _7-20 aralkyl group, or a C _2-10 acyl group. It represents.) Examples of the saturated aliphatic hydrocarbon group, aryl group, aralkyl group and acyl group for R ⁵⁶ and R ⁵⁷ are the same as those described above for R ⁵⁵ . However, specific examples of the acyl group further include a benzoyl group containing a halogen atom, such as a bromobenzoyl group (such as a p-bromobenzoyl group). It is preferred that at least one of R ⁵³ and R ⁵⁴ is a —CON (R ⁵⁶ ) R ⁵⁷ group.

In order to increase color density, at least one of R ⁵⁶ and R ⁵⁷ (preferably both) is a saturated aliphatic hydrocarbon group having 3 or less carbon atoms (for example, a methyl group, an ethyl group, etc., particularly a methyl group), Or it is preferable that it is a hydrogen atom.

When two or more compounds (I) are used in combination, the solubility (oil solubility) in an organic solvent is higher than when one of them is used alone. Since the oil solubility tends to be high, it is also preferable to use a combination of two or more kinds of compound (I) as the dye used in the liquid crystal display device. As an example of a combination that improves oil solubility, compound (I) (disulfonamide) having two N-substituted sulfamoyl groups and compound (I) (monosulfone having one N-substituted sulfamoyl group and one sulfo group) A combination with amide). Among such combinations, one of R ^{45 to} R ⁴⁸ and one of R ^{49 to} R ⁵² is an N-substituted sulfamoyl group, and the remainder is a hydrogen atom, and R ^{45 to} R A combination with a monosulfonamide in which one of ⁴⁸ is an N-substituted sulfamoyl group, one of R ^{49 to} R ⁵² is a sulfo group, and the remainder is a hydrogen atom is preferred. Monosulfonamide is particularly preferred because it has a lower molecular weight than disulfonamide and tends to increase color density.

  Preferable examples of formula (I) include compounds represented by formula (I-1) to formula (I-10).

さらに式（Ｉ）の好ましい例には、式（Ｉ−Ａ）で表されるような、Ｒ⁴⁵〜Ｒ⁴⁸の少なくとも１つ、並びにＲ⁴⁹〜Ｒ⁵²の少なくとも１つが、−ＳＯ₂ＮＨＲ⁵⁵基であり、残りの６つが水素原子である化合物も含まれる。

Furthermore, preferred examples of formula (I) include at least one of R ^{45 to} R ⁴⁸ , and at least one of R ^{49 to} R ⁵² , as represented by formula (IA), —SO ₂ NHR ^55. Also included are compounds in which the remaining six are hydrogen atoms.

式（Ｉ−Ａ）の好ましい例としては、式（Ｉ−１１）〜式（Ｉ−１８）が挙げられる。

Preferable examples of formula (IA) include formula (I-11) to formula (I-18).

Examples of the salt of compound (I) include a sulfonate when R ^{45 to} R ⁵² are a sulfo group, and a carboxylate when R ^{45 to} R ⁵² are a carboxy group. The cations forming these salts are not particularly limited, but considering solubility in solvents, alkali metal salts such as lithium salts, sodium salts and potassium salts; ammonium salts; and ethanolamine salts and alkylamine salts. Organic amine salts and the like are preferred. In particular, the organic amine salt is useful when it is contained in a resin curable compound. Further, since it is a non-metallic salt, it is also useful in fields where insulation is important.

Compound (I) can be produced by coupling a diazonium salt and a pyridone, as is well known in the dye field. For example, a compound of the formula (Ib) obtained by diazotizing a benzidine compound (diazo component) represented by the formula (Ia) with nitrous acid, nitrite or nitrite can be used as the diazonium salt (formula ( In Ia) and (Ib), R ^{45 to} R ⁵² represent the same meaning as described above.

そしてジアゾニウム塩（Ｉｂ）と、式（Ｉｃ）及び／又は（Ｉｄ）で表されるピリドン類（カップリング成分）とを、通常、水性溶媒中２０〜６０℃で反応させることにより、化合物（Ｉ）を製造することができる（式（Ｉｃ）及び（Ｉｄ）中、Ｒ⁴¹〜Ｒ⁴⁴、Ｒ⁵³及びＲ⁵⁴は、前記と同じ意味を表す。なお、式（Ｉｃ）及び（Ｉｄ）とは、同一であってもよい。）。

Then, by reacting the diazonium salt (Ib) with the pyridones (coupling component) represented by the formula (Ic) and / or (Id), usually in an aqueous solvent at 20 to 60 ° C., the compound (I (In the formulas (Ic) and (Id), R ^{41 to} R ⁴⁴ , R ⁵³ and R ⁵⁴ have the same meanings as described above. In the formulas (Ic) and (Id), , May be the same).

In the compound (I), at least one of R ^{45 to} R ⁵² is an N-substituted sulfamoyl group (hereinafter referred to as “sulfonamide compound (I)”), the compound (Ia) having an N-substituted sulfamoyl group is used. However, it is preferable to carry out the coupling reaction using the compound (Ia) having a sulfo group and then sulfonamid the sulfo group. For example, a compound in which at least one of R ^{45 to} R ⁵² in formula (I) is a sulfo group (hereinafter referred to as “azosulfonic acid (I)”) is synthesized, and a sulfo group (—SO ₃ H) is obtained by using a thionyl halide compound. ) Is a sulfonyl halide (—SO ₂ X; X is a halogen atom) to obtain a sulfonyl halide compound, and the sulfonamide is then sulfonamidated by reacting the sulfonyl halide compound with an amine to give the sulfonamide compound (I ) Can be obtained.

  Preferable examples of azosulfonic acid (I) include compounds represented by formulas (I-1) to (I-7), (I-9) and (I-10), and particularly preferable examples include: Examples thereof include compounds represented by formulas (I-1) to (I-3), (I-9) and (I-10). Examples of the thionyl halide compound include thionyl fluoride, thionyl chloride, thionyl bromide, thionyl iodide and the like, preferably thionyl chloride and thionyl bromide, and particularly preferably thionyl chloride. The amount of thionyl halide used is, for example, about 1 to 10 moles with respect to 1 mole of azosulfonic acid (I). When water is brought into the reaction system, it is preferable to use an excessive amount of the thionyl halide compound.

  The sulfonyl halide is carried out in a solvent. Examples of the solvent include ethers such as 1,4-dioxane (particularly preferably cyclic ethers); chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, dichloroethylene, trichloroethylene, perchloroethylene, dichloropropane, Halogenated hydrocarbons such as amyl chloride and 1,2-dibromoethane can be used. The amount of the solvent used is, for example, about 3 parts by mass (preferably 5 parts by mass or more) and 10 parts by mass or less (preferably 8 parts by mass or less) with respect to 1 part by mass of azosulfonic acid (I).

  In sulfonyl halide formation, it is preferable to use N, N-dialkylformamide (for example, N, N-dimethylformamide, N, N-diethylformamide, etc.) in combination. When N, N-dialkylformamide is used, the amount used is, for example, about 0.05 to 1 mol with respect to 1 mol of the thionyl halide compound. When azosulfonic acid (I) and N, N-dialkylformamide are mixed in advance in a solvent and then a thionyl halide compound is added, heat generation can be suppressed.

  The reaction temperature in the sulfonyl halide formation is, for example, 0 ° C. or higher (preferably 30 ° C. or higher) and 70 ° C. or lower (preferably 60 ° C. or lower). The reaction time is, for example, about 0.5 hours or more (preferably 3 hours or more) and 8 hours or less (preferably 5 hours or less).

  The sulfonyl halide compound prepared as described above may be isolated and then reacted with the amine, or may be reacted with the amine in the reaction mixture without isolation. In the case of isolation, for example, the reaction mixture and water may be mixed, and the precipitated crystals may be collected by filtration. The obtained crystals of the sulfonyl halide compound may be washed with water and dried as necessary before the reaction with the amine. In this specification, in order to distinguish this amine from the basic catalyst described later, hereinafter, it may be referred to as a reactive amine.

Examples of the reactive amine include a primary amine, and the primary amine is represented by the formula H ₂ N—R ⁵⁵ (R ⁵⁵ is the same as described above).
Specific examples of H ₂ N—R ⁵⁵ include n-propylamine, n-butylamine, n-hexylamine, dimethylhexylamine (such as 1,5-dimethylhexylamine), tetramethylbutylamine (1,1,3,3). 3-tetramethylbutylamine and the like), ethylhexylamine (such as 2-ethylhexylamine), aminophenylbutane (such as 3-amino-1-phenylbutane), and isopropoxypropylamine. The amount of the reactive amine used is about 3 mol or more and 10 mol or less (preferably 7 mol or less) with respect to 1 mol of the sulfonyl halide compound.

  The order of addition of the sulfonyl halide compound and the reactive amine is not particularly limited, but it is preferable to add (drop) the reactive amine to the sulfonyl halide compound. The reaction between the sulfonyl halide compound and the reactive amine is carried out in a solvent. Examples of the solvent include the same solvents as those used when preparing the sulfonyl halide compound.

  The reaction between the sulfonyl halide and the reactive amine is preferably performed in the presence of a basic catalyst. Examples of the basic catalyst include tertiary amines (particularly aliphatic tertiary amines such as triethylamine and triethanolamine), pyridine bases such as pyridine and methylpyridine, and the like. Among these, tertiary amines, particularly aliphatic tertiary amines such as triethylamine are preferable. The usage-amount of a basic catalyst is about 1.1 mol or more and 6 mol or less (preferably 5 mol or less) with respect to the reactive amine (the said amine made to react with a sulfonyl halide).

  When the reactive amine and the basic catalyst are added to the sulfonyl halide compound, the timing of adding the basic catalyst is not particularly limited, and may be either before or after the addition of the reactive amine. You may add at the same timing. Further, it may be added after mixing with the reactive amine in advance, or may be added separately from the reactive amine.

  The reaction temperature between the sulfonyl halide compound and the reactive amine is, for example, 0 ° C. or higher and 50 ° C. or lower (preferably 30 ° C. or lower). The reaction time is about 1 to 5 hours.

  The method for obtaining the target sulfonamide compound (I) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, it is preferable that the reaction mixture is mixed with an acid (for example, acetic acid) and water, and the precipitated crystals are collected by filtration. It is preferable that the acid and water are prepared in advance as an aqueous acid solution and then the reaction mixture is added to the aqueous solution. The temperature at which the reaction mixture is added is 10 ° C or higher, preferably 20 ° C or higher and 50 ° C or lower, preferably 30 ° C or lower. Moreover, after addition, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystals collected by filtration are washed with water or the like and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

〔式（ＩＩ）中、Ｚ⁶¹は、酸素原子又は硫黄原子を表す。
Ａ⁶¹は、カルボキシ基、スルホ基、スルファモイル基及びＮ−置換スルファモイル基よりなる群から選ばれる少なくとも１種の基を１個又は２個有するフェニル基、或いはスルホ基、スルファモイル基及びＮ−置換スルファモイル基よりなる群から選ばれる少なくとも１種の基を１〜３個有するナフチル基を表す。
Ｒ⁶¹及びＲ⁶²は、それぞれ独立して、水素原子、Ｃ_1-10飽和脂肪族炭化水素基、ヒドロキシ基が置換しているＣ_1-10飽和脂肪族炭化水素基、Ｃ_1-8アルコキシ基が置換しているＣ_1-10飽和脂肪族炭化水素基、Ｃ_1-8チオアルコキシ基が置換しているＣ_1-10飽和脂肪族炭化水素基、Ｃ_6-20アリール基、Ｃ_7-20アラルキル基、又はＣ_2-10アシル基を表す。
Ｒ⁶³〜Ｒ⁶⁶は、それぞれ独立して、水素原子、ハロゲン原子、Ｃ_1-10飽和脂肪族炭化水素基、ハロゲン化Ｃ_1-10飽和脂肪族炭化水素基、Ｃ_1-8アルコキシ基、カルボキシ基、スルホ基、スルファモイル基又はＮ−置換スルファモイル基を表す。〕 Examples of the yellow dye include a dye containing at least one selected from the group consisting of a compound represented by formula (II) (hereinafter sometimes referred to as “compound (II)”) and a salt thereof.

[In Formula (II), ^Z61 represents an oxygen atom or a sulfur atom.
A ⁶¹ is a phenyl group having one or two at least one group selected from the group consisting of a carboxy group, a sulfo group, a sulfamoyl group and an N-substituted sulfamoyl group, or a sulfo group, a sulfamoyl group and an N-substituted sulfamoyl group. A naphthyl group having 1 to 3 groups of at least one group selected from the group consisting of groups.
R ⁶¹ and R ⁶² are each independently a hydrogen atom, C _1-10 saturated aliphatic hydrocarbon group, C _1-10 saturated aliphatic hydrocarbon radical hydroxy group is substituted, C _1-8 alkoxy group There C _1-10 saturated aliphatic hydrocarbon radical which is substituted, C _1-8 C _1-10 saturated aliphatic hydrocarbon radical thioalkoxy group is substituted, C _6-20 aryl group, C _7-20 Represents an aralkyl group or a C _2-10 acyl group.
R ^{63 to} R ⁶⁶ each independently represent a hydrogen atom, a halogen atom, a C _1-10 saturated aliphatic hydrocarbon group, a halogenated C _1-10 saturated aliphatic hydrocarbon group, a C _1-8 alkoxy group, a carboxy Represents a group, a sulfo group, a sulfamoyl group or an N-substituted sulfamoyl group. ]

The phenyl group of A ⁶¹ may have two kinds of groups selected from the group consisting of a carboxy group, a sulfo group, a sulfamoyl group and an N-substituted sulfamoyl group, and the naphthyl group of A ⁶¹ is a sulfo group 2 or more of at least one group selected from the group consisting of sulfamoyl group and N-substituted sulfamoyl group. ^Examples of the phenyl group or naphthyl group of A ⁶¹ include those having one or both of a sulfo group and an N-substituted sulfamoyl group, and those having only a sulfo group or only an N-substituted sulfamoyl group are preferable. If an N-substituted sulfamoyl group is present, compound (II) is excellent in both water solubility and oil solubility and is preferred as a dye in the field of liquid crystal display devices. A ⁶¹ is preferably a phenyl group having one N-substituted sulfamoyl group or a naphthyl group having two N-substituted sulfamoyl groups, and particularly preferably a phenyl group having one N-substituted sulfamoyl group. .

Specific examples of the phenyl group A ⁶¹ having a sulfo group include those having only a sulfo group, for example, a phenyl group having one sulfo group (2-, 3- or 4-sulfophenyl group), and a phenyl having two sulfo groups Groups (2,4-disulfophenyl group etc.); those having a sulfo group and one other substituent, such as methyl-sulfophenyl group (4-methyl-2-sulfophenyl group, 4-methyl-3- Sulfophenyl group, 2-methyl-3-sulfophenyl group, etc.), dimethyl-sulfophenyl group (4,6-dimethyl-2-sulfophenyl group, etc.), methoxy-sulfophenyl group (4-methoxy-2-sulfophenyl group, etc.) Group, 4-methoxy-3-sulfophenyl group, 2-methoxy-3-sulfophenyl group, 2-methoxy-4-sulfophenyl group, etc.), hydroxy-sulfur Phenyl groups (2-hydroxy-3-sulfophenyl group, 2-hydroxy-4-sulfophenyl group and the like; and those having a sulfo group and two or more other substituents, such as hydroxy-nitro-sulfophenyl group (2 - such as hydroxy-3-nitro-5-sulfophenyl), and the like among these, also referred to as phenyl (mono sulfo phenyl group having one sulfo group);., and sulfo groups and C _1-4 saturated fat A phenyl group having an aromatic hydrocarbon group is preferred, a 3-sulfophenyl group, a 4-sulfophenyl group and a 4-methyl-3-sulfophenyl group are more preferred, and a 4-sulfophenyl group is particularly preferred.

Specific examples of the naphthyl group A ⁶¹ having a sulfo group include a naphthyl group having one sulfo group (5-, 6-, 7- or 8-sulfo-2-naphthyl group, 4-, 5-, 6- or 7 A naphthyl group having two sulfophenyl groups (6,8-, 4,8-, 5,7- or 3,6-disulfo-2-naphthyl group, 3,6- Or a 4,6-disulfo-1-naphthyl group) and a naphthyl group having three sulfo groups (a 3,6,8- or 4,6,8-trisulfo-2-naphthyl group). Among these, a naphthyl group having two sulfophenyl groups (also referred to as a disulfonaphthyl group) is preferable, and a disulfo-2-naphthyl group is more preferable.

Examples of the phenyl or naphthyl group having a sulfamoyl group or an N-substituted sulfamoyl group include examples of a phenyl or naphthyl group having a sulfo group, in which the sulfo group is replaced with a sulfamoyl group or an N-substituted sulfamoyl group. Examples of the N-substituted sulfamoyl group include an N-1 substituted sulfamoyl group, which can be represented by the formula —SO ₂ NHR ⁶⁷ . The R ⁶⁷ is, C _1-10 saturated aliphatic hydrocarbon group, C _1-8 C _1-10 saturated aliphatic hydrocarbon group which alkoxy group is substituted, C _6-20 aryl group, C _7-20 aralkyl Or a C _2-10 acyl group.

The saturated aliphatic hydrocarbon group for R ⁶⁷ may be linear, branched or cyclic. The carbon number of the saturated aliphatic hydrocarbon group does not include the carbon number of the substituent, and the number is 1 to 10, preferably 6 to 10. The saturated aliphatic hydrocarbon group may be substituted with a substituent such as an alkoxy group.
The aryl group for R ⁶⁷ may be unsubstituted or may have a substituent such as an alkyl group or a hydroxy group. Carbon number of the said aryl group is counted including carbon number of a substituent, and is 6-20, Preferably it is 6-10.
The alkyl part of the aralkyl group (arylalkyl group) for R ⁶⁷ may be linear or branched. The carbon number of the aralkyl group is usually 7 to 20, preferably 7 to 10.
The acyl group for R ⁶⁷ may be unsubstituted or may have a substituent such as a saturated aliphatic hydrocarbon group or an alkoxy group. Carbon number of an acyl group is counted including carbon number of a substituent, and the number is 2-10, Preferably it is 6-10.
Specific examples of R ⁶⁷ are the same as those described above for R ⁵⁵ .
R ⁶⁷ is preferably a branched saturated aliphatic hydrocarbon group or an aralkyl group in order to further enhance the color density, oil solubility, and the like.

The phenyl group or naphthyl group of A ⁶¹ is the essential substituent (in the case of phenyl group, at least one of carboxy group, sulfo group, sulfamoyl group and N-substituted sulfamoyl group, in the case of naphthyl group, sulfo group, sulfamoyl group) And at least one of N-substituted sulfamoyl groups), other substituents such as C _1-4 saturated aliphatic hydrocarbon groups (methyl group, ethyl group, etc.), C _1-4 alkoxy groups (methoxy group, An ethoxy group, etc.), a hydroxy group or a nitro group may be used alone or in combination.

The saturated aliphatic hydrocarbon group for R ⁶¹ and R ⁶² may be linear, branched or cyclic. The carbon number of the saturated aliphatic hydrocarbon group does not include the carbon number of the substituent. The carbon number is 1-10, preferably 2-8, more preferably 3-6. Examples of the saturated aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an ethylhexyl group (2-ethylhexyl group, etc. ), A cyclopentyl group, a cyclohexyl group, a cyclohexylalkyl group, and the like. The saturated aliphatic hydrocarbon group includes, as described above, a hydroxy group, a C _1-8 (preferably C _1-4 ) alkoxy group, or a C _1-8 (preferably C _1-4 ) thioalkoxy group. The substituent may be substituted. Examples of the substituted saturated aliphatic hydrocarbon group include a hydroxyethyl group (such as 2-hydroxyethyl group), an ethoxyethyl group (such as 2-ethoxyethyl group), and an ethylhexyloxypropyl group (3- (2-ethylhexyloxy) propyl). Group), methylthiopropyl group (3-methylthiopropyl group, etc.) and the like.

The aryl group of R ⁶¹ and R ⁶² may be unsubstituted or may have a substituent such as a saturated aliphatic hydrocarbon group, an alkoxy group, a carboxy group, a sulfo group, or a group having an ester bond. .
Carbon number of the said aryl group is counted including carbon number of a substituent, and is 6-20, Preferably it is 6-10. Examples of these aryl groups include substituted or unsubstituted phenyl groups such as a phenyl group, 2-, 3-, 4-methylphenyl group, 2-, 3-, 4-sulfophenyl group.

The alkyl part of the aralkyl group of R ⁶¹ and R ⁶² may be either linear or branched. The carbon number of the aralkyl group is counted including the carbon number of the substituent, and is 7 to 20, preferably 7 to 10. Examples of the aralkyl group include a phenylalkyl group such as a benzyl group.

The acyl group of R ⁶¹ and R ⁶² may be unsubstituted or may be bonded to a substituent such as a saturated aliphatic hydrocarbon group or an alkoxy group. Carbon number of an acyl group is counted including carbon number of a substituent, and the number is 2-10 normally, Preferably it is 6-10. Examples of the acyl group include an acetyl group, a benzoyl group, and a methoxybenzoyl group (such as a p-methoxybenzoyl group).

In order to further increase the color density, at least one of R ⁶¹ and R ⁶² (preferably both) is a group having 5 or less (preferably 3 or less) carbon atoms (for example, a methyl group or an ethyl group), hydrogen, It is preferred to select an atom. On the other hand, in order to increase the oil solubility of the azo compound (II), it is desirable to select a group having 6 or more carbon atoms for at least one (preferably both) of R ⁶¹ and R ⁶² , particularly substituted or unsubstituted. An aryl group (preferably a phenyl group) is desirable.

The halogen atom for R ^{63 to} R ⁶⁶ is preferably a fluorine, chlorine or bromine atom.
As in the case of R ⁶¹ and R ⁶² , the saturated aliphatic hydrocarbon group for R ^{63 to} R ⁶⁶ may be linear, branched or cyclic, and the carbon number thereof is 1 to 10, preferably Is 1-8, more preferably 1-4. Specific examples of the saturated aliphatic hydrocarbon group represented by R ^{63 to} R ⁶⁶ include the same as R ⁶¹ and R ⁶² . The saturated aliphatic hydrocarbon group of R ^{63 to} R ⁶⁶ may be substituted with a halogen atom, preferably a fluorine atom. Specific examples of the halogenated saturated aliphatic hydrocarbon group include a trifluoromethyl group.

The number of carbon atoms of the alkoxy groups R ⁶³ to R ⁶⁶ is 1-8, preferably 1-4. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, an n-propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.
Examples of the N-substituted sulfamoyl group for R ^{63 to} R ⁶⁶ include the same groups as those for A ⁶¹ in formula (II).

When A ⁶¹ is a phenyl group or naphthyl group having a sulfo group, in order to increase color density, R ^{63 to} R ⁶⁶ are preferably a hydrogen atom or a C _1-4 saturated aliphatic hydrocarbon group, more preferably One of R ^{63 to} R ⁶⁶ is a C _1-4 saturated aliphatic hydrocarbon group (particularly a methyl group or an ethyl group), and the remainder is a hydrogen atom, more preferably all of R ^{63 to} R ⁶⁶ are hydrogen atoms. is there.

In order to enhance color density and oil solubility, it is preferable to employ a trifluoromethyl group or an N-substituted sulfamoyl group for one or more of R ^{63 to} R ⁶⁶ . The remaining R ^{63 to} R ⁶⁶ are preferably a group other than a sulfo group because the oil solubility is further increased.

In order to enhance light resistance, at least one of R ^{63 to} R ⁶⁶ is a branched aliphatic hydrocarbon group (preferably a tertiary saturated aliphatic hydrocarbon group such as a tert-butyl group), 2 It is preferably a saturated aliphatic hydrocarbon group to which more than one halogen atom is bonded (preferably a saturated aliphatic hydrocarbon group to which three or more halogen atoms such as a trifluoromethyl group are bonded) and an N-substituted sulfamoyl group. .
When the group is bulky, stacking of azo dyes can be reduced, and oil solubility can be increased. Furthermore, when the substitution position is ortho to the azo group, the azo group can be protected and light resistance can be improved.

Of formula (II), preferred examples when A ⁶¹ has a sulfo group include formula (II-1) to formula (II-10).

Of formula (II), preferred examples when A ⁶¹ has an N-substituted sulfamoyl group include formula (II-11) to formula (II-20).

  Examples of the salt of compound (II) include sulfonate and carboxylate. The cations forming these salts are not particularly limited, but they tend to be highly soluble in solvents, so alkali metal salts such as lithium salts, sodium salts and potassium salts; ammonium salts; and ethanolamine salts and alkylamines. Organic amine salts such as salts are preferred. The organic amine salt is useful when it is contained in a resin curable compound. Furthermore, since it is a non-metallic salt, it is also useful in fields where insulation is important.

As is well known in the dye field, compound (II) is obtained by coupling diazonium salt with barbituric acid or thiobarbituric acid (hereinafter referred to as “(thio) barbituric acid”). ). For example, a compound of the formula (IIb) obtained by diazotizing an amine represented by the formula (IIa) (diazo component) with nitrous acid, nitrite or nitrite can be used as the diazonium salt (formula In (IIa) and (IIb), A ⁶¹ and R ^{63 to} R ⁶⁶ represent the same meaning as described above.

Then, the compound (II) can be produced by reacting the diazonium salt (IIb) with the (thio) barbituric acid (coupling component) represented by the formula (IIc) (in the formula (IIc), R ⁶¹ and R ⁶² represent the same meaning as described above).

  For example, preferred examples of the compound having a sulfo group in formula (II) (hereinafter referred to as “azosulfonic acid (II)”) include compounds represented by formulas (II-1) to (II-10), Particularly preferred examples include compounds represented by formulas (II-1), (II-2), (II-5), (II-6) and (II-9).

〔式（ＩＩＩ）中、Ｚ⁷¹及びＺ⁷²は、それぞれ独立に、酸素原子又は硫黄原子を表す。
Ｒ⁷¹〜Ｒ⁷⁴は、それぞれ独立して、水素原子、Ｃ_1-10飽和脂肪族炭化水素基、ヒドロキシ基が置換しているＣ_1-10飽和脂肪族炭化水素基、Ｃ_1-8アルコキシ基が置換しているＣ_1-10飽和脂肪族炭化水素基、Ｃ_1-8チオアルコキシ基が置換しているＣ_1-10飽和脂肪族炭化水素基、Ｃ_6-20アリール基、Ｃ_7-20アラルキル基、又はＣ_2-10アシル基を表す。
Ｒ⁷⁵〜Ｒ⁸²は、それぞれ独立して、水素原子、ハロゲン原子、Ｃ_1-10飽和脂肪族炭化水素基、ハロゲン化Ｃ_1-10飽和脂肪族炭化水素基、Ｃ_1-8アルコキシ基、カルボキシ基、スルホ基、スルファモイル基又はＮ−置換スルファモイル基を表す。〕 Examples of the yellow dye include a dye containing at least one selected from the group consisting of a compound represented by the formula (III) (hereinafter sometimes referred to as “compound (III)”) and salts thereof.

Wherein (III), Z ⁷¹ and Z ⁷² each independently represent an oxygen atom or a sulfur atom.
R ⁷¹ to R ⁷⁴ are each independently a hydrogen atom, C _1-10 saturated aliphatic hydrocarbon group, C _1-10 saturated aliphatic hydrocarbon radical hydroxy group is substituted, C _1-8 alkoxy group There C _1-10 saturated aliphatic hydrocarbon radical which is substituted, C _1-8 C _1-10 saturated aliphatic hydrocarbon radical thioalkoxy group is substituted, C _6-20 aryl group, C _7-20 Represents an aralkyl group or a C _2-10 acyl group.
R ^{75 to} R ⁸² each independently represents a hydrogen atom, a halogen atom, a C _1-10 saturated aliphatic hydrocarbon group, a halogenated C _1-10 saturated aliphatic hydrocarbon group, a C _1-8 alkoxy group, carboxy Represents a group, a sulfo group, a sulfamoyl group or an N-substituted sulfamoyl group. ]

The saturated aliphatic hydrocarbon group for R ^{71 to} R ⁷⁴ may be linear, cyclic, or branched. The carbon number of the saturated aliphatic hydrocarbon group does not include the carbon number of the substituent. The carbon number is 1-10, preferably 2-8, more preferably 3-6. The saturated aliphatic hydrocarbon group has a substituent such as a hydroxy group, a C _1-8 (preferably C _1-4 ) alkoxy group, or a C _1-8 (preferably C _1-4 ) thioalkoxy group. It may be.
Specific examples of the saturated aliphatic hydrocarbon group include the same as those in R ⁶¹ and R ⁶² described above.

The aryl group of R ^{71 to} R ⁷⁴ may be unsubstituted or may have a substituent such as a saturated aliphatic hydrocarbon group, an alkoxy group, a carboxy group, a sulfo group, or a group having an ester bond. . Carbon number of the said aryl group is counted including carbon number of a substituent, and is 6-20, Preferably it is 6-10. Examples of these aryl groups include phenyl group, 2-, 3-, 4-methylphenyl group, 2-, 3-, 4-methoxyphenyl group, 2-, 3-, 4-sulfophenyl group, and ethoxycarbonylphenyl group. Examples thereof include substituted or unsubstituted phenyl groups such as (4- (COOC ₂ H ₅ ) Ph group and the like).

The alkyl part of the aralkyl group (arylalkyl group) of R ^{71 to} R ⁷⁴ may be either linear or branched. The carbon number of the aralkyl group is counted including the carbon number of the substituent, and is usually 7 to 20, preferably 7 to 10. Specific examples of the aralkyl group are the same as those described above for R ⁶¹ and R ^62.

The acyl group of R ^{71 to} R ⁷⁴ may be unsubstituted or may be bonded to a substituent such as a saturated aliphatic hydrocarbon group or an alkoxy group. Carbon number of an acyl group is counted including carbon number of a substituent, and the number is 2-10, Preferably it is 6-10. Specific examples of the acyl group include the same as those described above for R ⁶¹ and R ^62.

In order to further increase the color density, at least one (preferably all) of R ^{71 to} R ⁷⁴ may be a group having 5 or less (preferably 3 or less) carbon atoms (for example, a methyl group or an ethyl group), hydrogen, It is preferred to select an atom. On the other hand, in order to increase the oil solubility of the compound (III), it is desirable to select a group having 6 or more carbon atoms as at least one (preferably all) of R ^{71 to} R ⁷⁴ , and particularly a substituted or unsubstituted aryl. A group (preferably a phenyl group) is desirable.

The halogen atom for R ^{75 to} R ⁸² is preferably a fluorine atom, a chlorine atom or a bromine atom.
The saturated aliphatic hydrocarbon group for R ^{75 to} R ⁸² may be linear, branched or cyclic, as in R ^{71 to} R ⁷⁴ , and the carbon number thereof is preferably 1 to 10, preferably Is 2-8, more preferably 3-6. Specific examples of the saturated aliphatic hydrocarbon group for R ^{75 to} R ⁸² are the same as those for R ^{71 to} R ⁷⁴ . The saturated aliphatic hydrocarbon group of R ^{75 to} R ⁸² may be substituted with a halogen atom, preferably a fluorine atom. Specific examples of the halogenated saturated aliphatic hydrocarbon group include a trifluoromethyl group.

The number of carbon atoms of the alkoxy groups R ⁷⁵ to R ⁸² is 1-8, preferably 1-4. For example, it is the same as those described above for R ⁶³ to R ^66.

The N-substituted sulfamoyl group of R ^{75 to} R ⁸² is, for example, an N-1-substituted sulfamoyl group and can be represented by the formula —SO ₂ NHR ⁸³ group. In this formula, R ⁸³ is, C _1-10 saturated aliphatic hydrocarbon group, C _1-8 C _1-10 saturated aliphatic hydrocarbon group which alkoxy group is substituted, C _6-20 aryl group, C _{7 A -20} aralkyl group or a C _2-10 acyl group.

In order to enhance oil solubility (that is, solubility in an organic solvent), at least one of R ^{75 to} R ⁸² is a branched aliphatic hydrocarbon group (preferably a tertiary group such as a tert-butyl group). A saturated aliphatic hydrocarbon group), a saturated aliphatic hydrocarbon group to which two or more halogen atoms are bonded (preferably a saturated aliphatic hydrocarbon group to which three or more halogen atoms such as a trifluoromethyl group are bonded) and N -A substituted sulfamoyl group is preferred.
Two or more of R ⁷⁵ to R ⁸² (for example, from R ⁷⁵ to R ⁸² 1 or more (in particular one), R ⁷⁵ to R ⁸² 1 or more from (especially one)) to be the above group Preferably, the substitution position of the group is more preferably a meta position or an ortho position with respect to the azo group.
When the group is bulky, stacking of the biphenyl moiety of the azo dye can be reduced, and oil solubility can be increased. Furthermore, when the substitution position is ortho to the azo group, the azo group can be protected and light resistance can be improved.

Preferably, at least one of R ^{75 to} R ⁸² is an N-substituted sulfamoyl group, more preferably at least one of R ^{75 to} R ⁷⁸ and at least one of R ^{79 to} R ⁸² is an N-substituted sulfamoyl group. It is particularly preferred that at least one of R ⁷⁵ and R ⁷⁸ and at least one of R ⁷⁹ and R ⁸² is an N-substituted sulfamoyl group.

The saturated aliphatic hydrocarbon group for R ⁸³ may be linear, branched or cyclic. The carbon number of the saturated aliphatic hydrocarbon group does not include the carbon number of the substituent, and the number is 1 to 10, preferably 6 to 10.
Aryl group R ⁸³ may be unsubstituted or may have a substituent such as a saturated aliphatic hydrocarbon group, or a hydroxy group. Carbon number of the said aryl group is counted including carbon number of a substituent, and is 6-20, Preferably it is 6-10.
The alkyl part of the aralkyl group represented by R ⁸³ may be either linear or branched. The carbon number of the aralkyl group is 7 to 20, preferably 7 to 10.
The acyl group of R ⁸³ may be unsubstituted or may have a substituent such as a saturated aliphatic hydrocarbon group or an alkoxy group. Carbon number of an acyl group is counted including carbon number of a substituent, and the number is 2-10, Preferably it is 6-10.
Specific examples of R ⁸³ include the same as those described above for R ⁵⁵ .

R ⁸³ is, for example, a methylbutyl group (1,1,3,3-tetramethylbutyl group), a methylhexyl group (1,5-dimethylhexyl group) in order to further increase the color density, oil solubility, and the like. Branched chain saturation such as ethylhexyl group (such as 2-ethylhexyl group), methylcyclohexyl group (such as 2-methylcyclohexyl group), phenylbutyl group (such as 3-amino-1-phenylbutyl group) An aliphatic hydrocarbon group or an aralkyl group is preferred.

  Compound (III) may be used alone or in combination of two or more.

When two or more compounds (III) are used in combination, the solubility (oil solubility) in an organic solvent is higher than when one of them is used alone. Since oil solubility tends to be high, it is also preferable to use a combination of two or more kinds of compound (III) as the dye of the liquid crystal display device. Examples of combinations that improve oil solubility include compound (III) (disulfonamide) having two N-substituted sulfamoyl groups and compound (III) (monosulfone having one N-substituted sulfamoyl group and one sulfo group) A combination with amide). Among such combinations, one of R ^{75 to} R ⁷⁸ and one of R ^{79 to} R ⁸² is an N-substituted sulfamoyl group, and the remainder is a hydrogen atom, and R ^{75 to} R A combination with a monosulfonamide in which one of ⁷⁸ is an N-substituted sulfamoyl group, one of R ^{79 to} R ⁸² is a sulfo group, and the remainder is a hydrogen atom is preferred. Monosulfonamide is particularly preferred because it has a lower molecular weight than disulfonamide and tends to increase color density.

Among the compounds (III) having an N-substituted sulfamoyl group, as represented by the formula (III-A), at least one of R ^{75 to} R ⁷⁸ and at least one of R ^{79 to} R ⁸² are —SO ₂ Compounds which are NHR ⁸³ groups with the remainder being hydrogen atoms are preferred.

  Preferred examples of formula (III) include formula (III-1) to formula (III-13).

  Preferable examples of formula (III) include formula (III-14) to formula (III-20).

Examples of the salt of compound (III) include a sulfonate when R ^{75 to} R ⁸² are sulfo groups, and a carboxylate when R ^{75 to} R ⁸² are carboxy groups. The cations forming these salts are not particularly limited, but considering solubility in solvents, alkali metal salts such as lithium salts, sodium salts and potassium salts; ammonium salts; and ethanolamine salts and alkylamine salts. Organic amine salts and the like are preferred. In particular, the organic amine salt is useful when it is contained in a resin curable compound. Further, since it is a non-metallic salt, it is also useful in fields where insulation is important.

As well known in the dye field, compound (III) is obtained by coupling diazonium salt with barbituric acid or thiobarbituric acid (hereinafter referred to as “(thio) barbituric acid”). ). For example, a compound of the formula (IIIb) obtained by diazotizing a benzidine compound (diazo component) represented by the formula (IIIa) with nitrous acid, nitrite or nitrite can be used as the diazonium salt (formula In (IIIa) and (IIIb), R ^{75 to} R ⁸² represent the same meaning as described above.

Compound (III) can be produced by reacting diazonium salt (IIIb) with (thio) barbituric acid (coupling component) represented by formula (IIIc) and formula (IIId) (formula in (IIIc) and formula (IIId), R ⁸⁴ and R ⁸⁵ represent the same meanings as defined above R ⁷¹ ~R ^74).

For example, preferred examples of the compound in which at least one of R ^{75 to} R ⁸² in formula (I) is a sulfo group (hereinafter referred to as “azosulfonic acid (I)”) include formulas (III-1) and (III-3) To (III-13), and particularly preferred examples include formulas (III-1), (III-3), (III-4), (III-5), (III-7). ).

〔式（ＩＶ）中、Ａ⁹¹は、カルボキシ基、スルホ基、スルファモイル基及びＮ−置換スルファモイル基よりなる群から選ばれる少なくとも１種の基を１個又は２個有するフェニル基、或いはスルホ基、スルファモイル基及びＮ−置換スルファモイル基よりなる群から選ばれる少なくとも１種の基を１〜３個有するナフチル基を表す。
Ｒ⁹¹は、水素原子、カルバモイル基、Ｎ−置換カルバモイル基又はシアノ基を表す。
Ｒ⁹²及びＲ⁹³は、それぞれ独立して、水素原子又はＣ_1-6飽和脂肪族炭化水素基を表す。
Ｒ⁹⁴〜Ｒ⁹⁷は、それぞれ独立して、水素原子、ハロゲン原子、Ｃ_1-10飽和脂肪族炭化水素基、ハロゲン化Ｃ_1-10飽和脂肪族炭化水素基、Ｃ_1-8アルコキシ基、カルボキシ基、スルホ基、スルファモイル基又はＮ−置換スルファモイル基を表す。〕 Examples of the yellow dye include a dye containing at least one selected from the group consisting of a compound represented by formula (IV) (hereinafter sometimes referred to as “compound (IV)”) and salts thereof.

[In the formula (IV), A ⁹¹ is a phenyl group having at least one group selected from the group consisting of a carboxy group, a sulfo group, a sulfamoyl group and an N-substituted sulfamoyl group, or a sulfo group, A naphthyl group having 1 to 3 at least one group selected from the group consisting of a sulfamoyl group and an N-substituted sulfamoyl group.
R ⁹¹ represents a hydrogen atom, a carbamoyl group, an N-substituted carbamoyl group or a cyano group.
R ⁹² and R ⁹³ each independently represents a hydrogen atom or a C _1-6 saturated aliphatic hydrocarbon group.
R ^{94 to} R ⁹⁷ each independently represents a hydrogen atom, a halogen atom, a C _1-10 saturated aliphatic hydrocarbon group, a halogenated C _1-10 saturated aliphatic hydrocarbon group, a C _1-8 alkoxy group, carboxy Represents a group, a sulfo group, a sulfamoyl group or an N-substituted sulfamoyl group. ]

The phenyl group of A ⁹¹ may have two or more groups selected from the group consisting of a carboxy group, a sulfo group, a sulfamoyl group and an N-substituted sulfamoyl group, and the naphthyl group of A ⁹¹ is a sulfo group. You may have 2 or more types of at least 1 type chosen from the group which consists of group, a sulfamoyl group, and N-substituted sulfamoyl group. ^Examples of the phenyl group or naphthyl group of A ⁹¹ include those having one or both of a sulfo group and an N-substituted sulfamoyl group, and those having only a sulfo group or only an N-substituted sulfamoyl group are preferable. If an N-substituted sulfamoyl group is present, compound (IV) is excellent in both water solubility and oil solubility and is preferred as a dye in the field of liquid crystal display devices. A ⁹¹ is preferably a phenyl group having one N-substituted sulfamoyl group or a naphthyl group having two N-substituted sulfamoyl groups, and particularly preferably a phenyl group having one N-substituted sulfamoyl group. .
Specific examples of A ⁹¹ include the same as those described above for A ^61.

Examples of the phenyl or naphthyl group having a sulfamoyl group or an N-substituted sulfamoyl group include examples of a phenyl or naphthyl group having a sulfo group, in which the sulfo group is replaced with a sulfamoyl group or an N-substituted sulfamoyl group. Examples of the N-substituted sulfamoyl group include an N-1 substituted sulfamoyl group, which can be represented by the formula —SO ₂ NHR ⁹⁸ . The R ⁹⁸ is, C _1-10 saturated aliphatic hydrocarbon group, C _1-8 C _1-10 saturated aliphatic hydrocarbon group which alkoxy group is substituted, C _6-20 aryl group, C _7-20 aralkyl Or a C _2-10 acyl group.
R ⁹⁸ includes the same as described above for R ⁵⁵ .

A ⁹¹ phenyl group or naphthyl group is the essential substituent (in the case of phenyl group, at least one of carboxy group, sulfo group, sulfamoyl group and N-substituted sulfamoyl group, in the case of naphthyl group, sulfo group, sulfamoyl group and In addition to N-substituted sulfamoyl groups, other substituents such as C _1-4 saturated aliphatic hydrocarbon groups (methyl group, ethyl group, etc.), C _1-4 alkoxy groups (methoxy group, ethoxy) Group, etc.), one or more hydroxy groups or nitro groups.

The saturated aliphatic hydrocarbon group for R ⁹² and R ⁹³ may be linear, branched or cyclic. The carbon number of the saturated aliphatic hydrocarbon group does not include the carbon number of the substituent. The carbon number is 1-6, preferably 1-4, more preferably 1 or 2. The saturated aliphatic hydrocarbon group includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, etc. It is. Since the color density tends to increase, R ⁹² and R ⁹³ are preferably a hydrogen atom or a saturated aliphatic hydrocarbon group having 4 or less (particularly 2 or less) carbon atoms. The saturated aliphatic hydrocarbon group for R ⁹² is preferably a methyl group or an ethyl group, more preferably a methyl group, from the viewpoint of color density and availability. The saturated aliphatic hydrocarbon group for R ⁹³ is preferably a C _2-4 saturated aliphatic hydrocarbon group, more preferably an ethyl group or an n-butyl group, and still more preferably from the viewpoints of color density and availability. An ethyl group.

The halogen atom for R ^{94 to} R ⁹⁷ is preferably a fluorine, chlorine or bromine atom.
The saturated aliphatic hydrocarbon group represented by R ^{94 to} R ⁹⁷ may be linear, branched or cyclic, and has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. It is.
The number of carbon atoms of the alkoxy group of R ^{94 to} R ⁹⁷ is 1 to 8, preferably 1 to 4. Specific examples of R ^{94 to} R ⁹⁷ include the same as those described above for R ^{63 to} R ^66. .

When A ⁹¹ is a phenyl group or naphthyl group having a sulfo group, R ^{94 to} R ⁹⁷ are preferably a hydrogen atom or a C _1-4 saturated aliphatic hydrocarbon group, more preferably, in order to increase color density. Two (especially one) of R ^{94 to} R ⁹⁷ are C _1-4 saturated aliphatic hydrocarbon groups (particularly methyl or ethyl groups), and the rest are hydrogen atoms, more preferably R ^{94 to} R ^97. Are all hydrogen atoms.

In order to increase color density and oil solubility, it is preferable to employ a trifluoromethyl group or an N-substituted sulfamoyl group for one or more of R ^{94 to} R ⁹⁷ . The remaining R ^{94 to} R ⁹⁷ are preferably groups other than sulfo groups, since the oil solubility is further increased.

In order to enhance light resistance, at least one of R ^{94 to} R ⁹⁷ is a branched aliphatic hydrocarbon group (preferably a tertiary saturated aliphatic hydrocarbon group such as a tert-butyl group), 2 It is preferably a saturated aliphatic hydrocarbon group to which more than one halogen atom is bonded (preferably a saturated aliphatic hydrocarbon group to which three or more halogen atoms such as a trifluoromethyl group are bonded) and an N-substituted sulfamoyl group. .
When the group is bulky, stacking of azo dyes can be reduced, and oil solubility can be increased. Furthermore, when the substitution position is ortho to the azo group, the azo group can be protected and light resistance can be improved.

Of formula (IV), preferred examples when A ⁹¹ has a sulfo group include formula (IV-1) to formula (IV-11).

Of formula (IV), preferred examples when A ⁹¹ has an N-substituted sulfamoyl group include formula (IV-12) to formula (IV-19).

  Examples of the salt of compound (IV) include sulfonate and carboxylate. The cations forming these salts are not particularly limited, but they tend to be highly soluble in solvents, so alkali metal salts such as lithium salts, sodium salts and potassium salts; ammonium salts; and ethanolamine salts and alkylamines. Organic amine salts such as salts are preferred. The organic amine salt is useful when it is contained in a resin curable compound. Furthermore, since it is a non-metallic salt, it is also useful in fields where insulation is important.

Compound (IV) can be produced by a method similar to the production method of compound (I) by coupling a diazonium salt and pyridones, as is well known in the dye field. For example, a compound of the formula (IVb) obtained by diazotizing an amine represented by the formula (IVa) (diazo component) with nitrous acid, nitrite or nitrite can be used as the diazonium salt (formula In (IVa) and (IVb), A ⁹¹ and R ^{94 to} R ⁹⁷ represent the same meaning as described above.

Then the diazonium salt (IVb), by reacting a pyridone compound represented by the formula (IVc) (coupling component), in can be prepared a compound (IV) (Formula (IVc), R ⁹¹ ~ R ⁹³ represents the same meaning as described above).

  For example, preferred examples of the compound having a sulfo group in formula (IV) (hereinafter referred to as “azosulfonic acid (IV)”) include compounds represented by formulas (IV-1) to (IV-11), Particularly preferred examples include those represented by the formulas (IV-1), (IV-2), (IV-5), (IV-6), (IV-8), (IV-9) and (IV-11). The compound which is made is mentioned.

〔式（Ｖ）中、Ａ¹⁰¹は、カルボキシ基、スルホ基、スルファモイル基及びＮ−置換スルファモイル基よりなる群から選ばれる少なくとも１種の基を１個又は２個有するフェニル基、或いはスルホ基、スルファモイル基及びＮ−置換スルファモイル基よりなる群から選ばれる少なくとも１種の基を１〜３個有するナフチル基を表す。
Ｒ¹⁰¹及びＲ¹⁰²は、それぞれ独立して、水素原子又はＣ_1-6飽和脂肪族炭化水素基を表す。
Ｒ¹⁰³及びＲ¹⁰⁴は、それぞれ独立して、水素原子、Ｃ_1-10飽和脂肪族炭化水素基、Ｃ_1-8アルコキシ基が置換しているＣ_1-10飽和脂肪族炭化水素基、Ｃ_6-20アリール基、Ｃ_7-20アラルキル基、又はＣ_2-10アシル基を表す。〕 Examples of the yellow dye include a dye containing at least one selected from the group consisting of a compound represented by the formula (V) (hereinafter sometimes referred to as “compound (V)”) and a salt thereof.

[In the formula (V), A ¹⁰¹ represents a phenyl group having at least one group selected from the group consisting of a carboxy group, a sulfo group, a sulfamoyl group and an N-substituted sulfamoyl group, or a sulfo group, A naphthyl group having 1 to 3 at least one group selected from the group consisting of a sulfamoyl group and an N-substituted sulfamoyl group.
R ¹⁰¹ and R ¹⁰² each independently represents a hydrogen atom or a C _1-6 saturated aliphatic hydrocarbon group.
R ¹⁰³ and R ¹⁰⁴ each independently represents a hydrogen atom, C _1-10 saturated aliphatic hydrocarbon group, C _1-8 C _1-10 saturated aliphatic hydrocarbon group which alkoxy group is substituted, C _{6 -20 represents an} aryl group, a C _7-20 aralkyl group, or a C _2-10 acyl group. ]

The phenyl group of A ¹⁰¹ may have two or more groups selected from the group consisting of a carboxy group, a sulfo group, a sulfamoyl group and an N-substituted sulfamoyl group, and the naphthyl group of A ¹⁰¹ is a sulfo group. You may have 2 or more types of at least 1 type chosen from the group which consists of group, a sulfamoyl group, and N-substituted sulfamoyl group. ^Examples of the phenyl group or naphthyl group of A ¹⁰¹ include those having one or both of a sulfo group and an N-substituted sulfamoyl group, and those having only a sulfo group or only an N-substituted sulfamoyl group are preferable. If an N-substituted sulfamoyl group is present, the compound (V) is excellent in both water solubility and oil solubility, and is preferred as a dye in the field of liquid crystal display devices. A ¹⁰¹ is preferably a phenyl group having one N-substituted sulfamoyl group or a naphthyl group having two N-substituted sulfamoyl groups, and particularly preferably a phenyl group having one N-substituted sulfamoyl group. .

Specific examples of the phenyl group A ¹⁰¹ having a sulfo group include those having a sulfo group and a carboxy group, that is, a carboxy-sulfophenyl group (such as 2-carboxy-4-sulfophenyl); those having only a sulfo group, such as 1 A phenyl group having two sulfo groups (2-, 3- or 4-sulfophenyl group), a phenyl group having two sulfo groups (such as 2,4-disulfophenyl group); a sulfo group and one other substitution Having a group such as methyl-sulfophenyl group (4-methyl-2-sulfophenyl group, 4-methyl-3-sulfophenyl group, 2-methyl-3-sulfophenyl group, 2-methyl-5-sulfophenyl group) Group), dimethyl-sulfophenyl group (4,6-dimethyl-2-sulfophenyl group, 2,4-dimethyl-6-sulfophenyl group), methoxy Si-sulfophenyl group (4-methoxy-2-sulfophenyl group, 4-methoxy-3-sulfophenyl group, 2-methoxy-3-sulfophenyl group, 2-methoxy-4-sulfophenyl group, etc.), hydroxy- A sulfophenyl group (2-hydroxy-3-sulfophenyl group, 2-hydroxy-4-sulfophenyl group, 2-hydroxy-5-sulfophenyl group, etc.); and a sulfo group and two or more other substituents And, for example, a hydroxy-nitro-sulfophenyl group (such as 2-hydroxy-3-nitro-5-sulfophenyl group). Among these, from the viewpoint of color density and water solubility, a phenyl group having one sulfo group (also referred to as a monosulfophenyl group); a phenyl group having a sulfo group and a hydroxy group; a phenyl group having a sulfo group and a methyl group; and A phenyl group having a sulfo group and a methoxy group is preferred, a 3-sulfophenyl group, a 4-sulfophenyl group and a 4-methyl-3-sulfophenyl group are more preferred, and a 4-sulfophenyl group is particularly preferred.

As a specific example of the naphthyl group A ¹⁰¹ having a sulfo group, a naphthyl group having one sulfo group (5-, 6-, 7- or 8-sulfo-2-naphthyl group, 4-, 5-, 6- or 7 A naphthyl group having two sulfophenyl groups (6,8-, 4,8-, 5,7- or 3,6-disulfo-2-naphthyl group, 3,6- Or a 4,6-disulfo-1-naphthyl group) and a naphthyl group having three sulfo groups (a 3,6,8- or 4,6,8-trisulfo-2-naphthyl group). Among these, a naphthyl group having two sulfophenyl groups (also referred to as a disulfonaphthyl group) is preferable, a disulfo-2-naphthyl group is more preferable, and a 6,8-disulfo-2-naphthyl group is more preferable.

Examples of the phenyl or naphthyl group having a sulfamoyl group or an N-substituted sulfamoyl group include examples of a phenyl or naphthyl group having a sulfo group, in which the sulfo group is replaced with a sulfamoyl group or an N-substituted sulfamoyl group. Examples of the N-substituted sulfamoyl group include an N-1 substituted sulfamoyl group, which can be represented by the formula —SO ₂ NHR ¹⁰⁵ . The R ¹⁰⁵ is, C _1-10 saturated aliphatic hydrocarbon group, C _1-8 C _1-10 saturated aliphatic hydrocarbon group which alkoxy group is substituted, C _6-20 aryl group, C _7-20 aralkyl Or a C _2-10 acyl group.

^Examples of R ¹⁰⁵ include the same as those described above for R ⁵⁵ .
R ¹⁰⁵ is preferably a branched saturated aliphatic hydrocarbon group or an aralkyl group in order to further enhance color density, oil solubility, and the like.

The phenyl group or naphthyl group of A ¹⁰¹ is the essential substituent (in the case of phenyl group, at least one of carboxy group, sulfo group, sulfamoyl group and N-substituted sulfamoyl group, in the case of naphthyl group, sulfo group, sulfamoyl group and In addition to N-substituted sulfamoyl groups, other substituents such as C _1-4 saturated aliphatic hydrocarbon groups (methyl group, ethyl group, etc.), C _1-4 alkoxy groups (methoxy group, ethoxy) Group, etc.), one or more hydroxy groups or nitro groups.

The saturated aliphatic hydrocarbon group for R ¹⁰¹ and R ¹⁰² may be linear, branched or cyclic. The carbon number of the saturated aliphatic hydrocarbon group does not include the carbon number of the substituent. The carbon number is 1-6, preferably 1-4, more preferably 1 or 2. The saturated aliphatic hydrocarbon group includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, etc. It is. Since the color density increases, R ¹⁰¹ and R ¹⁰² are preferably a hydrogen atom or a saturated aliphatic hydrocarbon group having 4 or less carbon atoms. The saturated aliphatic hydrocarbon group for R ¹⁰¹ is preferably a C _2-4 saturated aliphatic hydrocarbon group, more preferably an ethyl group or an n-butyl group, further preferably from the viewpoint of color density and availability. An ethyl group. The saturated aliphatic hydrocarbon group for R ¹⁰² is preferably a methyl group or an ethyl group, more preferably a methyl group, from the viewpoint of color density and availability.

The saturated aliphatic hydrocarbon group, aryl group, aralkyl group and acyl group for R ¹⁰³ and R ¹⁰⁴ are the same as those described above for R ⁵⁵ . In order to increase the color density, at least one of R ¹⁰³ and R ¹⁰⁴ (preferably both) is a saturated aliphatic hydrocarbon group having 3 or less carbon atoms (eg, a methyl group, an ethyl group, etc., particularly a methyl group). It is preferable to select a hydrogen atom. In order to enhance the solubility, it is preferable to select an acetyl group for at least one of R ¹⁰³ and R ¹⁰⁴ .

Of formula (V), preferred examples when A ¹⁰¹ has a sulfo group include formulas (V-1) to (V-13).

Of formula (V), preferred examples when A ¹⁰¹ has an N-substituted sulfamoyl group include formulas (V-14) to (V-17).

  Examples of the salt of compound (V) include sulfonate and carboxylate. The cations forming these salts are not particularly limited, but considering solubility in solvents, alkali metal salts such as lithium salts, sodium salts and potassium salts; ammonium salts; and ethanolamine salts and alkylamine salts. Organic amine salts and the like are preferred. The organic amine salt is useful when it is contained in a resin curable compound. Furthermore, since it is a non-metallic salt, it is also useful in fields where insulation is important.

Compound (V) can be produced by a method similar to the production method of compound (I) by coupling a diazonium salt and pyridones, as is well known in the dye field. For example, the formula (Va):
A ¹⁰¹ -NH ₂ (Va)
Formula (Vb) obtained by diazotizing amines (diazo component) represented by the formula (N) with nitrous acid, nitrite or nitrite
A ¹⁰¹ −N≡N ⁺ (Vb)
Can be used as the diazonium salt (in formulas (Va) and (Vb), A ¹⁰¹ represents the same meaning as described above).

Then the diazonium salt (Vb), by reacting a pyridone compound represented by the formula (Vc) (coupling component), in can be prepared a compound (V) (wherein (Vc), R ¹⁰¹ to R ¹⁰⁴ represents the same meaning as described above).

  For example, preferable examples of the compound having a sulfo group in formula (V) (hereinafter referred to as “azosulfonic acid (V)”) include compounds represented by formulas (V-1) to (V-3), Particularly preferred examples include compounds represented by formulas (V-1) and (V-2).

  The content of the yellow dye in the colorant (A) is preferably 1% to 50% and more preferably 1% to 30% with respect to the colorant (A).

Content of a coloring agent (A) is a mass fraction with respect to solid content in a coloring photosensitive resin composition, Preferably it is 25-60 mass%, More preferably, it is 27-55 mass%, Furthermore, Preferably it is 30-50 mass%. Here, the solid content in the colored photosensitive resin composition refers to the total amount of components excluding the solvent contained in the colored photosensitive resin composition.
Other dyes may be used in combination as long as the effects of the present invention are not affected.
When the content of the colorant (A) is in the above range, the color density when a color filter is obtained is sufficient, and the binder resin (B) can be contained in the composition in a necessary amount. This is preferable because a pattern with sufficient strength can be formed.

  The colored photosensitive resin composition of the present invention contains a binder resin (B). The binder resin (B) preferably contains a structural unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid. The content of the structural unit derived from the (meth) acrylic acid is a mole fraction, preferably 16 to 16 when the total mole number of all the structural units constituting the binder resin (B) is 100 mol%. It is 40 mol%, More preferably, it is 18-38 mol%. When the content of the structural unit derived from (meth) acrylic acid is within the above range, the solubility of the non-pixel portion is good during development, and the residue tends not to remain in the non-pixel portion after development. Yes, it is preferable.

  Examples of the other monomer that leads to the constituent unit of the binder resin other than the constituent unit derived from (meth) acrylic acid include, for example, aromatic vinyl compounds, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, and unsaturated compounds. Carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, vinyl cyanide compounds, unsaturated amides, unsaturated imides, aliphatic conjugated dienes, monoacryloyl group or mono at the end of the polymer molecular chain Examples thereof include macromonomers having a methacryloyl group and compounds capable of introducing a polymerizable unsaturated bond into the side chain. Examples of the compound capable of introducing a polymerizable unsaturated bond into the side chain include a compound that derives a unit represented by the formula (BI) and a compound that derives a unit represented by the formula (B-III). be able to.

[In formula (BI) and formula (B-III), Q ¹ and Q ² each independently represents a hydrogen atom or a C _1-6 alkyl group. ]

Specific examples of the binder resin include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate copolymer, and methacrylic acid / styrene. / Benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / constituent component represented by formula (BI) (wherein, in formula (BI), Q ¹ represents a methyl group, Q ² represents a hydrogen atom) / benzyl methacrylate copolymer, a component represented by formula (BI) (wherein, in formula (BI), Q ¹ represents a methyl group, Q ² represents a hydrogen atom.) / Benzyl methacrylate copolymer, methacrylic acid / constituent component represented by formula (B-III) Here, in formula (B-III), Q ¹ represents a methyl group, and Q ² represents a hydrogen atom.) / Styrene copolymer / tricyclodecanyl methacrylate copolymer, etc., preferably, Methacrylic acid / constituent component represented by formula (BI) (in the formula (BI), Q ¹ represents a methyl group and Q ² represents a hydrogen atom) / benzyl methacrylate. Polymer, component represented by formula (BI) (wherein, in formula (BI), Q ¹ represents a methyl group and Q ² represents a hydrogen atom) / benzyl methacrylate. Polymer, methacrylic acid / constituent component represented by formula (B-III) (wherein, in formula (B-III), Q ¹ represents a methyl group and Q ² represents a hydrogen atom) / Styrene copolymer / tricyclodecanyl methacrylate copolymer And the like.
Use of a resin having a polymerizable unsaturated bond in the side chain is preferred because the resulting coating film tends to have high solvent resistance.

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

  Content of binder resin (B) is a mass fraction with respect to solid content of a coloring photosensitive resin composition, and is 10-35 mass%, Preferably it is 12-33 mass%, More preferably, it is 13- 32% by mass. When the content of the binder resin (B) is in the above range, a pattern can be formed and the resolution and the remaining film ratio tend to be improved.

Binder resin having a component represented by the formula (BI), for example, methacrylic acid / component represented by the formula (BI) (here, Q ^{1 in the} formula (BI)) Represents a methyl group, R ² represents a hydrogen atom.) / Benzyl methacrylate copolymer is obtained by polymerizing methacrylic acid and benzyl methacrylate to obtain a two-component polymer, and the obtained two-component polymer and formula It can be obtained by reacting with a compound represented by (B-II) (here, Q ² represents a hydrogen atom in formula (B-II)).

Methacrylic acid / constituent component represented by formula (B-III) (wherein, in formula (B-III), Q ¹ represents a methyl group and Q ² represents a hydrogen atom) / styrene copolymer. The combined / tricyclodecanyl methacrylate copolymer can be obtained by reacting benzyl methacrylate, methacrylic acid, or a monomethacrylate copolymer having a tricyclodecane skeleton with glycidyl methacrylate.

  The polystyrene-reduced weight average molecular weight of the binder resin is 5,000 to 35,000, preferably 6,000 to 30,000, and more preferably 7,000 to 28,000. When the weight average molecular weight in terms of polystyrene is within the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility in the developing solution in the unexposed area is good, and the resolution tends to be improved.

  The colored photosensitive resin composition of the present invention contains a photopolymerizable compound (C). The photopolymerizable compound (C) is a compound that can be polymerized by an active radical, an acid, or the like generated from the photopolymerization initiator (D) when irradiated with light, and is, for example, polymerizable carbon-carbon unsaturated. Examples thereof include compounds having a bond.

The photopolymerizable compound (C) is preferably a trifunctional or higher functional photopolymerizable compound. Examples of the tri- or higher functional photopolymerizable compound include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. .
The photopolymerizable compounds (C) may be used alone or in combination of two or more.
Content of a photopolymerizable compound (C) is a mass fraction with respect to a colored photosensitive resin composition, Preferably it is 5-90 mass%, More preferably, it is 10-80 mass%, More preferably It is 20-70 mass%, Most preferably, it is 20-50 mass%, Most preferably, it is 20-35 mass%. When the content of the photopolymerizable compound (C) is in the above range, the coating film is sufficiently cured, the film thickness ratio before and after development is improved, and the undercut is difficult to enter into the pattern. It is preferable because it tends to be good.

The colored photosensitive resin composition of the present invention contains a photopolymerization initiator (D). Examples of the photopolymerization initiator (D) include acetophenone compounds, active radical generators, and acid generators.
Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, and 2-hydroxy-2-methyl-1-phenylpropane-1. -One, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1 -[4- (1-methylvinyl) phenyl] propan-1-one oligomers, and the like, preferably 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and the like. It is done.

  The active radical generator generates active radicals when irradiated with light. Examples of the active radical generator include benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, and oxime compounds.

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

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butyl). Peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

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

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

  Examples of the oxime compounds include O-acyloxime compounds, and specific examples thereof include 1- (4-phenylsulfanyl-phenyl) -butane-1,2-dione 2-oxime-O—. Benzoate, 1- (4-phenylsulfanyl-phenyl) -octane-1,2-dione 2-oxime-O-benzoate, 1- (4-phenylsulfanyl-phenyl) -octane-1-one oxime-O-acetate 1- (4-phenylsulfanyl-phenyl) -butan-1-one oxime-O-acetate and the like. Examples of the commercially available product include Irgacure OXE01 (manufactured by Ciba Japan).

  Examples of active radical generators other than those exemplified above include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl- 1,2′-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound, etc. can also be used. .

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

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

  Content of a photoinitiator (D) is a mass fraction with respect to the total amount of a binder polymer (B) and a photopolymerizable compound (C), Preferably it is 0.1-35 mass parts, More preferably Is 3 to 25% by mass. When the content of the photopolymerization initiator is within the above range, the sensitivity is increased, the exposure time is shortened, and the productivity is improved. On the other hand, the line width of the line and space pattern is resolved due to the sensitivity being too high. Is preferable because the line width tends not to be too large.

The colored photosensitive resin composition of the present invention may further contain a photopolymerization initiation aid (G). The photopolymerization initiation assistant (G) is usually used in combination with the photopolymerization initiator (D), and used to accelerate the polymerization of the photopolymerizable compound (C) whose polymerization has been initiated by the photopolymerization initiator. Compound.
Examples of the photopolymerization initiation aid (G) include amine compounds, alkoxyanthracene compounds, and thioxanthone compounds.
Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylbenzoate. Aminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4, Examples thereof include 4′-bis (ethylmethylamino) benzophenone, and among these, 4,4′-bis (diethylamino) benzophenone is preferable.

  Examples of the alkoxyanthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be mentioned.

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

  The photopolymerization initiation assistant (G) may be used alone or in combination of two or more. Moreover, as a photoinitiation adjuvant (G), a commercially available thing can also be used, and as a commercially available photoinitiation assistant (G), brand name "EAB-F" (Hodogaya Chemical Industry ( Etc.).

  Examples of the combination of the photopolymerization initiator (D) and the photopolymerization initiation assistant (G) in the colored photosensitive resin composition of the present invention include, for example, diethoxyacetophenone / 4,4′-bis (diethylamino) benzophenone, 2- Methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one / 4 4′-bis (diethylamino) benzophenone, benzyldimethyl ketal / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one / 4,4′-bis (diethylamino) benzophenone, 1-hydroxycyclohexylphenylke / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one oligomer / 4,4′-bis (diethylamino) ) Benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone, etc., preferably 2-methyl-2-morpholino Examples include -1- (4-methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone.

  When using these photoinitiator adjuvant (G), the usage-amount is 0.01-10 mol with respect to 1 mol of photoinitiators (D), Preferably it is 0.01-5 mol.

The colored photosensitive resin composition of the present invention may contain a crosslinking improver (E). When a crosslinking improver is included, the chemical resistance of the resulting coating film tends to be good, which is preferable.
As said crosslinking improving agent (E), an epoxy-type compound, a melamine derivative, etc. are mentioned, Preferably an epoxy-type compound is mentioned.
Examples of the epoxy compound include aromatic epoxy resins such as bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol F type epoxy resins, and novolak type epoxy resins, and fats. Cyclic epoxy resin, heterocyclic epoxy resin, glycidyl ester type resin, glycidyl amine type resin, epoxy resin such as epoxidation, brominated derivatives of the above epoxy resins, epoxidized products of aliphatic compounds, alicyclic compound epoxy Epoxides of aromatic compounds, epoxy compounds of aromatic compounds, epoxidized products of butadiene (co) polymers, epoxidized products of isoprene (co) polymers, (co) polymers of glycidyl (meth) acrylate, triglycidyl isocyanurate, etc. Preferably bisphenol A type epoxy resins, aromatic epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins.
The content of the crosslinking improver (E) in the colored photosensitive resin composition of the present invention is preferably 2 parts by mass or more with respect to 100 parts by mass of the total amount of the binder resin (B) and the photopolymerizable compound (C). Is 4 parts by mass or more, more preferably 10 parts by mass or more, particularly preferably 20 parts by mass or more, and 40 parts by mass or less, preferably 35 parts by mass or less.

  The colored photosensitive resin composition of the present invention contains a solvent (F). Examples of the solvent (F) include ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, N-methylpyrrolidone, dimethyl sulfoxide and the like.

Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol methyl ethyl ether. , Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol model Methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, methoxybutyl acetate, methoxypentyl acetate, anisole, phenetole, methylanisole Etc.
Examples of the aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.
Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, and cyclohexanone.
Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, hydroxymethylpentanone, methoxybutanol and the like.
Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3 -Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2- Ethyl methyl propionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutane Examples include methyl acid, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and γ-butyrolactone.
Examples of the amides include N, N-dimethylformamide and N, N-dimethylacetamide.
Among these, propylene glycol monomethyl ether acetate, ethyl lactate, and 4-hydroxy-4-methyl-2-pentanone are preferable, and it is more preferable to use these in combination.
Furthermore, the said solvent may be used individually or in combination of 2 or more types.

  Content of the solvent (F) in a colored photosensitive resin composition is a mass fraction with respect to a colored photosensitive resin composition, Preferably it is 70-95 mass%, More preferably, it is 75-90 mass%. . If the content of the solvent (F) is in the above range, the flatness at the time of coating will be good, and when the color filter is formed, the color density will not be insufficient and the display characteristics will tend to be good. preferable.

The colored photosensitive resin composition of the present invention may further contain a surfactant (H). Examples of the surfactant (H) include at least one selected from the group consisting of a silicone surfactant, a fluorine surfactant, and a silicone surfactant having a fluorine atom.
Examples of the silicone surfactant include surfactants having a siloxane bond. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH29PA, SH30PA, polyether-modified silicone oil SH8400 (trade name: Torresilicone; manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials) Japan GK)).
Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, Florard (trade name) FC430, FC431 (Sumitomo 3M Co., Ltd.), MegaFac (trade name) F142D, F171, F172, F173, F177, F177, F183, R30 (DIC) ), Ftop (trade name) EF301, EF303, EF351, EF351, EF352 (Mitsubishi Materials Electronics Chemicals), Surflon (tradename) S381, S382, SC101, SC105 (Asahi Glass) Co., Ltd.), E5844 (Daikin Fine Chemical Laboratory Co., Ltd.), BM-1000, BM-1100 (both trade names: manufactured by BM Chemie), and the like.
Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, MegaFuck (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation) and the like can be mentioned.
These surfactants may be used alone or in combination of two or more.
Content of surfactant (H) is a mass fraction with respect to a colored photosensitive resin composition, Preferably it is 0.0005-0.6 mass%, More preferably, it is 0.001-0.5 mass%. It is. When the content of the surfactant (H) is in the above range, the flatness of the resulting coating film tends to be favorable when the colored photosensitive resin composition is applied, which is preferable.

As a method for forming a color filter pattern using the colored photosensitive resin composition of the present invention, for example, the colored photosensitive resin composition of the present invention is applied to a substrate or another resin layer (for example, on a substrate). After the development, the colored layer is exposed to light through a photomask to form a colored layer by removing volatile components such as a solvent. A photolithography method that is cured by at least one of heating or exposure and a colored photosensitive resin composition are applied onto a substrate or another resin layer by an inkjet apparatus, and volatile components such as a solvent are removed for coloring. Examples thereof include an ink jet method in which a layer is formed and cured by at least one of heating and exposure.
Examples of the apparatus used for the coating include a spin coater, a slit coater, a curtain flow coater, a cast coating apparatus, and an inkjet apparatus.
In order to remove a volatile component such as a solvent, for example, the solvent can be removed by heating or reducing the pressure.
The photomask is formed with a light-shielding portion and a non-light-shielding portion according to the required pattern shape.
For example, exposure is performed using an apparatus such as a stepper or a mask aligner using a light source such as g-line, h-line, or i-line.
The colored layer after exposure is developed to form a pattern.
The development processing is performed using a developing device, and is usually performed by immersing in an alkaline solution or spraying the alkaline solution onto the colored layer. After the development, a rinsing process is usually performed to remove the alkaline solution that has contacted the colored layer.
After the rinsing treatment, the colored layer is usually dried using a drying device such as a dryer.
The colored layer after drying is cured by heating or exposure to obtain a pattern.

The obtained pattern forms a red layer of a color filter. For example, a green layer and a blue layer are separately formed, and these can be combined to form a color filter.
The red layer may be formed in a different order from other color layers.
Since the obtained color filter has good heat resistance, it is possible to manufacture, for example, an excellent quality image sensor or display device color filter.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples. Moreover, in the following Examples and Comparative Examples,% and part representing the content or amount used are based on mass unless otherwise specified.

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

  About the measurement of the polystyrene conversion weight average molecular weight of said resin, it carried out on condition of the following using GPC method.

Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Test liquid solid concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Reference material for calibration; TSK STANDARD POLYSTYRENE
F-40, F-4, F-1, A-2500, A-500
(Manufactured by Tosoh Corporation)

Synthesis example 2
After adding 80 parts of water to 10.5 parts of 2-amino-4-nitrophenol represented by the formula (a-1), 16.3 parts of 35% hydrochloric acid was added little by little under ice cooling, and dissolved. 24.7 parts of a 20% aqueous sodium nitrite solution was added and stirred for 2 hours to obtain a suspension containing a diazonium salt.

  After adding 65 parts of water and 3 parts of sodium hydroxide to 19 parts of 3-methyl-1- (4-sulfophenyl) -5-pyrazolone represented by the formula (c-1), 10% acetic acid was added under ice cooling. 100 parts of an aqueous sodium solution was added to obtain a pyrazolone solution.

  The following operations were performed under ice cooling. While stirring the pyrazolone solution, the suspension containing the diazonium salt was added dropwise by a pump over 15 minutes. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a dark solution. 20 parts of purified salt (sodium chloride) was added to the reaction solution and stirred for 1 hour. The red solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 27.1 parts (yield 95%) of the azo compound represented by the formula (b-1).

  After 150 parts of water and 100 parts of dimethylformamide are added and dissolved in 18.2 parts of the azo compound represented by the formula (b-1), 2.8 parts of chromium formate is added and heated at 100 ° C. for 5 hours. And a dark solution was obtained by stirring. After cooling to 25 ° C, 12 parts of a 20% aqueous sodium hydroxide solution was added, and after stirring for 30 minutes, 60 parts of purified salt (sodium chloride) was added to the reaction solution and stirred for 30 minutes. The dark solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 13.0 parts (yield 95%) of a chromium complex salt represented by the formula (AI-0).

得られた式（Ａ−Ｉ−０）で表されるクロム錯塩９．１部にメタノール２００部とジメチルホルムアミド１００部を加え溶解した後、式（ＩＩ−１１３）で表されるローダミン化合物４．８部を加え、３０分間撹拌することで暗赤色溶液を得た。減圧下５０℃で濃縮し、暗色固体を得た。得られた暗色固体に水２５０部を加え、濾過して得た暗色固体を減圧下６０℃で乾燥し、式（Ａ−Ｉ−１）で表される化合物を１０．６部（収率７６％）得た。式（ｅ−１）で表される化合物の透過率を、紫外可視分光光度計（Ｖ‐６５０ＤＳ；日本分光社製）（石英セル、光路長；１ｃｍ）を用いて測定した。図１は、式（Ａ−Ｉ−１）で表される化合物の透過率を示すグラフである。縦軸は透過率（％）を、横軸は波長（ｎｍ）を表す。

After adding 200 parts of methanol and 100 parts of dimethylformamide to 9.1 parts of the chromium complex salt represented by the formula (AI-0), the rhodamine compound represented by the formula (II-113) is dissolved. 8 parts were added and stirred for 30 minutes to obtain a dark red solution. Concentration at 50 ° C. under reduced pressure gave a dark solid. 250 parts of water was added to the obtained dark solid, and the dark solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 10.6 parts (yield 76) of the compound represented by the formula (AI-1). %)Obtained. The transmittance of the compound represented by the formula (e-1) was measured using an ultraviolet-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). FIG. 1 is a graph showing the transmittance of the compound represented by the formula (A-I-1). The vertical axis represents transmittance (%), and the horizontal axis represents wavelength (nm).

The structure of the compound represented by the formula (A-I-1) was determined by elemental analysis. As an analytical instrument, an ICP emission analyzer (ICPS-8100; manufactured by Shimadzu Corporation) was used.
C58.0 H5.1 N9.7 Cr1.11

実施例１
［着色感光性樹脂組成物１の調製］
（Ａ）着色剤：式（Ａ−Ｉ−１）で表される化合物 ６６ 部
（Ａ）着色剤：式（Ｉａ）で表される化合物 １７ 部
（Ａ）着色剤：Ｃ．Ｉ．ソルベントレッド１２５
（オラゾールレッドＧ；チバ・ジャパン社製） １７ 部
（Ｂ）樹脂：樹脂溶液Ｂ１ １５７ 部
（Ｃ）光重合性化合物：ジペンタエリスリトールヘキサアクリレート
（ＫＡＹＡＲＡＤ ＤＰＨＡ；日本化薬（株）製） ５０ 部
（Ｄ）光重合開始剤：イルガキュアＯＸＥ０１
（チバ・ジャパン社製） １５ 部
（Ｅ）溶剤：プロピレングリコールモノメチルエーテルアセテート １８９ 部
（Ｅ）溶剤：ジアセトンアルコール １００ 部
を混合して着色感光性樹脂組成物１を得た。

Example 1
[Preparation of colored photosensitive resin composition 1]
(A) Colorant: Compound represented by formula (AI-1) 66 parts (A) Colorant: Compound represented by formula (Ia) 17 parts (A) Colorant: C.I. I. Solvent Red 125
(Orazol Red G; manufactured by Ciba Japan) 17 parts (B) Resin: Resin solution B1 157 parts (C) Photopolymerizable compound: Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 Part (D) Photopolymerization initiator: Irgacure OXE01
(Ciba Japan Co., Ltd.) 15 parts (E) Solvent: 189 parts of propylene glycol monomethyl ether acetate (E) Solvent: 100 parts of diacetone alcohol were mixed to obtain a colored photosensitive resin composition 1.

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

[Evaluation]
Except not using a photomask, the same operation as pattern formation was performed and the cured coating film was obtained. About the obtained cured coating film, the xy chromaticity coordinates (Rx, Ry) in the XYZ color system of CIE were measured using a C light source with a colorimeter (OSP-SP-200; manufactured by Olympus Corporation). The contrast was measured using a contrast meter (color difference meter BM-5A; manufactured by Topcon Corporation). The results are shown in Table 1.

Comparative Example 1
[Preparation of Comparative Colored Photosensitive Resin Composition 1]
(A) Colorant: C.I. I. Pigment Red 177 46 parts (A) Colorant: C.I. I. Pigment Red 254 43 parts (A) Colorant: Compound represented by the following formula (6) containing melamine as a guest compound (commonly known as Pigment Yellow 150) 11 parts Acrylic pigment dispersant 5 parts Propylene glycol monomethyl ether acetate 137 parts And thoroughly disperse the pigment using a bead mill,
(B) Resin: Resin solution B1 157 parts (C) Photopolymerizable compound: Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Photopolymerization initiator: OXE-01
(Ciba Japan Co., Ltd.) 15 parts (E) Solvent: 289 parts of propylene glycol monomethyl ether acetate were mixed to obtain comparative colored photosensitive resin composition 1. A pattern having a thickness of 2.2 μm was formed and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2
[Preparation of comparatively colored photosensitive resin composition 2]
(A) Colorant: Compound represented by formula (A-I-1) 9 parts (A) Colorant: Compound represented by formula (7) (VALIFAST Red 1308;
24 parts (B) Resin: Resin solution B1 143 parts (C) Photopolymerizable compound: Dipentaerythritol hexaacrylate (KAYARAD DPHA; Nippon Kayaku Co., Ltd.) 50 parts (D) Photopolymerization initiator: OXE-01
(Ciba Japan Co., Ltd.) 15 parts (E) Solvent: 189 parts of propylene glycol monomethyl ether acetate (E) Solvent: 100 parts of diacetone alcohol were mixed to obtain comparative colored photosensitive resin composition 2. A pattern having a thickness of 2.2 μm was formed and evaluated in the same manner as in Example 1. The results are shown in Table 1.

  The colored pattern formed using the colored photosensitive resin composition of Example 1 has a higher contrast than the colored patterns formed using the colored photosensitive resin compositions of Comparative Example 1 and Comparative Example 2. confirmed. When the colored photosensitive resin composition of Example is used, a color filter with high contrast can be produced.

  According to the colored photosensitive resin composition of the present invention, a high-contrast color filter can be obtained.

Claims (8)

A colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (F) are included, and the colorant (A) is represented by the formula (AI). A colored photosensitive resin composition which is a colorant comprising a compound to be prepared and a yellow dye.

[In formula (AI), R ^{1 to} R ¹⁸ each independently represents a hydrogen atom, a halogen atom, a C _1-8 aliphatic hydrocarbon group, a nitro group, a phenyl group, —SO ₂ NHR ²¹¹ , —SO ₃ ^- or an ^{-COOR 212,} at least one -SO ₃ ^- represents a.
R ¹⁹ and R ²⁰ each independently represents a hydrogen atom, a methyl group, an ethyl group or an amino group.
R ²¹¹ and R ²¹² are each independently a hydrogen atom, a C _1-8 aliphatic hydrocarbon group, a cyclohexyl group, a C _7-10 alkylcyclohexyl group, a C _2-15 alkoxyalkyl group, —R ³¹ —CO—O. ^{-R 32, -R 31 -O-CO} -R 32, or represents a C _7-10 aralkyl group.
R ³¹ represents a divalent C _1-8 aliphatic hydrocarbon group, and R ³² represents a monovalent C _1-8 aliphatic hydrocarbon group.
M represents Cr or Co.
n represents an integer of 2 to 5.
D is to display the monovalent cation derived from a compound having a Hydron or xanthene skeleton, at least one represents a monovalent cation derived from a compound having a xanthene skeleton. ] R ^{1 to} R ¹⁸ each independently represents a hydrogen atom, a chlorine atom, a methyl group, a nitro group, —SO ₂ NHR ²¹¹ , —SO ₃ ^— or —COOR ²¹² , and at least one represents —SO ₃ ^— . The colored photosensitive resin composition according to claim 1.   The colored photosensitive resin composition according to claim 1 or 2, wherein the yellow dye is a dye containing a compound having an azo skeleton. The colored photosensitive resin composition according to any one of claims 1 to 3, wherein the yellow dye is at least one selected from the group consisting of a compound represented by formula (I) and a salt thereof.

Wherein (I), R ⁴¹ ~R ⁴⁴ independently represents a hydrogen atom, C _1-10 saturated aliphatic hydrocarbon group or a carboxy group.
R ^{45 to} R ⁵² each independently represents a hydrogen atom, a halogen atom, a C _1-10 saturated aliphatic hydrocarbon group, a halogenated C _1-10 saturated aliphatic hydrocarbon group, a C _1-8 alkoxy group, or a carboxy group. , A sulfo group, a sulfamoyl group, or an N-substituted sulfamoyl group.
R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom, a cyano group, a carbamoyl group, or an N-substituted carbamoyl group. ]   The colored photosensitive resin composition according to any one of claims 1 to 4, wherein the binder resin (B) is a resin having a polymerizable unsaturated bond in a side chain.   The pattern formed from the coloring photosensitive resin composition in any one of Claims 1-5.   A color filter comprising the pattern according to claim 6. Use of the colored photosensitive resin composition according to any one of claims 1 to 5 for producing a color filter.

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