JP2011173971A - Azo compound, azo dye, and coloring composition and colored article containing the azo compound or the azo dye - Google Patents

Abstract

（一般式（１）中、Ｘ¹〜Ｘ¹⁰はＨ等を表すが、Ｘ¹〜Ｘ⁵の１つは、パーフルオロアルキル基を表す。）
【選択図】図２An azo compound and an azo dye having excellent color characteristics such as coloring power and hue are provided.
An azo dye represented by the following general formula (1). General formula (1)

(In General Formula (1), X ^{1 to} X ¹⁰ represent H or the like, but one of X ^{1 to} X ⁵ represents a perfluoroalkyl group.)
[Selection] Figure 2

Description

  The present invention relates to an azo compound, an azo dye, a colored composition containing the azo compound or the azo dye, and a colored product.

  In recent years, a material for forming a color image has been mainly used as an image recording material, and specifically, an ink jet recording material, a thermal transfer recording material, an electrophotographic recording material, a transfer halogen. Silver halide photosensitive materials, printing inks, recording pens, and the like are actively used. In addition, a color filter is used for recording and reproducing a color image on an image pickup device such as a CCD in a photographing apparatus and on an LCD, PDP, organic electroluminescence, or electronic paper (electronic paper) in a display. In these color image recording materials and color filters, three primary colors (dyes and pigments) of the so-called additive color mixture method and subtractive color mixture method are used to display or record a full color image. In fact, there are no dyes that have absorption characteristics and color characteristics that can realize the above, and are suitable for various use conditions, and improvement is strongly desired.

  As the dye used in each of the above applications, the color characteristics required for each application and the required quality for each application are different, but pigments are mainly used as the dye from the viewpoint of the light resistance and heat resistance of the recorded matter. For example, in color filter applications, C.I. I. Pigment Red 254, 242 and the like are C.I. I. Pigment Red 57: 1 and the like are C.I. I. Pigment Red 122, 146, 147, 150, 176, 184, 269, C.I. I. Pigment Violet 19 and the like are C.I. I. Pigment Red 146, 147, 150, 176, 184, 269, etc. are used. In order to satisfy the required absorption characteristics and color characteristics, and the required quality for each application, these improve the purity (for example, Patent Documents 1 to 3) or devise the manufacturing method (Patent Document 4). Proposals have been made. However, even if it is placed in such an improved pigment, it cannot be said that it still satisfies sufficient chromatic characteristics, because the chemical structure itself of the compound constituting the pigment itself is This is probably because the desired color characteristics cannot be satisfied.

JP 2004-45523 A JP 2004-123866 A JP 2003-149869 A JP 2004-269607 A

  An object of the present invention is to provide an azo compound and an azo dye excellent in color characteristics such as coloring power and hue. It is another object of the present invention to provide a dispersion containing the azo compound or the azo dye, a colored composition, and a recorded matter having excellent color characteristics.

  As a result of intensive studies in view of the above circumstances, the present inventors have obtained a novel azo dye, which has been found to have excellent color characteristics, and have completed the present invention.

  That is, the present invention relates to an azo dye represented by the following general formula (1).

General formula (1)

(In General Formula (1), X ^{1 to} X ¹⁰ each independently have a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group that may have a substituent, or a substituent. May have an alkenyl group, an alkynyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Good aliphatic heterocyclic group, aromatic heterocyclic group optionally having substituent, hydroxyl group, alkoxyl group optionally having substituent, aryloxy group optionally having substituent, carboxyl Group, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, an alkylcarbonyl group which may have a substituent, and a substituent which may have a substituent Good arylcarbonyl group, carba Yl group, an optionally substituted alkylaminocarbonyl group, an optionally substituted arylaminocarbonyl group, a sulfo group, an optionally substituted alkylsulfonyl group, and a substituent. An arylsulfonyl group which may have, an sulfimoyl group, an alkylaminosulfonyl group which may have a substituent, an arylaminosulfonyl group which may have a substituent, and a substituent. An alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylcarbonylamino group which may have a substituent, an arylcarbonylamino group which may have a substituent, a substituent An alkoxycarbonylamino group that may have, an aryloxycarbonylamino group that may have a substituent, and a substituent An alkylsulfonylamino group which may have a substituent, an arylsulfonylamino group which may have a substituent, a ureido group, a sulfamoylamino group, a mercapto group, an alkylthio group which may have a substituent, and a substituent. An arylthio group which may have a substituent, a trialkylsilyl group which may have a substituent, a dialkylarylsilyl group which may have a substituent, an alkyldiarylsilyl group which may have a substituent, A triarylsilyl group which may have a substituent, a trialkylsiloxy group which may have a substituent, a dialkylarylsiloxy group which may have a substituent, or a substituent Good alkyldiarylsiloxy group, optionally substituted triarylsiloxy group, or alkyl group, aryl group, aliphatic heterocyclic group Or an amino group substituted with an aromatic heterocyclic group, and at least one of X ^{1 to} X ⁵ represents a perfluoroalkyl group. X ⁶ and X ⁷ , X ⁷ and X ⁸ , X ⁸ and X ⁹ , and X ⁹ and X ¹⁰ may be bonded to each other to form a ring. )

The present invention also relates to the above azo dye wherein X ⁴ is a perfluoroalkyl group, X ⁷ is a carbamoyl group or arylaminocarbonyl group, and X ¹⁰ is an alkoxyl group.

The present invention also relates to the above azo dye wherein X ¹ , X ² , X ³ , X ⁵ , X ⁶ , X ⁸ and X ⁹ are hydrogen atoms.

The present invention also relates to the above azo dye wherein X ¹ is a chlorine atom and X ⁴ is a perfluoroalkyl group.

The present invention also relates to the above azo dye, wherein X ⁷ is a carbamoyl group or arylaminocarbonyl group, and X ¹⁰ is an alkoxyl group.

The present invention also relates to the above azo dye wherein X ² , X ³ , X ⁵ , X ⁶ , X ⁸ and X ⁹ are hydrogen atoms.

  The present invention also relates to an azo compound represented by the following general formula (2).

General formula (2)

(In General Formula (2), X ^{11 to} X ²⁰ each independently have a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group that may have a substituent, or a substituent. May have an alkenyl group, an alkynyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Good aliphatic heterocyclic group, aromatic heterocyclic group optionally having substituent, hydroxyl group, alkoxyl group optionally having substituent, aryloxy group optionally having substituent, carboxyl Group, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, an alkylcarbonyl group which may have a substituent, and a substituent which may have a substituent Good arylcarbonyl group, carba A moyl group, an alkylaminocarbonyl group which may have a substituent, an arylaminocarbonyl group which may have a substituent, a sulfo group, an alkylsulfonyl group which may have a substituent, a substituent; An arylsulfonyl group which may have, an sulfimoyl group, an alkylaminosulfonyl group which may have a substituent, an arylaminosulfonyl group which may have a substituent, and a substituent. An alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylcarbonylamino group which may have a substituent, an arylcarbonylamino group which may have a substituent, a substituent An alkoxycarbonylamino group that may have, an aryloxycarbonylamino group that may have a substituent, and a substituent An alkylsulfonylamino group which may have a substituent, an arylsulfonylamino group which may have a substituent, a ureido group, a sulfamoylamino group, a mercapto group, an alkylthio group which may have a substituent, and a substituent. An arylthio group which may have a substituent, a trialkylsilyl group which may have a substituent, a dialkylarylsilyl group which may have a substituent, an alkyldiarylsilyl group which may have a substituent, A triarylsilyl group which may have a substituent, a trialkylsiloxy group which may have a substituent, a dialkylarylsiloxy group which may have a substituent, or a substituent Good alkyldiarylsiloxy group, optionally substituted triarylsiloxy group, or alkyl group, aryl group, aliphatic heterocyclic ring Or an amino group substituted with an aromatic heterocyclic group, at least one of X ¹¹ to X ¹⁵ represents a perfluoroalkyl group. X ¹⁶ and X ¹⁷ , X ¹⁷ and X ¹⁸ , X ¹⁸ and X ¹⁹ , and X ¹⁹ and X ²⁰ may be bonded to each other to form a ring. )

The present invention also relates to the above azo compound wherein X ¹⁴ is a perfluoroalkyl group, X ¹⁷ is a carbamoyl group or arylaminocarbonyl group, and X ²⁰ is an alkoxyl group.

The present invention also relates to the above azo compound wherein X ¹¹ , X ¹² , X ¹³ , X ¹⁵ , X ¹⁶ , X ¹⁸ and X ¹⁹ are hydrogen atoms.

The present invention also relates to the above azo compound wherein X ¹¹ is a chlorine atom and X ¹⁴ is a perfluoroalkyl group.

The present invention also relates to the above azo compound, wherein X ¹⁷ is a carbamoyl group or arylaminocarbonyl group, and X ²⁰ is an alkoxyl group.

The present invention also relates to the above azo compound wherein X ¹² , X ¹³ , X ¹⁵ , X ¹⁶ , X ¹⁸ and X ¹⁹ are hydrogen atoms.

  The present invention also provides the production of the above-mentioned azo compound characterized by reacting a naphthol compound represented by the following general formula (3) with a diazo compound of an aromatic amine represented by the following general formula (4). Regarding the method.

General formula (3)

(In General Formula (3), X ^{11 to} X ¹⁵ each independently have a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group that may have a substituent, or a substituent. May have an alkenyl group, an alkynyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Good aliphatic heterocyclic group, aromatic heterocyclic group optionally having substituent, hydroxyl group, alkoxyl group optionally having substituent, aryloxy group optionally having substituent, carboxyl Group, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, an alkylcarbonyl group which may have a substituent, and a substituent which may have a substituent Good arylcarbonyl group, carba A moyl group, an alkylaminocarbonyl group which may have a substituent, an arylaminocarbonyl group which may have a substituent, a sulfo group, an alkylsulfonyl group which may have a substituent, a substituent; An arylsulfonyl group which may have, an sulfimoyl group, an alkylaminosulfonyl group which may have a substituent, an arylaminosulfonyl group which may have a substituent, and a substituent. An alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylcarbonylamino group which may have a substituent, an arylcarbonylamino group which may have a substituent, a substituent An alkoxycarbonylamino group that may have, an aryloxycarbonylamino group that may have a substituent, and a substituent An alkylsulfonylamino group which may have a substituent, an arylsulfonylamino group which may have a substituent, a ureido group, a sulfamoylamino group, a mercapto group, an alkylthio group which may have a substituent, and a substituent. An arylthio group which may have a substituent, a trialkylsilyl group which may have a substituent, a dialkylarylsilyl group which may have a substituent, an alkyldiarylsilyl group which may have a substituent, A triarylsilyl group which may have a substituent, a trialkylsiloxy group which may have a substituent, a dialkylarylsiloxy group which may have a substituent, or a substituent Good alkyldiarylsiloxy group, optionally substituted triarylsiloxy group, or alkyl group, aryl group, aliphatic heterocyclic ring Or an amino group substituted with an aromatic heterocyclic group, at least one of X ¹¹ to X ¹⁵ represents a perfluoroalkyl group. )

General formula (4)

(In General Formula (4), X ^{16 to} X ²⁰ each independently have a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group that may have a substituent, or a substituent. May have an alkenyl group, an alkynyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Good aliphatic heterocyclic group, aromatic heterocyclic group optionally having substituent, hydroxyl group, alkoxyl group optionally having substituent, aryloxy group optionally having substituent, carboxyl Group, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, an alkylcarbonyl group which may have a substituent, and a substituent which may have a substituent Good arylcarbonyl group, carba A moyl group, an alkylaminocarbonyl group which may have a substituent, an arylaminocarbonyl group which may have a substituent, a sulfo group, an alkylsulfonyl group which may have a substituent, a substituent; An arylsulfonyl group which may have, an sulfimoyl group, an alkylaminosulfonyl group which may have a substituent, an arylaminosulfonyl group which may have a substituent, and a substituent. An alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylcarbonylamino group which may have a substituent, an arylcarbonylamino group which may have a substituent, a substituent An alkoxycarbonylamino group that may have, an aryloxycarbonylamino group that may have a substituent, and a substituent An alkylsulfonylamino group which may have a substituent, an arylsulfonylamino group which may have a substituent, a ureido group, a sulfamoylamino group, a mercapto group, an alkylthio group which may have a substituent, and a substituent. An arylthio group which may have a substituent, a trialkylsilyl group which may have a substituent, a dialkylarylsilyl group which may have a substituent, an alkyldiarylsilyl group which may have a substituent, A triarylsilyl group which may have a substituent, a trialkylsiloxy group which may have a substituent, a dialkylarylsiloxy group which may have a substituent, or a substituent Good alkyldiarylsiloxy group, optionally substituted triarylsiloxy group, or alkyl group, aryl group, aliphatic heterocyclic ring Or a substituted amino group in the aromatic heterocyclic group. X ¹⁶ and X ¹⁷ , X ¹⁷ and X ¹⁸ , X ¹⁸ and X ¹⁹ , and X ¹⁹ and X ²⁰ may be bonded to each other to form a ring. )

The present invention also relates to a naphthol compound represented by the following general formula (3).
General formula (3)

(In General Formula (3), X ^{11 to} X ¹⁵ each independently have a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group that may have a substituent, or a substituent. May have an alkenyl group, an alkynyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Good aliphatic heterocyclic group, aromatic heterocyclic group optionally having substituent, hydroxyl group, alkoxyl group optionally having substituent, aryloxy group optionally having substituent, carboxyl Group, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, an alkylcarbonyl group which may have a substituent, and a substituent which may have a substituent Good arylcarbonyl group, carba A moyl group, an alkylaminocarbonyl group which may have a substituent, an arylaminocarbonyl group which may have a substituent, a sulfo group, an alkylsulfonyl group which may have a substituent, a substituent; An arylsulfonyl group which may have, an sulfimoyl group, an alkylaminosulfonyl group which may have a substituent, an arylaminosulfonyl group which may have a substituent, and a substituent. An alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylcarbonylamino group which may have a substituent, an arylcarbonylamino group which may have a substituent, a substituent An alkoxycarbonylamino group that may have, an aryloxycarbonylamino group that may have a substituent, and a substituent An alkylsulfonylamino group which may have a substituent, an arylsulfonylamino group which may have a substituent, a ureido group, a sulfamoylamino group, a mercapto group, an alkylthio group which may have a substituent, and a substituent. An arylthio group which may have a substituent, a trialkylsilyl group which may have a substituent, a dialkylarylsilyl group which may have a substituent, an alkyldiarylsilyl group which may have a substituent, A triarylsilyl group which may have a substituent, a trialkylsiloxy group which may have a substituent, a dialkylarylsiloxy group which may have a substituent, or a substituent Good alkyldiarylsiloxy group, optionally substituted triarylsiloxy group, or alkyl group, aryl group, aliphatic heterocyclic ring Or an amino group substituted with an aromatic heterocyclic group, at least one of X ¹¹ to X ¹⁵ represents a perfluoroalkyl group. )

  The present invention also relates to a dispersion comprising at least one azo dye dispersed in a medium.

  The present invention also relates to a coloring composition comprising at least one azo dye and a resin.

  By using the azo compound, the azo dye and the azo compound or the azo dye of the present invention, it is possible to provide a colored composition having excellent color characteristics and a colored product using the same. Therefore, colored plastics, resins, paints, paints, electrophotographic toners, LCDs having excellent color characteristics can be obtained by dispersing the azo dyes of the present invention in various media or mixing them with various resins to form colored compositions. , PDP, organic electroluminescence, display such as electronic paper, and color filters used in imaging devices such as CCD, and various printing inks such as offset, gravure, flexo, screen, and ink jet can be used suitably.

2 is an infrared absorption spectrum of the compound (B) obtained in Example 1. 2 is an infrared absorption spectrum of the azo dye 1 obtained in Example 1. 2 is an infrared absorption spectrum of azo dye 2 obtained in Example 2. 4 is an infrared absorption spectrum of azo dye 3 obtained in Example 3. 4 is an infrared absorption spectrum of azo dye 4 obtained in Example 4. 4 is an infrared absorption spectrum of the azo dye 5 obtained in Example 5. 6 is an infrared absorption spectrum of the azo dye 6 obtained in Example 6. 4 is an infrared absorption spectrum of azo dye 7 obtained in Example 7. 4 is an infrared absorption spectrum of azo dye 8 obtained in Example 8. 4 is an infrared absorption spectrum of the azo dye 9 obtained in Example 9. 4 is an infrared absorption spectrum of the azo dye 10 obtained in Example 10. 4 is an infrared absorption spectrum of the azo dye 12 obtained in Example 12. 4 is an infrared absorption spectrum of the azo dye 13 obtained in Example 13. 4 is an infrared absorption spectrum of the azo dye 14 obtained in Example 14. 7 is an infrared absorption spectrum of the azo dye 15 obtained in Example 15. 2 is an infrared absorption spectrum of the azo dye 61 obtained in Example 61.

  Hereinafter, the present invention will be described in detail.

[Azo dyes and azo compounds]
First, the azo dye represented by the general formula (1) will be described in detail.

General formula (1)

(In General Formula (1), X ^{1 to} X ¹⁰ each independently have a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group that may have a substituent, or a substituent. May have an alkenyl group, an alkynyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Good aliphatic heterocyclic group, aromatic heterocyclic group optionally having substituent, hydroxyl group, alkoxyl group optionally having substituent, aryloxy group optionally having substituent, carboxyl Group, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, an alkylcarbonyl group which may have a substituent, and a substituent which may have a substituent Good arylcarbonyl group, carba Yl group, an optionally substituted alkylaminocarbonyl group, an optionally substituted arylaminocarbonyl group, a sulfo group, an optionally substituted alkylsulfonyl group, and a substituent. An arylsulfonyl group which may have, an sulfimoyl group, an alkylaminosulfonyl group which may have a substituent, an arylaminosulfonyl group which may have a substituent, and a substituent. An alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylcarbonylamino group which may have a substituent, an arylcarbonylamino group which may have a substituent, a substituent An alkoxycarbonylamino group that may have, an aryloxycarbonylamino group that may have a substituent, and a substituent An alkylsulfonylamino group which may have a substituent, an arylsulfonylamino group which may have a substituent, a ureido group, a sulfamoylamino group, a mercapto group, an alkylthio group which may have a substituent, and a substituent. An arylthio group which may have a substituent, a trialkylsilyl group which may have a substituent, a dialkylarylsilyl group which may have a substituent, an alkyldiarylsilyl group which may have a substituent, A triarylsilyl group which may have a substituent, a trialkylsiloxy group which may have a substituent, a dialkylarylsiloxy group which may have a substituent, or a substituent Good alkyldiarylsiloxy group, optionally substituted triarylsiloxy group, or alkyl group, aryl group, aliphatic heterocyclic group Or an amino group substituted with an aromatic heterocyclic group, and at least one of X ^{1 to} X ⁵ represents a perfluoroalkyl group. X ⁶ and X ⁷ , X ⁷ and X ⁸ , X ⁸ and X ⁹ , and X ⁹ and X ¹⁰ may be bonded to each other to form a ring. )

  Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a fluorine atom or a chlorine atom is preferable, and a chlorine atom is more preferable.

  Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, C1-C8 alkyl groups such as hexyl group, heptyl group, octyl group, 2-ethylhexyl group, trifluoromethyl group, pentafluoroethyl group, hexafluoropropyl group, hexafluoroisopropyl group, nonafluorobutyl group, It has a C1-C8 perfluoroalkyl group such as a nonafluoroisobutyl group, and further has a C1-C8 substituent such as a chloromethyl group, a hydroxymethyl group, a 2-hydroxyethyl group, or a carboxylmethyl group. Even an alkyl group is mentioned. Among these, an alkyl group having 1 to 4 carbon atoms is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is particularly preferable.

  Examples of the alkenyl group which may have a substituent include a vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1- Examples thereof include an alkenyl group having 2 to 8 carbon atoms which may have a substituent such as an octenyl group.

  Examples of the alkynyl group which may have a substituent include carbon such as ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group and 1-octynyl group. The alkynyl group which may have a substituent of several 2-8 is mentioned.

  In addition, the cycloalkyl group which may have a substituent has a substituent having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the cycloalkyl group may be mentioned.

  Examples of the aryl group which may have a substituent include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2,4-xylyl group, a p-cumenyl group, and a mesityl group. Monovalent monocyclic aromatic hydrocarbon group which may have a substituent having 6 to 18 carbon atoms, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 5-anthryl Monovalent which may have a substituent having 10 to 18 carbon atoms such as a group, 1-phenanthryl group, 9-phenanthryl group, 1-acenaphthyl group, 2-azurenyl group, 1-pyrenyl group, 2-triphenylyl group And a monovalent ring assembly hydrocarbon group which may have a substituent having 12 to 18 carbon atoms such as o-biphenylyl group, m-biphenylyl group and p-biphenylyl group. . Among these, an aryl group having 6 to 12 carbon atoms is preferable, and a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 1-naphthyl group, 2-naphthyl group, m-biphenylyl group, p- A biphenylyl group is more preferred.

  The aliphatic heterocyclic group which may have a substituent may have a substituent having 3 to 18 carbon atoms such as a 2-pyrazolino group, a piperidino group, a morpholino group, or a 2-morpholinyl group. A monovalent aliphatic heterocyclic group is mentioned.

  Examples of the aromatic heterocyclic group which may have a substituent include triazolyl group, 3-oxadiazolyl group, 2-furanyl group, 3-furanyl group, 2-furyl group, 3-furyl group and 2-thienyl. Group, 3-thienyl group, 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrazyl group, 2- Oxazolyl group, 3-isoxazolyl group, 2-thiazolyl group, 3-isothiazolyl group, 2-imidazolyl group, 3-pyrazolyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6- Quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 2-quinoxalinyl group, 2-benzofuryl group, 2-benzothienyl group, N-indolyl group, 3-carbazolyl group, N-carbyl group Bazoriru group, N- acridinyl group, 2-thiophenyl group, 3-thiophenyl group, bipyridyl group, and an aromatic heterocyclic group which may have a substituent group having 2 to 18 carbon atoms such phenanthrolyl group. Among these, an aromatic heterocyclic group having 2 to 12 carbon atoms is preferable, and 2-thienyl group, 2-pyridyl group, 4-pyridyl group, 2-imidazolyl group, 3-carbazolyl group, and N-carbazolyl group are more preferable. .

  In addition, examples of the alkoxyl group which may have a substituent include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a tert-butoxy group, an octyloxy group, and a tert-octyloxy group. Examples thereof include an alkoxyl group which may have a group. Among these, an alkoxyl group having 1 to 4 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is particularly preferable.

  In addition, the aryloxy group which may have a substituent includes 6 carbon atoms such as a phenoxy group, 4-tert-butylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 9-anthryloxy group. The aryloxy group which may have a substituent of -14 is mention | raise | lifted.

  Moreover, as the alkoxycarbonyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent having 2 to 14 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, and a benzyloxycarbonyl group. can give.

  Examples of the aryloxycarbonyl group which may have a substituent include aryloxycarbonyl groups which may have a substituent having 7 to 14 carbon atoms such as a phenoxycarbonyl group and a naphthyloxycarbonyl group. .

  Moreover, as the alkylcarbonyl group which may have a substituent, an alkylcarbonyl group which may have a substituent having 2 to 14 carbon atoms such as an acetyl group, a propionyl group, a pivaloyl group and a cyclohexylcarbonyl group. can give.

  Examples of the arylcarbonyl group which may have a substituent include arylcarbonyl groups which may have a substituent having 7 to 14 carbon atoms such as benzoyl group, toluoyl group, anisoyl group and cinnamoyl group. It is done.

  Examples of the alkylaminocarbonyl group which may have a substituent include N-methylaminocarbonyl group, N-ethylaminocarbonyl group, N, N-dimethylaminocarbonyl group, N, N-diethylaminocarbonyl group and the like. Examples thereof include an alkylaminocarbonyl group which may have a substituent having 2 to 16 carbon atoms.

  Examples of the arylaminocarbonyl group which may have a substituent include N-phenylaminocarbonyl group, N- (p-tolyl) aminocarbonyl group, N- (2,4-xylyl) aminocarbonyl group, N , N-diphenylaminocarbonyl group, N, N-di (p-tolyl) aminocarbonyl group, N, N-di (2,4-xylyl) aminocarbonyl group and other substituents having 7 to 18 carbon atoms An arylaminocarbonyl group which may be present. Of these, an arylaminocarbonyl group having 1 to 4 carbon atoms is preferred, an N-phenylaminocarbonyl group or N- (p-tolyl) aminocarbonyl group is more preferred, and an N-phenylaminocarbonyl group is particularly preferred.

  Examples of the alkylsulfonyl group that may have a substituent include alkylsulfonyl groups that may have a substituent of 1 to 8 carbon atoms such as a mesyl group, an ethylsulfonyl group, and a propylsulfonyl group. .

  Moreover, as the arylsulfonyl group which may have a substituent, the aryl which may have a substituent having 6 to 14 carbon atoms such as a phenylsulfonyl group, an o-tolylsulfonyl group, and a p-toluenesulfonyl group. A sulfonyl group is mentioned.

  Examples of the alkylaminosulfonyl group which may have a substituent include N-methylaminosulfonyl group, N-ethylaminosulfonyl group, N, N-dimethylaminosulfonyl group, N, N-diethylaminosulfonyl group and the like. And an alkylaminosulfonyl group optionally having a substituent having 1 to 8 carbon atoms.

  As the arylaminosulfonyl group which may have a substituent, N-phenylaminosulfonyl group, N- (p-tolyl) aminosulfonyl group, N- (2,4-xylyl) aminosulfonyl group, N , N-diphenylaminosulfonyl group, N, N-di (p-tolyl) aminosulfonyl group, N, N-di (2,4-xylyl) aminosulfonyl group and other substituents having 12 to 16 carbon atoms An arylsulfonyl group which may be present is exemplified.

  Moreover, as the alkylsulfinyl group which may have a substituent, the alkylsulfinyl which may have a substituent having 1 to 8 carbon atoms such as a methylsulfinyl group, an ethylsulfinyl group, and a propylsulfylyl group. Group.

  The arylsulfinyl group which may have a substituent may have a substituent having 6 to 14 carbon atoms such as a phenylsulfinyl group, an o-tolylsulfinyl group or a p-tolylsulfinyl group. An arylsulfinyl group is mentioned.

  Further, the alkylcarbonylamino group which may have a substituent may have a substituent having 2 to 14 carbon atoms such as an acetylamino group, a propionylamino group, a pivaloylamino group, and a cyclohexylcarbonylamino group. Examples thereof include an alkylcarbonylamino group.

  In addition, the arylcarbonylamino group which may have a substituent includes an arylcarbonyl which may have a substituent having 7 to 14 carbon atoms such as a benzoylamino group, a toluoylamino group, and an anisoylamino group. An amino group is mentioned.

  Moreover, as the alkoxycarbonylamino group which may have a substituent, a C2-C14 substituent such as an N-methoxycarbonylamino group, an N-ethoxycarbonylamino group, or an N-benzyloxycarbonylamino group. Examples thereof may include an alkoxycarbonylamino group which may have.

  The aryloxycarbonylamino group which may have a substituent may have a substituent having 7 to 14 carbon atoms such as an N-phenoxycarbonylamino group and an N-naphthyloxycarbonylamino group. An aryloxycarbonyl group.

  Moreover, as the alkylsulfonylamino group which may have a substituent, the alkyl which may have a C1-C8 substituent, such as a methylsulfonylamino group, an ethylsulfonylamino group, and a propylsulfonylamino group. A sulfonylamino group is mentioned.

  The arylsulfonylamino group which may have a substituent has a substituent having 6 to 14 carbon atoms such as phenylsulfonylamino group, o-tolylsulfonylamino group, p-tolylsulfonylamino group. An arylsulfonyl group which may be used is exemplified.

  Moreover, as the alkylthio group which may have a substituent, the alkylthio group which may have a C1-C8 substituent, such as a methylthio group, an ethylthio group, a tert-butylthio group, a hexylthio group, and an octylthio group. Can be given.

  Moreover, as an arylthio group which may have a substituent, you may have a C6-C14 substituent, such as a phenylthio group, 2-methylphenylthio group, and 4-tert- butylphenylthio group. An arylthio group.

  Examples of the trialkylsilyl group which may have a substituent include 3 to 24 carbon atoms such as a trimethylsilyl group, a triethylsilyl group, a dimethylethylsilyl group, a triisopropylsilyl group, a tributylsilyl group, and a trioctylsilyl group. And a trialkylsilyl group optionally having a substituent.

  Moreover, as the dialkylarylsilyl group which may have a substituent, the dialkyl which may have a substituent having 8 to 24 carbon atoms such as a dimethylphenylsilyl group, a diethylphenylsilyl group and a dimethyltolylsilyl group. An arylsilyl group is mentioned.

  The alkyldiarylsilyl group which may have a substituent may have a substituent having 13 to 24 carbon atoms such as a methyldiphenylsilyl group, an ethyldiphenylsilyl group, or a methylditolylsilyl group. An alkyldiarylsilyl group is mentioned.

  The triarylsilyl group which may have a substituent is a triarylsilyl group which may have a substituent having 18 to 24 carbon atoms such as a triphenylsilyl group, a tolylsilylsilyl group or a trixylsilyl group. Reel silyl is mentioned.

  In addition, an optionally substituted trialkylsiloxy group, trimethylsiloxy group, triethylsiloxy group, dimethylethylsiloxy group, triisopropylsiloxy group, tributylsiloxy group, trioctylsiloxy group, etc. Examples thereof include a trialkylsiloxy group which may have a substituent.

  Moreover, as the dialkylarylsiloxy group which may have a substituent, the dialkyl which may have a substituent having 8 to 24 carbon atoms such as a dimethylphenylsiloxy group, a diethylphenylsiloxy group and a dimethyltolylsiloxy group. An arylsiloxy group is mentioned.

  In addition, the alkyldiarylsiloxy group which may have a substituent may have a substituent having 13 to 24 carbon atoms such as a methyldiphenylsiloxy group, an ethyldiphenylsiloxy group, or a methylditolylsiloxy group. An alkyldiarylsiloxy group can be mentioned.

  The triarylsiloxy group which may have a substituent is a triarylsiloxy group, a triphenylsiloxy group, a trixylyloxy group, or a trivalent aryl group having 18 to 24 carbon atoms. An example is a reelsiloxy group.

  Furthermore, examples of the amino group substituted with an alkyl group, an aryl group, an aliphatic heterocyclic group, or an aromatic heterocyclic group include N-methylamino group, N-ethylamino group, N, N-diethylamino group, N, N-diisopropylamino group, N, N-dibutylamino group, N-benzylamino group, N, N-dibenzylamino group, N-phenylamino group, N-phenyl-N-methylamino group, N, N-diphenyl Amino group, N, N-bis (m-tolyl) amino group, N, N-bis (p-tolyl) amino group, N, N-bis (p-biphenylyl) amino group, bis [4- (4-methyl ) Biphenylyl] amino groups, N-α-naphthyl-N-phenylamino groups, N-β-naphthyl-N-phenylamino groups and the like substituted amino groups having 1 to 26 carbon atoms.

  The alkyl group which may have a substituent mentioned above, the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, the cycloalkyl group which may have a substituent An aryl group that may have a substituent, an aliphatic heterocyclic group that may have a substituent, an aromatic heterocyclic group that may have a substituent, and a substituent. An alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, and a substituent Optionally substituted alkylcarbonyl group, optionally substituted arylcarbonyl group, optionally substituted alkylaminocarbonyl group, optionally substituted arylaminocarbonyl group, substituted Have group Optionally substituted alkylsulfonyl group, optionally substituted arylsulfonyl group, optionally substituted alkylaminosulfonyl group, optionally substituted arylaminosulfonyl group, substituted Alkylsulfinyl group which may have a group, arylsulfinyl group which may have a substituent, alkylcarbonylamino group which may have a substituent, arylcarbonyl which may have a substituent An amino group, an alkoxycarbonylamino group which may have a substituent, an aryloxycarbonylamino group which may have a substituent, an alkylsulfonylamino group which may have a substituent, and a substituent. An arylsulfonylamino group which may have a substituent, an alkylthio group which may have a substituent, and a substituent which may have a substituent Reelthio group, optionally substituted trialkylsilyl group, optionally substituted dialkylarylsilyl group, optionally substituted alkyldiarylsilyl group, substituted A triarylsilyl group which may have a substituent, a trialkylsiloxy group which may have a substituent, a dialkylarylsiloxy group which may have a substituent, an alkyldiarylsiloxy group which may have a substituent As the substituent that the triarylsiloxy group that may have a substituent may have,

  Halogen atom, cyano group, nitro group, alkyl group optionally having substituent, alkenyl group optionally having substituent, alkynyl group optionally having substituent, having substituent A cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, an aromatic heterocyclic group which may have a substituent, A hydroxyl group, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, a carboxyl group, an alkoxycarbonyl group which may have a substituent, and a substituent; Aryloxycarbonyl group, optionally substituted alkylcarbonyl group, optionally substituted arylcarbonyl group, carbamoyl group, optionally substituted alkylaminocarbonyl , Optionally substituted arylaminocarbonyl group, sulfo group, optionally substituted alkylsulfonyl group, optionally substituted arylsulfonyl group, sulfimoyl group, substituted An alkylaminosulfonyl group which may have a group, an arylaminosulfonyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, and an aryl which may have a substituent Sulfinyl group, optionally substituted alkylcarbonylamino group, optionally substituted arylcarbonylamino group, optionally substituted alkoxycarbonylamino group, having substituent Aryloxycarbonylamino group which may have, alkylsulfonylamino group which may have substituent, which may have substituent Arylsulfonylamino group, ureido group, sulfimoylamino group, mercapto group, optionally substituted alkylthio group, optionally substituted arylthio group, optionally substituted Good trialkylsilyl group, optionally substituted dialkylarylsilyl group, optionally substituted alkyldiarylsilyl group, optionally substituted triarylsilyl group, substituent A trialkylsiloxy group which may have a substituent, a dialkylarylsiloxy group which may have a substituent, an alkyldiarylsiloxy group which may have a substituent, a tria which may have a substituent Examples thereof include a reelsiloxy group, or an amino group substituted with an alkyl group, an aryl group, an aliphatic heterocyclic group, or an aromatic heterocyclic group.

  Among these, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an cycloalkyl which may have a substituent Group, an aryl group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, an aromatic heterocyclic group which may have a substituent, and a substituent. An alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, and a substituent. An optionally substituted alkylcarbonyl group, an optionally substituted arylcarbonyl group, an optionally substituted alkylaminocarbonyl group, an optionally substituted arylaminocarbonyl group, Substituent An optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, an optionally substituted alkylaminosulfonyl group, an optionally substituted arylaminosulfonyl group , An optionally substituted alkylsulfinyl group, an optionally substituted arylsulfinyl group, an optionally substituted alkylcarbonylamino group, and optionally having a substituent An arylcarbonylamino group, an optionally substituted alkoxycarbonylamino group, an optionally substituted aryloxycarbonylamino group, an optionally substituted alkylsulfonylamino group, a substituent An arylsulfonylamino group which may have a substituent, an alkylthio group which may have a substituent, and a substituent which may have a substituent An arylthio group, a trialkylsilyl group which may have a substituent, a dialkylarylsilyl group which may have a substituent, an alkyldiarylsilyl group which may have a substituent, and a substituent. A triarylsilyl group which may have a substituent, a trialkylsiloxy group which may have a substituent, a dialkylarylsiloxy group which may have a substituent, an alkyldiarylsiloxy which may have a substituent Group and a triarylsiloxy group which may have a substituent,

In X ^{1 to} X ¹⁰ , the alkyl group which may have a substituent, the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, and a substituent A cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, an aromatic heterocyclic group which may have a substituent, a substituent An alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, An optionally substituted alkylcarbonyl group, an optionally substituted arylcarbonyl group, an optionally substituted alkylaminocarbonyl group, an optionally substituted aryl Aminocarbonyl group Alkylsulfonyl group which may have a substituent, arylsulfonyl group which may have a substituent, alkylaminosulfonyl group which may have a substituent, aryl which may have a substituent An aminosulfonyl group, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylcarbonylamino group which may have a substituent, and a substituent An arylcarbonylamino group which may have a substituent, an alkoxycarbonylamino group which may have a substituent, an aryloxycarbonylamino group which may have a substituent, an alkylsulfonylamino group which may have a substituent An arylsulfonylamino group which may have a substituent, an alkylthio group which may have a substituent, and a substituent An optionally substituted arylthio group, an optionally substituted trialkylsilyl group, an optionally substituted dialkylarylsilyl group, an optionally substituted alkyldiarylsilyl group, a substituent A triarylsilyl group which may have a substituent, a trialkylsiloxy group which may have a substituent, a dialkylarylsiloxy group which may have a substituent, an alkyl which may have a substituent It is synonymous with the diarylsiloxy group and the triarylsiloxy group which may have a substituent.

In the general formula (1), X ⁶ and X ⁷ , X ⁷ and X ⁸ , X ⁸ and X ⁹ , and X ⁹ and X ¹⁰ may be bonded to each other to form a ring.

In the general formula (1), at least one of X ^{1 to} X ⁵ represents a perfluoroalkyl group. Although the detailed reason is unknown, it is clear in the present invention that when at least one of these X ^{1 to} X ⁵ is a perfluoroalkyl group, it exhibits an excellent effect on color characteristics such as coloring power and hue. It is because it became. The perfluoroalkyl group referred to herein is a perfluoroalkyl having 1 to 8 carbon atoms such as trifluoromethyl group, pentafluoroethyl group, hexafluoropropyl group, hexafluoroisopropyl group, nonafluorobutyl group, nonafluoroisobutyl group, etc. Group.

Among these, the perfluoroalkyl group of X ^{1 to} X ⁵ is preferably a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, and trifluoromethyl group. Particularly preferred is a group. Moreover, as a substitution position, the case where X ⁴ is a perfluoroalkyl group is preferable because it exhibits an effect particularly excellent in color characteristics.

As the structure of the azo dye of the present invention represented by the general formula (1), particularly preferred combinations as the groups X ^{1 to} X ¹⁰ are the following forms (a) and / or (b).

(I) X ⁴ is preferably a perfluoroalkyl group, X ⁷ is a carbamoyl group or an arylaminocarbonyl group, X ¹⁰ is preferably an alkoxyl group, and X ¹ , X ² , X ³ , X ⁵ , X ⁶ , It is particularly preferable that X ⁸ and X ⁹ are hydrogen atoms.

(Ii) X ¹ is a chlorine atom, it is preferred that X4 is a perfluoroalkyl group, further more preferably X ⁷ is a carbamoyl group or an arylaminocarbonyl group, X ¹⁰ is an alkoxyl group, further, X ² , X ³ , X ⁵ , X ⁶ , X ⁸ and X ⁹ are particularly preferably hydrogen atoms.

  The present invention includes within its scope tautomers of the azo dyes represented by the general formula (1). The general formula (1) is shown in the form of an extreme structural formula among several tautomers that can be taken in terms of chemical structure, but may be a tautomer other than the structure described, You may use as a mixture containing these tautomers. For example, the azo dye represented by the general formula (1) can be a tautomer represented by the following general formula (1 ′). Therefore, the present invention includes within its scope the compound represented by the following general formula (1 '), which is a tautomer of the azo dye represented by the general formula (1).

General formula (1 ')

(Formula (1 ') X ¹ to X ¹⁰ in has the same meaning as X ¹ to X ¹⁰ in formula (1).)

  The azo dye represented by the general formula (1) of the present invention may be a dye in any crystalline form, also called polymorph, including tautomers thereof.

  Crystal polymorphs refer to the same chemical composition but different arrangement of molecules or ions in the crystal. The crystal structure determines the chemical and physical properties, and each polymorph can be distinguished by its rheology, color, and other color characteristics. Different polymorphs can be confirmed by powder X-ray diffraction measurement (X-Ray Diffraction) or X-ray crystal structure analysis (X-Ray Analysis). In the case where a crystalline polymorph exists in the azo dye represented by the general formula (1) of the present invention, any polymorph may be used, and a mixture of two or more polymorphs may be used. Is preferably based on a single component. That is, it is preferable that the crystalline polymorph is not mixed, and the content of the azo dye having a single crystal type is 70% to 100%, preferably 80% to 100%, more preferably 90% with respect to the whole azo dye. -100%, more preferably 95% -100, particularly preferably 100%. The main component is an azo dye having a single crystal type, which improves the regularity of the dye molecule arrangement, enhances intramolecular and intermolecular interactions, and facilitates the formation of higher-order three-dimensional networks. Become. As a result, it is preferable in terms of performance such as light fastness, heat fastness, humidity fastness, oxidizing gas fastness and solvent resistance as well as improvement in color characteristics. The mixing ratio of crystal polymorphs in azo dyes is based on solid physicochemical measurements such as single crystal X-ray crystal structure analysis, powder X-ray diffraction (XRD), crystal micrograph (TEM), IR (KBr method), etc. I can confirm. Control of these azo dyes and their tautomerism and crystal polymorphism can be controlled by the production conditions for producing the azo dyes.

  In the present invention, when the azo dye represented by the general formula (1) has an acidic group such as a sulfo group or a carboxyl group, a part or all of these acidic groups are of a salt type. Alternatively, a salt-type dye and a free acid-type dye may be mixed. As examples of the above-mentioned salt types, alkali metal salts such as Na, Li, and K, alkaline earth metal salts such as Mg, Ca, Sr, and Ba, and cations composed of nitrogen-containing compounds are preferable. As the acidic group, either a sulfo group or a carboxyl group is preferable, and a sulfo group is particularly preferable. As an example of the salt type, in the form of a lake pigment, a salt with an alkaline earth metal is preferable, and a lake pigment selected from Mg, Ca, Sr, and Ba is particularly preferable. On the other hand, if it is in the form of an acid dye, it is preferably a salt with a cation comprising a nitrogen-containing compound, and when selected only from the viewpoint of absorbance and coloring power, the nitrogen-containing compound has a molecular weight as low as possible. Those having a molecular weight of 400 or less are preferred.

  As an example of the nitrogen compound used for the cation which consists of a nitrogen-containing compound, the ammonium salt which may be substituted by the acyl group, the alkyl group, or the hydroxyalkyl group, or the salt of an organic amine is mentioned. Examples of organic amines include lower alkyl amines, hydroxy-substituted lower alkyl amines, acyl-substituted lower alkyl amines, and polyamines having 2 to 10 alkyleneimine units having 2 to 4 carbon atoms. In the case of these salt types, the type is not limited to one type, and a plurality of types may be mixed. Furthermore, in the structure of the azo dye used in the present invention, when a plurality of acidic groups are contained in one molecule, the plurality of acidic groups are salt type or acid type, and they may be the same or different from each other. Also good.

  In the present invention, the azo dye represented by the general formula (1) may be a hydrate containing water molecules in the crystal.

  The present invention also relates to an azo compound represented by the general formula (2), a tautomer thereof, a salt or a hydrate thereof. Moreover, the example of a substituent of the azo compound represented by General formula (2) of this invention, and the preferable combination of a substituent are the same as what was mentioned by the azo dye represented by General formula (1).

  The azo dye represented by the general formula (1) of the present invention and the azo compound represented by the general formula (2), tautomers, salts or hydrates thereof are not only improved in color characteristics, From the viewpoint of improving performance such as light fastness, heat fastness, humidity fastness, oxidizing gas fastness and solvent resistance, the molecular weight is preferably 1500 or less, more preferably 1200 or less, and even more preferably 1000 or less. 800 or less is particularly preferable.

  Below, the synthesis | combination of the azo dye of this invention is demonstrated in detail.

  The azo dye and azo compound of the present invention are represented by a coupling component (naphthol compound) represented by the general formula (3) or the following general formula (5) and the general formula (4) or the following general formula (6). It can be produced by a coupling reaction with a diazonium salt (diazo compound) prepared by a known method from a diazo component (aromatic amine).

General formula (5)

(In the general formula (5), X ¹ to X ⁵ are the same meanings as X ¹ to X ⁵ in the general formula (1).)

General formula (6)

(In the general formula (6), X ^{6 to} X ¹⁰ are respectively synonymous with X ^{6 to} X ¹⁰ in the general formula (1).)

  Some of the aromatic amines (diazo components) of the general formula (4) or the general formula (6) can be obtained as commercial products, but they are known and commonly used, for example, the method described in Japanese Patent No. 4022221. Can be manufactured. The diazonium chlorination reaction of an aromatic amine is performed, for example, in an acidic solvent such as sulfuric acid, phosphoric acid, and acetic acid, with a reagent such as sodium nitrite, nitrosylsulfuric acid, isoamyl nitrite, and the like at a temperature of 15 ° C. or less for about 10 minutes to 6 hours. It can be performed by reacting. In the coupling reaction, the diazonium salt obtained by the above method and the compound represented by the general formula (3) or the general formula (5) is 100 ° C. or lower, preferably 40 ° C. or lower, and 10 minutes to 12 hours. It can be performed by reacting to some extent.

  The solvent used for the coupling reaction is not particularly limited as long as it does not adversely affect the reaction. In addition to water, alcohol solvents such as methanol, ethanol, 2-propanol and 1-butanol, glycols such as ethylene glycol and diethylene glycol Solvents, monoalkyl ether solvents thereof, ketone solvents such as acetone and 2-butanone, non-aqueous solvents such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone Examples thereof include protic polar solvents, aromatic hydrocarbon solvents such as toluene and xylene, halogen solvents such as chloroform, chlorobenzene, o-dichlorobenzene and 1-chloronaphthalene, glacial acetic acid and pyridine. These are appropriately selected and used depending on the properties of the diazo component and the coupler component, but a mixed solvent in which a plurality of the above solvents are mixed can also be used. Further, during the coupling reaction, a surfactant may be added to promote dissolution of the diazo component or coupler component.

  In the case where the reaction is carried out in this manner, crystals of the azo dye may precipitate in the reaction solution, but when the azo dye is hardly soluble in water or an alcohol solvent, water or alcohol is added to the reaction solution. A system solvent or the like may be added to precipitate crystals, and the crystals may be collected by filtration. The crystals collected by filtration are washed and dried as necessary to obtain an azo dye represented by the general formula (1) or an azo compound represented by the general formula (2).

  When the azo dye represented by the general formula (1) or the azo compound represented by the general formula (2) obtained by the above production method exhibits properties of a pigment that is hardly soluble in water or an organic solvent, It is obtained as a crude pigment (crude) after completion of the reaction, but when used as a dispersion or coloring composition of the present invention described later, it is desirable to carry out post-treatment. Examples of post-processing methods include, for example, solvent particle milling process such as solvent salt milling, salt milling, dry milling, solvent milling, acid pasting, solvent heat treatment, etc., resin, surfactant and dispersant. The surface treatment process by etc. is mentioned.

  As the post-treatment of the azo dye represented by the general formula (1) or the azo compound represented by the general formula (2) of the present invention, it is preferable to perform solvent heating treatment and / or solvent salt milling. Here, examples of the solvent used for the solvent heat treatment include water, aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as chlorobenzene and o-dichlorobenzene, isopropanol, isobutanol, Examples include alcohol solvents such as butoxyethanol, aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone, glacial acetic acid, pyridine, and mixtures thereof. . An inorganic or organic acid or base may be further added to the solvents mentioned above. The temperature of the solvent heat treatment varies depending on the desired primary particle size of the pigment, but is preferably 40 to 150 ° C, more preferably 60 to 100 ° C. The treatment time is preferably 30 minutes to 24 hours. As solvent salt milling, for example, a crude pigment, an inorganic salt, and an organic solvent that does not dissolve the crude pigment are charged into a kneader and kneaded and ground therein. As the inorganic salt, a water-soluble inorganic salt can be preferably used. For example, an inorganic salt such as sodium chloride, potassium chloride, sodium sulfate is preferably used. Moreover, it is more preferable to use an inorganic salt having an average particle size of 0.5 to 50 μm. The amount of the inorganic salt used is preferably 3 to 20 times by mass, more preferably 5 to 15 times by mass with respect to the crude pigment. As the organic solvent, a water-soluble organic solvent can be suitably used, and the solvent easily evaporates due to a temperature rise during kneading, so that a high boiling point solvent is preferable from the viewpoint of safety. Examples of such organic solvents include diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, diethylene glycol Propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene Glycol or mixtures thereof. The amount of the water-soluble organic solvent used is preferably 0.1 to 5 times by mass with respect to the crude pigment. The kneading temperature is preferably 20 to 130 ° C, particularly preferably 40 to 110 ° C. As a kneader, for example, a kneader or a mix muller can be used. It is preferable to adjust the average particle shape of the pigment to 0.01 μm to 1 μm by these post-treatments.

  In addition, as a method for producing the azo dye represented by the general formula (1) or the azo compound represented by the general formula (2) of the present invention, an organic solvent solution of an azo dye or an azo compound-soluble substance is used as a flow reactor. It may be produced by a method of introducing a soluble dye into a pigment in the distribution process. Specifically, it is a method of producing a nanometer-sized azo dye or azo compound dispersion using a microreactor as a flow reactor, for example, International Publication No. 2005/105928, Japanese Patent Application Laid-Open No. 2007-284665. And the method described in JP-A-2009-203286.

  It is desirable that the azo dye represented by the general formula (1) and the azo compound represented by the general formula (2), tautomers, salts or hydrates thereof of the present invention have as high purity as possible. . Specifically, the purity is 90% or more, preferably 95% or more, more preferably 98% or more, and further preferably 99% or more. When the purity is low, for example, the dispersion stability and storage stability of the dispersion and the ink for ink jet recording, the printability, and the coloring power are impaired, or the dispersion stability, transparency, and coloring power of the coloring composition such as toner, This is because color reproducibility, gradation, light resistance, charging characteristics, and the like may be impaired.

  In addition, the azo dye represented by the general formula (1) and the azo compound represented by the general formula (2), a tautomer thereof, a salt or a hydrate thereof are used as raw materials in the production thereof. A naphthol compound represented by a general formula (3), an aromatic amine represented by a general formula (4), and other aromatic amines represented by the following general formula (7) produced by side reactions during production It is desirable that the content of impurities such as triazene derivatives represented by the following general formulas (8) and (9) is as low as possible.

General formula (7)

(In the general formula (7), X ¹ to X ⁵ are the same meanings as X ¹ to X ⁵ in the general formula (1).)

General formula (8)

(In the general formula (8), X ^{6 to} X ¹⁰ are respectively synonymous with X ^{6 to} X ¹⁰ in the general formula (1).)

General formula (9)

(In the general formula (9), X ¹ to X ¹⁰ are the same meanings as X ¹ to X ¹⁰ in the general formula (1).)

  Specifically, the content of these impurities is 400 ppm or less, preferably 200 ppm or less, more preferably 100 ppm or less, as the content of the naphthol compound represented by the general formula (3). Moreover, content of the aromatic amine represented by General formula (4) is 100 ppm or less, Preferably it is 80 ppm or less, More preferably, it is 60 ppm or less. The content of impurities such as aromatic amines and triazene derivatives represented by the general formulas (5) to (7) is 100 ppm or less, preferably 50 ppm or less.

  If the content of these impurities is large, the particle size, particle size distribution, and color characteristics of the azo dye itself are liable to be adversely affected, and the dispersion stability, storage stability, printability, and coloring of the dispersion and ink for ink jet recording are increased. There is a concern that the strength may be impaired, and the dispersion stability, transparency, coloring power, color reproducibility, gradation, light resistance, charging characteristics, and the like of the coloring composition such as toner may be impaired. In view of safety and health, it is desirable that the content of aromatic amine is particularly small.

  Further, the azo dye represented by the general formula (1) and the azo compound represented by the general formula (2), tautomers, salts or hydrates thereof of the present invention are particularly useful for inkjet recording inks. When used, it is desirable that the content of polyvalent metal ions is as small as possible. Here, the polyvalent metal ion refers to a divalent or higher metal ion, specifically, Ca, Mg, Fe, Cr, Ni, Zr, etc., and the content of each ion amount is 200 ppm or less, preferably 100 ppm or less, more preferably 50 ppm or less. This is because when the content of these polyvalent metal ions is large, there is a concern that the inkjet head may be clogged or the ejection stability may be reduced during printing by the inkjet method.

  Specific examples of the azo dye represented by the general formula (1) and the azo compound represented by the general formula (2) described above are shown below, but the present invention is not limited to the following examples.

[Dispersion]
The dispersion of the present invention contains at least one of an azo dye represented by the general formula (1) or an azo compound represented by the general formula (2), a tautomer, a salt or a hydrate thereof. It is characterized by. Thereby, it can be set as the dispersion excellent in the color characteristic and dispersion stability.

  The dispersion of the present invention may be aqueous or non-aqueous. As a medium for dispersing the pigment in the dispersion of the present invention, water, an organic solvent, a polymerizable monomer and the like can be used. When the dispersion of the present invention is an aqueous dispersion, it is possible to use a mixture containing water as a main component and optionally adding a hydrophilic organic solvent. Examples of the hydrophilic organic solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, isobutyl alcohol, 2-butanol, isobutanol, tert-butyl alcohol, pentanol, hexanol, cyclohexanol, and benzyl alcohol. , Alcohols such as diacetone alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol Polyhydric alcohols such as 1,5-pentanediol, glycerin, 1,2,6-hexanetriol, thiodiglycol, ethylene glycol Coal monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, Glycol derivatives such as triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate triethylene glycol monoethyl ether, ethylene glycol monophenyl ether, ethylene oxide adduct of diglycerin, ethanolamine Diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine and other amines, other formamide, N, N -Dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, thiodiethanol, thiodiglycerol, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3 -Water-soluble solvents such as dimethyl-2-imidazolidinone, acetonitrile, acetone, methyl ethyl ketone, ethylene carbonate, propylene carbonate, etc. .

  Furthermore, the aqueous dispersion of the present invention may contain an aqueous resin. Examples of the aqueous resin include a water-soluble resin that dissolves in water, a water-dispersible resin that disperses in water, a colloidal dispersion resin, or a mixture thereof. Specific examples of the aqueous resin include acrylic, styrene-acrylic, polyester, polyamide, polyurethane, and fluorine resins.

  In addition, surfactants and dispersants may be used to improve pigment dispersion and image quality. Examples of the surfactant include anionic, nonionic, cationic, and amphoteric surfactants. Any surfactant may be used, but anionic or nonionic surfactants may be used. It is preferable to use it. Examples of the anionic surfactant include fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl diaryl ether disulfonates, alkyl phosphates, and polyoxyethylene alkyls. Examples thereof include ether sulfate, polyoxyethylene alkyl aryl ether sulfate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester salt, glycerol borate fatty acid ester, polyoxyethylene glycerol fatty acid ester and the like.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin. Examples include fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, fluorine-based resins, and silicon-based resins.

  The non-aqueous dispersion comprises the azo dye represented by the general formula (1) or the azo compound represented by the general formula (2), a tautomer, a salt or a hydrate as a medium in a non-aqueous vehicle. It is distributed. Resins used in non-aqueous vehicles include, for example, petroleum resins, casein, shellac, rosin-modified maleic resin, rosin-modified phenolic resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, chlorinated rubber, oxidized rubber, hydrochloric acid Rubber, phenolic resin, alkyd resin, polyester resin, unsaturated polyester resin, amino resin, epoxy resin, vinyl resin, vinyl chloride, vinyl chloride-vinyl acetate copolymer, acrylic resin, methacrylic resin, polyurethane resin, silicone resin, fluorine Examples thereof include resins, drying oils, synthetic drying oils, styrene / maleic acid resins, styrene / acrylic resins, polyamide resins, polyimide resins, benzoguanamine resins, melamine resins, urea resins, chlorinated polypropylene, butyral resins, and vinylidene chloride resins. A photocurable resin may be used as the non-aqueous vehicle.

  Examples of the solvent used in the non-aqueous vehicle include aromatic solvents such as toluene, xylene, and methoxybenzene, and acetates such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Solvents, propionate solvents such as ethoxyethyl propionate, alcohol solvents such as methanol and ethanol, ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone solvents, aliphatic hydrocarbon solvents such as hexane, N, N-dimethylformamide, N, N-dimethylacetamide , Γ-butyrolactam, N-methyl-2-pyrrolidone, nitrogen compounds such as aniline, pyridine, lactone solvents such as γ-butyrolactone, carbamic acid such as 48:52 mixture of methyl carbamate and ethyl carbamate Examples include esters.

  The dispersion of the present invention can be obtained by dispersing the above azo dye or azo compound and an aqueous or non-aqueous medium with a dispersing device. The method for dispersing the dye is not particularly limited. For the dispersion, a generally used mixing and stirring device such as an anchor blade can be used. Among the mixing and stirring devices, Ultra Disper [Asada Steel Corporation, product name], Ebara Milder [Ebara Manufacturing Co., Ltd., product name], TK Homomixer, TK Pipeline Mixer, TK Homojetter, TK Homomic Line Flow, High-speed agitating and mixing devices such as Filmix [Special Machine Industry Co., Ltd., trade name], Clear Mix [M Technique Co., Ltd., trade name], KD Mill [Kinetic Dispersion Co., Ltd., trade name] and the like are preferable. In addition, kneading machines such as roll mills, bead mills, kneaders, extruders, etc., high-pressure homogenizers [Izumi Food Machinery Co., Ltd., trade name], mini-valve type 8.3H [Rannie, trade name], homo-valve type high-pressure homogenizers, micro Fluidizer (Microfluidics, trade name), Nanomizer (Nanomizer, trade name), Ultimateizer (Sugino Machine Co., trade name), Genus PY (Shiramizu Chemical Co., trade name), DeBEE2000 (Nippon BB Co., Ltd.) , Trade name] and the like, and a dispersion method using a chamber-type high-pressure homogenizer. Among these, a roll mill, a bead mill, a kneader, and a high-pressure homogenizer are preferable from the viewpoint of reducing the particle size. A plurality of these devices can be combined.

  After obtaining a dispersion by such a method, in order to remove precipitates and coarse particles, a step of further centrifuging to separate the precipitates may be included. As a device used for centrifugal separation, centrifugal filtration generally uses a centrifugal sedimentator for centrifugally sedimenting suspended matter by rotating a non-porous rotating bowl at high speed, and a rotating basket having pores or slits on a side wall.・ Dehydrators are known. In the present invention, among these, a centrifugal settling machine can be suitably used [for example, “Chemical Equipment Handbook” edited by the Chemical Engineering Society, revised second edition, second edition, Maruzen Co., Ltd., April 5, 1996, See page 798]. Examples of the centrifugal sedimentator include a centrifugal sedimentator such as a centrifugal sedimentation tube type, a cylindrical type, a separation plate type, a basket type, and a scriber type.

  In the present invention, the volume average particle diameter of the pigment contained in the dispersion is preferably 10 nm or more and 250 nm or less. The volume average particle diameter of the dye particles refers to the particle diameter of the dye itself, or, in the case where an additive such as a dispersant is attached to the dye, the particle diameter to which the additive is attached. A more preferable volume average particle size is 20 nm or more and 250 nm or less, and further preferably 20 nm or more and 230 nm or less. When the number average particle size of the particles in the dispersion is less than 10 nm, there are cases where the storage stability cannot be ensured, while when it exceeds 250 nm, the optical density may be lowered. Here, the volume average particle diameter is a value measured using a particle size distribution meter (Laser Doppler type particle size distribution meter “Microtrac UPA-150” manufactured by Nikkiso Co., Ltd.).

  The concentration of the pigment contained in the dispersion of the present invention is preferably in the range of 1 to 35% by mass, and more preferably in the range of 2 to 25% by mass. If the density is less than 1% by mass, sufficient image density may not be obtained when the dispersion is used alone as the ink. If the concentration exceeds 35% by mass, the dispersion stability may decrease.

  The dispersion containing the azo compound of the present invention can also contain the above-mentioned components constituting the dispersion, and the preferred concentration of the azo compound contained in the dispersion is the same as that described for the dye dispersion. .

  Applications of the azo dyes and azo compounds of the present invention include image recording materials for forming images, particularly color images, and specifically, thermal recording including ink jet recording materials described in detail below. Materials, pressure-sensitive recording materials, electrophotographic recording materials, transfer type silver halide photosensitive materials, printing inks, recording pens, etc., preferably inkjet recording materials, thermal recording materials, electrophotographic recording A material, and more preferably an ink jet recording material. Examples of the ink jet recording material include water-based ink jet recording ink, oil-based ink jet recording ink, active energy ray (ultraviolet light, visible light, infrared light, electron beam) curable ink jet recording ink, hot melt ink jet recording ink, and the like. . Further, the present invention can be applied to a solid-state imaging device such as a CCD, a color filter for recording / reproducing a color image used in a display such as an LCD or PDP, and a dyeing solution for dyeing various fibers.

(Coloring composition)
The colored composition of the present invention means a colored composition containing at least one azo dye or azo compound of the present invention and a resin. Although resin used here changes with the uses, resin which has alkali solubility for a color filter use, for example is preferable. In that case, the resin is preferably a copolymer which acts as a dispersion medium for the dye and is composed of structural units derived from an unsaturated carboxylic acid.

  Specific examples of the structural unit derived from the unsaturated carboxylic acid include a structural unit derived from acrylic acid and a structural unit derived from methacrylic acid. Acrylic acid and methacrylic acid can be used alone or in combination. In addition to these acrylic acid and methacrylic acid, at least one carboxylic acid selected from the group consisting of other unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides such as crotonic acid, itaconic acid, maleic acid, and fumaric acid. An acid can also be used in combination. A monomer containing a hydroxy group and a carboxyl group in the same molecule, such as α- (hydroxymethyl) acrylic acid, can also be used in combination.

  The resin is preferably a copolymer comprising a structural unit derived from the unsaturated carboxylic acid as described above and a structural unit copolymerizable with the structural unit derived from the unsaturated carboxylic acid. As the structural unit copolymerizable with the structural unit derived from the unsaturated carboxylic acid, a structural unit derived from a (meth) acrylic acid ester is preferable.

  Examples of (meth) acrylic acid esters include acrylate compounds. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) ) Unsaturated or substituted alkyl esters of unsaturated carboxylic acids such as acrylate and aminoethyl (meth) acrylate; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, Cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctyl Nyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, tricyclodecyl (meth) acrylate, tricyclodecyloxyethyl (meth) acrylate, adamantyl (meth) acrylate, norbornenyl ( Esters containing alicyclic groups of unsaturated carboxylic acids such as meth) acrylate, pinenyl (meth) acrylate, dicyclopentenyl (meth) acrylate and dicyclopentenyloxyethyl (meth) acrylate; such as glycidyl (meth) acrylate Unsaturated carboxylic acid glycidyl esters; unsaturated carboxylic acid oxetane esters such as oxetane (meth) acrylate; oligoethylene glycol monoalkyl (meth) acrylate And the like monounsaturated carboxylic acid esters of glycols, preferably, methyl (meth) acrylate, benzyl (meth) acrylate. Here, (meth) acrylate indicates acrylic acid ester or methacrylic acid ester.

  The resin may further contain other structural units capable of copolymerization with unsaturated carboxylic acid and acrylic ester. Other building blocks that can be copolymerized with unsaturated carboxylic acids and acrylates include aromatic vinyl compounds such as styrene, α-methylstyrene and vinyl toluene; vinyl carboxylates such as vinyl acetate and vinyl propionate. Examples thereof include structural units derived from esters; vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile; maleimide compounds such as N-phenylmaleimide.

  These compounds described above may be used alone or in combination of two or more.

  As a structural unit copolymerizable with a structural unit derived from an unsaturated carboxylic acid, a structural unit derived from a (meth) acrylic acid ester is preferable, and in particular, an unsubstituted or substituted alkyl ester of (meth) acrylic acid or (meth) A structural unit derived from an ester containing an alicyclic hydrocarbon group of acrylic acid is preferred.

  In the resin, the structural unit derived from the unsaturated carboxylic acid is preferably 10 to 50% by mass, preferably 15 to 40% by mass in terms of mass fraction among all the structural units of the copolymer. . When the structural unit derived from the unsaturated carboxylic acid is 10 to 50% by mass on the basis of the above, the solubility in the developer is sufficient, so that no residue is generated on the substrate in the unexposed area. It is preferable that the pixel portion of the exposed portion is not reduced during development and the entire pixel does not peel off.

  Copolymerization is generally carried out in a solvent using a polymerization initiator. Examples of the polymerization initiator include azo compounds such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (methyl 2-methylpropionate), benzoyl peroxide and tert-butyl peroxide. And peroxides. The solvent may be any solvent that dissolves each monomer, for example, glycol ether esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. Is mentioned. The reaction temperature may be determined in consideration of the decomposition temperature of the polymerization initiator and the boiling points of the solvent and the monomer. The side chain of the copolymer thus obtained can be modified with a compound having a photosensitive group to form a photosensitive resin. At this time, a catalyst for introducing a photosensitive group into the resin may be added. An example of the catalyst is trisdimethylaminomethylphenol. Moreover, you may add the additive for preventing a side reaction. Examples of the additive include hydroquinone.

  In addition, when the colored composition of the present invention is used as a photopolymerizable composition or a photocurable composition such as various resists, it is a sensitizer for the purpose of increasing the sensitivity and improving the film properties after photocuring. Or a photopolymerization initiator.

  Sensitizers that can be used in the coloring composition of the present invention include benzophenones, unsaturated ketones represented by chalcone derivatives and dibenzalacetone, and 1,2-diketones represented by benzyl and camphorquinone. Derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, polymethine dyes, acridine derivatives , Azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triary Rumethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, Examples include annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, and organoruthenium complexes. Other specific examples include Ogahara Shin et al., “Dye Handbook” (1986, Kodansha), Okawara Shin The sensitizers described in the eds. Et al., “Chemicals of Functional Dyes” (1981, CMC), edited by Tadasaburo Ikemori, “Special Functional Materials” (1986, CMC), and the like. It may be used two or more in an arbitrary ratio depending on the necessity. Among the sensitizers, thioxanthone derivatives include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone. Examples of benzophenones include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4′-dimethylbenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-bis. (Diethylamino) benzophenone and the like can be mentioned. Examples of coumarins include coumarin 1, coumarin 338 and coumarin 102. Examples of ketocoumarins include 3,3′-carbonylbis (7-diethylaminocoumarin). However, it is not limited to these. These sensitizers are contained in the colored composition in an amount of 0.1 to 10%, preferably 1 to 5%.

  Examples of the photopolymerization initiator that can be used in the coloring composition of the present invention include Irgacure 651, Irgacure 127, Irgacure 184, Darocur 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 1700, Irgacure 149, Irgacure 1800, Irgacure 1850, Irgacure 819, Irgacure 754, Irgacure 784, Irgacure 261, Irgacure OXE-01 (CGI124), CGI242 (Ciba Specialty Chemicals), Adekaoptomer N1414, Adekaoptomer N1717 (Asahi Denka), EsacureKIP series, Esa ureONE, Esacure 1001M (Lamberti), triazine derivatives described in JP-B-59-1281, JP-B-61-9621 and JP-A-60-60104, JP-A-59-1504 and JP-A-61. No. -243807, diazonium compounds described in Japanese Patent Publication No. 43-23684, Japanese Patent Publication No. 44-6413, Japanese Patent Publication No. 47-1604 and US Pat. No. 3,567,453, US Pat. No. 2,848,328. Description: Organic azide compounds described in US Pat. No. 2,852,379 and US Pat. No. 2,940,853, Japanese Patent Publication No. 36-22062, Japanese Patent Publication No. 37-13109, Japanese Patent Publication No. 38-18015, and Japanese Patent Publication No. 45- Ortho-quinone di described in Japanese Patent No. 9610 Various azides, including iodonium compounds described in JP-B-55-39162, JP-A-59-140203 and “MACROMOLECULES”, Vol. 10, page 1307 (1977) Onium compounds, azo compounds described in JP-A-59-142205, JP-A-1-54440, European Patent No. 109851, European Patent No. 126712, “Journal of Imaging Science (J IMAG.SCI.), Vol. 30, page 174 (1986), titanocenes described in JP-A No. 61-151197, “COORDINATION CHEMISTRY REVIEW” 84, 85-277 (1988) and JP-A-2-182701. Transition metal complexes containing a transition metal such as ruthenium, an aluminate complex described in JP-A-3-209477, a borate compound described in JP-A-2-157760, JP-A-55-127550, and 2,4,5-triarylimidazole dimer described in JP-A-60-202437, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1, 1'-biimidazole, carbon tetrabromide and organic halogen compounds described in JP-A-59-107344, JP-A-5-213861, JP-A-5-255347, JP-A-5-255421, JP-A-6-157623, JP-A-2000-344812, JP-A-2002-265512, Japanese Patent Application No. 2004-053009, and The sulfonium complex or oxosulfonium complex described in Japanese Patent Application No. 2004-263413, JP 2001-264530 A, JP 2001-261661 A, JP 2000-80068 A, JP 2001-233842 A, US Pat. No. 3,558,309. (1971), USP 4202697 specification (1980), JP-A No. 61-24558, JP-T 2004-534797, and JP-A No. 2004-359639, And bifunctional polymerization initiators described in JP-A-530372. These photopolymerization initiators are contained in the colored composition in an amount of 0.1 to 10%, preferably 1 to 5%. .

  As resin which can be used for the coloring composition of this invention, it is preferable that the weight average molecular weight of polystyrene conversion is 5,000-100,000, More preferably, it is 7,000-50,000. When the resin has a polystyrene-equivalent weight average molecular weight of 5,000 to 100,000, film loss is unlikely to occur during development, and the non-pixel portion is liable to be easily removed during development. The resin is usually contained in an amount of 5 to 90% by mass, preferably 10 to 70% by mass, based on the total solid content in the colored photosensitive resin composition. When the content of the resin is 5 to 90% by mass on the basis of the above, the solubility in the developer is sufficient, the development residue is hardly generated on the substrate of the non-pixel portion, and exposure is performed during development. It is preferable that the film thickness of the pixel portion of the portion does not easily decrease and the non-pixel portion tends to be easily removed.

  Of the resins that can be used in the colored composition of the present invention, as a resin used as a recording material using an electrophotographic method generally known as a toner, any known binder resin (binder resin) can be used, There is no particular limitation. The same applies to the polymerizable monomer constituting the binder resin in the production of the polymerization method and the aggregation method toner. Examples of the polymerizable monomer used in the production of the binder resin include styrene or styrene derivatives, methacrylic acid esters, acrylic acid esters, olefins, halogenated vinyls, vinyl esters, vinyl ethers, vinyl ketones. , Vinyl compounds, acrylic acid, methacrylic acid and the like, and these can be used alone or in combination. These polymerizable monomers are polymerized using a radical polymerization initiator such as an azo or diazo polymerization initiator, a peroxide polymerization initiator, a persulfate polymerization initiator, or hydrogen peroxide. be able to. Examples of resins used for the pulverization method include copolymers such as styrene / acrylic resins and styrene / methacrylic resins, polyester resins containing a crosslinking component if necessary, epoxy resins, urethane resins, and the like. These can be used alone or in combination.

  The charge control of the toner may be performed with a binder resin or the colorant itself, but a charge control agent may be used in combination as necessary. Similarly, any known charge control suitable for the toner can be used. For example, a quaternary ammonium salt or the like can be used as the positive charge control agent, and a salicylic acid metal complex or the like can be used as the negative charge control agent.

  Among the binder resins used in toner applications, examples of waxes include olefinic waxes, preferably low molecular weight polypropylene, polyethylene, paraffin wax, higher fatty acid esters, fatty acid amides, and silicon. In addition to these components, toner particles mainly composed of the resin and the colorant may be added with an internal additive or an external additive composed of inorganic fine particles or organic fine particles.

  Examples of the toner include a case where a magnetic material is contained and used as a one-component magnetic toner, a case where the toner is mixed with a so-called carrier and used as a two-component developer, and a case where a non-magnetic toner is used alone.

  The coloring composition of the present invention can contain a medium, but when a solvent is used as the medium, it is particularly suitable as an ink for ink jet recording. The coloring composition of the present invention can be prepared by dissolving or dispersing the azo dye of the present invention in a lipophilic medium or an aqueous medium as a medium. Preferably, an aqueous medium is used. The coloring composition of the present invention includes an ink composition excluding a medium. The coloring composition of the present invention may contain other additives as necessary within a range that does not impair the effects of the present invention. Other additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, Known additives (described in JP-A No. 2003-306623) such as a foaming agent, a viscosity modifier, a dispersant, a dispersion stabilizer, a rust inhibitor, and a chelating agent can be used. These various additives are directly added to the ink liquid in the case of water-based ink. In the case of oil-based inks, it is common to add an azo dye dispersion to the dispersion after preparation, but it may be added to the oil phase or water phase at the time of preparation.

[Ink for inkjet recording]
Next, the ink for ink jet recording will be described.
As the ink for ink jet recording (hereinafter sometimes referred to as “ink”), the dispersion of the present invention described above is used. Preferably, it adjusts by mixing a water-soluble solvent, water, etc. However, if there is no particular problem, the dispersion of the present invention may be used as it is.

  The content ratio of the dispersion in the ink is preferably in the range of 1 to 100% by mass, particularly in the range of 3 to 20% by mass in consideration of the hue, color density, and transparency of the image formed on the recording medium. Among them, the range of 3 to 10% by mass is most preferable.

  It is preferable to contain 0.1 to 20 parts by mass of the azo dye or azo compound of the present invention in 100 parts by mass of ink, more preferably 0.2 to 10 parts by mass. It is more preferable to contain -10 mass parts. Moreover, you may use together other pigment | dye (dye and pigment) with the pigment | dye of this invention for ink. When two or more kinds of dyes are used in combination, the total content of the dyes is preferably within the above range.

  The ink can be used not only for forming a single color image but also for forming a full color image. In order to form a full color image, a magenta color ink, a cyan color ink, and a yellow color ink can be used, and a black color ink may be further used to adjust the color tone.

  Furthermore, in addition to the coloring matter in the present invention, the following other pigments and dyes can be used for the ink at the same time. The pigment may be either an inorganic pigment or an organic pigment. If necessary, they can be used in combination with extender pigments.

  Examples of the inorganic pigment include carbon black, metal oxide, metal sulfide, and metal chloride. Of these, carbon black is preferred particularly for black aqueous inks. Examples of carbon black include furnace black, thermal lamp black, acetylene black, and channel black.

  Specifically, as carbon black used as a black water-based ink, specifically, No. manufactured by Mitsubishi Chemical Corporation. 2300, no. 900, HCF88, no. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, No2200B, etc. are Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700, etc. manufactured by Colombia, Regal 400R, Regal 330R, Regal 660R, Mogal L , Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc. are available from Degussa Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200C , Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Special Black 6, Special Black 5, SpecialBlack 4A, but Special Black 4 and the like can be used, but is not limited thereto.

  Specific examples of other inorganic pigments include, for example, Pigment Yellow 42, Pigment White 6, Pigment Blue 27, Pigment Blue 29, and Pigment Black 7.

  Examples of organic pigments include azo pigments, diazo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, perylene pigments, perinone pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, lake pigments, and diketopyrrolopyrrole pigments. Etc. Examples of the organic pigment used in the present invention include chromatic pigments such as a cyan pigment, a yellow pigment, a magenta pigment, a violet pigment, a green pigment, and an orange pigment. Note that the chromatic color means all colors other than a series of colors (achromatic colors) ranging from white to gray to black.

  Examples of yellow pigments that can be applied include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 35, 37, 42, 53, 55, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 108, 109 110, 117, 120, 128, 129, 138, 139, 147, 150, 151, 153, 154, 155, 174, 180, 181, 185, 188, 191, 198, 213 and the like.

  Examples of magenta pigments that can be applied include C.I. I. Pigment Red 1, 3, 5, 8, 9, 16, 17, 19, 22, 31, 38, 48: 1, 48: 2, 48: 3, 48: 4, 53: 2, 57: 1, 57 : 2, 57: 3, 81, 81: 1, 81: 2, 81: 3, 81: 4, 81: 5, 90, 112, 122, 123, 127, 146, 147, 149, 150, 176, 177 179, 184, 185, 188, 202, 206, 207, 209, 222, 242, 245, 254, 256, 269, C.I. I. Pigment violet 19, and the like.

  Examples of applicable cyan pigments include C.I. I. Pigment blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60, 80, C.I. I. Vat blue 4, 60, aluminum phthalocyanine and the like.

  Examples of applicable violet pigments include C.I. I. Pigment violet 1, 3, 5: 1, 16, 23, 27, 37, 38, 42 and the like.

  Examples of applicable green pigments include C.I. I. Pigment green 4, 7, 36, 58 and the like.

  Examples of applicable orange pigments include C.I. I. Pigment orange 5, 13, 16, 34, 36, 43, 48, 61, 71 and the like.

  Examples of yellow dyes that can be applied include C.I. I. Acid Yellow 23, C.I. I. Direct Yellow 86, 132, C.I. I. Solvent Yellow 29, 30 and the like.

  Examples of magenta dyes that can be applied include C.I. I. Acid Red 52, 92, 289, 249, 254, C.I. I. Direct Red 227, C.I. I. Solvent Red 18, 49, etc.

  Examples of applicable cyan dyes include C.I. I. Acid Blue 9, C.I. I. Direct Blue 86, 87, 199, C.I. I. Solvent Blue 70 and the like.

  Examples of applicable black dyes include C.I. I. Solvent Black 3, 7 and nigrosine black dye.

  These pigments and dyes can be used alone or in admixture of two or more at any ratio. Moreover, the solid solution of the said organic pigment is also mentioned. For example, as a solid solution of a magenta pigment, C.I. I. Pigment violet and C.I. I. Pigment Red solid solution is preferred, and C.I. I. Pigment violet 19 and C.I. I. Pigment Red 122 solid solution, or C.I. I. Pigment violet 19 and C.I. I. A solid solution of CI Pigment Red 202 is preferable. I. Pigment violet 19 and C.I. I. A solid solution of Pigment Red 202 is preferred. Furthermore, examples of extender pigments include silica, calcium carbonate, and talc.

  As the water-soluble solvent used in the ink for ink jet recording, the same ones that can be used as a medium for dispersing the dye in the dispersion of the present invention can be used. Alcohols, glycol derivatives, amines, other water-soluble solvents and the like can be used. The water-soluble solvent used in these ink jet recording inks may be used alone or in combination of two or more. Among these solvents, 2-propanol, acetone, methyl ethyl ketone, ethylene glycol, propylene glycol, glycerin, 1,2-propanediol, 1,3-propanediol, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, ethylene carbonate, An organic solvent miscible with water at an arbitrary ratio such as propylene carbonate and N-methyl-2-pyrrolidone is more preferable.

  The content of the water-soluble solvent is 1% by mass or more and 60% by mass or less, preferably 5% by mass or more and 40% by mass or less of the entire ink. When the amount of the water-soluble solvent in the ink is less than 1% by mass, a sufficient optical density may not be obtained. Conversely, when the amount is more than 60% by mass, the viscosity of the ink increases, Ink ejection characteristics may become unstable.

  Preferred physical properties of the ink for ink jet recording are as follows. The surface tension of the ink is preferably 20 mN / m or more and 60 mN / m or less. More preferably, it is 20 mN or more and 45 mN / m or less, More preferably, it is 25 mN / m or more and 35 mN / m or less. If the surface tension is less than 20 mN / m, liquid may overflow on the nozzle surface of the recording head, and printing may not be performed normally. On the other hand, if it exceeds 60 mN / m, the permeability to the recording medium after printing may be slow, and the drying time may be slow. The surface tension was measured using a Wilhelmy surface tension meter in an environment of 23 ° C. and 55% RH.

The viscosity of the ink varies depending on the structure and characteristics of the recording head, but is preferably 1.2 mPa · s or more and 20 mPa · s or less, more preferably 1.5 mPa · s or more and less than 15 mPa · s, and still more preferably 2. 0.5 mPa · s or more and less than 9.5 mPa · s. In particular, when the recording head is a thermal type, it is preferably from 2.5 mPa · s to 4.0 mPa · s, and when the recording head is a piezo type, it is from 3.5 mPa · s to 9.5 mPa · s. Preferably there is. When the viscosity of the ink is greater than 20 mPa · s, the dischargeability may be reduced. On the other hand, when it is smaller than 1.2 mPa · s, the long-term jetting property may deteriorate. The viscosity (including those described later) was measured using a rotational viscometer Rheomat 115 (manufactured by Contraves) at 23 ° C. and a shear rate of 1400 s ⁻¹ .

  In addition to the components described above, water is added to the ink in the range of the above-described preferable surface tension and viscosity. The amount of water added is not particularly limited, but is preferably 10% by mass to 99% by mass, and more preferably 30% by mass to 80% by mass with respect to the entire ink.

  Furthermore, if necessary, for the purpose of controlling properties such as ejection improvement, cellulose derivatives such as polyethyleneimine, polyamines, polyvinylpyrrolidone, polyethylene glycol, ethylcellulose, carboxymethylcellulose, polysaccharides and derivatives thereof, other water-soluble polymers, acrylics Polymer emulsion, polyurethane emulsion, polymer emulsion such as hydrophilic latex, hydrophilic polymer gel, cyclodextrin, macrocyclic amines, dendrimers, crown ethers, urea and its derivatives, acetamide, silicone surfactant, fluorine-based A surfactant or the like can be used.

  In order to adjust conductivity and pH, compounds of alkali metals such as potassium hydroxide, sodium hydroxide and lithium hydroxide, compounds of alkaline earth metals such as calcium hydroxide, ammonium hydroxide, triethanolamine , Nitrogen-containing compounds such as diethanolamine, ethanolamine, methyldiethanolamine, dimethylaminoethanol, 2-amino-2-methyl-1-propanol, acids such as sulfuric acid, hydrochloric acid and nitric acid, strong acid and weak alkali salts such as ammonium sulfate, acetic acid Organic acids such as propionic acid, lactic acid, succinic acid, glycolic acid, gluconic acid, and glyceric acid can be used. The degree of neutralization is not particularly limited, but is usually preferably 10 to 200%, more preferably 20 to 150%, and particularly preferably 50 to 150%. In addition, a pH buffer, an antioxidant, an antifungal agent, a viscosity modifier, a conductive agent, an ultraviolet absorber and the like can be added as necessary.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples at all. In the examples, “parts” represents parts by mass.

It should be noted that elemental analysis and infrared absorption spectrum were used in determining and identifying the structures of the azo dyes and azo compounds of the present invention. For elemental analysis, 2400 CHN Element Analyzer manufactured by Perkin Elmer was used. The infrared absorption spectrum was measured by a KBr tablet method with a resolution of 2 cm ⁻¹ using a Fourier transform outside spectrophotometer FT / IR-410 manufactured by JASCO Corporation.

[Method for producing azo pigment and azo compound]
In the present invention, the coupling component (naphthol compound) represented by the general formula (3) to the following general formula (5) can be synthesized by a known method. The azo dye and azo compound of the present invention include a coupling component (naphthol compound) represented by the general formula (3) to the following general formula (5), the general formula (4) to the following general formula (6). ) Can be produced (synthesized) from a diazo component (aromatic amine) represented by (1) by a coupling reaction with a diazonium salt (diazo compound) prepared by a known method. Specific production methods (synthesis methods) of the azo dyes and azo compounds of the present invention are specifically described below in Examples.

Example 1
Below, the specific synthesis method of the said azo dye 1 is shown with the reaction scheme (the following reaction scheme A). Other azo dyes and azo compounds according to the present invention can be synthesized by the same scheme. In addition, the manufacturing method (synthesis method) of an azo dye and an azo compound is not limited to the following method.

(1) Synthesis of Compound (B) To 57.3 g of toluene, 9.0 g (0.048 mol) of 2,3-hydroxynaphthoic acid and 0.12 g of N, N-dimethylformamide were added, heated to 85 ° C., 55.63 g (0.468 mol) of thionyl chloride was added dropwise over 15 minutes. After completion of the dropwise addition, the mixture was refluxed for 1 hour. The reaction solution was added dropwise over 30 minutes to a solution in which 8.09 g (0.050 mol) of separately prepared compound (A) and 26.4 g of toluene were heated to 85 ° C., and the mixture was heated to reflux for 2 hours. After cooling this reaction liquid to 95 ° C, 0.8 g of 28% aqueous ammonia solution and 2.0 g of water were added, and after stirring for 15 minutes at 95-100 ° C, toluene and unreacted compound (A) were removed by steam distillation. did. The precipitated reaction product was collected by filtration, washed with hot water, and dried to obtain 15.2 g (yield: 95.8%) of compound (B). The infrared absorption spectrum of compound (B) is shown in FIG.

(2) Synthesis of Azo Dye 1 After adding 3.63 g (0.015 mol) of Compound (C) to 72 g of water, 5.73 g of 35% hydrochloric acid was added and cooled to −2 to 0 ° C. After adding 4.22 g (0.015 mol) of 25% aqueous sodium nitrite solution to this solution, the mixture was stirred for 30 minutes while maintaining at 0 to 5 ° C. to prepare a diazonium solution. Separately, a coupler solution consisting of 5.60 g (0.015 mol) of the compound (B) obtained by the previous method, 8.81 g of 25% sodium hydroxide solution and 62 g of methyl alcohol was prepared. The prepared diazonium solution and coupler solution were simultaneously added dropwise over 10 minutes to a mixed solution consisting of 45 g of an acetic acid buffer solution having a pH of 5.4 and 50 g of methyl alcohol. After completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes, and further stirred for 15 minutes while maintaining at 60 ° C. The precipitated reaction product was collected by filtration, washed with a mixed solution of hot water and methanol, dried, and dried. Was obtained (yield: 98%). The infrared absorption spectrum of azo dye 1 is shown in FIG.

(Example 2)
(Synthesis of azo dye 2)
The same operation as in Example 1 was carried out except that 0.050 mol of 3-aminobenztrifluoride was used in place of the compound (A) used in Example 1, and 7.97 g (yield of azo dye 2 was obtained). Rate 98%). An infrared absorption spectrum of the azo dye 2 is shown in FIG.

(Example 3)
(Synthesis of Azo Dye 3)
The same procedure as in Example 1 was performed, except that 0.015 mol of 3-amino-4-methoxybenzamide was used instead of 3-amino-4-methoxybenzanilide used in Example 1, and azo dye 3 7.97 g (97% yield) was obtained. The infrared absorption spectrum of the azo dye 3 is shown in FIG.

Example 4
(Synthesis of azo dye 4)
Instead of the compound (A) used in Example 1, 0.050 mol amount of 3-aminobenztrifluoride, and 3-amino-4-methoxybenzamide instead of 3-amino-4-methoxybenzanilide The same operation as in Example 1 was carried out except that 0.015 mol was used, and 7.97 g (yield 97%) of azo dye 4 was obtained. The infrared absorption spectrum of the azo dye 4 is shown in FIG.

(Example 5)
(Synthesis of azo dye 5)
Instead of the compound (A) used in Example 1, 0.050 mol amount of 2-aminobenztrifluoride, and 3-amino-4-methoxybenzamide instead of 3-amino-4-methoxybenzanilide The same operation as in Example 1 was carried out except that 0.015 mol was used, and 7.97 g (yield 95%) of azo dye 5 was obtained. The infrared absorption spectrum of the azo dye 5 is shown in FIG.

(Example 6)
(Synthesis of azo dye 6)
Instead of the compound (A) used in Example 1, 0.050 mol amount of 5-chloro-2-aminobenztrifluoride, and 3-amino-4 instead of 3-amino-4-methoxybenzanilide Except that 0.015 mol amount of -methoxybenzamide was used, the same operation as in Example 1 was performed to obtain 7.97 g of azo dye 6 (yield 97%). An infrared absorption spectrum of the azo dye 6 is shown in FIG.

(Example 7)
(Synthesis of azo dye 7)
Instead of the compound (A) used in Example 1, 0.050 mol amount of 3,5-bis (trifluoromethyl) aniline and 3-amino-4-methoxybenzanilide instead of 3-amino-4-methoxybenzanilide The same operation as in Example 1 was carried out except that 0.015 mol of 4-methoxybenzamide was used, and 7.97 g (yield 96%) of azo dye 7 was obtained. An infrared absorption spectrum of the azo dye 7 is shown in FIG.

(Example 8)
(Synthesis of azo dye 8)
Instead of the compound (A) used in Example 1, 0.050 mol amount of 4-fluoro-3-aminobenztrifluoride, and 3-amino-4 instead of 3-amino-4-methoxybenzanilide The same operation as in Example 1 was carried out except that 0.015 mol amount of -methoxybenzamide was used to obtain 7.97 g (yield 96%) of azo dye 8. The infrared absorption spectrum of the azo dye 8 is shown in FIG.

Example 9
(Synthesis of azo dye 9)
Instead of the compound (A) used in Example 1, 0.050 mol amount of 2-chloro-5-aminobenztrifluoride, and 3-amino-4 instead of 3-amino-4-methoxybenzanilide The same operation as in Example 1 was carried out except that 0.015 mol amount of -methoxybenzamide was used, and 7.97 g (yield 97%) of azo dye 9 was obtained. An infrared absorption spectrum of the azo dye 9 is shown in FIG.

(Example 10)
(Synthesis of azo dye 10)
Instead of the compound (A) used in Example 1, 0.050 mol amount of 4-aminobenztrifluoride, and 3-amino-4-methoxybenzamide instead of 3-amino-4-methoxybenzanilide The same operation as in Example 1 was carried out except that 0.015 mol was used, and 7.97 g (yield 95%) of azo dye 10 was obtained. An infrared absorption spectrum of the azo dye 10 is shown in FIG.

(Example 11)
(Synthesis of azo dye 11)
An azo dye 11 was prepared in the same manner as in Example 1 except that 0.015 mol of 3-amino-4-methylbenzamide was used instead of 3-amino-4-methoxybenzanilide used in Example 1. 7.97 g (97% yield) was obtained.

(Example 12)
(Synthesis of azo dye 12)
Instead of 3-amino-4-methoxybenzanilide used in Example 1, 0.015 mol of 3-amino-4-methoxybenz- (2′-chloro-5′-trifluoromethyl) anilide was used. Were the same as in Example 1 to obtain 7.97 g of azo dye 12 (yield 96%). The infrared absorption spectrum of the azo dye 12 is shown in FIG.

(Example 13)
(Synthesis of azo dye 13)
Instead of the compound (A) used in Example 1, 0.050 mol amount of 3-aminobenztrifluoride, and instead of 3-amino-4-methoxybenzanilide, 3-amino-4-methoxybenz- The same operation as in Example 1 was performed except that 0.013 mol amount of (3′-trifluoromethyl) anilide was used, and 7.97 g (yield 95%) of azo dye 13 was obtained. An infrared absorption spectrum of the azo dye 13 is shown in FIG.

(Example 14)
(Synthesis of azo dye 14)
Instead of 3-amino-4-methoxybenzanilide used in Example 1, the same operation as in Example 1 was carried out except that 0.015 mol of the following compound (D) was used. 97 g (yield 95%) was obtained. The infrared absorption spectrum of the azo dye 14 is shown in FIG.

Compound (D)

(Example 15)
(Synthesis of azo dye 15)
Instead of (A) used in Example 1, 0.050 mol amount of 3-aminobenztrifluoride and 0.015 mol amount of compound (D) are used instead of 3-amino-4-methoxybenzanilide. Except that, the same operation as in Example 1 was performed to obtain 7.97 g (yield 97%) of azo dye 15. An infrared absorption spectrum of the azo dye 15 is shown in FIG.

(Example 16)
(Synthesis of azo dye 16)
The same as Example 1 except that 0.015 mol amount of 4′-amino-2′-methoxy-5′-methylbenzanilide was used instead of 3-amino-4-methoxybenzanilide used in Example 1. Thus, 7.97 g (yield 96%) of azo dye 16 was obtained.

(Example 17)
(Synthesis of azo dye 17)
The same operation as in Example 1 was performed except that 0.015 mol of 2-aminophenol was used instead of 3-amino-4-methoxybenzanilide used in Example 1, and 6.78 g of azo dye 17 was obtained. (Yield 93%).

(Example 18)
(Synthesis of azo dye 18)
An azo dye 18 was prepared in the same manner as in Example 1 except that 0.015 mol of 5-nitro-2-methoxyaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1. Was obtained (yield 96%).

(Example 19)
(Synthesis of azo dye 19)
The same procedure as in Example 1 was performed, except that 0.015 mol of 2-aminobenzonitrile was used instead of 3-amino-4-methoxybenzanilide used in Example 1. 05 g (yield 95%) was obtained.

(Example 20)
(Synthesis of azo dye 20)
The same operation as in Example 1 was carried out except that 0.015 mol of 2-aminostyrene was used instead of 3-amino-4-methoxybenzanilide used in Example 1, and 6.84 g of azo dye 20 was obtained. (Yield 92%) was obtained.

(Example 21)
(Synthesis of azo dye 21)
The same operation as in Example 1 was carried out except that 0.015 mol of 3-ethynylaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1, and 6.74 g of azo dye 21 was obtained. (Yield 91%) was obtained.

(Example 22)
(Synthesis of azo dye 22)
The same operation as in Example 1 was carried out except that 0.015 mol of 4-cyclohexylaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1, and 7.87 g of azo dye 22 was obtained. (Yield 95%).

(Example 23)
(Synthesis of azo dye 23)
The same procedure as in Example 1 was performed, except that 0.015 mol of 2- (4′-aminophenyl) pyridine was used instead of 3-amino-4-methoxybenzanilide used in Example 1. 7.94 g (yield 97%) of the dye 23 was obtained.

(Example 24)
(Synthesis of azo dye 24)
The same procedure as in Example 1 was performed, except that 0.015 mol of 4- (4′-aminophenyl) piperidine was used instead of 3-amino-4-methoxybenzanilide used in Example 1. 7.70 g (yield 93%) of the dye 24 was obtained.

(Example 25)
(Synthesis of azo dye 25)
The same operation as in Example 1 was carried out except that 0.015 mol of 2-phenoxyaniline was used in place of 3-amino-4-methoxybenzanilide used in Example 1, and 8.09 g of azo dye 25 was obtained. (Yield 96%).

(Example 26)
(Synthesis of azo dye 26)
The same operation as in Example 1 was carried out except that 0.015 mol of dimethyl aminoterephthalate was used instead of 3-amino-4-methoxybenzanilide used in Example 1, and 8.53 g of azo dye 26 was used. (Yield 97%).

(Example 27)
(Synthesis of azo dye 27)
The same procedure as in Example 1 was performed, except that 0.015 mol of 2′-aminoacetophenone was used in place of 3-amino-4-methoxybenzanilide used in Example 1, and azo dye 27 was added to 7. 45 g (yield 97%) was obtained.

(Example 28)
(Synthesis of azo dye 28)
In place of 3-amino-4-methoxybenzanilide used in Example 1, the same procedure as in Example 1 was performed except that 0.015 mol of 2-aminobenzoic acid phenyl ester was used. 8.41 g (yield 95%) was obtained.

(Example 29)
(Synthesis of azo dye 29)
The same operation as in Example 1 was carried out except that 0.015 mol of 2-aminobenzophenone was used instead of 3-amino-4-methoxybenzanilide used in Example 1, and 8.26 g of azo dye 29 was obtained. (Yield 96%).

(Example 30)
(Synthesis of azo dye 30)
An azo dye 30 was prepared in the same manner as in Example 1 except that 0.015 mol of 3-amino-N-methylbenzamide was used instead of 3-amino-4-methoxybenzanilide used in Example 1. 7.67 g (97% yield) was obtained.

(Example 31)
(Synthesis of azo dye 31)
The same procedure as in Example 1 was performed, except that 0.015 mol of 3-methylsulfonylaniline was used in place of 3-amino-4-methoxybenzanilide used in Example 1, and azo dye 31 was added to 7. 97 g (yield 97%) was obtained.

(Example 32)
(Synthesis of azo dye 32)
The same procedure as in Example 1 was performed, except that 0.015 mol of 3-phenylsulfonylaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1, and the azo dye 32 was changed to 8. 97 g (yield 98%) was obtained.

(Example 33)
(Synthesis of azo dye 33)
The same procedure as in Example 1 was carried out except that 0.015 mol of 3-sulfamoylaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1, and azo dye 33 was converted to 7 Obtained .81 g (yield 95%).

(Example 34)
(Synthesis of azo dye 34)
The same operation as in Example 1 was performed except that 0.015 mol of 3- (N, N-dimethyl) aminosulfonylaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1. Thus, 8.24 g (95% yield) of azo dye 34 was obtained.

(Example 35)
(Synthesis of azo dye 35)
The same procedure as in Example 1 was performed except that 0.015 mol of 3- (N-phenyl) aminosulfonylaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1, and azo 9.46 g (97% yield) of Dye 35 was obtained.

(Example 36)
(Synthesis of azo dye 36)
The same procedure as in Example 1 was performed, except that 0.015 mol of 3-methylsulfinylaniline was used in place of 3-amino-4-methoxybenzanilide used in Example 1, and azo dye 36 was added to 7. 82 g (yield 98%) was obtained.

(Example 37)
(Synthesis of azo dye 37)
The same procedure as in Example 1 was performed, except that 0.015 mol of 3-phenylsulfinylaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1, and azo dye 37 was added to 9. 73 g (yield 98%) was obtained.

(Example 38)
(Synthesis of azo dye 38)
The same procedure as in Example 1 was performed, except that 0.015 mol of 3-acetylaminoaniline was used in place of 3-amino-4-methoxybenzanilide used in Example 1, and azo dye 38 was added to 7. 59 g (yield 96%) was obtained.

(Example 39)
(Synthesis of azo dye 39)
The same procedure as in Example 1 was performed, except that 0.015 mol of 3-benzoylaminoaniline was used in place of 3-amino-4-methoxybenzanilide used in Example 1, and azo dye 39 was used in 8. 66 g (yield 98%) was obtained.

(Example 40)
(Synthesis of azo dye 40)
The same procedure as in Example 1 was carried out except that 0.015 mol of 3- (N-methoxycarbonyl) aminoaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1, and azo 7.76 g of dye 40 was obtained (yield 95%).

(Example 41)
(Synthesis of azo dye 41)
The same procedure as in Example 1 was carried out except that 0.015 mol of 3- (N-phenoxycarbonyl) aminoaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1, and azo 8.71 g (yield 96%) of the dye 41 was obtained.

(Example 42)
(Synthesis of azo dye 42)
The same procedure as in Example 1 was performed, except that 0.015 mol of 3- (N-methylsulfonyl) aminoaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1. 8.19 g (yield 97%) of the dye 42 was obtained.

(Example 43)
(Synthesis of azo dye 43)
The same procedure as in Example 1 was performed, except that 0.015 mol of 3- (N-benzenesulfonyl) aminoaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1, and azo 9.09 g (yield 97%) of the dye 43 was obtained.

(Example 44)
(Synthesis of azo dye 44)
The same operation as in Example 1 was carried out except that 0.015 mol of 3-ureidoaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1, and 7.44 g of azo dye 44 was obtained. (Yield 94%).

(Example 45)
(Synthesis of azo dye 45)
An azo dye was prepared in the same manner as in Example 1 except that 0.015 mol of 3- (N-sulfamoyl) aminoaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1. Thus, 8.12 g (yield 96%) of 45 was obtained.

(Example 46)
(Synthesis of azo dye 46)
The same operation as in Example 1 was carried out except that 0.015 mol of 2-mercaptoaniline was used in place of 3-amino-4-methoxybenzanilide used in Example 1, and 7.15 g of azo dye 46 was obtained. (Yield 95%).

(Example 47)
(Synthesis of azo dye 47)
The same operation as in Example 1 was carried out except that 0.015 mol of 4-methylthioaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1, and 7.35 g of azo dye 47 was used. (Yield 95%).

(Example 48)
(Synthesis of azo dye 48)
The same operation as in Example 1 was carried out except that 0.015 mol of 4-phenylthioaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1, and the azo dye 48 was changed to 8. 32 g (yield 96%) was obtained.

(Example 49)
(Synthesis of azo dye 49)
The same operation as in Example 1 was carried out except that 0.015 mol of 4-trimethylsilylaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1, and 7.81 g of azo dye 49 was used. (Yield 96%).

(Example 50)
(Synthesis of azo dye 50)
The same operation as in Example 1 was carried out except that 0.015 mol of 4-dimethylphenylsilylaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1, and azo dye 50 was changed to 8 .70 g (yield 96%) was obtained.

(Example 51)
(Synthesis of azo dye 51)
The same operation as in Example 1 was carried out except that 0.015 mol of 4-diphenylmethylsilylaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1, and azo dye 51 was prepared in 9%. .59 g (yield 96%) was obtained.

(Example 52)
(Synthesis of azo dye 52)
The same procedure as in Example 1 was performed, except that 0.015 mol of 4-triphenylsilylaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1, and 10% of azo dye 52 was obtained. 0.6 g (yield 97%) was obtained.

(Example 53)
(Synthesis of azo dye 53)
The same operation as in Example 1 was carried out except that 0.015 mol of 4-trimethylsiloxyaniline was used in place of 3-amino-4-methoxybenzanilide used in Example 1, and azo dye 53 was added in 8. 12 g (yield 97%) was obtained.

(Example 54)
(Synthesis of azo dye 54)
The same procedure as in Example 1 was carried out except that 0.015 mol of 4-dimethylphenylsiloxyaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1, and azo dye 54 was converted to 9 0.02 g (yield 97%) was obtained.

(Example 55)
(Synthesis of azo dye 55)
The same procedure as in Example 1 was carried out except that 0.015 mol of 4-diphenylmethylsiloxyaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1, and azo dye 55 was converted to 9 .92 g (yield 97%) was obtained.

(Example 56)
(Synthesis of azo dye 56)
The same procedure as in Example 1 was performed, except that 0.015 mol of 4-triphenylsiloxyaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1. 0.8 g (yield 97%) was obtained.

(Example 57)
(Synthesis of azo dye 57)
The same operation as in Example 1 was carried out except that 0.015 mol of 4- (N, N-dimethyl) aminoaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1, 7.46 g (97% yield) of azo dye 57 was obtained.

(Example 58)
(Synthesis of azo dye 58)
An azo dye was prepared in the same manner as in Example 1 except that 0.015 mol of 4- (N-phenyl) aminoaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1. 8.16 g (yield 97%) of 58 was obtained.

(Example 59)
(Synthesis of azo dye 59)
The same operation as in Example 1 was carried out except that 0.015 mol of 4- [N- (4-piperidyl)] aminoaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1. As a result, 8.18 g (yield 96%) of azo dye 59 was obtained.

(Example 60)
(Synthesis of azo dye 60)
The same operation as in Example 1 was carried out except that 0.015 mol of 4- [N- (thienyl)] aminoaniline was used instead of 3-amino-4-methoxybenzanilide used in Example 1. 8.16 g (96% yield) of azo dye 60 was obtained.

(Example 61)
Hereinafter, a specific method for synthesizing the azo dye 61 is shown together with its reaction scheme (the following reaction scheme A). Other azo dyes and azo compounds according to the present invention can be synthesized by the same scheme. In addition, the manufacturing method (synthesis method) of an azo dye and an azo compound is not limited to the following method.

Synthesis of Azo Dye 61 To a mixed solution consisting of 1.12 g of 25% sodium hydroxide solution and 13.2 g of water, 1.42 g (0.007 mol) of Compound (C) was added, so that the temperature would be −2 to 0 ° C. Cooled down. After adding 1.97 g (0.007 mol) of 25% aqueous sodium nitrite solution to this solution, the mixture was stirred for 15 minutes while maintaining at 0 to 5 ° C. This mixed solution was quickly added to a mixed solution consisting of 2.28 g of 35% hydrochloric acid, 10.0 g of water, ice, and 10.0 g while maintaining at −2 to 0 ° C., and then maintained at 0 to 5 ° C. Stir for 30 minutes. The reaction solution was added to a mixed solution consisting of 2.61 g (0.07 mol) of the compound (B) prepared separately by the previous method, 2.58 g of 25% sodium hydroxide solution and 14.0 g of methyl alcohol at 5 ° C. It was dropped in 15 minutes while maintaining the following. After completion of the dropwise addition, the mixture was stirred overnight at room temperature, 10 g of sodium chloride was added, and the mixture was stirred for 1 hour while maintaining at 65 ° C. The precipitated reaction product was collected by filtration, washed with 20% aqueous sodium chloride solution and dried. 3.62 g (yield: 89.2%) of azo dye 61 was obtained. An infrared absorption spectrum of the azo dye 61 is shown in FIG.

(Example 62)
(Synthesis of azo dye 62)
The same operation as in Example 1 was carried out except that 0.050 mol of 3-aminobenztrifluoride was used in place of the compound (A) used in Example 61, and 3.58 g of azo dye 62 was obtained (increased yield). Rate 90%).

(Example 63)
(Synthesis of azo dye 63)
Compound (E) used in Example 61: The same procedure as in Example 1 was conducted, except that 0.007 mol of 5-amino-2-naphthalenesulfonic acid was used instead of 2-anisidine-5-sulfonic acid. As a result, 3.57 g (yield 78%) of azo dye 63 was obtained.

(Example 64)
(Synthesis of azo dye 64)
Compound (E) used in Example 61: The same operation as in Example 1 was carried out except that 0.007 mol of 4-amino-1-naphthalenesulfonic acid was used instead of 2-anisidine-5-sulfonic acid. As a result, 3.40 g (yield 82%) of the azo dye 64 was obtained.

(Example 65)
(Synthesis of azo dye 65)
Compound (E) used in Example 61: The same procedure as in Example 1 was performed, except that 0.007 mol of 2-anisidine-5-benzoic acid was used instead of 2-anisidine-5-sulfonic acid. 3.77 g (95% yield) of azo dye 64 was obtained.

Example 66
(Synthesis of azo dye 66)
Instead of compound (A) used in Example 61, 0.050 mol amount of 3-aminobenztrifluoride, and compound (E): 2-anisidine-5 instead of 2-anisidine-5-sulfonic acid -Except having used 0.007 mol amount of benzoic acid, operation similar to Example 1 was performed and the azo pigment | dye 64 was obtained 3.57g (yield 96%).

表２ The structure and elemental analysis results of the azo dyes synthesized in Examples 1 to 66 are shown in Table 2.

Table 2

[Dispersion and inkjet recording ink]
Examples of the dispersion of the present invention and ink for ink jet recording using the same will be given below.

(Example 67)
2.5 parts of the azo dye 1 produced in Example 1, 0.5 part of sodium oleate, 5 parts of glycerin and 42 parts of water were mixed, and a planetary ball mill was used together with 100 parts of zirconia beads having a diameter of 0.1 mm. Dispersion was performed at 300 rpm for 6 hours. After the completion of dispersion, zirconia beads were separated to obtain dispersion 1.

(Examples 68 to 132)
Dispersions 2 to 66 were obtained in the same manner as in Example 67 except that the azo dyes 2 to 66 of the present invention were used instead of the azo dye 1 used in Example 67.

(Comparative Example 1)
In place of the azo dye 1 used in Example 1, C.I. I. Comparative dispersion 1 was obtained in the same manner as in Example 1 except that CI Pigment Red 269 (PR269, manufactured by Sanyo Dyeing Co., Ltd., trade name: Permanent Carmine 3810) was used.

(Comparative Example 2)
In place of the azo dye 1 used in Example 1, C.I. I. Comparative dispersion 2 was obtained in the same manner as in Example 1 except that CI Pigment Red 122 (PR122, manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: CROMOPHTAL Jet Magenta DMQ) was used.

(Comparative Example 3)
In place of the azo dye 1 used in Example 1, C.I. I. Comparative dispersion 3 was obtained in the same manner as in Example 1 except that CI Pigment Violet 19 (PV19, manufactured by Clariant Japan Co., Ltd., trade name: Hostaperm Red E5B02) was used.

(Evaluation of dispersion)
The evaluation methods and evaluation criteria for the evaluation items for the dispersion are shown below. The particle size and viscosity of the dispersion were measured according to the following method.

[Measuring method of particle size]
The particle size of the dispersion was measured using a particle size distribution meter (Laser Doppler type particle size distribution meter “Microtrac UPA-150” manufactured by Nikkiso Co., Ltd.). In addition, the particle diameter in a present Example and a comparative example means a volume average particle diameter.

[Measurement method of viscosity]
The viscosity of the dispersion was measured at 25 ° C. with a vibratory viscometer (Yamaichi Denki's viscometer “VM-100A”) in the low viscosity region and with a B-type viscometer for the medium viscosity region and above.

<Dispersion stability>
The dispersion was measured for changes in particle diameter and viscosity immediately after the dispersion was produced and after standing at 70 ° C. for 7 days in a closed polypropylene container. The evaluation criteria are shown below.
A: Change rate of particle diameter and viscosity is within ± 10%.
B: Change rate of particle diameter and viscosity is within ± 10% and within ± 20%.
C: The rate of change in particle size and viscosity exceeds ± 20%.
The results are shown in Table 1.

<Coloring power>
The dispersions obtained in the above Examples and Comparative Examples were No. No. 3 bar coater was used to apply to Seiko Epson Co., Ltd. photomat paper <Pigment only> (model number: KA450MM). The image density of the obtained coated material was measured using a reflection densitometer (X-Rite 938 manufactured by X-Rite), and the results are shown in Table 1 as “coloring power (OD)”.

<Hue>
About the hue, the chromaticity of the coated material obtained above was visually evaluated. The evaluation criteria are shown below.
A: Little yellowishness and great vividness (good).
B: Yellowishness is large or vividness is small.
C: Large yellowishness and small vividness (bad).

  The results are shown in Table 3. As is clear from the results in Table 3, it is clear that the dispersion using the azo dye of the present invention is superior in dispersion stability, coloring power, and hue as compared with the comparative dispersion.

(Example 133)
The polymer dispersant represented by Dispersant 10 described on page 22 of WO 2006/064193 was neutralized with an aqueous potassium hydroxide solution. 30 parts by mass of the synthesized azo dye 1 and 95 parts by mass of ion-exchanged water are added to 75 parts by mass of the resulting aqueous dispersant solution (solid content concentration 20%), and are mixed and roughly dispersed with a disper stirring blade. did. 600 parts by mass of zirconia beads having a diameter of 0.1 mm were put into the mixed and roughly dispersed liquid, and this was dispersed with a disperser (sand grinder mill) for 4 hours, and then separated into beads and a dispersion. While stirring the resulting mixture, 2 parts by mass of polyethylene glycol diglycidyl ether was slowly added at 25 ° C., and the mixture was stirred at 50 ° C. for 6 hours. Furthermore, impurities were removed using an ultrafiltration membrane having a fractional molecular number of 300K, and this was attached to a filter having a pore size of 5 μm (acetylcellulose membrane, outer diameter: 25 mm, manufactured by Fuji Film Co., Ltd.). By filtering with a syringe and removing coarse particles, a dispersion 67 having a solid content concentration of 10% was obtained.

(Examples 134 to 198)
Dispersions 68 to 132 were obtained in the same manner as in Example 67 except that the azo dyes 2 to 66 of the present invention were used instead of the azo dye 1 used in Example 133.

(Comparative Example 4)
In place of the azo dye 1 used in Example 133, C.I. I. Comparative dispersion 4 was obtained in the same manner as in Example 133, except that CI Pigment Red 269 (PR269, manufactured by Sanyo Dyeing Co., Ltd., trade name: Permanent Carmine 3810) was used.

(Comparative Example 5)
In place of the azo dye 1 used in Example 133, C.I. I. Comparative dispersion 5 was obtained in the same manner as in Example 133 except that CI Pigment Red 122 (PR122, manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: CROMOPHTAL Jet Magenta DMQ) was used.

(Comparative Example 6)
In place of the azo dye 1 used in Example 133, C.I. I. Comparative dispersion 6 was obtained in the same manner as in Example 133 except that CI Pigment Violet 19 (PV19, manufactured by Clariant Japan Co., Ltd., trade name: Hostaperm Red E5B02) was used.

  The results are shown in Table 4. As is clear from the results in Table 4, it is clear that the dispersion using the azo dye of the present invention is superior in dispersion stability, coloring power, and hue as compared with the comparative dispersion.

(Examples 199 to 264)
Each dispersion 67 to 132 obtained in Examples 133 to 198 is 5% by mass in solid content, 10% by mass of glycerin, 5% by mass of 2-pyrrolidone, 2% by mass of 1,2-hexanediol, triethylene glycol monobutyl ether. Each component was added so that it might become 2 mass%, propylene glycol 0.5 mass%, and ion-exchange water 75.5 mass%, and the obtained liquid mixture was filtered with a pore size 1 μm filter (acetylcellulose membrane, outer diameter: 25 mm, Ink jet recording inks 1 to 66 (inks 1 to 66) shown in Table 5 were obtained by filtering with a 20 ml syringe equipped with Fuji Film Co., Ltd.) and removing coarse particles.

(Comparative Examples 7-9)
Instead of the dispersions 67 to 132 obtained in Examples 133 to 198, the comparative dispersions 4 to 6 obtained in Comparative Examples 4 to 6 were used, respectively, in the same manner as in Examples 199 to 264. Comparative ink jet recording inks 1 to 3 (comparative inks 1 to 3) were obtained.

  The following evaluations were performed for the inks of Examples 133 to 198 and Comparative Examples 7 to 9. The results are shown in Table 5.

(Evaluation of ink for inkjet recording)
<Discharge stability>
After the ink jet recording ink was filled in the printer cartridge, 100 pages of images in which letters and fills were mixed were continuously printed on an A4 size plain paper at 20 to 25 ° C. in an environment of 40 to 60% RH. . The obtained printed matter (printed matter) was visually observed and evaluated according to the following indices.
A: Printing disorder is not recognized at all.
B: Although printing disorder was recognized, it was less than 10 places (practical level).
C: Disturbance of printing was observed in the range of 10 or more and less than 100.
D: Disturbance of printing was observed at 100 or more locations.

<Storage stability>
The ink-jet recording ink was measured in a polypropylene sealed container immediately after production of the ink-jet recording ink and after standing for 7 days, and the rate of change in particle size and viscosity was measured. The results are shown in Table 5 below. The evaluation criteria are shown below. The particle size and viscosity were measured by the same method as for the dispersion.
A: Change rate of particle diameter and viscosity is within ± 10%.
B: Change rate of particle diameter and viscosity is within ± 10% and within ± 20%.
C: The rate of change in particle size and viscosity exceeds ± 20%.

  In Table 5, “ejection stability” and “storage stability” are recorded by loading each ink jet recording ink into an ink liquid cartridge of a printer (model number: PX-101) manufactured by Seiko Epson Corporation. Evaluation was performed by printing a monochrome image pattern with the density changed stepwise in the recommended mode “clean” on a photo mat paper <special pigment> (model number: KA450MM) manufactured by Seiko Epson Corporation.

  As is apparent from the results in Table 5, the inkjet recording ink produced using the dispersion of the present invention was excellent in ejection stability and storage stability, and both were excellent in color characteristics.

[Coloring composition and toner]
Examples of the toner that is one of the colored compositions of the present invention will be given below.

Examples 265-330, Comparative Examples 10-12
[Crushing toner]
Using each of the azo dyes produced in Examples 1 to 66, 100 g of a polyester resin and 5 g of the dye were stirred and mixed in a ball mill, melt-kneaded, cooled, and pulverized and classified to obtain a pulverized toner. As Comparative Examples 10 to 12, pulverized toners were similarly obtained using known pigments shown in Table 6.

Examples 331 to 396, Comparative Examples 13 to 15
[Aggregating toner]
Using each of the azo dyes produced in Examples 1 to 66, an agglomerated toner was produced by the following method. As Comparative Examples 13 to 15, aggregation method toners were similarly obtained using known pigments shown in Table 7.

(1) Production of Colorant Dispersion Solution 80 g of ion-exchanged water and 3 g of alkylbenzene sulfonate were added to each 20 g of each azo dye and dispersed with a mechanical disperser to obtain a colored dispersion of each dye.

(2) Production of polymer emulsion In a reactor, 330 g of ester wax emulsion (as solid content) and 13 kg of ion-exchanged water were added and the temperature was raised to 90 ° C., 3 g of alkylbenzene sulfonate, 2.5 kg of styrene, n-butyl acrylate 650 g, 170 g of methacrylic acid, 330 g of 8% aqueous hydrogen peroxide solution and 330 g of 8% ascorbic acid aqueous solution were added. The reaction was continued at 90 ° C. for 7 hours to obtain a polymer emulsion.

(3) Production of Toner 9.5 g of a colorant dispersion was poured into 150 g of the polymer emulsion and mixed and stirred. 40 g of 0.5% aluminum sulfate solution was poured into this while stirring. The temperature was raised to 60 ° C., and stirring was continued for 2 hours, followed by filtration, washing and drying to obtain an agglomerated toner.

Examples 397 to 462, Comparative Examples 16 to 18
[Suspension polymerization toner]
Using each of the azo dyes produced in Examples 1 to 66, suspension polymerization toners were produced by the following method. As Comparative Examples 16 to 18, suspension polymerization toners were similarly obtained using known pigments shown in Table 8.

(1) Production of aqueous dispersion medium 710 g of ion-exchanged water and 450 g of 0.1 mol / liter trisodium phosphate aqueous solution were added to the reactor and heated to 65 ° C., and 68 g of 1.0 mol / liter calcium chloride aqueous solution was added. An aqueous dispersion medium containing a dispersion containing colloidal calcium phosphate was gradually added.

(2) Production of toner 30 g of ester wax was added to a dispersion obtained by adding 14 g of dye to 165 g of styrene monomer and 35 g of n-butyl acrylate and dispersed with a sand grinder, and dissolved at 80 ° C. Subsequently, 2 g of n-octyl-3-mercaptopropionic acid ester and 11 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator were gradually added to the aqueous dispersion medium while stirring. In addition, a solution containing the monomer was dispersed in water. Subsequently, a polymerization reaction was carried out at 65 ° C. for 10 hours. The toner was obtained by adjusting the pH, filtering, washing and drying.

(Evaluation of toner)
Hydrophobic silica (0.3 g) was externally added to 50 g of each of the toners obtained in the above Examples and Comparative Examples, and evaluation was performed by the following method using an electrophotographic printer. In the polymerized toner method, the dispersibility of the colorant and the stability of the dispersion were also evaluated. The evaluation results are shown in Tables 6-8.

<Transparency>
A solid image was printed on an OHP sheet, and the transparency of the image was observed. The evaluation criteria are as follows.
A: Good, B: Somewhat bad, C: Bad

<Coloring power>
A solid image was printed on an OHP sheet, and the coloring power of the image was observed. The evaluation criteria are as follows.
A: Good, B: Somewhat bad, C: Bad

<Dispersibility>
The dispersibility of the dye in the dispersion medium was observed. The evaluation criteria are as follows.
A: Good, B: Somewhat bad, C: Bad

<Dispersion stability>
It was observed whether there was no aggregation or sedimentation of the dye and a stable dispersion over time. The evaluation criteria are as follows.
A: Good, B: Somewhat bad, C: Bad

  As shown in Table 6, as compared with the examples, the comparative examples have poor dispersibility in the pulverized toner production, and are inferior in transparency and coloring power.

  As shown in Table 7, as compared with the examples, in the comparative examples, the dispersibility and dispersion stability are poor in the production of the aggregation method toner, and the transparency and coloring power are also inferior.

  As shown in Table 8, as compared with the Examples, the Comparative Example has poor dispersibility and dispersion stability in the production of the suspension polymerization method toner, and is inferior in transparency and coloring power.

Claims (16)

An azo dye represented by the following general formula (1).
General formula (1)

(In General Formula (1), X ^{1 to} X ¹⁰ each independently have a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group that may have a substituent, or a substituent. May have an alkenyl group, an alkynyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Good aliphatic heterocyclic group, aromatic heterocyclic group optionally having substituent, hydroxyl group, alkoxyl group optionally having substituent, aryloxy group optionally having substituent, carboxyl Group, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, an alkylcarbonyl group which may have a substituent, and a substituent which may have a substituent Good arylcarbonyl group, carba Yl group, an optionally substituted alkylaminocarbonyl group, an optionally substituted arylaminocarbonyl group, a sulfo group, an optionally substituted alkylsulfonyl group, and a substituent. An arylsulfonyl group which may have, an sulfimoyl group, an alkylaminosulfonyl group which may have a substituent, an arylaminosulfonyl group which may have a substituent, and a substituent. An alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylcarbonylamino group which may have a substituent, an arylcarbonylamino group which may have a substituent, a substituent An alkoxycarbonylamino group that may have, an aryloxycarbonylamino group that may have a substituent, and a substituent An alkylsulfonylamino group which may have a substituent, an arylsulfonylamino group which may have a substituent, a ureido group, a sulfamoylamino group, a mercapto group, an alkylthio group which may have a substituent, and a substituent. An arylthio group which may have a substituent, a trialkylsilyl group which may have a substituent, a dialkylarylsilyl group which may have a substituent, an alkyldiarylsilyl group which may have a substituent, A triarylsilyl group which may have a substituent, a trialkylsiloxy group which may have a substituent, a dialkylarylsiloxy group which may have a substituent, or a substituent Good alkyldiarylsiloxy group, optionally substituted triarylsiloxy group, or alkyl group, aryl group, aliphatic heterocyclic group Or an amino group substituted with an aromatic heterocyclic group, and at least one of X ^{1 to} X ⁵ represents a perfluoroalkyl group. X ⁶ and X ⁷ , X ⁷ and X ⁸ , X ⁸ and X ⁹ , and X ⁹ and X ¹⁰ may be bonded to each other to form a ring. ) The azo dye according to claim 1, wherein X ⁴ is a perfluoroalkyl group, X ⁷ is a carbamoyl group or an arylaminocarbonyl group, and X ¹⁰ is an alkoxyl group. ^{X 1, X 2, X 3} , X 5, X 6, X 8, claim 1 or 2 wherein the azo dye X ⁹ is a hydrogen atom. The azo dye according to claim 1, wherein X ¹ is a chlorine atom and X ⁴ is a perfluoroalkyl group. The azo dye according to claim 4, wherein X ⁷ is a carbamoyl group or an arylaminocarbonyl group, and X ¹⁰ is an alkoxyl group. The azo dye according to claim 4 or 5, wherein X ² , X ³ , X ⁵ , X ⁶ , X ⁸ and X ⁹ are hydrogen atoms. An azo compound represented by the following general formula (2).
General formula (2)

(In General Formula (2), X ^{11 to} X ²⁰ each independently have a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group that may have a substituent, or a substituent. May have an alkenyl group, an alkynyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Good aliphatic heterocyclic group, aromatic heterocyclic group optionally having substituent, hydroxyl group, alkoxyl group optionally having substituent, aryloxy group optionally having substituent, carboxyl Group, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, an alkylcarbonyl group which may have a substituent, and a substituent which may have a substituent Good arylcarbonyl group, carba A moyl group, an alkylaminocarbonyl group which may have a substituent, an arylaminocarbonyl group which may have a substituent, a sulfo group, an alkylsulfonyl group which may have a substituent, a substituent; An arylsulfonyl group which may have, an sulfimoyl group, an alkylaminosulfonyl group which may have a substituent, an arylaminosulfonyl group which may have a substituent, and a substituent. An alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylcarbonylamino group which may have a substituent, an arylcarbonylamino group which may have a substituent, a substituent An alkoxycarbonylamino group that may have, an aryloxycarbonylamino group that may have a substituent, and a substituent An alkylsulfonylamino group which may have a substituent, an arylsulfonylamino group which may have a substituent, a ureido group, a sulfamoylamino group, a mercapto group, an alkylthio group which may have a substituent, and a substituent. An arylthio group which may have a substituent, a trialkylsilyl group which may have a substituent, a dialkylarylsilyl group which may have a substituent, an alkyldiarylsilyl group which may have a substituent, A triarylsilyl group which may have a substituent, a trialkylsiloxy group which may have a substituent, a dialkylarylsiloxy group which may have a substituent, or a substituent Good alkyldiarylsiloxy group, optionally substituted triarylsiloxy group, or alkyl group, aryl group, aliphatic heterocyclic ring Or an amino group substituted with an aromatic heterocyclic group, at least one of X ¹¹ to X ¹⁵ represents a perfluoroalkyl group. X ¹⁶ and X ¹⁷ , X ¹⁷ and X ¹⁸ , X ¹⁸ and X ¹⁹ , and X ¹⁹ and X ²⁰ may be bonded to each other to form a ring. ) The azo compound according to claim 7, wherein X ¹⁴ is a perfluoroalkyl group, X ¹⁷ is a carbamoyl group or arylaminocarbonyl group, and X ²⁰ is an alkoxyl group. The azo compound according to claim 7 or 8, wherein X ¹¹ , X ¹² , X ¹³ , X ¹⁵ , X ¹⁶ , X ¹⁸ and X ¹⁹ are hydrogen atoms. The azo compound according to claim 7, wherein X ¹¹ is a chlorine atom and X ¹⁴ is a perfluoroalkyl group. The azo compound according to claim 10, wherein X ¹⁷ is a carbamoyl group or an arylaminocarbonyl group, and X ²⁰ is an alkoxyl group. The azo compound according to claim 10 or 11, wherein X ¹² , X ¹³ , X ¹⁵ , X ¹⁶ , X ¹⁸ and X ¹⁹ are hydrogen atoms. The azo compound according to any one of claims 7 to 12, wherein a naphthol compound represented by the following general formula (3) is reacted with a diazo compound of an aromatic amine represented by the following general formula (4). Manufacturing method.
General formula (3)

(In General Formula (3), X ^{11 to} X ¹⁵ each independently have a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group that may have a substituent, or a substituent. May have an alkenyl group, an alkynyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Good aliphatic heterocyclic group, aromatic heterocyclic group optionally having substituent, hydroxyl group, alkoxyl group optionally having substituent, aryloxy group optionally having substituent, carboxyl Group, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, an alkylcarbonyl group which may have a substituent, and a substituent which may have a substituent Good arylcarbonyl group, carba A moyl group, an alkylaminocarbonyl group which may have a substituent, an arylaminocarbonyl group which may have a substituent, a sulfo group, an alkylsulfonyl group which may have a substituent, a substituent; An arylsulfonyl group which may have, an sulfimoyl group, an alkylaminosulfonyl group which may have a substituent, an arylaminosulfonyl group which may have a substituent, and a substituent. An alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylcarbonylamino group which may have a substituent, an arylcarbonylamino group which may have a substituent, a substituent An alkoxycarbonylamino group that may have, an aryloxycarbonylamino group that may have a substituent, and a substituent An alkylsulfonylamino group which may have a substituent, an arylsulfonylamino group which may have a substituent, a ureido group, a sulfamoylamino group, a mercapto group, an alkylthio group which may have a substituent, and a substituent. An arylthio group which may have a substituent, a trialkylsilyl group which may have a substituent, a dialkylarylsilyl group which may have a substituent, an alkyldiarylsilyl group which may have a substituent, A triarylsilyl group which may have a substituent, a trialkylsiloxy group which may have a substituent, a dialkylarylsiloxy group which may have a substituent, or a substituent Good alkyldiarylsiloxy group, optionally substituted triarylsiloxy group, or alkyl group, aryl group, aliphatic heterocyclic ring Or an amino group substituted with an aromatic heterocyclic group, at least one of X ¹¹ to X ¹⁵ represents a perfluoroalkyl group. )
General formula (4)

(In General Formula (4), X ^{16 to} X ²⁰ each independently have a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group that may have a substituent, or a substituent. May have an alkenyl group, an alkynyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Good aliphatic heterocyclic group, aromatic heterocyclic group optionally having substituent, hydroxyl group, alkoxyl group optionally having substituent, aryloxy group optionally having substituent, carboxyl Group, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, an alkylcarbonyl group which may have a substituent, and a substituent which may have a substituent Good arylcarbonyl group, carba A moyl group, an alkylaminocarbonyl group which may have a substituent, an arylaminocarbonyl group which may have a substituent, a sulfo group, an alkylsulfonyl group which may have a substituent, a substituent; An arylsulfonyl group which may have, an sulfimoyl group, an alkylaminosulfonyl group which may have a substituent, an arylaminosulfonyl group which may have a substituent, and a substituent. An alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylcarbonylamino group which may have a substituent, an arylcarbonylamino group which may have a substituent, a substituent An alkoxycarbonylamino group that may have, an aryloxycarbonylamino group that may have a substituent, and a substituent An alkylsulfonylamino group which may have a substituent, an arylsulfonylamino group which may have a substituent, a ureido group, a sulfamoylamino group, a mercapto group, an alkylthio group which may have a substituent, and a substituent. An arylthio group which may have a substituent, a trialkylsilyl group which may have a substituent, a dialkylarylsilyl group which may have a substituent, an alkyldiarylsilyl group which may have a substituent, A triarylsilyl group which may have a substituent, a trialkylsiloxy group which may have a substituent, a dialkylarylsiloxy group which may have a substituent, or a substituent Good alkyldiarylsiloxy group, optionally substituted triarylsiloxy group, or alkyl group, aryl group, aliphatic heterocyclic ring Or a substituted amino group in the aromatic heterocyclic group. X ¹⁶ and X ¹⁷ , X ¹⁷ and X ¹⁸ , X ¹⁸ and X ¹⁹ , and X ¹⁹ and X ²⁰ may be bonded to each other to form a ring. ) A naphthol compound represented by the following general formula (3).
General formula (3)

(In General Formula (3), X ^{11 to} X ¹⁵ each independently have a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group that may have a substituent, or a substituent. May have an alkenyl group, an alkynyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Good aliphatic heterocyclic group, aromatic heterocyclic group optionally having substituent, hydroxyl group, alkoxyl group optionally having substituent, aryloxy group optionally having substituent, carboxyl Group, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, an alkylcarbonyl group which may have a substituent, and a substituent which may have a substituent Good arylcarbonyl group, carba A moyl group, an alkylaminocarbonyl group which may have a substituent, an arylaminocarbonyl group which may have a substituent, a sulfo group, an alkylsulfonyl group which may have a substituent, a substituent; An arylsulfonyl group which may have, an sulfimoyl group, an alkylaminosulfonyl group which may have a substituent, an arylaminosulfonyl group which may have a substituent, and a substituent. An alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylcarbonylamino group which may have a substituent, an arylcarbonylamino group which may have a substituent, a substituent An alkoxycarbonylamino group that may have, an aryloxycarbonylamino group that may have a substituent, and a substituent An alkylsulfonylamino group which may have a substituent, an arylsulfonylamino group which may have a substituent, a ureido group, a sulfamoylamino group, a mercapto group, an alkylthio group which may have a substituent, and a substituent. An arylthio group which may have a substituent, a trialkylsilyl group which may have a substituent, a dialkylarylsilyl group which may have a substituent, an alkyldiarylsilyl group which may have a substituent, A triarylsilyl group which may have a substituent, a trialkylsiloxy group which may have a substituent, a dialkylarylsiloxy group which may have a substituent, or a substituent Good alkyldiarylsiloxy group, optionally substituted triarylsiloxy group, or alkyl group, aryl group, aliphatic heterocyclic ring Or an amino group substituted with an aromatic heterocyclic group, at least one of X ¹¹ to X ¹⁵ represents a perfluoroalkyl group. ) A dispersion comprising at least one azo dye according to any one of claims 1 to 6 dispersed in a medium. A coloring composition comprising at least one azo dye according to any one of claims 1 to 6 and a resin.

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