JP4383156B2 - Ink jet ink, ink jet recording method, and composition for color toner - Google Patents

Description

  The present invention relates to an inkjet ink containing an azo dye, an inkjet recording method, and a composition for a color toner.

In recent years, a material for forming a color image has been mainly used as an image recording material. Specifically, an inkjet recording material, an electrophotographic recording material, a transfer type silver halide photosensitive material, a printing ink. Recording pens are actively used.
In these color image recording materials, in order to reproduce or record a full color image, so-called additive color mixing and subtractive color mixing three primary colors (dyes and pigments) are used, but a preferable color reproduction range can be realized. The fact is that there are no fast-moving dyes that have absorption characteristics and can withstand various use and environmental conditions, and improvements are strongly desired.

The ink jet recording method is rapidly spreading and further developing because of its low material cost, high speed recording, low noise during recording, and easy color recording.
Inkjet recording methods include a continuous method in which droplets are continuously ejected and an on-demand method in which droplets are ejected in accordance with image information signals. In the ejection method, liquid is applied by applying pressure with a piezo element. There are a method of ejecting droplets, a method of generating bubbles in ink by heat and ejecting droplets, a method of using ultrasonic waves, and a method of sucking and ejecting droplets by electrostatic force. As the ink for ink jet recording, water-based ink, oil-based ink, or solid (melted type) ink is used.

  For dyes used in such inks for ink jet recording, the solvent has good solubility or dispersibility, high-density recording is possible, hue is good, light, heat, in the environment Fast against active gases (NOx, ozone and other oxidizing gases, SOx, etc.), excellent fastness to water and chemicals, good fixability to image-receiving materials, and low bleeding. It is required that the ink has excellent storability, has no toxicity, has high purity, and can be obtained at low cost. However, it is extremely difficult to search for pigments that meet these requirements at a high level. In particular, when printing on an image receiving material that has a good black hue and is a dye that is fast to light, humidity, and heat, especially an ink receiving layer containing porous white inorganic pigment particles. It is strongly desired to be robust against oxidizing gases such as ozone in the environment.

  In color copiers and color laser printers that use electrophotography, toners in which a colorant is dispersed in resin particles are generally used. As performance required for color toners, absorption characteristics that can realize a preferable color gamut, especially high transparency (transparency), which is a problem when used in the Over Head Projector (hereinafter referred to as “OHP”), and use And various fastnesses under environmental conditions. As a toner, a pigment in which a pigment is dispersed as a coloring material is generally used. However, a toner using a pigment is excellent in light resistance, but is inferior to a dye in terms of color reproducibility, and further insoluble. Therefore, it is easy to agglomerate, and a decrease in transparency and a change in the hue of the transmitted color are problematic. On the other hand, a toner using a dye as a coloring material is disclosed in Patent Document 1 below. However, a toner using a dye as shown in these examples, on the contrary, is highly transparent and has no hue change. There is a problem with light resistance.

The dyes used in each of the above applications must have the following properties in common. That is, it has favorable absorption characteristics in terms of color reproducibility, fastness under the environmental conditions used, for example, light resistance, heat resistance, moisture resistance, resistance to oxidizing gases such as ozone, and other chemical fastness such as sulfurous acid gas For example, the property is good and the molar extinction coefficient is large.
Conventionally, disazo dyes and trisazo dyes have been generally used as black dyes. Non-heterocyclic compounds such as phenol, naphthol, naphthylamine, and aniline are widely used as raw materials for these disazo dyes and trisazo dyes. As the disazo dyes obtained from these raw materials, the dyes disclosed in Patent Document 2 are known, but all have the problem of poor light fastness, and fastness to oxidizing gases such as ozone. Is extremely inadequate.
In order to develop a colorant that is robust against oxidizing gases such as ozone, the present inventors have moved away from conventional raw materials such as phenol, naphthol, naphthylamine, and aniline, and mainly use heterocyclic compounds as raw materials. It came to the idea of doing. So far, water-insoluble disazo dyes and trisazo dyes containing two or more heterocycles have been described in Patent Document 3, Patent Document 4, etc., but these dyes are used for dyeing fibers. So-called disperse dyes and reactive dyes that have been developed, have the performance required by the present invention, that is, whether they have favorable absorption characteristics for color reproduction, and fastness (for example, light resistance) , Heat resistance, moisture resistance, particularly resistance to oxidizing gases such as ozone, which is a problem in ink jet image formation, and other chemical fastness properties such as sulfurous acid gas) are not disclosed at all. It is unclear as to whether it is optimal for image formation.
JP-A-8-123085 European Patent No. 0761771 German Patent 2743097 JP 59-133259 A

An object of the present invention is to solve the above conventional problems and achieve the following object.
That is, the object of the present invention is to provide (1) various colored compositions such as ink for printing such as inkjet and color toner for electrophotography, which give a colored image and coloring material excellent in hue and fastness. (2) To provide an ink jet recording method having a good hue by using the ink and capable of forming an image having high fastness against light and an active gas in the environment, particularly ozone gas. is there.

一般式（４）中：
Ａは置換されていてもよい芳香族基又は複素環基を表し、置換基を有する場合の置換基はハロゲン原子、アルコキシカルボニル基又はニトロ基である。ＸはＮ又は−Ｃ（Ｒ ₈ ）＝を表し、Ｒ ₈ はシアノ基、カルバモイル基、アシル基、アルコキシカルボニル基、アルキルスルホニル基、又はアリールスルホニル基を表す。Ｒ _７ はアルキル基又はアリール基を表す。
Ｂ _１ 及びＢ _２ はそれぞれ＝ＣＲ ₁ −及び−ＣＲ ₂ ＝を表し、Ｒ ₁ はシアノ基、Ｒ ₂ はアルキル基を表す。
Ｇは置換基を有してもよいアニリノ基を表し、置換基を有する場合の置換基はアルキル基、アルコキシ基、アルキルカルバモイル基である。
Ｒ _５ 及びＲ _６ は水素原子又は置換基を有してもよいアリール基を表し、置換基を有する場合の置換基はアルキル基、アルコキシ基、アルキルカルバモイル基である。但し、Ｒ ₅ 、Ｒ ₆ が同時に水素原子であることはない。
〔２〕
前記一般式（４）中：
Ａは置換されていてもよいフェニル基、ピリジル基又はベンゾチアゾリル基を表し、置換基を有する場合の置換基はハロゲン原子、アルコキシカルボニル基又はニトロ基であり、ＸはＮ又は−Ｃ（Ｒ ₈ ）＝を表し、Ｒ ₈ はシアノ基を表し、Ｒ _７ はアルキル基又はアリール基を表し、
Ｂ _１ 及びＢ _２ はそれぞれ＝ＣＲ ₁ −及び−ＣＲ ₂ ＝を表し、Ｒ ₁ はシアノ基、Ｒ ₂ はアルキル基を表し、
Ｇは置換基を有してもよいアニリノ基を表し、アニリノ基が置換基を有する場合の置換基は置換基を有してもよいフェニル基を表し、フェニル基が置換基を有する場合の置換基はアルキル基、アルコキシ基、アルキルカルバモイル基であり、
Ｒ _５ 及びＲ _６ は水素原子又は置換基を有してもよいフェニル基を表し、置換基を有する場合の置換基はアルキル基、アルコキシ基、アルキルカルバモイル基であり、但し、Ｒ ₅ 、Ｒ ₆ が同時に水素原子であることはないことを特徴とする〔１〕に記載のインクジェット用インク。
〔３〕
支持体上に白色無機顔料粒子を含有するインク受容層を有する受像材料上に、〔１〕〜〔２〕のいずれかに記載のインクジェット用インクを用いて画像を形成することを特徴とするインクジェット記録方法。
〔４〕
〔１〕〜〔３〕のいずれかに記載されるアゾ色素を少なくとも１種含有することを特徴とするカラートナー用組成物。
本発明は上記〔１〕〜〔４〕に関するものであるが、その他の事項についても記載した。 The inventors of the present invention have studied in detail azo dye derivatives aiming at good hue, high fastness to light and ozone, and highly soluble dye, and use a dye represented by the following general formula (4). It has been found that the above object of the present invention can be achieved.
That is, according to the present invention, an ink-jet ink, an ink-jet recording method, and a color toner composition having the following constitution are provided to achieve the above object of the present invention.
(1)
An ink-jet ink comprising at least one azo dye represented by the following general formula (4) and having at least one alkyl chain having 4 or more carbon atoms and having no ionic hydrophilic group.

In general formula (4):
A represents an optionally substituted aromatic group or heterocyclic group, and the substituent in the case of having a substituent is a halogen atom, an alkoxycarbonyl group or a nitro group. X represents N or —C (R ₈ ) ═, and R ₈ represents a cyano group, a carbamoyl group, an acyl group, an alkoxycarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group. R ₇ represents an alkyl group or an aryl group.
B ₁ and B ₂ each represent ═CR ₁ — and —CR ₂ ═ , R ₁ represents a cyano group, and R ₂ represents an alkyl group.
G represents an anilino group which may have a substituent, and the substituent in the case of having a substituent is an alkyl group, an alkoxy group or an alkylcarbamoyl group.
R ₅ and R ₆ represent a hydrogen atom or an aryl group which may have a substituent, and the substituent in the case of having a substituent is an alkyl group, an alkoxy group, or an alkylcarbamoyl group. However, R ₅ and R ₆ are not simultaneously hydrogen atoms.
[2]
In the general formula (4):
A represents an optionally substituted phenyl group, pyridyl group or benzothiazolyl group, and when having a substituent, the substituent is a halogen atom, an alkoxycarbonyl group or a nitro group, and X is N or —C (R ₈ ). =, R ₈ represents a cyano group, R ₇ represents an alkyl group or an aryl group,
B ₁ and B ₂ each represent ═CR ₁ — and —CR ₂ ═ , R ₁ represents a cyano group, R ₂ represents an alkyl group,
G represents an anilino group which may have a substituent, the substituent when the anilino group has a substituent represents a phenyl group which may have a substituent, and the substitution when the phenyl group has a substituent The group is an alkyl group, an alkoxy group, an alkylcarbamoyl group,
R ₅ and R ₆ represent a hydrogen atom or a phenyl group which may have a substituent, and the substituent in the case of having a substituent is an alkyl group, an alkoxy group, or an alkylcarbamoyl group, provided that R ₅ , R ₆ The inkjet ink according to [1], wherein are not simultaneously hydrogen atoms .
[3]
An ink jet comprising: forming an image using an ink jet ink according to any one of [1] to [2] on an image receiving material having an ink receiving layer containing white inorganic pigment particles on a support. Recording method.
[ 4]
A composition for a color toner, comprising at least one azo dye described in any one of [1] to [3] .
The present invention relates to the above [1] to [4], but other matters are also described.

Since the coloring composition of the present invention uses an azo dye excellent in solubility and fastness, a colored image or coloring material excellent in hue and fastness can be obtained. For example, a colored image excellent in hue and fastness can be obtained from an inkjet ink or an electrophotographic color toner composition.
Further, the use of the ink jet ink provides an ink jet recording method which has a good hue and can form an image having high fastness against light and an active gas in the environment, particularly ozone gas.

Hereinafter, the present invention will be described in more detail.
Azo dye
The azo dyes represented by the general formula (1) and the subordinate concepts of the general formula (2), the general formula (3), and the general formula (4) in the present invention will be described in detail.
First, groups and substituents constituting these general formulas will be described.

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

  In this specification, an aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. The aliphatic group may have a branch and may form a ring. The number of carbon atoms in the aliphatic group is preferably 1-20, and more preferably 1-16. The aryl part of the aralkyl group and the substituted aralkyl group is preferably phenyl or naphthyl, particularly preferably phenyl. Examples of aliphatic groups include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-hydroxypropyl, cyclohexyl group, benzyl group, 2-phenethyl group, vinyl group And allyl groups.

  In the present specification, the monovalent aromatic group means an aryl group and a substituted aryl group. The aryl group is preferably phenyl or naphthyl, particularly preferably phenyl. The monovalent aromatic group preferably has 6 to 20 carbon atoms, more preferably 6 to 16. Examples of the monovalent aromatic group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m-pivaloylaminophenyl. The divalent aromatic group is a divalent version of these monovalent aromatic groups, and examples thereof include phenylene, p-tolylene, p-methoxyphenylene, o-chlorophenylene, and naphthylene. .

  The heterocyclic group includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group, and N, O, and S can be exemplified as the hetero atom of the heterocyclic ring. Examples of the substituent include aliphatic groups, halogen atoms, alkyl and arylsulfonyl groups, acyl groups, acylamino groups, sulfamoyl groups, carbamoyl groups, and the like. Examples of the heterocyclic group include 2-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2-benzothiazolyl group, 2-benzoxazolyl group and 2-furyl group.

  The carbamoyl group includes a carbamoyl group having a substituent and an unsubstituted carbamoyl group. Examples of the substituent include an alkyl group. Examples of the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.

  The alkoxycarbonyl group includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. As the alkoxycarbonyl group, an alkoxycarbonyl group having 2 to 20 carbon atoms is preferable. Examples of the substituent include an alkoxy group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

  The aryloxycarbonyl group includes an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. As the aryloxycarbonyl group, an aryloxycarbonyl group having 7 to 20 carbon atoms is preferable. Examples of the substituent include an alkoxy group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

The heterocyclic oxycarbonyl group includes a heterocyclic oxycarbonyl group having a substituent and an unsubstituted heterocyclic oxycarbonyl group. The heterocyclic oxycarbonyl group is preferably a heterocyclic oxycarbonyl group having 2 to 20 carbon atoms. Examples of the substituent include an alkyl group. Examples of the heterocyclic oxycarbonyl group include a 2-pyridyloxycarbonyl group.
The acyl group includes an acyl group having a substituent and an unsubstituted acyl group. The acyl group is preferably an acyl group having 1 to 20 carbon atoms. Examples of the substituent include an alkoxy group. Examples of the acyl group include an acetyl group and a benzoyl group.

  The alkoxy group includes an alkoxy group having a substituent and an unsubstituted alkoxy group. As an alkoxy group, a C1-C20 alkoxy group is preferable. Examples of the substituent include an alkoxy group and a hydroxy group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, and a hydroxyethoxy group.

  The aryloxy group includes an aryloxy group having a substituent and an unsubstituted aryloxy group. The aryloxy group is preferably an aryloxy group having 6 to 20 carbon atoms. Examples of the substituent include an alkoxy group and an alkyl group. Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group, and an o-methoxyphenoxy group.

  The heterocyclic oxy group includes a heterocyclic oxy group having a substituent and an unsubstituted heterocyclic oxy group. The heterocyclic oxy group is preferably a heterocyclic oxy group having 2 to 20 carbon atoms. Examples of the substituent include an alkyl group and an alkoxy group. Examples of the heterocyclic oxy group include a 3-pyridyloxy group and a 3-thienyloxy group.

  The silyloxy group is preferably a silyloxy group substituted with an aliphatic group or aromatic group having 1 to 20 carbon atoms. Examples of the silyloxy group include trimethylsilyloxy and diphenylmethylsilyloxy.

  The acyloxy group includes an acyloxy group having a substituent and an unsubstituted acyloxy group. As the acyloxy group, an acyloxy group having 1 to 20 carbon atoms is preferable. Examples of the substituent include an alkyl group. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

  The carbamoyloxy group includes a carbamoyloxy group having a substituent and an unsubstituted carbamoyloxy group. Examples of the substituent include an alkyl group. Examples of the carbamoyloxy group include an N-methylcarbamoyloxy group.

  The alkoxycarbonyloxy group includes an alkoxycarbonyloxy group having a substituent and an unsubstituted alkoxycarbonyloxy group. As the alkoxycarbonyloxy group, an alkoxycarbonyloxy group having 2 to 20 carbon atoms is preferable. Examples of the alkoxycarbonyloxy group include a methoxycarbonyloxy group and an isopropoxycarbonyloxy group.

  The aryloxycarbonyloxy group includes an aryloxycarbonyloxy group having a substituent and an unsubstituted aryloxycarbonyloxy group. The aryloxycarbonyloxy group is preferably an aryloxycarbonyloxy group having 7 to 20 carbon atoms. Examples of the aryloxycarbonyloxy group include a phenoxycarbonyloxy group.

The amino group includes an amino group substituted with an alkyl group, an aryl group or a heterocyclic group, and the alkyl group, aryl group and heterocyclic group may further have a substituent. As the alkylamino group, an alkylamino group having 1 to 20 carbon atoms is preferable. Examples of the substituent include an alkoxy group. Examples of the alkylamino group include a methylamino group and a diethylamino group.
The arylamino group includes an arylamino group having a substituent, an unsubstituted arylamino group, and an anilino group. The arylamino group is preferably an arylamino group having 6 to 20 carbon atoms. Examples of the substituent include a halogen atom and an alkyl group. Examples of the arylamino group include a phenylamino group and a 2-chlorophenylamino group.
The heterocyclic amino group includes a heterocyclic amino group having a substituent and an unsubstituted heterocyclic amino group. As the heterocyclic amino group, a heterocyclic amino group having 2 to 20 carbon atoms is preferable. Examples of the substituent include an alkyl group and a halogen atom.

  The acylamino group includes an acylamino group having a substituent and an unsubstituted acylamino group. The acylamino group is preferably an acylamino group having 2 to 20 carbon atoms. Examples of the substituent include an alkoxy group. Examples of the acylamino group include an acetylamino group, a propionylamino group, a benzoylamino group, an N-phenylacetylamino group, and a 3,5-dichlorobenzoylamino group.

  The ureido group includes a ureido group having a substituent and an unsubstituted ureido group. The ureido group is preferably a ureido group having 1 to 20 carbon atoms. Examples of the substituent include an alkyl group and an aryl group. Examples of the ureido group include a 3-methylureido group, a 3,3-dimethylureido group, and a 3-phenylureido group.

  The sulfamoylamino group includes a sulfamoylamino group having a substituent and an unsubstituted sulfamoylamino group. Examples of the substituent include an alkyl group. Examples of the sulfamoylamino group include N, N-dipropylsulfamoylamino group.

  The alkoxycarbonylamino group includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. As the alkoxycarbonylamino group, an alkoxycarbonylamino group having 2 to 20 carbon atoms is preferable. Examples of the substituent include a halogen atom. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.

  The aryloxycarbonylamino group includes an aryloxycarbonylamino group having a substituent and an unsubstituted aryloxycarbonylamino group. The aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 20 carbon atoms. Examples of the substituent include an alkyl group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.

  The alkylsulfonylamino group and arylsulfonylamino group include a substituted alkyl and arylsulfonylamino group, and an unsubstituted alkyl and arylsulfonylamino group. As the sulfonylamino group, a sulfonylamino group having 1 to 20 carbon atoms is preferable. Examples of the substituent include an alkoxy group. Examples of these sulfonylamino groups include a methylsulfonylamino group, an N-phenyl-methylsulfonylamino group, a phenylsulfonylamino group, and a 4-methoxyphenylsulfonylamino group.

  The heterocyclic sulfonylamino group includes a heterocyclic sulfonylamino group having a substituent and an unsubstituted heterocyclic sulfonylamino group. The heterocyclic sulfonylamino group is preferably a heterocyclic sulfonylamino group having 1 to 12 carbon atoms. Examples of the substituent include an alkyl group. Examples of the heterocyclic sulfonylamino group include a 2-thiophenesulfonylamino group and a 3-pyridinesulfonylamino group.

  The heterocyclic sulfonyl group includes a heterocyclic sulfonyl group having a substituent and an unsubstituted heterocyclic sulfonyl group. The heterocyclic sulfonyl group is preferably a heterocyclic sulfonyl group having 1 to 20 carbon atoms. Examples of the substituent include an alkyl group. Examples of the heterocyclic sulfonyl group include a 2-thiophenesulfonyl group and a 3-pyridinesulfonyl group.

  The heterocyclic sulfinyl group includes a heterocyclic sulfinyl group having a substituent and an unsubstituted heterocyclic sulfinyl group. The heterocyclic sulfinyl group is preferably a heterocyclic sulfinyl group having 1 to 20 carbon atoms. Examples of the substituent include an alkyl group. Examples of the heterocyclic sulfinyl group include a 4-pyridinesulfinyl group.

  The alkylthio group, arylthio group and heterocyclic thio group include substituted alkyl, aryl and heterocyclic thio groups and unsubstituted alkyl, aryl and heterocyclic thio groups. Alkyl, aryl and heterocyclic thio groups are preferably those having 1 to 20 carbon atoms. Examples of the substituent include an alkoxy group. Examples of the alkyl, aryl and heterocyclic thio groups include a methylthio group, a phenylthio group, and a 2-pyridylthio group.

  The alkylsulfonyl group and arylsulfonyl group include substituted alkyl and arylsulfonyl groups, unsubstituted alkyl and arylsulfonyl groups. Examples of alkyl and arylsulfonyl groups include methylsulfonyl and phenylsulfonyl groups, respectively.

  The alkylsulfinyl group and arylsulfinyl group include substituted alkyl and arylsulfinyl groups, unsubstituted alkyl and arylsulfinyl groups. Examples of alkyl and arylsulfinyl groups include methylsulfinyl group and phenylsulfinyl group, respectively.

  The sulfamoyl group includes a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Examples of the substituent include an alkyl group. Examples of the sulfamoyl group include a dimethylsulfamoyl group and a bis- (2-hydroxyethyl) sulfamoyl group.

Next, general formulas (1), (2), (3) and (4) will be described.
In the following description, what has already been described applies to the group and the substituent.
In the general formula (1), A, B and C are each independently an optionally substituted aromatic group (A and C are monovalent aromatic groups such as aryl groups; B is a divalent aromatic group) A group such as an arylene group) or an optionally substituted heterocyclic group (A and C are monovalent heterocyclic groups; B is a divalent heterocyclic group). Examples of the aromatic ring include a benzene ring and a naphthalene ring, and examples of the hetero atom of the heterocyclic ring include N, O, and S. Examples of heterocycles include 5- to 7-membered rings. An aromatic ring, an aromatic ring, or another heterocyclic ring may be condensed with an aromatic ring or a heterocyclic ring.
The substituent may be an arylazo group or a heterocyclic azo group. In this case, a trisazo dye, a tetrakisazo dye or the like is formed.
Moreover, at least two of A, B, and C are preferably heterocyclic rings.

  A preferable heterocyclic group for C includes an aromatic heterocyclic group, more preferably an aromatic nitrogen-containing 6-membered heterocyclic ring, and particularly preferably an aromatic nitrogen-containing 6 represented by the following general formula (5). A membered heterocyclic group. When C is an aromatic nitrogen-containing 6-membered heterocyclic group represented by the following general formula (5), the general formula (1) corresponds to the general formula (3).

In the general formula (5), B ₁ and B ₂ each represent = CR ₁ -and -CR ₂ =, or either one represents a nitrogen atom and the other represents = CR ₁ -or -CR ₂ =. More preferably, each represents = CR _1- , -CR ₂ =.
R ₅ and R ₆ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or It represents a sulfamoyl group, and each group may further have a substituent. Preferable substituents represented by R ₅ and R ₆ include a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkyl or arylsulfonyl group. More preferably, they are a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, an alkyl or arylsulfonyl group. Most preferably, they are a hydrogen atom, an aryl group, and a heterocyclic group. Each group may further have a substituent. However, R ₅ and R ₆ are not simultaneously hydrogen atoms.

G, R ₁ and R ₂ are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, Heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (arylamino) Group, including heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, heterocyclic sulfonylamino group, nitro Group, alkylthio Group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, alkylsulfinyl group, arylsulfinyl group, heterocyclic sulfinyl group, or sulfamoyl group, each group is further substituted Also good.

  Examples of the substituent represented by G include a hydrogen atom, halogen atom, aliphatic group, aromatic group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, heterocyclic oxy group, amino group (arylamino group, complex Including a cyclic amino group), an acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkylthio group, an arylthio group, or a heterocyclic thio group, more preferably a hydrogen atom, A halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, an amino group (including an arylamino group and a heterocyclic amino group) or an acylamino group, among which a hydrogen atom, an arylamino group, and an acylamino group Most preferred. Each group may further have a substituent.

Preferable substituents represented by R ₁ and R ₂ include a hydrogen atom, an alkyl group, a halogen atom, an alkoxycarbonyl group, a carbamoyl group, a hydroxy group, an alkoxy group, and a cyano group. Each group may further have a substituent.
R ₁ and R ₅ , or R ₅ and R ₆ may combine to form a 5- to 6-membered ring.
Examples of the substituent in the case where each of the substituents represented by R ₁ , R ₂ , R ₅ , R ₆ and G further has a substituent include the substituents mentioned in the above G, R ₁ and R _2. it can. Moreover, it is preferable to further have an alkyl chain having 4 or more carbon atoms as a substituent at any position on R ₁ , R ₂ , R ₅ , R ₆ and G.

  A represents an aromatic group or a heterocyclic group, and is preferably an aryl group, a pyrazolyl group, an imidazolyl group, an isothiazolyl group, a thiadiazolyl group, or a benzothiazolyl group, and these groups may be further substituted. An aryl group having 4 or more alkyl chains, a pyrazolyl group, and an isothiazolyl group are preferable, and an aryl group and an pyrazolyl group having an alkyl chain having 4 or more carbon atoms are most preferable.

  Preferred heterocycles when B is a ring structure include thiophene rings, thiazole rings, imidazole rings, benzothiazole rings, and thienothiazole rings. Each heterocyclic group may further have a substituent. Of these, thiophene rings, thiazole rings, imidazole rings, benzothiazole rings, and thienothiazole rings represented by the following general formulas (a) to (e) are preferable. In addition, when B is a thiophene ring or a thiazole ring represented by the general formula (a) or (b) and C is a structure represented by the general formula (5), the general formula (1) This corresponds to equation (4).

In the general formulas (a) to (e), R ₉ to R ₁₇ represent a substituent having the same meaning as G, R ₁ and R ₂ in the general formula (3).

  In the present invention, a particularly preferred structure is a structure represented by the following general formula (6).

In the general formula (6), Z ₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Z ₁ is preferably an electron-withdrawing group having a σp value of 0.30 or more, more preferably an electron-withdrawing group of 0.45 or more, and particularly preferably an electron-withdrawing group of 0.60 or more. It is desirable not to exceed 0.0. Examples of preferable specific substituents include electron-withdrawing substituents described later. Among them, an acyl group having 2 to 20 carbon atoms, an alkyloxycarbonyl group having 2 to 20 carbon atoms, a nitro group, a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms, and a carbon number A carbamoyl group having 1 to 20 carbon atoms and a halogenated alkyl group having 1 to 20 carbon atoms are preferable. Particularly preferred are a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms, and most preferred is a cyano group.

A represents a substituent having the same meaning as A in formula (1).
R ₁ , R ₂ , R ₅ and R ₆ have the same meaning as in the general formula (3). R ₃ and R ₄ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl and arylsulfonyl group, or sulfamoyl group. Represents. Among these, a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, an alkyl or arylsulfonyl group is preferable, and a hydrogen atom, an aromatic group, and a heterocyclic group are particularly preferable. R ₇ has the same meaning as in the general formula (4). R ₇ is preferably a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, particularly preferably a hydrogen atom or an aromatic group.

Each group described in the general formula (6) may further have a substituent. When each of these groups further has a substituent, examples of the substituent include the substituents described in the general formula (3) and the groups exemplified as G, R ₁ and R ₂ .
Here, Hammett's substituent constant σp value used in this specification will be described. Hammett's rule is an empirical rule proposed by LP Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives, which is widely accepted today. Substituent constants determined by Hammett's rule include σp value and σm value, and these values can be found in many general books. For example, JA Dean edition, “Lange's Handbook of Chemistry” 12th edition, 1979 (Mc Graw-Hill), “Chemical domain” extra edition, 122, 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, which means that it can be found in the above-mentioned book and is limited only to a substituent having a known value in the literature. However, it goes without saying that even if the value is unknown, it also includes a substituent that would be included in the range when measured based on Hammett's rule. In addition, the general formulas (1), (2), (3), (4) and (6) of the present invention include those which are not benzene derivatives, but as a scale showing the electronic effect of the substituents. The σp value is used regardless of the replacement position. In the present invention, the σp value is used in this sense.

Examples of the electron-withdrawing group having a Hammett substituent constant σp value of 0.60 or more include a cyano group, a nitro group, and an alkylsulfonyl group (eg, methylsulfonyl group, arylsulfonyl group (eg, phenylsulfonyl group)). .
Examples of the electron-withdrawing group having a Hammett σp value of 0.45 or more include an acyl group (for example, acetyl group), an alkoxycarbonyl group (for example, dodecyloxycarbonyl group), an aryloxycarbonyl group (for example, m-chlorophenoxycarbonyl) in addition to the above. ), An alkylsulfinyl group (for example, n-propylsulfinyl), an arylsulfinyl group (for example, phenylsulfinyl), a sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dimethylsulfamoyl), a halogenated alkyl group ( For example, trifluoromethyl) can be mentioned.
As the electron-withdrawing group having a Hammett substituent constant σp value of 0.30 or more, in addition to the above, an acyloxy group (for example, acetoxy), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), halogen Alkoxy group (for example, trifluoromethyloxy), halogenated aryloxy group (for example, pentafluorophenyloxy), sulfonyloxy group (for example, methylsulfonyloxy group), halogenated alkylthio group (for example, difluoromethylthio), 2 An aryl group (eg, 2,4-dinitrophenyl, pentachlorophenyl) substituted with one or more electron-withdrawing groups having a σp value of 0.15 or more, and a heterocycle (eg, 2-benzoxazolyl, 2- Benzothiazolyl, 1-phenyl-2-benzimidazolyl) be able to.
Specific examples of the electron-withdrawing group having a σp value of 0.20 or more include a halogen atom in addition to the above.

A particularly preferred combination of substituents as the azo dye represented by the general formula (4) is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfonyl group, or an acyl group as R ₅ and R ₆ . More preferred are a hydrogen atom, an aryl group, a heterocyclic group, and a sulfonyl group, and most preferred are a hydrogen atom, an aryl group, and a heterocyclic group. However, R ₅ and R ₆ are not both hydrogen atoms.
G is preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an amino group or an acylamino group, more preferably a hydrogen atom, a halogen atom, an amino group or an acylamino group, most preferably a hydrogen atom, amino Group, an acylamino group.
B ₁ and B ₂ are preferably ═CR ₁ — and —CR ₂ ═, respectively, and R ₁ and R ₂ are preferably a hydrogen atom, an alkyl group, a halogen atom, a cyano group, a carbamoyl group, a carboxyl group, A hydroxy group, an alkoxy group and an alkoxycarbonyl group, more preferably a hydrogen atom, an alkyl group, a carboxyl group, a cyano group and a carbamoyl group. X is preferably —C (R ₈ ) ═, and R ₈ is preferably a cyano group, a carbamoyl group, an acyl group, an alkoxycarbonyl group, an alkylsulfonyl group or an arylsulfonyl group, and most preferably a cyano group. is there. R ₇ is preferably a hydrogen atom, a heterocyclic group, or an aromatic group, and most preferably a hydrogen atom or an aromatic group.

  In addition, about the preferable combination of a substituent of the compound represented by the said General formula (1), the compound whose at least 1 of a various substituent is the said preferable group is preferable, and many more various substituents are the said preferable. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

  In the present invention, the dye represented by the general formulas (1), (2), (3), (4) and (6) includes at least one alkyl chain having 4 or more carbon atoms. That is, it is preferable that at least one of A, B and C in the general formula (1) includes at least one alkyl chain having 4 or more carbon atoms and two or more alkyl chains having 4 or more carbon atoms. More preferably, it is an alkyl chain having 6 or more carbon atoms. Most preferably, it is a dye having a total carbon number of 12 or more when the carbon numbers of all alkyl chains having 4 or more carbon atoms are added. When the dye contains at least one alkyl chain having 4 or more carbon atoms, the oil solubility of the dye is improved. The upper limit of the total number of carbon atoms of all alkyl chains having 4 or more carbon atoms is about 60.

  The dyes represented by the general formulas (1), (2), (3), (4) and (6) do not contain an ionic hydrophilic group in the molecule and are not water-soluble. In the present invention, the ionic hydrophilic group is a substituent that easily dissociates in water to form an ion (sulfo group, phosphono group, etc.) or a substituent that exists in the form of a salt, and has a pKa of 3 or more. Free substituents (such as carboxyl groups) are not applicable.

  Specific examples of the azo dye represented by the general formula (1) are shown below, but the azo dye used in the present invention is not limited to the following examples.

  The dyes represented by the general formulas (1), (2), (3), (4), and (6) can be synthesized by a coupling reaction between a diazo component and a coupler. The synthesis example of the pigment | dye represented by General formula (1), (2), (3), (4), (6) below is shown.

[Synthesis Example of Dye a-1]
2.00 g of diazo component A-1 was suspended in 20 ml of acetic acid and 20 ml of 85% phosphoric acid, and 2.8 g of concentrated sulfuric acid and 0.6 g of nitrosylsulfuric acid 0.6 g were added while maintaining the liquid temperature at −2 ° C. to 0 ° C. . This solution was added to a solution prepared by dissolving 4.59 g of coupler component B-1 in 40 ml of acetic acid and 30 ml of DMF with stirring, and reacted at 0 to 5 ° C. for 1 hour. The reaction solution was filtered, washed with water, and purified with a silica gel column to obtain 4.89 g (yield: 73%) of the target product a-1. M / S = 763 [lambda] max = 611.0 nm (chloroform).
The synthesis route is shown below.

[Synthesis Example of Dye d-2]
1.30 g of diazo component D-2 and 3.0 g of coupler component B-1 are suspended in 20 ml of formic acid, and 0.40 g of sodium nitrite is further added while maintaining the liquid temperature at 7 ° C. to 10 ° C. The reaction was carried out at 7-10 ° C for a time. This liquid was discharged with ice water, and the slurry was filtered, washed with water, and purified with a silica gel column to obtain 1.23 g (yield 28%) of the target product d-2. M / S = 739, λmax = 579.8 nm (chloroform)
The synthesis route is shown below.

The coloring matter in the present invention is mainly an ink-jet ink composition and a color toner composition of the present invention described below, and its application includes an image recording material for forming an image, particularly a color image. Specifically, there are pressure sensitive recording materials, electrophotographic recording materials, transfer type silver halide photosensitive materials, printing inks, recording pens, and the like, including ink jet recording materials described in detail below, preferably ink jets. A system recording material and a recording material using an electrophotographic system, and more preferably an ink jet system recording material.
The coloring matter in the present invention can be used by adjusting the physical properties such as solubility, dispersibility, and heat mobility suitable for the application with a substituent. Moreover, the pigment | dye in this invention can be used also in a dissolved state, an emulsified dispersion state, and also a solid dispersion state according to the system to be used.

<Inkjet ink composition>
The ink-jet ink composition of the present invention contains a dye represented by the above general formula (1). The inkjet ink composition of the present invention used for the inkjet ink can be prepared by dissolving and / or dispersing the coloring matter of the present invention in an oleophilic medium or an aqueous medium. Preferably, an aqueous medium is used, and an aqueous ink is preferable. You may contain another additive in the range which does not impair the effect of this invention as needed. 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, Well-known additives, such as a foaming agent, a viscosity modifier, a dispersing agent, a dispersion stabilizer, a rust preventive agent, a chelating agent, are mentioned. When oil-soluble dyes are used in the form of a dispersion, these various additives are generally added to the dispersion after the preparation of the dye dispersion, but are added to the oil phase or the aqueous phase at the time of preparation. Also good.

  The anti-drying agent is preferably used for the purpose of preventing clogging due to drying of the ink-jet ink composition of the present invention at an ink jet port of a nozzle used in an ink-jet recording system.

  The anti-drying agent is preferably a water-soluble organic solvent having a vapor pressure lower than that of water. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin. Polyhydric alcohols typified by trimethylolpropane, etc., lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether , Heterocyclic compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethylmorpholine, sulfolane, dimethylsulfoxy , Sulfur-containing compounds such as 3-sulfolene, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred. Moreover, said drying inhibitor may be used independently and may be used together 2 or more types. These drying inhibitors are preferably contained in the ink in an amount of 10 to 50% by mass.

  The penetration enhancer is preferably used for the purpose of allowing ink jet ink to penetrate better into paper. Examples of the penetration enhancer include alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, and nonionic surfactants. it can. If these are contained in the ink in an amount of 5 to 30% by mass, they usually have a sufficient effect, and it is preferable to use them in a range of addition amounts that do not cause printing bleeding and paper loss (print through).

  The ultraviolet absorber is used for the purpose of improving image storage stability. Examples of the ultraviolet absorber include benzotriazoles described in JP-A Nos. 58-185677, 61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194433, US Pat. No. 3,214,463, etc., JP-B Nos. 48-30492, 56-211141, Cinnamic acid compounds described in, for example, Kaihei 10-88106, JP-A-4-298503, 8-53427, 8-239368, 10-182621, JP-A-8- No. 501291, etc., triazine compounds, Research Disclosure No. Compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used.

  The anti-fading agent is used for the purpose of improving image storage stability. As the anti-fading agent, various organic and metal complex anti-fading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like. More specifically, Research Disclosure No. No. 17643, Nos. VII to I, J; 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in US Pat. No. 15,162, or the compounds represented by the general formulas and compound examples of representative compounds described on pages 127 to 137 of JP-A-62-215272 can be used.

  Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. It is preferable to use 0.02 to 1.00% by mass of these in the ink composition for inkjet.

  The neutralizer (organic base, inorganic alkali) can be used as the pH adjuster. For the purpose of improving the storage stability of the inkjet ink composition, the pH adjuster is preferably added so that the inkjet ink composition has a pH of 6 to 10, and added so as to have a pH of 7 to 10. Is more preferable.

  Examples of the surface tension adjusting agent include nonionic, cationic and anionic surfactants. The surface tension of the inkjet ink composition of the present invention is preferably 20 to 60 mN / m. Furthermore, 25-45 mN / m is preferable. The viscosity of the ink composition for inkjet according to the present invention is preferably 30 mPa · s or less. Furthermore, it is more preferable to adjust to 20 mPa · s or less.

  Examples of the surfactant include fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate, alkyl phosphate ester salt, naphthalene sulfonate formalin condensate, polyoxyethylene alkyl Anionic surfactants such as sulfate salts, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid Nonionic surfactants such as esters and oxyethyleneoxypropylene block copolymers are preferred. Further, SURFYNOLS (Air Products & Chemicals), which is an acetylene-based polyoxyethylene oxide surfactant, is also preferably used. An amine oxide type amphoteric surfactant such as N, N-dimethyl-N-alkylamine oxide is also preferred. Furthermore, pages (37) to (38) of JP-A-59-157636, Research Disclosure No. The surfactants described in 308119 (1989) can also be used.

  As the antifoaming agent, fluorine-based, silicone-based compounds, chelating agents represented by EDTA, and the like can be used as necessary.

  When the dye in the present invention is dispersed in an aqueous medium, the dye is used as described in JP-A No. 11-286637, Japanese Patent Application Nos. 2000-78491, 2000-80259, and 2000-62370. Colored fine particles containing an oil-soluble polymer and an aqueous medium are dispersed in an aqueous medium, or Japanese Patent Application Nos. 2000-78454, 2000-78491, 2000-203856, 2000-203857. It is preferable to disperse the dye in the present invention dissolved in a high boiling point organic solvent in an aqueous medium as described in the description. The specific method for dispersing the dye in the present invention in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additive, and the amount used thereof are preferably those described in the aforementioned patent. it can. Alternatively, the azo dye may be dispersed in a fine particle state as a solid. At the time of dispersion, a dispersant or a surfactant can be used. Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.), ultrasonic method, high pressure emulsification dispersion method (high pressure homogenizer) Specific examples of commercially available devices include gorin homogenizers, microfluidizers, DeBEE2000, and the like. Regarding the method for preparing the above inkjet ink, besides the aforementioned patents, JP-A Nos. 5-148436, 5-295212, 7-97541, 7-82515, and 7-118584 are disclosed. Details are described in Japanese Patent Application Laid-Open No. 11-286637 and Japanese Patent Application No. 2000-87539, and can also be used for the preparation of inkjet inks using the inkjet ink composition of the present invention.

  As the aqueous medium, a mixture containing water as a main component and optionally adding a water-miscible organic solvent can be used. Examples of the water-miscible organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyvalent Alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (eg , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl Ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether , Triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amine (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine) , Triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl- 2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone). In addition, the said water miscible organic solvent may use 2 or more types together.

  The ink composition for inkjet according to the present invention preferably contains 0.2 to 30 parts by mass of the pigment according to the present invention in 100 parts by mass. Moreover, you may use together with the pigment | dye in this invention, the black pigment | dye of this invention, or another black pigment | dye for the inkjet ink composition of this invention. When two or more kinds of dyes are used in combination, the total content of the dyes is preferably within the above range. In addition, other color pigments may be used in combination to adjust the black color tone.

  The ink-jet ink composition of the present invention can be used not only for monochromatic image formation but also for full-color image formation. Magenta, cyan, and yellow inks can be used to form a full color image. Any yellow pigment can be used as a mixture. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines, heterocycles such as pyrazolone and pyridone, and open-chain active methylene compounds as coupling components (hereinafter sometimes referred to as “coupler components”) An azomethine dye having an open-chain active methylene compound as a coupler component; a methine dye such as a benzylidene dye or a monomethine oxonol dye; a quinone dye such as a naphthoquinone dye or an anthraquinone dye; Other dye types include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, acridinone dyes and the like.

  In addition, any magenta dye that can be applied to the present invention can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines, etc. as coupler components; for example, azomethine dyes having pyrazolones, pyrazolotriazoles, etc. as coupler components; for example arylidene dyes, styryl dyes, merocyanine dyes, cyanine dyes, Methine dyes such as oxonol dyes; Carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, etc., condensed polycycles such as dioxazine dyes, etc. A pigment | dye etc. can be mentioned.

  Any cyan dye that can be applied to the present invention can be used. For example, aryl or hetaryl azo dyes having phenols, naphthols, anilines, etc. as coupler components; for example, azomethine dyes having phenols, naphthols, heterocyclic rings such as pyrrolotriazole, etc. as coupler components; cyanine dyes, oxonol dyes, Polymethine dyes such as merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes; phthalocyanine dyes; anthraquinone dyes; indigo / thioindigo dyes.

Each of the above dyes may exhibit yellow, magenta, and cyan colors only after a part of the chromophore is dissociated. In this case, the counter cation is an alkali metal or an inorganic cation such as ammonium. Alternatively, it may be an organic cation such as pyridinium or quaternary ammonium salt, and may further be a polymer cation having these in a partial structure.
Furthermore, in the present invention, a carbon black dispersion, particularly a self-dispersing carbon black may be applied.

<Inkjet recording method>
In the ink jet recording method of the present invention, energy is supplied to the ink jet ink comprising the ink jet ink composition of the present invention, and a known image receiving material, that is, plain paper, resin-coated paper, for example, JP-A-8-169172, JP-A-8-27693, JP-A-2-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238783, JP-A-10-153898, JP-A-10-217473. 10-235995, 10-337947, 10-217597, 10-337947, etc., inkjet paper, film, electrophotographic co-paper, fabric, glass, metal An image is formed on ceramics.

  In forming an image, a polymer latex compound may be used in combination for the purpose of imparting glossiness or water resistance or improving weather resistance. The timing of applying the latex compound to the image receiving material may be before, after, or simultaneously with the application of the colorant. Therefore, even if the addition place is in the image receiving paper, It may be in ink or may be used as a liquid material of polymer latex alone. Specifically, Japanese Patent Application Nos. 2000-363090, 2000-315231, 2000-354380, 2000-343944, 2000-268952, 2000-299465, 2000 The method described in the specification of -297365 can be preferably used.

The recording paper and recording film used for ink jet printing using the ink jet ink comprising the ink jet ink composition of the present invention will be described below. The support in recording paper and recording film is made of chemical pulp such as LBKP and NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMPMP, CGP, and waste paper pulp such as DIP. Additives such as known pigments, binders, sizing agents, fixing agents, cationic agents, paper strength enhancers, etc. can be mixed and manufactured using various devices such as long net paper machines and circular net paper machines. is there. In addition to these supports, either synthetic paper or plastic film sheet may be used, and the thickness of the support is preferably 10 to 250 μm and the basis weight is preferably 10 to 250 g / m ² . The support may be provided with an ink receiving layer and a backcoat layer as they are, or after a size press or anchor coat layer is provided with starch, polyvinyl alcohol or the like, an ink receiving layer and a backcoat layer may be provided. Further, the support may be flattened by a calendar device such as a machine calendar, a TG calendar, or a soft calendar. In the present invention, as the support, paper and plastic films laminated on both sides with polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) are more preferably used. It is preferable to add a white pigment (for example, titanium oxide or zinc oxide) or a coloring pigment (for example, cobalt blue, ultramarine blue, or neodymium oxide) to the polyolefin.

  The ink receiving layer provided on the support contains a pigment and an aqueous binder. As the pigment, a white pigment is preferable, and as the white pigment, calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, Examples thereof include white inorganic pigments such as barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide and zinc carbonate, and organic pigments such as styrene pigments, acrylic pigments, urea resins and melamine resins. The white pigment contained in the ink receiving layer is preferably a porous inorganic pigment, and particularly white inorganic pigment fine particles such as synthetic amorphous silica having a large pore area. As the synthetic amorphous silica, both anhydrous silicic acid obtained by a dry production method and hydrous silicic acid obtained by a wet production method can be used, but it is particularly desirable to use hydrous silicic acid.

Examples of the aqueous binder contained in the ink receiving layer include water-soluble polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, polyalkylene oxide derivatives, and the like. Water-dispersible polymers such as water-soluble polymers, styrene-butadiene copolymer latexes, and acrylic emulsions. These aqueous binders can be used alone or in combination of two or more. In the present invention, among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and resistance to peeling of the ink receiving layer.
The ink receiving layer can contain a mordant, a water resistance agent, a light resistance improver, a surfactant, and other additives in addition to the pigment and the aqueous binder.

The mordant added to the ink receiving layer is preferably immobilized. For that purpose, a polymer mordant is preferably used.
Regarding the polymer mordant, JP-A-48-28325, JP-A-54-74430, JP-A-54-124726, JP-A-55-22766, JP-A-55-142339, JP-A-60-23850, 60-23851, 60-23852, 60-23853, 60-57836, 60-60643, 60-118834, 60-122940, 60 No. 122941, No. 60-122942, No. 60-235134, JP-A No. 1-161236, US Pat. No. 2,484,430, No. 2,548,564, No. 3148061, No. 3,309,690. Description, 4115124, 4124386, 41938 0 Pat, specification Nos. 4,273,853, specification Nos. 4,282,305, there is described in the 4,450,224 Pat like. An image receiving material containing a polymer mordant described in JP-A-1-161236, pages 212 to 215 is particularly preferred. When the polymer mordant described in the publication is used, an image with excellent image quality is obtained and the light resistance of the image is improved.

  The water-proofing agent is effective in making the image water-resistant. As these water-proofing agents, cationic resins are particularly desirable. Examples of such cationic resins include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide, colloidal silica, etc. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable. is there. The content of these cationic resins is preferably 1 to 15% by mass, particularly 3 to 10% by mass, based on the total solid content of the ink receiving layer.

  Examples of the light fastness improver include zinc sulfate, zinc oxide, hindered amine-based antioxidants, benzophenone-based and benzotriazole-based ultraviolet absorbers, and the like. Of these, zinc sulfate is particularly preferred.

  The surfactant functions as a coating aid, a peelability improver, a slippage improver or an antistatic agent. The surfactant is described in JP-A Nos. 62-173463 and 62-183457. An organic fluoro compound may be used in place of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compound include a fluorine-based surfactant, an oily fluorine-based compound (for example, fluorine oil), and a solid fluorine compound resin (for example, tetrafluoroethylene resin). The organic fluoro compounds are described in JP-B-57-9053 (columns 8 to 17), JP-A-61-20994, and 62-135826. Examples of other additives added to the ink receiving layer include pigment dispersants, thickeners, antifoaming agents, dyes, fluorescent whitening agents, preservatives, pH adjusters, matting agents, and hardening agents. . The ink receiving layer may be one layer or two layers.

  The recording paper and the recording film may be provided with a backcoat layer, and examples of components that can be added to this layer include a white pigment, an aqueous binder, and other components. Examples of white pigments contained in the backcoat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and aluminum silicate. White inorganic pigments such as diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrous halloysite, magnesium carbonate, magnesium hydroxide And organic pigments such as styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, urea resin and melamine resin.

  As the aqueous binder contained in the backcoat layer, styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose Water-soluble polymers such as hydroxyethyl cellulose and polyvinyl pyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of other components contained in the backcoat layer include antifoaming agents, foam suppressors, dyes, fluorescent brighteners, preservatives, and water resistance agents.

  Polymer latex may be added to the constituent layers (including the backcoat layer) of the ink jet recording paper and recording film. The polymer latex is used for the purpose of improving film physical properties such as dimensional stabilization, curling prevention, adhesion prevention, and film cracking prevention. The polymer latex is described in JP-A Nos. 62-245258, 62-136648, and 62-110066. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to a layer containing a mordant, cracking and curling of the layer can be prevented. Also, curling can be prevented by adding a polymer latex having a high glass transition temperature to the backcoat layer.

  The inkjet ink comprising the inkjet ink composition of the present invention is not limited to an inkjet recording system, and is a known system, for example, a charge control system that discharges ink using electrostatic attraction, and a vibration pressure of a piezo element. Drop-on-demand method (pressure pulse method), acoustic ink method that converts electrical signals into acoustic beams, irradiates ink and ejects ink using radiation pressure, and heats ink to form bubbles It is used in thermal ink jet systems that utilize the pressure. Inkjet recording methods use a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method is included.

<Color Toner>
The color toner composition of the present invention is characterized by containing at least one azo dye represented by any one of the above general formulas (1) to (4) and (6). The composition for a color toner of the present invention contains a binder resin for a color toner, a release agent, a charge control agent, and a carrier as necessary, in addition to the coloring matter in the present invention. The pigment in the present invention is preferably contained in an amount of 0.1 part by mass or more, particularly preferably 1.0 part by mass or more, based on 100 parts by mass of the color toner composition of the present invention.
As the binder resin for a color toner into which a dye is introduced in the present invention, all commonly used binders can be used. For example, a styrene resin, an acrylic resin, a styrene-acrylic resin, a polyester resin, and the like can be given.
Inorganic fine powders and organic fine particles may be externally added to the toner for the purpose of improving fluidity and controlling charging. Silica fine particles and titania fine particles whose surface is treated with an alkyl group-containing coupling agent or the like are preferably used. These have a number average primary particle diameter of preferably 10 to 500 nm, and more preferably 0.1 to 20% by mass in the toner.

  As the release agent, all conventionally used release agents can be used. Specific examples include polyolefins such as low molecular weight polypropylene, low molecular weight polyethylene, and ethylene-propylene copolymer, microcrystalline wax, carnauba wax, sazol wax, and paraffin wax. These addition amounts are preferably 1 to 5% by mass in the toner.

  The charge control agent may be added as necessary, but is preferably colorless from the viewpoint of color development. Examples thereof include those having a quaternary ammonium salt structure and those having a calixarene structure.

  As the carrier, either an uncoated carrier constituted only by magnetic material particles such as iron or ferrite, or a resin-coated carrier obtained by coating the surface of the magnetic material particles with a resin or the like may be used. The average particle size of the carrier is preferably 30 to 150 μm in terms of volume average particle size.

  The image forming method to which the color toner composition of the present invention is applied is not particularly limited. For example, a method of forming a color image by repeatedly forming a color image on a photoconductor to form an image, Examples thereof include a method in which an image formed on a body is sequentially transferred to an intermediate transfer body or the like, a color image is formed on the intermediate transfer body or the like, and then transferred to an image forming member such as paper to form a color image.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1 (Example of Dispersed Ink)
(Preparation of sample 101)
3.75 g of the above exemplified azo dye a-1 and 7.04 g of sodium dioctylsulfosuccinate, 4.22 g of the following high boiling point organic solvent (s-2), and 5.63 g of the following high boiling point organic solvent (s-11). And dissolved in 70 ml of ethyl acetate at 70 ° C. 500 ml of deionized water was added to this solution while stirring with a magnetic stirrer to prepare an oil-in-water type coarse particle dispersion. Next, this coarse particle dispersion was micronized by passing it through a microfluidizer (MICROFLUIDEX INC) five times at a pressure of 600 bar. Further, the resulting emulsion was desolvated with a rotary evaporator until the odor of ethyl acetate disappeared. An ink was prepared by adding 140 g of diethylene glycol, 50 g of glycerin, 7 g of SURFYNOL465 (Air Products & Chemicals) and 900 ml of deionized water to the fine emulsion of the hydrophobic pigment thus obtained.

(Production of samples 102 to 107)
Samples 102 to 107 were produced in the same manner as the sample 101 except that the dye a-1 of the sample 101 was changed to the dye shown in Table 7 below.

(Preparation of comparative samples 108 to 110)
As a comparison, after adding deionized water to the following components to make 1 liter, the mixture was stirred for 1 hour while heating at 30 to 40 ° C., then adjusted to pH = 9 with 10 mol / L of KOH, and the average pore size was adjusted to 0. Ink comparison samples 108 to 110 were prepared by vacuum filtration with a 25 μm microfilter.

Composition of comparative ink solutions 108 to 110:
Comparative dye 25 g described in Table 7
Diethylene glycol 20g
Glycerin 120g
230 g of diethylene glycol monobutyl ether
2-Pyrrolidone 80g
Triethanolamine 17.9g
Benzotriazole 0.06g
Surfynol TG 8.5g
PROXEL XL2 1.8g

  The structure of the comparative dye used is as follows.

(Image recording and evaluation)
The following evaluation was performed on the ink samples 101 to 107 and the comparative samples 108 to 110. The results are shown in Table 7 below.
In Table 7, each evaluation shows that each ink-jet ink is made into photo glossy paper (manufactured by Fuji Photo Film Co., Ltd .; ink-jet paper, photo grade) with an ink-jet printer (manufactured by EPSON Corporation; PM-700C). It was evaluated after the image was recorded.

<Printing performance>
After setting the cartridge in the printer and confirming the ejection of ink from all nozzles, an image was output on 20 sheets of A4 paper, and the disorder of printing was evaluated according to the following criteria.
A: There was no disorder in printing from the start to the end of printing.
B: Output with printing disturbance occurred.
C: The printing was disturbed from the start to the end of printing.

<Thin lines blur>
For fine line bleeding, a fine line pattern was printed and left for 2 days under conditions of 35 ° C. and 80% RH, and then the bleeding was visually evaluated. The case where there was no bleeding was rated as ◯, and the case where there was bleeding as x.

<Paper dependence>
The color tone of the image formed on the photo glossy paper and the image formed separately on the PPC plain paper are compared, and when the difference between the two images is small A (good), when the difference between the two images is large B (defect) was evaluated in two stages.

<Water resistance>
The photo glossy paper on which the image was formed was dried at room temperature for 1 hour, then dipped in water for 30 seconds, naturally dried at room temperature, and observed for bleeding. Evaluation was made in three stages, with A indicating no bleeding, B indicating slight bleeding, and C indicating large bleeding.

<Light resistance>
The photo glossy paper on which the image is formed is irradiated with xenon light (85000 lx) for 10 days using a weather meter (Atlas C.I65), and the image density before and after the xenon irradiation is measured using a reflection densitometer (X-Rite 310TR). And measured as a dye residual ratio. The reflection density was measured at three points of 1, 1.5 and 2.0.
At any concentration, the dye residual ratio is 90% or more, A is 1 point less than 90% B, 2 points less than 90% C, and all concentrations are less than 90% D, in four stages. evaluated.

<Ozone resistance>
The photo glossy paper on which the image has been formed is left in a box where the ozone gas concentration is set to 0.5 ppm for one week, and the image density before and after being left under ozone gas is measured using a reflection densitometer (X-Rite 310TR). It was evaluated as a dye residual ratio. The reflection density was measured at three points of 1, 1.5 and 2.0. The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.
At any concentration, the dye residual ratio is 90% or more, A is 1 point less than 90% B, 2 points less than 90% C, and all concentrations are less than 90% D, in four stages. evaluated.

  As is clear from Table 7, the ink-jet ink comprising the ink-jet ink composition of the present invention has excellent dispersion stability (solubility) (excellent printing performance and fine line bleeding), low paper dependency, water resistance, light resistance And excellent in ozone resistance.

Example 2 (Example of Dispersed Ink)
The same ink produced in Example 1 is packed in a cartridge of an inkjet printer BJ-F850 (manufactured by CANON), and an image is printed on the photo glossy paper GP-301 of the same printer, and the same evaluation as in Example 1 is performed. As a result, the same results as in Example 1 were obtained.

[Example 3 (Example of toner composition)]
After mixing and pulverizing 3 parts by mass of the exemplified azo dye a-1 in the present invention and 100 parts by mass of a toner resin [styrene-acrylic acid ester copolymer; trade name Hymer TB-1000F (manufactured by Sanyo Kasei)] The mixture was heated and mixed at 150 ° C., and after cooling, coarsely pulverized using a hammer mill, and then finely pulverized by an air jet type pulverizer. Further, classification was performed to select 1 to 20 micron, and a toner was obtained. To 10 parts by mass of the toner, 900 parts by mass of carrier iron powder (trade name: EFV250 / 400; manufactured by Nippon Iron Powder) was uniformly mixed to obtain a developer. Similarly, a sample was prepared in the same manner except that 3 parts by mass of the dye shown in Table 8 was used. Using these developers, copying was performed with a dry plain paper electrophotographic copying machine [trade name NP-5000; manufactured by Canon Inc.].

In the evaluation test, a reflection image (an image on paper) and a transmission image (an OHP image) were respectively produced on paper and OHP by the above image forming method using a developer using the color toner composition of the present invention. The method shown was carried out. The toner adhesion amount was evaluated in the range of 0.7 ± 0.05 (mg / cm ² ).

The obtained image was evaluated for hue and light fastness.
The hue was visually evaluated in three stages: best, good and poor. The evaluation results are shown in Table 8 below. In Table 8 below, o indicates that the hue is the best; Δ indicates that the hue is good, and x indicates that the hue is poor.
With respect to light fastness, after measuring the image density Ci immediately after recording, the image was irradiated with xenon light (85,000 lux) for 10 days using a weather meter (Atlas C.165), and then the image again. The density Cf was measured, and the dye residual ratio ({(Ci−Cf) / Ci} × 100%) was calculated from the difference in image density before and after the xenon light irradiation and evaluated. The image density was measured using a reflection densitometer (X-Rite 310TR). The evaluation results are shown in Table 8 below. In Table 8 below, the case where the dye residual ratio is 90% or more is shown as ◯, the case where it is 90 to 80% is shown as Δ, and the case where it is less than 80% is shown as ×.

  The transparency of the OHP image was evaluated by the following method. The visible spectral transmittance of an image is measured with a “330 type self-recording spectrophotometer” manufactured by Hitachi, Ltd., using an OHP sheet on which toner is not supported as a reference, the spectral transmittance at 650 nm is obtained, and the transparency of the OHP image is measured. It was. Spectral transmittance of 80% or more was evaluated as ◯, 70-80% as Δ, and 70% or less as X. Table 8 shows the above results.

  As is apparent from Table 8, since the faithful color reproduction and high OHP quality are exhibited by using the color toner composition of the present invention, the color toner composition of the present invention is suitable for use as a full color toner. Yes. Furthermore, since the light resistance is good, an image that can be stored for a long time can be provided.

Claims (4)

An ink-jet ink comprising at least one azo dye represented by the following general formula (4) and having at least one alkyl chain having 4 or more carbon atoms and having no ionic hydrophilic group.

In general formula (4):
A represents an optionally substituted aromatic group or heterocyclic group, and the substituent in the case of having a substituent is a halogen atom, an alkoxycarbonyl group or a nitro group. X represents N or —C (R ₈ ) ═, and R ₈ represents a cyano group, a carbamoyl group, an acyl group, an alkoxycarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group. R ₇ represents an alkyl group or an aryl group.
B ₁ and B ₂ each represent ═CR ₁ — and —CR ₂ ═ , R ₁ represents a cyano group, and R ₂ represents an alkyl group.
G represents an anilino group which may have a substituent, and the substituent in the case of having a substituent is an alkyl group, an alkoxy group or an alkylcarbamoyl group.
R ₅ and R ₆ represent a hydrogen atom or an aryl group which may have a substituent, and the substituent in the case of having a substituent is an alkyl group, an alkoxy group, or an alkylcarbamoyl group. However, R ₅ and R ₆ are not simultaneously hydrogen atoms. In the general formula (4):
A represents an optionally substituted phenyl group, pyridyl group or benzothiazolyl group, and when having a substituent, the substituent is a halogen atom, an alkoxycarbonyl group or a nitro group, and X is N or —C (R ₈ ). =, R ₈ represents a cyano group, R ₇ represents an alkyl group or an aryl group,
B ₁ and B ₂ each represent ═CR ₁ — and —CR ₂ ═ , R ₁ represents a cyano group, R ₂ represents an alkyl group,
G represents an anilino group which may have a substituent, the substituent when the anilino group has a substituent represents a phenyl group which may have a substituent, and the substitution when the phenyl group has a substituent The group is an alkyl group, an alkoxy group, an alkylcarbamoyl group,
R ₅ and R ₆ represent a hydrogen atom or a phenyl group which may have a substituent, and the substituent in the case of having a substituent is an alkyl group, an alkoxy group, or an alkylcarbamoyl group, provided that R ₅ , R ₆ The inkjet ink according to claim 1, wherein is not a hydrogen atom at the same time . An ink jet recording method comprising: forming an image on an image receiving material having an ink receiving layer containing white inorganic pigment particles on a support using the ink jet ink according to claim 1 . A composition for color toner, comprising at least one azo dye according to any one of claims 1 to 3 .