JP2003049100A - Color composition for image forming, ink for ink jet recording and method for ink jet recording - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a color composition for image forming, having good hue and capable of forming images having high fastness under several kinds of application conditions and circumstances, to provide an ink for ink jet recording, and to provide a method for ink jet recording. SOLUTION: The color composition for image forming comprises an azo dye having at least one phosphono group in the dye molecule and containing an aromatic nitrogen-containing 6-membered heterocycle as a coupling component. The ink for the ink jet recording is provided by using the composition and the method for ink jet recording is also provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a coloring composition containing an aromatic nitrogen-containing heterocyclic azo dye for use in image formation,
The present invention relates to an inkjet recording ink and an inkjet recording method.

[0002]

2. Description of the Related Art In recent years, as an image recording material, a material for forming a color image has been mainly used, and specifically, an ink jet recording material, a heat transfer recording material, and an electrophotographic recording material. Materials, transfer-type silver halide photosensitive materials, printing inks, recording pens, etc. are widely used. Further, a color filter is used for recording and reproducing a color image in an image pickup device such as a CCD in a photographing device and in an LCD or a PDP in a display. In these color image recording materials and color filters, colorants (dyes and pigments) of three primary colors of so-called additive color mixture method and subtractive color mixture method are used in order to reproduce or record a full color image, but preferable color reproduction It is the actual situation that there is no robust colorant that has absorption characteristics that can realize the range and can withstand various use conditions and environmental conditions, and improvement is strongly desired.

The ink jet recording method is rapidly spreading and further developing because of low material cost, high speed recording, low noise during recording, and easy color recording. is there. Ink jet recording methods include a continuous method for continuously ejecting droplets and an on-demand method for ejecting droplets according to an image information signal. There are a method of ejecting liquid, a method of generating bubbles in the ink by heat to eject a droplet, a method of using ultrasonic waves, or a method of sucking and ejecting a droplet by electrostatic force. Further, as the ink for inkjet recording,
Water-based ink, oil-based ink, or solid (melting type) ink is used.

With respect to the colorant used in such ink jet recording ink, the solubility or dispersibility in a solvent is good, high density recording is possible, the hue is good, the light, It is robust against heat and active gases in the environment (NOx, oxidizing gases such as ozone, as well as SOx, etc.), has excellent fastness to water and chemicals, and has good fixability to image receiving materials. It is required that the ink does not easily bleed, that it has excellent storage stability as an ink, that it has no toxicity, that it has high purity, and that it can be obtained at low cost. However, it is extremely difficult to find a colorant that meets these requirements at a high level. In particular, it has good magenta hue and is fast against light, humidity, and heat. Above all, when printing on an image receiving material having an ink receiving layer containing porous white inorganic pigment particles It is strongly desired to be robust against oxidizing gases such as ozone.

The colorants used in the above-mentioned respective applications must have the following properties in common. That is,
It has good absorption characteristics in terms of color reproducibility, fastness under the environmental conditions used, for example, light resistance, heat resistance, humidity resistance, resistance to oxidizing gases such as ozone, and chemical resistance fastness to sulfurous acid gas. Good, high molar extinction coefficient, etc.

Heretofore, phenol, naphthol, aniline and the like have been widely used as coupling components for azo dyes. As an azo dye having a good hue obtained by these coupling components, JP-A-11-209673 can be used.
The dyes disclosed in Japanese Patent Publication No. 3020660 and the like are known, but they have a problem of poor light fastness. To improve this, a colorant having a good hue and improved light fastness is recently disclosed in Japanese Patent Application No. 2000-220.
No. 649. However, the colorants known in these publications and specifications are extremely insufficient in fastness to an oxidizing gas such as ozone. In order to develop a coloring agent that is robust against oxidizing gases such as ozone, the inventors of the present application have decoupled from the conventional coupling components such as phenol, naphthol, and aniline to couple nitrogen-containing heterocyclic compounds. The idea came to be used as an ingredient. So far, patent applications relating to azo dyes containing pyridine or pyrazine as a coupling component have been disclosed in JP-A-49-74718, EP23309, DE2.
513949, DE283202, DE252550
No. 5, etc. are known, but at the time, it was not known that these dyes were used for image formation such as ink jet, and in the azo dyes described in these,
The fastness to light, heat, humidity and active gas in the environment was insufficient, and the hue was also insufficient as a magenta dye.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems in the prior art and achieve the following objects. That is, the object of the present invention is to provide a colored image or coloring material having excellent hue and fastness, and an image that can be preferably used for preparing an ink for printing such as an inkjet or a dyeing solution for dyeing various fibers. It is to provide a colored composition for formation. Another object of the present invention is to provide an inkjet recording ink and an inkjet recording method which can form an image having a good hue and having high fastness to an active gas in the light and environment, particularly ozone gas. Especially.

[0008]

Means for Solving the Problems The present inventors have studied in detail various dye compound derivatives aiming at a dye having a good hue and high fastness to light and ozone. It has been found that the above problems can be solved by an azo dye having a 6-membered heterocycle as a coupling component. That is, according to the present invention, the coloring composition for image formation, the ink for inkjet recording, and the inkjet recording method having the following constitutions are provided, and the above object of the present invention is achieved. 1. An azo dye having an aromatic nitrogen-containing 6-membered heterocycle as a coupling component, which contains an azo dye having at least one phosphono group in the dye molecule. 2. The coloring composition for image formation as described in 1 above, wherein the azo dye is represented by the following general formula (1). General formula (1)

[0009]

[Chemical 3]

In the above general formula (1): A represents the residue of the 5-membered heterocyclic diazo component A-NH ₂ . B ¹ and B ² each = CR ¹ -, - or represents a CR ² =, or either one nitrogen atom and the other = CR ¹ - represents a or -CR ² =. R ⁵ and R ⁶ are each independently a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or Represents a sulfamoyl group. Each group may further have a substituent. G, R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an 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, acylamino group , Ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkyl or arylthio group, alkyl and arylsulfonyl Represents a heterocyclic sulfonyl group, an alkyl- or arylsulfinyl group, heterocyclic sulfinyl group, a sulfamoyl group, a sulfo group or a heterocyclic thio group,. Each group may be further substituted. Further, R ¹ and R ⁵ , or R ⁵ and R ⁶ are bonded to each other to form 5
A 6-membered ring may be formed. However, it has at least one phosphono group in the general formula (1). 3. The coloring composition for image formation as described in 1 or 2 above, wherein the azo dye is represented by the following general formula (2). General formula (2)

[0011]

[Chemical 4]

In the general formula (2): Z ¹ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Z
² represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. R ¹ , R ² , R ⁵ and R ⁶ have the same meanings as in the case of the general formula (1). R ³ and R ⁴ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfonyl group or a sulfamoyl group. Q
Represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Each of the groups Z ¹ , Z ² , R ^{1 to} R ⁶ , and Q may further have a substituent. However, it has at least one phosphono group in the general formula (1). 4. An ink for inkjet recording, a heat-sensitive recording material, a color toner, or a color filter, which comprises the coloring composition described in 2 or 3 above. 5. An ink jet recording method comprising forming an image on the image receiving material having an ink receiving layer containing white inorganic pigment particles on a support, using the ink for ink jet recording described in 4 above.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. [Azo Dye] First, the azo dye represented by the general formula (1) in the present invention will be described in detail. In the general formula (1), A is a 5-membered heterocyclic diazo component A-NH2.
Represents the residue of. Examples of the heteroatom of the 5-membered heterocycle are N,
O and S can be mentioned. Nitrogen-containing 5 is preferred
It is a membered heterocycle, and an aliphatic ring, an aromatic ring or another heterocycle may be condensed with the heterocycle. Examples of the preferred heterocycle of A include a pyrazole ring, an imidazole ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, a benzothiazole ring, a benzoxazole ring and a benzisothiazole ring. Each heterocyclic group may further have a substituent. Among them, a pyrazole ring, an imidazole ring, an isothiazole ring, a thiadiazole ring and a benzothiazole ring represented by the following general formulas (a) to (f) are preferable.

[0014]

[Chemical 5]

R ^{7 to} R in the above general formulas (a) to (f)
²⁰ represents the same substituent as the substituents G, R ¹ and R ² described later. Of the above general formulas (a) to (f), preferred are the pyrazole ring and the isothiazole ring represented by the general formulas (a) and (b), and the most preferred are the general formula (a). Is a pyrazole ring. B ¹ and B ² are each = C
R ¹ -, - or represents a CR ² =, or either one nitrogen atom and the other = CR ¹ - or represents a -CR ² =, respectively = CR ¹ -, - more those that represent CR ² = preferable. R
⁵ and R ⁶ are each independently a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl or arylsulfonyl group, or a sulfamoyl group. And each group may further have a substituent.
Preferred substituents represented by R ⁵ and R ⁶ include a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkyl or arylsulfonyl group. More preferably, a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group,
It is an alkyl or aryl sulfonyl group. Most preferably, it is a hydrogen atom, an aryl group or a heterocyclic group. Each group may further have a substituent. However, R ⁵ and R ⁶ are not hydrogen atoms at the same time.

G, R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group or an aryloxy group. Carbonyl 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 , An acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group,
Aryloxycarbonylamino group, alkyl or aryl sulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkyl or arylthio group, alkyl or aryl sulfonyl group, heterocyclic sulfonyl group, alkyl or aryl sulfinyl group, heterocyclic sulfinyl group, sulfamoyl Represents a group, a sulfo group, or a heterocyclic thio group, and each group may be further substituted.

Preferred substituents represented by G are a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, a heterocyclic oxy group, an amino group and an acylamino group. Groups, ureido groups, sulfamoylamino groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups, alkyl or arylthio groups, and heterocyclic thio groups, more preferably hydrogen atoms, halogen atoms, alkyl groups, hydroxy groups. , An alkoxy group, an aryloxy group, an acyloxy group, an amino group, or an acylamino group, with a hydrogen atom, an arylamino group, and an amide group being most preferable. Each group may further have a substituent.

Preferred substituents represented by R ¹ and R ² are a hydrogen atom, an alkyl group, an alkoxycarbonyl group,
Mention may be made of carboxyl groups, carbamoyl groups, hydroxy groups, alkoxy groups, and cyano groups. Each group may further have a substituent. R ¹ and R ⁵ or R
⁵ and R ⁶ may combine to form a 5- or 6-membered ring. A, R
^When each of the substituents represented by ¹ , R ² , R ⁵ , R ⁶ and G further has a substituent, examples of the substituent include the substituents described above in G, R ¹ and R ^2. . When the azo dye represented by the general formula (1) is a water-soluble dye, A, R ¹ ,
It is preferable to further have another ionic hydrophilic group as a substituent at any position on R ² , R ⁵ , R ⁶ , and G in addition to the phosphono group. The ionic hydrophilic group as a substituent includes a sulfo group, a carboxyl group, a quaternary ammonium group and the like. As the ionic hydrophilic group, a carboxyl group and a sulfo group are preferable. Carboxyl group,
The phosphono group and the sulfo group may be in a salt state,
Examples of salt forming counterions are ammonium ions,
Alkali metal ions (eg, lithium ion, sodium ion, potassium ion) and organic cations (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylerphosphonium ion) are included.

The substituents represented by G, R ¹ , R ² and R ⁵ , R ⁶ will be described in detail below. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

In the present specification, the 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,
It is more preferably 1 to 16. The aryl part of the aralkyl group and the substituted aralkyl group is preferably phenyl or naphthyl, particularly preferably phenyl. Examples of the aliphatic group include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl, 4-sulfobutyl, cyclohexyl group, benzyl group, 2-phenethyl group. Mention may be made of groups, vinyl groups and allyl groups.

In the present specification, the aromatic group means an aryl group and a substituted aryl group. The aryl group is preferably phenyl or naphthyl, with phenyl being particularly preferred. The aromatic group preferably has 6 to 20 carbon atoms, and more preferably has 6 to 16 carbon atoms. Examples of aromatic groups include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl.

In the present specification, the heterocyclic group includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group.
The heterocycle may be condensed with an aliphatic ring, an aromatic ring or another heterocycle. The heterocyclic group is preferably a 5- or 6-membered heterocyclic group. Examples of the substituent include an aliphatic group, a halogen atom, an alkyl and arylsulfonyl group, an acyl group, an acylamino group, a sulfamoyl group, a carbamoyl group, an ionic hydrophilic group 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 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic 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 12 carbon atoms is preferable. The substituent includes an ionic hydrophilic 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 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of heterocyclic oxycarbonyl groups include 2
-Pyridyloxycarbonyl groups are included.

The acyl group includes an acyl group having a substituent and an unsubstituted acyl group. As an acyl group,
An acyl group having 1 to 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic 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 the alkoxy group, an alkoxy group having 1 to 12 carbon atoms is preferable. Examples of the substituent include an alkoxy group, a hydroxyl group, and an ionic hydrophilic group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, a hydroxyethoxy group and a 3-carboxypropoxy group.

The aryloxy group includes an aryloxy group having a substituent and an unsubstituted aryloxy group. The aryloxy group has 6 to 1 carbon atoms.
Two aryloxy groups are preferred. Examples of the substituent include an alkoxy group and an ionic hydrophilic 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 12 carbon atoms. Examples of the substituent include an alkyl group,
An alkoxy group and an ionic hydrophilic group are included. Examples of the heterocyclic oxy group include a 3-pyridyloxy group and a 3-thienyloxy group.

The silyloxy group has 1 carbon atom.
A silyloxy group substituted with an aliphatic group or an aromatic group of 12 is preferable. 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 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic 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. The alkoxycarbonyloxy group has 2 to 12 carbon atoms.
The alkoxycarbonyloxy group of is preferred. Examples of the alkoxycarbonyloxy group include a methoxycarbonyloxy group and an isopropoxycarbonyloxy group.

The aryloxycarbonyloxy group includes
The aryloxycarbonyloxy group having a substituent and the unsubstituted aryloxycarbonyloxy group are included. The aryloxycarbonyloxy group is preferably an aryloxycarbonyloxy group having 7 to 12 carbon atoms. Examples of the aryloxycarbonyloxy group include a phenoxycarbonyloxy group.

The amino group includes an unsubstituted amino group and an amino group substituted with an alkyl group, an aryl group or a heterocyclic group, and the alkyl group, the aryl group or the heterocyclic group further has a substituent. May be. As the alkylamino group, an alkylamino group having 1 to 6 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group. The arylamino group includes
The arylamino group having a substituent and the unsubstituted arylamino group are included. As the arylamino group, an arylamino group having 6 to 12 carbon atoms is preferable. Examples of the substituent include a halogen atom and an ionic hydrophilic group. Examples of the arylamino group include an anilino group and a 2-chloroanilino group.

The acylamino group includes an acylamino group having a substituent. As the acylamino group,
An acylamino group having 2 to 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the acylamino group include an acetylamino group, a propionylamino group, a benzoylamino group, an N-phenylacetylamino group and a 3,5-disulfobenzoylamino group.

The ureido group includes a ureido group having a substituent and an unsubstituted ureido group. The ureido group is preferably an ureido group having 1 to 12 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 sulfamoylamino groups include N, N
-Includes dipropylsulfamoylamino.

The alkoxycarbonylamino group includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. The alkoxycarbonylamino group has 2 to 12 carbon atoms.
The alkoxycarbonylamino group of is preferred. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.

The aryloxycarbonylamino group includes
The aryloxycarbonylamino group having a substituent and the unsubstituted aryloxycarbonylamino group are included. The aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.

The alkyl and aryl sulfonylamino groups include an alkyl and aryl sulfonylamino group having a substituent and an unsubstituted alkyl and aryl sulfonylamino group. The sulfonylamino group is preferably a sulfonylamino group having 1 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group.
Examples of the sulfonylamino group include a methanesulfonylamino group, an N-phenyl-methylsulfonylamino group, a phenylsulfonylamino group, and a 3-carboxyphenylsulfonylamino 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 ionic hydrophilic group. Examples of heterocyclic sulfonylamino groups include:
A 2-thiophenesulfonylamino group and a 3-pyridinesulfonylamino group are included.

The alkyl, aryl and heterocyclic thio groups include an alkyl, aryl and heterocyclic thio group having a substituent and an unsubstituted alkyl, aryl and heterocyclic thio group. The alkyl, aryl and heterocyclic thio groups preferably have 1 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkyl, aryl and heterocyclic thio groups include a methylthio group, a phenylthio group and a 2-pyridylthio group.

The alkyl and aryl sulfonyl groups include an alkyl and aryl sulfonyl group having a substituent and an unsubstituted alkyl and aryl sulfonyl group. Examples of the alkyl and aryl sulfonyl groups may include a methyl sulfonyl group and a phenyl sulfonyl group, respectively.

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 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic sulfonyl group include a 2-thiophene sulfonyl group and a 3-pyridine sulfonyl group.

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

The heterocyclic sulfinyl group includes a heterocyclic sulfinyl group having a substituent and an unsubstituted heterocyclic sulfinyl group. As the heterocyclic sulfinyl group, a heterocyclic sulfinyl group having 1 to 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic sulfinyl group include 4-pyridinesulfinyl group.

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 di- (2-hydroxyethyl) sulfamoyl group.

In the present invention, particularly preferred azo dyes are those in which the general formula (1) is represented by the general formula (2).
In the formula, 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-attracting group having a σp value of 0.30 or more, more preferably 0.45 or more, and more preferably 0.60 or more. Particularly preferred, but not more than 1.0 is preferred. Examples of preferable specific substituents include electron-withdrawing substituents described later, and among them, an acyl group having 2 to 12 carbon atoms, an alkyloxycarbonyl group having 2 to 12 carbon atoms, a nitro group, a cyano group , An alkylsulfonyl group having 1 to 12 carbon atoms, and 6 to 18 carbon atoms
The arylsulfonyl group, a carbamoyl group having 1 to 12 carbon atoms and a halogenated alkyl group having 1 to 12 carbon atoms are preferable. Particularly preferred is a cyano group, having 1 to 12 carbon atoms.
And an arylsulfonyl group having 6 to 18 carbon atoms, and the most preferred is a cyano group.

R ¹ , R ² , R ⁵ and R ⁶ have the same meanings as in the general formula (1). R ³ and R ⁴ are each independently a hydrogen atom,
It represents an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl or arylsulfonyl group, or a sulfamoyl group. Details of these groups are the same as those in the description of G, R ¹ and R ² above. Among them, 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. Z ² represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Q
Represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Among them, Q is preferably a group consisting of a non-metal atom group necessary for forming a 5- to 8-membered ring. The 5- to 8-membered ring may be substituted, may be a saturated ring or may have an unsaturated bond. Of these, an aromatic group and a heterocyclic group are particularly preferable. Preferred non-metal atoms include nitrogen, oxygen, sulfur and carbon atoms. Specific examples of the 5- to 8-membered ring include a benzene ring,
Cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole ring, benzimidazole ring, oxazole ring, benzoxazole ring, thiazole ring, Examples thereof include a benzothiazole ring, an oxane ring, a sulfolane ring and a thiane ring.

Each group described in the general formula (2) may further have a substituent. When each of these groups further has a substituent, examples of the substituent include the substituent described in the general formula (1), the groups exemplified for G, R ¹ and R ² , and the ionic hydrophilic group.

In addition to the phosphono group as a substituent, it may further have another ionic hydrophilic group at any position on A, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and G. Is preferred. The ionic hydrophilic group as a substituent includes a sulfo group, a carboxyl group, a quaternary ammonium group and the like. As the ionic hydrophilic group, a carboxyl group and a sulfo group are preferable. The carboxyl group, the phosphono group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic cation. (Eg, tetramethyl ammonium ion, tetramethyl guanidinium ion, tetramethyl phosphonium ion).

Here, the Hammett's substituent constant σp value used in the present specification will be described in relation to the substituent Z ¹ . Hammett's rule is used to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives.
According to the rule of thumb proposed by LP Hammett in
This is widely accepted today. There are σp values and σm values for the substituent constants obtained by the Hammett's rule, and these values can be found in many general textbooks.
For example, JA Dean, "Lange's Handbook of Chemis"
Try ”12th Edition, 1979 (McGraw-Hill) and“ Chemical Area ”special edition, No. 122, pp. 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, which means that it is limited only to a substituent having a known value found in the literature. It goes without saying that even if the value is unknown in the literature, it also includes a substituent that will be included in the range when measured based on the Hammett's rule. Further, in the general formulas (1) and (2) of the present invention, a substance which is not a benzene derivative is also included, but the σp value is used as a measure of the electron effect of a substituent regardless of the substitution position. In the present invention, the σp value is used in such a meaning.

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, an alkylsulfonyl group (for example, a methanesulfonyl group, an arylsulfonyl group (for example, a benzenesulfonyl group)). Examples of the electron withdrawing group having a Hammett σp value of 0.45 or more include an acyl group (eg, acetyl group), an alkoxycarbonyl group (eg, dodecyloxycarbonyl group), an aryloxycarbonyl group (eg, m -Chlorophenoxycarbonyl), an alkylsulfinyl group (for example, n-propylsulfinyl), an arylsulfinyl group (for example, phenylsulfinyl), a sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dimethylsulfamoyl), a halogen Alkyl group (eg If, it can be exemplified trifluoromethyl).

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 (eg acetoxy), a carbamoyl group (eg N
-Ethylcarbamoyl, N, N-dibutylcarbamoyl), halogenated alkoxy group (for example, trifluoromethyloxy), halogenated aryloxy group (for example,
Pentafluorophenyloxy), a sulfonyloxy group (eg, methylsulfonyloxy group), a halogenated alkylthio group (eg, difluoromethylthio group), and two or more electron-withdrawing groups having a σp value of 0.15 or more. Aryl groups (eg 2,4-dinitrophenyl, pentachlorophenyl), and heterocycles (eg 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl) can be mentioned. σ
Specific examples of the electron withdrawing group having a p value of 0.20 or more include:
In addition to the above, examples thereof include a halogen atom.

Particularly preferred combinations of substituents for the azo dye represented by the general formula (1) are as follows. (A) R ⁵ and R ⁶ are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfonyl group or an acyl group, and more preferably a hydrogen atom, an aryl group, a heterocyclic group or a sulfonyl group. , Most preferably a hydrogen atom, an aryl group or a heterocyclic group. However, R ⁵ and R ⁶ are not both hydrogen atoms. (B) G is preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an amino group or an acylamino group, more preferably a hydrogen atom, a halogen atom, an amino group or an acylamino group, and most preferably a hydrogen atom. , An amino group and an acylamino group. (C) A is preferably a pyrazole ring, an imidazole ring, an isothiazole ring, a thiadiazole ring, or a benzothiazole ring, more preferably a pyrazole ring or an isothiazole ring, and most preferably a pyrazole ring. (D) B ¹ and B ² are respectively = CR ¹ −, −CR ² =
And each of R ¹ and R ² is preferably a hydrogen atom, an alkyl group, a halogen atom, a cyano group, a carbamoyl group, a carboxyl group, a hydroxyl group, an alkoxy group or an alkoxycarbonyl group, and more preferably a hydrogen atom or an alkyl group. Group, cyano group and carbamoyl group.

Regarding the preferred combination of the substituents of the compound represented by the general formula (1), a compound in which at least one of the various substituents is the above preferred group is preferable, and more various substituents are preferable. The compound having the preferable groups is more preferable, and the compound having all the substituents as the preferable groups is most preferable.

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

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

[Table 3]

[0063]

[Table 4]

[0064]

[Table 5]

The synthesis examples of the azo dye represented by the general formula (1) are shown below. [Synthesis Example 1]: Synthesis of dye (a-6)

[0066]

[Chemical 6]

<Synthesis of Intermediate (a-6a)> 5-amino-3-tert-butyl-4-cyanopyrazole (1) 8 g
(48.7 mmol), concentrated hydrochloric acid (15 ml) and water (50 ml) were stirred at an internal temperature of 5 ° C, and sodium nitrite (3.36 g, 48.7 mmol) was added portionwise over 10 minutes. After stirring for 10 minutes as it is, coupling component
(2) 14.6 g (40.6 mmol) of sodium acetate 50 g, pyrozine 5
The above diazonium salt was added over 10 minutes to a three-necked flask which had been cooled to an internal temperature of 5 ° C. After the addition of the diazonium salt, the reaction solution was stirred as it was for 30 minutes, 300 ml of saturated saline was added, and the precipitated dye (a-6a) was filtered off. Yield 24.2g, 93%. <Synthesis of Dye (a-6)> 10.7 g (20 mmol) of Dye (a-6a)
In addition, 15 g (60 mmol) of the heterylating agent (3), potassium carbonate 8.8
g and 50 ml of DMAc were added, and the mixture was heated and stirred at 100 ° C. for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, 200 ml of 1N HCl aqueous solution was added, and the precipitated dye (a-6) was separated by filtration. Further, this crude crystal was recrystallized from acetonitrile. Yield 15.4g, 80% yield. λ
max = 558nm (DMF solution) m / z (posi) = 960

The azo dye represented by the general formula (1) or (2) (hereinafter, also referred to as "dye of the present invention") is used as an image recording material for forming an image, particularly a color image. Specifically, it is an inkjet recording material. The dye of the present invention is used by adjusting the physical properties such as solubility, dispersibility, and heat transferability suitable for its use with a substituent. Further, the dye of the present invention can be used in a dissolved state, an emulsified dispersed state, and even a solid dispersed state depending on the system used.

[Inkjet Recording Ink] The inkjet recording ink can be prepared by dissolving and / or dispersing the azo dye in a lipophilic medium or an aqueous medium. Preferably, an aqueous medium is used. If necessary, other additives are contained 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 accelerators, ultraviolet absorbers, preservatives,
Known additives such as antifungal agents, pH adjusting agents, surface tension adjusting agents, defoaming agents, viscosity adjusting agents, dispersants, dispersion stabilizers, rust preventives and chelating agents can be mentioned. In the case of water-soluble ink, these various additives are added directly to the ink liquid. When the oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after preparation of the dye dispersion, but it may be added to the oil phase or the water phase during the preparation.

The anti-drying agent is preferably used for the purpose of preventing clogging due to drying of the inkjet ink at the ink ejection port of the nozzle used in the inkjet recording system. As the anti-drying agent, a water-soluble organic solvent having a vapor pressure lower than that of water is preferable. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-
Propanediol, 1,2,6-hexanetriol,
Polyhydric alcohols represented by acetylene glycol derivatives, glycerin, trimethylolpropane, etc., ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether,
Lower alkyl ethers of polyhydric alcohols such as triethylene glycol monoethyl (or butyl) ether, 2
-Pyrrolidone, N-methyl-2-pyrrolidone, 1,3-
Heterocycles such as dimethyl-2-imidazolidinone, N-ethylmorpholine, sulfolane, dimethyl sulfoxide,
Examples thereof include sulfur-containing compounds such as 3-sulfolene, polyfunctional compounds such as diacetone alcohol and diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferable. The above-mentioned anti-drying agents may be used alone or in combination of two or more kinds. It is preferable that the drying inhibitor is contained in the ink in an amount of 10 to 50% by mass.

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

The ultraviolet absorber is used for the purpose of improving the storability of images. As a UV absorber, JP-A-58
-185677, 61-190537,
Japanese Patent Laid-Open No. 2-782, Japanese Patent Laid-Open No. 5-97075,
Benzotriazole compounds described in JP-A-9-34057, JP-A-46-2784, JP-A-5-
Benzophenone compounds described in JP-A-194483, U.S. Pat. No. 3,214,463, etc.
8-30492, 56-21141, JP-A-10-88106 and the like, cinnamic acid compounds, JP-A-4-298503 and 8-53342.
No. 7, JP-A 8-239368, and JP-A 10-182.
No. 621, Japanese Patent Publication No. 8-501291, etc., triazine compounds, Research Disclosure No. A compound which absorbs ultraviolet rays and fluoresces, which is represented by the compounds described in No. 24239 and stilbene compounds and benzoxazole compounds, that is, a so-called fluorescent brightening agent can also be used.

The anti-fading agent is used for the purpose of improving the storability of images. 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, indans, chromanes, alkoxyanilines, heterocycles, etc., and metal complexes include nickel. Complex, zinc complex and the like. More specifically, Research Disclosure No. 176
No. 43, Item VII, I to J, ibid. 15162, the same No. 18716, page 650, left column, same No. 36544
Pp. 527, ibid. 307105, page 872, same N
o. The compounds described in the patent cited in 15162 and the compounds included in the general formulas and the compound examples of the representative compounds described on pages 127 to 137 of JP-A No. 62-215272 can be used.

As a fungicide, sodium dehydroacetate,
Sodium benzoate, sodium pyridinethione-1-
Oxide, p-hydroxybenzoic acid ethyl ester,
1,2-benzisothiazolin-3-one and salts thereof and the like can be mentioned. These are 0.02-1.0 in the ink
It is preferable to use 0% by mass.

As the pH adjusting agent, a neutralizing agent (organic base,
Inorganic alkali) can be used. For the purpose of improving the storage stability of the inkjet ink, the pH adjusting agent is preferably added to the inkjet ink at pH 6 to 10 for summer, and more preferably at pH 7 to 10.

Examples of the surface tension adjusting agent include nonionic, cationic or anionic surfactants. The surface tension of the inkjet ink of the present invention is 20 to 60 m.
N / m is preferable and 25 to 45 mN / m is more preferable. The viscosity of the inkjet recording ink of the present invention is preferably 30 mN / m or less. It is more preferable to adjust to 20 mN / m or less. Examples of the surfactant include fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfonate, alkylnaphthalene sulfonate, dialkylsulfosuccinate, alkyl phosphate ester salt, naphthalene sulfonate formalin condensate, polyoxyethylene alkyl sulfate. Anionic surfactants such as ester salts, polyoxyethylene alkyl ethers,
Nonionic surfactants such as polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, and oxyethyleneoxypropylene block copolymer are preferable. In addition, SURFYNOLS (Air Products & Ch), which is an acetylene-based polyoxyethylene oxide surfactant, is used.
(Medicals, Inc.) is also preferably used. Also, N,
Also preferred are amine oxide type amphoteric surfactants such as N-dimethyl-N-alkylamine oxide. Furthermore,
Research Disclosure No. pp. 37-38, JP-A-59-157636. 308119 (1989
It is also possible to use those listed as the surfactants described in (Year).

As the defoaming agent, a fluorine-based compound, a silicone-based compound, a chelating agent typified by EDTA, or the like can be used if necessary.

When the azo dye of the present invention is dispersed in an aqueous medium, JP-A No. 11-286637, Japanese Patent Application No. 2000-78491, and JP-A No. 2000-78491.
As described in each of the publications such as 000-80259 and 2000-62370, the colored fine particles containing a dye and an oil-soluble polymer are dispersed in an aqueous medium, or Japanese Patent Application Nos. 2000-78454 and 2000-784.
As described in each specification of No. 91, No. 2000-203856, No. 2000-203857, etc., it is preferable to disperse the dye of the present invention dissolved in a high boiling point organic solvent in an aqueous medium. The specific method for dispersing the azo dye in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additive, and the amount thereof are preferably those described in the above publications and the like. . Alternatively, the azo dye may be dispersed in a fine particle state as it is as a solid.

At the time of dispersion, a dispersant or a surfactant can be used. As a dispersing device, a simple stirrer or 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) A specific commercially available device is a Gohlin homogenizer, microfluidizer, DeBEE2000, etc.). Regarding the method for preparing the above ink jet recording ink, in addition to the above-mentioned publications, etc.
No. 48436, No. 5-295312, No. 7-9754.
1, No. 7-82515, No. 7-118584, JP-A No. 11-286637, Japanese Patent Application No. 2000-87539.
The details are described in the respective publications and the like of the publication and can be used for the preparation of the inkjet recording ink of the present invention.

As the aqueous medium, a mixture containing water as a main component and a water-miscible organic solvent added thereto can be used, if desired. Examples of water-miscible organic solvents are alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyhydric alcohols. Classes (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (for example, 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), amines (eg,
Ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (for example,
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) included. The water-miscible organic solvent may be used in combination of two or more kinds.

Inkjet recording ink 10 of the present invention
The azo dye is preferably contained in an amount of 0.2 parts by mass or more and 10 parts by mass or less in 0 parts by mass. Further, in the ink jet recording ink of the present invention, other colorants may be used in combination with the azo dye. When two or more colorants are used in combination, the total content of the colorants is preferably within the above range.

The ink jet recording ink of the present invention comprises
It can be used for full-color image formation as well as single-color image formation. To form a full-color image,
A magenta color tone ink, a cyan color tone ink, and a yellow color tone ink can be used, and a black color tone ink may be further used to adjust the color tone. Any applicable yellow dye can be used. For example, an aryl or heterylazo dye having phenols, naphthols, anilines, heterocycles such as pyrazolone and pyridone, and open-chain active methylene compounds as a coupling component (hereinafter referred to as a coupler component); Azomethine dyes containing open-chain active methylene compounds; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes; and other dyes Examples thereof include quinophthalone dyes, nitro / nitroso dyes, acridine dyes and acridinone dyes.

As the applicable cyan dye, any cyan dye can be used. For example, aryl or heterylazo dyes having phenols, naphthols, anilines and the like as coupler components; for example, azomethine dyes having phenols, naphthols and heterocycles such as pyrrolotriazole as coupler components;
Examples thereof include polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; phthalocyanine dyes; anthraquinone dyes; indigo / thioindigo dyes.

Each of these dyes may exhibit yellow and cyan colors only after a part of the chromophore is dissociated, in which case the counter cation is an alkali metal or an inorganic cation such as ammonium. It may be an organic cation such as a pyridinium or quaternary ammonium salt, or a polymer cation having a partial structure thereof. Examples of applicable black materials include disazo, trisazo, and tetraazo dyes, and carbon black dispersions.

[Inkjet Recording Method] In the inkjet recording method of the present invention, energy is applied to the inkjet recording ink to obtain a known image receiving material, that is, plain paper or resin-coated paper, for example, JP-A-8-169172. No. 8-27693, No. 2-276670, No. 7-276789, No. 9-323475, No. 62-23878, No. 10-
No. 153989, No. 10-217473, No. 10-235995, No. 10-337947, No. 10-21797, No. 10-33794.
An image is formed on inkjet-dedicated paper, film, electrophotographic co-paper, cloth, glass, metal, porcelain, etc. described in Japanese Patent Publication No.

When forming an image, a polymer latex compound may be used together for the purpose of imparting glossiness, water resistance and improving weather resistance. The latex compound may be applied to the image receiving material before, after, or at the same time as the application of the colorant, so that the place of addition is also in the image receiving paper, It may be in the ink, or may be used as a liquid substance of the polymer latex alone. Specifically, Japanese Patent Application 2000-363090
Issue 2000-315231 Issue 2000-354380 Issue 2000-34394
No. 4, 2000-268952, 2000-299465, 2000-2973
The method described in each specification of No. 65 can be preferably used.

The recording paper and recording film used for ink jet printing using the ink of the present invention will be described below. Supports for recording paper and recording film are chemical pulp such as LBKP and NBKP, G
P, PGW, RMP, TMP, CTMP, CMP, CG
It consists of mechanical pulp such as P, waste paper pulp such as DIP,
If necessary, conventionally known pigments, binders, sizing agents,
Mixing additives such as fixing agent, cationic agent, paper strengthening agent,
Those manufactured by various devices such as a Fourdrinier paper machine and a cylinder paper machine can be used. In addition to these supports, synthetic paper or plastic film sheet may be used. The thickness of the support is 10 to 250 μm, and the basis weight is 10 to 250 g.
/ M ² is desirable. The support may be provided with the ink receiving layer and the back coat layer as it is, or may be provided with the ink receiving layer and the back coat layer after the size press or the anchor coat layer is provided with starch, polyvinyl alcohol or the like. Further, the support may be subjected to flattening treatment by a calendar device such as a machine calendar, a TG calendar and a soft calendar. In the present invention, as the support,
A paper and a plastic film having both surfaces laminated with a polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and their copolymers) are more preferably used. It is preferable to add a white pigment (eg, titanium oxide, zinc oxide) or a coloring dye (eg, cobalt blue, ultramarine blue, neodymium oxide) to the polyolefin.

The ink receiving layer provided on the support is
It 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. As the white pigment contained in the ink receiving layer, a porous inorganic pigment is preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, both silicic acid anhydride obtained by the dry production method and hydrous silicic acid obtained by the wet production method can be used, but it is particularly preferable to use hydrous silicic acid.

As the aqueous binder contained in the ink receiving layer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinylpyrrolidone, polyalkylene oxide, polyalkylene oxide derivative. Water soluble polymer such as styrene butadiene latex,
Examples thereof include water-dispersible polymers such as acrylic emulsion. 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 peeling resistance of the ink receiving layer. The ink receiving layer contains a mordant, a water resistance agent, a light resistance improver, in addition to a pigment and an aqueous binder.
Surfactants and other additives can be contained.

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 and JP-A-54-74430 are used.
No. 54-124726, No. 55-22766,
No. 55-142339, No. 60-23850, No. 6
0-23851, 60-2852, 60-2
3853, 60-57836, 60-6064.
No. 3, No. 60-118834, No. 60-122940
No. 60-122941, No. 60-122942
No. 60-235134, JP-A-1-161236.
Publications, US Pat. Nos. 2,484,430 and 25,485.
No. 64, No. 3148061, No. 3309690, No. 4115124, No. 4124386, No. 41938.
No. 00, No. 4273853, No. 4282305, and No. 4450224. JP-A-1-
An image receiving material containing a polymer mordant described on pages 212 to 215 of JP-A-161236 is particularly preferable. When the polymer mordant described in the publication is used, an image with excellent image quality can be obtained and the light resistance of the image can be improved.

The waterproofing agent is effective for waterproofing the image,
A cationic resin is particularly preferable as the water-proofing agent. Examples of such a cationic resin include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide, colloidal silica, and the like. 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, and particularly 3 to 3% by mass based on the total solid content of the ink receiving layer.
It is preferably 10% by mass.

Examples of the light resistance improver include zinc sulfate, zinc oxide, hindered amine type antioxidants, benzophenone type and benzotriazole type ultraviolet absorbers, and the like. Of these, zinc sulfate is particularly preferable.

The surfactant is a coating aid, a peelability improver,
Functions as a slipperiness improver or antistatic agent. The surfactant is described in JP-A-62-173463 and JP-A-62-183457. An organic fluoro compound may be used instead 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). Regarding organic fluoro compounds, Japanese Patent Publication No. 57-9
No. 053 (columns 8 to 17), JP-A-61-20994.
And No. 62-135826. Other additives added to the ink receiving layer include pigment dispersants, thickeners, defoamers, dyes, optical brighteners, preservatives,
Examples thereof include pH adjusters, matting agents, hardeners and the like. The ink receiving layer may be one layer or two layers.

A back coat layer may be provided on the recording paper and the recording film, and components that can be added to this layer include a white pigment, an aqueous binder, and other components. Examples of the white pigment contained in the back coat 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. , Diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudo-boehmite, aluminum hydroxide, alumina, lithopone, zeolite,
Examples thereof include white inorganic pigments such as hydrolyzed halloysite, magnesium carbonate and magnesium hydroxide, organic pigments such as styrene plastic pigments, acrylic plastic pigments, polyethylene, microcapsules, urea resins and melamine resins.

As the aqueous binder contained in the back coat layer, styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin are used. , Water-soluble polymers such as carboxymethyl cellulose, hydroxyethyl cellulose and polyvinylpyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of other components contained in the back coat layer include a defoaming agent, a defoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water resistance agent.

Polymer latex may be added to the constituent layers (including the back coat layer) of the ink jet recording paper and recording film. The polymer latex is used for the purpose of improving physical properties of the film such as dimensional stabilization, curl prevention, adhesion prevention, and film cracking prevention. Regarding the polymer latex, JP-A Nos. 62-245258 and 62-1
It is described in each publication of 316648 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 or curling of the layer can be prevented. Curling can also be prevented by adding a polymer latex having a high glass transition temperature to the back coat layer.

The ink of the present invention is not limited to an ink jet recording system, and is a known system, for example, a charge control system in which ink is ejected by using electrostatic attraction, or a drop-on-demand system in which vibration pressure of a piezo element is used. Method (pressure pulse method), an acoustic ink jet method in which an electric signal is converted into an acoustic beam to irradiate the ink and the ink is ejected using radiation pressure, and a bubble is formed by heating the ink and the generated pressure is used. It is used for a thermal inkjet system and the like. The inkjet recording method uses a method of ejecting a large number of low density inks called photo ink in a small volume, a method of improving image quality by using a plurality of inks having substantially the same hue but different densities, and a colorless transparent ink. Method is included.

[0098]

[Example 1]

(Preparation of Aqueous Ink) The following components were stirred for 1 hour while being heated at 30 to 40 ° C., and then pressure-filtered using a microfilter having an average pore size of 0.8 μm and a diameter of 47 mm to prepare an ink liquid A. . -Composition of Ink Liquid A- Azo Dye Specific Example a-6 5 parts by mass Diethylene glycol 9 parts by mass Tetraethylene glycol monobutyl ether 9 parts by mass Glycerin 7 parts by mass Diethanolamine 2 parts by mass Water 70 parts by mass

Ink liquid B was prepared in the same manner as ink liquid A, except that the azo dye was changed as shown in Table 6 below.
~ L was prepared.

(Image recording and evaluation) Using the ink liquids A to L, a photo glossy paper (Fuji Photo Film Co., Ltd. inkjet paper, Super Photo) was used with an inkjet printer (PM-700C, Seiko Epson Corporation). The image was recorded on the grade). The hue, light fastness and ozone gas resistance of the obtained image were evaluated.
The hue was visually evaluated on the basis of 3 grades: best, good and bad. The evaluation results are shown in Table 6 below. In Table 6 below,
◯ means that the hue is the best; Δ means that the hue is good; and x means that the hue is poor.

The light fastness was measured by measuring the image density Ci immediately after recording and then irradiating the image with xenon light (85,000 lux) for 7 days using a weather meter (Atlas C.165). The image density Cf was measured again, and the dye residual rate ({(Ci-Cf) / Ci} × 100%) was calculated from the difference in image density before and after the xenon light irradiation, and evaluated. Image density is measured by reflection densitometer (X-Rite310T
R). The residual ratio of dye is 1 for reflection density,
It was measured at three points of 1.5 and 2.0. The evaluation results are shown in Table 6 below. In Table 6 below, the case where the residual dye rate is 80% or more at any concentration is indicated as ◯, the case where two points are less than 80% is indicated as Δ, and the case where all the concentrations are less than 80% is indicated as x.

Regarding the ozone gas resistance, the image immediately after recording was left for 24 hours in a box in which the ozone gas concentration was set to 0.5 ppm, and the image density before and after being left under ozone gas was measured by a reflection densitometer (X-Rite310TR). Was used to evaluate the residual dye rate. 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 manufactured by APPLICS (model: OZG-EM-01). When the residual dye rate is 70% or more at any concentration, ○, 1 or 2 points are less than 70% △, and at all concentrations 70
When it was less than%, it was rated as × and evaluated in three stages.

[0103]

[Table 6]

[0104]

[Chemical 7]

[0105]

[Chemical 8]

As shown in Table 6, the ink liquids A to
The magenta images obtained from H were sharper than the magenta images obtained from the comparative ink liquids I to L. Further, the images obtained using the ink liquids A to H of the present invention were excellent in light fastness and ozone gas resistance.

Further, using the ink liquids A to H, an ink jet printer (PM-700C, manufactured by Seiko Epson Corp.) was used to produce glossy paper (MJ
An image was recorded on A4S3P, manufactured by Seiko Epson Corporation. When the hue and light fastness of the obtained images were evaluated, the same results as in Table 6 were obtained.

[0108]

The coloring composition for image formation of the present invention has absorption properties excellent in color reproducibility as a dye of three primary colors and is sufficiently fast against light, heat, humidity and active gas in the environment. Since a novel dye having properties is used, a colored image or coloring material excellent in hue and fastness can be provided.
In particular, it is preferably used for preparing inks for printing such as ink jet and dyeing solutions for dyeing various fibers.
The ink jet recording ink and the ink jet recording method using the coloring composition of the present invention form an image having a good hue and having high fastness to active gas in the light and environment, particularly ozone gas. You can

Continued front page    F-term (reference) 2C056 FC01                 2H086 BA15 BA33 BA56                 4J039 BC03 BC05 BC07 BC12 BC19                       BC20 BC32 BC33 BC36 BC40                       BC50 BC51 BC54 BC55 BC57                       EA34 EA35 EA44 GA24

Claims (5)

[Claims] 1. An azo dye having an aromatic nitrogen-containing 6-membered heterocycle as a coupling component, which comprises an azo dye having at least one phosphono group in the dye molecule. Coloring composition. 2. The coloring composition for image formation according to claim 1, wherein the azo dye is represented by the following general formula (1). General formula (1) In the above general formula (1): A is a 5-membered heterocyclic diazo component A-
Represents a residue of NH ₂ . B ¹ and B ² are respectively = CR ¹ −,
-CR ² = or represents, or either one nitrogen atom and the other = CR ¹ - or an -CR ² =. R ⁵ , R ⁶
Each independently represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group or a sulfamoyl group. Each group may further have a substituent. G, R
¹ and R ² are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxy group. Carbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group,
Acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkyl and arylthio group, alkyl or arylsulfonyl group, It represents a heterocyclic sulfonyl group, an alkyl or aryl sulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, a sulfo group, or a heterocyclic thio group. Each group may be further substituted. Further, R ¹ and R ⁵ , or R ⁵ and R ⁶ may be bonded to form a 5- or 6-membered ring. However, it has at least one phosphono group in the general formula (1). 3. The coloring composition for image formation according to claim 1, wherein the azo dye is represented by the following general formula (2). General formula (2) In general formula (2): Z ¹ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Z ² represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. R ¹ ,
R ² , R ⁵ and R ⁶ have the same meanings as in the case of the general formula (1).
R ³ and R ⁴ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfonyl group or a sulfamoyl group. Q is a hydrogen atom,
It represents an aliphatic group, an aromatic group or a heterocyclic group. Z ¹ above,
Each group of Z ² , R ^{1 to} R ⁶ and Q may further have a substituent. However, it has at least one phosphono group in the general formula (2). 4. An inkjet recording ink comprising the coloring composition according to claim 2. 5. An ink jet recording method comprising forming an image on the image receiving material having an ink receiving layer containing white inorganic pigment particles on a support, using the ink for ink jet recording according to claim 4. .