JP2003277661A - Compound, ink and inkjet printing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an ink having good hue and capable of forming printed images of high fastness under various service conditions and environmental conditions. <P>SOLUTION: The ink contains at least one kind of dye of formula (1) (wherein, R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>are each H or a monovalent group, one of them being a substituent bearing an azo-substituted heterocyclic group; and Z is a nitrogen atom or a carbon atom with a hydrogen atom or monovalent group bound thereto). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an azo dye, an ink containing the dye, an ink jet recording method, a heat-sensitive recording material, a color toner and a color filter.

[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. In addition, color filters are used to record and reproduce color images in imaging devices such as CCDs in photographing equipment and in LCDs and PDPs in displays. These color image recording materials and color filters use dyes (dyes and pigments) of the three primary colors of so-called additive color mixing method and subtractive color mixing method in order to display or record a full-color image. It is the actual situation that there is no robust dye that has absorption characteristics that can realize the above 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. The ejection method is a droplet that is applied with pressure by a piezo element. 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.

The dye used in such ink jet recording ink has good solubility or dispersibility in a solvent and high density recording is possible.
Good hue, active gas in light, heat and environment (N
It is robust against SOx as well as oxidizing gases such as Ox and ozone, has excellent fastness to water and chemicals, has good fixability to the image receiving material and does not bleed, and is stored as an ink It is required to have excellent properties, be non-toxic, have high purity, and be available at low cost. However, it is extremely difficult to provide a dye satisfying these requirements at a high level. In particular, when a dye having a good yellow hue and being robust against light, humidity, and heat, particularly when printing on an image receiving material having an ink receiving layer containing porous white inorganic pigment particles, Robustness against oxidizing gases such as ozone in the environment is strongly desired.

In color copiers and color laser printers utilizing the electrophotographic system, toners in which a coloring material is dispersed in resin particles are generally widely used. As the performance required for color toner, absorption characteristics that can realize a preferable color gamut, especially Over HeadPro
high transparency (transparency), which is a problem when used in an injector (hereinafter referred to as OHP), and various robustness under the environmental conditions used. A toner in which a pigment as a coloring material is dispersed in particles is disclosed in JP-A-62-157051.
JP-A No. 62-255956 and JP-A No. 6-118715 disclose that these toners are excellent in light resistance, but they are insoluble and easily aggregate, resulting in deterioration of transparency and hue change of transmitted color. Becomes On the other hand, a toner using a dye as a coloring material is disclosed in JP-A-3-276161 and JP-A-3-276161.
No. 209912 and No. 8-123085, these toners, on the contrary, have high transparency and no hue change, but have a problem in light resistance.

The heat-sensitive transfer recording has advantages that the apparatus is small and the cost can be reduced, the operation and maintenance are easy, and the running cost is low. As the performance required for dyes used in thermal transfer recording, absorption characteristics capable of achieving a preferable color reproduction range, compatibility of heat transferability and fixability after transfer, thermal stability, and various robustness of the obtained image are obtained. However, none of the conventionally known dyes satisfy all of these performances. For example, for the purpose of improving fixability and light resistance, a heat-sensitive transfer recording material and an image forming method in which a heat-diffusible dye is chelated by a transition metal ion previously added to an image receiving material are disclosed in JP-A-60-239.
No. 8, etc., the absorption characteristics of the chelate dye formed are unsatisfactory, and there are environmental problems due to the use of transition metals.

Since a color filter is required to have high transparency, a method called a dyeing method for coloring with a dye has been performed. For example, a color filter can be manufactured by sequentially repeating a method of forming a pattern by subjecting a dyeable photoresist to pattern exposure and development, and then dyeing with a filter dye, for all filter colors. U.S. Pat.
The color filter can also be produced by the method using a positive resist described in JP-A-8,501 and JP-A-6-35182. These methods have high transmittance due to the use of dyes, and the optical characteristics of the color filter are excellent, but there is a limit to light resistance and heat resistance, and a dye having excellent various resistance and high transparency is desired. Was there. On the other hand, a method of using an organic pigment having excellent light resistance and heat resistance in place of the dye is widely known, but it has been difficult to obtain dye-like optical characteristics with a color filter using the pigment.

The dyes used in each of the above-mentioned 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 resistance fastness such as sulfurous acid gas. And the like.
In particular, there is a strong demand for a dye that has a good yellow hue and that is robust against light, moist heat and active gases in the environment, particularly oxidizing gases such as ozone. An azo dye is typical as a yellow dye skeleton used in an inkjet recording ink.

As the representative azo dye, there is disclosed in Japanese Patent Laid-Open No.
Aminopyrazole azo dyes and pyrazolone azo chelate dyes described in 7-5770 and 58-147470, pyrazolone azo dyes described in JP-A-57-642775, pyridone azo dyes described in JP-A-6-184481, and JP-A-5-255625. And 5-331396
And stilbene azo dyes described in JP-A-57-657
Examples thereof include bisazo dyes described in No. 57.
Further, JP-A-2-24191 discloses a thiadiazole-azo-pyrazole dye for thermal transfer. Further, J.Soc.Dye & Colorurists 102,176-181 (1986) describes a dye having a triazinylpyrazole skeleton, but the use in inkjet ink, thermal transfer ink sheet, color toner and color filter is described. It has not been.

These dyes are discolored and decolored by an oxidizing gas such as nitric oxide gas or ozone, which is often taken up as an environmental problem these days, and at the same time, the printing density is lowered. Further, many dyes are not always satisfactory in light resistance. In the future, when the field of use expands and it is widely used for exhibits such as advertisements, it is often exposed to light, heat, humidity and active gas in the environment, so it has a particularly good hue, Light fastness, wet heat fastness and active gases in the environment (NO _x ,
There is an increasing demand for dyes and ink compositions having excellent fastness to oxidizing gases such as ozone as well as SO _x . However, it is extremely difficult to search for an azo dye and a yellow ink which satisfy these requirements at a high level.

[0011]

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 present invention provides 1) a novel dye having absorption properties excellent in color reproducibility as a dye of three primary colors and having sufficient fastness to active gas in light, heat, humidity and environment. 2) Ink for printing such as inkjet, ink sheet for thermal recording material, color toner for electrophotography, display and CCD such as LCD, PDP, etc., which give colored images and coloring materials excellent in hue and fastness. Various coloring compositions such as color filters used in the image pickup device of 3) are provided, and 3) In particular, the use of the dye has a good hue and is robust against active gas in light, wet heat and environment, particularly ozone gas. Provided are an ink and an inkjet recording method capable of forming an image having high property, and 4).
It is an object of the present invention to provide a novel dye derivative having a specific structure that can be a useful organic compound used in industry, agriculture, medicine, academics, or the like, or an intermediate thereof.

[0012]

DISCLOSURE OF THE INVENTION The inventors of the present invention have studied in detail a pyrazolylazo dye derivative aiming at a dye having a good hue and high fastness to light, ozone and heat and humidity. The inventors have found that the above problems can be solved by a compound represented by the following general formula (1) having a specific dye structure which has not been achieved, and have completed the present invention. Means for solving the above problems are as follows. That is, the present invention is: An ink comprising at least one kind of dye represented by the following general formula (1),

[0013]

[Chemical 3]

(In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent group, and R ¹ , R ²
And one of R ³ represents a substituent having a heterocyclic group substituted with an azo group, and Z represents a nitrogen atom or a hydrogen atom or a carbon atom to which a monovalent group is bonded. ) 2. The ink according to item 1, wherein the dye represented by the general formula (1) is a dye represented by the following general formula (2):

[0015]

[Chemical 4]

(Where R is^FourRepresents a monovalent group, R^FiveIs
-OR⁸Or -NHR⁹Represents R ⁸And R⁹Is water
Represents an elementary atom or a monovalent group, R⁶And R⁷Is that
Independently represent a hydrogen atom or a monovalent group, Ar is an ari
Group or heterocyclic group. ) 3. The dye represented by the general formula (2) is represented by the following general formula
Item 1 above, which is a dye represented by (3)
Ink described in,

[0017]

[Chemical 5]

(In the formula, R ¹⁰ is a hydrogen atom, an alkyl group,
Represents a cycloalkyl group, an aralkyl group, an alkoxy group or an aryl group, R ¹¹ and R ¹² each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a sulfo group or a heterocyclic group, Het represents an aromatic heterocyclic group, and each substituent may further have a substituent. ) 4. 5. An ink jet recording method, wherein an image is formed on an image receiving material having an ink receiving layer containing white inorganic pigment particles on a support, using the ink according to any one of 1 to 3 above. ． 5. An ink sheet comprising the dye represented by any one of the general formulas (1) to (3) described in any one of 1 to 3 above; 6. A color toner comprising the dye represented by any one of the general formulas (1) to (3) described in any one of the above items 1 to 3. 7. A color filter comprising the dye represented by any one of the above general formulas (1) to (3) according to any one of 1 to 3. 8. The compound represented by the general formula (3), and Compound represented by the following general formula (4)

[0019]

[Chemical 6]

(In the formula, R ¹⁰ is a hydrogen atom, an alkyl group,
Represents a cycloalkyl group, an aralkyl group, an alkoxy group or an aryl group, R ¹¹ and R ¹² each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a sulfo group or a heterocyclic group, one of X and Y represents a nitrogen atom and the other represents -C (-R ¹³⁾ =. R ¹³ is a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkylthio group, an alkylsulfonyl group, an alkylsulfinyl group, an alkyloxycarbonyl group,
It represents a carbamoyl group, an alkoxy group, an aryl group, an arylthio group, an arylsulfonyl group, an arylsulfinyl group, an aryloxy group or an acylamino group. Each substituent may further have a substituent. )
Is provided.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. [Azo Dye] The azo dye in the invention is represented by the above general formula (1). The general formula (1) will be described in detail below. In the present invention, the monovalent group is the same as the substituent which the aryl group described later has. The heterocyclic group having an azo group is the same as Ar in the general formula (2), and pyrazole is preferable.

More preferably, it is an azo dye represented by the general formula (2). The aryl group represented by Ar is the same as the aryl group described later. The heterocyclic group represented by Ar is preferably a 5- or 6-membered ring, which may be further condensed. Further, it may be an aromatic hetero ring or a non-aromatic hetero ring. For example, pyridine,
Pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan,
Benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole,
Benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine,
Examples thereof include imidazolidine and thiazoline. Among them, an aromatic heterocyclic group is preferable, and when the preferable examples are exemplified in the same manner as above, pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrazole, imidazole, benzimidazole, triazole, thiazole, benzothiazole, isothiazole, benziso Thiazole,
Thiadiazole may be mentioned. Thiadiazole is most preferred. They may have a substituent, and examples of the substituent are the same as those of the aryl group described later.

More preferably, the dye represented by the general formula (3) is used. The general formula (3) will be described in detail.
The alkyl group represented by R ¹⁰ includes a substituted or unsubstituted alkyl group. The substituted or unsubstituted alkyl group is preferably an alkyl group having 1 to 30 carbon atoms. Examples of the substituent are the same as those of the aryl group described later. Of these, a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, a sulfo group (which may be in the form of a salt) and a carboxyl group (which may be in the form of a salt) are preferable. Examples of said alkyl groups are methyl, ethyl, butyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, hydroxyethyl, cyanoethyl and 4
-Sulfobutyl may be mentioned.

The cycloalkyl group represented by R ¹⁰ includes a substituted or unsubstituted cycloalkyl group. The substituted or unsubstituted cycloalkyl group has 5 to 5 carbon atoms.
30 cycloalkyl groups are preferred. Examples of the substituent are the same as those of the aryl group described later. Examples of the cycloalkyl group include cyclohexyl, cyclopentyl, and 4-n-dodecylcyclohexyl.

The aralkyl group represented by R ¹⁰ includes a substituted or unsubstituted aralkyl group. The substituted or unsubstituted aralkyl group is preferably an aralkyl group having 7 to 30 carbon atoms. Examples of the substituent are the same as those of the aryl group described later. Examples of the aralkyl group may include benzyl and 2-phenethyl.

The alkoxy group represented by R ¹⁰ includes a substituted or unsubstituted alkoxy group. The substituted or unsubstituted alkoxy group is preferably an alkoxy group having 1 to 30 carbon atoms. Examples of the substituent include the same as the substituent of the aryl group described later. Examples of the alkoxy group may include methoxy, ethoxy, isopropoxy, n-octyloxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy.

The aryl group represented by R ¹⁰ includes a substituted or unsubstituted aryl group. The substituted or unsubstituted aryl group is preferably an aryl group having 6 to 30 carbon atoms. Examples of the substituent of the aryl group represented by R ¹⁰ include a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group and a nitro group. Group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), acylamino group, Aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfone Group, alkyl or arylsulfinyl group, alkyl or aryl sulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group Alternatively, a silyl group may be mentioned as an example.

The aryl group represented by R ¹⁰ will be described in detail below. Halogen atom represents a chlorine atom, a bromine atom, an iodine atom, etc., an alkyl group, an alkoxy group,
The cycloalkyl group and aralkyl group are as defined above. The alkenyl group represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. Examples thereof include substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl, 2-cyclopenten-1-yl and 2-cyclohexen-1-yl. The alkynyl group is a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, and examples thereof include ethynyl and propargyl. The aryl group is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl and m.
-Chlorophenyl and o-hexadecanoylaminophenyl. The heterocyclic group is a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and more preferably has 3 to 30 carbon atoms. It is a 5- or 6-membered aromatic heterocyclic group. For example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl.

The aryloxy group is a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylamino. It is phenoxy. The silyloxy group is a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy or t-butyldimethylsilyloxy. The heterocyclic oxy group is a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy. The acyloxy group is a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyl. Oxy, benzoyloxy and p-methoxyphenylcarbonyloxy. The carbamoyloxy group has 1 to 30 carbon atoms.
A substituted or unsubstituted carbamoyloxy group, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, N-n-octyl It is carbamoyloxy. The alkoxycarbonyloxy group is a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy. The aryloxycarbonyloxy group is a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy.

The amino group is a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, for example, amino, methylamino, dimethylamino, anilino, N- Methyl-anilino and diphenylamino. The acylamino group is a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example, formylamino, acetylamino, pivaloylamino, Lauroylamino, benzoylamino, 3,4
It is 5-tri-n-octyloxyphenylcarbonylamino. The aminocarbonylamino group is a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms,
For example, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino. The alkoxycarbonylamino group is a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t
-Butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino. The aryloxycarbonylamino group is a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m-n-octyloxyphenoxycarbonylamino. The sulfamoylamino group is a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino. .
The alkyl or arylsulfonylamino group is a substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino. , 2,3,5-trichlorophenylsulfonylamino and p-methylphenylsulfonylamino.

The alkylthio group is a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, for example, methylthio, ethylthio, n-hexadecylthio. The arylthio group is a substituted or unsubstituted arylthio having 6 to 30 carbon atoms, for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio. The heterocyclic thio group is a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, for example, 2-benzothiazolylthio or 1-phenyltetrazol-5-ylthio.

The sulfamoyl group is a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N. -Acetylsulfamoyl, N-benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl). The alkyl or arylsulfinyl group is a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-
Methylphenylsulfinyl. The alkyl or arylsulfonyl group is a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, for example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-
It is methylphenylsulfonyl.

The acyl group is a formyl group and has 2 to 30 carbon atoms.
Substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, heterocyclic carbonyl bonded to the carbonyl group at a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms Base,
For example, acetyl, pivaloyl, 2-chloroacetyl,
Stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl.

The aryloxycarbonyl group has 7 carbon atoms.
To 30 substituted or unsubstituted aryloxycarbonyl groups such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl. The alkoxycarbonyl group is a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl. The carbamoyl group is a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl). It is carbamoyl.

The phosphino group is a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino and methylphenoxyphosphino. The phosphinyl group is a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, for example, phosphinyl, dioctyloxyphosphinyl and diethoxyphosphinyl. The phosphinyloxy group has 2 carbon atoms
To 30 substituted or unsubstituted phosphinyloxy groups, for example diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy. The phosphinylamino group is a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino or dimethylaminophosphinylamino. The silyl group is a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl.

Among the substituents of the aryl group represented by R ¹⁰ mentioned above, those having a hydrogen atom may be substituted with the above group after removing the hydrogen atom. Examples of such a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. More specifically, methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl and benzoylaminosulfonyl groups can be mentioned.

The halogen atom, alkoxy group and amino group represented by R ¹¹ and R ¹² are the same as the above-mentioned substituents of the aryl group. The heterocyclic group represented by R ¹¹ and R ¹² is the same as the heterocyclic group represented by Ar in the general formula (2). R ¹⁰
Is preferably an alkyl group, and R ¹¹ and R ¹² are preferably amino groups.

Het represents an aromatic heterocyclic group, and preferred examples thereof are the same as those described above. Pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrazole, imidazole, benzimidazole, triazole, thiazole, benzothiazole, and isothiol. Thiazole,
Examples thereof include benzisothiazole and thiadiazole.
Thiadiazole is most preferred. They may have a substituent, and examples of the substituent are the same as the above-mentioned substituents of the aryl group.

A particularly preferable dye is a compound represented by the general formula (4). One of X and Y is a nitrogen atom, and the other is -C (-R ¹³ ) =. More preferably, X is -C (-R ¹³ ) = and Y is a nitrogen atom. Halogen atom, alkyl group, alkylthio group, alkylsulfonyl group, alkylsulfinyl group, alkoxycarbonyl, carbamoyl group, alkoxy group, aryl group, arylthio group, arylsulfonyl group, arylsulfinyl group, aryloxy group represented by R ^13. And the acylamino group are the same as the above-mentioned aryl substituents. R ¹³ is a hydrogen atom,
An alkyl group, an alkylthio group and an aryl group are preferable.

Specific examples of the dyes represented by the general formula (1), (2), (3) or (4) (exemplary dyes 1 to 61) are shown below. The dyes used in the present invention are as follows: It is not limited to the following example. In the specific examples, Me means methyl, Et means ethyl, and Ph means phenyl.

[0041]

[Chemical 7]

[0042]

[Chemical 8]

[0043]

[Chemical 9]

[0044]

[Chemical 10]

[0045]

[Chemical 11]

[0046]

[Chemical 12]

[0047]

[Chemical 13]

[0048]

[Chemical 14]

[0049]

[Chemical 15]

[0050]

[Chemical 16]

The dye of the present invention can be synthesized by the following method. As a typical example, a method for synthesizing Dye 2 will be described.

[0052]

[Chemical 17]

[Synthesis Example] 10 g of cyanuric chloride was dissolved in 150 ml of acetone, and 160 ml of an aqueous solution containing 13.6 g of taurine and 11.5 g of sodium carbonate under ice-cooling.
The mixture was added below ℃ and stirred at room temperature for 8 hours. Acetone 200
ml was added and the precipitated crystals were filtered to give 22 g of (a)
Got (A) 8.1 g was dissolved in 25 ml of water, and 2 g of hydrazine
Was added, the mixture was heated at 70 ° C. for 2 hours, concentrated, and the precipitated crystals were filtered to obtain 5.7 g of (b). (B) 5.7 g, pivaloyl acetonitrile 1.8 g,
A solution of 3.6 g of sodium hydrogen carbonate, 30 ml of water and 30 ml of ethanol was heated for 2 hours, 8 ml of hydrochloric acid was added, and the mixture was further heated for 2 hours. After concentration, the crystals are filtered, and 5.
7 g of (c) was obtained. (C) 3.4 g, methanol 20 ml, acetic acid 13 ml,
A mixed solution of 5.5 g of sodium acetate was cooled to 10 ° C or lower. Separately, 0.81 g of 5-amino-2,4-thiadiazole was used to prepare a diazo liquid, which was added to the mixed liquid at 10 ° C. or lower and stirred at room temperature for 2 hours. After filtering the precipitated crystals, column chromatography was performed using Sephadex to obtain 1 g of dye 2. λmax 441.9 nm (H ₂ O), ε: 2.15 × 10 ⁴ (d
m ³ / mol cm)

Other dyes can be similarly synthesized.
Table 1 shows the maximum absorption wavelength λmax of the representative dyes.

[0055]

[Table 1]

The dye of the present invention may be used as an image recording material for forming an image, especially a color image,
Specifically, the ink jet recording material described in detail below, thermal recording material, pressure sensitive recording material, recording material using electrophotographic method, transfer type silver halide photosensitive material, printing ink, recording pen, etc. Yes, an inkjet recording material, a heat-sensitive recording material, and a recording material using an electrophotographic method are preferable, and an inkjet recording material is more preferable. In addition, CCDs and other solid-state imaging devices and L
It can also be applied to color filters for recording and reproducing color images used in displays such as CDs and PDPs, and dyeing solutions for dyeing various fibers. The dye of the present invention is used by adjusting 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, or a solid dispersed state depending on the system used.

[Ink] The ink of the present invention means an ink containing at least one kind of the dye of the present invention.
The ink of the present invention may contain a medium,
When a solvent is used as the medium, it is particularly suitable as an inkjet recording ink. The ink of the present invention can be prepared by using a lipophilic medium or an aqueous medium as a medium and dissolving and / or dispersing the dye of the present invention therein. Preferably, an aqueous medium is used. The ink of the present invention also includes an ink composition excluding the medium. 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 agent, emulsion stabilizer, penetration promoter, ultraviolet absorber,
Known additives such as antiseptics, 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, acetylene glycol derivative, glycerin. , Lower alkyl ethers of polyhydric alcohols such as trimethylolpropane, ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether, etc. , 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocycles such as N-ethylmorpholine, sulfolane, dimethyl sulfoxide, 3 Sulfur-containing compounds such as sulfolane, diacetone alcohol, polyfunctional compounds such as 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. These drying inhibitors are contained in the ink in an amount of 10 to 50% by mass.
It is preferable to contain.

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, 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. Examples of the ultraviolet absorber include JP-A-58-185677 and JP-A-61-190537.
Japanese Patent Laid-Open No. 2-782 and Japanese Patent Laid-Open No. 5-97075.
And benzotriazole compounds described in JP-A-9-34057, JP-A-46-2784,
Japanese Unexamined Patent Publication No. 5-194843, U.S. Pat. No. 32,144
No. 63, etc., benzophenone compounds, JP-B-48-30492, JP-A-56-21141,
Cinnamic acid compounds described in JP-A-10-88106 and the like, JP-A-4-298503 and 8-534.
No. 27, No. 8-239368, No. 10-18.
No. 2621, Japanese Patent Publication No. 8-501291, etc., triazine compounds, Research Disclosure No. Compounds described in JP-A No. 24239, stilbene compounds and benzoxazole compounds, which fluoresce by absorbing ultraviolet rays, so-called fluorescent whitening agents 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. Hydroquinones as organic anti-fading agents,
Alkoxyphenols, dialkoxyphenols,
There are phenols, anilines, amines, indanes, chromanes, alkoxyanilines, heterocycles and the like, and metal complexes include nickel complexes and zinc complexes. More specifically, Research Disclosure No.
17643, items VII, I through J, ibid. 1516
2, the same No. 18716, page 650, left column, same No. 36
544, page 527, ibid. 307105, page 872,
Same No. The compounds described in the patent cited in 15162 and pages 127 to 13 of JP-A No. 62-215272.
The compounds included in the general formulas of the representative compounds and the compound examples described on page 7 can be used.

As the antifungal agent, sodium dehydroacetate, sodium benzoate, sodium pyridinethione-
Examples thereof include 1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. These are 0.02 to 0.02 in the ink.
It is preferable to use 1.00% by mass. Details of these are described in "Encyclopedia of Antibacterial and Antifungal Agents" (edited by the Japanese Society for Antibacterial and Antifungal Encyclopedia Editorial Committee). Examples of the rust preventive agent include acid sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and benzotriazole. These are 0.02 to 0.02 in the ink.
It is preferable to use 5.00% by mass.

The neutralizing agent (organic base, inorganic alkali) can be used as the pH adjusting agent. The pH
The adjusting agent has a pH of 6 to 10 for the purpose of improving the storage stability of the inkjet ink.
It is preferable to add it so that it becomes, and it is more preferable to add it so that it may become pH 7-10.

Examples of the surface tension adjusting agent include nonionic, cationic or anionic surfactants. still,
The surface tension of the inkjet ink of the present invention is 20 to 6
0 mN / m is preferred. Furthermore, 25 to 45 mN / m is preferable. The viscosity of the inkjet ink of the present invention is preferably 30 mPa · s or less. 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, 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-59-157,636. 308119 (198
It is also possible to use those listed as the surfactants described in (9 years).

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 compound 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.
0-80259, as described in 2000-62370, or by dispersing colored fine particles containing a dye and an oil-soluble polymer in an aqueous medium,
Japanese Patent Application No. 2000-78454, 2000-78491, 2000-203856
No. 2000-203857, 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 dye of the present invention 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 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. 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 Gorin homogenizer, a microfluidizer,
DeBEE2000 etc.) can be used. Regarding the method for preparing the above ink jet recording ink,
In addition to the above-mentioned patents, JP-A-5-148436 and 5-
295312, 7-97541, 7-8251.
5, No. 7-118584, JP-A No. 11-28663.
No. 7, Japanese Patent Application No. 2000-87539, the details are described, and it can be used for the preparation of the inkjet recording ink of the invention.

As the aqueous medium, a mixture containing water as a main component and, if desired, a water-miscible organic solvent added thereto can be used. Examples of the water-miscible organic solvent include alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec.
-Butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol),
Polyhydric 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 (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. 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, dimethylsulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, Acetone) is included. The water-miscible organic solvent may be used in combination of two or more kinds.

It is preferred that 100 parts by mass of the ink of the present invention contain 0.2 part by mass or more and 10 parts by mass or less of the compound of the present invention. In addition, the ink of the present invention may use other dyes together with the compound of the present invention. When two or more kinds of dyes are used in combination, the total content of the dye compounds is preferably within the above range.

The ink of the present invention can be used not only for monochromatic image formation but also for full color image formation. In order to form a full-color image, magenta tone ink,
A cyan tone ink and a yellow tone ink can be used, and a black tone ink may be further used to adjust the tone.

Further, the ink of the present invention can simultaneously use another yellow dye in addition to the dye of the present invention. 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); for example, a coupler component Azomethine dyes having open-chain type active methylene compounds and the like; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes; and other dyes Examples of the seed include quinophthalone dye, nitro / nitroso dye, acridine dye, acridinone dye and the like.

Any magenta dye can be used as the applicable magenta dye. For example, aryl or heterylazo 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, etc., quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, etc., condensed polycycles such as dioxazine dyes, etc. Examples thereof include dyes.

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

Each of the above-mentioned dyes may exhibit yellow, magenta, and cyan colors only after a part of the chromophore is dissociated, and the counter cation in that case is an alkali metal or an inorganic metal such as ammonium. It may be a cation, an organic cation such as a pyridinium or a 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 ink to obtain a known image receiving material such as plain paper, resin coated paper,
For example, JP-A-8-169172 and JP-A-8-2769.
No. 3, gazette No. 2-276670 gazette, and No. 7-2767.
No. 89, No. 9-323475, and Japanese Patent Laid-Open No. 62-
No. 238,83, JP-A Nos. 10-153989, 10-217473, and 10-23599.
5, gazette 10-337947, gazette 10-21.
Images are formed on inkjet-dedicated papers, films, electrophotographic common papers, cloths, glass, metals, ceramics, etc. described in Japanese Patent Nos. 7597 and 10-337947.

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,
2000-315231, 2000-354380, 2000-343944, 200
The methods described in 0-268952, 2000-299465, and 2000-297365 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 them, 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 may contain a mordant, a water-proofing 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 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 water-proofing agent is effective for making images water-proof, and as the water-proofing agent, a cationic resin is particularly desirable. As such a cationic resin, polyamide polyamine epichlorohydrin, polyethyleneimine,
Examples thereof include polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide and colloidal silica. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable. The content of these cationic resins is preferably 1 to 15% by mass based on the total solid content of the ink receiving layer, and particularly 3
It is preferably from 10 to 10% by mass.

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

The above-mentioned surfactant functions as a coating aid, a peeling property improving agent, a sliding property improving agent or an antistatic agent. For the surfactant, see JP-A-62-173463.
No. 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, JP-B-57-9053 (columns 8 to 17), JP-A-61-2
It is described in each publication of 0994 and 62-135826. Other additives added to the ink receiving layer include pigment dispersants, thickeners, defoamers, dyes, optical brighteners,
Preservatives, pH adjusters, matting agents, hardeners and the like can be mentioned. 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.

The aqueous binder contained in the back coat layer includes styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin. , 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 crack 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, a drop-on-demand system in which vibration pressure of a piezo element is used. (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 by using radiation pressure, and a bubble is formed by heating the ink and the generated pressure is used. It is used in thermal inkjet systems. 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.

[Color Toner] As the binder resin for the color toner into which the dye of the present invention is introduced, all commonly used binders can be used. For example, styrene resin, acrylic resin, styrene / acrylic resin, polyester resin, etc. may be mentioned. The compound of the present invention is contained in an amount usually used without any particular limitation.
Inorganic fine powder or 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. It is preferable that these have a number average primary particle diameter of 10 to 500 nm, and further, 0.1 to 20% by mass is added to the toner.

As the release agent, all the release agents which have been conventionally used can be used. Specific examples thereof include olefins such as low molecular weight polypropylene / low molecular weight polyethylene / ethylene-propylene copolymer, and microcrystalline wax / carnauba wax / sazol wax / paraffin wax. The addition amount of these is preferably 1 to 5% by mass in the toner.

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

As the carrier, either an uncoated carrier composed only of magnetic material particles such as iron or ferrite, or a resin coated carrier in which the surface of the magnetic material particles is coated with a resin may be used. The volume average particle diameter of the carrier is preferably 30 to 150 μm.

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

[Heat-sensitive transfer material] The heat-sensitive recording material has been transferred corresponding to the ink sheet in which the dye of the present invention is coated on the support together with the binder, and the heat energy applied from the thermal head according to the image recording signal. It consists of an image-receiving sheet that fixes the dye. The ink sheet is prepared by dissolving the compound of the present invention in a solvent together with a binder, or by dispersing the compound in a solvent in the form of fine particles to prepare an ink liquid, coating the ink on a support and appropriately drying. Can be formed. The compound of the present invention is contained in an amount usually used without any particular limitation. As the preferable binder resin, ink solvent, support and image-receiving sheet which can be used, those described in JP-A-7-137466 can be preferably used.

In order to apply the heat-sensitive recording material to a heat-sensitive recording material capable of recording a full-color image, a cyan ink sheet containing a heat-diffusible cyan dye capable of forming a cyan image and a magenta image are formed. It is preferable that a magenta ink sheet containing a heat-diffusible magenta dye and a yellow ink sheet containing a heat-diffusible yellow dye capable of forming a yellow image are successively applied on a support to form a yellow image. In addition, an ink sheet containing a black image forming substance may be further formed, if necessary.

[Color Filter] As a method for forming a color filter, a method of first forming a pattern with a photoresist and then dyeing it, or JP-A-4-1635.
52, JP-A-4-128703, and JP-A-4-175753, there is a method of forming a pattern with a photoresist containing a dye. As a method used when introducing the dye of the present invention into a color filter, any of these methods may be used, but preferred methods are described in JP-A-4-175753 and JP-A-6-35182. A positive resist composition containing a thermosetting resin, a quinonediazide compound, a cross-linking agent, a dye and a solvent, and after coating it on a substrate, exposing it through a mask to develop the exposed portion. Then, a positive type resist pattern is formed, the whole surface of the positive type resist pattern is exposed, and then the positive type resist pattern after exposure is cured to form a color filter. Further, a black matrix can be formed according to a conventional method to obtain an RGB primary color system or Y, MC complementary color system color filter.

Regarding the thermosetting resin, the quinonediazide compound, the crosslinking agent, and the solvent used in this case, and the amounts used thereof, those described in the above patent can be preferably used. The compound of the present invention is contained in an amount usually used without any particular limitation.

[0097]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

Example 1 Deionized water was added to the following ingredients to make 1 liter, and then 3
The mixture was stirred for 1 hour while heating at 0 to 40 ° C. Then K
PH was adjusted to 9 with OH 10 mol / L, average pore size
A yellow ink liquid was prepared by vacuum filtration with a 0.25 μm microfilter.

[Composition of Ink Liquid A] Yellow dye 2 of the present invention 2 8.9 g 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 (Product name, manufactured by Air Products) PROXEL XL2 1.8g (Product name, manufactured by ICI Co., Ltd.)

Ink liquid B was prepared in the same manner as ink liquid A, except that the dye was changed as shown in Table 2 below.
And C were made. At this time, the comparative dyes A and B in Table 2 were used as comparative ink liquids to prepare ink liquids 101 and 102. When the dye was changed, it was used so that the amount of the dye added was equimolar to the ink liquid A.

(Image recording and evaluation) The above examples (ink liquids A to C) and comparative examples (ink liquids 101 and 102).
The following evaluations were performed for the inkjet ink. The results are shown in Table 2. In addition, in Table 2,
For "color tone", "paper dependency", "water resistance", "light resistance" and "ozone gas resistance", each ink jet ink is filled in a cartridge, and an ink jet printer (EPS
ON Co., Ltd .; product name PM-700C with photo gloss paper (EPSON company PM photo paper <gloss> (product name KA
It is evaluated after recording an image on 420PSK, EPSON).

<Color Tone> The color tone was visually evaluated in three grades of A (best), B (good) and C (bad).
Also, the value of λmax of the reflection spectrum on PM photo paper is shown.

<Paper Dependency> Printing was performed on the photo glossy paper or the plain paper for PPC with the print density setting of the printer set to toner save. By comparing the color tones of the image formed on the photo glossy paper and the image formed separately on the PPC plain paper, the case where the difference between the two images is small is A (good), and the case where the difference between the two images is large is It was evaluated as B (poor) in two stages.

<Water resistance> The photo glossy paper on which the above image was formed was dried at room temperature for 1 hour, immersed in deionized water for 10 seconds, and naturally dried at room temperature, and bleeding was observed. The one with little bleeding was A, the one with moderate bleeding was B, and the one with many bleeding was C.

<Light resistance> Xenon light (85000 lx) was applied to the photo glossy paper on which the image was formed by using a weather meter (Atlas CI65 (trade name)).
After irradiating for a day, the image density before and after the xenon irradiation was measured using a reflection densitometer (X-Rite 310TR, manufactured by X-Rite), and the residual dye ratio [(post-irradiation density / pre-irradiation density) x 1
00%]. The reflection density was measured at three image densities of 1, 1.5 and 2.0 before irradiation. A at 1% or less of 70% or less at 70% or more, and 70% at all concentrations
The case of less than was set as C, and evaluated in three stages.

<Ozone resistance> The photo glossy paper on which the above image was formed was left in a box set in a dark place at room temperature and in a dark place with an ozone gas concentration of 0.5 ± 0.1 ppm for 7 days, before and after being left under ozone gas. Image density is measured by reflection densitometer (X-Rite3
10TR) and the residual dye rate [(concentration after irradiation / concentration before irradiation) × 100%] was evaluated. As for the reflection density, the image density before irradiation is 1, 1.5 and 2.
It was measured at three points of 0. The ozone gas concentration in the box is
Ozone gas monitor made by APPLICS (Model: OZG
-EM-01). At any concentration, the case where the residual dye ratio was 70% or more was evaluated as A, 1 or 2 points was less than 70% as B, and the case where all the concentrations were less than 70% was evaluated as C.

[0107]

[Table 2]

[0108]

[Chemical 18]

As is clear from Table 2, the ink-jet ink of the present invention was excellent in color tone, less dependent on paper, and excellent in water resistance, light resistance and ozone resistance. In particular, it is clear that the image storability such as light resistance and ozone resistance is excellent. Moreover, it was also excellent in moist heat resistance.

Example 2 The same cartridge prepared in Example 1 was used to print an image on the inkjet paper Photo Glossy Paper EX (trade name) manufactured by Fuji Photo Film Co., Ltd. by the same machine as in Example 1,
When the same evaluation as above was performed, the same results as in Example 1 were obtained.

Example 3 The same ink liquid prepared in Example 1 was filled in a cartridge of an ink jet printer BJ-F850 (trade name, manufactured by CANON), and the photo glossy paper GP of the same company was used in the same machine.
When an image was printed on -301 (trade name) and evaluated in the same manner as in Example 1, the same results as in Example 1 were obtained.

Example 4 (Preparation of Ink Liquid D) 3.75 g of Dye 9 of the present invention, 7.04 g of sodium dioctylsulfosuccinate were used, 4.22 g of the following high boiling point organic solvent (S-2), and the following high boiling point organic solvent. It was dissolved at 70 ° C. in 5.63 g of (S-11) and 50 ml of ethyl acetate. To this solution, 500 ml of deionized water was added while stirring with a magnetic stirrer to prepare an oil-in-water type coarse particle dispersion. Next, this coarse particle dispersion is mixed with a microfluidizer (MICROFLU).
The particles were made into fine particles by passing them five times at a pressure of 600 bar by IDEX INC). The resulting emulsion was desolvated with a rotary evaporator until the odor of ethyl acetate disappeared. To the fine emulsion of the hydrophobic dye thus obtained, 140 g of diethylene glycol,
Glycerin 50g, SURFYNOL465 (trade name,
Air Products & Chemicals) 7
g, and 900 ml of deionized water were added to prepare an ink liquid D.

[0113]

[Chemical 19]

(Preparation of Ink Liquid E) For Ink Liquid D, Ink Liquid E and Comparative Ink Liquid 103 were prepared in the same manner as Ink Liquid D, except that Dye 9 was changed to an equimolar dye of Table 3 below. .

(Image recording and evaluation) The following evaluations were performed on the ink liquids D and E and the comparative ink liquid 103. The results are shown in Table 2 below. In Table 3, "Color tone (λm
ax) ”,“ paper dependence ”,“ water resistance ”,“ light resistance ”, and“ ozone gas resistance ”are the same as those described in Example 1, respectively.

[0116]

[Table 3]

[0117]

[Chemical 20]

As is clear from Table 3, the ink jet ink of the present invention was excellent in color developability and color tone, had little paper dependency, and was excellent in water resistance, light resistance and ozone resistance.

Example 5 An image of the same cartridge prepared in Example 4 was printed on an inkjet paper photo glossy paper EX manufactured by Fuji Photo Film Co., Ltd. by the same machine as in Example 4, and the same evaluation as in Example 4 was carried out. The same results as in Example 4 were obtained.

Example 6 The same ink prepared in Example 4 was packed in a cartridge of an ink jet printer BJ-F850 (manufactured by CANON), and an image was printed on the photo glossy paper GP-301 of the same company by the same machine. When the same evaluation as in Example 4 was performed, the same results as in Example 4 were obtained.

Example 7 3 parts by mass of Dye 9 of the present invention, a resin for toner [styrene-
Acrylic ester copolymer; trade name Hymer TB-
1000 F (manufactured by Sanyo Kasei)] 100 parts by mass are mixed and pulverized by a ball mill, heated to 150 ° C. for melt-mixing, cooled, coarsely pulverized by a hammer mill, and then finely pulverized by an air jet fine pulverizer. did. Further classify 1
-20 micron was selected as a toner. This toner 1
Carrier iron powder (trade name: EFV250)
/ 400; made by Nippon Iron Powder) 900 parts by mass were uniformly mixed to obtain a developer. Similarly, a sample was prepared in the same manner except that the coloring agent shown in Table 4 was used in an amount of 3 parts by mass for the dye and 6 parts by mass for the pigment. Dry type plain paper electrophotographic copying machine [trade name NP-5000; Canon Co., Ltd.]
Made].

The evaluation test was carried out by using the developer using the color toner of the present invention and the paper and O by the above-mentioned image forming method.
A reflection image (image on paper) and a transmission image (OHP image) were prepared on the HP, respectively, and the following method was used. The toner adhesion amount is 0.7 ± 0.05 (mg / c
It was evaluated in the range of m ² ).

The hue and light fastness 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 4 below. In Table 4 below, ◯ indicates that the hue is the best; Δ indicates that the hue is good, and x indicates that the hue is poor. Regarding light fastness, after measuring the image density Ci immediately after recording, after irradiating the image with xenon light (85,000 lux) for 5 days using a weather meter (Atlas C.165),
The image density Cf was measured again, and the dye residual ratio ({(Ci-Cf) / Ci} ×) was calculated from the difference in image density before and after the irradiation with xenon light.
100%) was calculated and evaluated. The image density was measured using a reflection densitometer (X-Rite 310TR). The evaluation results are shown in Table 4 below. In Table 4 below, the residual dye ratio is 90%
The above cases are shown as ◯, 90 to 80% as Δ, and less than 80% as x.

The transparency of the OHP image was evaluated by the following method. "330 type self-recording spectrophotometer" made by Hitachi Ltd.
The visible spectral transmittance of the image was measured by using the OHP sheet on which the toner is not carried by (product name) as a reference, and the spectral transmittance at 650 nm was determined and used as a measure of the transparency of the OHP image. Spectral transmittance of 80% or more is ◯, 70
-80% was designated as Δ and 70% or less was designated as x. The above results are shown in Table 4.

[0125]

[Table 4]

As is apparent from Table 4, since the color toner of the present invention exhibits faithful color reproduction and high OHP quality, the color toner of the present invention is suitable for use as a full color toner. Further, since it has good light resistance, it is possible to provide an image that can be stored for a long period of time.

Example 8 <Preparation of thermal transfer dye-donating material> A polyethylene terephthalate film (manufactured by Teijin) having a thickness of 6 μm and having a heat-resistant lubrication treatment on the back side was used as a support, and the following composition was formed on the surface of the film. The coating composition for a thermal transfer dye-donating layer was applied and formed by wire bar coating so that the thickness when dried was 1.5 μm, to prepare a thermal transfer dye-donating material (5-1) as an ink sheet. Coating composition for thermal transfer dye-donating layer: Dye 21 10 mmol Polyvinyl butyral resin 3 g (Denka Butyral 5000-A (trade name) manufactured by Denki Kagaku) Toluene 40 ml Methyl ethyl ketone 40 ml Polyisocyanate (Takenate D110N (trade name) manufactured by Takeda Pharmaceutical Co., Ltd.) 0.2 ml Then, in the same manner as described above except that the dye 21 was changed to the other dyes shown in Table 5, the thermal transfer dye-donating material of the present invention and the comparative thermal transfer dye-donating materials (5-2) and (5-3 ) Were created respectively.

(Preparation of Thermal Transfer Image Receiving Material) As a support, a synthetic paper having a thickness of 150 μm (YUPO-FPG-manufactured by Oji Yuka)
150) was used to apply the following composition to the surface by wire bar coating so that the thickness when dried was 8 μm, to prepare a thermal transfer image-receiving material. Drying was performed for 30 minutes in an oven at a temperature of 100 ° C. after temporary drying with a dryer. Coating composition for image receiving layer: Polyester resin (Vylon-280 (trade name) manufactured by Toyobo) 22 g Polyisocyanate (KP-90 (trade name) manufactured by Dainippon Ink and Chemicals) 4 g Amino-modified silicone oil (KF-857 (manufactured by Shin-Etsu Silicone) Product name)) 0.5g Methyl ethyl ketone 85ml Toluene 85ml Cyclohexanone 15ml

The thermal transfer dye-donating materials (5-1) to (5-3) obtained as described above and the thermal transfer image-receiving material are superposed so that the thermal transfer dye-donating layer and the image-receiving layer are in contact with each other, and thermal transfer is carried out. A thermal head is used from the support side of the dye-donor element, and the output of the thermal head is 0.25 W / dot.
Pulse width 0.15 to 15 ms, dot density 6 dots /
Printing was performed under the condition of mm, and a yellow dye was imagewise dyed on the image receiving layer of the image receiving material. Table 5 shows the maximum color densities of the obtained images. Thermal transfer dye-donor element of the present invention (5-
In 1) and (5-2), clear image recording without uneven transfer was obtained. Next, each of the recorded thermal transfer image-receiving materials obtained as described above was irradiated with Xe light (17,000 lux) for 5 days, and the light stability of the color image was examined. The status A reflection density after irradiation of the portion showing the status A reflection density of 1.0 was measured, and its stability was evaluated by the residual rate (percentage) with respect to the reflection density of 1.0 before irradiation. The results are shown in Table 5.

[0130]

[Table 5]

[0131]

[Chemical 21]

As described above, the dye of the present invention was excellent in light fastness as compared with the dye for comparison. The hue was also fresh.

Example 9 A method for manufacturing a color filter was carried out by using a silicon wafer, a thermosetting resin, a quinonediazide compound, a crosslinking agent,
A positive resist composition containing a dye and a solvent was spin-coated, the solvent was evaporated by heating, and then exposure was performed through a mask to decompose the quinonediazide compound. If necessary, after heating, development was carried out to obtain a mosaic pattern. Exposure is made by Hitachi, Ltd. i-line exposure stepper HITACHI LD
-5010-i (NA = 0.40) (trade name). As the developer, SOPD or SOPD-B (both are trade names) manufactured by Sumitomo Chemical Co., Ltd. was used. <Preparation of positive resist composition> m-cresol / p-
Cresol / formaldehyde (reaction molar ratio = 5/5 /
7.5) 3.4 parts by mass of cresol novolak resin (polystyrene-equivalent mass average molecular weight 4300) obtained from the mixture,
The following formula

[0134]

[Chemical formula 22]

O-naphthoquinonediazide-5-sulfonic acid ester prepared by using the phenol compound represented by the formula (on average, two hydroxyl groups are esterified) 1.8
Parts by mass, 0.8 parts by mass of hexamethoxymethylolated melamine, 20 parts by mass of ethyl lactate and the pigment 1 of the present invention shown in Table 6.
A positive resist composition was obtained by mixing parts by mass. <Preparation of Color Filter> A silicon wafer was spin-coated with the obtained positive resist composition, and then the solvent was evaporated. After exposing the silicon wafer, heat it at 100 ° C and remove the exposed area by alkali development to remove 0.8 μm.
A positive colored pattern having a resolution of m was obtained. After exposing the whole surface, it was heated at 150 ° C. for 15 minutes to obtain a yellow complementary color filter. Comparative Example Instead of the yellow dye of the present invention used in the above examples, Sumitomo Chemical Co., Ltd.'s Oreosol Yellow 2 was used.
1 part by mass of G (trade name) was mixed to obtain a positive resist composition. A silicon wafer was spin-coated with this positive resist composition, and then the solvent was evaporated. After exposing the silicon wafer, it was alkali-developed to obtain a positive type colored pattern having a resolution of 1 μm. After exposing this all over,
A yellow color filter was obtained by heating at 150 ° C for 10 minutes. <Evaluation> The transmission spectrum of the obtained yellow color filter was measured, and the short-wave side of the spectrum important for color reproduction,
Relative evaluation of the break on the long wave side. ◯ means good, Δ means acceptable level, and x means unacceptable level. For light fastness, use a weather meter (Atlas C.I65) to measure xenon light (85000 l).
x) is irradiated for 7 days, the image density before and after xenon irradiation is measured, and the residual dye ratio [(density after irradiation / density before irradiation) × 10
0%].

[0136]

[Table 6]

It can be seen that the dye of the present invention has sharp cuts on the short-wave side and the long-wave side of the spectrum as compared with the comparative example, and is excellent in color reproducibility. Further, it was found that the light fastness was superior to that of the comparative compound.

[0138]

EFFECTS OF THE INVENTION According to the present invention, 1) As a dye of three primary colors, it has excellent absorption characteristics with excellent color reproducibility, and has sufficient fastness to light, heat, humidity and active gas in the environment. Inks for printing such as inkjet, ink sheets for thermal recording materials, color toners for electrophotography, LCDs, PDPs, etc. that provide new dyes and 2) provide colored images and coloring materials with excellent hue and fastness. Display and CCD
We provide various coloring compositions such as color filters used in imaging devices such as, dyeing solutions for dyeing various fibers,
3) In particular, the present invention provides an ink jet recording ink and an ink jet recording method which have a good hue by using the dye and can form an image having high fastness to an active gas in the light and the environment, particularly an ozone gas. can do.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07D 413/14 C07D 417/14 417/14 C09B 29/48 C09B 29/48 B41J 3/04 101Y (72) Inventor Manabu Ogawa 200 Onakasato, Fujinomiya-shi, Shizuoka Fuji Photo Film Co., Ltd. F-term (reference) 2C056 EA13 FC02 FC06 2H086 BA15 BA33 BA55 4C063 AA01 AA03 BB02 BB09 CC29 CC43 CC52 CC67 DD22 EE10 4J039 BC40 BC51 BC72 BC54 BC54 BC53 BC77 BE02 BE12 CA03 EA17 EA35 EA37 EA38 GA24

Claims (3)

[Claims] 1. An ink comprising at least one kind of dye represented by the following general formula (1). [Chemical 1] (In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent group, and ^one of R ¹ , R ² and R ³ has a heterocyclic group substituted with an azo group. Represents a substituent, and Z represents a nitrogen atom, or a hydrogen atom or a carbon atom to which a monovalent group is bonded.) 2. An ink jet recording method, wherein an image is formed using the ink according to claim 1 on an image receiving material having an ink receiving layer containing white inorganic pigment particles on a support. 3. A compound represented by the following general formula (3). [Chemical 2] (In the formula, R ¹⁰ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group or an aryl group, and R ¹¹ and R ¹² are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group. , An amino group, a sulfo group, and a heterocyclic group, Het represents an aromatic heterocyclic group, and each substituent may further have a substituent.)