JP2000355660A - Tetraalkyl-substituted nitrogen-containing heterocycle- bonded type azo colorant, ink for ink jet using same, ink jet recording method, and thermal transfer recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable an image having an excellent hue and a high fastness to light, heat, air, water, chemicals, etc., to be formed in ink jet recording by using an azo colorant having a specified chemical structure. SOLUTION: This colorant is represented by formula I (wherein Z is a group of atoms necessary for forming, together with the N atom, a 5- to 7-membered ring; R1 is H, an oxy radical, or an aliphatic, aliphatic oxy, acyl, aliphatic oxycarbonyl, aryloxycarbonyl, or acyloxy group; R2, R3, R4, and R5 are each alkyl provided R2 may combine with R3 to form a ring and so may R4 with R5; and Dye is a colorant group necessary for forming an azo colorant. Preferably, the azo colorant represented by formula I is a compound represented by formula II (wherein R1 and Dye are each the same as in formula I). By using an azo colorant represented by formula I, a thermal transfer colorant- donative material having a high stability to light, heat, air, chemicals, etc., can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel tetraalkyl-substituted nitrogen-containing heterocycle (preferably a 2,2,6,6-tetramethylpiperidine ring) having high robustness to light, heat, air, chemicals and the like. Type dye. In addition, the present invention relates to an inkjet recording method, particularly to an inkjet ink for forming an image having an excellent hue and having high robustness against light, heat, air, water, chemicals, and the like, and an inkjet recording method using the same. It is. Further, the present invention relates to a thermal transfer recording material for performing image recording by heating corresponding to image information.

[0002]

2. Description of the Related Art Dyes used in ink-jet inks have high solubility in solvents, high density recording is possible, good hue, light, heat, air,
Excellent fastness to water, chemicals, etc., good fixability to image receiving materials, low bleeding, excellent storage stability as ink, no toxicity, high purity, low cost It is necessary to have requirements such as availability. However, it is extremely difficult to select a dye that meets these requirements at a high level. In particular, a dye excellent in light fastness is strongly desired.

[0003] From such a viewpoint, various ink jet dyes and pigments have been proposed and studied, but none of them satisfy all the required performances at present. For example,
Known C.I. I. It is difficult to achieve both hue and fastness by using numbered dyes and pigments.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an azo dye having excellent spectral characteristics and high fastness to light, heat, air, chemicals and the like. Another object of the present invention is to provide an inkjet ink and an inkjet recording method suitable for forming a highly robust image. Another object of the present invention is to provide a thermal transfer dye-providing material containing an azo dye having high stability to light, heat, air, chemicals and the like.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found an azo dye represented by the following general formula (I) and have achieved the above objects effectively, And found that the disadvantages of the prior art can be improved. That is, the above object of the present invention is achieved by the following inventions (1) to (5).

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

[0007]

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In the formula, Z forms a 5- to 7-membered ring together with an N atom.
Represents the group of atoms required to form R₁Is a hydrogen atom, oxy
Radical group, aliphatic group, aliphatic oxy group, acyl group, fat
Aliphatic oxycarbonyl group, aryloxycarbonyl
Represents an acyloxy group. R _Two , R_Three , R_Four And R
_Five Each represents an alkyl group;_Two And R_Three , R_Four And R_Five But
Each may form a ring. Dye forms azo dyes
Represents a necessary dye group. (2) The azo dye represented by the general formula (I) has the following general formula
The azo according to (1), which is represented by the formula (Ia)
Pigment.

[0009]

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In the formula, R ₁ represents a hydrogen atom, an oxy radical group, an aliphatic group, an aliphatic oxy group, an acyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, or an acyloxy group. Dye represents a dye group necessary for forming an azo dye. (3) An inkjet ink comprising the azo dye represented by the general formula (I). The case where the azo dye represented by the general formula (I) is represented by the general formula (Ia) is preferable. (4) In an ink jet recording method for recording an image on an image receiving material by ejecting ink in a droplet form, the ink comprises:
An ink jet recording method comprising the ink according to (3). (5) A thermal transfer recording material comprising a thermal transfer dye-providing material and a thermal transfer image-receiving material, wherein at least one of the dyes used is an azo dye represented by the general formula (I) described in (1). Thermal transfer recording material. General formula (I)
The case where the azo dye represented by the general formula (Ia) is represented by the formula (Ia) is preferable.

[0011]

When a group in the present specification contains an aliphatic moiety, the aliphatic moiety may be linear, branched or cyclic and saturated or unsaturated. Represents alkyl, alkenyl, cycloalkyl, or cycloalkenyl, which may be unsubstituted or have a substituent. When an aryl moiety is included, the aryl moiety may be a single ring or a condensed ring, and may be unsubstituted or have a substituent. When a heterocyclic moiety is included, the heterocyclic moiety has a hetero atom (for example, a nitrogen atom, a sulfur atom, or an oxygen atom) in the ring. May be a single ring or a condensed ring,
It may be unsubstituted or have a substituent. The substituent in the present invention may be any group that can be substituted, such as an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aryloxy group, and a heterocyclic oxy group. Group, aliphatic oxycarbonyl group,
Aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, arylsulfonyloxy group, heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic Sulfonamide group, arylsulfonamide group, heterocyclic sulfonamide group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group, fat Aromatic sulfinyl group, aryl sulfinyl group,
Aliphatic thio group, arylthio group, hydroxy group, cyano group, sulfo group, carboxyl group, aliphatic oxyamino group, aryloxyamino group, carbamoylamino group,
Examples thereof include a sulfamoylamino group, a halogen atom, a sulfamoylcarbamoyl group, a carbamoylsulfamoyl group, a dialiphatic oxyphosphinyl group, and a diaryloxyphosphinyl group.

In the formula (I), Z represents an atom group necessary for forming a 5- to 7-membered ring together with an N atom,
This is the case where a six-membered ring is formed, and more preferably the case where a six-membered ring is formed. Examples of the 5- to 7-membered ring include a piperidine ring and a pyrrolidine ring. These rings are R ₂
May have to R ₅ other than substituent include those similar to the substituents described as "substituent in the invention" above as substituent. Preferably it is a piperidine ring. R ₁ is preferably an alkyl group having 10 or less carbon atoms which may have a substituent as a hydrogen atom, an oxyradical group, or an aliphatic group, for example, a methyl group, an ethyl group,
-An alkenyl group having 10 or less carbon atoms which may have a substituent such as a methanesulfonamidoethyl group, for example, an allyl group, a vinyl group or the like, which may preferably have a substituent as an aliphatic oxy group. A C 1 or less alkoxy group which may have a substituent such as a methoxy group, an ethoxy group or a 2-methoxyethoxy group;
An alkenyloxy group of 0 or less, for example, an allyloxy group or the like, preferably an alkylcarbonyl group having 10 or less carbon atoms which may have a substituent as an acyl group, for example, an acetyl group, a propionyl group or the like; An alkenylcarbonyl group having 10 or less carbon atoms which may have a substituent such as an acryloyl group and a methacryloyl group; and an arylcarbonyl group having 10 or less carbon atoms which may have a substituent such as a benzoyl group and a fatty acid. As the aromatic oxycarbonyl group, an alkoxycarbonyl group having 10 or less carbon atoms which may have a substituent, for example, a methoxycarbonyl group, an ethoxycarbonyl group, etc., may have 10 or less carbon atoms which may have a substituent. Alkenyloxycarbonyl group such as aryloxycarbonyl group, aryl The oxycarbonyl group is preferably an aryloxycarbonyl group having 12 or less carbon atoms which may have a substituent, such as a phenoxycarbonyl group or an acyloxy group preferably having 10 or less carbon atoms which may have a substituent. And an arylcarbonyloxy group having 12 or less carbon atoms which may have a substituent, for example, an acetoxy group, a propanoyloxy group, etc., and represents, for example, a benzoyloxy group. From the viewpoint of the effects of the present invention, R ₁ is preferably a hydrogen atom, an oxy radical group, an aliphatic group, an aliphatic oxy group, more preferably a hydrogen atom, an oxy radical group, and more preferably an oxy radical group. The case is most preferable. R _{2 to} R ₅ each represent an alkyl group (1 to 20, preferably 1 to 8, more preferably 1 to 3, for example, methyl group, ethyl group, n-propyl group) which may be the same or different. Represent. R ₂ and R ₃ , and R ₄ and R ₅ may each form a ring (preferably a 5- to 7-membered ring, such as cyclohexyl). Dye represents a dye moiety necessary for forming an azo dye. The azo dye represented by the general formula (I) is preferably a compound represented by the general formula (Ia). (Ia) wherein, R ₁ and Dye has the same meaning as R ₁ and Dye in formula (I), and preferred ranges are also the same. Dye is preferably an azo dye represented by the following general formula (II).

[0013]

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In the formula, A and B each represent a substitutable aromatic group or a heterocyclic group. More specifically, A is preferably an aryl group such as phenyl, phenol and naphthol, and a heterocyclic group such as pyrazole, isothiazole, thiazole, pyrazolotriazole and pyrrolotriazole, and more preferably a phenol derivative (preferably Formula (A-1)), naphthol derivative (preferably the following general formula (A-2)), aniline derivative (preferably the following general formula (A-3)), pyrazole derivative (preferably the following general formula (A
-4)), a pyrazolotriazole derivative (preferably the following general formula (A-5)) and a pyrrolotriazole derivative (preferably the following general formula (A-6)), more preferably a phenol derivative (preferably The following general formula (A-1)), an aniline derivative (preferably the following general formula (A-3)), a pyrazole derivative (preferably the following general formula (A-4)), a pyrazolotriazole derivative (preferably the following general formula (A-5)), most preferably a phenol derivative (preferably the following general formula (A-1)). The preferred general formula structure is shown below.

[0015]

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In the general formulas (A-1) to (A-6), R
_a1~ R_a13 , R_a15 ~ R_a21 , R_{a2 Three} ~ R_a25 Is hydrogen field
Represents a child or a substituent. R_a1, R_a2Is an acylamino group
(Preferably, it has 2 to 20 carbon atoms which may have a substituent.
Acylamino group, for example, acetylamino
Group, propionylamino group, benzoylamino group, 3-
(N-4- (1-oxy radical-2,2,6,6-te
Tramethylpiperidylcarbamoyl) propionylami
Group), an alkyl group (preferably having a substituent)
Alkyl groups having 1 to 8 carbon atoms, such as methyl
Group, pivaloyl group), halogen atom (for example,
Element, chlorine), aliphatic oxycarbonylamino group (preferred)
Or an alcohol having 2 to 10 carbon atoms which may have a substituent.
A xycarbonylamino group such as methoxyca
Rubonylamino group and butoxycarbonylamino group) are preferred.
More preferably, R _a1Is an acylamino group,
More preferred R_a2Is an acylamino group (with additional substituents)
May be linked to a tetraalkyl-substituted nitrogen-containing heterocyclic group.
May be tied). R_a3, R_a4Is preferably a hydrogen atom
No.

B will be described in detail. B is preferably an aryl group such as phenyl and naphthyl, and a heteryl group such as pyrazolyl, isothiazolyl, thiazolyl, thiadiazolyl, benzoisothiazolyl, and heterocyclic fused isothiazolyl, more preferably a pyrazolyl derivative (preferably the following general formula (B -1)), an isothiazolyl derivative (preferably the following general formula (B-2)), a thiadiazolyl derivative (preferably the following general formula (B-3)), and a benzoisothiazolyl derivative (preferably the following general formula (B-4) )), And more preferably an isothiazolyl derivative (preferably the following general formula (B-
2)), a thiadiazolyl derivative (preferably the following general formula:
(B-3)), a benzoisothiazolyl derivative (preferably the following general formula (B-4)), particularly preferably a thiadiazolyl derivative (preferably the following general formula (B-3)), It is a derivative (preferably the following general formula (B-4)), and most preferably a benzoisothiazolyl derivative (preferably the following general formula (B-4)). The preferred general formula structure is shown below.

[0018]

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In the general formulas (B-1) to (B-4), R
_b1~ R_b10 Represents a hydrogen atom or a substituent. R_b6Is ant
-Yl group (preferably having 6 carbon atoms which may have a substituent
And 20 aryl groups, for example, a phenyl group, 3
-Methanesulfonylphenyl group),
A 2,2,6,6-tetramethylpiperidine group
They may be connected. R_b9Is an aliphatic sulfonyl group (preferably
Or an alkyl having 1 to 8 carbon atoms which may have a substituent.
A sulfonyl group, for example, methylsulfonyl
Group), a sulfo group, a sulfamoyl group (N-unsubstituted
, Mono-substituted or di-substituted,
Preferably, N-4- (1-oxyradical-2,2,
6,6-tetramethylpiperidyl) -substitution) is preferred.
R_b7, R_b8, R_b10 Is preferably a hydrogen atom. Effect of the present invention
In terms of the result, the general formula (II) is the same as the general formula (A-1) and the general formula (B
-1) to Heterylazopheno composed of general formula (B-4)
Is preferred, and isothiazolylazof
Enol dye, thiadiazolyl azophenol color
Is a benzoisothiazolylazophenol dye
Is preferred, and thiadiazolylazophenol-based colors
Is a benzoisothiazolylazophenol dye
The case is most preferable. Tetraal in the general formula (I)
A killed nitrogen-containing heterocyclic ring (the compound represented by the general formula (Ia),
2,6,6-tetramethylpiperidine ring) and azo dye
The bond may be located at any possible position, and may be represented by the general formula (II)
A or B represented by Preferred place
Replacement position is R_a1, R_a2, R_a5, R_a7, R_a11 , R
_a12 , R _a16 , R_a17 , R_a19 , R_a21 , R_a24 Etc.
Or R_b3, R_b5, R_b6, R_b8, R _b9, R_b10 And so on.
In this case, the bond is merely a bond or a divalent linking group.
As long as it is a bondable group, for example, a divalent aliphatic
Group, divalent aryl group, carbonyl group, carbonyl group
Si group, N-substituted amide group, oxy group, N-substituted carbamoyl
Group, oxycarbonyl group, sulfonyloxy group, N-substitution
Sulfonamide group, N-substituted amino group, oxycarbonyl
And an amino group. A preferred bond is tet
Laalkyl-substituted nitrogen-containing heterocyclic group substituted with nitrogen atom
Sulfonamide group, tetraalkyl-substituted nitrogen-containing heterocycle
Acylamino group in which the group is substituted with a nitrogen atom, tetraalkyl
Carbonyl substituted with an oxygen atom
And particularly preferably a tetraalkyl group.
A sulfone in which a substituted nitrogen-containing heterocyclic group is substituted with a nitrogen atom
When the mid group or tetraalkyl-substituted nitrogen-containing heterocyclic group is a nitrogen atom
It is an acylamino group substituted by a child. Tet in these cases
Laalkyl-substituted nitrogen-containing heterocyclic group is 2,2,6,6-tetrame
More preferably, it is a tyl piperidyl group.

Preferred specific examples of the dye represented by formula (I) of the present invention are shown below, but the dye of the present invention is not limited thereto. When the dye represented by the general formula (I) is used as a water-soluble dye, it is preferable that Dye has an ionic hydrophilic group. Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, and a quaternary ammonium group. In particular, it preferably has one or more sulfo groups. When the dye represented by the general formula (I) is used as an oil-soluble dye, a dye having no sulfo group is preferable.

[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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The azo dye represented by the general formula (I) is prepared by adding the nitrogen-containing heterocyclic derivative (preferably a 2,2,6,6-tetramethylpiperidine derivative) to the A or B site of the general formula (II) in advance. ), An azo coupling reaction, and a synthesis method. After synthesizing the azo dye, a nitrogen-containing heterocyclic derivative (preferably 2,2,6,6-tetramethylpiperidine is provided with an appropriate functional group. Derivatives)
Either one may be synthesized, but the latter is more convenient and preferred. A specific synthesis method will be described in Examples described later.

The ink-jet recording method includes a method using an oil-based ink, a method using an aqueous ink, a method using a solid ink at room temperature, and the like. Is also applicable. Hereinafter, the solvent used in the ink of the present invention and its use will be described.

The liquid medium of the oil-based ink of the present invention is used by appropriately selecting it from an ordinary organic solvent as needed. Specifically, for example, ethanol, pentanol,
Alcohols such as heptanol, octanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, phenylpropyl alcohol, furfuryl alcohol, anis alcohol, ethylene glycol monoethyl ether, ethylene glycol monophenyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Butyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol diacetate, ethylene glycol monoethyl ether acetate, propylene glycol Diacetate, etc. Recall derivatives, benzyl methyl ketone and diacetone alcohol, cyclohexanone, butyl phenyl ether, benzyl ethyl ether, ethers such as hexyl ether, ethyl acetate, amyl acetate, benzyl acetate, phenyl ethyl acetate,
Phenoxyethyl acetate, ethyl phenylacetate, benzyl propionate, ethyl benzoate, butyl benzoate, ethyl laurate, butyl laurate, isopropyl myristate, isopropyl palmitate, triethyl phosphate, tributyl phosphate, diethyl phthalate, phthalic acid Dibutyl, diethyl malonate, dipropyl malonate, diethyl diethyl malonate, diethyl succinate, dibutyl succinate, diethyl glutarate, diethyl adipate, dibutyl adipate, di (2-methoxyethyl) adipate, diethyl sebacate, maleate Esters such as diethyl phosphate, dibutyl maleate, dioctyl maleate, diethyl fumarate, dioctyl fumarate, 3-hexenyl cinnamate, petroleum ether, petroleum benzyl, tetralin, delican, 1-A Hydrocarbon solvents such as benzene, dimethylnaphthalene, acetonitrile, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, sulfolane, propylene carbonate, N-methyl-2-pyrrolidone, N-vinyl-2 Polar solvents such as -pyrrolidone, N, N-diethyldodecaneamide. These solvents may be used alone or as a mixture of two or more.

The dye of the present invention may be used by dissolving it in the above organic solvent, or may be used by dispersing it with an appropriate dispersant. For the specific method of adjusting the oil-based ink used for such an ink-jet ink, the methods described in JP-A-3-231975 and JP-T-5-508883 can be referred to.

The liquid medium of the aqueous ink of the present invention is used by appropriately selecting it from water and a water-soluble organic solvent as needed. Specifically, for example, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol Glycol,
Polyhydric alcohols such as polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, 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, tri Chi glycol monomethyl ether, triethylene glycol monoethyl ether, glycol derivatives such as ethylene glycol monophenyl ether, ethanolamine, diethanolamine, triethanolamine, N- methyldiethanolamine, N- ethyldiethanolamine, morpholine, N
Amines such as ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine, 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,
Examples include polar solvents such as acetone. Two or more of these solvents may be used together with water.

The dye of the present invention may be used by dissolving the dye of the present invention in a mixed solvent of water and the above-mentioned water-soluble organic solvent. If the dye is insoluble as it is, various dispersing machines (for example,
Ball mill, sand mill, attritor, roll mill,
Fine particles may be formed using an agitator mill, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, jet mill, ang mill, or the like, or dispersed using an appropriate dispersant or surfactant after dissolving the dye in an organic solvent. Can be used. Specific methods for adjusting the aqueous ink used for such an ink-jet ink are described in JP-A-5-148436 and 5-29.
No. 5312, No. 7-97541, No. 7-82515
And the methods described in JP-A No. 7-118584 can be referred to.

The liquid medium of the solid ink of the present invention uses a phase-change solvent which is solid at room temperature and is molten when the ink is heated and jetted. Specifically, for example,
Beeswax, carnauba wax, rice wax, wood wax, jojoba oil, whale wax, candelilla wax, lanolin, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, natural wax such as petrolatum, polyethylene wax,
Chlorinated hydrocarbons, organic acids such as palmitic acid, stearyl acid, behenic acid, tiglic acid, 2-acetonaphthobehenic acid, 12-hydroxystearic acid, dihydroxystearic acid, dodecanol, tetradecanol, hexadecanol, eicosanol, Docosanol, tetracosanol, hexacosanol, octacosanol, dodecenol, myricyl alcohol, tetracenol, hexadecenol, eicosenol, docosenol, pinene glycol, hinokiol, butynediol, nonanediol, isophthalyl alcohol, mesicerin, hexanediol, decanediol, Tetradecanediol, hexadecanediol, docosandiol, tetracosandiol, tvneol, phenylglycerin, eicosandiol, Kutanjioru, alcohols such as phenyl propylene glycol, bisphenol A,
Phenols such as p-α cumylphenol, glycerin of the above-mentioned organic acids, organic acid esters such as ethylene glycol and diethylene glycol, cholesterol stearate, cholesterol palmitate, cholesterol myristate, cholesterol behenate, cholesterol laurate, melysin Cholesterol fatty acid esters such as acid cholesterol, saccharose stearate,
Saccharose palmitate, saccharose behenate, saccharose laurate, saccharose melissate, lactose stearate, lactose palmitate, lactose behenate, lactose laurate, lactose melinate, etc., benzoylacetone, diacetbenzene, benzophenone, Ketones such as tricosanone, heptacosanone, heptatriacontanone, hentriacontanone, stearone, lauron, oleic amide, lauric amide, stearic amide, ricinoleic amide, palmitic amide;
Tetrahydrofuranamide, erucamide, myristic amide, 12-hydroxystearic acid amide,
N-stearyl erucamide, N-oleyl stearamide, N, N-ethylenebislauric amide,
N, N-ethylenebisstearic acid amide, N, N-ethylenebisbehenic acid amide, N, N-xylylenebisstearic acid amide, N, N-butylenebisstearic acid amide, N, N-dioleyladipamide , N, N
Amides such as dioleyl sebacamide, N, N-distearyl sebacamide, N, N-distearyl terephthalamide, phenacetin, toluamide, acetamide, p-toluenesulfonamide, ethylbenzenesulfonamide, butylbenzenesulfone And sulfonamides such as amides.

The phase change temperature of the solid solvent is from 60 to 200 ° C., more preferably from 80 to 150 ° C. The dye of the present invention may be used by dissolving the dye of the present invention in the above-mentioned solid solvent in a molten state by heating, or may be used by dispersing or dissolving it together with an appropriate dispersant or binder. For a specific method of adjusting such an ink for ink jet, see JP-A-5-18 / 1990.
6723 and 7-70490 can be referred to. The dye of the present invention is preferably contained in an amount of 0.2 to 10 parts by weight per 100 parts by weight of the ink.
The case of 5 to 6 parts by weight is more preferable. A dye other than the dye of the present invention may be appropriately added to the ink used in the present invention as desired. Various additives may be appropriately added to the ink of the present invention as desired. Such additives include viscosity adjusters, surface tension adjusters, specific resistance adjusters, film adjusters, ultraviolet absorbers, antioxidants, anti-fading agents, fungicides, rust inhibitors, dispersants, interfaces Activators and the like. The viscosity of the ink of the present invention is preferably adjusted to 40 cp or less in the case of an aqueous ink or an oil-based ink. The surface tension of the ink of the present invention is preferably adjusted to 20 dyn / cm to 100 dyn / cm in the case of an aqueous ink or an oil-based ink.

To form a full color image, the magenta tone inks of the present invention can be used with cyan and yellow tone inks. Further, it can be used together with a black color ink to adjust the color tone. In the ink jet recording method of the present invention, the recording paper used is not particularly limited. However, it is desirable to use coated paper from the viewpoint of image quality and image storage durability. Hereinafter, desirable modes of the recording paper will be described.

In the ink jet recording method of the present invention, it is desirable to use a recording paper containing a polymer mordant. Examples of polymer mordants include JP-A-48-28325.
No. 54-74430, No. 54-124726, No. 55-22766, No. 5
5-142339, 55-23850, 60-23851, 60-23852
No. 60-23853, No. 60-57836, No. 60-60643, No. 60
-118834 , 60-122940, 60-122941, 60-1229
No. 42, No. 60-235134, JP-A-1-161236,
U.S. Pat.Nos. 2,484,430, 2,548,564, 3,148,061
Nos. 3,309,690, 4,115,124, 4,124,386
Nos. 4,193,800, 4,273,853, 4,282,305
No. 4,450,224, etc. In particular, it is desirable to use a recording paper containing a polymer mordant described in JP-A-1-161236, pp. 212-215.
This polymer mordant provides excellent image quality and improves light fastness.

In the ink jet recording method of the present invention, a recording paper containing an inorganic pigment can be used.
The type of the inorganic pigment is not particularly limited, and any inorganic pigment can be used. For example, silica pigment, alumina pigment, titanium dioxide pigment, zinc oxide pigment,
Zirconium oxide pigment, mica-like iron oxide, lead white, lead oxide pigment, cobalt oxide pigment, strontium chromate, molybdenum-based pigment, smectite, magnesium oxide pigment, calcium oxide pigment, calcium carbonate pigment, mullite, etc. Alternatively, two or more kinds can be used. In the ink jet recording method of the present invention, recording paper containing various hydrophilic binders can be used. As the hydrophilic binder, any compound including gelatin or a derivative thereof, polyvinyl alcohol or a derivative thereof, polyalkylene oxide or a derivative thereof, and other superabsorbent polymers can be used. As examples thereof, those described in JP-A-1-161236, pages 215 to 222, can be used. In the image forming method of the present invention, it is desirable to use a recording paper containing a matting agent. As the matting agent, a conventionally known matting agent can be used, and as an example, JP-A-1-161236
Those described on pages 63 to 264 can be used.

In the ink jet recording method of the present invention, recording paper hardened with a hardener can be used. There are no particular restrictions on the type of hardener, and known hardeners, for example, those described on page 222 of JP-A-1-161236 can be used. In the image forming method of the present invention, recording paper hardened with a hardener can be used. There are no particular restrictions on the type of hardener, and known hardeners, for example, those described on page 222 of JP-A-1-161236 can be used. In the constituent layers of the recording medium used in the image forming method of the present invention, various surfactants can be used for the purpose of coating aid, improving releasability, improving slipperiness, and preventing static charge. Specific examples of the surfactant are described in JP-A-62-173463 and JP-A-62-1.
No. 83457 and the like. Further, an organic fluoro compound may be included for the above purpose. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8-17, and JP-A-61-20994 and 62-13.
No. 5,826, a fluorine-based surfactant,
Or hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as ethylene tetrafluoride resin.

The constituent layers (including the back layer) of the recording medium can contain various polymer latexes for the purpose of improving film physical properties such as dimensional stability, curl prevention, adhesion prevention and film crack prevention. . Specifically, Japanese Patent Application Laid-Open No. Sho 62
-245258, 62-136648, 62
Any of the polymer latexes described in JP-A-110066 can be used. In particular, when a polymer latex having a low glass point transition (40 ° C. or less) is used for the mordant layer, the mordant layer can be prevented from cracking and curl can be improved, and if a polymer latex having a high glass transition point is used for the back layer, An anti-curl effect is obtained.

In the ink jet recording method of the present invention, an anti-fading agent may be used in the constituent layers of the recording paper used. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes. As an example,
JP-A-1-161236, pages 225 to 247, can be used. A fluorescent whitening agent may be used for the recording medium. In particular, it is preferable that a fluorescent whitening agent is incorporated in the recording medium, or it is contained in ink or the like and supplied from outside to the recording medium. In the present invention, the support of the recording medium is not particularly limited, but is laminated on both sides with a polyolefin (for example, a homopolymer such as polyethylene, polystyrene, polyethylene terephthalate, or polybutene, or a copolymer of any combination thereof). A paper or plastic support (however, a white pigment such as titanium oxide and zinc oxide, and a coloring dye such as cobalt blue, ultramarine blue and neodymium oxide are preferably contained in the polyolefin) is also preferably used. The ink jet recording method of the present invention is not particularly limited in the recording method used, and can be used regardless of a continuous method or an on-demand method. There is no limitation on the type of the ink jet head, and it can be preferably used for all printers including a bubble jet (registered trademark) type, a thermal jet type, and a type using ultrasonic waves.

Recent advances in ink-jet systems have been remarkable, for example, a method of ejecting a large number of low-density inks called photo inks in a small volume, and improving image quality by using a plurality of inks having substantially the same hue and different densities. Many new methods have been proposed and put into practical use, such as a method using a colorless and transparent ink. The image forming method of the present invention is preferably used for any of these methods, but the improvement effect is remarkable particularly in a printer that prints a large amount of low-density ink at a high print speed and forms an image close to a photograph. Be demonstrated.

The dye represented by the general formula (I) of the present invention is
It is contained in a color material layer on a support and is used as a thermal transfer dye-providing material for image formation of a thermal transfer system. Next, the case where the heat transferable dye of the present invention is used for image formation of a thermal transfer system will be described in detail below. Usually, in order to form a full-color image, dyes of three colors, yellow, magenta and cyan, are required. Therefore, a color other than the dye represented by the general formula (I) of the present invention can be selected from conventionally known dyes to form a full-color image. When the dye used in the present invention is a dissociable dye, the other colors are preferably also dissociable dyes. For example, azo dyes having an phenolic hydroxyl group, azomethine dyes and methine dyes can be mentioned.

The thermal transfer dye-providing material can be used in the form of a sheet, a continuous roll, or a ribbon. The yellow, magenta, and cyan dyes are usually arranged on a support so as to form independent regions. The dye of the present invention can be dissolved or dispersed in a suitable solvent together with a binder resin and coated on a support, or can be printed on the support by a printing method such as a gravure method. It is preferable that the thickness of the dye-donating layer containing these dyes is set to a range of usually about 0.2 to 5 μm, particularly 0.4 to 2 μm in dry film thickness. Dye coating amount is 0.03-1 g / m
² , more preferably 0.1 to 0.6 g / m ² .

Examples of the binder resin used together with the above-mentioned coloring matter include polyamide resin, polyester resin, epoxy resin, polyurethane resin, polyacrylic resin (for example, polymethyl methacrylate, polyacrylamide, polystyrene-2-acrylonitrile), and polyvinyl resin. Vinyl resins such as pyrrolidone, polyvinyl chloride resins (for example, vinyl chloride-vinyl acetate copolymer),
Polycarbonate resin, polystyrene, polyphenylene oxide, cellulose resin (for example, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose triacetate), polyvinyl alcohol resin, ( For example, partially saponified polyvinyl alcohol such as polyvinyl alcohol, polyvinyl acetal, and polyvinyl butyral), petroleum resin, rosin derivative, cumarone-indene resin, terpene resin, polyolefin resin (for example, polyethylene and polypropylene) are used. In the present invention, such a binder resin is, for example, a dye 100
It is preferred to use about 20 to 600 parts by weight per part by weight. In the present invention, any of conventionally known ink solvents can be used as the ink solvent for dissolving or dispersing the dye and the binder resin.

As a support of the thermal transfer dye-donor material, polyethylene terephthalate; polyamide; polycarbonate; glassine paper; condenser paper; cellulose ester; fluoropolymer; polyether; polyacetal; polyolefin; polyimide; polyphenylene sulfide; polypropylene; polysulfone; Is mentioned. The thickness of the support of the thermal transfer dye-providing material is generally 2 to 30 μm. An undercoat layer may be provided as needed. A slipping layer may be provided to prevent the thermal head from sticking to the dye-providing material. The slipping layer is composed of a lubricating material with or without a polymer binder, such as a surfactant, a solid or liquid lubricant or a mixture thereof.

In order to prevent sticking due to the heat of the thermal head when printing from the back side and to improve the slip, the dye donating material is preferably subjected to anti-sticking treatment on the side of the support on which the dye donating layer is not provided. . For example,
It is preferable to provide a heat-resistant slip layer mainly composed of a reaction product of a polyvinyl butyral resin and an isocyanate, an alkali metal salt or an alkaline earth metal salt of a phosphoric acid ester, and a filler. The dye-providing material may be provided with a hydrophilic barrier layer for preventing the diffusion of the dye toward the support.

The dye-providing material may be provided with an undercoat layer. In the present invention, any undercoating layer may be used as long as it has a desired effect. Preferred specific examples include (acrylonitrile-vinylidene chloride-acrylic acid) copolymer (weight ratio 14: 80: 6), (butyl acrylate) -2-aminoethyl methacrylate-2-hydroxyethyl methacrylate) copolymer (weight ratio 30:20:50), linear / saturated polyesters such as Bostick 7650 (Mhart, Postick, Chemical Group) ) Or chlorinated high density poly (ethylene-trichloroethylene) resins. The coating amount of the undercoat layer is not particularly limited, but is usually used in an amount of 0.1 to 2.0 g / m ² .

In the present invention, the thermal transfer dye-providing material is superimposed on the thermal transfer image-receiving material, and from either side, preferably from the back side of the thermal transfer dye-providing material, heat is applied according to image information by a heating means such as a thermal head. By applying energy, the dye in the dye-donor layer can be transferred to the thermal transfer image-receiving material according to the magnitude of the heating energy. Further, an anti-fading agent can be transferred in the same manner. The heating means is not limited to a thermal head, and a known means such as a laser beam (for example, a semiconductor laser), an infrared flash, and a hot pen can be used. In systems using a laser, the dye-donor material contains a material that strongly absorbs the laser beam. The absorbent material is present in a layer below the dye and / or is mixed with the dye. The laser beam is modulated with electrical signals representing the shape and color of the original image, and only the areas of the dye that need to be present on the dye-donor material to reconstruct the original color of interest are heated and thermally transferred. A more detailed description of the process is given in GB 2,083,726A. UK Patent 2,083,726
The absorbing material disclosed in the specification for the laser system is carbon. In the present invention, the thermal transfer dye-providing material is combined with a thermal transfer image-receiving material to form a print using various thermal print printers, facsimile or magnetic recording, optical recording, etc., image printing, television, CRT It can be used to create prints from the screen.

In a preferred embodiment of the present invention, the dye-donor material comprises a polyethylene terephthalate support coated on a cyan dye, a magenta dye and a yellow dye in successive repetition zones. A color transfer image is formed. Of course, when this process is performed in a single color, a monochrome transfer image is obtained.
Ion gas lasers such as argon and krypton, metal vapor lasers such as copper, gold and cadmium, ruby and YA for thermal transfer of dye from dye-donor to image-receiving material.
Several types of lasers can be used, such as a solid state laser such as G, or a semiconductor laser such as gallium-arsenic that emits in the infrared region of 750-870 nm. However, in practice,
Semiconductor lasers are advantageous in terms of small size, low cost, stability, reliability, durability and ease of modulation.

The thermal transfer image-receiving material used in combination with the thermal transfer dye-providing material of the present invention comprises a basic substance having a function of receiving a dye transferred from the dye-providing material onto a support and dissociating the received dye. And / or an image receiving layer containing a mordant alone or together with a binder substance. (Hereinafter, the basic substance and the mordant will be referred to as a dye fixing agent.) The dye fixing agent is a compound having a primary to tertiary, more preferably a tertiary amino group, a nitrogen-containing heterocyclic group. And compounds having these quaternary cation groups.

[0051]

The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these embodiments. Example 1 Synthesis of Dye (2) of the Present Invention Dye (2) of the present invention was synthesized by the following route.

[0052]

Embedded image

(A) 23 g was dissolved in 100 ml of water and 14 ml of triethylamine, and 43 ml of concentrated hydrochloric acid was stirred at 10 to 15 ° C.
Was dropped. Dissolve 8.3 g of sodium nitrite in 20 ml of water,
The solution of the above (a) was added dropwise at 5-8 ° C under stirring, and then
Stirred for 0 minutes. On the other hand, 20.8 g of (b) was dissolved in 100 ml of water and 70 ml of triethylamine, and the above diazonium salt was added dropwise at 9 to 11 ° C. with stirring. After the dropwise addition, the reaction solution is cooled to 25 ° C.
After stirring for 30 minutes, the mixture was added to 500 ml of a 25% saline solution containing 26 ml of concentrated hydrochloric acid. The precipitated crystals are filtered and 25%
The mixture was washed with brine and dried to obtain reddish brown crystals (c). (C) 47.1 g was dissolved in 100 ml of dimethylformamide and 20 ml of triethylamine, and 15 g of methanesulfonyl chloride was added dropwise at 15 to 20 ° C. with stirring. After stirring for 30 minutes after the dropwise addition, the mixture was poured into 400 ml of 25% saline. The precipitated crystals were filtered, washed with 100 ml of 25% saline solution and dried to obtain yellow crystals (d). Melting point 257-259 ° C yield 38
g Yield 69.1% (d) 20 g of dimethylacetamide and 100 ml of acetonitrile were added to 20 g, and 45 g of phosphorus oxychloride was added to 9 g with stirring.
It was added dropwise at 1212 ° C. After the dropwise addition, the mixture was stirred at 70 ° C for 1 hour, cooled to 30 ° C, and poured into 200 ml of 10 ° C water. The precipitated crystals were filtered, washed with 100 ml of cold water, and dried under reduced pressure to obtain yellow crystals (e). Melting point 244-245 ° C Yield 9.8 g Yield
49.2% (f) Dissolve 1.8g in dimethylformamide 20ml,
1.0 ml of pyridine is added and (e) 5.
5 g was added slowly. After stirring for 1 hour after the addition, 4 g of diethylamine was added, and the mixture was heated and stirred at 30 ° C. for 30 minutes, and then poured into 60 ml of water containing 3 ml of concentrated hydrochloric acid. The precipitated crystals were filtered and washed with 100 ml of cold water to obtain dark red crystals. The crystals were dissolved in 5 ml of dimethylformamide, 50 ml of acetonitrile was added, and the precipitated crystals were filtered, washed with 30 ml of acetonitrile, dried, and dried.
Red crystals (the present dye (2)) were obtained. Melting point 147-153
℃ Yield 3.2 g Yield 53.4% λmax 677 nm (DMF)

(Example 2) Synthesis of dye (15) of the present invention Example 1 was repeated except that 1.8 g of (f) in Example 1 was changed to 2 g of 4-amino-2,2,6,6-tetramethylpiperidine. Was synthesized in the same manner as in Example 1 to obtain a black crystal (Dye (15) of the present invention). Melting point
246-251 ° C Yield 3.5 g Yield 60.0% λmax 676 nm
(DMF)

(Example 3) Commercially available uncoated base paper (basis weight 64)
g / m ² ), 43 parts of hollow fine particles of styrene-acrylate copolymer (particle diameter: 0.3 to 0.4 μ) (solid content weight ratio, the same applies hereinafter), and fumed silica (particle diameter: 12 μm)
17 parts, styrene butadiene copolymer latex 12
, 18 parts of polyvinyl acetate latex, and 10 parts of polymethyl methacrylate fine particles (particle size: about 8 μm) were applied using a wire bar so that the solid content was 10 g / m ^2. Created. Ink jet recording was carried out on this recording paper at 8 dots / mm using an electrostatic acceleration type ink jet apparatus equipped with a head having a nozzle hole diameter of 50 μm.

[Ink Liquid A] Dye (3) of the present invention 6 parts by weight Diethyl phthalate 30 parts by weight Diisopropyl adipate 44 parts by weight N, N-diethyl dodecaneamide 20 parts by weight This ink liquid has good ejection properties. A clear, high-density magenta image was obtained. Even when the paper printed with this ink was immersed in water for 10 minutes, no bleeding or running of the image was observed.

Example 4 Ink liquids B to F having the following compositions were prepared. [Ink liquid B] Dye (2) of the present invention 6 parts by weight Dibutyl adipate 70 parts by weight Benzyl alcohol 20 parts by weight [Ink liquid C] Dye of the present invention (6) 6 parts by weight Dibutyl maleate 61 parts by weight Diethyl phthalate 22 parts by weight N-methylpyrrolidone 5 parts by weight [Ink liquid D] Dye of the present invention (14) 6 parts by weight Diethyl adipate 41 parts by weight Diethyl phthalate 30 parts by weight Dipropylene glycol monomethyl ether 20 parts by weight [Ink liquid E] Dye of the present invention (15) 6 parts by weight Dibutyl maleate 54 parts by weight Diethyl phthalate 25 parts by weight Benzyl alcohol 15 parts by weight [Ink liquid F] (Comparative example) Comparative dye A 6 parts by weight Dibutyl maleate 54 parts by weight Phthalate Diethyl acid 25 parts by weight Benzyl alcohol 15 parts by weight

[0058]

Embedded image

Each of these ink liquids was printed on Fuji Photo Film inkjet paper, Super Photo Grade (photo glossy paper) in the same manner as in Example 2. Ink liquids B to F all exhibited good ejection properties, and in the case of ink liquids B to E, clear cyan images were obtained. The density reduction rate after leaving the printed images of A to E in room light for 3 months was 3% or less in each case, which was good.

<Example of aqueous ink> (Example 5) An ink liquid G having the following composition was prepared. [Ink liquid G] Dye (1) of the present invention 4 parts by weight Diethylene glycol 9 parts by weight Tetraethylene glycol monobutyl ether 9 parts by weight Glycerin 7 parts by weight Diethanolamine 1 part by weight Water 70 parts by weight

After stirring the above composition for 1 hour while heating at 30 to 40 ° C., the average pore diameter was 0.8 μm and the diameter was 47 mm.
The mixture was filtered under pressure using a microfilter of the formula (1) to obtain the desired ink. Ink G except that the dye was changed as shown in Table 1.
Ink liquids H to M were prepared in the same manner as described above. Inkjet printer PM-700 using the above inks G to M
C (manufactured by Seiko Epson) was used to print on Fuji Photo Film inkjet paper, Super Photo Grade (photo glossy paper) to obtain an image sample.

The hue and light fastness were evaluated using the obtained image samples. (Hue) The hue was evaluated as ○, Δ, and × according to the following Δ. χ = concentration value (absorbance) at 550 nm / maximum concentration value in cyan part (absorbance) ○ when の is 0.15 or less △ when χ is 0.16 to 0.24 × χ when 0.25 or more The images obtained from the ink liquids G to K were clearer cyan images than the image obtained from the ink liquid M of the comparative example. (Light fastness) Image samples were obtained from Atlas C.I. Using an I65 weather meter, irradiate with xenon light (85,000 lux) for 3 days, measure the image density before and after xenon irradiation using a reflection densitometer (X-Rite 310TR), and determine the light stability of the image. Evaluation was made based on the dye remaining rate. At the three points where the reflection density before irradiation was 1.0, 1.5, and 2.0, the light fastness was evaluated by the following ○, Δ, and ×. The results are shown in Table 1. It can be seen that in the case of the ink of the present invention, an image having excellent light fastness can be obtained. Light fastness: ○ 80% or more for all three density points △ 80% or more for one or two density points, less than 80% for others × Less than 80% for all three density points

[0063]

[Table 1]

[0064]

Embedded image

On the other hand, using the inks G to M, an ink jet printer PM-700C (manufactured by Seiko Epson Corporation) was used to print on a glossy paper (MJA4S3P) manufactured by Seiko Epson Corporation for exclusive use of Super Fine, and an image sample was obtained in the same manner as described above. . Both the hue and the light fastness were almost the same as those in Table 1. However, better results were obtained when Fuji Photo Film inkjet paper and Super Photo Grade (photo glossy paper) were used.

Example 6 (Preparation of Thermal Transfer Dye Donor Material (1-1)) A 6 μm-thick polyethylene terephthalate film having a heat-resistant lubricating treatment applied to the back surface was used as a support. The thickness of the coating composition for a thermal transfer dye-providing layer having the following composition was 1.5 μm when dried by wire bar coating.
m to form a thermal transfer dye-providing material (1-
1) was created.

[0067]

[Table 2]

Next, the thermal transfer dye-providing material of the present invention and comparative thermal transfer dye-providing materials (1-2) to (1-5) were prepared in the same manner as described above except that the dye (2) of the present invention was changed to another dye. Was created respectively.

[0069]

[Table 3]

(Preparation of Thermal Transfer Image-Receiving Material A) Synthetic paper having a thickness of 150 μm (YUPO-FPG, manufactured by Oji Yuka)
-150), a coating composition for an image receiving layer having the following composition having a thickness of 8 when dried by wire bar coating on the surface.
It was coated to a thickness of μm to form a thermal transfer image-receiving material.
Drying was carried out in a oven at a temperature of 100 ° C. for 30 minutes after preliminary drying with a drier.

[0071]

[Table 4]

Next, the recorded image receiving material is applied for 3 days to 1700
The image was irradiated with a 0 lux fluorescent light, and the light fastness of the image was examined.
The dye remaining ratio in the portion having a reflection density of 1.0 was evaluated. Further, the degree of bleeding of the image after observing the recorded image receiving material in an oven at 60 ° C. for 2 weeks was observed. The criteria are
5 when the image has hardly changed from before storage, 3 when the image is slightly blurred, 1 when the image is very blurred and blurred
Indicated by In addition, the cases considered to be intermediate between the respective cases were evaluated as 4 and 2, respectively, and evaluated on a 5-point scale. Table 5 shows the results. It can be seen that when the dye of the present invention was used, the transfer density was high, a clear image was obtained, and the image was not blurred over time. In addition, there was no color transfer (contamination due to transfer of dye from the transfer image surface due to contact between the front surface with the transfer image and the front or back surface of the image receiving paper without the transfer image).

[0073]

[Table 5]

As described above, the azo dye represented by the general formula (I) of the present invention is a dye having excellent light fastness, and can provide a clear image for inkjet inks. As a result, a clear image with little color transfer was obtained.

[0075]

The present invention has excellent spectral characteristics,
An azo dye having high fastness to heat, air, chemicals, and the like was obtained, and an inkjet ink and an inkjet recording method capable of forming an image having high fastness were obtained.
Further, a thermal transfer dye-providing material having high stability against light, heat, air, chemicals, and the like was obtained.

Claims (5)

[Claims] 1. An azo dye represented by the following general formula (I). Embedded imageIn the formula, Z is necessary to form a 5- to 7-membered ring together with the N atom
Atomic group. R₁Is a hydrogen atom, an oxy radical group,
Aliphatic group, aliphatic oxy group, acyl group, aliphatic oxyca
Rubonyl group, aryloxycarbonyl group, acyloxy
Represents a group. R _Two , R_Three , R_Four And R_Five Is each archi
R_Two And R_Three , R_Four And R_Five Form a ring
You may. Dye has the dye groups necessary to form azo dyes.
Represent. 2. The azo dye according to claim 1, wherein the azo dye represented by the general formula (I) is represented by the following general formula (Ia). Embedded image In the formula, R ₁ is a hydrogen atom, an oxy radical group, an aliphatic group,
It represents an aliphatic oxy group, an acyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, or an acyloxy group. Dye represents a dye group necessary for forming an azo dye. 3. An inkjet ink comprising an azo dye represented by the general formula (I). 4. An ink jet recording method for recording an image on an image receiving material by ejecting ink in the form of droplets, wherein the ink is the ink according to claim 3 . 5. A thermal transfer recording material comprising a thermal transfer dye-providing material and a thermal transfer image-receiving material, wherein at least one of the dyes used is the azo dye according to claim 1.