JP2003064273A - New compound, dyestuff, ink composition, ink-jet recording ink, and ink-jet recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new compound or a dyestuff excellent in light fastness, dark heat fastness, ozone resistance and the like and exhibiting high concentration black, and to provide an ink composition and the like containing the dyestuff. SOLUTION: The ink composition contains the compound or the dyestuff expressed by formula (1). In formula (1), Z1 , Z2 , Z4 , Z5 , Z7 , Z8 , and Z9 independently denote a nitrogen atom or a CR11 group. Z3 , Z6 , and Z10 independently denote a non-metal atomic group capable of forming a 5-7 member ring. R1 and R2 independently denote a halogen atom, an alkoxy group, a hydroxy group, or a substituted or non-substituted amino group. R3 and R4 independently denote a hydrogen atom or a substituted group. m denotes 0 or a; n denotes an integer of 0-4; and q denotes 1 or 2. R11 denotes a hydrogen atom or a substituted group. When n is a plural number, R2 may be the same of different to each other. When q is 2, Z8 , Z9 and Z10 may be the same of different to each other.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel compound having an electron-donating group at a specific position in the molecule (azomethine compound and methine compound), a novel dye, an ink composition containing the dye, and the ink. The present invention relates to an inkjet recording ink containing a composition, and an inkjet recording method using the inkjet recording ink.

[0002]

2. Description of the Related Art A dye showing a black color is used not only for printing character information but also as a black plate in a color image. However, there are many technically difficult points in developing a dye exhibiting a neutral black color, and a great deal of research and development has been conducted, but few have sufficient performance. Therefore, a plurality of pigments of various hues are mixed to form a black color, but the development of a pigment that exhibits a high concentration of neutral black color by itself is the most strongly demanded technology at present. It is an issue.

With the spread of ink jet printers in recent years, black pigments have become more important than ever. Inkjet printers print character information more frequently than other types of specialized printers. Therefore, there is a problem that the black dye used in the ink jet printer must satisfy the required performance both when it is used for the black image portion of image information and when it is used for the character information portion.

The performance required of the black dye is as follows.
A neutral black color at high density, excellent ink suitability and ink stability, image fastness (light,
Heat, atmospheric humidity, chemicals, atmosphere, various gases in the atmosphere,
High against water and friction, printed media (paper)
Little change in hue due to, excellent dyeability in image receiving paper, easy to synthesize and low cost,
For example, it is harmless to humans and animals.

Hitherto, a bisazo dye has been proposed as a black dye. However, conventionally known black dyes have problems that the density is low, the hue is not neutral black, and the image fastness is poor. Moreover, some black dyes have a structure having harmful chromium ions in the molecule, which is problematic in terms of safety for humans and animals.

[0006]

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 is highly concentrated and neutral,
To provide a novel compound and a dye which satisfy various performances required for an ink composition exhibiting a black color and an ink for inkjet recording, are inexpensive and easy to synthesize, and a dye suitably used for recording by a thermal transfer system. With the goal. Further, in addition to being excellent in printing performance, the color tone is also preferable, light fastness, dark storability, and excellent image fastness such as ozone resistance, capable of exhibiting a high concentration of black, and containing the above dye. It is an object of the present invention to provide the following novel ink composition and an inkjet recording ink containing the ink composition. It is another object of the present invention to provide an inkjet recording method which gives a black image having excellent image performance by using the inkjet recording ink.

[0007]

Means for Solving the Problems The inventors of the present invention have made earnest studies on compounds and dyes having an electron-donating group at a specific position in the molecule, which are novel structures which have not been known so far. A novel compound (azomethine compound and methine compound) exhibiting excellent performance as a dye, a dye, an ink composition containing the dye, an inkjet recording ink containing the ink composition, and the inkjet recording ink The present invention has been completed by finding out an ink jet recording method for performing recording.

That is, means for solving the above problems are as follows. <1> A compound represented by the following general formula (1).

[0009]

[Chemical 3]

In the general formula (1), Z ₁ , Z ₂ , Z
₄ , Z ₅ , Z ₇ , Z ₈ and Z ₉ each independently represent a nitrogen atom or a CR ₁₁ group. Z _3, Z _6, and Z ₁₀ each independently represent a non-metallic atomic group which can form a 5- to 7-membered ring. R ₁
And R ₂ each independently represent a halogen atom, an alkoxy group, a hydroxy group, or a substituted or unsubstituted amino group. R ₃ and R ₄ each independently represent a hydrogen atom or a substituent. m represents 0 or 1. n represents an integer of 0-4. q represents 1 or 2. R ₁₁ represents a hydrogen atom or a substituent. When n is plural, R ₂ may be the same or different. When q is 2, Z ₈ , Z ₉ and Z ₁₀ may be the same or different from each other.

<2> A dye represented by the following general formula (1).

[0012]

[Chemical 4]

In the general formula (1), Z ₁ , Z ₂ , Z
₄ , Z ₅ , Z ₇ , Z ₈ and Z ₉ each independently represent a nitrogen atom or a CR ₁₁ group. Z ₃ , Z ₆ and Z ₁₀ are each independently
It represents a non-metallic atomic group capable of forming a 5- to 7-membered ring. R ₁ and R ₂ are each independently a halogen atom or Hammett σ
It represents an electron-donating group having a p-value that is more negative than -0.20. R ₃ and R ₄ each independently represent a hydrogen atom or a substituent. m represents 0 or 1. n represents an integer of 0-4. q represents 1 or 2. R ₁₁ represents a hydrogen atom or a substituent. When n is plural, R ₂ may be the same or different. When q is 2, Z ₈ , Z ₉ and Z ₁₀ may be the same or different from each other.

<3> The dye according to <2>, which is contained in a thermal transfer dye-providing material and used for thermal transfer recording.

<4> An ink composition containing the dye according to <2>.

<5> An inkjet recording ink containing the ink composition according to <4>.

<6> An ink jet recording method characterized in that the ink jet recording ink according to the above <5> is used to perform recording on an image receiving material having an ink receiving layer containing a white pigment on a support. Is.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The novel compound (azomethine compound and methine compound), novel dye, ink composition, ink jet recording ink, and ink jet recording method of the present invention will be described in detail below.

(Novel Compounds and Dyes) Here, the compounds and dyes of the present invention will be described. The novel compound of the present invention is characterized by being represented by the following general formula (1).

[0020]

[Chemical 5]

In the general formula (1), Z ₁ , Z ₂ and Z
₄ , Z ₅ , Z ₇ , Z ₈ and Z ₉ each independently represent a nitrogen atom or a CR ₁₁ group. Z _3, Z _6, and Z ₁₀ each independently represent a non-metallic atomic group which can form a 5- to 7-membered ring. R ₁
And R ₂ each independently represent a halogen atom, an alkoxy group, a hydroxy group, or a substituted or unsubstituted amino group. R ₃ and R ₄ each independently represent a hydrogen atom or a substituent. m represents 0 or 1. n represents an integer of 0-4. q represents 1 or 2. R ₁₁ represents a hydrogen atom or a substituent. When n is plural, R ₂ may be the same or different. When q is 2, Z ₈ , Z ₉ and Z ₁₀ may be the same or different from each other.

The dye of the present invention has the general formula (1)
In the general formula (1), R ₁ and R ₂ are each independently a halogen atom or an electron donation having a Hammett's σp value of a value more negative than −0.20. It has the same meaning as the compound represented by the general formula (1) except that it represents a sexual group.

In the general formula (1), Z ₁ , Z ₂ , Z
₄ , Z ₅ , Z ₇ , Z ₈ and Z ₉ each independently represent a nitrogen atom or a CR ₁₁ group. R ₁₁ represents a hydrogen atom or a substituent, and examples of the substituent include a halogen atom, an alkyl group (cycloalkyl group, bicycloalkyl group, and the like,
(Including an alkyl group having a plurality of cyclo rings)), an alkenyl group (including an alkenyl group having a plurality of cyclo rings such as a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group, a cyano group, Hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including anilino group), Acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, Famoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, arylazo group, heterocyclic azo group, imide group, phosphino group, phosphinyl group, Preferable examples include a phosphinyloxy group, a phosphinylamino group and a silyl group.

Among the above R ₁₁ , halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonyl group. Amino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group,
A sulfo group, an alkylsulfonyl group, an arylsulfonyl group and an acyl group are preferred.

Among the above halogen atoms, for example, fluorine, chlorine, bromine and iodine are more preferable. Among the above alkyl groups, an alkyl group having 1 to 20 carbon atoms is more preferable, and a methyl group and an ethyl group are particularly preferable. Among the aryl groups, for example, a phenyl group and a naphthyl group are more preferable. Among the above heterocyclic groups, for example, a benzoxazolyl group and a benzimidazolyl group are more preferable. Among the alkoxy groups, an alkoxy group having 1 to 20 carbon atoms is more preferable, and for example, a methoxy group and an ethoxy group are particularly preferable. Among the amino groups, an amino group having 0 to 20 carbon atoms is more preferable, and, for example, an amino group, a methylamino group and an anilino group are particularly preferable. Among the above acylamino groups, an acylamino group having 1 to 20 carbon atoms is more preferable, and for example, a formamide group, an acetamido group, and a benzamide group are particularly preferable. Among the aminocarbonylamino groups, an aminocarbonylamino group having 1 to 20 carbon atoms is more preferable, and for example, a phenylaminocarbonylamino group is particularly preferable. Among the alkoxycarbonylamino groups, an alkoxycarbonylamino group having 2 to 20 carbon atoms is more preferable, for example,
A methoxycarbonylamino group and a benzyloxycarbonylamino group are particularly preferable. Among the alkyl and aryl sulfonyl groups, an alkyl and aryl sulfonylamino group having 1 to 20 carbon atoms is more preferable, for example,
A methanesulfonamide group and a benzenesulfonamide group are particularly preferable. Among the above alkylthio groups, the number of carbon atoms is 1
The alkylthio group of -20 is more preferable, and the methylthio group is particularly preferable. Among the alkyl and aryl sulfonyl groups, an alkyl and aryl sulfonyl group having 1 to 20 carbon atoms is preferable, for example, a methane sulfonyl group,
A benzenesulfonyl group is more preferred. Among the above acyl groups, an acyl group having 1 to 20 carbon atoms is more preferable, and for example, a formyl group, an acetyl group and a benzoyl group are particularly preferable.

In the general formula (1), Z ₅ and Z ₇ are preferably nitrogen atoms. Also, Z ₃ and Z ₁₀ are 5
~ Represents a group of non-metallic atoms capable of forming a 7-membered ring, and the formed 5- to 7-membered ring is a heterocyclic ring in which atoms forming a saturated or unsaturated skeleton are selected from carbon, nitrogen, oxygen and sulfur. , And a benzene ring, which may be further condensed at an appropriate position. Examples of the 5-membered ring include:
Furan, thiophene, pyrrole, pyrazole, imidazole, triazole, oxazole, isoxazole, thiazole, isothiazole, thiadiazole and dihydro forms thereof and dioxolane are preferable.
As the 6-membered ring, for example, benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, and dihydro, tetrahydro and dioxirane thereof are preferable. As the 7-membered ring, for example, azepine and its dihydro form, tetrahydro form and the like are preferable.
These 5- to 7-membered rings may be substituted with the substituents described for R ₁₁ .

In the general formula (1), Z ₆ is 5 to
A non-metallic atomic group capable of forming a 7-membered ring is represented, and as the formed 5- to 7-membered ring, a heterocyclic ring in which an atom forming a saturated or unsaturated skeleton is selected from carbon, nitrogen, oxygen and sulfur, Examples thereof include a benzene ring, which may be further condensed at an appropriate position. The 5-membered ring is preferably pyrrole, pyrazole, imidazole, triazole or tetrazole. The 6-membered ring is preferably pyridine, pyrimidine, pyridazine, pyrazine, triazine and dihydro compounds thereof. As the 7-membered ring,
Azepine, diazepine and triazepine are preferred. These 5- to 7-membered rings may be substituted with the substituent described for R ₁₁ .

In the case of the novel compounds of the present invention, R ₁ and R
Each ₂ independently represents a halogen atom, an alkoxy group, a hydroxy group, or a substituted or unsubstituted amino group. The substituent in the substituted amino group is the same as the substituent represented by R ₁₁ , and the substituents may be bonded to each other. Further, in the case of the dye of the present invention, R ₁ and R ₂ are each independently a halogen atom (eg, fluorine, chlorine, bromine, iodine) or a Hammett's σp value is a negative value less than −0.20. It represents an electron-donating group that it has.

The Hammett's σp value is described in various textbooks. For example, “structure-activity relationship of drug-
Guidelines for Drug Design and Action Mechanism Research "(Area of Chemistry, Special Issue No. 122; Nankodo (1979)), Chem.
Rev. 91, 165 (1991) etc. are detailed. Specific examples of the electron-donating group having a Hammett's σp value smaller than −0.20 include an alkoxy group (eg, methoxy: −0.27; ethoxy: −0.24; carboxylmethoxy). : -0.33; benzyloxy:-
0.42), an amino group (for example, amino: -0.66;
Methylamino: -0.84; Ethylamino: -0.6
1; Butylamino: -0.51; Dimethylamino:-
0.83; phenylamino: -0.40; diphenylamino: -0.22), hydroxylamino group (-0.3)
4), a hydrazino group (-0.55), a benzylideneamino group (-0.55), a hydroxyl group (-0.37) and the like.

In the novel compounds and dyes represented by the above general formula (1) of the present invention, R ₁ and R ₂ are preferably substituted amino groups, and among them, for example, dodecylamino group, dimethylamino group, phenyl. An amino group and a diphenylamino group are particularly preferable.

In the general formula (1), m represents 0 or 1, and m is preferably 1. n represents an integer of 0 to 4, and n is preferably 0 or 1. Both m and n are never 0.

In the general formula (1), R ₃ and R
₄ each independently represents a hydrogen atom or a substituent, and R ₃ and R
₄ and may combine with each other to form a ring. Further, R ₄ and Z ₉ may combine with each other to form a ring. As R ₃ and R ₄ , an alkyl group having 1 to 20 carbon atoms (for example, a methyl group,
An ethyl group and an isopropyl group) and an aryl group having 6 to 20 carbon atoms (for example, a phenyl group and a naphthyl group) are preferable.
The alkyl group having 1 to 20 carbon atoms is an alkoxycarbonyl group having 2 to 20 carbon atoms (for example, methoxycarbonyl group), cyano group, carboxyl group, phosphoryl group, sulfo group, hydroxy group, sulfone having 1 to 20 carbon atoms. It may be substituted with an amide group (eg, methanesulfonamide) or the like. The aryl group having 6 to 20 carbon atoms may be substituted with the substituent represented by R ₁₁ .

R ₃ and R ₄ may combine with each other to form a nitrogen-containing heterocycle, and examples of the nitrogen-containing heterocycle include pyrrole, pyrazole, imidazole, triazole, azepine, and dihydro forms thereof. Preferable examples thereof include tetrahydro form, piperazine, morpholine and the like. The nitrogen-containing heterocycle may be substituted with a substituent represented by R ₁₁ at an appropriate position, or the benzene ring may be condensed.

R ₄ and R ₉ may combine with each other to form a nitrogen-containing heterocycle, and specific examples of the nitrogen-containing heterocycle include pyrrole, pyrazole, imidazole, triazole, azepine, and their dihydro form and tetrahydro. Body, piperazine, morpholine, etc.
The benzene ring which may be substituted with the substituent represented by R ₁₁ may be condensed. It is preferable that the constituent atoms of Z ₁ and Z ₂ , Z ₈ and Z ₉ are bonded to each other to form a 5- to 7-membered ring, and the atoms constituting the ring skeleton include carbon atom, nitrogen atom and oxygen atom. It is preferably selected from sulfur atoms. As the ring formed, a benzene ring optionally substituted with the substituent represented by R ₁₁ is particularly preferable.

The compound represented by the general formula (1) and the dye represented by the general formula (1) are represented by the following general formula (2) to
It is preferably represented by the general formula (5), and among them, particularly preferably represented by the following general formula (2).

[0036]

[Chemical 6]

In the general formula (2), Z ₁₁ , Z ₁₂ , Z
₁₃ , Z ₁₄ , Z ₁₅ and Z ₁₆ each independently represent a nitrogen atom or a CR ₂₁ group. In the general formula (2), R ₁ ,
_{R 2, R 3, R 4} , m, n, Z 1, Z 2, Z 4, Z 5, Z 7, Z
₈ and Z ₉ have the same meanings as in the general formula (1). R ₂₁ represents a hydrogen atom or a substituent, and examples of the substituent include the substituents described for R ₁₁ . The constituent atoms of Z ₁₃ and Z ₁₄ may combine with each other to preferably form a 5- to 7-membered ring. The atoms constituting the ring skeleton are preferably selected from carbon atom, nitrogen atom, oxygen atom and sulfur atom. As the ring formed, a benzene ring optionally substituted with the substituent represented by R ₁₁ is particularly preferable.

In the general formula (2), Z_Five, Z₇, Z
₁₄Represents a nitrogen atom, Z₁, Z₂, Z _Four, Z₁₁, Z₁₂, Z
₁₃, Z₁₄, Z₈, Z₉, Z₁₅, And Z₁₆Is CR_{twenty one}Represents
It is particularly preferable that m represents 1 and n is 0.
Yes.

[0039]

[Chemical 7]

In the general formula (3), Z ₁₁ , Z ₁₄ and Z
₁₅ , Z ₁₆ , Z ₁₇ , and Z ₁₈ each independently represent a nitrogen atom or a CR ₃₁ group, and R ₁ , R ₂ , R ₃ , R ₄ , m, n, Z ₁ ,
Z ₂ , Z ₄ , Z ₅ , Z ₇ , Z ₈ and Z ₉ are represented by the general formula (1).
Is synonymous with that in. R ₃₁ represents a hydrogen atom or a substituent, and examples of the substituent include the substituents described for R ₁₁ . The constituent atoms of Z ₁₇ and Z ₁₈ may be bonded to each other to preferably form a 5- to 7-membered ring. The atom constituting the ring skeleton is preferably selected from a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom,
As the ring formed, a benzene ring optionally substituted with the substituent represented by R ₁₁ is particularly preferable.

In the above general formula (3), Z ₅ and Z ₇ represent nitrogen atoms, and Z ₁ , Z ₂ , Z ₄ , Z ₁₁ , Z ₁₂ , Z ₁₇ ,
Z ₁₈ , Z ₈ , Z ₉ , Z ₁₅ and Z ₁₆ represent CR ₃₁ , and m is 1.
Is particularly preferable and n is 0.

[0042]

[Chemical 8]

In the general formula (4), Z₁₁, Z₁₂,
Z₁₅, Z₁₆, Z₁₉, And Z₂₀Are each independently a nitrogen atom or
Is CR₄₁Represents a group, R₁, R₂, R₃, R_Four, M, n,
Z₁, Z_Two, Z _Four, Z₅, Z₇, Z₈And Z₉Is the above general formula
It is synonymous with that in (1).

In the general formula (4), R ₄₁ represents a hydrogen atom or a substituent, and examples of the substituent include the substituents described for R ₁₁ . It is preferable that the constituent atoms of Z ₁₉ and Z ₂₀ are bonded to each other to form a 5- to 7-membered ring. The atom constituting the ring skeleton is preferably selected from a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom, and the ring formed is a benzene ring which may be substituted with the substituent represented by R _11. Is particularly preferable.

In the general formula (4), Z ₅ and Z ₇ represent a nitrogen atom, and Z ₁ , Z ₂ , Z ₄ , Z ₁₁ , Z ₁₂ , Z ₁₉ and
Z ₂₀ , Z ₈ , Z ₉ , Z ₁₅ and Z ₁₆ represent CR ₄₁ , and m is 1
Is particularly preferable and n is 0.

[0046]

[Chemical 9]

In the general formula (5), Z ₁₁ , Z ₁₂ ,
Z ₁₅ and Z ₁₆ each independently represent a nitrogen atom or a CR ₅₁ group, and are R ₁ , R ₂ , R ₃ , R ₄ , m, n, Z ₁ , Z ₂ , Z ₄ ,
Z ₅ , Z ₇ , Z ₈ and Z ₉ have the same meanings as in the general formula (1).

In the above general formula (5), R ₅₁ and R ₅
Represents a hydrogen atom or a substituent, and the substituent is R
_The substituents mentioned in ₁₁ can be mentioned. In the general formula (5), Z ₅ and Z ₇ represent a nitrogen atom, and Z ₁ ,
Z ₂ , Z ₄ , Z ₁₁ , Z ₁₂ , Z ₈ , Z ₉ , Z ₁₅ , and Z ₁₆ are C
Particularly preferred is the case where R ₅₁ is represented, m is 1, and n is 0.

The compounds and dyes of the present invention have two broad absorption bands in the visible region and exhibit a color close to black,
A dye having an absorption band different from that of the compound or dye of the present invention may be used in combination in order to obtain a black color with no tint.
The peak of one absorption band exists at 430 to 480 nm,
The other peak preferably exists at 570 to 630 nm. The compounds and dyes of the present invention, depending on the structure,
Coordinates with metal ions to form a so-called chelate dye. Various known metal ions are used for the chelate. Among them, copper, nickel, iron, cobalt, zinc, chromium and the like are preferably used. However, since the chromium ion is toxic, the chromium ion is not preferable in the case where the human is in direct contact such as an ink jet recording ink. On the other hand, chromium ions can be used for applications where humans do not come into direct contact. The chromium chelate dye may have improved light fastness, and is preferably used when high fastness is required. Therefore, the copper chelate is more preferable in the compound and the dye of the present invention from the viewpoint of satisfying the required performance for the dye such as toxicity and fastness.

The compounds and dyes of the present invention can dye materials made of cellulose. In addition, it is possible to dye a material having a carbonamide bond. Therefore, it can be widely used for dyeing leather, textiles, and paper.

A typical use of the compound and dye of the present invention is an ink composition prepared by dissolving the compound and dye in a liquid medium. In particular, it is preferably used as an ink for inkjet recording containing the ink composition.

The compounds and dyes of the present invention can be used in image forming materials such as ink compositions, ink jet recording inks, sublimation type diffusion transfer and diffusion transfer type photographic light-sensitive materials. When used in the ink composition or the inkjet recording ink, the content of the compound and dye of the present invention is preferably 0.1 to 20% by mass, and 0.2 to
15 mass% is more preferable. When used in the sublimation type diffusion transfer, the coating amount of the compound and dye of the present invention,
0.03 to 1 g / m ² is preferable, and 0.1 to 0.6 g / m ^2.
m ² is more preferable. When it is used in the diffusion transfer type photographic light-sensitive material, the compound and the dye as 0.
02~5.0mmol / m ² is preferably contained, it is more preferably contained 0.2~1mmol / m ^2. Further, the compounds and dyes of the present invention may be used as a mixture of two or more, or may be used in combination with a compound exhibiting another color, depending on the purpose.

The compounds and dyes of the present invention can be used in combination with the dyes shown below (hereinafter sometimes referred to as "dye"). Any yellow dye that can be used in combination 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, azomethine dyes having open-chain active methylene compounds as coupler components; methine dyes such as benzylidene dyes and monomethineoxonol dyes;
For example, there are quinone dyes such as naphthoquinone dyes and anthraquinone dyes, and other dye types include quinophthalone dyes, nitro-nitroso dyes, acridine dyes, and acridinone dyes.

As the magenta dye that can be used in combination, any magenta dye can be used. 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.,
Examples thereof include condensed polycyclic dyes such as dioxazine dyes.

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

The dye that can be used in combination may be one that exhibits yellow, magenta, and cyan colors only after a part of the chromophore is dissociated, and in that case, the counter cation is an inorganic metal such as an alkali metal or ammonium. Cation, an organic cation such as a pyridinium or a quaternary ammonium salt, or a polymer cation having a partial structure thereof.

Next, synthetic examples of the compounds and dyes of the present invention will be described. <Synthesis Example> The compounds and dyes represented by the general formula (1) include azomethine compounds (Z ₄ = N) and methine compounds (Z ₄
= CR) can be used for the synthesis. In the case of an azomethine compound (Z ₄ = N), JP-A-4-126772 and JP-A-2000-32794
It can be easily synthesized by reacting a compound represented by the following formula with an amine compound represented by the following formula under oxidative conditions according to the method described in JP-A No. 0 and the like. Furthermore, it can also be synthesized by a condensation reaction of a compound represented by the following formula and a nitroso compound represented by the following formula. In the case of a methine compound (Z ₄ = CR), it can be synthesized by a condensation reaction between a compound represented by the following formula and an aldehyde or ketone compound represented by the following formula.

[0058]

[Chemical 10]

[0059]

[Chemical 11]

[0060]

[Chemical 12]

[0061]

[Chemical 13]

Specific examples of the compounds and dyes of the present invention are shown below, but the present invention is not limited thereto. For the sake of clarity, the notation is expressed as "(2) -number", but the compounds and dyes represented by the general formulas (2) to (5) are, as described above, all common Included in the compounds and dyes represented by formula (1).

[0063]

[Chemical 14]

[0064]

[Chemical 15]

[0065]

[Chemical 16]

[0066]

[Chemical 17]

[0067]

[Chemical 18]

[0068]

[Chemical 19]

[0069]

[Chemical 20]

[0070]

[Chemical 21]

[0071]

[Chemical formula 22]

[0072]

[Chemical formula 23]

[0073]

[Chemical formula 24]

[0074]

[Chemical 25]

[0075]

[Chemical formula 26]

[0076]

[Chemical 27]

[0077]

[Chemical 28]

[0078]

[Chemical 29]

[0079]

[Chemical 30]

[0080]

[Chemical 31]

[0081]

[Chemical 32]

[0082]

[Chemical 33]

[0083]

[Chemical 34]

[0084]

[Chemical 35]

[0085]

[Chemical 36]

[0086]

[Chemical 37]

[0087]

[Chemical 38]

[0088]

[Chemical Formula 39]

[0089]

[Chemical 40]

[0090]

[Chemical 41]

[0091]

[Chemical 42]

[0092]

[Chemical 43]

[0093]

[Chemical 44]

[0094]

[Chemical formula 45]

[0095]

[Chemical formula 46]

[0096]

[Chemical 47]

[0097]

[Chemical 48]

[0098]

[Chemical 49]

[0099]

[Chemical 50]

[0100]

[Chemical 51]

[0101]

[Chemical 52]

[0102]

[Chemical 53]

[0103]

[Chemical 54]

[0104]

[Chemical 55]

[0105]

[Chemical 56]

[0106]

[Chemical 57]

[0107]

[Chemical 58]

[0108]

[Chemical 59]

[0109]

[Chemical 60]

[0110]

[Chemical formula 61]

[0111]

[Chemical formula 62]

[0112]

[Chemical formula 63]

[0113]

[Chemical 64]

(Ink Composition and Inkjet Recording Ink) The use of the compound of the present invention in an inkjet system will be described. Hereinafter, the ink composition of the present invention and the ink for inkjet recording will be described in detail. The ink composition of the present invention is characterized by being an ink composition containing a dye represented by the general formula (1). The ink jet recording ink of the present invention is characterized by containing the ink composition.

The ink composition of the present invention comprises the dye of the present invention,
Alternatively, it can be prepared by dissolving and / or dispersing the dye of the present invention and the dye in an aqueous medium. In the present invention, "aqueous medium" means water, or a mixture of a small amount of a water-miscible organic solvent and water, if necessary, with addition of additives such as a wetting agent, a stabilizer, and a preservative. To do.

Suitable examples of water-miscible organic solvents that can be used in the ink composition of the present invention include alcohols, polyhydric alcohols, glycol derivatives, amines, and other polar solvents.

Among the above alcohols, for example, methanol, ethanol, propanol, isopropanol,
Butanol, isobutanol, sec-butanol, t
-Butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol are preferred.

Among the above polyhydric alcohols, for example,
Ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol,
Pentanediol, glycerin, hexanetriol,
Thiodiglycol is preferred.

Among the glycol derivatives, for example,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene Glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether and ethylene glycol monophenyl ether are preferred.

Among the above amines, for example, ethanolamine, diethanolamine, triethanolamine,
N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine and tetramethylpropylenediamine are preferred.

Among the above other polar solvents, for example,
Formamide, N, N-dimethylformamide, N, N
-Dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile and acetone are preferred. . The water-miscible organic solvent may be used alone or in combination of two or more.

The dye of the present invention and the dye which can be used in combination are
In the case of an oil-soluble dye, the ink composition can be prepared by dissolving the oil-soluble dye in a high boiling point organic solvent and emulsifying and dispersing it in an aqueous medium. The boiling point of the high-boiling organic solvent used in the present invention is 150 ° C. or higher,
It is preferably 70 ° C. or higher.

Examples of the high boiling point organic solvent include phthalic acid esters, phosphoric acid or phosphonic acid esters, benzoic acid ester acids, amides, alcohols or phenols, aliphatic esters, aniline derivatives, and chlorinated compounds. Paraffins, trimesic acid esters, dodecylbenzene, diisopropylnaphthalene, phenols,
Suitable examples include carboxylic acids and alkylphosphoric acids.

Among the phthalic acid esters, for example, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-ter).
t-amylphenyl) isophthalate, bis (1,1-
Diethylpropyl) phthalate is preferred.

Among the above phosphoric acid or phosphonic acid esters, for example, diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, dioctyl butyl phosphate, tricyclohexyl phosphate, tri-
2-Ethylhexyl phosphate, tridodecyl phosphate, di-2-ethylhexyl phenyl phosphate are preferred.

Among the benzoic acid ester acids, for example, 2-ethylhexylbenzoate, 2,4-dichlorobenzoate, dodecylbenzoate and 2-ethylhexyl-p-hydroxybenzoate are preferable.

Among the above amides, for example, N, N-
Diethyl dodecane amide and N, N-diethyl lauryl amide are preferred. Among the above alcohols or phenols, isostearyl alcohol, 2,4-di-te
Preferred is rt-amylphenol.

Among the above aliphatic esters, for example,
Dibutoxyethyl succinate, di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanoate, tributyl citrate, diethyl azelate, isostearyl lactate and trioctyl citrate are preferred.

Among the above aniline derivatives, N, N-dibutyl-2-butoxy-5-tert-octylaniline and the like are preferable. Among the chlorinated paraffins,
Paraffins having a chlorine content of 10% to 80% are preferable.

Among the trimesic acid esters, for example, tributyl trimesic acid is preferable. Among the above-mentioned phenols, for example, 2,4-di-tert-amylphenol, 4-dodecyloxyphenol, 4-dodecyloxycarbonylphenol and 4- (4-dodecyloxyphenylsulfonyl) phenol are preferable.

Among the above carboxylic acids, for example, 2-
(2,4-di-tert-amylphenoxybutyric acid, 2-
Ethoxyoctanedecanoic acid is preferred. Among the alkyl phosphoric acids, for example, di-2 (ethylhexyl) phosphoric acid, diphenyl phosphoric acid and the like are preferable.

In the present invention, the high boiling point organic solvent is 1
They may be used alone or in combination of two or more. For example, a combination of tricresyl phosphate and dibutyl phthalate, a combination of trioctyl phosphate and di (2-
Examples thereof include a combination use with ethylhexyl) sebacate and a combination use with dibutyl phthalate and poly (Nt-butyl acrylamide).

Examples of compounds other than the above-mentioned high-boiling point organic solvents used in the present invention and / or methods for synthesizing these high-boiling point organic solvents include, for example, US Pat.
No. 2,027, No. 2,533,514, No. 2,7
No. 72,163, No. 2,835,579, No. 3,
594, 171, No. 3,676, 137, No. 3,689, 271, No. 3,700, 454, No. 3,748, 141, No. 3,764, 336,
No. 3,765,897, No. 3,912,515
No. 3,936,303, No. 4,004,92
No. 8, No. 4,080,209, No. 4,127,4
No. 13, No. 4,193,802, No. 4,207,
No. 393, No. 4,220,711, No. 4,23
9,851, 4,278,757, and 4,3
53,979, 4,363,873, 4,
No. 430,421, No. 4,430,422, No. 4,464,464, No. 4,483,918, No. 4,540,657, No. 4,684,606,
No. 4,728,599, No. 4,745,049
No. 4, No. 4,935, 321, No. 5,013, 63
9, European Patent Nos. 276,319A and 286,2.
No. 53A, No. 289, 820A, No. 309, 15
No. 8A, No. 309, 159A, No. 309, 160
No. A, No. 509, 311A, No. 510, 576A
, East German Patents 147,009, 157,147
No. 159, 573, 225, 240A,
Descriptions of British Patent No. 2,091,124A, JP-A Nos. 48-47335, 50-26530 and 51-
No. 25133, No. 51-26036, No. 51-279.
No. 21, No. 51-27922, No. 51-149028
No. 52, No. 52-46816, No. 53-1520, No. 5
No. 3-1521, No. 53-15127, No. 53-14
6622, 54-91325, and 54-1062.
No. 28, No. 54-118246, No. 55-59464
No. 56, No. 56-64333, No. 56-81836, No. 59-204041, No. 61-84641, No. 62.
-118345, 62-247364, 63-
167357, 63-214744, and 63-3.
No. 01941, No. 64-9452, No. 64-9454
No. 64-68745, JP-A-1-101543.
No. 1, No. 1-202454, No. 2-792, No. 2-4
No. 239, No. 2-43541, No. 4-29237,
4-30165, 4-232946, 4-3
It is described in each publication and the like of No. 46338.

The high-boiling organic solvent is preferably used in an amount of 0.01 to 3.0 times by mass with respect to the oil-soluble dye (the dye of the present invention and the dye that can be used together).
It is more preferable to use 1 to 1.0 times the amount.

In the present invention, the oil-soluble dye and the high boiling point organic solvent are used by emulsifying and dispersing in an aqueous medium. When emulsifying and dispersing, a low boiling point organic solvent may be used depending on the case from the viewpoint of emulsifying property. The low boiling point organic solvent means an organic solvent having a boiling point of about 30 ° C. or higher and 150 ° C. or lower at normal pressure.
Suitable examples of the low boiling point organic solvent include esters, alcohols, ketones, amides, and ethers. Among the above esters, for example, ethyl acetate, butyl acetate, ethyl propionate, β-ethoxyethyl acetate, methyl cellosolve acetate are preferably used. Among the above alcohols, for example, isopropyl alcohol, n-butyl alcohol, and secondary butyl alcohol are preferably used. Among the above ketones, for example, methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone are preferably used. Among the above amides, for example, dimethylformamide and N-methylpyrrolidone are preferably used. Among the ethers, for example,
Tetrahydrofuran and dioxane are preferably used. However, the low boiling point organic solvent is not limited to the above preferred examples.

In the emulsification dispersion, a high-boiling organic solvent and, in some cases, an oil phase in which a dye is dissolved in a mixed solvent of a low-boiling organic solvent are dispersed in an aqueous phase containing water as a main component to form a fine oil phase. It is done to make oil drops. At this time, an additive such as a surfactant, a wetting agent, a dye stabilizer, an emulsion stabilizer, a preservative, an antifungal agent, etc., which will be described later, is added to either or both of the aqueous phase and the oil phase, if necessary. be able to.

As the emulsification dispersion method, a method of adding an oil phase to an aqueous phase is generally used, but a so-called phase inversion emulsification method of dropping an aqueous phase into the oil phase can also be preferably used.

In emulsifying and dispersing in the present invention, various surfactants can be used. For example, anionic compounds such as fatty acid salt, alkyl sulfate ester salt, alkyl benzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate, alkyl phosphate ester salt, naphthalene sulfonate formalin condensate, polyoxyethylene alkyl sulfate ester salt, etc. A surfactant,
Nonionics such as polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethyleneoxypropylene block copolymer Surfactants are preferred. In addition, SURFYNO which is an acetylene-based polyoxyethylene oxide surfactant
LS (Air Products & Chemicals
Company) is also preferably used. In addition, N, N-dimethyl-
Also preferred are amine oxide type amphoteric surfactants such as N-alkyl amine oxides. Furthermore, JP-A-59-1
57, 636, pages (37) to (38), Research Disclosure No. 308119 (1989
It is also possible to use those listed as the surfactants described in (Year).

Further, for the purpose of stabilizing immediately after emulsification, a water-soluble polymer may be added in combination with the above-mentioned surfactant. As the water-soluble polymer, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, polyacrylic acid, polyacrylamide and copolymers thereof are preferably used. It is also preferable to use natural water-soluble polymers such as polysaccharides, casein and gelatin. Furthermore, for the stabilization of the dye dispersion, acrylic acid esters, methacrylic acid esters, vinyl esters, acrylamides, methacrylamides, olefins, styrenes, which are substantially insoluble in an aqueous medium, Polyvinyl, polyurethane, polyester obtained by polymerization of vinyl ethers and acrylonitrile,
Polyamide, polyurea, polycarbonate, etc. can also be used together. These polymers are --SO _2- , --C
It preferably contains OO-. When using these polymers which are substantially insoluble in an aqueous medium,
It is preferably used in an amount of 20% by mass or less of the high boiling point organic solvent, and more preferably 10% by mass or less.

When an oil-soluble dye or a high-boiling organic solvent is dispersed by the emulsification dispersion method to prepare an aqueous ink, it is particularly important to control the particle size. In order to increase the color purity and density when an image is formed by inkjet, it is essential to reduce the average particle size of dispersed particles. The volume average particle size of the dispersed particles in the present invention is preferably 1 μm or less, and 5 to 100 nm.
Is more preferable.

The methods for measuring the volume average particle size and particle size distribution of the dispersed particles include static light scattering method, dynamic light scattering method, centrifugal sedimentation method, and pages 417 to 418 of Experimental Chemistry Course 4th Edition. It can be easily measured by a known method such as using the described method. For example, dilute with distilled water so that the particle concentration in the ink is 0.1 to 1% by mass,
It can be easily measured with a commercially available volume average particle size measuring device (for example, Microtrac UPA (manufactured by Nikkiso Co., Ltd.)). Further, according to the dynamic light scattering method utilizing the laser Doppler effect, the particle size can be measured up to a small size, which is particularly preferable. The volume average particle diameter is an average particle diameter weighted by particle volume, and in a set of particles, a sum of diameters of individual particles multiplied by the volume of the particles is divided by a total volume of the particles. . The volume average particle size is described in “Chemistry of Polymer Latex” (Soichi Muroi, Polymer Publishing Association), page 119.

It has also been clarified that the presence of coarse particles plays a very important role in printing performance. That is, it was found that the coarse particles clog the nozzles of the head or form stains even if the nozzles are not clogged, resulting in non-ejection of ink or misalignment of ejection, which has a serious influence on printing performance. In order to prevent this, 10 μm or less of particles having a particle size of 5 μm or more and 1 μm in 1 μl of the ink composition.
It is important to suppress the number of particles of m or more to 1000 or less. As a method for removing these coarse particles, a known centrifugation method, microfiltration method or the like can be used. These separating means may be performed immediately after the emulsification dispersion, or may be performed immediately after the addition of various additives such as a wetting agent and a surfactant to the emulsification dispersion and immediately before filling the ink cartridge.

A mechanical emulsifying device can be used as an effective means for reducing the average particle size and eliminating coarse particles. As the emulsifying device, known devices such as a simple stirrer or impeller stirring system, an in-line stirring system, a mill system such as a colloid mill, and an ultrasonic system can be used, but the use of a high pressure homogenizer is particularly preferable. The high-pressure homogenizer is described in US Pat. No. 4,533,254 and JP-A-6-4.
A detailed mechanism is described in Japanese Patent No. 7264. As a commercially available device, a Gohlin homogenizer (APV
GAULIN INC. ), A microfluidizer (MICROFLUIDEX INC.), An optimizer (Sugino Machine Co., Ltd.), etc. are mentioned.

A high pressure homogenizer having a mechanism for atomizing in an ultrahigh pressure jet stream as described in US Pat. No. 5,720,551 is particularly effective for the emulsification and dispersion of the present invention. As an example of an emulsifying device using this ultrahigh pressure jet flow, DeBEE2000 (BEE
INTERNATIONAL LTD. ) Is mentioned.

The pressure for emulsification with the high-pressure emulsifying and dispersing apparatus is 50 MPa or more, preferably 60 MPa or more, and more preferably 180 MPa or more. In the present invention, at the time of the emulsification and dispersion, it is particularly preferable to use two or more kinds of emulsification devices in combination by, for example, emulsifying and dispersing with a stirring emulsifying machine and then passing the mixture through a high-pressure homogenizer. Also preferred is a method in which after emulsifying and dispersing in one of these emulsifying apparatuses, additives such as a wetting agent and a surfactant are added, and then the cartridge is filled with the ink and then passed through a high-pressure homogenizer again.

When a low-boiling point organic solvent is used in addition to the high-boiling point organic solvent during the emulsification and dispersion, it is preferable to remove the low-boiling point organic solvent from the viewpoint of stability of the emulsion and safety and hygiene. As a method of removing the low boiling point organic solvent,
Various known methods such as an evaporation method, a vacuum evaporation method, and an ultrafiltration method can be adopted depending on the kind of the solvent. The step of removing the low boiling point organic solvent is preferably carried out as soon as possible immediately after emulsification.

When the ink composition of the present invention is used as an ink for ink jet recording, a drying inhibitor for preventing clogging due to dry operation at the ink ejection port, a penetration for allowing the ink to better penetrate the paper. Additives such as accelerators, UV absorbers, antioxidants, viscosity modifiers, surface tension modifiers, dispersants, dispersion stabilizers, antifungal agents, rust preventives, pH adjusters, defoamers and chelating agents. Can be appropriately selected and used in an appropriate amount.

As the anti-drying agent, a water-soluble organic solvent having a vapor pressure lower than that of water is preferable. As a concrete example,
For ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivative, glycerin, trimethylolpropane, etc. Representative polyhydric alcohols, lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, and triethylene glycol monoethyl (or butyl) ether, 2-pyrrolidone, Heterocycles such as N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and N-ethylmorpholine, sulfolane, dimethyl sulfoxide, 3-
Sulfur-containing compounds such as sulfolene, diacetone alcohol,
Preferable examples include polyfunctional compounds such as diethanolamine and urea derivatives. Among these, polyhydric alcohols such as glycerin and diethylene glycol are more preferable.
Further, the above anti-drying agent may be used alone,
You may use 2 or more types together. These drying inhibitors are preferably contained in the inkjet recording ink in an amount of 10 to 50% by mass.

Examples of the penetration enhancer include alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, and nonionic surfactants. Can be used. These are 10 in the ink for ink jet recording.
If it is contained in an amount of up to 30% by mass, a sufficient effect can be obtained, and it is preferable to use it within the range of the addition amount that does not cause bleeding of printing and paper drop (print through).

The ultraviolet absorber is used for improving the storability of an image, and is disclosed in, for example, JP-A-5-56.
Benzotriazole compounds described in JP-A Nos. 8-185677, 61-190537, JP-A-2-782, 5-97075, 9-34057, and the like, JP-A-46-2784 Japanese Patent Laid-Open No. 5-194843, US Pat. No. 3,214,463.
Compounds described in Japanese Patent Publication No. Sho-48
No. 30492, No. 56-21114, and the cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, and JP-A-8-53427.
JP-A-8-239368, JP-A-10-1826.
21, the triazine-based compounds described in JP-A-8-501291, Research Disclosure No. A compound which absorbs ultraviolet rays and fluoresces, which is represented by the compounds described in No. 24239 and stilbene compounds and benzoxazole compounds, that is, a so-called fluorescent brightening agent can also be used.

The antioxidant is used for the purpose of improving the storability of images, and for example, various organic type and metal complex type anti-fading agents can be used. As the organic anti-fading agent, hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromanes,
Preferable examples are alkoxyanilines and heterocycles. Examples of the metal complex-based anti-fading agent include nickel complexes and zinc complexes. Specifically, Research Disclosure No. 17643 VII I-J
Item, the same No. 15162, the same No. 18716, 650
Page left column, No. 36544, page 527, ibid. Thirty
7105, page 872, ibid. The compounds described in the patent cited in 15162 and JP-A-62-215272.
The compounds included in the general formulas and the compound examples of the typical compounds described on pages 127 to 137 of the publication can be used.

Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and salts thereof. To be These are 0.02 to 5% in the ink.
It is preferable to use 100% by mass. The details of these antifungal agents are described in "Encyclopedia of Antibacterial and Antifungal Agents" (edited by the Japan Antibacterial and Antifungal Society Encyclopedia Editorial Committee).

Examples of the rust preventive agent include acid sulfite, sodium thiosulfate, ammonium thioglycolate,
Examples thereof include diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite, and benzotriazole. These are preferably used in the ink for inkjet recording in an amount of 0.02 to 5.00% by mass.

The pH adjusting agent can be preferably used from the viewpoint of adjusting pH, imparting dispersion stability, and the like.
It is preferable to add 4.5 to 10.0,
More preferably, it is added so as to have a pH of 6 to 10.0. As the pH adjuster, basic ones such as organic bases and inorganic alkalis are preferable, and acidic ones such as organic acids and inorganic acids are preferable. In the basic pH adjusting agent,
Among the above-mentioned organic bases, triethanolamine, diethanolamine, N-methyldiethanolamine, dimethylethanolamine and the like are more preferable, and among the above-mentioned inorganic alkalis, alkali metal hydroxides, carbonates, ammonia and the like are more preferable. Among the alkali metal hydroxides, for example, sodium hydroxide, lithium hydroxide, potassium hydroxide and the like are particularly preferable, and among the carbonates, sodium carbonate, sodium hydrogencarbonate and the like are particularly preferable. In the acidic pH adjuster, acetic acid, propionic acid, trifluoroacetic acid, alkylsulfonic acid and the like are preferable among the organic acids, and hydrochloric acid, sulfuric acid, phosphoric acid and the like are more preferable among the inorganic acids.

Various surface active agents may be used as the surface tension adjusting agent. For example, fatty acid salt, alkyl sulfate salt, alkylbenzene sulfonate,
Anionic surfactants such as alkyl naphthalene sulfonate, dialkyl sulfosuccinate, alkyl phosphate ester salt, naphthalene sulfonate formalin condensate, polyoxyethylene alkyl sulfate ester salt, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl Nonionic surfactants such as ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, glycerin fatty acid esters, oxyethyleneoxypropylene block copolymers, and acetylene polyoxyethylene oxide. SURFYNOLS (AirPro)
Ducts & Chemicals), amine oxide type amphoteric surfactants such as N, N-dimethyl-N-alkylamine oxide, and JP-A-59-157,6.
No. 36, pages (37) to (38), Research Disclosure No. Suitable examples thereof include the surfactants described in 308119 (1989). The surface tension of the inkjet recording ink of the present invention is 20 to 6
0 mN / m is preferable, and 25 to 45 mN / m is more preferable.

The viscosity adjusting agent may be used for the purpose of adjusting the viscosity of the ink for ink jet recording.
Examples of the viscosity modifier include water-soluble polymers such as celluloses and polyvinyl alcohol, nonionic surfactants, and the like. For more details, Chapter 9 of "Viscosity Control Technology" (Technical Information Institute, 1999) and "Chemicals for Inkjet Printers (Supplement to 98) -Development Trends and Prospect Survey of Materials-" (CMC, 1997)
Pp. 162-174. The viscosity of the inkjet recording ink used in the present invention is as follows.
30 mPa · s or less is preferable, and 20 mPa · s or less is more preferable.

Further, in the ink jet recording ink of the present invention, as the dispersant and the dispersion stabilizer, the above-mentioned cation,
Anionic and nonionic surfactants, defoaming agents such as fluorine-based compounds, silicone-based compounds, and chelating agents typified by EDTA can also be used as necessary.

(Inkjet recording method) Next, the inkjet recording method of the present invention will be described. The inkjet recording method of the present invention is characterized in that recording is performed on an image receiving material having an ink receiving layer containing a white pigment on a support, using the inkjet recording ink containing the ink composition. To do. In the inkjet recording method of the present invention, recording is performed on the image receiving material using an inkjet recording ink containing the ink composition, but there is no particular limitation on the ink nozzles or the like used at that time. It can be selected as appropriate.

The following recording paper and recording film are preferable as the image receiving material in the ink jet recording method of the present invention. A preferable recording paper and recording film are formed by laminating a support and an ink receiving layer, and if necessary, laminating other layers such as a back coat layer. Each layer including the ink receiving layer may be one layer or two or more layers.

The support may be LBKP or NBKP.
Chemical pulp such as GP, PGW, RMP, TMP, CT
MP, CMP, CGP, etc. mechanical pulp, DIP, etc. waste paper pulp, etc.
It is possible to use those produced by mixing additives such as a binder, a sizing agent, a fixing agent, a cationic agent, and a paper strength enhancer, and manufactured by various devices such as a Fourdrinier paper machine and a cylinder paper machine. Other than these, synthetic paper, plastic film sheet, etc. may be used.

The thickness of the support is from 10 to 250.
It is about μm, and the basis weight is preferably 10 to 250 g / m ² .

An ink receiving layer and a back coat layer may be directly provided on the support as an image receiving material, or a size press or an anchor coat layer may be provided with starch, polyvinyl alcohol or the like, and then the ink receiving layer and the back coat layer may be provided. A layer may be provided to serve as an image receiving material. The support may be flattened by a calendar device such as a machine calendar, a TG calendar, a soft calendar or the like.

Among the above-mentioned supports, polyolefin (eg, polyethylene, polystyrene, polyethylene terephthalate, polybutene and their copolymers) is used on both sides.
The paper and plastic film laminated with are 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 has a porous material, an aqueous binder, a mordant, a water-proofing agent,
A light resistance improver, a surfactant, a hardener, and other additives are contained. Further, the ink receiving layer preferably contains a pigment as a porous material.

As the above-mentioned 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, Suitable examples include inorganic white pigments such as lithopone, zeolite, 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. Among these white pigments,
Porous white inorganic pigments are preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, either silicic anhydride obtained by a dry production method or hydrous silicic acid obtained by a wet production method can be used, but it is particularly preferable to use hydrous silicic acid. These pigments may be used alone or in combination of two or more.

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. Examples thereof include water-soluble polymers such as derivatives, water-dispersible polymers such as styrene-butadiene latex and acrylic emulsion. These aqueous binders may be used alone or in combination of two or more. Among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable from the viewpoint of adhesion to the pigment and peeling resistance of the ink receiving layer.

The mordant is preferably immobilized. For that purpose, a polymer mordant is preferably used. The polymer mordant is described in JP-A-48-
No. 28325, No. 54-74430, No. 54-124
No. 726, No. 55-22766, No. 55-14233.
No. 9, No. 60-23850, No. 60-23851,
No. 60-23852, No. 60-23853, No. 60
-57836, 60-60643, 60-11
8834, 60-122940, 60-122
No. 941, No. 60-122942, No. 60-2351.
34, JP-A-1-161236, U.S. Pat. Nos. 2,484,430, 2,548,564, and 31,480.
No. 61, No. 3309690, No. 4115124, No. 4124386, No. 4193800, No. 42738.
No. 53, No. 4282305, and No. 4450224. The polymer mordants described on pages 212 to 215 of JP-A-1-161236 are particularly preferable. By using the polymer mordant described in the publication, 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 the image water-proof, and a cationic resin is preferable. Examples of the cationic resin include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide, and colloidal silica. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable. The content of the cationic resin is preferably 1 to 15% by mass and more preferably 3 to 10% by mass based on the total solid content of the ink receiving layer.

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

The surface active agent functions as a coating aid, a peeling property improving agent, a sliding property improving agent or an antistatic agent. Regarding the above-mentioned surfactant, JP-A-62-1734
No. 63 and No. 62-183457 are mentioned. An organic fluoro compound may be used instead of the surfactant. The organic fluoro compound is
It is preferably hydrophobic. Examples of the organic fluoro compound include a fluorine-based surfactant, an oily fluorine-based compound (eg, fluorine oil) and a solid fluorine compound resin (eg, tetrafluoroethylene resin). Regarding the organic fluoro compound, JP-B-57-9053 (columns 8 to 17), JP-A-61-20994, and JP-A-62-20994.
It is described in each publication of -135826.

As the above-mentioned hardener, JP-A-1-1612 is used.
The materials described on page 222 of Japanese Patent No. 36 can be used.

Examples of the other additives include pigment dispersants, thickeners, defoamers, dyes, optical brighteners, preservatives and pH.
Examples include regulators, matting agents, and hardeners. 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 which 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, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudo-boehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrohaloysite, magnesium carbonate, magnesium hydroxide, etc. Examples thereof include white inorganic pigments, styrene plastic pigments, acrylic plastic pigments, polyethylene, microcapsules, organic pigments such as urea resins and melamine resins.

As the aqueous binder contained in the back coat layer, styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch,
Examples thereof include water-soluble polymers such as cationized starch, casein, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose and polyvinyl pyrrolidone, 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 whitening agent, a preservative, and a water resistance agent.

A polymer fine particle dispersion may be added to the constituent layers (including the back layer) of the recording paper and the recording film. The polymer fine particle dispersion is used for the purpose of improving physical properties of the film such as dimensional stabilization, curl prevention, adhesion prevention, and film cracking prevention. For the polymer fine particle dispersion, see JP-A Nos. 62-245258 and 62-1.
It is described in each publication of No. 36648 and No. 62-110066. The glass transition temperature is low (40 ° C or lower)
When the polymer fine particle dispersion is added to the layer containing the mordant, cracking or curling of the layer can be prevented.
Curling can also be prevented by adding a polymer fine particle dispersion having a high glass transition temperature to the back layer.

The ink jet recording system of the present invention includes:
There is no particular limitation, and known methods such as a charge control method that discharges ink by using electrostatic attraction, a drop-on-demand method (pressure pulse method) that uses the oscillating pressure of a piezo element, and an acoustic signal as an acoustic beam are used. The acoustic inkjet method of irradiating the ink and discharging the ink by using the radiation pressure, and the thermal inkjet (bubble jet (R)) method of heating the ink to form bubbles and utilizing the generated pressure Either may be used. The ink jet recording method is a method of ejecting a large number of low density ink 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 method. A method using ink is included.

(Thermal Transfer Dye) The above general formula (1) of the present invention.
The dye represented by the following is preferably contained in the thermal transfer dye-providing material and used for thermal transfer recording. When the dye of the present invention is used in a thermal transfer recording system, the dye is referred to as "thermal transfer dye". The thermal transfer dye will be described below. The thermal transfer dye-providing material is preferably contained in the thermal transfer dye-providing material, and the thermal transfer dye-providing material can be used in the form of a sheet or a continuous roll or ribbon. The thermal transfer dye-donor element has a support and a dye-donor layer.

In the thermal transfer dye-donor element, each dye is
Usually, they are arranged on the support so as to form independent regions. For example, each dye area is arranged on one support in a frame-sequential or line-sequential manner. It is also possible to prepare a thermal transfer dye-donor material in which each dye is provided on a separate support, and then perform thermal transfer of the dye to one thermal transfer image-receiving material in sequence.

The thermal transfer dyes are preferably dissolved or dispersed in a suitable solvent together with the binder resin and applied on the support, or printed on the support by a printing method such as a gravure method. The thickness of the dye-donor layer containing the dye is preferably set to a dry film thickness of usually about 0.2 to 5 μm, and particularly preferably set to 0.4 to 2 μm. The coating amount of the thermal transfer dye is preferably 0.03 to 1 g / m ² , and 0.1 to 0.
6 g / m ² is more preferable.

As the binder resin, any binder resin conventionally known for such purpose can be used. Usually, it has a high heat resistance and does not hinder the migration of the dye when heated. Is selected. For example, polyamide-based resin, polyester-based resin, epoxy-based resin, polyurethane-based resin, polyacrylic-based resin (for example, polymethylmethacrylate, polyacrylamide, polystyrene-2-acrylonitrile), vinyl-based resin such as polyvinylpyrrolidone, poly Vinyl chloride resin (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 pro Pionate, cellulose acetate butyrate, cellulose triacetate), polyvinyl alcohol-based resin (for example, polyvinyl alcohol, polyvinyl alcohol) Vinyl acetal, partially saponified polyvinyl alcohol such as polyvinyl butyral), petroleum resins, rosin derivatives, coumarone - indene resins, terpene resins, polyolefin resins (e.g., polyethylene, polypropylene), etc. are preferably used. The binder resin in the present invention is, for example, a dye 100
It is preferably used in a ratio of about 20 to 600 parts by mass per part by mass. As the ink solvent used for dissolving or dispersing the dye and the binder resin in the present invention, any conventionally known ink solvent can be used.

As the support for the thermal transfer dye-donating material, any conventionally known one can be used. For example, polyethylene terephthalate; polyamide; polycarbonate; glassine paper; condenser paper; cellulose ester; fluoropolymer; polyether; polyacetal; polyolefin; polyimide; polyphenylene sulfide; polypropylene; polysulfone; cellophane and the like. The thickness of the support of the thermal transfer dye-donor element is generally 2 to 30 μm. An undercoat layer may be provided on the support, if desired. Further, a dye diffusion preventing layer made of a hydrophilic polymer may be provided between the support and the dye donating layer. This further improves the transfer density. As the hydrophilic polymer, the above water-soluble polymer can be used. Further, a slipping layer may be provided to prevent the thermal head from sticking to the dye-donor element. The slipping layer is composed of a lubricant material with or without a polymeric binder, such as a surfactant, a solid or liquid lubricant, or a mixture thereof.

The thermal transfer dye-providing material is subjected to a sticking-preventing treatment on the side of the support on which the dye-donating layer is not provided, in order to prevent sticking due to the heat of the thermal head when printing from the back side and to improve slippage. Is good. For example, (1) a reaction product of a polyvinyl butyral resin and an isocyanate, (2) an alkali metal salt or an alkaline earth metal salt of a phosphoric acid ester, and (3) a heat-resistant slip layer mainly containing a filler are provided. Is good. The polyvinyl butyral resin has a molecular weight of 60,000-2.
It is preferably about 100,000, having a glass transition point of 80 to 110 ° C., and having a mass% of vinyl butyral portion of 15 to 40% from the viewpoint of many reaction sites with isocyanate. Examples of the alkali metal salt or alkaline earth metal salt of the phosphoric acid ester include Gafac RD7 manufactured by Toho Kagaku.
20 or the like is used, and it may be used in an amount of 1 to 50% by mass, preferably 10 to 40% by mass, based on the polyvinyl butyral resin. The heat-resistant slip layer is preferably accompanied by heat resistance in the lower layer, a combination of a synthetic resin that can be cured by heating and its curing agent, for example, polyvinyl butyral and polyvalent isocyanate, acrylic polyol and polyvalent isocyanate, cellulose acetate and titanium. A chelating agent or a combination of polyester and an organic titanium compound may be provided by coating.

The thermal transfer dye-providing material may be provided with a hydrophilic dye barrier layer in order to prevent the dye from diffusing toward the support. The hydrophilic dye barrier layer preferably contains a hydrophilic substance useful for the intended purpose. Generally, gelatin, poly (acrylamide), poly (isopropylacrylamide), butyl methacrylate graft gelatin, ethyl methacrylate graft gelatin, cellulose monoacetate, methyl cellulose, poly (vinyl alcohol), poly (ethyleneimine), poly (acrylic acid) ), A mixture of poly (vinyl alcohol) and poly (vinyl acetate), a mixture of poly (vinyl alcohol) and poly (acrylic acid), or a mixture of cellulose monoacetate and poly (acrylic acid). The result is obtained. Among them, poly (acrylic acid), cellulose monoacetate, or poly (vinyl alcohol) is particularly preferable.

The thermal transfer dye-providing material may be provided with an undercoat layer. The undercoat layer may be any undercoat layer as long as it has a desired function, and preferable specific examples include the following. That is, (acrylonitrile-vinylidene chloride-acrylic acid) copolymer (mass ratio 14: 8
0: 6), (butyl acrylate--2-aminoethyl methacrylate--2-hydroxyethyl methacrylate) copolymer (mass ratio 30:20:50), linear / saturated polyester such as Bostik 7650 (Mhart). , Bostik Chemical Group) or chlorinated high density poly (ethylene-trichloroethylene) resin. There is no particular limitation on the coating amount of the undercoat layer,
It is usually used in an amount of 0.1 to 2.0 g / m ² .

In thermal transfer, a thermal transfer dye-providing material is superposed on a thermal transfer image-receiving material, and heat energy corresponding to image information is applied from either side, preferably from the back side of the thermal transfer dye-providing material, by heating means such as a thermal head. By giving the dye, the dye in the dye-donor layer can be applied to the thermal transfer image-receiving material according to the amount of heating energy, and a color image having excellent sharpness and resolution gradation can be obtained. Further, an anti-fading agent can be similarly transferred.

The heating means is not limited to the thermal head, but a known means such as a laser beam (for example, a semiconductor laser) infrared flash and a heating pen can be used. In laser-based systems, the thermal transfer dye-donor material preferably contains an absorbing material that strongly absorbs the laser beam. Examples of the absorbent material include US Pat. No. 4,973,572.
No. 4948777, No. 4948778, No. 49
No. 48776, No. 4942141, No. 4952552
No. 5035040, 4912083, 61
Carbon black described in each specification such as 97474,
Infrared absorbing cyanine dyes and the like are preferable. When the thermal transfer dye-providing material is irradiated with a laser beam, the absorbing material converts light energy into heat energy and immediately transfers the heat to a nearby dye, whereby heat for transferring the dye to the image receiving material. It is heated to the transition temperature. The absorptive material is preferably present below the dye in a layered state and / or in a mixed state with the dye. The laser beam is modulated with an electrical signal that represents the shape and color of the original image, heating only the areas of the dye that need to be present on the thermal transfer dye-donor material to reconstruct the original target color and transferring heat. . For a more detailed description of this process, see British Patent 2,0.
83,726A. The absorbing material disclosed in British Patent 2,083,726A for its laser system is carbon. In the present invention, the thermal transfer dye-providing material is used in combination with a thermal transfer image-receiving material to perform printing using various printers of thermal printing method, facsimile, or magnetic recording method, print creation of image by optical recording method, television, C
It can be used to create prints from the RT screen. For details of the thermal transfer recording method, reference can be made to JP-A-60-34895.

A preferred embodiment of the thermal transfer dye-providing material is a thermal transfer dye-providing material comprising a polyethylene terephthalate support coated with the thermal transfer dye.
A transfer image is formed by performing the above steps. Thermal Transfer Dye Thermal transfer of dye from dye-donor material to image-receiving material involves the use of an ion gas laser such as argon or krypton,
Metal vapor lasers such as copper, gold and cadmium, solid state lasers such as ruby and YAG, or 750-870nm
Several lasers can be used, such as semiconductor lasers such as gallium-arsenide, which emit in the infrared region of. 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 above-mentioned thermal transfer dye-providing material is a support provided with an image-receiving layer for receiving the dye transferred from the thermal transfer dye-providing material. The image-receiving layer receives a heat-transferable dye that migrates from the heat-transfer dye-providing material during printing, and a substance capable of receiving the heat-transferable dye having a function of dyeing the heat-transferable dye, It is preferable that it is a coating having a thickness of about 0.5 to 50 μm, which is contained alone or together with other binder substances.

The following resins can be given as typical examples of the polymer which can receive the heat transferable dye. (A) As those having an ester bond, dicarboxylic acid components such as terephthalic acid, isophthalic acid, and succinic acid (these dicarboxylic acid components may be substituted with a sulfo group or a carboxyl group) and ethylene glycol, Propylene glycol, neopentyl glycol,
Polyester resin obtained by condensation of bisphenol A and the like: polyacrylic acid ester resin or polymethacrylic acid ester resin such as polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate and polybutyl acrylate: polycarbonate resin: polyvinyl acetate resin: styrene acrylate Resin: Vinyltoluene acrylate resin and the like can be mentioned. In particular,
JP-A-59-101395, 63-7971, 63-7972, 63-9733, 60-29.
Those described in each publication of No. 4862 can be mentioned. As a commercially available product, Byron 290 manufactured by Toyobo,
Byron 200, Byron 280, Byron 300, Byron 103, Byron GK-140, Byron GK-
130, ATR-2009, ATR-2010 made by Kao
Etc. can be used.

(B) Examples of those having a urethane bond include polyurethane resins. (C) As the resin having an amide bond, a polyamide resin and the like can be mentioned. (D) Examples of those having a urea bond include urea resins. (E) Examples of those having a sulfone bond include polysulfone resins. (F) Others having a highly polar bond include:
Examples thereof include polycaprolactone resin, styrene-maleic anhydride resin, and polyacrylonitrile resin.

In addition to the above-mentioned synthetic resin, a mixture or copolymer of these can be used. In addition, JP-A 1-188
The basic compounds and / or mordants described in Japanese Patent No. 391 and Japanese Patent No. 3-83685 can also be used. In particular, the compound having a p-hydroxy group in Ar in the dye of the present invention is a so-called dissociative dye, and therefore it is preferable to form an image in the image receiving layer in the presence of a basic compound and / or a mordant. (Hereinafter, the basic compound and the mordant may be referred to as "dye fixing agent".)

The dye fixing agent has a compound having a primary to tertiary amino group (more preferably a compound having a tertiary amino group), a compound having a nitrogen-containing heterocyclic group, and a quaternary cation group. Compounds are preferred. Among these, polymer dye fixing agents are particularly preferable. Examples of the polymer dye fixing agent include polymers containing a repeating unit represented by the following general formula (A).

[0194]

[Chemical 65]

In the above general formula (A), a ₁ represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 4 carbon atoms. D ₁ represents a divalent group connecting a carbon atom and D ₂ . D ₂ is a tertiary amino group, a nitrogen-containing heterocyclic group,
Alternatively, it represents a quaternary cation group.

The a ₁ is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.), a cyano group, or an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group). Groups, etc.) are preferred, and of these, a hydrogen atom and a methyl group are more preferred.

The above D ₁ is -OCO-, -COO
_{-, - (CH 2) V} -, - SO 2 -, - COO- (CH 2)
_{V -, - OCO- (CH 2} ) V -, - O -, - CONH
_{-, - CON (R 1)} -, - SO 2 N (R 1) -, - CO
NHCONH -, - CONHCOO-, or -C ₆ H ₄ -
In group, or configured based a combination thereof are preferred are represented, -OCO -, - OCO- (CH 2) V -, -
_{COO- (CH 2) v -,} - CH 2 - or -C ₆ H ₄ -CH ₂
-Is more preferable. The V represents an integer of 1 to 3. Wherein R ₁ has the same meaning as R ₁ in the general formula (1).
Wherein D ₁ is -C ₆ H ₄ - When referring to a benzene ring may have a substituent. As the substituent, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg,
Preferable examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a chloromethyl group, a methoxymethyl group and the like), an alkoxy group (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like).

The D₂Is a tertiary amino group,
N (D₃) D_FourIs preferred. D₃And D _FourAre each independently
R in the general formula (1)₁Is synonymous with. The D₃When
D_FourAnd may form a ring structure. As the ring structure
Is a 5- or 6-membered ring which may contain oxygen, nitrogen or sulfur
Is preferred. The D₃And D_FourAs each independently, charcoal
An alkyl group having a prime number of 1 to 6 or a benzyl group is preferable.
The D₂Represents a nitrogen-containing heterocyclic group, the nitrogen-containing heterocyclic group
The group is preferably an imidazole group or a pyridyl group.
However, these may have a substituent. As the substituent
R in the general formula (1)₁And a substituent synonymous with
Can be mentioned. The D₂Is a quaternary cation group,
A quaternary ammonium group and a quaternary imidazole group are preferred.
The D₂Is a quaternary ammonium group, the following general
The group represented by formula (B) is preferred.

[0199]

[Chemical formula 66]

In the general formula (B), D ₅ , D ₆ and D ₇ each independently have the same meaning as R ₁ in the general formula (1). D ₅ and D ₆ , D ₆ and D ₇ , and D ₅ and D ₇ may form a ring structure, and the ring structure has the same meaning as the ring structure formed by D ₃ and D ₄ . M represents an anion that neutralizes the cation charge in the substituent. The anion may be either an inorganic anion or an organic anion, and is preferably a perchlorate ion, an iodine ion, a bromine ion, or a substituted aryl sulfonate ion (for example, p-toluene sulfonate ion). .. D ₅ , D ₆ and D ₇ are each independently preferably an alkyl group having 1 to 6 carbon atoms or a benzyl group.

When D ₂ represents a quaternary imidazole group, a group represented by the following general formula (C) is preferable.

[0202]

[Chemical formula 67]

In the general formula (C), D ₈ has the same meaning as R ₁ in the general formula (1). M has the same meaning as M in the general formula (B). The D ₈ is preferably a substituted or unsubstituted alkyl group. In the general formula (C), Ra, Rb and Rc are each independently
Hydrogen atom, alkyl group having 1 to 20 carbon atoms or 6 to carbon atoms
20 represents the aryl group.

The repeating unit (polymer component) represented by the general formula (A) is contained in the polymer in an amount of 10 mol% to 100 mol%. Further, as the other polymer component that may be contained in the polymer together with the polymer component represented by the general formula (A), copolymerization with the polymer component represented by the general formula (A) and other repeating Any monomer may be used as long as it can serve as a unit. As the other polymer component, vinyl compounds are preferable, and more specifically, methacrylic acid esters, acrylic acid esters, styrenes, heterocyclic vinyls and the like can be mentioned. These other monomers are used within the range of not more than 90 mol% in the total polymer components of the polymer dye fixing agent. The repeating unit represented by the general formula (A) and the other polymer component may be present in the polymer in any of a random form and a block form.

Specific representative examples of the polymer dye fixing agent used in the present invention are shown below, but the invention is not limited thereto.

When D ₂ in the general formula (A) is a nitrogen-containing heterocyclic group, an imidazole group and a pyridyl group are preferable, and the following specific examples are given. Specific examples of homopolymers and copolymers containing a vinyl monomer unit having a tertiary imidazole group include US Pat.
No. 2,305, No. 4,115,124, No. 3,1
48,061, JP-A-60-118834, 60
The dye fixing agents described in JP-A-122941, JP-A-62-244043, JP-A-62-244036 and the like can be mentioned. Preferred specific examples of homopolymers and copolymers containing a vinyl monomer unit having a quaternary imidazolium salt include British Patent No. 2,056,101,
No. 2,093,041 and No. 1,594,961
U.S. Pat. Nos. 4,124,386 and 4,11
No. 5,124, No. 4,273,853, No. 4,4
50,224, dye fixing agents described in JP-A-48-28325 and the like. Other preferable specific examples of homopolymers and copolymers containing a vinyl monomer unit having a quaternary ammonium salt include U.S. Pat. Nos. 3,709,690 and 3,898,088.
No. 3,958,995, JP-A-60-57836.
No. 60, No. 60-60643, No. 60-122940,
Examples thereof include dye fixing agents described in JP-A Nos. 60-122942 and 60-235134.

The molecular weight of the polymer dye fixing agent in the present invention is preferably 1 × 10 ³ to 1 × 10 ⁶ , and 1 × 1.
Especially preferred is 0 ^{4 to} 2 × 10 ⁵ . The polymer dye fixing agent can also form the image receiving layer by itself. It can also be used as a mixture with the synthetic resin described below. The coating amount of the polymer dye fixing agent is 0.2 to 30.
preferably ^{g / m 2, 0.5~15g / m} 2 is more preferable. The Tg of the polymer dye fixing agent is 0 to 12
0 degreeC is preferable and 30-70 degreeC is more preferable. Also,
The polymer dye fixing agent is preferably a polymer having a tertiary amino group, and more preferably a polymer having a tertiary amino group as a pendant. The polymer dye fixing agent is preferably easily soluble in an organic solvent containing substantially no water. As the organic solvent,
Toluene, xylene, methylene chloride, chloroform dichloroethane, hexane, pentane, acetone, cyclohexane, methyl ethyl ketone, ethyl acetate, butyl acetate, dimethylacetamide, dimethylformamide, methanol, ethanol, isopropanol, acetonitrile, propionitrile, terrahydrofuran, diethyl ether And so on.

The most preferable polymer dye fixing agent is a derivative of polyvinyl alcohol having a tertiary amino group as a pendant. The mixing ratio in the case of mixing with a synthetic resin can be easily determined by those skilled in the art according to the type and composition of the polymer dye fixing agent and the image forming process to be applied. It is preferable to use a synthetic resin ratio of 10/90 to 100/0. The synthetic resin may be any one that can accept the dye transferred from the transfer sheet, and specifically, the synthetic resins (a) to (f) described above are used.

In the thermal transfer image-receiving material, particularly in the image-receiving layer, a high-boiling organic solvent or a thermal solvent can be contained as a substance capable of receiving the heat transferable dye or as a dye diffusing agent. Specific examples of the high boiling point organic solvent and the thermal solvent include JP-A Nos. 62-174754 and 62-245.
253, 61-209444, 61-2005.
No. 38, No. 62-8145, No. 62-9348, No. 62-30247, No. 62-136646 can be mentioned.

The image-receiving layer of the thermal transfer image-receiving material may have a structure in which a substance capable of receiving the heat transferable dye is dispersed and carried in a water-soluble binder. As the water-soluble binder used in this case, various known water-soluble polymers can be used, and water-soluble polymers having a group capable of undergoing a crosslinking reaction by a hardening agent are preferable. The image receiving layer may be composed of two or more layers. When it is composed of two or more layers, a synthetic resin having a low glass transition point is used for the layer closer to the support, or a high boiling organic solvent or a thermal solvent is used to enhance the dyeing property to the dye. In the outermost layer, a synthetic resin having a higher glass transition point is used, or the amount of high-boiling organic solvent or thermal solvent used is minimized or not used, and surface stickiness, adhesion with other substances, It is desirable to have a structure that prevents failures such as retransfer to another substance after transfer and blocking with a thermal transfer dye-donating material. The total thickness of the image receiving layer is preferably in the range of 0.5 to 50 μm, and 3 to 3
The range of 0 μm is particularly preferable. In the case of a two-layer structure, the outermost layer is preferably in the range of 0.1 to 2 μm, 0.2
It is particularly preferable to be in the range of ˜1 μm.

The thermal transfer image-receiving material may have an intermediate layer between the support and the image-receiving layer. The intermediate layer is any one of a cushion layer, a porous layer, and a dye diffusion preventing layer or a layer having two or more functions of these, depending on the constituent material, and may also serve as an adhesive in some cases. The dye diffusion-preventing layer particularly serves to prevent the heat transferable dye from diffusing into the support. The binder constituting the diffusion prevention layer may be water-soluble or organic solvent-soluble, but a water-soluble binder is preferable. As a specific example thereof, the water-soluble binders mentioned above as the binder of the image receiving layer, particularly gelatin are preferable. The porous layer is a layer which prevents the heat applied during the thermal transfer from diffusing from the image receiving layer to the support and plays a role of effectively utilizing the applied heat.

The image receiving layer, cushion layer, porous layer, diffusion preventing layer, adhesive layer, etc. constituting the thermal transfer image receiving material are silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate. Fine powders of synthetic zeolite, zinc oxide, lithobon, titanium oxide, alumina, etc. may be contained.

The support used for the thermal transfer image-receiving material can withstand the transfer temperature and has smoothness, whiteness, slipperiness, and
Any material can be used as long as it satisfies the requirements in terms of friction properties, antistatic properties, and dents after transfer.
Examples of the support include synthetic paper (synthetic paper such as polyolefin-based or polystyrene-based), high-quality paper, art paper, coated paper, cast-coated paper, wallpaper, backing paper, synthetic resin or emulsion-impregnated paper, synthetic rubber latex. Paper support such as impregnated paper, synthetic resin internal paper, paperboard, cellulose fiber paper, polyolefin coated paper (paper coated on both sides with polyethylene), polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, methacrylate, polycarbonate, etc. Various plastic films or sheets and films or sheets treated to give white reflectivity to this plastic can be used. Further, a laminated body formed by any combination of the above can also be used.

A fluorescent brightening agent may be used in the thermal transfer image-receiving material. As an example, K. Vevnkatara
man edition “The Chemistry of Syn
thematic Dyes "Vol. 5, Chapter 8, JP-A-61-
The compounds described in Japanese Patent No. 143752 and the like can be mentioned. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds, 2,5-dibenzoxazolethiophene compounds, etc. Can be mentioned. The fluorescent whitening agent can be used in combination with an anti-fading agent.

In order to improve the releasability of the thermal transfer dye-donor material and the thermal transfer image-receiving material, in the layers constituting the dye-donor material and / or the image-receiving material, in particular, the outermost layer corresponding to the contact surface of both materials is used. It is preferable to include a release agent. Examples of the release agent include solid substances such as polyethylene wax, amide wax, and Teflon (R) powder, or wax-like substances: Fluorine-based and phosphoric ester-based surfactants: Paraffin-based, silicone-based, and fluorine-based oils Any conventionally known release agent can be used, but silicone oil is particularly preferable. As the silicone oil, in addition to non-modified silicone oil, modified silicone oil such as carboxy-modified, amino-modified or epoxy-modified can be used. Examples thereof include various modified silicone oils described on pages 6 to 18B of "Modified Silicone Oil" technical data issued by Shin-Etsu Silicone Co., Ltd. When used in an organic solvent-based binder, when an amino-modified silicone oil having a group capable of reacting with a crosslinking agent of the binder (for example, a group capable of reacting with an isocyanate) is also emulsified and dispersed in a water-soluble binder. Is effectively a carboxy-modified silicone oil (for example, Shin-Etsu Silicone Co., Ltd .: trade name X-22-3710).

The layers constituting the thermal transfer dye-donating material and the thermal transfer image-receiving material may be hardened with a hardener. When the organic solvent-based polymer is cured, the hardeners described in JP-A Nos. 61-199997 and 58-215398 can be used. For polyester resins, the use of isocyanate hardeners is particularly preferred. For curing the water-soluble polymer, U.S. Pat. No. 4,678,739, column 41, JP-A-59 is used.
-116655, 62-245261, 61-
The hardeners described in each publication of 18942 are suitable for use. More specifically, aldehyde type hardener (formaldehyde etc.), aziridine type hardener, epoxy type hardener, vinyl sulfone type hardener (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-
Examples thereof include methylol type hardeners (dimethylolurea etc.) and polymer hardeners (compounds described in JP-A-62-234157).

An anti-fading agent may be used in the thermal transfer dye donating material and the thermal transfer image receiving material. As the anti-fading agent, the above-mentioned compounds can be used.

In the constituent layers of the thermal transfer dye-donor material and the thermal transfer image-receiving material, various surfactants may be used for the purpose of coating aid, improvement of releasability, improvement of slipperiness, prevention of electrification, acceleration of development and the like. it can. For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol alkyl ethers, polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, silicones Non-ionic surfactants such as poly (ethylene oxide adducts), glycidol derivatives (eg, alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars: alkylcarboxylic acid salts, Alkyl sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates, - acyl -
N-alkyl taurines, sulfosuccinates,
Anionic surfactants containing carboxy groups such as sulfoalkyl polyethylene alkyl phenyl ethers and polyoxyethylene alkyl phosphates, and acidic groups such as sulfo groups, phospho groups, sulfate ester groups and phosphate ester groups: amino acids, amino Double-sided surfactants such as alkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkyl betaines, amine oxides: alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, heterocycles such as viridinium and imidazolium Cationic surfactants such as quaternary ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used. Specific examples of these are disclosed in JP-A-62-173463 and JP-A-62-1834.
No. 57, etc. Further, when dispersing a substance capable of receiving a heat transferable dye, a release agent, an anti-fading agent, an ultraviolet absorber, a fluorescent brightening agent and other hydrophobic compounds in a water-soluble binder, an interface as a dispersion aid is obtained. Preference is given to using activators. For this purpose, in addition to the above-mentioned surfactants, the compounds described in JP-A-59-157636, 37-
The surfactants described on page 38 are particularly preferably used.

The constituent layers of the thermal transfer dye-donor material and the thermal transfer image-receiving material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification and improving releasability. As a typical example of the organic fluoro compound, Japanese Patent Publication No. 57-90
No. 53, columns 8 to 17, JP-A Nos. 61-20944 and 6;
Fluorine-based surfactants described in JP-A No. 2-135826, or oily fluorine-based compounds such as fluorine oil or hydrophobic fluorine compounds such as solid fluorine compound resins such as tetrafluoroethylene resin. To be

A matting agent can be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. Examples of the matting agent include silicon dioxide, polyolefin, and polymethacrylate. JP-A-61-88256 (2)
In addition to the compounds described in page 9), benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like are disclosed in JP-A-63-274944 and 63-274952.
There are compounds described in each publication of the publication.

The compound represented by the general formula (1) of the present invention is represented by a silver halide color photographic light-sensitive material using a dye-donor compound (for example, an instant color light-sensitive material typified by a photorama system, pictrography). Heat-developable color photosensitive material). When it is used in these light-sensitive materials, it is disclosed in JP-A-2000-2000.
The techniques described in JP-A-330249, JP-A-2000-56441, and JP-A-10-142764 can be used respectively.

[0222]

EXAMPLES Example 1 Synthesis of Exemplified Compound <Synthesis of Exemplified Compound (2) -2> Compound (2) -2 described above as an exemplary compound was synthesized by the following method. 7. 3-tert-butyl-5-cyanomethyl-1,2,4-triazole which can be synthesized by a conventional method from cyano-substituted iminoethyl acetate obtained by reacting malononitrile and hydrogen chloride gas in ethanol, and pivaloyl hydrazide 20 g (0.05 mol) was dissolved in 20 ml of THF, 7.60 g (0.05 mol) of DBU was added, and further 13.9 g (0.0) of 4'-bromophenacyl bromide.
(5 mol) was added, and the mixture was stirred at room temperature for 2 hours. Ethyl acetate and water were added to this, liquid separation, washing with water and concentration were performed, and the obtained oily substance was purified by silica gel column chromatography (hexane / ethyl acetate = 3/1) to give 1- (4′-
2.75 g of bromophenacyl) -3-tert-butyl-5-cyanomethyl-1,2,4-triazole was obtained as an oil (yield 15%). Next, this oily substance was dissolved in 20 ml of tert-butanol, 1.00 g of potassium tert-butoxide was added, and the mixture was heated under reflux for 15 minutes. After returning to room temperature, ethyl acetate and dilute hydrochloric acid water were added, liquid separation and water washing were performed, and the organic solvent was distilled off, followed by crystallization with ethyl acetate / hexane to give 2-tert-butyl-6-
(4-Bromophenyl) -7-cyano-1H-pyrrolo [1,2-b] [1,2,4] triazole was added to 1.50.
g (yield 58%) was obtained. 20 ml of ethyl acetate
, 1.40 ml of triethylamine was added, and 4- {N, N-di (4-methylphenyl) amino} was added.
0.90 g of aniline was added, 0.30 g of 1,3-dichloro-5,5-dimethylhydantoin was added little by little, and the mixture was stirred at room temperature for 30 minutes. Water was added for liquid separation, the solvent was distilled off, and the residue was purified by silica gel column chromatography (hexane / ethyl acetate = 20/1) and crystallized using hexane to give Exemplified Compound (2) -2 as 1 .4
1 g (yield 75%) was obtained. When the mass spectrum of the obtained exemplary compound was measured, the following results were obtained. Mass: M ⁺ = 627

Example 2 Preparation and Evaluation of Water-Soluble Dye Ink <Preparation of Water-Soluble Dye Ink> Deionized water was added to the following components to make 1 liter, and the mixture was heated at 30 to 40 ° C. for 1 hour. It was stirred. After that, pH was adjusted to 9 with KOH 10 mol / l and filtered under reduced pressure with a microfilter having an average pore size of 0.25 μm to prepare a light magenta ink for comparison.

[0224] -Light magenta ink- ・ Magenta dye (A-1) 7.5 g / l ・ Diethylene glycol 150g / l ・ Urea 37g / l ・ Glycerin 130g / l ・ Triethylene glycol monobutyl ether 130g / l ・ Surfynol 465 12.5 g / l ・ Triethanolamine 6.9g / l ・ Benzotriazole 0.08 g / l ・ PROXEL XL2 3.5g / l

In the preparation of the light magenta ink, the magenta ink of the ink set 101 was prepared in the same manner as in the preparation of the light magenta ink except that the kind of the dye and the organic solvent used were changed as shown in Table 1 below. Ink, light cyan ink, cyan ink, yellow ink, and black ink were prepared.

[0226]

[Table 1]

[0227]

[Chemical 68]

[0228]

[Chemical 69]

<Preparation of Ink Sets 102 to 126> Next, in the preparation of the ink set 101, the dyes used in the black ink were changed to the dyes of the present invention shown in Table 2 below. Ink sets 102 to 126 were prepared in the same manner as the ink set 101. When the black dye was changed, it was used so that the addition amount was equimolar to the ink set 101. When two or more black dyes were used in combination, they were used in equimolar amounts so that the total amount added would be equimolar to the ink set 101.

<Evaluation of Image Fastness> Next, the ink sets 101 to 126 were replaced with ink jet printer PM6.
70C (manufactured by EPSON) cartridges were packed, and an image was printed on the inkjet paper photo glossy paper EX manufactured by Fuji Photo Film Co., Ltd. by the same machine to evaluate the image fastness.

Regarding the image fastness, a black solid image printed sample was prepared and evaluated by the following method. Regarding the light fastness, the image density Ci immediately after printing is X
After measurement with -rite 310, the image was irradiated with xenon light (85,000 lux) for 10 days using a weather meter manufactured by Atlas Co., and then the image density Cf was measured again, and the residual dye ratio Cf / Ci * 100. Was evaluated. Regarding the dark heat storability, the concentration before and after storing the sample under the condition of 80 ° C. and 15% RH for 14 days was measured by X-ri.
It was measured by te310, and the dye residual rate was obtained and evaluated by the same calculation method as the evaluation of light fastness. Regarding ozone resistance, the concentration before and after storing the sample for 3 days under the condition that the ozone concentration is 1.0 ppm is X-
The dye residual ratio was measured by a rite 310 and evaluated. The obtained results are shown in Table 2 below.

[0232]

[Table 2]

As is clear from Table 2 above, it was confirmed that the dye of the present invention is extremely fast against light and ozone fading.

(Example 3) Preparation and evaluation of oil-soluble dye ink <Preparation of ink set 201> Black dye ((3) -22)
8 g, dioctyl sulfosuccinic acid 5 g, high boiling organic solvent (S-1) 6 g, high boiling organic solvent (S-2) 10 g,
It was dissolved in 50 ml of ethyl acetate at 70 ° C. 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 treated with a microfluidizer (MICROFLUIDEX INC) at 60M.
The particles were atomized by passing it 5 times at a pressure of Pa (600 bar). Further, the resulting emulsion was desolvated by a rotary evaporator until the odor of ethyl acetate disappeared. In this way, 140 g of diethylene glycol and 64 of glycerin were added to the fine emulsion of the hydrophobic dye thus obtained.
g, SURFYNOL465 (AirProducts
& Chemicals) 7 g, and additives such as urea, 900 ml of deionized water, and KOH 10
An ink set 201 was prepared by adjusting PH = 9 at mol / l. The volume average particle size of the obtained emulsion-dispersed ink was 51 nm when measured using Microtrac UPA (Nikkiso Co., Ltd.).

Next, the ink set 2 was prepared in the same manner as the ink set 201 except that the dye of the ink set 201 was changed to the black dye of the present invention shown in Table 3 below.
02-223 was produced. When the dye was changed, it was used so that the addition amount was an equimolar amount to the black dye in the ink set 201. The ink set 101 manufactured in Example 1 was used as a comparative ink set using a water-soluble dye.

<Evaluation of Image Fastness> Next, these ink sets 201 to 223 and 101 are packed in a cartridge of an ink jet printer PM670C (manufactured by EPSON), and the same machine is used for ink jet paper photo gloss paper EX manufactured by Fuji Photo Film. Example 2 by printing an image on
Similarly, the image fastness was evaluated.

[0237]

[Table 3]

[0238]

[Chemical 70]

As is clear from Table 3, the dye of the present invention was confirmed to have extremely high fastness to light and ozone.

Example 4 Evaluation as Thermal Transfer Dye <Preparation of Thermal Transfer Dye Donor Material> A polyethylene terephthalate film having a thickness of 5 μm having a heat resistant slipping layer provided on one side was used as a support, and the heat resistant slide of this support was used. Composition (1) for coating a dye-donor layer having the following composition on the side opposite to the side provided with a functional layer
Using a gravure coater, the thickness after drying is 0.6
to give a thermal transfer dye-donor material 301
(Hereinafter, it may be simply referred to as "dye donating material".)
Got

[0241] -Dye Donor Layer Coating Composition (1)- ・ Dye (R-1) 10 g ・ Polyvinyl butyral (Denka Butyral 5000A: manufactured by Denki Kagaku) 10 g ・ Silicone oil (KF-96: manufactured by Shin-Etsu Chemical) 0.2 g ・ Polyisocyanate (Takenate D110N: manufactured by Takeda Yakuhin) 0.5 g ・ Methyl ethyl ketone 100ml ・ Toluene 80 ml

Next, the composition (1) for coating the dye-donor layer
In, the thermal transfer dye-donating materials 302 to 318 were produced in the same manner as the thermal transfer dye-donating material except that the dye (R-1) was changed to the dyes shown in Table 4 below. The amount of the dye added was adjusted to be equimolar to the amount of the dye (R-1).

<Preparation of Thermal Transfer Image Receiving Material> As a support,
Using a laminated synthetic paper having a thickness of 150 μm, a receiving layer coating composition (1) having the following composition was applied to the surface using a wire bar coater so that the dry thickness was 5 μm, and thermal transfer was performed. An image receiving material (hereinafter sometimes simply referred to as "image receiving material") was produced. Drying was carried out for 1 hour in an oven at 80 ° C. after temporary drying using a dryer.

[0244] -Receptor layer coating composition (1)- ・ Polyester resin (TOYOBO Byron-280) 26g ・ Polyisocyanate (KP-90: manufactured by Dainippon Ink and Chemicals) 4 g ・ Amino-modified silicone oil (Shin-Etsu Silicone KP-857) 0.5g ・ Methyl ethyl ketone 100ml ・ Toluene 50 ml ・ Cyclohexanone 10 ml

<Transfer Experiment> A transfer experiment was conducted using the thermal transfer dye-donor materials 301 to 318 obtained as described above and the thermal transfer dye image-receiving material. The thermal transfer dye-donor material and the thermal transfer image-receiving material are superposed so that the dye-donor layer and the receptor layer are in contact with each other, and a thermal head is used from the support side of the thermal transfer dye-donor material, and the output of the thermal head is 0.25 W / dot. , Pulse width 0.1-10 msec,
When a dye was imagewise dyed on the receptor layer of the image-receiving material by heating under a condition of a dot density of 6 dots / mm, a clear image recording without transfer unevenness was obtained.

<Evaluation of Image Fastness> As the light fastness, the image density Ci immediately after printing is expressed by X-
rite310 After measuring with a visual filter, the image was irradiated with xenon light (85,000 lux) for 14 days using a weather meter manufactured by Atlas, and then the image density Cf was measured again, and the residual dye ratio Cf / Ci * 100. Was evaluated. Regarding the dark heat storability, the concentration before and after storing the sample under the condition of 80 ° C. and 15% RH for 14 days was measured by X-ri.
It was measured by te 310, and the residual dye ratio was obtained and evaluated by the same calculation method as the evaluation of light fastness. The results of and are shown in Table 4 below.

[0247]

[Table 4]

[0248]

[Chemical 71]

As is clear from Table 4, the dye of the present invention was confirmed to exhibit extremely good image fastness (light and dark heat) even in the thermal transfer recording system.

[0250]

INDUSTRIAL APPLICABILITY According to the present invention, a novel compound which satisfies various performances required for a high-concentration, neutral, black-colored ink composition and an inkjet recording ink, is inexpensive, and is easy to synthesize And a dye, and a dye excellent in image fastness, which is suitably used for a thermal transfer recording system can be provided. Further, in addition to being excellent in printing performance, the color tone is also preferable, light fastness, dark heat fastness, and excellent image fastness such as ozone resistance, capable of exhibiting a high concentration of black, and containing the above dye. It is possible to provide a novel ink composition comprising the above, and an inkjet recording ink containing the ink composition. Further, by using the inkjet recording ink, an inkjet recording method which gives a black image having excellent image performance. Can be provided.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07D 471/04 104 C07D 487/04 138 4H056 105 139 4J039 487/04 137 140 140 138 144 139 487/12 140 C09B 55/00 A 144 C09D 11/00 487/12 B41J 3/04 101Y C09B 55/00 B41M 5/26 K C09D 11/00 101K (72) Inventor Yuuji Kaneko 210 Nakanuma, Minamiashigara, Kanagawa Prefecture Fuji Photo Film Co., Ltd. the inner (72) inventor Hideaki Naruse Kanagawa Prefecture Minamiashigara Nakanuma 210 address Fuji photo film Co., Ltd. in the F-term (reference) 2C056 EA13 FC01 2H086 BA55 2H111 AA26 AA27 BA38 4C050 AA01 BB04 BB05 CC04 CC05 CC06 CC07 CC08 DD02 EE01 EE02 EE04 EE05 FF03 FF05 FF10 GG03 GG04 HH03 HH04 4C 065 AA03 BB04 BB05 CC01 DD02 EE02 HH02 HH05 JJ03 KK05 KK10 LL06 PP03 PP09 4H056 CA01 CC02 CC08 CE02 CE03 CE07 DD03 DD15 DD29 4J039 BC05 BC06 BC07 BC12 BC19 BC20 BC32 BC33 BC44 BC50 BC51 BC52 BC53 BC71 BC74 BC55 BC74 BC74 BC55 GA24

Claims (6)

[Claims] 1. A compound represented by the following general formula (1): [Chemical 1] In the general formula (1), Z ₁ , Z ₂ , Z ₄ , Z ₅ , Z ₇ ,
Z ₈ and Z ₉ each independently represent a nitrogen atom or a CR ₁₁ group. Z _3, Z _6, and Z ₁₀ each independently represent a non-metallic atomic group which can form a 5- to 7-membered ring. R ₁ and R ₂ are each independently a halogen atom, an alkoxy group, a hydroxy group,
Alternatively, it represents a substituted or unsubstituted amino group. R ₃ and R ₄
Each independently represent a hydrogen atom or a substituent. m is 0
Or represents 1. n represents an integer of 0-4. q represents 1 or 2. R ₁₁ represents a hydrogen atom or a substituent. When n is plural, R ₂ may be the same or different. When q is 2, Z ₈ , Z ₉ and Z ₁₀ may be the same or different from each other. 2. A dye represented by the following general formula (1). [Chemical 2] In the general formula (1), Z ₁ , Z ₂ , Z ₄ , Z ₅ ,
Z ₇ , Z ₈ and Z ₉ are each independently a nitrogen atom or CR ₁₁
Represents a group. Z _3, Z ₆ and Z ₁₀ each independently represent a non-metallic atomic group which can form a 5- to 7-membered ring. R ₁ and R ₂ are each independently a halogen atom or a Hammett's σp value of −
It represents an electron donating group having a negative value than 0.20. R
₃ and R ₄ each independently represent a hydrogen atom or a substituent.
m represents 0 or 1. n represents an integer of 0-4. q
Represents 1 or 2. R ₁₁ represents a hydrogen atom or a substituent. When n is plural, R ₂ may be the same or different. When q is 2, Z ₈ , Z ₉ and Z ₁₀ are
They may be the same as or different from each other. 3. The dye according to claim 2, wherein the dye is contained in a thermal transfer dye-donor element and used for thermal transfer recording. 4. An ink composition containing the dye according to claim 2. 5. An inkjet recording ink comprising the ink composition according to claim 4. 6. An ink jet recording method using the ink for ink jet recording according to claim 5 to perform recording on an image receiving material having an ink receiving layer containing a white pigment on a support.