JPH0517701A - Indoaniline pigment compound containing metal ion, indophenol pigment compound containing metal ion, optical recording material and thermosensitive transfer recording material - Google Patents

Abstract

PURPOSE:To provide a new indoaniline pigment compound containing metal ion, having excellent light resistance and heat-resistance and suitable as an optical recording material and a thermosensitive transfer recording material. CONSTITUTION:The pigment compound of formula I [M<2+> is chelating metal ion (preferably Ni<2+> or Cu<2+>; X and Y are H, halogen or univalent organic group; (l) and (m) are integer of 1-4; Z<-> is anion; B is non-metallic atom group forming 5-or 6-membered ring together with adjacent N atom]. The compound can be produced by carrying out the oxidative coupling of a compound of formula II with a compound of formula III using an oxidizing agent under alkaline condition and reacting the obtained pigment of formula IV with a metal salt of formula M<+>Z<-> or M<2+>(A)3*2(Z<->).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal ion-containing indoaniline dye compound, a metal ion-containing indophenol dye compound, and an optical recording material and a heat-sensitive transfer recording material using these dye compounds.

[0002]

[Prior art and technical problems to be solved by the present invention]
Image recording using a laser, high-density information recording preservation,
In recent years, their development has been particularly advanced as a reproducing means (for example, an optical disk) and a high-density image recording means (for example, a thermal transfer recording material using a laser as a heat mode).
In general, an optical disc is one in which a thin recording layer provided on a circular substrate is irradiated with a laser beam focused to about 1 μm ^{2 for} high density information recording.

In the recording, the absorption of the irradiated laser light energy causes a change in the recording layer at that location due to heat.
(Heat mode) or change by light (photon mode)
Is induced to generate shape changes and structural changes such as decomposition, evaporation, and dissolution. In addition, the reproduction of the recorded information is performed by reading the difference in reflectance between the portion where the deformation is caused by the laser light and the portion where the deformation is not caused by the laser light as an optical signal or a magnetic signal.

Therefore, since the optical recording medium needs to efficiently absorb the energy of the laser light, the absorption of the laser light of a specific wavelength used for recording is large, and the information can be reproduced accurately. It is necessary that the reflectance with respect to a laser beam of a specific wavelength used for reproduction is high.

Various types of optical recording media are known as this type of optical recording medium. For example, JP-A-55-97
Japanese Patent No. 033 discloses a substrate in which a single layer of a phthalocyanine dye is provided. However, phthalocyanine dyes have problems that they have low sensitivity, that they have a high decomposition point and are difficult to deposit, and that they have very low solubility in organic solvents and cannot be used for coating by coating. Was there.

Further, JP-A-58-83344 discloses a phenalene dye and JP-A-58-224793 discloses a naphthoquinone dye provided in a recording layer. However, although such a dye has the advantage of being easy to deposit, it has a problem of low reflectance. Further, Japanese Patent Application Laid-Open No. 63-227569 discloses a metal-containing indoaniline compound in order to improve these problems. However, the spectral absorption wavelength is still a short wavelength, and storage stability is also a problem. Was not enough.

The dyes disclosed in these known patents do not necessarily satisfy the following performances required for optical recording media. (1) Sufficient storage stability (2) Good solubility in a solvent (3) Coating by coating is possible (4) High reflectance for laser light of a specific wavelength (5) Spectral absorption wavelength is good (6) Manufacturing cost is low The present invention has been made based on the above circumstances.

That is, an object of the present invention is to provide a metal ion-containing dye compound excellent in the above-mentioned properties, particularly in storage stability (light resistance and heat resistance) and solubility in a solvent, and an optical recording medium using the dye. And to provide a thermal transfer recording medium.

[0009]

The invention according to claim 1 for achieving the above object is a metal ion-containing indoaniline dye compound represented by the following general formula (Formula 1),

[0010]

[Chemical 1]

[Wherein, M ²⁺ represents a chelatable metal ion, and X and Y each independently represent a hydrogen atom, a halogen atom or a monovalent organic group. l and m represents an integer of 1 to 4, Z ^- represents respectively an anion. B is a 5-membered or 6-membered with an adjacent nitrogen atom.
Represents a non-metal atomic group forming a member ring. The invention according to claim 2 is a metal ion-containing indoaniline dye compound represented by the following general formula (Formula 2),

[0012]

[Chemical 2]

[0013] ^{[However, M 2+, Y, l,} m and Z ^- is have the same meaning as described in claim 1. X ^{1
_{Is, -COOR, -CONRR 1, -SO 2}} NRR 1,
At least ^one group selected from the group consisting of —NHCONRR ¹ , —NHCOOR, —CN, and —NO ₂ (provided that R represents an alkyl group or an aryl group, and R ¹ is independent of the aforementioned R). Represents a hydrogen atom, an alkyl group or an aryl group). R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group. ] The invention according to claim 3 is a metal ion-containing indophenol dye compound represented by the following general formula (Formula 3),

[0014]

[Chemical 3]

[0015] ^{[However, M 2+, Y, l,} m and Z ^- is have the same meaning as described in claim 1. X ²
Represents a hydrogen atom or a monovalent group excluding an acylamino group. The invention according to claim 4 is a support, and the general formula (Chemical formula 1), (Chemical formula 2) and (Chemical formula 3) described in claim 1 formed on the support. An optical recording material having a recording layer containing at least one metal ion-containing dye compound selected from the group consisting of:
The invention according to claim 5 is characterized in that the coloring material layer containing a coloring material transferable by heat and / or the layer adjacent to the coloring material layer is represented by the following general formula (Formula 4). A heat-sensitive transfer recording material containing:

[0016]

[Chemical 4]

[Wherein M ²⁺ , l, m and are Z ⁻
Represents the same meaning as in claim 1. X ¹¹ and Y ¹¹ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group. R ⁰ represents a 6-membered nitrogen-containing aromatic heterocycle together with the adjacent nitrogen atom and the double bond of the aromatic ring. J is -NR ¹¹ R ¹² (wherein R ¹¹ and R ¹² each independently represent a hydrogen atom and an alkyl group, and R ¹¹ and R ¹² together with an adjacent nitrogen atom form a 5- or 6-membered ring; Represents a non-metal atom group to be formed) or -OR ¹³ (wherein R ¹³ represents a hydrogen atom or an alkyl group which may have a substituent). The present invention will be described in more detail. -Metal ion-containing dye compound (metal ion-containing indoaniline dye compound and metal ion-containing indophenol dye compound) -In the general formula (Formula 1), M ^<2+> represents a chelatable metal ion. Preferable examples of this metal ion include binary transition metal ions, particularly Ni ²⁺ and C.
^Examples thereof include u ²⁺ , Fe ²⁺ , Co ²⁺ , Cr ²⁺ and Zn ²⁺ . Among these, Ni ²⁺ and Cu ²⁺ are preferable.

X and Y each independently represent a hydrogen atom or a monovalent organic group. Preferable examples of the monovalent organic group include an alkyl group (eg, a linear or branched alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, and an n-butyl group) and a cycloalkyl group. Group (eg, cyclopentyl group, cyclohexyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), alkenyl group (eg, 2-propenyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), alkoxy group (For example, a linear or branched alkoxy group having 1 to 12 carbon atoms such as a methoxy group, an ethoxy group, an isopropoxy group, and an n-butoxy group), an aryloxy group (for example, a phenoxy group), a cyano group, an acylamino group. (For example, an acetylamino group, a propionylamino group, etc., for example, a straight-chain or branched alkylcarbonyl group having 1 to 12 carbon atoms. Amino group, phenylcarbonylamino group etc.), arylamino group (eg phenylamino group), alkylthio group (eg methylthio group, ethylthio group, n-butylthio group etc.), arylthio group (eg phenylthio group), sulfonylamino group (eg Methanesulfonylamino group,
Benzenesulfonylamino group, etc., ureido group (eg, 3-methylureido group, 3,3-dimethylureido group,
1,3-dimethylureido group, etc.), carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group or other straight-chain or branched alkylaminocarbonyl group having 1 to 12 carbon atoms), sulfamoyl group (eg, Ethylsulfamoyl group, dimethylsulfamoyl group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group etc.), aryloxycarbonyl group (eg phenoxycarbonyl group etc.), sulfonyl group (eg methanesulfonyl group,
A linear or branched alkylsulfonyl group having 1 to 12 carbon atoms such as butanesulfonyl group, a phenylsulfonyl group, etc., an acyl group (for example, an acetyl group, a propanoyl group,
Butyroyl group, etc.), amino group (methylamino group, ethylamino group, dimethylamino group, etc.), cyano group, nitro group and the like.

The alkyl group or phenyl group may further have a substituent, and examples of the substituent include the above monovalent groups. Preferred X is a hydrogen atom, an alkyl group,
An alkylcarbonylamino group and an acetoxycarbonyl group, and preferable Y is a hydrogen atom, an alkyl group or an alkoxy group.

L and m are integers of 1 to 4, preferred 1 is 1, and preferred m is 1. B represents a non-metal atom group forming a 5- or 6-membered ring with an adjacent nitrogen atom, and a preferable heterocyclic group formed by B and the adjacent nitrogen atom is a pyrrolidino group, a piperidino group or a morpholino group. Can be mentioned. Z ⁻ represents an anion, and preferable examples thereof include tetraphenylboron anion, acetate anion, p-methylphenylsulfonate anion, and perchlorate anion.

Specific examples of the metal ion-containing indoaniline compound represented by the general formula (Formula 1) are shown below.

[0022]

[Chemical 5]

[0023]

[Chemical 6]

[0024]

[Chemical 7]

[0025]

[Chemical 8]

[0026]

[Chemical 9]

[0027]

[Chemical 10]

[0028]

[Chemical 11]

[0029]

[Chemical 12]

[0030]

[Chemical 13]

[0031]

[Chemical 14]

[0032]

[Chemical 15]

[0033]

[Chemical 16]

[0034]

[Chemical 17]

[0035]

[Chemical 18]

[0036]

[Chemical 19]

[0037]

[Chemical 20]

[0038]

[Chemical 21]

[0039]

[Chemical formula 22]

[0040]

[Chemical formula 23]

[0041]

[Chemical formula 24]

In the general formula (Formula 2), M ²⁺ , Y, l,
m and Z ^- is having the same meaning as those in the general formalized 1.

Preferred M ²⁺ are Ni ²⁺ and Cu
²⁺ can be mentioned. X ¹ is -COOR, -CO
NRR ¹ , -SO ₂ NRR ¹ , -NHCONRR ¹ ,-
It is at least one group selected from the group consisting of NHCOOR, —CN, and —NO ₂ (provided that R represents an alkyl group or an aryl group, and R ¹ is a hydrogen atom, an alkyl group independently of R). Represents a group or an aryl group). R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group.

Preferred X ¹ is an alkyl group or N-
There are alkylaminocarbonyl group, acetoxycarbonyl group, alkoxycarbonyl group, alkoxycarbonylamino group, alkylcarbamoylamino group, dialkylaminocarbonyl group, aryloyloxyamino group, pyrrolidylsulfonyl group, alkylsulfonyl group and the like, and preferable Y is Examples include a hydrogen atom, an alkyl group, an acetoxy group, and an acetoxyamino group. Preferred l is 1 and preferred m are 1 and 2. Preferable examples of R ₁ and R ₂ include a substituent, for example, a linear alkyl group having 1 to 3 carbon atoms which may have a hydroxyl group.

Examples of preferable Z ⁻ include tetraphenylboron anion, acetate anion, p-methylphenylsulfonate anion and perchlorate anion.

Specific examples of the metal ion-containing indoaniline compound represented by the general formula (Formula 2) are shown below.

[0047]

[Chemical 25]

[0048]

[Chemical formula 26]

[0049]

[Chemical 27]

[0050]

[Chemical 28]

[0051]

[Chemical 29]

[0052]

[Chemical 30]

[0053]

[Chemical 31]

[0054]

[Chemical 32]

[0055]

[Chemical 33]

[0056]

[Chemical 34]

[0057]

[Chemical 35]

[0058]

[Chemical 36]

[0059]

[Chemical 37]

[0060]

[Chemical 38]

[0061]

[Chemical Formula 39]

[0062]

[Chemical 40]

[0063]

[Chemical 41]

[0064]

[Chemical 42]

[0065]

[Chemical 43]

[0066]

[Chemical 44]

In the general formula (Formula 3), M ²⁺ , Y, l,
m and Z ^- is having the same meaning as those in the general formalized 1. X ² represents a hydrogen atom or a monovalent group excluding an acylamino group. ^Examples of preferable M ²⁺ include Ni ²⁺ and Cu ²⁺ . Preferred X ² is a hydrogen atom, a halogen atom, an alkyl group, an N-alkylaminocarbonyl group, an acetoxycarbonyl group, an alkoxycarbonylamino group or the like, and a preferred Y is a hydrogen atom, an alkyl group, an acetoxy group or an acetoxyamino group. and so on. Preferred l is 1 and preferred m are 1 and 2.

Preferred examples of Z ⁻ include tetraphenylboron anion, acetate anion, p-methylphenylsulfonate anion and perchlorate anion. Specific examples of the metal ion-containing indophenol compound represented by the general formula (Formula 3) are shown below.

[0069]

[Chemical formula 45]

[0070]

[Chemical formula 46]

[0071]

[Chemical 47]

[0072]

[Chemical 48]

[0073]

[Chemical 49]

[0074]

[Chemical 50]

[0075]

[Chemical 51]

[0076]

[Chemical 52]

[0077]

[Chemical 53]

[0078]

[Chemical 54]

[0079]

[Chemical 55]

[0080]

[Chemical 56]

—Method for Producing Metal Ion-Containing Dye Compound— A general synthesis example of the metal ion-containing indoaniline compound represented by the general formula (Formula 1) will be described.

(Synthesis Example) As raw material compounds, compounds represented by the general formula (Formula 57), the general formula (Formula 58), the general formula (Formula 59), the general formula (Formula 60), and the general formula (Formula 61) were used. use.

[0083]

[Chemical 57]

[0084]

[Chemical 58]

[0085]

[Chemical 59]

[0086]

[Chemical 60]

[0087]

[Chemical formula 61]

By oxidatively coupling the compound represented by the general formula (Formula 57) with the compound represented by the general formula (Formula 57) under an alkaline condition using an oxidizing agent, the compound represented by the general formula (Formula 59) can be obtained. The dyes shown can easily be obtained. Next, the compound represented by the general formula (Formula 1) is produced by reacting the dye represented by the general formula (Formula 59) with the metal salt represented by the general formula (Formula 60). can do. In the general formula, M ²⁺ , Z ⁻ ,
X, Y, l, m and B are as described above.

A represents a coordination compound capable of forming a coordination bond with a metal ion, and these coordination compounds can be selected, for example, from the coordination compounds described in Chelate Chemistry (5) (Nankodo). .

Next, a general synthesis example of the metal ion-containing indoaniline compound represented by the general formula (Formula 2) will be described. (Synthesis Example) As the raw material compounds, compounds represented by the general formula (62), the general formula (63), the general formula (64), the general formula (60) and the general formula (Chemical formula 61) are used.

[0091]

[Chemical formula 62]

[0092]

[Chemical formula 63]

[0093]

[Chemical 64]

The compound represented by the general formula (Chemical Formula 62) is oxidatively coupled with the compound represented by the general formula (63) under an alkaline condition using an oxidizing agent, to thereby form the compound represented by the general formula (64). The dye can be easily obtained.
Then, the dye represented by the general formula (64) and the general formula (6
0) or the metal salt represented by the general formula (61) can be reacted to produce the compound represented by the general formula (Formula 2). In the general formula, M ²⁺ , Z ⁻ , X ¹ ,
Y, l, m, R ₁ and R ₂ are as described above.

Further, a general synthesis example of the metal ion-containing indophenol compound represented by the general formula (Formula 3) will be described. (Synthesis Example) As the raw material compounds, compounds represented by the general formula (Formula 65), the general formula (66), the general formula (67), the general formula (60) and the general formula (61) are used.

[0096]

[Chemical 65]

[0097]

[Chemical formula 66]

[0098]

[Chemical formula 67]

By oxidatively coupling the compound represented by the general formula (Formula 65) with the compound represented by the general formula (66) under an alkaline condition using an oxidizing agent, the compound represented by the general formula (67) is obtained. The dye can be easily obtained.
Then, the dye represented by the general formula (67) and the general formula (6
0) or the metal salt represented by the general formula (61) can be reacted to produce the compound represented by the general formula (Formula 3). In the general formula, M ²⁺ , Z ⁻ , X ³ ,
Y, 1, m, and R ₃ are as described above.

—Optical Recording Body— The optical recording medium of the present invention basically comprises a substrate and a recording layer, and further, if necessary, an undercoat layer on the substrate and a protective layer on the recording layer. It is provided. The recording layer may be provided on both sides of the substrate, or may be provided on only one side. The substrate may be transparent or opaque to the laser light used. As the material of the substrate material,
Examples thereof include glass, plastic, paper, plate-shaped or foil-shaped supports for general recording materials, and plastics are preferable from various points. Examples of the plastic include acrylic resin, methacrylic resin, vinyl acetate resin, vinyl chloride resin, nitrocellulose, polyethylene resin, polypropylene resin, polycarbonate resin, polyimide resin, epoxy resin, polysulfone resin and the like.

The recording layer can be formed from the metal ion-containing dye compound of the present invention and a binder. As the metal ion-containing dye compound contained in this recording layer,
At least one metal ion-containing dye compound selected from the general formulas (Formula 1), (Formula 2) and (Formula 3) is used.

As the above-mentioned binder, polyvinyl chloride resin, polyvinyl acrylate resin, polyvinyl pyrrolidone resin, nitrocellulose, cellulose acetate,
Known resins such as polyvinyl butyral and polycarbonate are used. The weight ratio of the metal ion-containing dye compound to the binder is preferably 0.01 or more.

In order to improve the stability and light resistance of the recording material, the recording layer has a transition metal chelate compound (eg, acetylacetonate chelate, bisphenyldithiol, salicylaldehyde oxime, bisdithio-) as a singlet oxygen quencher. (alpha-diketone etc.) may be contained. Further, other dyes can be used in combination if necessary. The other dye may be another type of the same type of compound, or may be a dye of another type such as a triarylmethane type dye, an azo dye, a cyanine type dye, and a squarylium type dye.

The thickness of the recording layer in the optical recording medium of the present invention is usually 0.0001 to 5 μm, preferably 0.001.
It is 1 to 3 μm. As the film forming method, a vacuum deposition method,
Sputtering method, doctor blade method, casting method,
The film can also be formed by a commonly used thin film forming method such as a spinner method, a dipping method, and a solvent dissolution coating method.

In the case of the solvent dissolution coating method, a coating film can be easily formed by evaporating the solvent and drying after coating. As a coating solvent for forming the recording layer by a solvent dissolution coating method, tetrachloroethane, bromoform, dibromoethane, ethyl cellosolve, methyl ethyl ketone, tetrahydrofuran, xylene, chlorobenzene, cyclohexanone or the like having a boiling point of 50 to 160 ° C. is preferably used. To be done.

Recording on the optical recording material obtained as described above is carried out in a recording layer of 1 μm on both sides or one side of the substrate.
^It is carried out by shining a laser beam focused on about ² , preferably a semiconductor laser beam. The part irradiated with laser light is decomposed by absorption of laser energy,
Thermal deformation of the recording layer such as evaporation and melting occurs. The recorded information is reproduced by reading the difference in reflectance between the portion where the laser beam is thermally deformed and the portion where the laser beam is not thermally deformed.

The laser light used for the optical recording medium is N
₂ laser, He-Cd laser, Ar laser, He
-Ne laser, ruby laser, semiconductor laser, dye laser and the like can be mentioned, but the semiconductor laser is particularly preferable from the viewpoints of lightness, easy handling, compactness and the like. -Thermal transfer recording material-The thermal transfer recording material of the present invention is formed on a support,
The color material layer containing the color material or a layer adjacent to the color material layer contains the metal ion-containing dye compound represented by the general formula (Formula 4).

In the above general formula (Formula 4) showing the metal ion-containing dye compound used in the thermal transfer recording material of the present invention, M ²⁺ represents a chelatable metal ion. Suitable examples of this metal ion include divalent transition metal ions, particularly Ni ²⁺ , Cu ²⁺ , Fe ²⁺ and C.
o ²⁺ , Cr ²⁺ and Zn ²⁺ can be mentioned. Among these, Ni ²⁺ , Cu ²⁺ and Co ²⁺ are preferable,
Particularly preferred is Ni ²⁺ .

X ¹¹ and Y ¹¹ are each independently a hydrogen atom, a halogen atom (preferably a fluorine atom, a chlorine atom,
Bromine atom) represents a monovalent organic group.

Examples of the monovalent organic group are the same as the examples of the organic group represented by X in the general formula (Formula 1).

R ⁰ is a 6-membered nitrogen-containing aromatic heterocycle (provided that
It may have a substituent on the ring. ) Represents. Preferred R
⁰ forms a heterocycle represented by the following formulas (Formula 68, Formula 69, Formula 70).

[0112]

[Chemical 68]

[0113]

[Chemical 69]

[0114]

[Chemical 70]

J is --NR ¹¹ R ¹² (provided that R ¹¹ and R ¹² each independently represent a hydrogen atom and an alkyl group, and R ¹¹ and R ¹² are a 5-membered or 6-membered together with an adjacent nitrogen atom. Represents a non-metal atom group forming a ring), —OR ¹³ (wherein R ¹³ represents an alkyl group which may have a substituent) or a hydroxy group. The substituent for R ¹³ includes an aryl group (eg, phenyl group), an alkoxy group (eg, methoxy group, ethoxy group, etc.), an amino group (eg, methylamino group, ethylamino group, etc.), an acylamino group (eg, acetyl group, etc.). ), A sulfonyl group (for example, a methanesulfonyl group, etc.),
Examples thereof include an alkoxycarbonyl group (for example, a methoxycarbonyl group), a cyano group, a nitro group, a halogen atom (for example, a chlorine atom and a fluorine atom), an alkylsulfonylamino group (for example, a methanesulfonylamino group) and a hydroxy group.

Z ⁻ represents an anion. Examples of the anion include Cl ⁻ , Br ⁻ , ClO ₄ ⁻ , R ¹⁴ COO ⁻ , R
¹⁴ SO ₃ ⁻ , R ¹⁴ ₄ B ⁻ and SO ₄ ²⁻ are preferable. However,
R ¹⁴ represents an alkyl group, a cycloalkyl group, or an aryl group.

Examples of the alkyl group represented by R ¹⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and an octyl group. These alkyl groups are substituted with a halogen atom. You can do it. The preferred alkyl group represented by R ¹⁴ has 1 to 4 carbon atoms which may be substituted by a halogen atom.
Is an alkyl group.

Examples of the cycloalkyl group represented by R ¹⁴ include a cyclopentyl group, a cyclohexyl group and a cyclooctyl group. A cyclohexyl group can be mentioned as a preferable cycloalkyl group.

The aryl group represented by R ¹⁴ is a phenyl group having a substituent such as a phenyl group or an alkyl group,
Examples thereof include a naphthyl group and a naphthyl group having a substituent such as an alkyl group.

The metal ion-containing dye compound represented by the general formula (Formula 4) includes the metal ion-containing dye compounds represented by the general formulas (Formula 1), (Formula 2) and (Formula 3). However, as a specific example of the metal ion-containing dye compound suitable for this thermal transfer recording material,
Wherein M ²⁺ , X ¹¹ , m, Y ¹¹ , J and Z in Table 1 and Table 2 are compounds (1) to (18) and
Examples thereof include compound (19) represented by 2) and compound (20) represented by (Chemical Formula 73).

[0121]

[Table 1]

[0122]

[Table 2]

[0123]

[Chemical 71]

[0124]

[Chemical 72]

[0125]

[Chemical formula 73]

The color material contained in the color material layer is selected according to a thermal transfer recording method, that is, a thermal melting transfer method or a sublimation transfer method. In the present invention, a color material suitable for the sublimation transfer method is used. preferable. Therefore, the heat-diffusible dye (sublimable dye) is preferable as the coloring material, and for example, the cyan dyes are disclosed in JP-A-59-78896 and JP-A-59-2.
No. 27948, No. 60-24996, No. 60-535.
63, 60-130735, 60-13129.
No. 2, No. 60-239289, No. 61-19396
No. 61-22993, No. 61-31292, No. 61-31467, No. 61-35994, No. 61-.
48989, 61-148269, 62-19.
No. 1191, No. 63-912288, No. 63-9128
Naphthoquinone dyes, anthraquinone dyes, azomethine dyes and the like described in JP-A No. 7 and 63-290793 and the like.

As the magenta dye, JP-A-59-78 can be used.
896, JP-A-60-30392, JP-A-60-3
0394, JP60-253595, JP61
-262190, JP 63-5992, JP 6
3-205288, JP-A-64-159, JP-A-6-
Examples thereof include anthraquinone dyes, azo dyes, azomethine dyes and the like described in each publication such as 4-63194.

As the yellow dye, JP-A-59-78 can be used.
896, JP-A-60-27594, JP-A-60-3
1560, JP-A-60-53565, JP-A-61-1.
Examples thereof include methine dyes, azo dyes, quinophthalone dyes, and anthryothothiazole dyes described in JP-A No. 12394 and JP-A No. 63-122594.

The colorant is particularly preferably obtained by a coupling reaction of a compound having an active methylene group of open or closed type with an oxidized form of a p-phenylenediamine derivative or an oxidized form of a p-aminophenol derivative. An azomethine dye and a phenol, or an indoaniline dye obtained by a coupling reaction between a naphthol derivative and an oxidized form of a p-phenylenediamine derivative or an oxidized form of a p-aminophenol derivative. In the case of these coloring materials, high sensitivity and good color reproducibility are achieved especially in the constitution of the present invention.

A chelatable dye represented by the following general formula (Formula 74) or the following general formula (Formula 75) can also be preferably used.

[0131]

[Chemical 74]

[Wherein, X ³ represents a group of atoms necessary for completing an aromatic carbocycle or heterocycle in which at least one ring is composed of 5 to 7 atoms, And at least one of adjacent positions of carbons bonded to the azo bond is (a) a nitrogen atom, or (b) a carbon atom substituted with a nitrogen atom, an oxygen atom or a sulfur atom, and X ⁴ is at least 1 G represents a group of atoms necessary for completing an aromatic carbocycle or heterocycle in which one ring is composed of 5 to 7 atoms, and G represents a chelating group. ]

[0133]

[Chemical 75]

[In the formula, X ³ has the same meaning as defined in the general formula (Formula 74), Z ¹ represents an electron-withdrawing group, and Z ² represents an alkyl group or an aryl group. ] In a thermal transfer recording material using a chelatable dye represented by the general formula (Formula 74) or the general formula (Formula 75), the dye reacts with a metal ion added in the image receiving layer of the image receiving material. By forming a chelating dye by using the above, an image having excellent fixability and weather resistance can be obtained.

In the present invention, as the binder which is one component of the color material layer, a water-soluble polymer such as cellulose type, polyacrylic acid type, polyvinyl alcohol type, polyvinylpyrrolidone type, acrylic resin, methacrylic resin,
Examples thereof include polymers soluble in organic solvents such as polystyrene, polycarbonate, polysulfone, polyether sulfone, polyvinyl butyral, polyvinyl acetal, nitrocellulose, and ethyl cellulose.

As the layer adjacent to the color material layer in the present invention, a layer (undercoat layer) provided between the color material layer and the support or a layer (protective layer) provided above the color material layer. ) And the like. Examples of the undercoat layer include an adhesive layer provided for the purpose of enhancing the adhesiveness between the color material layer and the support, and a diffusion prevention layer provided for preventing the color material from diffusing to the support side.

These layers are composed mainly of the polymer forming the binder, and various additives (for example, release agents, adhesives, heat-melting substances, etc.) are added if necessary. . Further, in the case of the diffusion preventing layer, gelatin is preferably used in addition to the binder.

The amount of the metal ion-containing dye compound used in the present invention is usually 0.01 to 1 per 1 m ^{2 of} the support.
It is 0 g, and more preferably 0.05 to 5.0 g. The amount of the coloring material is usually a support 1 m ² per 0.05-5 g, more preferably 0.1 to 2.
It is 0 g. The amount of the binder used in the color material layer and the layer adjacent to the color material layer is usually 0.1 g to 50 g, and preferably 0.2 to 5 g per 1 m ^{2 of} the support.

The color material layer has a dry film thickness of 0.1.
μm to 5 μm, preferably 0.5 to 3 μm.

The support has good dimensional stability,
Any material can be used as long as it can withstand the heat of recording with a thermal head, but a thin paper such as condenser paper or glassine paper, or a heat resistant plastic film such as polyethylene terephthalate, polyamide or polycarbonate can be used. The thickness of this support is 2 to 30 μm.
Further, the support may have an undercoat layer for the purpose of improving the adhesiveness with the binder and preventing the dye from being transferred to the support or dyeing.

Further, the back surface of the support (the side opposite to the ink layer)
May have a slipping layer for the purpose of preventing the head from sticking to the support. The coloring material layer is generally prepared by dissolving one or two or more of the coloring materials together with a binder and optionally a metal ion-containing dye compound in a solvent or dispersing them in the form of fine particles to prepare a coating material for forming the coloring material layer. It is obtained by applying this color material layer-forming coating material on a support and drying.

When a polymer soluble in an organic solvent is used as the binder, the binder may be used not only by dissolving it in the organic solvent but also in the form of latex dispersion. As a solvent for preparing the color material layer-forming coating material, water, alcohols (eg ethanol, propanol), cellosolves (eg methylcellosolve), esters (eg ethyl acetate), aromatics (eg toluene, Examples thereof include xylene, chlorobenzene), ketones (eg acetone, methyl ethyl ketone), ethers (eg tetrahydrofuran, dioxane), chlorine-based solvents (eg chloroform, trichloroethylene) and the like.

The color material layer-forming coating material thus obtained was applied on a support using a bar coater, roll coater, reverse roll coater, knife coater, rod coater, air doctor coater, screen printing, gravure printing or the like. Applied to. The heat-sensitive transfer recording material of the present invention basically comprises (1) a color material comprising a metal ion-containing dye compound of the present invention represented by the general formula (Formula 4), a color material and a binder on a support. (2) A structure in which a layer is provided, a coloring material layer comprising a coloring material and a binder is provided on a support, and the coloring material layer is further provided on the coloring material layer according to the present invention represented by the general formula (Formula 4). A structure formed by stacking layers containing a metal ion-containing dye compound, or (3)
A color material layer containing a color material and a binder and a layer adjacent to the color material layer are formed on a support, and the metal according to the present invention represented by the general formula (Formula 4) is formed on both layers. Although it has a structure containing an ion-containing dye compound, a heat-melting layer containing a heat-melting compound as described in JP-A-59-106,997 is provided on the color material layer. May be.

The heat fusible compound is 65 to 13
A colorless or white compound having a melting point of 0 ° C. is preferably used, and examples thereof include waxes such as carnauba wax, beeswax and candeli wax, higher fatty acids such as stearic acid and behenic acid, alcohols such as xylitol, acetamide and benzamide. And ureas such as phenylurea and diethylurea.

These heat-meltable layers may contain, for example, polyvinylpyrrolidone or
Polymers such as polyvinyl butyral and saturated polyester may be contained. The heat-sensitive transfer recording material of the present invention can form an image of one color by including a kind of color material in the color material layer, but when recording a full color image, a cyan color containing a cyan dye is used. It is preferable that a total of three layers, that is, a material layer, a magenta coloring material layer containing a magenta dye, and a yellow coloring material layer containing a yellow dye, are sequentially and repeatedly coated on the same surface of the support. Even in such a case, the three layers contain the metal ion-containing dye compound represented by the general formula (Formula 4) according to the present invention.

If necessary, a yellow color material layer, a magenta color material layer, a cyan color material layer and a color material layer containing a black image-forming substance, a total of four layers, are sequentially repeated on the same surface of the support. It may be painted. The thermal transfer recording material of the present invention can form an image on the image receiving material as follows.

For example, as shown in FIG. 1, the image receiving material 3
Is composed of an image-receiving substrate 1 and an image-receiving layer 2, and the heat-sensitive transfer recording material 6 is composed of a support 4 and a color material layer 5 containing a metal ion-containing dye compound, the heat-sensitive transfer recording material 6 and the image-receiving material 3 are colored. When the material layer 5 and the image receiving layer 2 are superposed so as to be in contact with each other and irradiated with light corresponding to image information, for example, laser light, from the side of the support 4, the color material layer 5 has the general formula (Formula 4). The metal ion-containing dye compound according to the present invention converts the light energy of laser light into heat energy to generate heat, and the heat generation causes the coloring material (sublimable dye) in the coloring material layer 5 to be generated.
Migrates to the image receiving material 3, and an image is formed on the image receiving layer 2 by the color material.

The image receiving substrate can be generally formed of paper, a plastic film, or a paper-plastic film composite. The image-receiving layer is formed of one or more polymer layers of polyester resin, polyvinyl chloride resin, copolymer resin of vinyl chloride and other monomer (such as vinyl acetate), polyvinyl butyral, polyvinyl pyrrolidone, polycarbonate, etc. can do.

The image receiving layer preferably contains a basic compound and / or a mordant. The basic compound is not particularly limited, but an inorganic or organic basic compound is used, and examples thereof include calcium carbonate, sodium carbonate, sodium acetate, alkylamine and the like.

Examples of the mordant include compounds having a tertiary amino group, compounds having a nitrogen-containing heterocyclic group, and compounds having a quaternary cation group thereof. Further, the image-receiving layer may optionally contain a releasing agent such as silicone oil, an antioxidant, and an image stabilizer such as a UV absorber. Further, in the color material layer, the general formula (Chem.
4) or a sublimable dye represented by the general formula
When the sublimable dye represented by 5) is contained, it is desirable that the metal ion be present in the image receiving material or in the heat fusible layer.

As the metal ion, there can be used the I-th group of the periodic table.
To divalent and polyvalent metals belonging to Group VIII, among which Al, Co, Cr, Cu, Fe, Mg,
Mn, Mo, Ni, Sn, Ti and Zn are preferred,
Ni, Cu, Cr, Co and Zn are particularly preferable. Examples of the compound that supplies these metal ions (hereinafter, also referred to as a metal source) include inorganic or organic salts of the metal and complexes of the metal, and among these, salts and complexes of organic acids are preferable.

Specific examples are Ni ²⁺ , Cu ²⁺ and Cr.
A salt of a lower fatty acid such as acetic acid or the like with ²⁺ , Co ²⁺ and Zn ²⁺ ,
Examples thereof include salts of higher fatty acids such as stearic acid and salts of aromatic carboxylic acids such as benzoic acid and salicylic acid. Further, a complex represented by the following general formula can also be preferably used. _{[M '(Q 1) l} (Q 2) m (Q 3) n] p + (W -) p where in the above formula, M' is a metal ion, preferably N
i ²⁺ , Cu ²⁺ , Cr ²⁺ , Co ²⁺ , Zn ²⁺ .

Q ₁ , Q ₂ and Q ₃ each represent a coordination compound capable of forming a coordination bond with the metal ion represented by M ′, and they may be the same as or different from each other. Examples of these coordination compounds include chelate chemistry (5) (Nankodo)
Can be selected from the coordination compounds described in. W represents an organic anion, and specific examples thereof include a tetraphenylboron anion and an alkylbenzene sulfonate anion.

L (L of the alphabet) represents an integer of 1, 2 or 3, m represents 1, 2 or 0, and n
Represents 1 or 0, and these are determined depending on whether the complex represented by the above general formula is tetradentate or hexadentate, or the number of ligands of Q ₁ , Q ₂ and Q _3. Determined by p represents 1 or 2, but is preferably 2.

When p is 2, the coordination group of the coordination compound represented by Q ₁ , Q ₂ and Q ₃ is not anionized. In addition to the above, Japanese Patent Publication No. 36-11535
No. 5, JP-A-55-48210 and JP-A-55-129346.
The complex compounds described in each of the publications can be used as the metal source.

[0156] The addition amount of the metal source is usually provided to the image-receiving material or the thermally fusible layer is preferably ^{0.5~20g / m 2, 1~20g / m} 2 is more preferable. Next, an example of a suitable image receiving material is shown in FIG. As shown in FIG. 2, the image receiving material includes polyethylene layers 11 a and 11 on both sides of the paper 10.
b is laminated, and a polyvinyl chloride layer 12 as an image receiving layer is further laminated on the polyethylene layer 11a on one side thereof.

As another preferred embodiment of the present invention, a heat-sensitive transfer recording material is provided on a support, a color material layer formed on the support, and adjacent to the color material layer, and the above-mentioned general formula (Formula 4) When composed of a layer containing the metal ion-containing dye compound according to the present invention shown in, when the thermal transfer recording material and the image receiving material are overlapped and irradiated with a laser beam corresponding to image information from the support side, The metal ion-containing dye compound according to the present invention represented by the general formula (Formula 4), which is contained in the layer adjacent to the color material layer, generates heat by converting light energy of laser light into heat energy. ,
Due to this heat generation, the color material in the color material layer diffuses and transfers to the image receiving material, and an image is formed by the color material in the image receiving layer.

As another mode of the heat-sensitive transfer recording material, as shown in FIG.
And a coloring material layer 5 provided on the surface thereof and containing the metal ion-containing dye compound according to the present invention represented by the general formula (Formula 4), and a heat-fusible layer 9 provided on the surface thereof. At this time, when the thermal transfer recording material 10 and the image receiving material 3 are overlapped and irradiated with laser light corresponding to image information from the support 4 side, the general material contained in the color material layer 5 is used. The metal ion-containing dye compound according to the present invention represented by the formula (Formula 4) converts the light energy of laser light into heat energy to generate heat, and this heat generation causes
The color material in the color material layer 5 diffuses and transfers to the heat-fusible layer 9, and then the heat-meltable substance 9a containing the color material causes cohesive failure or interfacial peeling to transfer to the image receiving material 3.

The image receiving material 3 has the following structure as shown in FIG.
It may be an image receiving material used for a thermal transfer recording material having a color material layer on a support, or may be composed of only an image receiving substrate. In any case, the image receiving material 3 is not particularly limited in its material as long as it can hold the peeled heat-fusible layer thereon. As described in detail above, during image formation using the thermal transfer recording material of the present invention, the metal ion-containing dye compound of the present invention converts light energy corresponding to image information into heat energy. Then, the converted heat energy causes the dye to diffuse and move from the color material layer to the image receiving material to form an image on the surface of the image receiving material, or the converted heat energy melts the color material layer to contain the dye. The molten layer is subjected to cohesive failure or interface failure to form an image on the image receiving material.

[0160]

EXAMPLES Specific examples using the metal ion-containing dye compound of the present invention are shown below, but the present invention is not limited thereto. (Examples 1 to 6, Comparative Example 1) Polyvinyl chloride [n = 1100, manufactured by Wako Pure Chemical Industries, Ltd.] and a metal ion-containing dye compound of the present invention (compound number in Table 3 1) with a mixture of
It was coated at 5.0 g / m ² and light absorption density = 2.0 to obtain an optical recording material.

Further, instead of the above-mentioned metal ion-containing dye compound, a compound other than the present invention, that is, comparative compound- (a)
An optical recording material was prepared in the same manner as described above except that (Chemical Formula 76) was used.

[0162]

[Chemical 76]

These optical recording materials were replaced with a xenon lamp.
Irradiation was carried out for 4 hours, the concentration before irradiation (D ₀ ) and after irradiation (D) was measured, and the value of (D / D ₀ ) × 100 was determined as the residual ratio (%)
The light resistance was evaluated as. The results are shown in Table 3.

Further, the optical recording material was allowed to stand for 7 days in an environment of relative humidity 70% and temperature 60 ° C., and similarly the density before and after the standing was measured to evaluate the heat resistance. As is clear from Table 3, it is understood that the optical recording materials of the present invention are improved in light resistance and heat resistance and are excellent in storage stability.

[0165]

[Table 3]

(Examples 7 to 12) Optical recording materials were prepared in the same manner as in the above-mentioned examples except that the kinds of the metal ion-containing dye compounds were changed to those shown in Table 4, and their light resistance and heat resistance were measured. The results are shown in Table 4. As is clear from Table 4, it is understood that the optical recording materials of the present invention are improved in light resistance and heat resistance and are excellent in storage stability.

[0167]

[Table 4]

(Examples 13 to 15) Optical recording materials were prepared in the same manner as in the above-mentioned examples except that the kinds of the metal ion-containing dye compounds were changed to those shown in Table 5, and their light resistance and heat resistance were measured. The results are shown in Table 5. As is clear from Table 5, it is understood that the optical recording materials of the present invention are improved in light resistance and heat resistance and are excellent in storage stability.

[0169]

[Table 5]

(Example 16) <Preparation of heat-sensitive transfer recording material> On a polyethylene terephthalate base having a thickness of 100 μm and undercoated with gelatin, a coating solution having the following composition was added at a dye loading of 1.0 g / m ^2.
A thermal transfer recording material 1 was prepared by coating the above.

Coating liquid: Cyan dye (Note 1) ... 5
g Metal ion-containing dye compound of the present invention (Note 2) ... 3
g Nitrocellulose resin ... 10
g Methyl ethyl ketone ... 200
ml Note 1: The structure of the cyan dye is represented by Chemical formula 77.

[0172]

[Chemical 77]

Note 2: The metal ion-containing dye compound of the present invention is represented by Chemical formula 78.

[0174]

[Chemical 78]

<Preparation of Image Receiving Material> Laminate both sides with polyethylene [A polyvinyl chloride coated side contains a white pigment (titanium dioxide) and a bluing agent. ] On the polyethylene layer of the coated paper, polyvinyl chloride (coating amount 10 g /
m ² ) was applied to prepare an image receiving material.

Silicone oil 0.15 is used for the image receiving layer.
g / m ² was included. <Image formation> Next, the image receiving material is wound around a drum, the image receiving layer surface of the image receiving material and the color material layer surface of the thermal transfer recording material 1 are overlapped, and then the spot diameter is 40 μm while rotating the drum at 160 rpm. The cyan dye was transferred onto the image receiving material by irradiating a laser beam of 830 nm with an exposure time of 5 milliseconds.

The irradiation energy was about 45 microwatts / μm ² . A cyan image having a density of 1.64 was obtained on the image receiving material. (Comparative Examples 2 to 4) Thermal transfer recording material A (Comparative Example 2) and infrared rays formed in the same manner as in Example 16 except that the metal ion-containing dye compound (Chemical Formula 78) of the present invention was removed from the coating liquid. A thermal transfer recording material B (Comparative Example 3) formed in the same manner as in Example 16 except that carbon was added in place of the metal ion-containing dye compound (Chemical Formula 78) of the present invention as an absorbing compound, and an infrared absorbing compound. As an example, a metal ion-containing dye compound (Chemical Formula 78) of the present invention was replaced with the following infrared absorbing dye (Chemical Formula 79). 78)
Same as. A thermal transfer recording material C (Comparative Example 4) was prepared.

A cyan image was formed on each of the heat-sensitive transfer recording materials A, B and C by the same method as in the case of the heat-sensitive transfer recording material 1, but the heat-sensitive transfer recording material A almost gave a transferred image. However, with the thermal transfer recording material B, only a transfer image having a density of 1.24 was obtained. With the thermal transfer recording material C, an image having a density (1.59) substantially the same as that of the thermal transfer recording material 1 was obtained.

Infrared dye

[0180]

[Chemical 79]

On the other hand, the thermal transfer recording material 1 and the thermal transfer recording material C were placed in an environment of 86 ° C. and a relative humidity of 50%.
The material was left for one day to evaluate the preservability of the material. When image recording was performed on the thermal transfer recording material 1 after storage and the comparative thermal transfer recording material C under the same conditions as above, a cyan image having a density of 1.62 was obtained with the thermal transfer recording material 1, but the thermal transfer recording was performed. In Material C, the concentration dropped to 0.92.

It is presumed that this is because the infrared absorbing dye in the thermal transfer recording material C was decomposed during storage, the infrared density was lowered, and the thermal energy conversion efficiency of laser light was lowered. On the other hand, the thermal transfer recording material 1 of the present invention is
A good image can be obtained by laser recording, and the storage stability is also good.

Example 17 Instead of the metal ion-containing dye compound (Chemical Formula 78) in the thermal transfer recording material 1, Table 1 was used.
And the numbers (2), (3), (4), (6) in Table 2
(9), (10), (12), (19), and (2
0) The same heat-sensitive transfer recording material 2 as the heat-sensitive transfer recording material 1 except that the metal ion-containing dye compound represented by 0) is used (the addition amount is equimolar to the metal ion-containing dye compound (Chemical Formula 78)).
10 were produced. When image recording was performed on these thermal transfer recording materials by the same method as in Example 19, a cyan image almost the same as in the case of thermal transfer recording material 1 could be obtained.

Example 18 Instead of the cyan dye of the thermal transfer recording material 1, the following dyes (Chemical formula 80), (Chemical formula 81),
The same thermal transfer recording materials 11 to 14 as the thermal transfer recording material 1 were prepared except that (Chemical Formula 82) and (83) were used. Images were formed on the obtained thermal transfer recording materials 11 to 14 by the same method as in Example 16.

The image-receiving materials for the heat-sensitive transfer recording material 13 and the heat-sensitive transfer recording material 14 further contain the following compound (metal source-attached amount 5 g / m ² ) in the image-receiving layer.

Metal source: [Ni (C ₂ H ₅ NHCH ₂ CH ₂ NH ₂ )] ²⁺ [(C
_{6 H 5) 4 B] 2} -

[0187]

[Chemical 80]

[0188]

[Chemical 81]

[0189]

[Chemical formula 82]

[0190]

[Chemical 83]

For the thermal transfer recording materials 11 to 14, yellow or magenta images having the densities shown in Table 6 were obtained.

[0192]

[Table 6]

By using the heat-sensitive transfer material of the present invention, yellow, magenta and cyan images can be obtained, and thus full color images can be obtained.

The images obtained with the heat-sensitive transfer recording material 13 and the heat-sensitive transfer recording material 14 had better image fixability than other images.

Example 19 The metal ion-containing dye compound of the present invention used in Example 16 (Chemical Formula 78) was converted to (Chemical Formula 7),
Example 1 except that (Chemical formula 28) and (Chemical formula 48) were changed.
Thermal transfer recording materials 15, 16 and 17 were prepared in the same manner as in 6, and images were formed. In addition, 86 of these materials
The material was allowed to stand for 3 days in an environment of ° C and relative humidity of 50% to evaluate the storability of the material.

Thermal transfer recording materials 15, 16, 1 after storage
When image recording was performed on No. 7, the thermal transfer recording material 15 had a density of 1.58 (before storage of 1.60), and the thermal transfer recording material 16 had a density of 1.60 (before storage of 1.62).
The density of the thermal transfer recording material 17 was 1.58 (1.5
It was 9).

As described above, these thermal transfer recording materials 1
Similar to the heat-sensitive transfer recording material 1, Nos. 5, 16 and 17 gave good images by laser recording and had good storage stability.

[0198]

The metal ion-containing dye compound of the present invention is
It has excellent storage stability such as light resistance and heat resistance, and high solubility in organic solvents. Therefore, when an optical recording material or a thermal transfer recording material is prepared, the coating liquid containing the metal ion-containing dye compound can be prepared smoothly and quickly, and the obtained optical recording material and the image recording material of the present invention can be obtained. The thermal transfer recording material is excellent in storage stability of the recording layer and the image.

Since the optical recording material of the present invention has a high reflectance and a high contrast, recording and reproduction can be surely performed. Further, the heat-sensitive transfer recording material of the present invention can form a clear image with good fixability on the image receiving material by irradiating light according to the image information.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing an image forming principle of a thermal transfer recording material of the present invention.

FIG. 2 is an explanatory diagram showing an example of an image receiving material.

FIG. 3 is an explanatory diagram showing the image forming principle in the aspect of the heat-sensitive transfer recording material of the present invention.

[Explanation of symbols]

1 support 2 Image receiving layer 3 Image receiving material 4 support 5 heat sensitive layer 6 Thermal transfer recording material 9 Heat-fusible layer 10 Thermal transfer recording material.

Claims (5)

[Claims] 1. A metal ion-containing indoaniline dye compound represented by the following general formula (Formula 1). [Chemical 1] [ ^Wherein M ²⁺ represents a chelatable metal ion, and X and Y each independently represent a hydrogen atom, a halogen atom or a monovalent organic group. l and m are 1 to
4 of an integer, Z ^- represents respectively an anion. Also,
B represents a non-metal atom group which forms a 5- or 6-membered ring with the adjacent nitrogen atom. ] 2. A metal ion-containing indoaniline dye compound represented by the following general formula (Formula 2). [Chemical 2] [However, M ²⁺ , Y, l, m and Z ^- are defined in the above-mentioned claim 1.
Has the same meaning as described in. X ¹ is -COO
R, -CONRR ¹ , -SO ₂ NRR ¹ , -NHCON
It is at least one group selected from the group consisting of RR ¹ , —NHCOOR, —CN, and —NO ₂ (provided that R represents an alkyl group or an aryl group, and R ¹ independently of R above). Represents a hydrogen atom, an alkyl group or an aryl group.). R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group. ] 3. A metal ion-containing indophenol dye compound represented by the following general formula (Formula 3). [Chemical 3] [However, M ²⁺ , Y, l, m and Z ^- are defined in the above-mentioned claim 1.
Has the same meaning as described in. X ² represents a hydrogen atom or a monovalent group excluding an acylamino group. ] 4. A support, and one selected from the general formulas (Chemical formula 1), (Chemical formula 2) and (Chemical formula 3) defined on the support, which are formed on the support. An optical recording body comprising a recording layer containing at least one metal ion-containing dye compound. 5. A color material layer containing a color material transferable by heat and / or a layer adjacent to the color material layer contains a metal ion-containing dye compound represented by the following general formula (Formula 4). A thermal transfer recording material characterized by: [Chemical 4] [However, in the formula, M ²⁺ , 1, m, and Z ⁻ have the same meanings as in claim 1. X ¹¹ and Y ¹¹ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group. R ⁰ represents a 6-membered nitrogen-containing aromatic heterocycle together with the adjacent nitrogen atom and the double bond of the aromatic ring. J is
—NR ¹¹ R ¹² (provided that R ¹¹ and R ¹² each independently represent a hydrogen atom and an alkyl group, and R ¹¹ and R ¹² together with the adjacent nitrogen atom form a 5- or 6-membered ring; Represents a metal atom group), or -OR
¹³ (wherein, R ¹³ represents. An alkyl group which may have a hydrogen atom or a substituent group). ]