JP2946665B2 - Manufacturing method of optical recording medium - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for manufacturing an optical recording medium. An example of the optical recording is an optical disk.
In particular, with the advent of compact, highly reliable and inexpensive semiconductor lasers, read-only optical disks such as compact disks (CDs), and write-once optical disks using Te-based inorganic materials as recording media have been put to practical use. . On the other hand, an organic dye-based optical disk using a laser absorbing dye as a new write-once medium has been studied. The greatest feature of this organic dye-based optical disk is that it can be formed by a coating method such as a spin coating method, and high productivity under normal pressure is expected to reduce the cost in the future.

Generally, an optical disc irradiates a thin recording layer provided in a circular gas with a laser beam focused to about 1 μm,
It performs high-density information recording. The recording is generated by thermal deformation such as decomposition, evaporation, and dissolution of the recording layer generated by absorption of the irradiated laser energy, and the recorded information is reproduced by the laser beam. This is performed by reading the difference between the reflectance of the raised portion and the reflectance of the portion not raised.

In addition, guide grooves are formed in advance on the recording surface of the optical disc in order to perform accurate recording / reproduction. Normal,
This guide groove is formed by a photopolymer method or an injection molding method. In the former case, however, there is a disadvantage that the productivity is low and the cost is high because the mold is formed from the photopolymer. In the latter case, the injection molding method provides excellent productivity and inexpensive disks can be produced.However, resins that can be used in the injection molding method are required to have fluidity at the time of heating, so there are restrictions on materials, and in general the resin is resistant. Poor solvent properties. When forming a thin film of a laser absorbing dye by solution coating on such an injection molded plastic transparent substrate, it is necessary that the guide groove on the substrate is not exposed to the coating solvent. Only Cellsolve solvents are known (see JP-A-62-67068).
In addition, there is almost no laser-absorbing dye that is dissolved at a high concentration in the cellsolve solvent, and the cellsolve solvent has a problem as a coating solvent for an injection-molded plastic substrate.

[Problems to be Solved by the Invention] Therefore, as a result of intensive studies on a solvent that can be uniformly applied without disturbing an injection-molded plastic transparent substrate and that dissolves a laser-absorbing dye at a high concentration, an epoxy alcohol-based or epoxy-based The inventors have found that an ether solvent has the appropriateness, and arrived at the present invention.

An object of the present invention is to provide a method for manufacturing an optical recording medium using a solvent that can uniformly apply an injection-molded transparent plastic substrate without disturbing and that dissolves a laser absorbing dye at a high concentration. is there.

[Means for solving the problem]

The present invention is characterized in that an organic solvent solution of a laser absorbing dye is applied on a transparent substrate and then dried to produce an optical recording medium, wherein an epoxy alcohol solvent or an epoxy ether solvent is used as the organic solvent. The gist is a method of manufacturing an optical recording medium.

 Hereinafter, the present invention will be described in detail.

Examples of the transparent substrate used in the present invention include substrates made of glass, plastic, and the like, and a plastic substrate is preferable from various points. Examples of the plastic substrate include substrates made of acrylic resin, methacrylic resin, vinyl acetate resin, vinyl chloride resin, nitrocellulose, polyethylene resin, polypropylene resin, polycarbonate resin, polyimide resin, polysulfone resin, and the like.

Particularly preferred substrates include injection-molded polycarbonate resin substrates and methacrylic resin substrates which are excellent in mass productivity and have practical levels of birefringence, softening point and heat resistance.

Examples of the laser-absorbing dye include those that are dissolved in a high concentration in an epoxy alcohol-based or epoxy ether-based solvent, have absorption in a wavelength band of 600 to 900 nm, and have a molecular absorption coefficient of 10 ⁴ to 10 ⁵ cm ^−1. Are preferred.

Particularly preferred dyes are those represented by the following general formulas (I) and (I)
Dyes containing at least one compound selected from the compounds represented by I], [III], [IV] and [V] are exemplified.

General formula [I] (Wherein ring A ¹ and B ¹ each independently represents a benzene ring or a naphthalene ring which may have a substituent, R ¹
And R ^2, each independently, an alkyl group or a substituent an alkenyl group having 2 to 10 carbon atoms which may have a 1 to 8 carbon atoms which may have a substituent, X ^- Represents an anion, and n is an integer of 0 to 4. And a cyanine compound represented by the formula:

General formula (II) (Wherein A ² and B ² are each independently R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkoxyalkoxy group, a halomethyl group or a halogen atom, and R ⁷ and R ⁸ independently represents a hydrogen atom or a halogen atom. 9,19-dioxadinaphtho- [3,2,1-de; 3,2,1-op] pentacene derivatives represented by the formula:

General formula (III) [Wherein, one of R ⁹ and R ¹⁰ is —O (C ₂ H ₄ O)
_p ¹¹ (wherein R ¹¹ represents an alkyl group which may be branched, p is a number of 1 to 6), the other is a hydrogen atom, and A ³ is VO , Cu, Ni or Co. ] The compound represented by these.

General formula (IV) (Wherein, M represents a metal atom, and rings A ⁴ and B ³ may each independently have a substituent. Q is a residue of an aromatic amine which may have a substituent. And m is 2 or 3
And Z ⁻ represents an anion. A) a metal-containing indoaniline compound represented by the formula:

General formula [V] (Where A ⁵ represents a residue that forms a heterocycle with the carbon and nitrogen atoms to which it is attached, and B ⁴ together with the two carbon atoms to which it is attached. And X represents a group having an active hydrogen.) A complex compound of an azo compound and a metal represented by the formula:

Examples of the substituents on the benzene ring or naphthalene ring represented by rings A ¹ and B ¹ include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, an alkyl group such as a methyl group and an ethyl group, a trifluoromethyl group and the like. A halogenated alkyl group of
Examples include an alkoxy group such as a methoxy group and an ethoxy group, an alkoxyalkoxy group such as a methoxyethoxy group, and an alkoxyalkyl group such as an ethoxyethyl group.

Examples of the alkyl group having 1 to 8 carbon atoms which may have a substituent represented by R ¹ and R ² include a methyl group, an ethyl group, a linear or branched propyl group, a butyl group, a pentyl group,
A hexyl group, a heptyl group, and an octyl group; and an optionally substituted alkenyl group having 2 to 10 carbon atoms is an allyl group, a 2-methylallyl group, a 3-methylallyl group, a 2-bromoallyl group, -Bromoallyl group, 2-chloroallyl group, 3-chloroallyl group and the like.

X ^- and Z ^-, as the anion ^{represented, I -, Br -, Cl} -, C
_{^{lO 4 -, PF 6 -,}} BF 4 -, SCN -, And the like.

As the alkyl group represented by R ³ , R ⁴ , R ⁵ and R ⁶ , a methyl group, an ethyl group, a linear or branched propyl group,
Examples thereof include an alkyl group having 1 to 8 carbon atoms such as a butyl group, a pentyl group, a heptyl group, a hexyl group, and an octyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a linear or branched propoxy group, a butoxy group, a pentyloxy group, a heptyloxy group, a hexyloxy group, and an alkoxy group having 1 to 8 carbon atoms such as an octyloxy group. No. Examples of the alkoxyalkoxy group include a methoxyethoxy group, an ethoxyethoxy group, an ethoxypropoxy group, and a butoxyethoxy group. Examples of the halomethyl group include a chloromethyl group and a bromomethyl group.
Examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom.

Examples of the halogen atom represented by R ⁷ and R ⁸ include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom.

The alkyl group represented by R ^11, include straight chain or branched chain alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, butyl group.

Examples of the metal atom represented by M include Group VIII, Group Ib, Group II
Examples include group b, group IIIb, group IVa, group Va, group VIa and group VIIa metal atoms, preferably Ni, Cu and Co.

Examples of the substituent of the ring A ⁴ and B ^4, a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acylamino group, an alkoxycarbonylamino group, etc. alkylsulfonylamino group.

Examples of the residue of the aromatic amine which may have a substituent represented by Q include tetrahydroquinolines and the following general formula: (Wherein, R ¹⁴ and R ¹⁵ each represent a hydrogen atom, a halogen atom, an alkyl group, an acylamino group, an alkoxy group, an alkylsulfonylamino group or an alkoxycarbonylamino group. R ¹² and R ¹³ each represent a hydrogen atom, a carbon atom An alkyl group which may have a substituent of 1 to 20, an aryl group or a cyclohexyl group;
As a substituent of the aryl group or the cyclohexyl group, for example, it may have an alkoxy group, an alkoxyalkoxy group, an alkoxyalkoxyalkoxy group, an allyloxy group, an aryl group, an aryloxy group, a cyano group, a hydroxy group, or a tetrahydrofuryl group. ).

The residue forming a heterocyclic ring represented by A ^5, for example, the following formula (Wherein, R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an acylamino group, an alkoxy group, a nitro group or an alkoxyalkyl group).

The residue forming an aromatic ring or a heterocyclic ring represented by B ^4, for example, the following formula (Wherein R ¹⁸ is a hydrogen atom, a halogen atom, an alkyl group,
Represents an acylamino group or an alkoxy group, R ¹⁹ and R
²⁰ independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, each of which independently represents an alkoxy group, an alkoxy group, It may have a substituent selected from an alkoxy group, an alkoxyalkoxyalkoxy group, an allyloxy group, an aryl group, an aryloxy group, a cyano group, a hydroxy group and a tetrahydrofurfuryl group. ). Examples of the group having an active hydrogen represented by X include a hydroxyl group, a carboxylic acid group, and a sulfonic acid group. Examples of the metal that forms a complex compound with an azo compound include Group VIII, Group Ib, Group IIb, and Group III.
Examples include metals of Group b, Group IVa, Group Va, Group VIa, and Group VIIa, and preferably include Ni, Cu, and Co metal atoms.

Among the laser absorbing dyes represented by the above general formulas [I], [II], [III], [IV] and [V], preferred examples include the following compounds.

The laser absorbing dyes represented by the above general formulas [I], [II], [III], [IV] or [V] can be used alone or in an appropriate combination. An optical recording medium is manufactured by spin coating a solution dissolved in a solvent or an epoxy ether-based solvent.

Any binder may be used as long as it dissolves in an epoxy alcohol-based or epoxy ether-based solvent.

As the epoxy alcohol type solvent used in the present invention, an epoxy alcohol type solvent or an epoxy ether type solvent usually having 3 to 10 carbon atoms can be mentioned, for example, the following ones.

Among them, preferred are those having a boiling point of 120 to 170.
° C, especially 2,3-epoxy-1-propanol and di (1,2-dimethyl-1,2-epoxypropyl) ether.

Further, these solvents may be mixed with a fluoroalcohol-based solvent such as octafluoropropyl alcohol or tetrafluoropropyl alcohol, or 3-hydroxy-3-methyl-2-butanone or diacetone alcohol.

The ratio of the laser absorbing dye to the epoxy alcohol-based solvent or epoxy ether-based solvent is particularly preferably 0.5 to 3.0% by weight. The ratio of the laser absorbing dye to the binder is desirably 10% by weight or more.

The solution in which the dye is dissolved is preferably filtered through a 0.3 μm or less filter.

The rotation speed of the spin coating is preferably from 500 to 2000 rpm. After the spin coating, if necessary, a treatment such as heating or exposure to a solvent vapor may be performed.

 The thickness of the coating film is preferably 300 to 1500 °.

Furthermore, a transition metal chelate compound (acetylacetonate chelate, bisphenyldithiol,
Salicylaldehyde oxime, bisdithio-α-diketone, etc.).

The recording film of the optical recording medium of the present invention may be provided on both sides of the substrate, or may be provided only on one side.

Recording on the recording medium obtained as described above is performed by irradiating a laser beam, preferably a semiconductor laser beam, focused to about 1 μm on a recording layer provided on both sides or one side of the substrate. In the part irradiated with the laser beam,
Thermal deformation of the recording layer such as decomposition, evaporation, and dissolution occurs due to absorption of laser energy.

Reproduction of recorded information is performed by reading the difference in reflectance between a portion where thermal deformation has occurred and a portion where thermal deformation has not occurred using a laser beam.

As the light source, various lasers can be used, but a semiconductor laser is particularly preferable in terms of price and size. As the semiconductor laser, a laser having a center wavelength of 830 nm and a center wavelength of 780 nm is desirable.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to examples, but the examples do not limit the present invention.

Example 1 The following structural formula 0.15 g of a metal-containing indoaniline-based compound represented by
-Dissolved in 10 g of epoxy-1-propyl alcohol,
The solution was obtained by filtration through a 0.22 nm filter. This solution
5 ml was dropped on a 1.2-mm-thick injection-molded polycarbonate resin substrate (diameter: 5 inches) having a 1.6-μm pitch groove and applied by a spinner method at a rotation speed of 1000 rpm. After the application, it was dried at 60 ° C. for 10 minutes. The maximum absorption wavelength of the coating film is 795 nm as shown in FIG. 1, and the reflectance is 31%.
(830 nm).

While rotating the resin substrate on which the recording layer was formed at 4 m / s, a semiconductor laser light having a center wavelength of 830 nm, a pulse width of 200
Irradiation for nsec resulted in a C / N ratio of 53dB at an output of 6mW. The storage stability (60 ° C., 80% RH) was also good.

Example 2 The following structural formula Is dissolved in 10 g of a 1: 1 mixed solution of di (1,2-dimethyl-1,2-epoxypropyl) ether and 3-hydroxy-3-methyl-2-butanone. And a 0.22 μm filter to obtain a solution. 5 ml of this solution was dropped onto a 1.2 mm thick 1.6 μm pitch injection-molded polycarbonate resin substrate (5 inches in diameter) with grooves, and 800 rpm by a spinner method.
Was applied at a rotation speed of. After the application, it was dried at 60 ° C. for 10 minutes.
The maximum absorption wavelength of the coating film was 805 nm as shown in FIG. 2, and the reflectance was 31% (830 nm).

While rotating the substrate on which the recording layer was formed at 4 m / s,
Irradiation with a semiconductor laser light having a center wavelength of 830 nm at a pulse width of 500 nsec yielded a C / N ratio of 54 dB at an output of 6 mW. The storage stability (60 ° C., 80% RH) was also good.

Comparative Examples 1-2 Using the metal-containing indoaniline-based dye shown in Example 1, for solvents other than the epoxy alcohol-based or epoxy ether-based solvent of the present invention, the solubility of the dye and the effect on the injection-molded polycarbonate transparent substrate [whitening And the presence or absence of groove sag], and the crystallization of the coating film was compared. As a result, the example of the present invention was remarkably superior.

In addition, when the same comparison was performed using the metal-containing indoaniline dye shown in Example 2, the Example of the present invention was significantly superior.

Example 3 1 g of the cyanine dye of the present invention represented by the above formula [V] is represented by the following structural formula Dissolved in 50 g of an epoxy alcohol-based solvent represented by
The solution was filtered through a 2 μm filter to obtain a solution. This solution 2
ml on a 700 mm deep, 0.7 μm wide, injection-molded polymethacrylic resin substrate with a groove (130 mm in diameter).
The coating was performed at a rotation speed of 0 rpm. After the application, it was dried at 60 ° C. for 10 minutes. For film thickness measurement, apply to glass plate under the same conditions
When the film thickness was measured by the step, it was 1500 °. The maximum absorption wavelength of the coating film was 790 mm, and the peak was broad.

When this coating film was irradiated with a semiconductor laser beam having a center wavelength of 830 nm at an output of 6 mW and a beam diameter of 1 μm, a width of about 1 μm was obtained.
An extremely clear hole (pit) having a contour of m and a pit length of about 2 μm was formed. The C / N ratio was 52 dB. Storage stability (6
0 ° C., 80% RH).

Example 4 1 g of the cyanine dye of the present invention represented by the above formula [VI] and 1.5 g of nitrocellulose (RB-20, manufactured by Daicel Chemical Industries, Ltd.) It was dissolved in 50 g of a one-to-one mixture of CF ₃ CF ₂ CF ₂ OH and filtered through a 0.22 μm filter to obtain a solution. 3 ml of this solution was dropped onto a grooved injection-molded polymethacrylic resin substrate (120 mm) having a depth of 650 mm and a width of 0.7 μm, and was applied at a rotation speed of 1500 rpm. After the application, it was dried at 60 ° C. for 10 minutes. In order to measure the film thickness, it was applied to a glass plate in the same manner and measured by α-step to find that the film thickness was 1200 °. The maximum absorption wavelength of the coating film was 820 nm, and the peak was broad.

When this coating film was irradiated with a semiconductor laser beam having a center wavelength of 830 nm at an output of 6 mW and a beam diameter of 1 μm, a width of about 1 μm was obtained.
A very clear pit having a contour of m and a pit length of about 2 μm was formed. The C / N ratio was 51 dB. Storage stability (60 ℃, 8
0% RH) was also good.

Example 5 Melting point: 180-185 ° C Molecular extinction coefficient (ε): 8.2 × 10 ⁴ Mass spectrum: 628 (M ⁺ ) λmax in chloroform solution: 720 nm 1.0 g of the dye represented by the above general formula [VII] 50 g of an epoxy alcohol solvent which is a 1: 1 mixture with
And filtered through a 0.22 μm filter to obtain a solution. 2 ml of this solution is dropped onto a polymethyl methacrylate resin substrate (diameter 120 mm) with a groove made of an ultraviolet curable resin having a depth of 700 mm and a width of 0.7 μm, and 1000 r by a spinner method.
The coating was performed at a rotation speed of pm. After the application, it was dried at 60 ° C. for 10 minutes. The film was applied to a glass plate under the same conditions, and the film thickness was measured by Cristep to be 800 °. The maximum absorption wavelength of the coating film was 705 nm, and the reflectance was 33% (830 nm). The shape of the spectrum was broad.

When this coating film was irradiated with a semiconductor laser light having a center wavelength of 780 nm at an output of 6 mW and a beam diameter of 1 μm, a width of about 1 μm was obtained.
A very clear pit having a contour of m and a pit length of about 2 μm was formed. In the evaluation of the dynamic characteristics, the C / N ratio was as high as 51 dB (8 mW), and the storage stability (60 ° C., 80% RH) was good.

Example 6 The following structural formula Molecular absorption coefficient (ε): 8.0 × 10 ⁴ λmax in chloroform solution: 790 nm Mass spectrum: 648 (M ⁺ ) Melting point: 270 to 275 ° C. 1.0 g of a dye represented by the following structural formula Dissolve in 50 g of the represented epoxy alcohol solvent, 0.2
The solution was filtered through a 2 μm filter to obtain a solution. This solution 2
ml was dropped onto an injection-molded polycarbonate resin substrate (130 mm) and applied by a spinner method at a rotation speed of 1000 rpm. After the application, it was dried at 60 ° C. for 10 minutes. The film was applied to a glass plate under the same conditions, and the film thickness was measured by Cristep to be 750 °. The maximum absorption wavelength of the obtained injection-molded polycarbonate resin substrate measured by a spectrophotometer was 760 nm, which had a broad absorption spectrum at 600 to 900 nm, indicating that near infrared rays were effectively absorbed.

When this coating film was irradiated with a semiconductor laser beam having a center wavelength of 830 nm at an output of 6 mW and a beam diameter of 1 μm, a width of about 1 μm was obtained.
A very clear pit having a contour of m and a pit length of about 2 μm was formed. In the evaluation of the dynamic characteristics, the C / N ratio was as high as 50 dB, and the storage stability (60 ° C., 80% RH) was good.

Example 7 The light absorbing substance of the compound represented by the above structural formula is represented by the following structural formula 2% dissolved in epoxy alcohol solvent represented by
Is prepared, and this solution is spin-coated (rotation speed 10
(00 rpm) on an injection-molded methacrylic resin substrate with a groove. The maximum absorption wavelength of the coated thin film (recording layer) was 840 nm, and the absorption peak was broad.

A laser beam with a center wavelength of 830 nm is output to this thin film at 4 mW,
When irradiated with a beam diameter of about 1 μm, extremely clear pits with a width of about 1 μm and a pit length of about 2 μm were formed,
The C / N ratio at that time was 51 dB. In addition, the storage stability of the writing performance with semiconductor laser light after storage for 10 days in a constant temperature / humidity chamber at a temperature of 60 ° C and a relative humidity of 80%.
According to the C / N ratio, it was 51 dB.

Example 8 And a complex compound of Ni metal with the following structural formula A 2% solution was prepared by dissolving a 1: 1 mixture of the above in an epoxy ether-based solvent, and this solution was applied to an injection-molded polycarbonate resin substrate with grooves by spin coating (at 1,000 rpm). The maximum absorption wavelength of the applied thin film (recording layer) was 720 nm, and the absorption peak was broad.

A 7 mW laser beam with a center wavelength of 830 nm is output to this thin film.
Irradiation with a beam diameter of about 1 μm resulted in formation of a very clear pit having a width of about 1 μm and a pit length of about 2 μm, and the C / N ratio at that time was 51 dB. Its storage stability is in a constant temperature and humidity chamber at a temperature of 60 ° C and a relative humidity of 80%.
According to the C / N ratio of the writing performance by the semiconductor laser light after storage for 10 days, it was 51 dB.

[Effects of the Invention] According to the present invention, a laser-absorbing dye is dissolved in a high concentration, and can be uniformly applied without damaging the injection-molded plastic transparent substrate (whitening, groove dripping, etc.), and without crystallization during application. Since the obtained coating film has excellent storage stability, high reflectance, high sensitivity and a high C / N ratio, and an optical recording medium can be manufactured, the method of the present invention is industrially extremely useful. .

[Brief description of the drawings]

FIG. 1 shows the light absorption characteristics of the injection molded polycarbonate resin substrate obtained in Example 1 measured by a spectrophotometer.
The figure shows the light absorption characteristics of the injection molded polycarbonate resin substrate obtained in Example 2 using a spectrophotometer. In each figure, the vertical axis represents the absorbance (left), the reflectance (right), and the horizontal axis represents the wavelength.

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Takako Tsukahara 1000 Kamoshita-cho, Midori-ku, Yokohama-shi, Kanagawa Prefecture, Mitsubishi Chemical Research Institute (56) References JP-A-3-203690 (JP, A) JP-A Sho 64-75454 (JP, A) JP-A-62-193880 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) B41M 5/26

Claims (3)

(57) [Claims] 1. An organic solvent solution of a laser absorbing dye is applied on a transparent substrate and then dried to produce an optical recording medium, wherein an epoxy alcohol solvent or an epoxy ether solvent is used as the organic solvent. Characteristic method for producing an optical recording medium. 2. The method according to claim 1, wherein the transparent substrate is an injection-molded transparent plastic substrate. 3. The method according to claim 1, wherein the laser absorbing dye has the following general formula [I]:
3. The dye according to claim 1, wherein the dye is a dye containing at least one compound selected from the compounds represented by [II], [III], [IV] and [V]. The production method described in 1. General formula [I] (Wherein ring A ¹ and B ¹ each independently represents a benzene ring or a naphthalene ring which may have a substituent, R ¹
And R ^2, each independently, an alkyl group or a substituent an alkenyl group having 2 to 10 carbon atoms which may have a 1 to 8 carbon atoms which may have a substituent, X ^- Represents an anion, and n is an integer of 0 to 4. And a cyanine compound represented by the formula: General formula (II) (Wherein A ² and B ² are each independently R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkoxyalkoxy group, a halomethyl group or a halogen atom, and R ⁷ and R ⁸ independently represents a hydrogen atom or a halogen atom. 9,19-dioxadinaphtho- [3,2,1-de; 3,2,1-op] pentacene derivatives represented by the formula: General formula (III) [Wherein, one of R ⁹ and R ¹⁰ is —O (C ₂ H ₄ O)
_p ¹¹ (wherein R ¹¹ represents an alkyl group which may be branched, p is a number of 1 to 6), the other is a hydrogen atom, and A ³ is VO , Cu, Ni or Co. ] The compound represented by these. General formula (IV) (Wherein, M represents a metal atom, and rings A ⁴ and B ³ may each independently have a substituent. Q is a residue of an aromatic amine which may have a substituent. And m is 2 or 3
And Z ⁻ represents an anion. A) a metal-containing indoaniline compound represented by the formula: General formula [V] (Where A ⁵ represents a residue that forms a heterocycle with the carbon and nitrogen atoms to which it is attached, and B ⁴ together with the two carbon atoms to which it is attached. And X represents a group having an active hydrogen.) A complex compound of an azo compound and a metal represented by the formula: