JP3039739B2 - Aminium salt compound and optical recording medium using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an infrared absorbing compound having excellent light resistance and durability, and an optical recording medium using the same, which is excellent in reproduction light deterioration and storage stability.

[0002]

2. Description of the Related Art Generally, an optical recording medium such as an optical disk or an optical card has small optically detectable pits, for example, about 1 .mu.m, provided on a recording layer provided on a substrate having a spiral, circular or linear groove. By forming, information can be recorded at high density.

For example, when a laser beam focused on the surface of a recording layer is scanned, information is written on the recording layer by absorbing the laser energy to form optically detectable pits. For example, in the heat mode recording method, the recording layer absorbs thermal energy and evaporates or decomposes at the site to form concave pits, thereby recording information. As a recording layer of such an optical recording medium, a material mainly using an inorganic substance such as a metal thin film such as an aluminum vapor-deposited film, a chalcogenide-based amorphous glass film such as a bismuth thin film or a tellurium oxide thin film has been proposed. On the other hand, in recent years, it has been proposed to use an organic dye whose physical properties can be changed by light having a relatively long wavelength in the recording layer. And, for example, as the organic dye thin film, when using a polymethine dye having a large light absorption for laser light, an azulene dye, a pyrylium dye, or the like,
A light absorbing / reflecting film exhibiting metallic luster (reflectance: 10 to 50%) is obtained, and an optical recording medium capable of laser recording and capable of reflection reading is obtained. Especially as the laser light source, the oscillation wavelength is 650 ~
If a 900 nm semiconductor laser is used, the device can be downsized,
There is an advantage that cost can be reduced.

However, when an organic dye is used for the recording layer,
There has been a problem that the organic dye is deteriorated by repeated irradiation of the reproduction light, and the reproduction characteristics of the optical recording medium are deteriorated.

[0005] In order to improve the light resistance of an organic dye, a metal chelate complex (particularly, a Ni chelate complex) which is a singlet oxygen quencher or a USP 4,6
As disclosed in US Pat. Nos. 56,121 and US Pat. No. 4,923,390, there is known a method of adding an aminium salt / diimonium salt compound as a stabilizer to a recording layer.

However, since the metal chelate complex has low solubility in a solvent that can be applied to a plastic substrate, there is a problem that it cannot be added in an amount that can sufficiently improve light resistance. Also, US Pat. No. 4,626,496 proposes a method of adding a larger amount of a metal complex to a recording layer by forming a double salt with a dye, in which case the light resistance of the organic dye is improved. However, there is a problem that the density of the organic dye in the recording layer is reduced, and the recording sensitivity is reduced. In addition, in the method of adding an aminium salt or a diimonium salt compound to the recording layer, the counter ion is merely an acid anion, so that a large amount of addition is required to further improve light resistance. As a method for improving the light resistance with a small amount of addition to such a problem, an example using a double salt compound of an aminium salt / diimonium salt cation and a metal complex anion is disclosed in JP-A-62-19 / 1987.
No. 3891. According to this method, light resistance and recording / reproducing characteristics are improved as compared with the conventional method. However, when an aminium salt / diimonium salt cation substituted with a dialkylamino group is used, a solvent of a double salt compound with a metal complex anion is used. Solubility in solvents such as aliphatic hydrocarbons, alcohols and ketones that can be directly applied to plastic substrates is still insufficient, especially for optical recording media in which the recording layer is formed by a solvent coating method. There is a problem that the noise level tends to increase.

Also, an optical disk having excellent light resistance, comprising a recording layer comprising a double salt compound of a diimonium salt cation and a metal complex anion, and a reflective layer on the recording layer, is disclosed in
For example, diimonium salt cations include, for example, diimonium salts of N.N.N'.N'-tetrakis (dialkylamino-substituted phenyl) -p-phenylenediamine and N.N.N'.N ′
A diimmonium salt of -tetrakis (dialkoxyalkylamino-substituted phenyl) -p-phenylenediamine is described, but an organic dye recording layer containing these double salt compounds has a storage stability under high temperature and high humidity. The effect of improving the light resistance of the recording layer was still insufficient.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional example, and has as its object to have a large absorption region in the infrared region and to be applicable to a plastic substrate. To provide a novel aminium salt compound having good solubility in organic solvents.

Another object is to make it possible to remarkably improve the light fastness of the organic dye recording layer, at the same time suppress the decrease in recording sensitivity, and further deteriorate the storage stability at high temperatures and high humidity. It is to provide an optical recording medium without any problem.

[0010]

The aminium salt compound of the present invention has a structure represented by the following general formula (I).

[0011]

[Outside 46] (In the formula

[0012]

[Outside 53] Is any of monovalent metal complex anions represented by the following formulas (III) to (IX), and R _{1 to} R ₈ are a hydrogen atom or an alkyl group, a substituted alkyl group, an alkoxyalkyl group,
It represents a substituted alkoxyalkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group or a substituted aralkyl group. Provided that at least one of R _{1 to} R ₈ is a monovalent selected from a substituted or unsubstituted alkoxyalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group and a substituted or unsubstituted aralkyl group. Is an organic residue. Also n
Is 1 or 2)

[Outside 54] (Wherein R _{9 to} R ₁₂ each represent a hydrogen atom,
Is an unsubstituted alkyl group or a substituted or unsubstituted amino
Group or substituted or unsubstituted alkoxy group or halo
And M represents a transition metal atom);

[Outside 55] (Wherein R _{13 to} R ₁₆ each represent a substituted or unsubstituted
Alkyl group or substituted or unsubstituted aryl group or shea
And M represents a transition metal atom);

[Outside 56] ( Wherein R _{17 to} R ₂₀ are each a hydrogen atom, substituted or
Unsubstituted alkyl group, substituted or unsubstituted amino group,
Substituted or unsubstituted aryl group, substituted or unsubstituted
Represents an alkoxy group or a halogen atom, and M is
Transition metal atom);

[Outside 57] (Wherein R _{21 to} R ₂₄ are each a hydrogen atom, a substituted or
Unsubstituted alkyl group, substituted or unsubstituted amino group,
Substituted or unsubstituted aryl group, substituted or unsubstituted
Represents an alkoxy group or a halogen atom, and M is
Transition metal atom);

[Outside 58] (Wherein R _{25 to} R ₂₈ each represent a hydrogen atom,
Unsubstituted alkyl group, substituted or unsubstituted amino group,
Substituted or unsubstituted aryl group, substituted or unsubstituted
Represents an alkoxy group or a halogen atom, and M is
Transition metal atom);

[Outside 59] (Where M represents a transition metal atom);

[Outside 60] (Wherein, M represents a transition metal atom).

The optical recording medium of the present invention is an optical recording medium having a substrate and an organic recording layer, wherein the recording layer contains a compound represented by the following general formula (I). It is characterized by the following.

[0014]

[Outside 48] (In the formula

[0015]

[Outside 61] Is any of monovalent metal complex anions represented by the following formulas (III) to (IX), and R _{1 to} R ₈ are a hydrogen atom or an alkyl group, a substituted alkyl group, an alkoxyalkyl group,
It represents a substituted alkoxyalkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group or a substituted aralkyl group. Provided that at least one of R _{1 to} R ₈ is a monovalent selected from a substituted or unsubstituted alkoxyalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group and a substituted or unsubstituted aralkyl group. Is an organic residue. Also n
Is 1 or 2)

[Outside 62] (Wherein R _{9 to} R ₁₂ each represent a hydrogen atom,
Is an unsubstituted alkyl group or a substituted or unsubstituted amino
Group or substituted or unsubstituted alkoxy group or halo
And M represents a transition metal atom);

[Outside 63] (Wherein R _{13 to} R ₁₆ each represent a substituted or unsubstituted
Alkyl group or substituted or unsubstituted aryl group or shea
And M represents a transition metal atom);

[Outside 64] (Wherein R _{17 to} R ₂₀ are each a hydrogen atom, substituted or
Unsubstituted alkyl group, substituted or unsubstituted amino group,
Substituted or unsubstituted aryl group, substituted or unsubstituted
Represents an alkoxy group or a halogen atom, and M is
Transition metal atom);

[Outside 65] (Wherein R _{21 to} R ₂₄ are each a hydrogen atom, a substituted or
Unsubstituted alkyl group, substituted or unsubstituted amino group,
Substituted or unsubstituted aryl group, substituted or unsubstituted
Represents an alkoxy group or a halogen atom, and M is
Transition metal atom);

[Outside 66] (Wherein R _{25 to} R ₂₈ each represent a hydrogen atom,
Unsubstituted alkyl group, substituted or unsubstituted amino group,
Substituted or unsubstituted aryl group, substituted or unsubstituted
Represents an alkoxy group or a halogen atom, and M is
Transition metal atom);

[Outside 67] (Where M represents a transition metal atom);

[Outside 68] (Wherein, M represents a transition metal atom).

The aminium salt compound of the present invention has a structure represented by the following general formula (II).

[0017]

[Outside 50] (In the formula

[0018]

[Outside 69] Is any of monovalent metal complex anions represented by the following formulas (III) to (IX), and R ′ _{1 to} R ′ ₈ are R ′ _m and R ′ _{m + 1} (where m = 1, 3, All of the combinations of (5) and (7) represent the atoms necessary to form a substituted or unsubstituted 5-membered ring, a substituted or unsubstituted 6-membered ring, or a substituted or unsubstituted 7-membered ring together with N. n is 1 or 2]

[Outside 70] (Wherein R _{9 to} R ₁₂ each represent a hydrogen atom,
Is an unsubstituted alkyl group or a substituted or unsubstituted amino
Group or substituted or unsubstituted alkoxy group or halo
And M represents a transition metal atom);

[Outside 71] (Wherein R _{13 to} R ₁₆ each represent a substituted or unsubstituted
Alkyl group or substituted or unsubstituted aryl group or shea
And M represents a transition metal atom);

[Outside 72] (Wherein R _{17 to} R ₂₀ are each a hydrogen atom, substituted or
Unsubstituted alkyl group, substituted or unsubstituted amino group,
Substituted or unsubstituted aryl group, substituted or unsubstituted
Represents an alkoxy group or a halogen atom, and M is
Transition metal atom);

[Outside 73] (Wherein R _{21 to} R ₂₄ are each a hydrogen atom, a substituted or
Unsubstituted alkyl group, substituted or unsubstituted amino group,
Substituted or unsubstituted aryl group, substituted or unsubstituted
Represents an alkoxy group or a halogen atom, and M is
Transition metal atom);

[Outside 74] (Wherein R _{25 to} R ₂₈ each represent a hydrogen atom,
Unsubstituted alkyl group, substituted or unsubstituted amino group,
Substituted or unsubstituted aryl group, substituted or unsubstituted
Represents an alkoxy group or a halogen atom, and M is
Transition metal atom);

[Outside 75] (Where M represents a transition metal atom);

[Outside 76] (Wherein, M represents a transition metal atom).

Further, the optical recording medium of the present invention comprises a substrate and
An optical recording medium having an organic recording layer, characterized in that the recording layer contains a compound represented by the following general formula (II).

[0020]

[Outside 52] (In the formula

[0021]

[Outside 77] Is any of monovalent metal complex anions represented by the following formulas (III) to (IX), and R ′ _{1 to} R ′ ₈ are R′m
And all of the combinations of R′m + 1 (where m = 1, 3, 5, 7) together with N form a substituted or unsubstituted 5-membered ring, substituted or unsubstituted 6-membered ring, or substituted or unsubstituted 7-membered ring. Shows the group of atoms required for formation. n is 1 or 2]

[Outside 78] (Wherein R _{9 to} R ₁₂ each represent a hydrogen atom,
Is an unsubstituted alkyl group or a substituted or unsubstituted amino
Group or substituted or unsubstituted alkoxy group or halo
And M represents a transition metal atom);

[Outside 79] (Wherein R _{13 to} R ₁₆ each represent a substituted or unsubstituted
Alkyl group or substituted or unsubstituted aryl group or shea
And M represents a transition metal atom);

[Outside 80] (Wherein R _{17 to} R ₂₀ are each a hydrogen atom, substituted or
Unsubstituted alkyl group, substituted or unsubstituted amino group,
Substituted or unsubstituted aryl group, substituted or unsubstituted
Represents an alkoxy group or a halogen atom, and M is
Transition metal atom);

[Outside 81] (Wherein R _{21 to} R ₂₄ are each a hydrogen atom, a substituted or
Unsubstituted alkyl group, substituted or unsubstituted amino group,
Substituted or unsubstituted aryl group, substituted or unsubstituted
Represents an alkoxy group or a halogen atom, and M is
Transition metal atom);

[Outer 82] (Wherein R _{25 to} R ₂₈ each represent a hydrogen atom,
Unsubstituted alkyl group, substituted or unsubstituted amino group,
Substituted or unsubstituted aryl group, substituted or unsubstituted
Represents an alkoxy group or a halogen atom, and M is
Transition metal atom);

[Outside 83] (Where M represents a transition metal atom);

[Outside 84] (Wherein, M represents a transition metal atom).

Next, the present invention will be described in detail.

The aminium salt compound of the present invention is represented by the following general formula (I).

[0024]

[Outside 54] In the above general formula (I),

[0025]

[Outside 55] Is a metal complex anion, and R _{1 to} R ₈ of the aminium salt cation represent a hydrogen atom or a monovalent organic residue. In the present invention, at least one of R _{1 to} R ₈ is selected from a substituted or unsubstituted alkoxyalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group and a substituted or unsubstituted aralkyl group. 1
It is preferably a valent organic residue. And R _{1 to} R ₈
By selecting at least one of the above substituents from the group of substituents, light resistance is improved as compared with conventional ones, and an aminium salt compound having good solvent solubility can be obtained.
By including the aminium salt compound in the recording layer, it is possible to obtain an optical recording medium having extremely excellent light resistance, stability against repeated reproduction, and excellent productivity.

Specific examples of preferred monovalent organic residues as R _{1 to} R _{8 in the} aminium salt compound represented by the above general formula (I) include an alkoxyalkyl group (for example, methoxymethyl, 2-methoxy Ethyl, 3-methoxypropyl, 2-methoxypropyl, 4-methoxybutyl, 3-methoxybutyl, 2-methoxybutyl, 5-methoxypentyl, 4-methoxypentyl, 3-methoxypentyl, 2-methoxypentyl, 6-methoxy Hexyl, ethoxymethyl, 2-ethoxyethyl, 3-ethoxypropyl, 2-ethoxypropyl, 4-ethoxybutyl, 3-ethoxybutyl, 5-ethoxypentyl, 4-
Ethoxypentyl, 6-ethoxyhexyl, propoxymethyl, 2-propoxyethyl, 3-propoxypropyl, 4-propoxybutyl, 5-propoxypentyl, etc., substituted alkoxyalkyl groups (for example, dichloromethoxymethyl group, 2-difluoromethoxyethyl group) Alkenyl group (for example, vinyl group, propenyl group,
Butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, etc., substituted alkenyl group (eg, 1,2-dichlorovinyl group, 2,3-dibromopropenyl group, etc.), alkynyl group (eg, propargyl group, butynyl group, Pentynyl group, hexynyl group, etc.), substituted alkynyl group (eg, 2,3-dichloropropargyl etc.),
Aralkyl groups (for example, benzyl group, phenethyl group, α-
Naphthylmethyl group, β-naphthylmethyl group, etc.) and substituted aralkyl groups (eg, carboxybenzyl group, sulfobenzyl group, p-methylbenzyl group, etc.).
Further, the monovalent organic residue of R _{1 to} R ₈ is converted to an alkyl group (for example, a methyl group, an ethyl group, an n-propyl group,
o-propyl group, n-butyl group, iso-butyl group, t
-Butyl group, n-amyl group, t-amyl group, n-hexyl group, n-octyl group, t-octyl group and the like, and substituted alkyl group (for example, 2-hydroxyethyl group and 3-hydroxypropyl group) At least one of R _{1 to} R ₈ , especially R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆
And at least two of the combinations of the organic residues R ₇ and R ₈
The group is a monovalent organic residue selected from a substituted or unsubstituted alkoxyalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group and a substituted or unsubstituted aralkyl group; Preferably, all of R _{1 to} R ₈ are the above-mentioned substituted or unsubstituted alkoxyalkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, and substituted or unsubstituted The use of a monovalent organic residue selected from aralkyl groups improves the storage stability of the recording layer of an optical recording medium containing the aminium salt compound of the present invention in a high temperature and high humidity. This is preferable in that In particular, when a substituted or unsubstituted alkoxyalkyl group is used, the solvent solubility of the double salt compound of the present invention can be further improved, which is preferable.

In the present invention, R _{1 to} R ₈ are preferably an organic residue having 2 to 8, particularly 3 to 8, carbon atoms.

The aminium salt compound of the present invention has a structure represented by the following general formula (II).

[0029]

[Outside 56]

In the above general formula (II)

[0031]

[Outside 57] Is a metal complex anion, and R _'1 to R' ₈ of the aminium salt cation R _'1 and R' _2, R _'3 and R' _4,
R _'5 and R' ₆ and 5 membered rings at least one pair is a substituted or unsubstituted with the nitrogen atom in combination R _'7 and R _8,
A group of atoms necessary to form a substituted or unsubstituted 6-membered ring or a substituted or unsubstituted 7-membered ring is shown. In the present invention, the 5-membered ring includes, for example, a pyrrolidine ring, the 6-membered ring includes, for example, a piperidine ring, a morpholine ring, a tetrahydropyridine ring, and the 7-membered ring includes, for example, a cyclohexylamine ring. When R ′ _m and R ′ _{m + 1} (where m = 1, 3, 5, 7) are an atomic group constituting a morpholine ring, the solvent solubility of the double salt compound of the present invention is further improved. This is preferable.

In the general formula (II), R ′ ₁
And R _'2, R' ₃ and R _'4, R' ₅ and R _'6 and, R'
At least two sets a substituted or unsubstituted 5-membered ring, that to form a 6-membered ring or a substituted or unsubstituted 7-membered ring substituted or unsubstituted preferably of ₇ and the combination of R _'8,
In particular, the substituted or unsubstituted 5-membered ring, substituted or unsubstituted 6-membered ring, or substituted or unsubstituted in all combinations of R ' _m and R' _{m + 1} (where m = 1, 3, 5, 7) It is preferable to form a 7-membered ring.

Further, all the aromatic rings of the compounds represented by the above general formulas (I) and (II) are substituted with a lower alkyl group having 1 to 5 carbon atoms, a lower alkoxy group, a halogen atom, a hydroxyl group, a cyano group and the like. It may be. Further, in the general formulas (I) and (II), n is 1 or 2.

Next, specific examples of the aminium salt cation used in the infrared absorbing compounds represented by formulas (I) and (II) of the present invention are shown in Tables 1-1 and 1-2. However, for simplicity, for example, when the aminium salt cation of the general formula (I) is n = 1, R _{1 to} R ₄ are an ethyl group, and R _{5 to} R ₈ are a propenyl group, they are represented as follows.

[0035]

[Table 1]

[0036] Also, the aminium salt cation in the formula (II) n = 2, R _'1 and R' _2, R _'3 and R' _4, R _'5 and R' ₆ and R _'7 and R' ₈ When a 5-membered ring is formed by the combination of the above, they are indicated as follows.

[0037]

[Table 2]

[0038]

[Table 3]

[0039]

[Table 4]

[0040]

[Table 5]

Next, a metal complex anion paired with the above-mentioned aminium salt cation

[0042]

[Outside 58] Will be described.

Various metal complexes can be used as the counter anion in the present invention, and examples thereof include metal complex compounds represented by formulas (III) to (IX). However, M in the following general formula is Ni, Co, Mn,
Indicates a transition metal atom such as Cu, Pb, and Pt.

[0044]

[Outside 59] (Wherein R _{9 to} R ₁₂ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, or a halogen atom.)

[0045]

[Outside 60] (In the formula, R _{13 to} R ₁₆ each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a cyano group.)

[0046]

[Outside 61] (Wherein, R _{17 to} R ₂₀ each represent a hydrogen atom-substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a halogen atom. .)

[0047]

[Outside 62] (Wherein R _{21 to} R ₂₄ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group,
Represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a halogen atom. )

[0048]

[Outside 63] (Wherein R _{25 to} R ₂₈ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group,
Represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a halogen atom. )

[0049]

[Outside 64]

R in the above general formulas (III) to (VII)
The substituted or unsubstituted alkyl group At a ₉ to R _28,
For example, methyl group, ethyl group, n-propyl group, iso-
Propyl group, n-butyl group, sec-butyl group, iso
-Butyl group, t-butyl group, n-amyl group, t-amyl group, n-hexyl group, n-octyl group, t-octyl group and the like.

Examples of the substituted or unsubstituted alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group and an iso-propyloxy group.

Further, R _{9 to} R ₁₂ , R _{17 to} R ₂₀ , R _{21 to} R ₂₄
And the substituted amino group in R _{25 to} R ₂₈ includes a dimethylamino group, a diethylamino group, a dipropylamino group, an acetylamino group, a benzoylamino group and the like.

Further, R _{13 to} R ₁₆ , R _{17 to} R ₂₀ , R _{21 to} R ₂₄
And the substituted or unsubstituted aryl group in R _{25 to} R ₂₈ include, for example, a phenyl group, a tolyl group, a xylyl group,
Examples include an ethylphenyl group, a chlorophenyl group, a nitrophenyl group, a methoxyphenyl group, a dimethoxyphenyl group, a trimethoxyphenyl group, and an ethoxyphenyl group.

Next, specific examples of the anion of the metal complex used in the present invention are shown in Tables 2-1 to 2-6.

[0055]

[Table 6]

[0056]

[Table 7]

[0057]

[Table 8]

[0058]

[Table 9]

[0059]

[Table 10]

[0060]

[Table 11]

The general formulas (I) and (II) of the present invention
Is a double salt compound in which the aminium salt cation and the metal complex compound form a salt, and specific examples thereof are shown in Tables 3-1 and 3-2.

[0062]

[Table 12]

[0063]

[Table 13]

In the present invention, a double salt compound using a metal complex in which at least one of R _{13 to} R ₁₆ is an alkoxy-substituted aryl group as an anion, or at least one of R _{9 to} R ₁₂ is a halogen atom A double salt compound using a metal complex that has been used has excellent solvent solubility, and improves the light resistance without impairing the storage stability of the recording layer when it is included in the recording layer together with an organic dye. The deterioration of the layer can be effectively suppressed, and in this regard, the general formula (I)
Double salt compounds using the metal complex anions shown in II) and (IV) are preferred in the present invention.
Double salt compounds using the metal complex anion of (III) -5 shown in 1 and (IV) -5 shown in Table 2-2 are particularly preferable.

Next, a method for synthesizing the compounds represented by formulas (I) and (II) of the present invention will be described. First, an aminium salt compound having an acid anion (for example, perchlorate ion, iodine ion, chloride ion, hexafluoroantimonate ion, etc.) as a counter ion is synthesized.
This aminium salt compound is disclosed in US Pat.
No. 81, U.S. Pat. No. 3,575,871, U.S. Pat. No. 3,484,467, and JP-A-61-69991, etc., and can be synthesized, for example, as follows.

[0066]

[Outside 65]

The amino compound obtained by the above-mentioned Ullmann reaction and reduction reaction is subjected to alkoxyalkylation by selective substitution,
After substitution by alkenylation, aralkylation, or alkynylation, an aminium salt cation of the aminium salt compound of the general formula (I) can be obtained by an oxidation reaction.

When R _{1 to} R ₈ are asymmetric,
This selective substitution needs to be performed in multiple steps, and from the viewpoint of cost, it is preferable that R _{1 to} R ₈ be the same.

Further, the aminium salt cation of the aminium salt compound of the general formula (II) is converted to R in the step of the selective substitution reaction in the method for synthesizing the aminium salt cation of the aminium salt compound of the general formula (I). _'m and R' _{m + 1} (where, m = 1, 3, 5, 7) 5-membered ring is substituted or unsubstituted with N, 6-membered ring substituted or unsubstituted, substituted or unsubstituted 7-membered ring An appropriate alkylating agent may be used to obtain

For example, to form a pyrrolidine ring,
4-dibromobutane, 1,4-dichlorobutane, 1,4
-Alkylation with diiodobutane or the like, and 1,5-dibromopentane, 1,5-dichloropentane, 1,5-diiodopentane, etc. are used for the piperidine ring. In the morpholine ring,
After hydroxyethylation with bromoethanol or the like, dehydration can be performed by acid treatment to form a morpholine ring, and tetrahydropyridine ring can be cyclized by acid treatment after methacrylation with methacrylic bromide or the like. In the cyclohexylamine ring, cyclization such as 1,6-difluorohexane is performed.

In particular, in the cyclization reaction of an amino group, the reaction proceeds more quickly than in the case of alkylation, the yield is better, and the production advantage is greater than that of a conventional propyl or butyl compound.

On the other hand, an anion-type metal complex whose counter ion is a cation is, for example, a Journal of American Chemical Society (Journal of Amer).
ican Chemical Society) 196
No. 87, p. 1483, Shrouzer (S
and can be synthesized, for example, according to the following steps.

[0073]

[Outside 66] (R and R 'are alkyl groups, aromatic rings, etc., X is a halogen atom, M is a transition metal)

[0074]

[Outside 67]

The neutral metal complex obtained by the above reaction 1) or 2) is converted into an anion form by adding p-phenylenediamine in dimethyl sulfoxide, and then converted into an anion form in alcohol.
A quaternary alkyl ammonium salt is added to obtain a metal complex anion.

The cation in this case is particularly

[0077]

[Outside 68] And the like are preferred.

Next, equimolar amounts of the aminium salt compound and the anionic metal complex are dissolved in a polar solvent. As the polar solvent to be used, N, N-dimethylformamide and the like are preferable. The concentration may be about 0.01 mol / l.

Thereafter, an aqueous solvent, especially water, is added thereto,
Metathesis occurs and precipitates. The amount of water to add is 10
What is necessary is just to make a large excess of twice or more.

The reaction temperature is preferably from room temperature to about 90 ° C. Next, the two liquid phases are separated, filtered and dried, and, if necessary, repeated twice or three times, and then recrystallized with DMF-ethanol or the like to obtain the double salt compound of the present invention.

In addition to the above-mentioned method, a neutral one, which is an intermediate of the metal complex anion, is dissolved in methylene chloride or the like, and this is combined with an acid anion. The double salt compound of the present invention can also be obtained by adding an equimolar amount of an aminium salt compound, concentrating and recrystallizing. Alternatively, in addition to the above method, a neutral metal complex anion intermediate may be dissolved in methylene chloride or the like, an aminium salt compound may be added in an equimolar amount, concentrated, and recrystallized.

The double salt compound of the aminium salt cation and the metal complex anion exemplified above has a maximum absorption wavelength of 90.
It is at 0 nm or more and has a large absorption peak with an extinction coefficient of about several hundred thousand.

Such an infrared absorbing compound is suitably used for a heat insulating film, sunglasses, etc. in addition to the use as a material for an optical recording medium.

The aminium salt compound of the present invention can be used by being contained in a recording layer containing an organic dye of an optical recording medium.

As the near-infrared absorbing dye for forming the organic dye recording layer used in combination with the aminium salt compound of the present invention as an optical recording medium, generally known dyes are used, for example, cyanine dyes. And merocyanine dyes, croconium dyes, squarium dyes, azurenium dyes, polymethylene dyes, naphthoquinone dyes, pyrylium dyes, phthalocyanine dyes, naphthalocyanine dyes, and naphtholactam dyes.

Among these organic dyes, cationic dyes typified by polymethine, cyanine and azurenium are preferred in that they have excellent storage stability of the recording layer. This is particularly preferable because the storage stability of the recording layer is not reduced even when mixed with the double salt compound of the present invention.

The cationic dyes are listed below.

A polymethine dye represented by formula (X):

[0089]

[Outside 69] In the formula, A, B, D and E represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted It represents a group selected from a styryl group and a substituted or unsubstituted heterocyclic group. r
₁ ', r _2' is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cyclic alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group and a substituted or unsubstituted aryl And k represents 0 or 1, l represents 0, 1 or 2,

[0090]

[Outside 70] Represents an anion.

A dye represented by formula (XI):

[0092]

[Outside 71] Where A, B, D, E and

[0093]

[Outside 72] Is as defined above, and r _{1 to} r ₅ are a hydrogen atom, a halogen atom,
It represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Y represents a divalent organic residue having an atomic group necessary for completing a 5- or 6-membered ring. p,
q is 0, 1 or 2.

A dye represented by formula (XII):

[0095]

[Outside 73] Where A, B, D, E, r ₂ , r ₃ , Y and

[0096]

[Outside 74] Is as defined above.

A dye represented by formula (XIII):

[0098]

[Outside 75] In the formula, A, B, D, E, r ₁ , r ₂ , r ₃ , r ₄ , p and q are as defined above,

[0099]

[Outside 76] An azurenium-based dye represented by the general formula (XIV), (XV), or (XVI).

[0100]

[Outside 77]

Here, R _{29 to} R ₃₅ represent a hydrogen atom, a halogen atom (a chlorine atom, a bromine atom, an iodine atom) or a monovalent organic residue. The monovalent organic residue can be selected from a wide range.

And at least one of R ₂₉ and R ₃₀ , R ₃₀ and R ₃₁ , R ₃₁ and R ₃₂ , R ₃₂ and R ₃₃ , R ₃₃ and R _34, and R ₃₄ and R _35. Alternatively, an unsubstituted fused ring may be formed. The condensed ring is a 5-, 6-, or 7-membered condensed ring, and is an aromatic ring (such as benzene, naphthalene, chlorobenzene, bromobenzene, methylbenzene, ethylbenzene, methoxybenzene, or ethoxybenzene), or a heterocyclic ring (furan). Ring, benzofuran ring, pyrrole ring, thiophene ring, pyridine ring, quinoline ring, thiazole ring and the like, and aliphatic ring (dimethylene, trimethylene, tetramethylene and the like).

[0103]

[Outside 78] Represents an anion as defined above.

F represents a divalent organic residue linked by a double bond. Specific examples of the present invention containing such F include those represented by the following general formulas (1) to (12). However, in the formula

[0105]

[Outside 79] Represents the following azurenium salt nucleus, in which

[0106]

[Outside 80] The right side except F indicates F.

Azurenium salt nucleus

[0108]

[Outside 81]

[0109]

[Outer 82] R ₂₉ ′ to R ₃₅ ′ have the same meaning as R _{29 to} R ₃₅ .

Also,

[0111]

[Outside 83] And the azulene salt nucleus on the right side in the above formula (3) may be symmetric or asymmetric.

[0112]

[Outside 84] In the formula, J represents a group of nonmetallic atoms necessary to complete the nitrogen-containing heterocyclic ring.

[0113]

[Outside 85] In the formula, R ₃₈ represents a substituted or unsubstituted aryl group or a cationic group thereof.

[0114]

[Outside 86] In the formula, R ₃₉ represents a heterocyclic group or a cationic group thereof.

[0115]

[Outside 87] In the formula, R ₄₀ represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group.

[0116]

[Outside 88]

[0117]

[Outside 89] In the formula, Z ₂ represents an optionally substituted pyran, thiapiran, selenapyran, tellropyran, benzopyran, benzothiapiran, benzoselenapyran, benzotellopyran, naphthopyran, naphthiapyran or naphthoselenapyran, an atom group necessary for completing naphthotellopyran. Is shown.

L represents a sulfur atom, an oxygen atom or a selenium atom, a tellurium atom.

R ₄₁ and R ₄₂ represent a hydrogen atom, an alkoxyl group, a substituted or unsubstituted aryl group, an alkenyl group,
Represents a heterocyclic group. S represents an integer from 1 to 8.

In addition, as a suitable dye, general (XVI)
Dyes represented by I), (XVIII), (XIX) and (XX).

[0121]

[Outside 90]

[0122]

[Outside 91]

The above formulas (XVII) to (XXIII)
In the formula, L ₁ and L _{2 each} represent a substituted nitrogen atom, sulfur atom, oxygen atom, selenium atom or tellurium atom, and Z ₁ represents an optionally substituted pyrylium, thiopyrylium, selenapyrylium, telluropyrylium, benzopyrylium , Benzothiopyrylium, benzoselenapyrylium, benzotelluropyrylium, naphthopyrylium, naphthothiopyrylium, naphthoselenapyrylium or a group of atoms necessary to complete naphthoterilopyrylium, Z ₂ is a pyran which may be substituted , Thiopyran, selenapyran, telluropyran, benzopyran, benzothiopyran, benzoselenapyran,
A benzotelluropyran, a naphthopyran, a naphthothiopyran, a naphthoselenapyran or a group of atoms necessary to complete naphthotellopyran, where t is 0 or 1. R ₄₃
Represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group (r ₃ ′ to r ₇ ′ are the aforementioned r ₁ ′,
Synonymous with r ₂ '. ).

K, q, J, r ₁ ′, r ₂ ′ r ₁ , Y,

[0125]

[Outside 92] Is as defined above. t is 0 or 1.

In the general formula (XXIV), K ₁ , K
₂ represents a substituted or unsubstituted aromatic amine residue, for example, a nitrogen atom, an oxygen atom, or a heterocyclic amine residue containing a sulfur atom, or the following general formula

[0127]

[Outside 93] The group shown by these is mentioned. And A 'and B' are
A substituted or unsubstituted alkyl group having a hydrogen atom or a C ₁ -C _20, an aryl group or a cycloalkyl group,
D 'and E' represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom. M ′ is Ni, Cu, C
o represents a Zn metal atom.

The abbreviations in the above general formula will be described in more detail.

A, B, D and E each represent a hydrogen atom or a substituted or unsubstituted alkyl group (for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl) , Iso-butyl group, t-butyl group, n-amyl group, t-amyl group, n-hexyl group, n
-Octyl group, t-octyl group, etc.), and further, a cyclic alkyl group (for example, cyclohexyl group, etc.), an alkenyl group (vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, Dodecynyl group, prenyl group, etc.), aralkyl group (eg, benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group, etc.), substituted aralkyl group (eg, carboxybenzyl group, sulfobenzyl group, hydroxybenzyl group) Etc.) substituted or unsubstituted aryl groups (phenyl, α-naphthyl, β-naphthyl,
Tolyl, xylyl, biphenyl, ethylphenyl, chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl, nitrophenyl, diethylaminophenyl, dimethylaminophenyl, dimethoxyaminophenyl, dibenzylaminophenyl, etc.).

R ₁ , r ₂ , r ₃ , r ₄ , and r ₅ are a hydrogen atom, a halogen atom (a chlorine atom, a bromine atom, an iodine atom, etc.);
A substituted or unsubstituted alkyl group (methyl, ethyl, n
-Propyl, isopropyl, n-butyl, t-butyl,
n-amyl, n-hexyl, n-octyl, 2-ethylhexyl, t-octyl, etc., alkoxy group (methoxy, ethoxy, propoxy, butoxy, etc.), substituted or unsubstituted aryl group (phenyl, tolyl, xylyl, ethyl) Phenyl, chlorophenyl, nitrophenyl, dimethylaminophenyl, α-naphthyl, β-naphthyl, etc.). Y is a divalent hydrocarbon group, for example,-
CH ₂ —CH ₂ —, — (CH ₂ ) ₃ —,

[0131]

[Outside 94] -CH = CH-,

[0132]

[Outside 95] And the 5- or 6-membered ring may be condensed with a benzene ring, a naphthalene ring or the like.

R _{29 to} R ₃₅ and R ₂₉ ′ to R ₃₅ ′ each represent a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom,
Other than a substituted or unsubstituted alkyl group (methyl, ethyl, n-propyl, isopropyl, n
-Butyl, t-butyl, n-amyl, n-hexyl, n
-Octyl, 2-ethylhexyl, t-octyl and the like), and substituted or unsubstituted alkoxy groups (methoxy,
Ethoxy, propoxy, butoxy, etc.), substituted or unsubstituted aryl groups (phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, nitrophenyl, dimethylaminophenyl, diethylaminophenyl, α-naphthyl, β-naphthyl, dipropylaminophenyl, Dibenzylaminophenyl, diphenylaminophenyl, etc.) and substituted or unsubstituted aralkyl groups (benzyl,
2-phenylethyl, 2-phenyl-1-methylethyl, bromobenzyl, 2-bromophenylethyl, methylbenzyl, nitrobenzyl), an acyl group (acetyl,
Propionyl, butyryl, valeryl, benzoyl, trioil, naphthoyl, phthaloyl, furoyl, etc., substituted or unsubstituted amino groups (amino, dimethylamino,
Diethylamino, dipropylamino, acetylamino,
Benzoylamino), substituted or unsubstituted styryl groups (such as styryl, dimethylaminostyryl, diethylaminostyryl, dipropylaminostyryl, and methylstyryl), nitro group, hydroxy group, carboxyl group,
A cyano group or a substituted or unsubstituted arylazo group (phenylazo, α-naphthylazo, β-naphthylazo, dimethylaminophenylazo, chlorophenylazo, nitrophenylazo, methoxyphenylazo, tolylazo, etc.), a substituted or unsubstituted heterocyclic group (for example, , Pyridyl, quinolyl, lepidyl, methylpyridyl, furyl, thienyl, indolyl, pyrrole, carbazolyl, N-ethylcarbazolyl, etc.), 2,2
-Diphenylvinyl group, 2-phenyl-2-methylvinyl group, 2- (dimethylaminophenyl) -2-phenylvinyl group, 2- (diethylaminophenyl) -2-phenylvinyl group, 2- (dibenzylaminophenyl) -2
-Phenylvinyl group, 2,2-di (diethylaminophenyl) vinyl group, 2,2-di (methoxyphenyl) vinyl group, 2,2-di (ethoxyphenyl) vinyl group, 2-
(Dimethylaminophenyl) -2-methylvinyl group, 2
-(Diethylaminophenyl) -2-ethylvinyl group).

Also, R ₂₉ ′ to R ₃₅ ′ may form a condensed ring similarly to R _{29 to} R ₃₅ .

R ₃₆ represents a hydrogen atom, a nitro group, a cyano group,
Represents an alkyl group (eg, methyl, ethyl, propyl, butyl) or an aryl group (eg, phenyl, tolyl, xylyl).

R ₃₇ is a substituted or unsubstituted alkyl group (methyl, ethyl, n-propyl, isopropyl, n-
Butyl, t-butyl, n-amyl, n-hexyl, n-
Octyl, 2-ethylhexyl, t-octyl, etc.),
Cyclic alkyl groups (cyclohexyl, cyclopropyl),
Aralkyl groups (benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, α-naphthylmethyl, β-naphthylmethyl), substituted aralkyl groups (methylbenzyl, ethylbenzyl, dimethylbenzyl, trimethylbenzyl, chlorobenzyl, Bromobenzyl), aryl group (phenyl, tolyl, xylyl, α-
Represents naphthyl, β-naphthyl) or a substituted aryl group (chlorophenyl, dichlorophenyl, trichlorophenyl, ethylphenyl, etc.).

R ₃₈ represents a substituted or unsubstituted aryl group (phenyl, tolyl, xylyl, biphenyl, α-naphthyl,
β-naphthyl, anthralyl, pyrenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, bromophenyl, dibromophenyl, tribromophenyl, ethylphenyl, diethylphenyl, nitrophenyl, aminophenyl, dimethylaminophenyl, diethylaminophenyl, dipropylaminophenyl, morpholino Phenyl, piperidinylphenyl, piperazinophenyl, diphenylaminophenyl, acetylaminophenyl, benzoylaminophenyl, acetylphenyl, benzoylphenyl, cyanophenyl, etc.) R ₃₉ is furan, thiophene, benzofuran, thionaphthene, dibenzofuran, carbazole, phenothiazine , Phenoxazine,
Represents a monovalent heterocyclic group derived from a heterocyclic ring such as pyridine.

R ₄₀ represents a hydrogen atom, an alkyl group (methyl, ethyl, propyl, butyl, etc.) or a substituted or unsubstituted aryl group (phenyl, tolyl, xylyl, biphenyl, ethylphenyl, chlorophenyl, nitrophenyl, aminophenyl, dimethyl Aminophenyl, diethylaminophenyl, acetylaminophenyl, α-naphthyl, β-naphthyl, anthralyl, pyrenyl and the like).

R ₄₁ and R ₄₂ are a hydrogen atom, an alkyl group (eg, methyl, ethyl, propyl, butyl), an alkoxy group (eg, methoxy, ethoxy, propoxy), an aryl group (phenyl, tolyl, xylyl, chlorophenyl,
Biphenyl, methoxyphenyl, etc.), a substituted or unsubstituted styryl group (styryl, p-methylstyryl, o
-Chlorostyryl, etc.), substituted or unsubstituted 4-
Phenyl 1,3-butadienyl group (4-phenyl 1,3
-Butadienyl, 4- (p-methylphenyl) -1,3
-Butadienyl and the like, or a substituted or unsubstituted heterocyclic group (quinolyl, pyridyl, carbazolyl, furyl and the like).

J is pyridine, thiazole, benzothiazole, naphthothiazole, oxazole, benzoxazole, naphthoxazole, imidazole, benzimidazole, naphthimidazole, 2-quinoline, 4-quinoline,
A group of atoms necessary to complete a nitrogen-containing heterocyclic ring such as quinoline, isoquinoline, or indole. Halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), alkyl group (methyl, ethyl, propyl, butyl, etc.) , An aryl group (phenyl, tolyl, xylyl, etc.) and an alkyl (benzyl, p-trimethyl, etc.).

[0141]

[Outside 96] Is an anion, chloride ion, bromide ion, iodide ion, perchlorate ion, benzenesulfonate ion, p-toluenesulfonate ion, methyl, sulfate ion, ethyl sulfate ion, propyl sulfate ion ,
Tetrafluoroborate ion, tetraphenylborate ion, hexafluorophosphate ion, benzenesulfinate ion, acetate ion, trifluoroacetate ion, propionate, acid ion, benzoate ion, oxalic acid Salt ion, succinate ion, malonate ion, oleate ion, stearate ion,
Citrate ion, monohydrogen diphosphate ion, dihydrogen monophosphate ion, pentachlorostannate ion, chlorosulfonate ion, fluorosulfonate ion, trifluoromethanesulfonate ion, hexafluoroantimony It represents phosphate ion, molybdate ion, tungstate ion, titanate ion, zirconate ion and the like.

R ₁ ′, r ₂ ′, r ₃ ′, r ₄ ′, r ₅ ′,
r ₆ ′ and r ₇ ′ represent a hydrogen atom or an alkyl group (for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, iso-butyl group, t-butyl Group, n-amyl group, t-amyl group, n-
Hexyl group, n-octyl group, t-octyl group, etc.), a cyclic alkyl group (eg, cyclohexyl group, etc.), a substituted or unsubstituted alkenyl group (vinyl group,
Propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, dodecynyl group, prenyl group, etc., aralkyl group (eg, benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group) And substituted aralkyl groups (eg, carboxybenzyl group, sulfobenzyl group, hydroxybenzyl group, etc.).

The amount of the double salt compound of the aminium salt cation of the above general formula (I) or (II) and the metal complex anion added to these dyes is 1 to 100% based on the total solid content. 60% by weight, preferably 1 to 40% by weight, more preferably 5 to 25% by weight is suitable. The polymethine dyes represented by the general formulas (X) and (XI) and the cyanine dyes represented by the general formulas (XXI) and (XXII) can be used in combination with the double salt compound of the present invention to provide a recording sensitivity and a recording layer. Excellent storage stability and light resistance,
In addition, the degree of deterioration of the recording layer due to reproduction light is small, and it is particularly suitable as an optical recording medium.

In the present invention, a binder may be contained in the recording layer comprising the organic dye thin film. As the binder, for example, nitrocellulose, cellulose phosphate,
Cellulose sulfate, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose myristate, cellulose palmitate, cellulose acetate / propionate,
Cellulose esters such as cellulose acetate / butyrate, cellulose ethers such as methylcellulose, ethylcellulose, propylcellulose and butylcellulose; vinyl resins such as polystyrene, polyvinylchloride, polyvinylacetate, polyvinylbutyral, polyvinylacetal, polyvinylalcohol and polyvinylpyrrolidone Kind,
Copolymer resins such as styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer, vinyl chloride vinyl acetate copolymer, polymethyl methacrylate, polymethyl acrylate, polybutyl acrylate, polyacrylic acid, polymethacrylic acid, poly Acrylic resins such as acrylamide and polyacrylonitrile, polyesters such as polyethylene terephthalate, poly (4,4
-Isopropylidenediphenylene-co-1,4-cyclohexylene dimethylene carbonate), poly (ethylenedioxy-3,3-phenylenethiocarbonate), poly (4,4-isopropylidenediphenylenecarbonate-co-terephthalate) , Poly (4,4-isopropylidene diphenylene carbonate), poly (4,4-s
ec-butylidene diphenylene carbonate), poly (4,4-isopropylidene diphenylene carbonate-block-oxyethylene) and other polyarylate resins, or polyamides, polyimides, epoxy resins, phenolic resins, polyethylene, polypropylene And polyolefins such as chlorinated polyethylene.

The recording layer may contain a surfactant, an antistatic agent, a stabilizer, a dispersible flame retardant, a lubricant, a plasticizer, and the like.

An undercoat layer may be provided between the recording layer and the substrate, and a protective layer may be provided on the recording layer.

As the undercoat layer, for the purpose of imparting solvent resistance, improving the reflectivity, or improving the repetitive reproduction, the protective layer is used to protect the recording layer from scratches, dust, dirt, etc. and to improve the environmental stability of the recording layer. Used for The materials used for these are mainly inorganic compounds, metals or organic high molecular compounds. As the inorganic compound, for example, SiO
₂ , MgF ₂ , SiO, TiO ₂ , ZnO, TiN, Si
As a metal such as N, for example, Zn, Cu, Ni, A
l, Cr, Ge, Se, Cd, etc., and ionomer resin, polyamide resin, vinyl resin, natural polymer, epoxy resin, silane coupling agent, silicone resin, liquid rubber, etc. Can be done.

As the substrate, a plastic such as polyester, polycarbonate, acrylic resin, polyolefin resin, phenol resin, epoxy resin, polyamide, polyimide, glass, metal or the like can be used.

The organic solvent that can be used for coating depends on whether it is in a dispersed state or a dissolved state, but it is generally alcohols such as methanol, ethanol, isopropanol, diacetone alcohol, acetone, methyl ethyl ketone, and cyclohexanone. Ketones; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; sulfoxides such as dimethyl sulfoxide; ethers such as tetrahydrofuran, dioxane and ethylene glycol monomethyl ether; methyl acetate; ethyl acetate; Esters such as butyl, chloroform, methylene chloride, dichloroethylene, carbon tetrachloride, aliphatic halogenated hydrocarbons such as trichloroethylene, benzene, toluene, xylene,
Aromatic compounds such as monochlorobenzene and dichlorobenzene, aliphatic hydrocarbons such as n-hexanecyclohexanoligogroin, and fluorine-based solvents such as tetrafluoropropanol and pentafluoropropanol can be used.

The coating can be performed by using a coating method such as a dip coating method, a spray coating method, a spinner coating method, a bead coating method, a wire bar coating method, a blade coating method, a roller coating method, and a curtain coating method. .

The thickness of the recording layer formed using such a solvent is 50 to 100 μm, preferably 200 to 1 μm.
μm is appropriate.

[0152]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Synthesis Example 1) The double salt compound N was prepared by the following method.
o. (I) -4 was synthesized. First, 1.4 g of nickel (II) bisdithiobenzyl (trade name: MIR-101 Midori Kagaku Co., Ltd.) and 1.8 g of p-phenylenediamine were dissolved in 10 ml of dimethyl sulfoxide, and 3.2 g of tetrabutylammonium bromide was added thereto. 60 ml of an ethanol solution was added dropwise, and the mixture was further stirred to precipitate red needles, which were collected by filtration, washed with water and purified by recrystallization to obtain 0.8 g of nickel (II) bisdithiobenzyltetrabutylammonium. When the absorption spectrum of this crystal was measured, it was confirmed that λmax 930 nm of MIR-101 was shifted to 950 nm by a long wavelength, so that it became an anion.

N, N, N ', N'-tetrakis- (p-
0.5 g of dimethoxyethylaminophenyl) -p-benzoquinone-aminium perchlorate in 50 ml of DMF
To the solution dissolved in the above was added 0.5 g of the above nickel bisdithiobenzyltetrabutylammonium, and the mixture was heated with stirring at 50 ° C. for 3 hours. The reaction solution was poured into water, and the obtained precipitate was washed with water and dried, and then recrystallized to obtain a double salt compound 0.1.
7 g were obtained.

The differential scanning calorimetry was performed, and the disappearance of the perchlorate peak at 270 ° C. and elemental analysis confirmed that the desired double salt compound was obtained.

Elemental analysis: C ₈₂ H ₉₆ N ₆ O ₈ S ₄ Ni Calculated: C: 66.52, H: 6.54, N: 5.68 Found: C: 66.28, H: 6. 65, N: 5.60

(Synthesis Example 2) A double salt compound (I) -15 was synthesized by the following method. First, N, N, N ', N'-
Tetrakis- (p-dipropenylaminophenyl) -p
Nickel-bis (trichlorobenzenedithiol) tetra (n-butyl) ammonium (trade name: PA-1006; manufactured by Mitsui Toatsu Fine Co., Ltd.) was prepared by dissolving 1.0 g of benzoquinone-aminium perchlorate in 90 ml of DMF. Then, the mixture was heated and stirred at 50 ° C. for 3 hours. This reaction solution was poured into water, and the resulting precipitate was washed with water.
After drying, recrystallization was performed to obtain 0.95 g of a double salt compound.

The disappearance of the perchlorate peak at 270 ° C. was measured by a differential scanning calorimeter, and the elemental analysis confirmed that the desired double salt compound was obtained.

Elemental analysis: C ₆₆ H ₆₂ N ₆ Cl ₆ S ₄ Ni
(Molecular weight 1338.948)

[0160]

[Outside 97]

(Synthesis Example 3) The double salt compound (I
I) -4 was synthesized. First, 0.5 g of N, N, N ', N'-tetrakis (2-methylpyrrolidinophenyl) -p-benzoquinone-aminium perchlorate was added to DMF70.
0.68 g of nickel-bis (trimethoxybenzenedithiol) tetra (n-butyl) ammonium was added to the solution dissolved in ml, and the mixture was heated with stirring at 50 ° C. for 3 hours. The reaction solution was poured into water, and the obtained precipitate was washed with water and dried, and then recrystallized to obtain a double salt compound. The disappearance of the peak of the perchlorate at 270 ° C. was confirmed by measurement with a differential scanning calorimeter, and it was confirmed by elemental analysis that the desired double salt compound was obtained.

Elemental analysis: C ₉₀ H ₁₁₂ N ₆ O ₁₂ S ₄ Ni
(Molecular weight 1656.8818)

[0163]

[Outside 98]

(Example 1) Wallet size (length 54)
mm, 85 mm in width) on a polycarbonate (hereinafter abbreviated as “PC”) substrate 11 having a thickness of 0.4 mm, a strip-shaped pre-groove 12 having a width of 3 μm, a pitch of 12 μm, and a length of 85 mm provided by a hot press method. IR-820 (manufactured by Nippon Kayaku) as a polymethine dye and the double salt compound No. (I) -1 mixed at a weight ratio of 80:20 3
A solution in which 97 parts by weight of diacetone alcohol was dissolved by weight was applied by a bar coating method to obtain a recording layer 13 having a thickness of 950 °.

Further, a PC protective substrate 15 having a wallet size of 0.3 mm was laminated thereon via an acrylate-ethylene copolymer dry film to be an adhesive layer 14 and bonded using a hot roll. Thus, an optical card having a close contact structure was produced (see FIGS. 1 and 2).

The optical card thus obtained has an oscillation wavelength of 830.
The reflectivity from the recording layer when a semiconductor laser beam having a wavelength of 0.2 nm was irradiated at a power of 0.2 mW through a PC substrate having a thickness of 0.4 mm was measured using an optical card recording / reproducing apparatus (manufactured by Canon). Next, the optical card was driven at a rate of 60 mm / sec in a direction along the pregroove 12 while using a semiconductor laser having an oscillation wavelength of 830 nm to obtain a thickness of 0.4 mm.
mm PC board, recording power 3.5 mW, recording pulse 80 μsec, recording track 1 between pre-grooves
6, information is reproduced, and reproduced at a reproduction power of 0.2 mW.
The contrast ratio [(AB) / A, where A: signal intensity of an unrecorded portion, and B: signal intensity of a recorded portion] was measured.

Next, the reflectance and the contrast ratio of the optical card after standing for 1000 hours at 65 ° C. and 85% RH were measured (environmental storage stability).

Further, the optical card of Example 1 in which the information was newly prepared and information was recorded in exactly the same manner was irradiated with a 1 KW / m ² xenon lamp for 200 hours, and the reflectance and contrast ratio were measured (light stability). ).

Table 4 shows the results.

(Example 2) In Example 1, the double salt compound N
o. No. (I) -1 An optical card was prepared in the same manner as in Example 1 except that (I) -4 was used, and evaluated in the same manner as in Example 1. Table 4 shows the results.

[0171]

[Table 14]

(Examples 3 and 4) An optical card was prepared in the same manner as in Example 1 except that the combination of the polymethylene dye and the double salt compound used in Example 1 was changed to the following combination of the dye and the double salt compound. Was prepared and evaluated.

[0173]

[Table 15]

Comparative Example 1 An optical card was prepared and evaluated in the same manner as in Example 3, except that the double salt compound (I) -1 used in Example 3 was omitted.

Table 5 shows the results of Examples 3 and 4 and Comparative Example 1.

[0176]

[Table 16]

(Comparative Examples 2 to 4) The double salt compound No. An optical card was prepared and evaluated in the same manner as in Example 3 except that (I) -1 was a compound shown in Table 6 below.

[0178]

[Table 17]

(Comparative Example 5) In Example 3, the double salt compound N
o. An optical card was prepared and evaluated in the same manner as in Example 3, except that (I) -1 was changed to a double salt compound represented by the following structural formula.

[0180]

[Outside 99]

(Comparative Example 6) In Example 4, the double salt compound N
o. An optical card was prepared and evaluated in the same manner as in Example 4, except that (I) -15 was changed to the double salt compound represented by the following structural formula.

[0182]

[Outside 100]

[0183]

[Table 18]

Example 5 and Comparative Example 7 An optical card of Example 5 was manufactured in the same manner as in Example 3.

In the same manner as in Comparative Example 5, Comparative Example 7
Was manufactured.

The optical cards of Example 5 and Comparative Example 7 thus obtained were recorded on an optical card recording / reproducing apparatus (manufactured by Canon Inc.).
And the optical card is not driven, and the oscillation wavelength 830 is set.
nm laser with an output of 0.2 mW and a thickness of 0.
One point of the recording layer is continuously irradiated through a 4 mm PC substrate, and the reflectance from the recording layer is measured. The time required for the reflectance of the recording layer to decrease by 5% from the initial value (reproduction light deterioration time) ) Was measured.

The results of Example 5 and Comparative Example 8 are shown in Table-8.

[0188]

[Table 19]

Example 6 and Comparative Example 8 An optical card of Example 6 was produced in the same manner as in Example 4.

Further, an optical card of Comparative Example 8 was produced in the same manner as in Comparative Example 6.

With respect to the optical cards of Example 6 and Comparative Example 8 thus obtained, the reproduction light deterioration time was measured in the same manner as in Example 5.

The results of Example 6 and Comparative Example 9 are shown in Table-9.

[0193]

[Table 20]

(Examples 7 to 11) The combinations of the polymethylene dyes and double salt compounds used in Example 1 are shown in Table 10 below.
An optical card was prepared and evaluated in the same manner as in Example 1 except that the combination of the dye and the double salt compound shown in (1) was used.

The double salt compound No. used in Example 8 (I)
An optical card was prepared and evaluated in the same manner as in Example 11, except that -11 was excluded.

Table 11 shows the results of Examples 7 to 11 and Comparative Example 9.

[0197]

[Table 21]

[0198]

[Table 22]

(Examples 12 to 15) On a PC board having a spiral tracking groove having a width of 0.6 μm and a pitch of 1.6 μm formed on a surface having a diameter of 130 mmφ and a thickness of 1.2 mm produced by injection molding. A recording layer having a thickness of 950 ° was formed by spin coating a solution obtained by dissolving 5 parts by weight of a mixture of an organic dye and the double salt compound shown in Table 12 below in 95 parts by weight of diacetone alcohol. A 0.3 mm spacer was sandwiched between the inner and outer peripheral sides of the medium thus obtained, and the medium was bonded to another PC protective substrate with an ultraviolet-curable adhesive to obtain an air-sandwich optical disk.

The optical disk manufactured in this manner was
pm, and a semiconductor laser beam having an oscillation wavelength of 830 nm is made incident through a PC substrate to obtain a recording power of 8 m.
Information was written at W at a recording frequency of 3 MHz, reproduced at a read power of 0.8 mW, and the reproduced waveform was analyzed for spectrum (scanning filter, bandwidth 30 KHz) to measure the C / N ratio (carrier / noise ratio).

Next, the information recording section of this optical disc is set to 10
^The C / N ratio was measured after the reproduction was repeated ^five times. or,
The reflectance of the recording light at a wavelength of 830 nm was measured with a spectrophotometer (trade name: U-3400; manufactured by Hitachi, Ltd.) through a PC substrate.

Further, this optical disc was subjected to an environmental storage stability test and a light stability test under the same conditions as in Example 1, and
Thereafter, the reflectance of the recording layer and the C / N ratio of the recording pit were measured. The results are shown in Table-13.

[0203]

[Table 23]

(Comparative Examples 10 and 11) Examples 12 and 1
Double salt compound No. 5 used in No. 5 (I) -8 and (I) -5
Optical discs were prepared and evaluated in the same manner as in Examples 12 and 15, except that the above conditions were excluded. The results are shown in Table-13.

(Comparative Example 12) The double salt compound No. An optical disk was produced in the same manner as in Example 12 except that (I) -8 was changed to the following metal complex compound.
As a result, as shown in Table 13, since the solubility of the following metal complex was poor, crystals were precipitated after coating. As a result, the noise level of the reproduced signal from this optical disk was very wide, and the C / N ratio was large. Could not be measured.

[0206]

[Outside 101]

[0207]

[Table 24]

(Examples 16 and 17) Diameter 130 mmφ,
1.2 mm thick polymethyl methacrylate (hereinafter referred to as “P
Abbreviated as “MMA”) 2P method (photo-polymer method) using an epoxy-acrylate UV curable resin on the substrate
To provide a pre-groove layer having a thickness of 30 μm. A solution prepared by dissolving 2 parts by weight of a mixture of a combination of an organic dye and a double salt compound shown in Table 14 below in 1.2-dichloroethane was applied onto the substrate by a spinner coating method, and the dried film thickness was 900 mm.
An optical disc was produced in the same manner as in Example 12, except that the organic thin film recording layer was formed.

The optical disk manufactured as described above was used in Example 12
The measurement and evaluation were performed in the same manner as described above. The results are shown in Table-16.

[0210]

[Table 25]

(Examples 18 and 19) 4 parts by weight of a mixture of a combination of an organic dye and a double salt compound shown in Table 15 below and 1 part by weight of a nitrocellulose resin (Ohales Lacquer, manufactured by Daicel Chemical Industries, Ltd.) were used. A liquid mixed with 95 parts by weight of acetone alcohol was applied on a polycarbonate substrate having a diameter of 130 mm and a thickness of 1.2 mm provided with a pregroove by a spinner coating method to form an organic thin film recording layer having a dry film thickness of 950 °. In the same manner as in Example 8, an optical disk was manufactured.

The optical disk manufactured in this manner was used in Example 12
The measurement was performed in the same manner as described above. The results are shown in Table-16.

[0213]

[Table 26]

[0214]

[Table 27]

Example 20 The organic dye of Example 1 and the double salt compound No. Mixture of (I) -1 (weight ratio 8
0:20) A solution in which 3 parts by weight of diacetone alcohol was dissolved in 97 parts by weight of diacetone alcohol was dried by a roll coating method on a 0.4 mm-thick PC substrate with a wallet-sized pre-groove used in Example 1. A recording layer having a thickness of 1000 ° was produced.

In this way, the recording layer was continuously applied to 200 PC boards, and then 200 optical cards were manufactured in the same manner as in Example 1.

Then, the order of application of the recording layer is first,
Optical cards manufactured using the 10th, 50th, 100th, and 200th substrates, respectively (hereinafter referred to as optical card Nos.
1, No. 10, No. 50, no. 100 and No.
200) and mounted on the optical card recording / reproducing apparatus, and the optical card was moved 60 mm / s in the direction along the pregroove.
While driving at ec, using a semiconductor laser having an oscillation wavelength of 830 nm, a spot size of 3 μmφ, a recording power of 3.5 mW, and a recording pulse of 50 μm were taken from the side of the PC board having a thickness of 0.4 mm.
Information was recorded on the recording track between the pre-grooves in μsec, and then reproduced at a read power of 0.2 mW, and the reproduced waveform was subjected to spectrum analysis (scanning filter bandwidth 1 kHz) to measure the C / N ratio. . The results are shown in Table-17.

Example 21 The double salt compound No. (I) -1 is No. 200 optical cards were produced in the same manner as in Example 20 except that (I) -8 was used instead. 1, No. 10,
No. 50, no. 100 and No. The C / N of 200 optical cards was measured. The results are shown in Table-17.

(Example 22) The double salt compound No. (I) -1 is No. (II) 200 optical cards were prepared in the same manner as in Example 20 except that the optical card was replaced with No. 4 except that the optical card was replaced with No. (II) -4. 1, No. 1
0, No. 50, no. 100 and No. The C / N ratio of 200 optical cards was measured. The results are shown in Table-17.

(Comparative Example 13) The double salt compound No. 200 optical cards were produced in the same manner as in Example 20 except that (I) -1 was replaced with the double salt compound used in Comparative Example 6, and No. 2 was prepared in the same manner as in Example 20. 1, N
o. 10, No. 50, no. 100 and No. 200
The C / N ratio of the optical card was measured. Table 17 shows the results.
Shown in

[0221]

[Table 28]

In Comparative Example 13, the noise level increased and the C / N ratio decreased as the number of sheets increased. This is because the solvent solubility of the double salt compound used in Comparative Example 14 was not sufficient, and solids such as microcrystals were easily precipitated even by a slight change in the concentration of the coating solution caused when the double salt compound was coated on a plurality of substrates. This is considered to have caused noise.
On the other hand, the conjugates of the aminium salt cation and the metal complex anion of the present invention of Examples 20 to 22 have high solubility in solvents that do not impair the plastic, and crystals are less likely to be formed even by a slight concentration change in the coating step. Therefore, it is considered that crystals are less likely to be mixed into the recording layer, and an optical recording medium having a low noise level can always be stably obtained.

[0223]

As described above, according to the present invention, the light resistance of an organic dye can be significantly improved.
Also, by including the organic dye in the recording layer of the optical recording medium, the deterioration of the recording layer due to the reproduction light can be effectively suppressed.

Further, since an excellent light deterioration suppressing effect is exhibited even with a small amount of addition to the dye, the light resistance of the recording layer can be improved and the reproduction deterioration can be suppressed without lowering the recording sensitivity of the optical recording medium. .

The complex of the metal complex with the aminium salt compound into which an alkoxyalkyl group, a morpholine ring or an alkenyl group, an alkynyl group or the like has been introduced has a very good solubility in a general-purpose organic solvent that does not impair the plastic, so Productivity is greatly improved.

An optical recording medium having excellent storage stability even under high temperature and high humidity environment conditions can be obtained.

An optical recording medium having a clear threshold with respect to laser power can be obtained without deteriorating excellent characteristics such as high reflectance and high sensitivity of the organic dye.

[Brief description of the drawings]

FIG. 1 is a schematic plan view of an optical card according to the present invention.

FIG. 2 is a schematic cross-sectional view of the optical card of FIG. 1 taken along line AA '.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 11 Substrate 12 Pre-groove 13 Recording layer 14 Adhesive layer 15 Protective substrate 16 Recording track

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI C07D 295/02 C07D 295/02 Z C07F 1/08 C07F 1/08 D 3/06 3/06 13/00 13/00 A15 / 00 15/00 C 15/04 15/04 15/06 15/06 G11B 7/24 516 G11B 7/24 516 (56) References JP-A-64-38490 (JP, A) JP-A-64-75454 (JP, A) JP-A-64-31693 (JP, A) JP-A-3-16785 (JP, A) JP-A-63-67187 (JP, A) JP-A-63-31792 (JP, A) JP-A-62-193891 (JP, A) JP-A-4-226788 (JP, A) JP-A-4-201385 (JP, A) JP-A-4-112083 (JP, A) (58) Int.Cl. ⁷ , DB name) C07C 211/54 C07C 211/56 C07C 217/08 C07D 207/20 C07D 295/02 C07F 1/08 C07F 3/06 C07F 13/00 C07F 15/00 C07F 15/04 C07F 15/06 G11B 7/24 516 CA (STN) REGISTRY (STN)

Claims (38)

(57) [Claims] 1. An aminium salt compound having a structure represented by the following general formula (I). [Outside 1] (In the formula (I) Is any of monovalent metal complex anions represented by the following formulas (III) to (IX), and R _{1 to} R ₈ are a hydrogen atom or
Alkyl group, substituted alkyl group, alkoxyalkyl group,
Substituted alkoxyalkyl, alkenyl, substituted alk
Nyl group, alkynyl group, substituted alkynyl group, aralkyl
Represents a group or a substituted aralkyl group . Provided that at least one of R _{1 to} R ₈ is a monovalent selected from a substituted or unsubstituted alkoxyalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group and a substituted or unsubstituted aralkyl group. Is an organic residue. Also n
Is 1 or 2) (Wherein R _{9 to} R ₁₂ each represent a hydrogen atom,
Amino's also unsubstituted alkyl group substituted or unsubstituted
Group or substituted or unsubstituted alkoxy group or halo
And M represents a transition metal atom); (Wherein R _{13 to} R ₁₆ each represent a substituted or unsubstituted
Alkyl group or substituted or unsubstituted aryl group or shea
And M represents a transition metal atom); (Wherein R _{17 to} R ₂₀ are each a hydrogen atom, substituted or
Unsubstituted alkyl group, substituted or unsubstituted amino group,
Substituted or unsubstituted aryl group, substituted or unsubstituted
Represents an alkoxy group or a halogen atom, and M is
A transition metal atom); (Wherein R _{21 to} R ₂₄ are each a hydrogen atom, a substituted or
Unsubstituted alkyl group, substituted or unsubstituted amino group,
Substituted or unsubstituted aryl group, substituted or unsubstituted
Represents an alkoxy group or a halogen atom, and M is
A transition metal atom); (Wherein R _{25 to} R ₂₈ each represent a hydrogen atom,
Unsubstituted alkyl group, substituted or unsubstituted amino group,
Substituted or unsubstituted aryl group, substituted or unsubstituted
Represents an alkoxy group or a halogen atom, and M is
A transition metal atom); (Wherein M represents a transition metal atom); (Wherein, M represents a transition metal atom). Wherein R ₁ to R ₈ is C 2 -C 8 carbon atoms, alkyl
Group, substituted alkyl group, alkoxyalkyl group, substituted
Alkoxyalkyl, alkenyl, substituted alkenyl
Group, alkynyl group, substituted alkynyl group, aralkyl group
The aminium salt compound according to claim 1, which is a substituted aralkyl group . 3. An alkyl having 3 to ₈ carbon atoms, wherein R _{1 to} R ₈ have 3 to ₈ carbon atoms.
Group, substituted alkyl group, alkoxyalkyl group, substituted
Alkoxyalkyl, alkenyl, substituted alkenyl
Group, alkynyl group, substituted alkynyl group, aralkyl group
Others aminium salt compound according to claim 2 is a substituted aralkyl group. 4. At least two of the combinations of R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ and R ₇ and R ₈ are all substituted or unsubstituted alkoxyalkyl groups, substituted or unsubstituted The aluminum salt compound according to claim 1, which is a monovalent organic residue selected from alkenyl, substituted or unsubstituted alkynyl and substituted or unsubstituted aralkyl. 5. A monovalent wherein all of R _{1 to} R ₈ are selected from a substituted or unsubstituted alkoxyalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group and a substituted or unsubstituted aralkyl group. The aminium salt compound according to claim 1, which is an organic residue represented by the formula: 6. The aminium salt compound according to claim 1, wherein said metal complex anion is a nickel complex anion. 7. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ ,
The aminium salt compound according to claim 1, wherein at least one of R ₇ and R ₈ is an alkoxyalkyl group. 8. An aminium salt compound having a structure represented by the following general formula (II). [Outside 10] [In the formula [Outside 11] Is a monovalent metal represented by the following formulas (III) to (IX):
It is any complex anion represents a monovalent metal complex anion, R _'1 ~R' ₈ is R'm and R'm + 1 (where m =
All of the combinations of 1, 3, 5, and 7) form together with N an atom group necessary to form a substituted or unsubstituted 5-membered ring, a substituted or unsubstituted 6-membered ring, or a substituted or unsubstituted 7-membered ring. Show. n is 1 or 2. (Wherein R _{9 to} R ₁₂ each represent a hydrogen atom,
Is an unsubstituted alkyl group or a substituted or unsubstituted amino
Group or substituted or unsubstituted alkoxy group or halo
And M represents a transition metal atom); (Wherein R _{13 to} R ₁₆ each represent a substituted or unsubstituted
Alkyl group or substituted or unsubstituted aryl group or shea
And M represents a transition metal atom); (Wherein R _{17 to} R ₂₀ are each a hydrogen atom, substituted or
Unsubstituted alkyl group, substituted or unsubstituted amino group,
Substituted or unsubstituted aryl group, substituted or unsubstituted
Represents an alkoxy group or a halogen atom, and M is
A transition metal atom); (Wherein R _{21 to} R ₂₄ are each a hydrogen atom, a substituted or
Unsubstituted alkyl group, substituted or unsubstituted amino group,
Substituted or unsubstituted aryl group, substituted or unsubstituted
Represents an alkoxy group or a halogen atom, and M is
A transition metal atom); (Wherein R _{25 to} R ₂₈ each represent a hydrogen atom,
Unsubstituted alkyl group, substituted or unsubstituted amino group,
Substituted or unsubstituted aryl group, substituted or unsubstituted
Represents an alkoxy group or a halogen atom, and M is
A transition metal atom); (Wherein M represents a transition metal atom); (Wherein, M represents a transition metal atom). 9. The 5-membered ring is a pyrrolidine ring.
Aminium salt compound of 8 . 10. The aminium salt compound according to claim 8 , wherein said 6-membered ring is a piperidine ring, a morpholine ring or a tetrahydropyridine ring. 11. The aminium salt compound according to claim 8 , wherein said 7-membered ring is a cyclohexylamine ring. 12. The aminium salt compound according to claim 8 , wherein at least one of the combinations of R′m and R′m + 1 forms a substituted or unsubstituted morpholine ring. 13. The aminium salt compound according to claim 8 , wherein at least one of R _{13 to} R ₁₆ is an alkoxy-substituted aryl group. 14. The aminium salt compound according to claim 8 , wherein said transition metal atom is nickel. 15. An optical recording medium comprising a substrate and an organic dye recording layer, wherein the recording layer contains a compound represented by the following general formula (I). [Outside 19] (In the formula (I) Is a monovalent metal complex represented by the following formulas (III) to (IX):
Is any of the body anion, R ₁ to R ₈ is a hydrogen atom or
Alkyl group, substituted alkyl group, alkoxyalkyl group,
Substituted alkoxyalkyl, alkenyl, substituted alk
Nyl group, alkynyl group, substituted alkynyl group, aralkyl
Represents a group or a substituted aralkyl group . Provided that at least one of R _{1 to} R ₈ is a monovalent selected from a substituted or unsubstituted alkoxyalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group and a substituted or unsubstituted aralkyl group. Is an organic residue. Also n
Is 1 or 2) (Wherein R _{9 to} R ₁₂ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, or a halogen atom, and M represents a transition metal atom. (Shown); (Wherein R _{13 to} R ₁₆ each represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group or cyano group, and M represents a transition metal atom). (Wherein R _{17 to} R ₂₀ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group,
Represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a halogen atom, and M represents a transition metal atom); (Wherein R _{21 to} R ₂₄ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group,
Represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a halogen atom, and M represents a transition metal atom. (Wherein R _{25 to} R ₂₈ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group,
Represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a halogen atom, and M represents a transition metal atom); (Wherein M represents a transition metal atom); (Wherein, M represents a transition metal atom). 16. R ₁ to R ₈ is of 2-8 carbon atoms, Al
Kill group, substituted alkyl group, alkoxyalkyl group, substituted
Alkoxyalkyl, alkenyl, substituted alkenyl
Group, alkynyl group, substituted alkynyl group, aralkyl group
The optical recording medium according to claim 15 , which is a substituted aralkyl group . 17. R ₁ to R ₈ is of 3-8 carbon atoms, Al
Kill group, substituted alkyl group, alkoxyalkyl group, substituted
Alkoxyalkyl, alkenyl, substituted alkenyl
Group, alkynyl group, substituted alkynyl group, aralkyl group
17. The optical recording medium according to claim 16 , which is a substituted aralkyl group . 18. R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆
And at least two of the combinations of the organic residues R ₇ and R ₈
All the groups are substituted or unsubstituted alkoxyalkyl groups,
The optical recording medium according to claim 15 , which is a monovalent organic residue selected from a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, and a substituted or unsubstituted aralkyl group. 19. A monovalent wherein all of R _{1 to} R ₈ are selected from a substituted or unsubstituted alkoxyalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group and a substituted or unsubstituted aralkyl group. 16. The optical recording medium according to claim 15 , which is an organic residue. 20. The optical recording medium according to claim 15 , wherein said metal complex anion has the following structure. [Outside 28] 21. The substituents R _{13 to} R of the general formula (IV)
The optical recording medium according to claim 15 , wherein at least one of ₁₆ is an alkoxy-substituted aryl group. 22. The optical recording medium according to claim 15 , wherein said metal complex anion has the following structure. [Outside 29] (Wherein, M represents a transition metal atom). 23. The optical recording medium according to claim 15 , wherein said transition metal atom is nickel. 24. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R
_6, at least one optical recording medium according to claim 15 which is an alkoxyalkyl group of R ₇ and R _8. 25. The recording layer having the following general formulas (X) and (X)
16. The optical recording medium according to claim 15 , comprising at least one polymethine dye represented by I). [Outside 30] (Where A, B, D and E represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group,
And a group selected from a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted styryl group, and a substituted or unsubstituted heterocyclic group.
r ₁ ′ and r ₂ ′ represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cyclic alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group and a substituted or unsubstituted And k is 0 or 1, 1 is 0, 1 or 2, and Means an anion). [Outside 32] (Where A, B, D, E and Has the same meaning as described above, and r _{1 to} r ₅ represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Y represents an alkylene group having an atomic group necessary to complete a 5- or 6-membered ring.
p and q are 0, 1 or 2. 26. The recording layer according to claim 20, wherein the recording layer has the following general formula (XXI):
16. The optical recording medium according to claim 15 , comprising at least one cyanine dye represented by (XXIII). [Outside 34] (In the above formula, J is a group of atoms necessary to complete the nitrogen-containing heterocycle, r ₁ ′ to r ₇ ′ are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cyclic alkyl group, Or an unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a group selected from a substituted or unsubstituted aryl group, and k is 0 or 1, 1 is 0, 1 or 2,
q is 0, 1 or 2, and t is 0 or 1. Y represents an alkylene <br/> group having an atomic group necessary for forming a 5- or 6-membered ring, G ^- represents an anion residue. [Outside 35] 27. An optical recording medium comprising a substrate and an organic dye recording layer, wherein the recording layer contains a compound represented by the following general formula (II). [Outside 36] [In the formula (II) Is any of monovalent metal complex anions represented by the following formulas (III) to (IX) , and R ′ _{1 to} R ′ ₈ are R ′ _m
And R 'm _{+ 1} (where m = 1, 3, 5, 7) all <br/> 5-membered ring substituted or unsubstituted with N, 6-membered ring or a substituted or unsubstituted substituted or unsubstituted combinations of A group of atoms necessary to form a substituted 7-membered ring is shown. n is 1 or 2] (Wherein R _{9 to} R ₁₂ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, or a halogen atom, and M represents a transition metal atom. (Shown); (Wherein R _{13 to} R ₁₆ each represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group or cyano group, and M represents a transition metal atom). (Wherein R _{17 to} R ₂₀ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group,
Represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a halogen atom, and M represents a transition metal atom. (Wherein R _{21 to} R ₂₄ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group,
Represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a halogen atom, and M represents a transition metal atom. (Wherein R _{25 to} R ₂₈ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group,
Represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group or a halogen atom, and M represents a transition metal atom); (Where M represents a transition metal atom); (Wherein, M represents a transition metal atom). 28. The optical recording medium according to claim 27 , wherein said five-membered ring is a pyrrolidine ring. 29. The optical recording medium according to claim 27 , wherein said six-membered ring is a piperidine ring, a morpholine ring or a tetrahydropyridine ring. 30. The optical recording medium according to claim 27 , wherein said 7-membered ring is a cyclohexylamine ring. 31. R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆
And at least two of the combinations of the organic residues R ₇ and R ₈
28. The optical recording medium according to claim 27 , wherein the set comprises a substituted or unsubstituted 5-membered ring, a substituted or unsubstituted 6-membered ring, or a substituted or unsubstituted 7-membered ring. 32. The optical recording medium according to claim 27 , wherein said metal complex anion has the following structure. [Outside 45] 33. The substituents R _{13 to} R of the general formula (IV)
The optical recording medium according to claim 27 , wherein at least one of ₁₆ is an alkoxy-substituted aryl group. 34. The optical recording medium according to claim 27 , wherein said metal complex anion has the following structure. [Outside 46] (Wherein, M represents a transition metal atom). 35. The optical recording medium according to claim 27 , wherein said transition metal atom is nickel. 36. _{R '1, R' 2,} R '3, R' 4,
_{R '5, R' 6,} R at least one set optical recording medium according to claim 27 obtained by forming a morpholine ring of a combination of _'7, R' _8. 37. The recording layer having the following general formulas (X) and (X)
28. The optical recording medium according to claim 27 , comprising at least one polymethine dye represented by I). [Outside 47] (Where A, B, D and E represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group,
And a group selected from a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted styryl group, and a substituted or unsubstituted heterocyclic group.
r ₁ ′ and r ₂ ′ represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cyclic alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group and a substituted or unsubstituted And k represents 0 or 1, 1 represents 0, 1 or 2, and Means an anion). [Outside 49] (Where A, B, D, E and Has the same meaning as described above, and r _{1 to} r ₅ represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Y represents an alkylene group having an atomic group necessary to complete a 5- or 6-membered ring.
p and q are 0, 1 or 2). 38. The recording layer having the following general formula (XXI)
The optical recording medium according to claim 27 , comprising at least one cyanine dye represented by (XXIII). [Outside 51] (In the above formula, J is a group of atoms necessary to complete the nitrogen-containing heterocycle, r ₁ ′ to r ₇ ′ are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cyclic alkyl group, Or an unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a group selected from a substituted or unsubstituted aryl group, and k is 0 or 1, 1 is 0, 1 or 2,
q is 0, 1 or 2, and t is 0 or 1. Y represents an alkylene group having an atomic group necessary to complete a 5- or 6-membered ring, and G represents an anion residue. [Outside 52]