JPH07133475A - Infrared rays absorbing compound and optically recording medium using the same - Google Patents

Abstract

PURPOSE:To provide an IR rays absorbing compound consisting of a specific triaryl compound, good in solubility in organic solvents enabling to coat the compound on plastic substrates, excellent in light resistance and storage stability, and useful for optical recording media, etc. CONSTITUTION:This IR rays absorbing compound is represented by the formula [R1-R6 are H, monovalent organic group; one or more of R1-R6 are (substituted) alkoxyalkyl, (substituted)alkenyl, (substituted)alkinyl, (substituted)cycloalkyl; the combinations of R1 and R2, R3 and R4, and R5 and R6 form a (substituted) five-membered ring, a (substituted) six-membered ring, or a (substituted) seven- membered ring together with N; R7-R9 are H, halogen, lower alkyl, lower alkoxy, cyano, hydroxyl group; X<-> is monovalent metal complex anion]. A recording layer containing the infrared light-absorbing compound is formed on a substrate to provide an optical recording medium.

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 and an optical recording medium using the same, and more particularly to an infrared absorbing compound for improving light resistance and storage stability in an optical disc or an optical card, and an optical recording using the same. Recording medium

[0002]

2. Description of the Related Art Generally, optical disks and optical cards are
Small, optically detectable (eg, about 1 μm) pits formed in a thin recording layer on a substrate can be made into spiral or circular and linear track configurations to store high density information. To write information on such a disk, a laser focused on the surface of the laser-sensitive layer is scanned, and pits are formed only on the surface irradiated with this laser beam, and the pits are spirally or circularly and linearly tracked. It is formed in the form of. The laser sensitive layer can absorb laser energy to form an optically detectable pit. For example, in the heat mode recording method, the laser-sensitive layer absorbs thermal energy, and a small recess (pit) can be formed at that portion by evaporation or melting. Further, in another heat mode recording method, a pit having an optically detectable density difference can be formed at the position by absorbing the irradiated laser energy.

By using an organic dye thin film as the recording layer having a high reflectance, the optical contrast of the recording pit can be set high. For example, when a polymethine dye, an azulene dye, a cyanine dye, a pyrylium dye, or the like, which has large light absorption for laser light, is used as the organic dye thin film, a metallic luster (reflectance of 10 to 50) is obtained.
%), A laser recording is possible and an optical recording medium capable of reflection reading is obtained.

Particularly, as a laser light source, the oscillation wavelength is 500 to 9
The use of a 00 nm semiconductor laser has the advantage that the device can be downsized and the cost can be reduced. However, the organic dye thin film generally has a problem that the recording / reproducing characteristics and the storage stability are deteriorated due to the fact that the material is easily changed by heat and light.

In order to solve such problems, there is known a method of adding an aminium salt / diimonium salt compound or a metal chelate complex (especially Ni chelate complex) which is a singlet oxygen quencher into a recording layer in order to improve light resistance. ing.

However, since the metal chelate complex has a low solubility in a solvent which can be applied to a plastic substrate, there is a problem that it cannot be added in an amount sufficient to improve light resistance. In addition, a method has been proposed in which a larger amount is added to the recording layer by forming a double salt of a metal complex and a dye, and there is a problem that the light resistance can be improved but the recording sensitivity is lowered.

In addition, in the method of adding the aminium salt / diimonium salt compound to the recording layer, the counter ion is a mere acid anion, and therefore a large amount of addition is necessary for improving the light resistance. As a method for remarkably improving the light resistance with a small amount of addition to such problems, an example using a double salt compound of an aminium salt / diimonium salt cation and a metal complex anion is disclosed in JP-A-62-193891. Have been described. By this method, light resistance and recording / reproducing characteristics are improved as compared with the conventional method, but when an aminium salt / diimonium salt cation substituted with a dialkylamino group is used, it becomes a solvent for a double salt compound with a metal complex anion. The solubility of aliphatic hydrocarbons, alcohols, and
The solubility of ketones in solvents was low.

Further, an optical disk excellent in light resistance provided with a recording layer comprising a mixture of a diimonium salt cation and a metal complex anion and a reflective layer on the recording layer is disclosed in JP-A-3-164.
No. 292, for example, as a diimonium salt cation, for example, a diimonium salt of N, N, N ′, N′-tetrakis (dialkylamino-substituted phenyl) -p-phenylenediamine or N, N, N ′, N ′. -Tetrakis (dialkoxyalkylamino-substituted phenyl) -p
-A diimonium salt of phenylenediamine has been described, but these double salt compounds are still insufficient in storage stability and stability against reproducing light.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional examples, and an object of the present invention is to have a large absorption region in the infrared region and to coat a plastic substrate. It is to provide a novel infrared absorbing compound having good solubility in an organic solvent.

For other purposes, the light resistance can be remarkably improved with a small addition amount, and at the same time, since the addition amount can be small, the recording sensitivity can be suppressed from being lowered, and the storage stability can be remarkably improved. An object of the present invention is to provide an optical recording medium that can be used.

[0011]

That is, the present invention is an infrared absorbing compound represented by the following general formula (I) or (II).

[0012]

[Chemical 10]

(In the formula, R _{1 to} R ₆ represent a hydrogen atom or a monovalent organic residue, and at least one of R _{1 to} R ₆ is a substituted or terminal-substituted alkoxyalkyl group, or a substituted or terminal-substituted alkoxyalkyl group. An alkenyl group, a substituted or terminal-substituted alkynyl group, a substituted or terminal-substituted cycloalkyl group, or a combination of R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ with N or a terminally substituted group 5-membered ring, 6-membered ring substituted or late-substituted, to form a 7-membered ring substituted or late substituted .R ₁ to R ₆ each may be the even or the same have gone .R ₇ to R of ₉ represents a hydrogen atom, a halogen group, a lower alkyl group, a lower alkoxy group, a cyano group or a hydroxyl group, and X ⁻ represents a monovalent metal complex anion.)

The present invention also provides an optical recording medium comprising a substrate and a recording layer, wherein the recording layer has the following general formula (I).
Alternatively, it is an optical recording medium containing a compound represented by (II).

[0015]

[Chemical 11]

(In the formula, R _{1 to} R ₆ represent a hydrogen atom or a monovalent organic residue, and at least one of R _{1 to} R ₆ is a substituted or terminal-substituted alkoxyalkyl group, or a substituted or terminal-substituted alkoxyalkyl group. An alkenyl group, a substituted or terminal-substituted alkynyl group, a substituted or terminal-substituted cycloalkyl group, or a combination of R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ with N or a terminally substituted group 5-membered ring, 6-membered ring substituted or late-substituted, to form a 7-membered ring substituted or late substituted .R ₁ to R ₆ each may be the even or the same have gone .R ₇ to R of ₉ represents a hydrogen atom, a halogen group, a lower alkyl group, a lower alkoxy group, a cyano group or a hydroxyl group, and X ⁻ represents a monovalent metal complex anion.)

The present invention will be described in detail below. The infrared absorbing compound of the present invention is represented by the following general formula (I) or (II).

[0018]

[Chemical 12]

In the above general formula (I) or (II), X ⁻ is a monovalent metal complex anion, and R _{1 to} R ₆ of the triarylamine compound cation are a hydrogen atom or a monovalent organic residue. Show. Further, at least one of R _{1 to} R ₆ is a substituted or terminal-substituted alkoxyalkyl group, a substituted or terminal-substituted alkenyl group, a substituted or terminal-substituted alkynyl group, a substituted or terminal-substituted cycloalkyl group, or R ₁ and A combination of R ₂ , R ₃ and R ₄ , R ₅ and R ₆ together with N and substituted or unsubstituted 5-membered ring,
Substituted or terminal substituted 6-membered ring, substituted or terminal substituted 7
It is preferable to form a member ring. Then, by selecting at least one of R _{1 to} R ₆ from the above substituent group, it is possible to obtain an infrared absorbing compound having improved light resistance and good solvent solubility as compared with conventional ones. Further, by including this infrared absorbing compound in the recording layer, an optical recording medium having excellent light resistance and stability against repeated reproduction and having good productivity can be obtained.

Next, examples of the monovalent organic residue of R _{1 to} R ₆ include, for example, alkyl groups (eg, methyl group, ethyl group, n-propyl group, iso-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, etc., substituted alkyl group (for example, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 2-acetoxyethyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group) , Methoxyethyl group, ethoxyethyl group, methoxypropyl group, etc., alkenyl group (eg, vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, etc.), alkynyl group (eg, propargyl group) , Butynyl group, pentynyl group, hexynyl group, etc., alkoxyalkyl group (eg, methoxymethyl group, 2-methoxyethyl group, 3-methoxypropyl group, 2-methoxypropyl group, 4-methoxybutyl group, 3-methoxybutyl group) Group, 2-methoxybutyl group, 5-meth Shipenchiru group, 4-methoxybutyl group, 3-methoxy-pentyl group, 2-methoxy-pentyl group, 6-methoxy hexyl group, ethoxymethyl group, 2-
Ethoxyethyl group, 3-ethoxypropyl group, 2-ethoxypropyl group, 4-ethoxybutyl group, 3-ethoxybutyl group, 5-ethoxypentyl group, 4-ethoxypentyl group, 6-ethoxyhexyl group, propoxymethyl group, 2-propoxyethyl group, 3-propoxypropyl group, 4-propoxybutyl group, straight-chain or branched alkoxyalkyl group such as 5-propoxypentyl group), cycloalkyl group (for example, cyclopentyl group,
A cyclohexyl group, a cycloheptyl group, etc.).

R _{1 to} R ₆ may be different or the same.

An object of the present invention is to provide an infrared absorbing compound having extremely good solvent solubility and an optical recording medium having good light resistance. Another object is to provide a novel infrared absorbing compound having good heat resistance and an optical recording medium having excellent heat resistance.

In the present invention, when at least one of R _{1 to} R ₆ is a substituted or unsubstituted alkoxyalkyl group, solvent solubility is further improved, which is preferable. R ₇
R ₉ represents a hydrogen atom, a halogen group, a lower alkyl group, a lower alkoxy group, a cyano group or a hydroxyl group.

Next, the general formula (I) or (I
Specific examples of the triaryl compound cation used for the infrared absorbing compound represented by I) are shown below. However, for simplification, for example, in the case where the triaryl compound cation of the general formula (I) is R _{1 to} R ₄ are ethyl groups, R _{5 to} R ₆ are allyl groups, and R _{7 to} R ₉ are hydrogen atoms, Display as shown below.

[0025]

[Chemical 13]

In the general formula (II), R ₁ and R
_When R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ are combined to form a 5-membered ring and R _{7 to} R ₉ are chlorine atoms, they are represented as follows.

[0027]

[Chemical 14]

[0028]

[Chemical 15]

[0029]

[Chemical 16]

[0030]

[Chemical 17]

[0031]

[Chemical 18]

Next, the metal complex anion X ⁻ paired with the above-mentioned triaryl compound cation will be described. In the present invention, various metal complexes can be used as the counter anion, and examples thereof include metal complex compounds represented by the general formulas (III) to (IX). However, in the following general formula, M is Ni, Co, M
The transition metal atoms such as n, Cu, Pb and Pt are shown.

[0033]

[Chemical 19]

(In the formula, 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 aryl group or a halogen group.)

[0035]

[Chemical 20]

(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.)

[0037]

[Chemical 21]

(In the formula, R _{17 to} R ₂₀ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted aryl group or a halogen atom.)

[0039]

[Chemical formula 22]

(In the formula, R _{21 to} R ₂₄ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted aryl group or a halogen atom.)

[0041]

[Chemical formula 23]

(In the formula, R _{25 to} R ₂₈ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted aryl group or a halogen atom.)

[0043]

[Chemical formula 24]

Specific examples of the metal complex anion used in the present invention will be given below, but the present invention is not limited thereto.

[0045]

[Chemical 25]

[0046]

[Chemical formula 26]

[0047]

[Chemical 27]

[0048]

[Chemical 28]

[0049]

[Chemical 29]

[0050]

[Chemical 30]

The general formula (I) or (I
The compound represented by I) is a double salt compound in which the triarylamine compound cation and the metal complex compound anion form a salt, and specific examples thereof are shown below.

[0052]

[Chemical 31]

[0053]

[Chemical 32]

[0054]

[Chemical 33]

[0055]

[Chemical 34]

Next, the general formula (I) or (I
The method for synthesizing the compound represented by I) will be described. First, a triarylamine compound having an acid anion (for example, perchlorate ion, iodine ion, chlorine ion, hexafluoroantimonate ion, etc.) as a counter ion is synthesized.

The triarylamine compound is Che
mische Berichte 92, 245 (1
959) and can be easily obtained by oxidizing the corresponding triarylamine with silver perchlorate, silver hexafluoroantimony, or the like. For example, it can be manufactured by the following process.

[0058]

[Chemical 35]

The final product can be obtained by substituting the amino compound obtained by the above reduction reaction by alkylation, alkenylation, aralkylation, alkynylation, cyclization, etc. by selective substitution.

When R _{1 to} R ₆ are not targeted,
It is necessary to carry out this alkylation in multiple stages, and it is preferable in terms of cost that R _{1 to} R ₆ are the same.

On the other hand, an anion-type metal complex whose counter ion is a cation is described in, for example, Journal of American.
Chemical Society (Journal of Amer
ican Chemical Society) 196
5 years, Vol. 87, p. 1483, and can be synthesized according to the method of Schlauzer et al.

For example, it can be manufactured by the following process.

[0063]

[Chemical 36] (R and R'are alkyl groups, aromatic rings, etc., X is halogen, and M is transition metal.)

[0064]

[Chemical 37] (X represents halogen and M represents a transition metal.)

The neutral metal complex obtained by the above reaction was added to D
In MSO, p-phenylenediamine is added to make an anion body, and then in alcohol, a quaternary alkylammonium salt is added to make a metal complex anion body. In this case, as the cation, in particular, N ⁺ (CH ₃ ) ₄ , N ⁺
Tetraalkylammonium such as (C ₄ H ₉ ) ₄ is preferred.

Next, equimolar amounts of the cationic triarylamine compound and the anionic metal complex are dissolved in a polar solvent. The polar solvent used is preferably N, N-dimethylformamide or the like.

The concentration may be about 0.01 mol / l.

After this, an aqueous solvent, especially water, is added to this to cause metathesis and precipitate. The amount of water added may be a 10-fold or greater excess. The reaction temperature ranges from room temperature to 90.
℃ is good.

Then, the two liquid phases are separated, filtered and dried, and if necessary, this is repeated 2-3 times, and then DM
Recrystallization with F-ethanol or the like gives the double salt compound of the present invention.

In addition to the above method, a neutral intermediate of a metal complex anion is dissolved in methylene chloride or the like, and an equimolar amount of a triarylamine compound which is a bond with an acid anion is added thereto. The double salt compound of the present invention can also be obtained by concentrating and recrystallizing.

The double salt compound of the triarylamine compound cation and the metal complex anion exemplified above has a maximum absorption wavelength of 850 nm or more and an absorption coefficient as large as several hundred thousand. Such infrared absorbing compounds are used for heat insulating films, sunglasses, etc. in addition to the use as materials for optical recording media.

The infrared absorbing compound of the present invention can be used by being contained in an organic dye thin film of an optical recording medium.
As shown in FIG. 1, the optical recording medium of the present invention contains a double salt compound of a triarylamine compound cation represented by the general formula (I) or (II) and a metal complex anion on a substrate 1. It can be formed by providing the recording layer 2.

As the substrate, plastics such as polycarbonate, polyester, acrylic resin, polyolefin resin, phenol resin, epoxy resin, polyamide and polyimide, glass or metals can be used.

As a recording layer, as a near infrared absorbing dye forming an organic dye thin film used in combination with a double salt compound of a triarylamine compound cation represented by the above general formula (I) or (II) and a metal complex anion. A commonly known dye is used as, for example, a cyanine dye, a merocyanine dye, a croconium dye, a squarylium dye, an azurenium dye, a polymethine dye, a naphthoquinone dye, a pyrylium dye, a phthalocyanine dye. , Triphenylmethane dye, xanthene dye, anthraquinone dye, dioxazine dye,
Tetrahydrocholine dye, triphenothiazine dye, phenanthrene dye, naphthalocyanine dye,
There are naphtholactam dyes, aminium salt / diimonium salt dyes, and metal chelate complex dyes. Alternatively, metals and metal compounds such as Al, Te, Bi,
It may be mixed and dispersed or laminated with Sn, In, Se, SnO, TeO ₂ , As, Cd, or an ultraviolet absorber.

Among these organic dyes, cationic dyes typified by polymethine dyes, cyanine dyes, and azurenium dyes are preferable because of excellent storage stability of the recording layer. Further, the cationic dyes shown below also have recording sensitivity. It is particularly preferable because it is good and does not deteriorate the storage stability of the recording layer even when mixed with the double salt compound of the present invention.

The cationic dyes are listed below. A polymethine dye represented by the general formula (IX).

[0077]

[Chemical 38]

In the formula, A, B, D and E are hydrogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted aralkyl groups, substituted or unsubstituted aryl groups, substituted Alternatively, it represents a group selected from an unsubstituted styryl group and a substituted or unsubstituted heterocyclic group. r ₁ and r ₂ are hydrogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted cyclic alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted aralkyl groups and substituted or unsubstituted aryl groups Represents a group selected from, k is 0 or 1, L is 0, 1 or 2, and G ⁻ is an anion.

A dye represented by the general formula (X).

[0080]

[Chemical Formula 39]

[0081] In the formula, A, B, D, E and G ^- In the as defined _above, r 1 ~r ₅ is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group Show. Y represents a divalent organic residue having an atomic group necessary for completing a 5-membered ring or a 6-membered ring. m, n
Is 0, 1 or 2.

A dye represented by formula (XI).

[0083]

[Chemical 40]

Where A, B, D, E, r ₁ , r
₂ , r ₃ , Y and G ⁻ are as defined above.

A dye represented by formula (XII).

[0086]

[Chemical 41] In the formula, A, B, D, E, r ₁ , r ₂ , r ₃ , r
₄ , m and n are as defined above, and Z ⁻ is

[0087]

[Chemical 42] Indicates.

General formula (XIII), (XIV) or (X
An azurenium dye represented by V).

[0089]

[Chemical 43]

In the formula, R _{29 to} R ₃₅ represent a hydrogen atom, a halogen atom (chlorine atom, bromine atom, iodine atom) or a monovalent organic residue. A wide variety of monovalent organic residues can be selected.

In addition, R ₂₉ and R ₃₀ , R ₃₀ and R ₃₁ , R
_At least one combination of ₃₁ and R ₃₂ , R ₃₂ and R ₃₃ , R ₃₃ and R _34, and R ₃₄ and R ₃₅ may form a substituted or unsubstituted fused ring. The condensed ring is a 5-, 6-, or 7-membered condensed ring, which is an aromatic ring (benzene, naphthalene, chlorobenzene, bromobenzene, methylbenzene, ethylbenzene, methoxybenzene, ethoxybenzene, etc.), heterocycle (furan Ring, benzofuran ring, pyrrole ring, thiophene ring, pyridine ring, quinoline ring, thiazole ring, etc.), and aliphatic ring (dimethylene, trimethylene, tetramethylene, etc.).

G ⁻ has the same meaning as above and represents an anion. F
Represents a divalent organic residue bonded by a double bond.
Specific examples of the present invention containing such F include those represented by the following general formulas (1) to (11). However, Q ⁺ in the formula represents the following azurenium salt nucleus, and F on the right side excluding Q ⁺ in the formula.

Azurenium salt nucleus (Q ⁺ ).

[0094]

[Chemical 44]

[0095]

[Chemical formula 45]

R ₂₉ ′ to R ₃₅ ′ have the same meanings as R _{29 to} R ₃₅ .

Further, the azurenium salt nucleus represented by Q ⁺ and the azulene salt nucleus on the right side in the above formula (3) may be symmetrical or asymmetrical.

[0098]

[Chemical formula 46]

[0099]

[Chemical 47]

[0100]

[Chemical 48] In the formula, I represents a nonmetallic atom group necessary for completing the nitrogen-containing heterocycle.

[0101]

[Chemical 49] In the formula, R ₃₈ represents a substituted or unsubstituted aryl group or a cation group thereof. p represents an integer from 1 to 8.

[0102]

[Chemical 50] In the formula, R ₃₉ represents a heterocyclic group or a cation group thereof.

[0103]

[Chemical 51] In the formula, R ₄₀ represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group.

[0104]

[Chemical 52]

[0105]

[Chemical 53]

In the formula, Z ₂ is pyran which may be substituted,
The group of atoms necessary for completing thiapyran, serenapyran, telluropyran, benzopyran, benzothiapyran, benzoselenapyran, benzotellopyran, naphthopyran, naphthothiapyran or naphthoserenapyran, naphthoterulopyran is shown.

L represents a sulfur atom, an oxygen atom, a selenium atom or a tellurium atom. R ₄₁ and R ₄₂ represent a hydrogen atom, an alkoxyl group, a substituted or unsubstituted aryl group, an aralkyl group, or a heterocyclic group.

Next, as a preferable dye, a compound represented by the general formula (XV
I), (XVII), (XVIII), and (XIX) represent dyes.

[0109]

[Chemical 54]

[0110]

[Chemical 55]

The above general formulas (XVI), (XVII),
In (XVIII) and (XIX), L ₁ and L _{2 each} represent a substituted nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom or a tellurium atom, and Z ₁ represents an optionally substituted pyrylium, thiopyrylium or selenapyryl. Atoms necessary for completing llium, telluropyrylium, benzopyrylium, benzothiopyrylium, benzoselenapyrylium, benzotelulopyrylium, naphthopyrylium, naphthothiopyrylium, naphthoselenapyrylium or naphthoteluropyrylium, Z ₂ Represents a group of atoms necessary to complete the optionally substituted pyran, thiopyran, serenapyran, telluropyran, benzopyran, benzothiopyran, benzoselenapyran, benzotelulopyran, naphthopyran, naphthothiopyran, naphthoserenapyran or naphthoterropyran.

S is an integer of 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 above-mentioned r
₁ ', _{r 2'} is synonymous with. k, n, I, r
_{1 ', r 2', r} 1, Y, Z -, G - has the same meaning as defined above.

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

A, B, D and E are each a hydrogen atom or an alkyl group (eg, 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 further other alkyl groups such as substituted alkyl groups (eg, 2-hydroxyethyl group,
3-hydroxypropyl group, 4-hydroxybutyl group,
2-acetoxyethyl group, methoxyethyl group, ethoxyethyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 2-sulfoethyl group,
3-sulfopropyl group, 4-sulfobutyl group, 3-sulfatepropyl group, 4-sulfatebutyl group, N-
(Methylsulfonyl) -carbamylmethyl group, 3- (acetylsulfamyl) propyl group, 4- (acetylsulfamyl) butyl group, etc.), cyclic alkyl group (for example,
Cyclohexyl group, etc., allyl group (CH ₂ ═CH—
CH ₂ —), 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.) and substituted aralkyl groups (eg, carboxybenzyl group, sulfobenzyl group, hydroxybenzyl group, etc.) are included.

Further, a substituted or unsubstituted aryl group (eg, phenyl group, α-naphthyl group, β-naphthyl group, tolyl group, xylyl group, biphenyl group, ethylphenyl group, methoxyphenyl group, ethoxyphenyl group, dimethoxy group). Phenyl group, hydroxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, dibromophenyl group, nitrophenyl group, diethylaminophenyl group, dimethylaminophenyl group, dimethoxyaminophenyl group, dibenzylaminophenyl group and the like).

R ₁ , r ₂ , r ₃ , r ₄ , r ₅
Is a hydrogen atom, a halogen atom (chlorine atom, bromine atom, iodine atom, etc.), an alkyl group (methyl group, ethyl group, n-
Propyl group, isopropyl group, n-butyl group, t-butyl group, n-amyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, t-octyl group, etc., alkoxy group (methoxy group, ethoxy group). Group, propoxy group,
Butoxy group), substituted or unsubstituted aryl group (phenyl group, tolyl group, xylyl group, ethylphenyl group, methoxyphenyl group, ethoxyphenyl group, chlorophenyl group, nitrophenyl group, dimethylaminophenyl group, α-naphthyl group) , Β-naphthyl group).

Y is a divalent hydrocarbon group, for example,

[0118]

[Chemical 56] Etc., and these 5-membered ring 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 ′ are not only a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.) but also a substituted or unsubstituted alkyl group (methyl group). , Ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-amyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, t-octyl group, etc.), substitution Or an unsubstituted alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), a substituted or unsubstituted aryl group (phenyl group, tolyl group, xylyl group, ethylphenyl group, methoxyphenyl group, dimethoxyphenyl group, Trimethoxyphenyl group, ethoxyphenyl group, chlorophenyl group, nitrophenyl group, dimethylaminophenyl group, diethyl Aminophenyl group, α-naphthyl group, β-
Naphthyl group, dipropylaminophenyl group, dibenzylaminophenyl, diphenylaminophenyl group, etc.), substituted or unsubstituted aralkyl group (benzyl group, 2-phenylethyl group, 2-phenyl-1-methylethyl group, bromo) Benzyl group, 2-bromophenylethyl group, methylbenzyl group, methoxybenzyl group, nitrobenzyl group), acyl group (acetyl group, propionyl group, propylyl group, valeryl group, benzoyl group, trioyl group, naphthoyl group, phthaloyl group, Floyl group, etc.), substituted or unsubstituted amino group (amino group, dimethylamino group, diethylamino group, dipropylamino group,
Acetylamino group, benzoylamino group, etc.), substituted or unsubstituted styryl group (styryl group, dimethylaminostyryl group, diethylaminostyryl group, dipropylaminostyryl group, methoxystyryl group, ethoxystyryl group, methylstyryl group, etc.), nitro Group, hydroxy group, carboxyl group, cyano group or substituted or unsubstituted arylazo group (phenylazo group, α-naphthylazo group, β-naphthylazo group, dimethylaminophenylazo group, chlorophenylazo group, nitrophenylazo group, methoxyphenylazo group , Tolylazo group, etc.), or a substituted or unsubstituted heterocyclic group (eg, pyridyl group, quinolyl group, lepidyl group, methylpyridyl group, furyl group, thienyl group, indolyl group, pyrrole group, carbazolyl group, N
-Ethylcarbazolyl group), 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 and the like).

R ₂₉ ′ to R ₃₅ ′ may also form a condensed ring in the same manner as R _{29 to} R ₃₅ . R ₃₆ is a hydrogen atom,
It represents a nitro group, a cyano group, an alkyl group (methyl group, ethyl group, propyl group, butyl group, etc.) or an aryl group (phenyl group, tolyl group, xylyl group, etc.).

R ₃₇ is an alkyl group (methyl group, ethyl group, propyl group, butyl group, etc.), a substituted alkyl group (2
-Hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3-hydroxypropyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-chloropropyl group, 3-bromopropyl group, 3-carboxy Propyl group, etc., cyclic alkyl group (cyclohexyl group,
Cyclopropyl group), allyl group, aralkyl group (benzyl group, 2-phenylethyl group, 3-phenylpropyl group, 4-phenylbutyl group, α-naphthylmethyl group, β
-Naphthylmethyl group), substituted aralkyl group (methylbenzyl group, ethylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, chlorobenzyl group, bromobenzyl group, etc.), aryl group (phenyl group, tolyl group, xylyl group, α- Naphthyl group, β-naphthyl group) or substituted aryl group (chlorophenyl group, dichlorophenyl group, trichlorophenyl group, ethylphenyl group, methoxyphenyl group, dimethoxyphenyl group, aminophenyl group, nitrophenyl group, hydroxyphenyl group, etc.) Represent.

R ₃₈ is a substituted or unsubstituted aryl group (phenyl group, tolyl group, xylyl group, biphenyl group, α-
Naphthyl group, β-naphthyl group, anthryl group, pyrenyl group, methoxyphenyl group, dimethoxyphenyl group, trimethoxyphenyl group, ethoxyphenyl group, diethoxyphenyl group, chlorophenyl group, dichlorophenyl group, trichlorophenyl group, bromophenyl group, Dibromophenyl group, tribromophenyl group, ethylphenyl group, diethylphenyl group, nitrophenyl group, aminophenyl group, dimethylaminophenyl group, diethylaminophenyl group, dibenzylaminophenyl group, dipropylaminophenyl group, morpholinophenyl group, Piperidinylphenyl group, piperazinophenyl group, diphenylaminophenyl group, acetylaminophenyl group, benzoylaminophenyl group, acetylphenyl group, benzoylphenyl group, cyanophenyl group It represents the like group).

R ₃₉ represents a monovalent heterocyclic group derived from a heterocycle such as furan, thiophene, benzofuran, thionaphthene, dibenzofuran, carbazole, phenothiazine, phenoxazine and pyridine.

R ₄₀ is a hydrogen atom, an alkyl group (methyl group, ethyl group, propyl group, butyl group, etc.) or a substituted or unsubstituted aryl group (phenyl group, tolyl group, xylyl group, biphenyl group, ethylphenyl group, Chlorophenyl group, methoxyphenyl group, ethoxyphenyl group,
Nitrophenyl group, aminophenyl group, dimethylaminophenyl group, diethylaminophenyl group, acetylaminophenyl group, α-naphthyl group, β-naphthyl group, anthrylyl group, pyrenyl group and the like).

R ₄₁ and R ₄₂ are hydrogen atom, alkyl group (methyl group, ethyl group, propyl group, butyl group, etc.), alkoxyl group (methoxy group, ethoxy group, propoxy group, ethoxyethyl group, methoxyethyl group, etc.) , An aryl group (phenyl group, tolyl group, xylyl group, chlorophenyl group, biphenyl group, methoxyphenyl group, etc.), a substituted or unsubstituted styryl group (styryl group, p-methylstyryl group, o-chlorostyryl group,
p-methoxystyryl group), substituted or unsubstituted 4-phenyl 1,3-butadienyl group (4-phenyl 1,3-butadienyl group, 4- (p-methylphenyl))
-1,3-butadienyl group) or a substituted or unsubstituted heterocyclic group (quinolyl group, pyridyl group, carbazolyl group, furyl group, etc.).

I is pyridine, thiazole, benzothiazole, naphthothiazole, oxazole, benzoxazole, naphthoxazole, imidazole, benzimidazole, naphthimidazole, 2-quinoline, 4-
A group of atoms required to complete a nitrogen-containing heterocycle such as quinoline, isoquinoline or indole, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), alkyl group (methyl group, ethyl group, propyl group, (Eg, butyl group), aryl group (phenyl group, tolyl group, xylyl group, etc.), aralkyl group (benzyl group, p-tolylmethyl group, etc.).

G ^- is an anion, and is a chloride ion, bromine ion, iodine ion, perchlorate ion, benzenesulfonate ion, P-toluenesulfonate ion, methylsulfate ion, ethylsulfate ion, propylsulfate ion. Ion, tetrafluoroborate ion, tetraphenylborate ion, hexafluorophosphate ion, benzenesulfinate ion, acetate ion, trifluoroacetate ion, propionate ion, benzoate ion, shu Salt, succinate, malonate, oleate, stearate, citrate, monohydrogen diphosphate, dihydrogen monophosphate, pentachlorostannate Ion, chlorosulfonate ion, fluorosulfonate ion, trifluorometa Sulfonate ion, hexafluoroantimonate ion, molybdate ion,
It represents tungstate ion, titanate ion, zirconate ion and the like.

R ₁ ′, r ₂ ′, r ₃ ′, r
₄ ′, r ₅ ′, r ₆ ′, r ₇ ′ are hydrogen atoms or alkyl groups (for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, t -Butyl group, n-amyl group, t-amyl group,
n-hexyl group, n-octyl group, t-octyl group, etc.), and other alkyl groups such as substituted alkyl groups (eg, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, Methoxyethyl group, 2-acetoxyethyl group, carboxymethyl group,
2-carboxyethyl group, 3-carboxypropyl group,
2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-sulfatepropyl group, 4-sulfatebutyl group, N- (methylsulfonyl) -carbamylmethyl group, 3- (acetylsulfamyl) Propyl group, 4- (acetylsulfamyl) butyl group, etc.), cyclic alkyl group (eg, cyclohexyl group), 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 (for example, benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group, etc.), substituted aralkyl group (for example, carboxybenzyl group, Sulfobenzyl group, hydroxybenzyl group, etc.).

In the present invention, the recording layer 2 is formed on the substrate 1 by various methods such as a coating method and a vapor deposition method.
When the coating method is used, it can be formed by coating on the substrate 1 a solution in which a double salt compound of a triarylamine compound cation and a metal complex anion is dissolved or dispersed in an organic solvent. Further, if necessary, a binder may be mixed in the recording layer to form a film in consideration of film-forming property and coating film stability.

The organic solvent that can be used for coating varies depending on whether the above-mentioned double salt compound of the triarylamine compound cation and the metal complex anion is in a dispersed state or in a dissolved state, but generally an alcohol solvent. Solvents such as ketone type, amide type, ether type, ester type, aliphatic halogenated hydrocarbon type, aromatic type and aliphatic hydrocarbon type can be used.

Examples of the binder include nitrocellulose, ethyl cellulose, polystyrene, polyvinylpyrrolidone, polymethylmethacrylate and polyamide. If necessary, wax, higher fatty acid, and amides (for example, oleylamide) are used as additives.

To the above binders, plasticizers such as dioctyl phthalate, dibutyl phthalate and tricresyl phosphate, oil agents such as mineral oil and vegetable oil, dispersants such as sodium alkylbenzene sulfonate and polyoxyethylene alkylphenyl ether, and other additives are added. It is possible to enhance the film forming property of the recording layer and the stability of the coating film by appropriately mixing the agents.

The coating can be carried out using a coating method such as a dip coating method, a spray coating method, a spinner coating method, a bead coating method, a Meyer bar coating method, a blade coating method, a roller coating method or a gravure coating method. .

The above general formula (I) or (I
The content of the double salt compound of the triarylamine compound cation represented by I) and the metal complex anion is usually 5 to 7
0% by weight, preferably 10 to 50% by weight is desirable. 5
If it is less than 70% by weight, the effect of suppressing photodegradation is insufficient, and if it exceeds 70% by weight, the amount of organic dye becomes small, and sufficient light absorption and sufficient light reflectance for laser light cannot be obtained.

The thickness of the recording layer 2 is 100Å to 20 μm.
m, preferably 200Å to 1 μm. Further, as shown in FIG. 2, the optical recording medium of the present invention has a protective layer 3 which is transparent to the recording and reproducing laser light on the recording layer 2.
Can be provided. The protective layer 3 may be opaque when irradiated with light from the substrate 1 side.

Further, as shown in FIG. 3, an undercoat layer 4 may be provided between the substrate 1 and the recording layer 2. Further, as shown in FIG. 4, it is possible to use both the protective layer 3 and the undercoat layer 4.

The undercoat layer has (a) improved adhesion, (b) water or gas barrier, (c) improved storage stability of the recording layer, (d) improved reflectance, and (e) solvent It is provided for the purpose of protecting the substrate, and (f) forming pregrooves. For the purpose of (a), various materials such as ionomer resin, polyamide resin, vinyl resin, natural polymer, silicone, liquid rubber or various substances such as silane coupling agent are used for the purpose of (a). For the purposes of (b) and (c), an inorganic compound such as SiO ₂ or MgF may be used in addition to the above polymer material.
₂ , SiO, TiO ₂ , ZnO, TiN, SiN, etc.,
Metals or semi-metals such as Zn, Cu, S, Ni, C
r, Ge, Se, Cd, Ag, Al or the like can be used. For the purpose of (d), metals such as Al, A
g or the like, or an organic thin film having a metallic luster, such as a cyanine dye, a polymethine dye, and an azulene dye, can be used. For the purposes of (e) and (f), an ultraviolet curable resin, a thermosetting resin, a thermoplastic resin or the like can be used. The thickness of the undercoat layer is 50Å-100
μm, preferably 200Å to 30 μm is suitable.

The protective layer is provided for the purpose of protecting it from scratches, dust, stains, etc., and improving the storage stability and reflectance of the recording layer, and the same material as that of the undercoat layer is used as the material thereof. can do. The thickness of the protective layer is 100 Å or more, preferably 1000 Å or more.

At this time, even if the undercoat layer and / or the protective layer contain the double salt compound of the triarylamine compound cation of the general formula (I) or (II) of the present invention and the metal complex anion. Good. Further, the undercoat layer or the protective layer may contain a stabilizer, a dispersant, a flame retardant, a lubricant, an antistatic agent, a surfactant, a plasticizer and the like.

Further, as another constitution of the optical recording medium according to the present invention, the recording layer 2 using the two recording mediums of the same constitution shown in FIGS. 1 to 4 (in some cases, one of them is the substrate only) is used. It may be a so-called air sandwich structure in which is placed inside and sealed, or a so-called close contact structure (bonding structure) in which the layers are adhered via the protective layer 3.
In the case of a close contact structure, the adhesive layer may contain a double salt compound of the triarylamine compound cation represented by the general formula (I) or (II) of the present invention and a metal complex anion.

As described above, in the present invention, at least one of the organic dye thin film, the subbing layer, the recording auxiliary layer, the protective layer and the adhesive layer is provided with a thoria represented by the general formula (I) or (II). A double salt compound of a reel amine compound cation and a metal complex anion may be contained, but the content is preferably in the range of 1 to 70% by weight, preferably 10 to 50% by weight.

The optical recording medium of the present invention can be recorded by irradiation with a gas laser such as a helium-neon laser (oscillation wavelength 633 nm), but is preferably 75.
A method of recording by irradiating a laser beam having a wavelength of 0 nm or more, particularly a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength of 830 nm) with a laser beam having an oscillation wavelength in the near infrared or infrared region is suitable. Also,
The above-mentioned laser beam can be used for reading. At this time, writing and reading can be performed by lasers having the same wavelength, or lasers having different wavelengths can be performed.

[0143]

EXAMPLES Next, examples of the present invention will be described, but the invention is not limited thereto. However, unless otherwise specified, all parts are by weight.

Synthesis Example 1 14.5 parts of tris (4-nitrophenyl) amine, 1.4 parts of 5% palladium-carbon hydrogenation catalyst and 90 ml of ethanol were placed in a 250 ml autoclave, and hydrogen gas was supplied at a pressure of 5.0 kg / g. The mixture was stirred at 90 ° C. in cm ² until the theoretical amount was absorbed. After completion of the reaction, 300 ml of ethanol was added and hot filtration was performed to remove the catalyst. The mother liquor was evaporated to 7.6
Some tris (4-aminophenyl) amine was obtained. The purity was 99.5% by high-speed liquid chromatography analysis.

By NMR (d ₆ -DMSO) analysis, δ
Absorption of an amino group for 6H at 4.20 to 5.02 ppm and absorption of an aromatic ring for 12H of a broad doublet at δ 6.09 to 6.82 ppm were measured.

<Synthesis of (2 ′)> 3 parts of the above amino compound was heated and stirred at 100 to 130 ° C. together with 20 parts of dimethylformamide, 0.9 part of anhydrous sodium hydrogencarbonate and 4.7 parts of methoxyethyl iodide. . After reacting for 36 hours, the reaction solution was poured into 230 parts of ice water and extracted with ethyl acetate. After drying, it was purified with a silica gel column. Acquisition amount 2.
7 copies. The disappearance of absorption due to NH stretching vibration of the amino group was confirmed by infrared absorption analysis.

2 parts of this compound was dispersed in 20 parts of acetone, and equimolar silver perchlorate was added with stirring. At room temperature 1
After reacting for a period of time, the precipitated silver was separated by filtration, the filtrate was diluted with isopropyl ether and allowed to stand, and the precipitated crystals were collected by filtration. 1.2 copies acquired. Synthesized in this way (2 ')
Was a compound having a large absorption in the infrared region having an absorption maximum wavelength of 974 nm. Elemental analysis value: calculated as C ₃₆ H ₅₄ N ₄ ClO ₁₀ (%); C: 58.57 H: 7.37
N: 7.59 Found (%); C: 58.43 H: 7.55
N: 7.51

<Synthesis of (2 ″)> 1 part of tris (4-dimethoxyethylaminophenyl) amine used in the synthesis of (2 ′) was dispersed in 18 parts of acetone, and a 2-fold molar hexafluoride was added with stirring. Silver antimonate was added, and after reacting at room temperature for 1 hour, the precipitated silver was separated by filtration, the filtrate was diluted with isopropyl ether, and 10.70 parts of precipitated crystals were collected by filtration. The compound (2 ″) was a compound having a large absorption in the infrared region having an absorption maximum wavelength of 982 nm.

The example explained above is for the case where the anions are perchloric acid and antimony hexafluoride, but when using other anions, the desired compound can be easily obtained by using a silver salt corresponding thereto. You can For example,
AgBF ₄ , AgSO ₄ , AgNO ₃ , AgSO ₃ C ₆
A silver salt such as H ₄ CH ₃ or AgSO ₃ CF ₃ can be used. In addition to this, it can also be obtained by electrolytic oxidation.

<Synthesis of (I) -28> (2 ') 0.60
0.56 g of nickel bis (trichlorobenzenedithiol) tetra (n-butyl) ammonium salt (trade name: PA-1006, manufactured by Mitsui Toatsu Fine Co., Ltd.) was added to a solution of 50 g of DMF in 50 ml, and the mixture was added at 50 ° C. for 3 hours. Heated and stirred. The reaction solution was poured into water, the obtained precipitate was washed with water, dried and then recrystallized to give 0.80 g of a double salt compound.
Got

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

Elemental analysis value: C ₄₈ H ₅₆ N ₄ Cl ₆ NiO ₆
Calculated value (%) as S ₄ ; C: 48.67 H: 4.76
N: 4.73 Found (%); C: 46.23 H: 4.93
N: 4.62

<Synthesis of (II) -26> 1.5 g of nickel bisdithiobenzyl (trade name: MIR-101, manufactured by Midori Kagaku Co., Ltd.) and 1.9 g of p-phenylenediamine were dissolved in 12 ml of dimethyl sulfoxide. When 60 ml of an ethanol solution of 3.3 g of tetra (n-butyl) ammonium bromide was added dropwise thereto, red needle crystals were precipitated.

This was collected by filtration, washed with water and purified by recrystallization to obtain 1.1 g of nickel bisdithiobenzyl tetrabutylammonium. When the absorption spectrum of this crystal was measured, λ _max 930 nm of MIR101 was 950 nm.
It was confirmed that the substance became an anion due to the long wavelength shift.

0.9 g of the above-mentioned nickel bis (dithiobenzyl) tetrabutylammonium was added to a solution prepared by dissolving 0.4 g of (2 ″) in 40 ml of DMF, and the mixture was heated and stirred at 50 ° C. for 3 hours. The obtained precipitate was washed with water, dried and then recrystallized to give the double salt compound 0.9.
5 g was obtained.

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

Elemental analysis: calculated value (%) as C ₉₂ H ₉₄ N ₄ O ₆ S ₈ Ni ₂ ; C: 64.03 H: 5.49
N: 3.25 Found (%); C: 63.82 H: 5.70
N: 3.49

Next, examples in which the infrared absorbing compounds represented by the general formulas (1) and (II) are used as an optical recording material will be described.

Example 1 A wallet-sized 0.4 mm thick polycarbonate (hereinafter abbreviated as "PC") substrate was provided with a pre-groove by a hot press method, and IR-820 (made by Japan) as a polymethine dye was provided thereon. (Manufactured by Yakuhin) and 3 parts by weight of a mixture of the infrared absorbing compound (I) -4 (weight ratio 75:25) in 97 parts by weight of diacetone alcohol is applied by a bar coating method and then dried. As a result, a recording layer having a thickness of 1000Å was obtained.

Further, an optical recording medium having a close contact structure was prepared by a heat roll method with a wallet-sized 0.3 mm PC substrate with an acrylic ester-ethylene copolymer dry film interposed therebetween.

The optical card thus obtained has an oscillation wavelength of 830n.
m semiconductor laser beam with an output of 0.3 mW and radiated through a 0.4 mm-thick PC substrate, the reflectance from the recording layer is measured by an optical card recording / reproducing device (Canon Corp.).
Manufactured).

Then, using a semiconductor laser having an oscillation wavelength of 830 nm for the optical card, a recording power of 3.5 mW and a recording pulse of 80 μsec were passed through a PC substrate having a thickness of 0.4 mm.
The information is written with and reproduced with a reproduction power of 0.2 mW, and the contrast ratio

[0163]

[Equation 1] (However, A: signal intensity of the end recording portion, B: signal intensity of the recording portion) were measured.

Next, this optical card was placed at 65 ° C. and 85% RH.
The reflectance and the contrast ratio were measured after standing for 1000 hours under the conditions (1) (environmental storage stability). Further, the optical card of Example 1 which was newly prepared and recorded in exactly the same manner was irradiated with a xenon lamp light of 1 KW / m ² for 200 hours, and the reflectance and the contrast ratio were measured (light stability).

The results are shown in Table 1.

[0166]

[Table 1]

Examples 2 to 7 Polymethine dye and double salt compound (I) used in Example 1
An optical card was prepared and evaluated in the same manner as in Example 1 except that the combination of the dyestuff and the double salt compound shown in Tables 2 and 3 below was used. The optical cards of Examples 2 to 7 were measured in the same manner as in Example 1. The results are shown in Table-5.

Comparative Examples 1 and 2 Double salt compound Nos. Used in Examples 2 and 4 (I)-
An optical card was prepared and evaluated in the same manner as in Examples 2 and 4 except that 8, (I) -9 was omitted. The results are shown in Table-5.

[0169]

[Table 2]

[0170]

[Table 3]

Comparative Examples 3 to 4 The double salt compound No. 1 used in Example 2 was used. An optical card was prepared and evaluated in the same manner as in Example 2 except that the following compound was used instead of (I) -8. The results are shown in Table-5.

[0172]

[Table 4]

[0173]

[Table 5]

Examples 8 to 12 On a PC substrate having a diameter of 130 mmφ and a thickness of 1.2 mm and provided with pregrooves by injection molding, 5 parts by weight of a mixture of the organic dye and the double salt compound shown in Table 6 below was used. A solution dissolved in 95 parts by weight of acetone alcohol was spin-coated to form a recording layer having a thickness of 900Å. An optical disc having an air sandwich structure was obtained by sandwiching 0.3 mm spacers on the inner and outer peripheries of the medium thus obtained and bonding it to another PC protective substrate with an ultraviolet curable adhesive.

The optical disc thus created is stored at 1800r.
The semiconductor laser beam with an oscillation wavelength of 830 nm is irradiated through the PC substrate, the information is written at a recording frequency of 3 MHz with a recording power of 8 mW, and the read power is 0.
Playback at 6 mW, spectrum analysis (scanning filter, bandwidth 30 KHz) of the playback waveform, and C / N
The ratio (carrier / noise ratio) was measured.

Next, the information recording section of this optical disk is set to 10
The C / N ratio was measured after repeated reproduction ⁵ times. Also,
A spectrophotometer (trade name: U-3400; Hitachi, Ltd.) for the reflectance of the recording layer at a wavelength of 830 nm through a PC substrate
It was measured at.

Further, this optical disk was subjected to an environmental preservation stability test and a light stability test under the same conditions as in Example 1, and thereafter the reflectance and C / N ratio in a spectrophotometer were measured. The results are shown in Table-7.

Comparative Examples 5 and 6 Double salt compound Nos. Used in Examples 8 and 11 (I)-
Optical discs were produced and evaluated in the same manner as in Examples 8 and 11, except that 3 and (II) -26 were omitted.
The results are shown in Table-7.

Comparative Example 7 Double salt compound No. 1 used in Example 8 An optical disc was produced in the same manner as in Example 8 except that (I) -3 was changed to the following metal complex compound. Since the solubility of the following metal complex was poor, crystals were deposited after coating, and as a result, the noise level width of the reproduced signal from this optical disk was so wide that C / N could not be measured.

[0180]

[Chemical 57]

[0181]

[Table 6]

[0182]

[Table 7]

Examples 13 and 14 On a polymethylmethacrylate (hereinafter abbreviated as "PMMA") substrate having a diameter of 130 mmφ and a thickness of 1.2 mm, a 2P method (photopolymer method) was performed by using an epoxy-acrylate ultraviolet curing resin. ), A pre-groove having a thickness of 30 μm was provided. A solution prepared by dissolving 2 parts by weight of a mixture of a combination of organic dyes and double salt compounds shown in Table 8 below in 1,2-dichloroethane was applied on the substrate by a spinner coating method, and an organic thin film having a dry film thickness of 900 liters was applied. An optical disc was produced in the same manner as in Example 8 except that the recording layer was formed.

The optical disk thus prepared was measured and evaluated in the same manner as in Example 8. The results are shown in Table-10.

[0185]

[Table 8]

Examples 15 and 16 4 parts by weight of a mixture of a combination of an organic dye and a double salt compound shown in Table 9 below and 1 part by weight of nitrocellulose resin (Ohhales Rucker, manufactured by Daicel Chemical Industries Ltd.) were added to diacetone. A solution prepared by mixing 95 parts by weight of alcohol was applied by a spinner coating method onto a polycarbonate substrate having a diameter of 130 mmφ and a thickness of 1.2 mm provided with a pre-groove to form an organic thin film recording layer having a dry film thickness of 950 Å. Example 8
An optical disc was produced in the same manner as in.

The optical disc thus prepared was measured in the same manner as in Example 8. The results are shown in Table-10.

[0188]

[Table 9]

[0189]

[Table 10]

[0190]

As described above, the composite compound of the triarylamine compound cation represented by the general formula (I) or (II) and the metal complex anion of the present invention and the optical recording medium using the same are provided. Thus, it is possible to obtain an optical recording medium having a significantly improved light resistance and having an excellent photodegradation suppressing effect even with a small amount added to the dye. An optical recording medium having excellent storage stability can be obtained under high temperature and high humidity environmental conditions. An optical recording medium having a clear threshold value for laser power can be obtained without deteriorating the excellent characteristics such as high reflectance and high sensitivity of the organic dye. And so on.

[Brief description of drawings]

FIG. 1 is a sectional view showing an embodiment of an optical recording medium of the present invention.

FIG. 2 is a sectional view showing another embodiment of the optical recording medium of the present invention.

FIG. 3 is a cross-sectional view showing another embodiment of the optical recording medium of the present invention.

FIG. 4 is a sectional view showing another embodiment of the optical recording medium of the present invention.

[Explanation of symbols]

 1 substrate 2 recording layer 3 protective layer 4 undercoat layer

Claims (12)

[Claims] 1. An infrared absorbing compound represented by the following general formula (I). [Chemical 1] (In the formula, R _{1 to} R ₆ represent a hydrogen atom or a monovalent organic residue, and at least one of R _{1 to} R ₆ is a substituted or terminal-substituted alkoxyalkyl group, a substituted or terminal-substituted alkenyl group, A substituted or unsubstituted alkynyl group, a substituted or unsubstituted cycloalkyl group, or R
_{The combination of 1} and R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ together with N forms a substituted or terminal-substituted 5-membered ring, a substituted or terminal-substituted 6-membered ring, or a substituted or terminal-substituted 7-membered ring. .
R _{1 to} R ₆ may be different or the same. R _{7 to} R ₉ represent a hydrogen atom, a halogen group, a lower alkyl group, a lower alkoxy group, a cyano group or a hydroxyl group.
X ⁻ represents a monovalent metal complex anion. ) 2. The infrared absorbing compound according to claim 1, wherein the metal complex anion is a nickel complex anion. 3. The metal complex anion is represented by the following general formula (I
The infrared absorbing compound according to claim 1, which is an anion represented by II). [Chemical 2] (In the formula, each of R _{9 to} R ₁₂ represents a hydrogen atom, a substituted or terminal-substituted alkyl group, a substituted or terminal-substituted amino group, a substituted or terminal-substituted aryl group, or a halogen atom. M represents a transition metal atom. .) 4. The metal complex anion is represented by the following general formula (I
The infrared absorbing compound according to claim 1, which is an anion represented by V). [Chemical 3] (In the formula, R _{13 to} R ₁₆ each represent a substituted or terminal-substituted alkyl group, a substituted or terminal-substituted aryl group or a cyano group. M represents a transition metal atom.) 5. An infrared absorbing compound represented by the following general formula (II). [Chemical 4] (In the formula, R _{1 to} R ₆ represent a hydrogen atom or a monovalent organic residue, and at least one of R _{1 to} R ₆ is a substituted or terminal-substituted alkoxyalkyl group, a substituted or terminal-substituted alkenyl group, A substituted or unsubstituted alkynyl group, a substituted or unsubstituted cycloalkyl group, or R
_{The combination of 1} and R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ together with N forms a substituted or terminal-substituted 5-membered ring, a substituted or terminal-substituted 6-membered ring, or a substituted or terminal-substituted 7-membered ring. .
R _{1 to} R ₆ may be different or the same. R _{7 to} R ₉ represent a hydrogen atom, a halogen group, a lower alkyl group, a lower alkoxy group, a cyano group or a hydroxyl group.
X ⁻ represents a monovalent metal complex anion. ) 6. The infrared absorbing compound according to claim 5, wherein the metal complex anion is a nickel complex anion. 7. The metal complex anion is represented by the following general formula (I
The infrared absorbing compound according to claim 5, which is an anion represented by II). [Chemical 5] (In the formula, each of R _{9 to} R ₁₂ represents a hydrogen atom, a substituted or terminal-substituted alkyl group, a substituted or terminal-substituted amino group, a substituted or terminal-substituted aryl group, or a halogen atom. M represents a transition metal atom. .) 8. The metal complex anion is represented by the following general formula (I
The infrared absorbing compound according to claim 5, which is an anion represented by V). [Chemical 6] (In the formula, R _{13 to} R ₁₆ each represent a substituted or terminal-substituted alkyl group, a substituted or terminal-substituted aryl group or a cyano group. M represents a transition metal atom.) 9. An optical recording medium comprising a substrate and a recording layer, wherein the recording layer has the following general formula (I) or (II):
An optical recording medium containing a compound represented by: [Chemical 7] (In the formula, R _{1 to} R ₆ represent a hydrogen atom or a monovalent organic residue, and at least one of R _{1 to} R ₆ is a substituted or terminal-substituted alkoxyalkyl group, a substituted or terminal-substituted alkenyl group, A substituted or unsubstituted alkynyl group, a substituted or unsubstituted cycloalkyl group, or R
_{The combination of 1} and R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ together with N forms a substituted or terminal-substituted 5-membered ring, a substituted or terminal-substituted 6-membered ring, or a substituted or terminal-substituted 7-membered ring. .
R _{1 to} R ₆ may be different or the same. R _{7 to} R ₉ represent a hydrogen atom, a halogen group, a lower alkyl group, a lower alkoxy group, a cyano group or a hydroxyl group.
X ⁻ represents a monovalent metal complex anion. ) 10. The optical recording medium according to claim 9, wherein the metal complex anion is a nickel complex anion. 11. The optical recording medium according to claim 9, wherein the metal complex anion is an anion represented by the following general formula (III). [Chemical 8] (In the formula, each of R _{9 to} R ₁₂ represents a hydrogen atom, a substituted or terminal-substituted alkyl group, a substituted or terminal-substituted amino group, a substituted or terminal-substituted aryl group, or a halogen atom. M represents a transition metal atom. .) 12. The optical recording medium according to claim 9, wherein the metal complex anion is an anion represented by the following general formula (IV). [Chemical 9] (In the formula, R _{13 to} R ₁₆ each represent a substituted or terminal-substituted alkyl group, a substituted or terminal-substituted aryl group or a cyano group. M represents a transition metal atom.)