JP2003064274A - Dipyrromethene metal chelate compound and light recording medium using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light recording medium capable of recording and reproduction with shortwave laser having a wavelength of 520-690 nm, excellent in durability and suitable for high density and high speed recording, and to provide a dipyrromethene metal chelate compound for use in the same. SOLUTION: The light recording medium contains the dipyrromethene metal chelate compound expressed by formula 1 in a recording layer. (In formula 1, A denotes a 2-pyrrolyl group in which hetero atom-containing five member rings are fused). Specifically, examples include a compound of (D-1).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel dipyrromethene metal chelate compound and an optical recording medium using the same, capable of recording and reproducing at a higher density than ever before.

[0002]

2. Description of the Related Art At present, a DVD having a capacity of 4.7 GB has been developed and commercialized as an optical recording medium having a larger capacity than a CD. Since the DVD is a read-only medium, an optical recording medium capable of recording and reproducing corresponding to this capacity is desired. Among them, the write-once type is called DVD-R.

In order to perform high-density recording on DVD, the emission wavelength of laser light is around 630 nm to 680 nm, which is shorter than that of CD. Examples of dyes for such organic dye-based optical recording media for short wavelength use include cyanine, azo,
Benzopyran, benzodifuranone, indigo, dioxazine, porphyrin dyes and the like have been proposed, and are disclosed in JP-A-4-74690 and JP-A-5-38878,
JP-A-6-40161, JP-A-6-40162, JP-A-6-199045, JP-A-6-33
No. 6086, No. 7-76169, No. 7-125441, No. 7-262604, No. 9-156218, No. 9-193.
No. 544, No. 9-193545, No. 9-193547, No. 9-194748, No. 9-202052, No. 9-2672.
562, JP-A-9-274732, etc., but there is a problem of durability and a problem peculiar to short wavelength applications, for example, a place where a small pit should be opened with a narrowed laser beam has an influence on the surroundings. Jitter, deterioration of crosstalk in the radial direction due to the formation of pits with a large distribution and a large distribution, deterioration of modulation due to extremely small pits, and At present, there is no solution to the problems such as reduction in reflectance and deterioration in sensitivity due to selection of an organic dye having an appropriate optical constant (refractive index, extinction coefficient) for the recording layer.

Further, as seen in the increase in the recording speed in the CD-R, an optical recording medium compatible with high-speed recording which is twice as fast as the normal recording speed in the DVD-R is desired in the future. ing. However, there are problems such as deterioration of recording sensitivity and deterioration of jitter associated with high speed recording.

The inventors of the present invention have previously disclosed Japanese Patent Laid-Open No. 10-2261.
72, JP-A-11-092682, JP-A-11-165465, and JP-A-11-227332.
JP-A-11-227333, JP-A-11-227333
No. 3,210,981 discloses an optical recording medium using a novel dipyrromethene metal chelate compound.
Further improvement in high-speed recording / reproducing characteristics at double speed or more is desired.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an optical recording medium which is capable of recording and reproducing with a short wavelength laser having a wavelength of 520 to 690 nm and which is excellent in durability and suitable for high density and high speed recording. To provide.

[0007]

DISCLOSURE OF THE INVENTION The inventors of the present invention have further earnestly studied an optical recording medium using a dipyrromethene metal chelate compound as disclosed in JP-A-10-226172 and others, and as a result, dipyrromethene metal chelate. By selecting a specific substituent in the compound, it is possible to obtain an optical recording medium that is not only excellent in recording characteristics and durability, but also capable of recording at a higher speed than the conventional recording speed. The present invention has been completed and the present invention has been completed.

That is, the present invention is a dipyrromethene metal chelate compound of a dipyrromethene compound represented by the following general formula (1) and a metal ion.

[0009]

[Chemical 5]

[In the formula, R _{1 to} R ₅ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a substituent having 20 or less carbon atoms, or Unsubstituted alkyl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, alkenyl group, acyl group, alkoxycarbonyl group, carbamoyl group, acylamino group, aralkyl group,
Represents an aryl group or a heteroaryl group, R ₆ is
A halogen atom, a substituted or unsubstituted aryl group having 20 or less carbon atoms, a heteroaryl group, an alkoxy group, an alkylthio group, an aryloxy group, or an arylthio group is represented, and A is a 5-membered ring containing a hetero atom which is condensed. Represents a 2-pyrrolyl group. ]

A is the following general formula (a1) or (a
The dipyrromethene metal chelate compound according to claim 2, which is selected from any of 2) and is a 2-pyrrolyl group in which a 5-membered ring containing a hetero atom is condensed.

[0012]

[Chemical 6]

[Wherein R _{7 to} R ₁₁ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a substituent having 20 or less carbon atoms, or Unsubstituted alkyl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, alkenyl group, acyl group, alkoxycarbonyl group, carbamoyl group, acylamino group, aralkyl group,
Represents an aryl group or a heteroaryl group, X ₁ is
It represents an oxygen atom, a sulfur atom, or a substituted or unsubstituted nitrogen atom represented by the following general formula (d).

—N (R ₁₅ ) — (d) (In the formula, R ₁₅ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 20 or less carbon atoms, an alkenyl group, an acyl group, an alkoxycarbonyl group, an aralkyl group, Represents an aryl group or a heteroaryl group.)]

A is the following general formula (b1), (b2),
Alternatively, a dipyrromethene metal chelate compound selected from the group (b3), wherein the 5-membered ring containing a hetero atom is a condensed 2-pyrrolyl group.

[0016]

[Chemical 7]

[In the formula, R ₇ , R _{12 to} R ₁₄ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, or a carbon number of 20 or less. A substituted or unsubstituted alkyl group of
An alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an alkenyl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an acylamino group, an aralkyl group, an aryl group, or a heteroaryl group,
Y ₁ is an oxygen atom, a sulfur atom, or the following general formula (d)
Represents a substituted or unsubstituted nitrogen atom.

—N (R ₁₅ ) — (d) (In the formula, R ₁₅ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 20 or less carbon atoms, an alkenyl group, an acyl group, an alkoxycarbonyl group, an aralkyl group, Represents an aryl group or a heteroaryl group.)]

A is the following general formula (c1) or (c
The dipyrromethene metal chelate compound according to claim 2, which is selected from any of 2) and is a 2-pyrrolyl group in which a 5-membered ring containing a hetero atom is condensed.

[0020]

[Chemical 8]

[In the formula, R ₇ is a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a substituted or unsubstituted alkyl group having 20 or less carbon atoms, an alkoxy group. A group, an alkylthio group, an aryloxy group, an arylthio group, an alkenyl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an acylamino group, an aralkyl group, an aryl group or a heteroaryl group, Z ₁ is an oxygen atom or a sulfur atom Or a substituted or unsubstituted nitrogen atom represented by the following general formula (d).

—N (R ₁₅ ) — (d) (In the formula, R ₁₅ is a hydrogen atom, a substituted or unsubstituted alkyl group having 20 or less carbon atoms, an alkenyl group, an acyl group, an alkoxycarbonyl group, an aralkyl group, Represents an aryl group or a heteroaryl group.)]

An optical recording medium having at least a recording layer and a reflective layer on a substrate, wherein the recording layer contains at least one dipyrromethene metal chelate compound described in

At the laser wavelength, the recording layer has a refractive index of 1.8 or more and an extinction coefficient of 0.04 to 0.40.
The optical recording medium according to item 1.

The present invention relates to an optical recording medium capable of recording and reproducing with respect to a laser beam selected from a wavelength range of 520 to 690 nm.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

In the dipyrromethene metal chelate compound represented by the general formula (1), specific examples of R _{1 to} R ₅ are:
Hydrogen atom; halogen atom such as fluorine, chlorine, bromine, iodine; nitro group; cyano group; hydroxy group; amino group; carboxyl group; sulfonic acid group; methyl group, ethyl group, n-
Propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, 2-methylbutyl group, 1-methylbutyl group, neo-
Pentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, cyclo-pentyl group, n-hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methyl Pentyl group, 3,3-dimethylbutyl group, 2,3-
Dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,2-dimethylbutyl group, 1,1-dimethylbutyl group, 3-ethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group , 1,2,2-trimethylbutyl group, 1,1,2-trimethylbutyl group, 1-ethyl-2-methylpropyl group, cyclo-hexyl group, n-heptyl group, 2-methylhexyl group, 3-methyl Hexyl group, 4-methylhexyl group, 5-methylhexyl group, 2,4-dimethylpentyl group, n-octyl group, 2-ethylhexyl group, 2,5-dimethylhexyl group, 2,5,5-trimethylpentyl group , 2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group, 3,5,5-trimethylhexyl group, n-nonyl group, n-decyl group, 4-ethyloctyl group, 4-ethyl-4 ,Five
-Dimethylhexyl group, n-undecyl group, n-dodecyl group, 1,3,5,7-tetraethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, n-tridecyl group, 6-methyl- 4-butyloctyl group, n-tetradecyl group, n-pentadecyl group, 3,5-dimethylheptyl group, 2,6-dimethylheptyl group, 2,4-dimethylheptyl group, 2,2,5,5-tetramethyl A substituted or unsubstituted alkyl group having 20 or less, preferably 15 or less carbon atoms such as hexyl group, 1-cyclo-pentyl-2,2-dimethylpropyl group, 1-cyclo-hexyl-2,2-dimethylpropyl group;

Methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, t-butoxy group, n-pentoxy group,
A substituted or unsubstituted alkoxy group having 20 or less, preferably 15 or less carbon atoms such as iso-pentoxy group, neo-pentoxy group, n-hexyloxy group, n-dodecyloxy group; methylthio group, ethylthio group, n-propylthio group Group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-
Butylthio group, t-butylthio group, n-pentylthio group, is
20 carbon atoms such as o-pentylthio group, 2-methylbutylthio group, 1-methylbutylthio group, neo-pentylthio group, 1,2-dimethylpropylthio group, 1,1-dimethylpropylthio group
Or less, preferably 15 or less, substituted or unsubstituted alkylthio group;

Phenoxy group, 2-methylphenoxy group, 4-
A substituted or unsubstituted aryloxy group having 20 or less, preferably 15 or less carbon atoms such as methylphenoxy group, 4-t-butylphenoxy group, 2-methoxyphenoxy group, 4-iso-propylphenoxy group; and a phenylthio group, 4 A substituted or unsubstituted arylthio group having 20 or less, preferably 15 or less carbon atoms such as -methylphenylthio group, 2-methoxyphenylthio group, 4-t-butylphenylthio group; vinyl group, propenyl group, 1 -Butenyl group, iso-butenyl group, 1-pentenyl group, 2-pentenyl group, 2-methyl-1-butenyl group, 3-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2,2- Dicyanovinyl group, 2-cyano-2-methylcarboxyl vinyl group, 2-cyano-2-methylsulfone vinyl group, 2-phenyl-
A substituted or unsubstituted alkenyl group having 20 or less, preferably 15 or less carbon atoms such as 1-butenyl group; formyl group, acetyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group Group, iso-butylcarbonyl group, sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group,
a substituted or unsubstituted acyl group having 20 or less, preferably 15 or less carbon atoms such as iso-pentylcarbonyl group, neo-pentylcarbonyl group, 2-methylbutylcarbonyl group, nitrobenzylcarbonyl group;

A substituted or unsubstituted alkoxycarbonyl group having 20 or less, preferably 15 or less carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, an isopropyloxycarbonyl group and a 2,4-dimethylbutyloxycarbonyl group; a carbamoyl group; acetyl A substituted or unsubstituted acylamino group having 20 or less, preferably 15 or less carbon atoms such as amino group, ethylcarbonylamino group, butylcarbonylamino group; benzyl group, nitrobenzyl group, cyanobenzyl group, hydroxybenzyl group, methylbenzyl group , Dimethylbenzyl group, trimethylbenzyl group, dichlorobenzyl group, methoxybenzyl group, ethoxybenzyl group, trifluoromethylbenzyl group, naphthylmethyl group, nitronaphthylmethyl group, cyanonaphthylmethyl group, hydroxynaphthyl A substituted or unsubstituted aralkyl group having a carbon number of 20 or less, preferably 15 or less, such as a methyl group, a methylnaphthylmethyl group, a trifluoromethylnaphthylmethyl group;

Phenyl group, nitrophenyl group, cyanophenyl group, hydroxyphenyl group, methylphenyl group,
Dimethylphenyl group, trimethylphenyl group, ethylphenyl group, diethylphenyl group, triethylphenyl group, n-propylphenyl group, di (n-propyl) phenyl group, tri (n-propyl) phenyl group, iso-propylphenyl group, Di (iso-propyl) phenyl group, tri (iso-propyl) phenyl group, n-butylphenyl group, di (n-butyl) phenyl group, tri (n-butyl) phenyl group, iso-butylphenyl group, di ( iso-butyl) phenyl group, tri (iso-butyl) phenyl group, sec-butylphenyl group, di (sec-butyl) phenyl group, tri (sec-butyl) phenyl group, t-butylphenyl group, di (t- Butyl) phenyl group, tri (t-butyl) phenyl group, dimethyl-t-butylphenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group,
Iodophenyl group, methoxyphenyl group, ethoxyphenyl group, trifluoromethylphenyl group, N, N-dimethylaminophenyl group, naphthyl group, nitronaphthyl group, cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl group, fluoronaphthyl group, Chloronaphthyl group, bromonaphthyl group, iodonaphthyl group, methoxynaphthyl group,
A substituted or unsubstituted aryl group having 20 or less, preferably 15 or less carbon atoms, such as a trifluoromethylnaphthyl group or an N, N-dimethylaminonaphthyl group;

Carbons such as pyrrolyl group, thienyl group, furanyl group, oxazoyl group, isoxazoyl group, oxadiazoyl group, imidazoyl group, benzoxazoyl group, benzothiazoyl group, benzimidazoyl group, benzofuranyl group, indoyl group and isoindoyl group. A substituted or unsubstituted heteroaryl group having a number of 20 or less, preferably 15 or less; and the like.

Specific examples of R ₇ include halogen atoms such as fluorine, chlorine, bromine and iodine; phenyl group, nitrophenyl group, cyanophenyl group, hydroxyphenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group, Ethylphenyl group, diethylphenyl group, triethylphenyl group, n-propylphenyl group, di (n-propyl) phenyl group, tri (n-propyl) phenyl group, iso-propylphenyl group, di (iso-propyl) phenyl group ,bird
(iso-propyl) phenyl group, n-butylphenyl group, di (n
-Butyl) phenyl group, tri (n-butyl) phenyl group, iso
-Butylphenyl group, di (iso-butyl) phenyl group, tri
(iso-butyl) phenyl group, sec-butylphenyl group, di-
(sec-butyl) phenyl group, tri (sec-butyl) phenyl group, t-butylphenyl group, di (t-butyl) phenyl group,
Tri (t-butyl) phenyl group, dimethyl-t-butylphenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, iodophenyl group, methoxyphenyl group,
Ethoxyphenyl group, trifluoromethylphenyl group,
N, N-dimethylaminophenyl group, naphthyl group, nitronaphthyl group, cyanonaphthyl group, hydroxynaphthyl group,
Methylnaphthyl group, fluoronaphthyl group, chloronaphthyl group, bromonaphthyl group, iodonaphthyl group, methoxynaphthyl group, trifluoromethylnaphthyl group, N, N-dimethylaminonaphthyl group having 20 or less carbon atoms, preferably 15 or less carbon atoms A substituted or unsubstituted aryl group;

Carbons such as pyrrolyl group, thienyl group, furanyl group, oxazoyl group, isoxazoyl group, oxadiazoyl group, imidazoyl group, benzoxazoyl group, benzothiazoyl group, benzimidazoyl group, benzofuranyl group, indoyl group and isoindoyl group. A substituted or unsubstituted heteroaryl group having a number of 20 or less, preferably 15 or less; a methoxy group, an ethoxy group, an n-propoxy group,
iso-propoxy group, n-butoxy group, iso-butoxy group, se
c-butoxy group, t-butoxy group, n-pentoxy group, iso-pentoxy group, neo-pentoxy group, n-hexyloxy group,
n-dodecyloxy group etc. has 20 or less carbon atoms, preferably 1
A substituted or unsubstituted alkoxy group of 5 or less;

Methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, iso-pentylthio group, 2 -Methylbutylthio group, 1-methylbutylthio group, neo-pentylthio group, 1,
A substituted or unsubstituted alkylthio group having 20 or less, preferably 15 or less carbon atoms such as 2-dimethylpropylthio group and 1,1-dimethylpropylthio group; phenoxy group, 2-methylphenoxy group, 4-methylphenoxy group, A substituted or unsubstituted aryloxy group having 20 or less, preferably 15 or less carbon atoms such as 4-t-butylphenoxy group, 2-methoxyphenoxy group, 4-iso-propylphenoxy group;

A substituted or unsubstituted arylthio group having 20 or less, preferably 15 or less carbon atoms such as phenylthio group, 4-methylphenylthio group, 2-methoxyphenylthio group, 4-t-butylphenylthio group; Etc. can be mentioned.

A represents a 2-pyrrolyl group in which a 5-membered ring containing a hetero atom is condensed, and is preferably a compound represented by the general formula (a)
1), (a2), (b1), (b2), (b3), (c
1) or a 2-pyrrolyl group represented by (c2).

In the 2-pyrrolyl group represented by the general formula (a1) or the general formula (a2), in which a 5-membered ring containing a hetero atom is condensed, a specific example of R _{7 to} R ₁₁ is a hydrogen atom; Halogen atom such as fluorine, chlorine, bromine, iodine; nitro group; cyano group; hydroxy group; amino group; carboxyl group; sulfonic acid group; methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl Group, iso-butyl group, sec-
Butyl group, t-butyl group, n-pentyl group, iso-pentyl group, 2-methylbutyl group, 1-methylbutyl group, neo-pentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, cyclo -Pentyl group, n-hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1 , 3-Dimethylbutyl group, 2,2-dimethylbutyl group, 1,2-dimethylbutyl group, 1,1-dimethylbutyl group, 3-
Ethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, 1,2,2-trimethylbutyl group, 1,1,2-trimethylbutyl group, 1-ethyl-2-methylpropyl group, cyclo-hexyl group, n- Heptyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 2,
4-dimethylpentyl group, n-octyl group, 2-ethylhexyl group, 2,5-dimethylhexyl group, 2,5,5-trimethylpentyl group, 2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group Group, 3,5,5-trimethylhexyl group, n-nonyl group,
n-decyl group, 4-ethyloctyl group, 4-ethyl-4,5-dimethylhexyl group, n-undecyl group, n-dodecyl group, 1,3,
5,7-tetraethyloctyl group, 4-butyloctyl group, 6,
6-diethyloctyl group, n-tridecyl group, 6-methyl-4-
Butyloctyl group, n-tetradecyl group, n-pentadecyl group, 3,5-dimethylheptyl group, 2,6-dimethylheptyl group, 2,4-dimethylheptyl group, 2,2,5,5-tetramethylhexyl group A substituted or unsubstituted alkyl group having 20 or less carbon atoms, preferably 15 or less, such as 1-cyclo-pentyl-2,2-dimethylpropyl group and 1-cyclo-hexyl-2,2-dimethylpropyl group;

Methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, t-butoxy group, n-pentoxy group,
A substituted or unsubstituted alkoxy group having 20 or less, preferably 15 or less carbon atoms such as iso-pentoxy group, neo-pentoxy group, n-hexyloxy group, n-dodecyloxy group; methylthio group, ethylthio group, n-propylthio group Group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-
Butylthio group, t-butylthio group, n-pentylthio group, is
20 carbon atoms such as o-pentylthio group, 2-methylbutylthio group, 1-methylbutylthio group, neo-pentylthio group, 1,2-dimethylpropylthio group, 1,1-dimethylpropylthio group
Or less, preferably 15 or less, substituted or unsubstituted alkylthio group; phenoxy group, 2-methylphenoxy group, 4-methylphenoxy group, 4-t-butylphenoxy group, 2-methoxyphenoxy group, 4-iso-propylphenoxy group A substituted or unsubstituted aryloxy group having 20 or less, preferably 15 or less carbon atoms such as a group; carbon such as phenylthio group, 4-methylphenylthio group, 2-methoxyphenylthio group, 4-t-butylphenylthio group 20 or less, preferably 15 or less, substituted or unsubstituted arylthio group;

Vinyl group, propenyl group, 1-butenyl group,
iso-butenyl group, 1-pentenyl group, 2-pentenyl group, 2-
Methyl-1-butenyl group, 3-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2,2-dicyanovinyl group, 2-cyano-2-
2 carbon atoms such as methylcarboxyl vinyl group, 2-cyano-2-methylsulfone vinyl group, 2-phenyl-1-butenyl group
0 or less, preferably 15 or less, substituted or unsubstituted alkenyl group; formyl group, acetyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso-butylcarbonyl group,
sec-Butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, iso-pentylcarbonyl group, neo-
Pentylcarbonyl group, 2-methylbutylcarbonyl group,
Substituted or unsubstituted acyl group having 20 or less, preferably 15 or less carbon atoms such as nitrobenzylcarbonyl group; carbon number such as methoxycarbonyl group, ethoxycarbonyl group, isopropyloxycarbonyl group, 2,4-dimethylbutyloxycarbonyl group 20 or less, preferably 15 or less, substituted or unsubstituted alkoxycarbonyl group; carbamoyl group; acetylamino group, ethylcarbonylamino group, butylcarbonylamino group, etc., having 20 or less carbon atoms, preferably 15 or less, substituted or unsubstituted Acylamino group;

Benzyl group, nitrobenzyl group, cyanobenzyl group, hydroxybenzyl group, methylbenzyl group,
Dimethylbenzyl group, trimethylbenzyl group, dichlorobenzyl group, methoxybenzyl group, ethoxybenzyl group, trifluoromethylbenzyl group, naphthylmethyl group, nitronaphthylmethyl group, cyanonaphthylmethyl group, hydroxynaphthylmethyl group, methylnaphthylmethyl group, A substituted or unsubstituted aralkyl group having 20 or less, preferably 15 or less carbon atoms such as trifluoromethylnaphthylmethyl group; phenyl group, nitrophenyl group, cyanophenyl group, hydroxyphenyl group, methylphenyl group,
Dimethylphenyl group, trimethylphenyl group, ethylphenyl group, diethylphenyl group, triethylphenyl group, n-propylphenyl group, di (n-propyl) phenyl group, tri (n-propyl) phenyl group, iso-propylphenyl group, Di (iso-propyl) phenyl group, tri (iso-propyl) phenyl group, n-butylphenyl group, di (n-butyl) phenyl group, tri (n-butyl) phenyl group, iso-butylphenyl group, di ( iso-butyl) phenyl group, tri (iso-butyl) phenyl group, sec-butylphenyl group, di (sec-butyl) phenyl group, tri (sec-butyl) phenyl group, t-butylphenyl group, di (t- Butyl) phenyl group, tri (t-butyl) phenyl group, dimethyl-t-butylphenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group,
Iodophenyl group, methoxyphenyl group, ethoxyphenyl group, trifluoromethylphenyl group, N, N-dimethylaminophenyl group, naphthyl group, nitronaphthyl group, cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl group, fluoronaphthyl group, Chloronaphthyl group, bromonaphthyl group, iodonaphthyl group, methoxynaphthyl group,
A substituted or unsubstituted aryl group having 20 or less, preferably 15 or less carbon atoms, such as a trifluoromethylnaphthyl group or an N, N-dimethylaminonaphthyl group;

Carbon such as pyrrolyl group, thienyl group, furanyl group, oxazoyl group, isoxazoyl group, oxadiazoyl group, imidazoyl group, benzoxazoyl group, benzothiazoyl group, benzimidazoyl group, benzofuranyl group, indoyl group, isoindoyl group A substituted or unsubstituted heteroaryl group having a number of 20 or less, preferably 15 or less; and the like.

Specific examples of X ₁ include an oxygen atom, a sulfur atom, and a substituted or unsubstituted nitrogen atom represented by the following general formula (d).

—N (R ₁₅ ) — (d) In the substituted or unsubstituted nitrogen atom represented by the general formula (d), specific examples of R ₁₅ include a hydrogen atom; a methyl group,
Ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, 2-methylbutyl group, 1- Methylbutyl group, neo-pentyl group, 1,2-dimethylpropyl group,
1,1-dimethylpropyl group, cyclo-pentyl group, n-hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,2-dimethylbutyl group, 1,
1-dimethylbutyl group, 3-ethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, 1,2,2-trimethylbutyl group,
1,1,2-trimethylbutyl group, 1-ethyl-2-methylpropyl group, cyclo-hexyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-
Methylhexyl group, 2,4-dimethylpentyl group, n-octyl group, 2-ethylhexyl group, 2,5-dimethylhexyl group,
2,5,5-Trimethylpentyl group, 2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group, 3,5,5-trimethylhexyl group, n-nonyl group, n-decyl group, 4- Ethyloctyl group, 4-ethyl-4,5-dimethylhexyl group, n-undecyl group, n-dodecyl group, 1,3,5,7-tetraethyloctyl group,
4-butyloctyl group, 6,6-diethyloctyl group, n-tridecyl group, 6-methyl-4-butyloctyl group, n-tetradecyl group, n-pentadecyl group, 3,5-dimethylheptyl group,
2,6-dimethylheptyl group, 2,4-dimethylheptyl group, 2,
2,5,5-Tetramethylhexyl group, 1-cyclo-pentyl-2,2
-Substituted or unsubstituted alkyl groups having 20 or less, preferably 15 or less carbon atoms such as dimethylpropyl group and 1-cyclo-hexyl-2,2-dimethylpropyl group;

Vinyl group, propenyl group, 1-butenyl group,
iso-butenyl group, 1-pentenyl group, 2-pentenyl group, 2-
Methyl-1-butenyl group, 3-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2,2-dicyanovinyl group, 2-cyano-2-
2 carbon atoms such as methylcarboxyl vinyl group, 2-cyano-2-methylsulfone vinyl group, 2-phenyl-1-butenyl group
0 or less, preferably 15 or less, substituted or unsubstituted alkenyl group; formyl group, acetyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso-butylcarbonyl group,
sec-Butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, iso-pentylcarbonyl group, neo-
Pentylcarbonyl group, 2-methylbutylcarbonyl group,
A substituted or unsubstituted acyl group having 20 or less, preferably 15 or less carbon atoms such as a nitrobenzylcarbonyl group;

A substituted or unsubstituted alkoxycarbonyl group having 20 or less, preferably 15 or less carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, isopropyloxycarbonyl group, 2,4-dimethylbutyloxycarbonyl group; benzyl group, nitro Benzyl group, cyanobenzyl group, hydroxybenzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, dichlorobenzyl group, methoxybenzyl group, ethoxybenzyl group, trifluoromethylbenzyl group, naphthylmethyl group, nitronaphthylmethyl group, A substituted or unsubstituted aralkyl group having 20 or less, preferably 15 or less carbon atoms such as a cyanonaphthylmethyl group, a hydroxynaphthylmethyl group, a methylnaphthylmethyl group, a trifluoromethylnaphthylmethyl group;
Phenyl, nitrophenyl, cyanophenyl, hydroxyphenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, n-propylphenyl, di (n-propyl) ) Phenyl group, tri (n-propyl) phenyl group, iso-propylphenyl group, di (iso-propyl) phenyl group, tri (iso-propyl) phenyl group, n
-Butylphenyl group, di (n-butyl) phenyl group, tri (n-
Butyl) phenyl group, iso-butylphenyl group, di (iso-
Butyl) phenyl group, tri (iso-butyl) phenyl group, se
c-Butylphenyl group, di (sec-butyl) phenyl group, tri
(sec-Butyl) phenyl group, t-butylphenyl group, di (t-
Butyl) phenyl group, tri (t-butyl) phenyl group, dimethyl-t-butylphenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, iodophenyl group,
Methoxyphenyl group, ethoxyphenyl group, trifluoromethylphenyl group, N, N-dimethylaminophenyl group,
Naphthyl group, nitronaphthyl group, cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl group, fluoronaphthyl group, chloronaphthyl group, bromonaphthyl group, iodonaphthyl group, methoxynaphthyl group, trifluoromethylnaphthyl group, N, N-dimethyl A substituted or unsubstituted aryl group having 20 or less, preferably 15 or less carbon atoms such as aminonaphthyl group;

Carbon such as pyrrolyl group, thienyl group, furanyl group, oxazoyl group, isoxazoyl group, oxadiazoyl group, imidazoyl group, benzoxazoyl group, benzothiazoyl group, benzimidazoyl group, benzofuranyl group, indoyl group, isoindoyl group A substituted or unsubstituted heteroaryl group having a number of 20 or less, preferably 15 or less; and the like.

General formula (b1), (b2), or (b
3), which is a condensed 5-membered ring containing a hetero atom
In the -pyrrolyl group, specific examples of R ₇ and R _{12 to} R ₁₄ include R _{7 to} R in the general formulas (a1) and (a2).
The same substituents as ₁₁ can be mentioned.

Specific examples of Y ₁ include an oxygen atom, a sulfur atom, and a substituted or unsubstituted nitrogen atom represented by the general formula (d).

In the 2-pyrrolyl group represented by the general formula (c1) or (c2), in which a 5-membered ring containing a hetero atom is condensed, specific examples of R ₇ include the general formula (a).
The same substituents as R ₇ in 1) and (a2) can be mentioned.

Specific examples of Z ₁ include an oxygen atom, a sulfur atom, and a substituted or unsubstituted nitrogen atom represented by the general formula (d).

In the dipyrromethene metal chelate compound of the dipyrromethene compound represented by the general formula (1) and a metal ion, a specific example of the metal ion is not particularly limited as long as it is a transition element capable of forming a chelate with the dipyrromethene compound. It is not done, but groups 8, 9 and 10 (group VIII),
Group 11 (Ib group), Group 12 (IIb group), Group 3 (IIIa group),
Examples thereof include metal ions of Group 4 (IVa group), Group 5 (Va group), Group 6 (VIa group) and Group 7 (VIIa group), preferably nickel, cobalt, iron, ruthenium, rhodium, palladium and copper. , Osmium, iridium, platinum, zinc and the like, and copper and cobalt are particularly preferable from the viewpoint of light resistance.

The dipyrromethene metal chelate compound of the present invention represented by the general formula (1) and the metal ion is not limited, and examples thereof include Aust. J. Che.
m., 1965, 11, 1835-45, Heteroatom Chemistry, Vol.
It is produced according to the method described in 1, 5, 389 (1990), USP-4,774,339, USP-5,433,896 and the like. Typically, the following 2
It can be produced by a stepwise reaction.

First, in the first step, the compound represented by the general formula (2) and the compound represented by the general formula (3), or the compound represented by the general formula (4) and the compound represented by the general formula (5) are used. Is reacted in the presence of an acid catalyst such as hydrobromic acid or hydrochloric acid in a suitable solvent to obtain a dipyrromethene compound represented by the general formula (1). Next, in the second stage, the general formula (1)
Dipyrromethene compound represented by and nickel, cobalt,
A dipyrromethene metal chelate of a dipyrromethene compound represented by the general formula (1) with a metal ion by reacting with an acetate or halide of a metal such as iron, ruthenium, rhodium, palladium, copper, osmium, iridium, platinum and zinc. Obtain the compound.

[0055]

[Chemical 9] [In the formulas (2) to (5), R _{1 to} R ₆ and A have the same meanings as described above. ]

Table 1 shows specific examples of the dipyrromethene metal chelate compound of the present invention represented by the general formula (1) and the metal ion. In the table, D-1 to D-
160 represents the serial number of the dipyrromethene metal chelate compound of the dipyrromethene compound represented by the general formula (1) and a metal ion, and 1-1 to 1-160 represent the general formula (1).
Represents the serial number of the dipyrromethene compound.

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

[Table 3]

[0060]

[Table 4]

[0061]

[Table 5]

[0062]

[Table 6]

[0063]

[Table 7]

[0064]

[Table 8]

[0065]

[Table 9]

[0066]

[Table 10]

[0067]

[Table 11]

[0068]

[Table 12]

[0069]

[Table 13]

[0070]

[Table 14]

[0071]

[Table 15]

[0072]

[Table 16]

[0073]

[Table 17]

[0074]

[Table 18]

[0075]

[Table 19]

[0076]

[Table 20]

A specific configuration of the present invention will be described below. The optical recording medium refers to both a read-only optical read-only medium in which information is recorded in advance and an optical recording medium in which information can be recorded and reproduced. However, here, as a suitable example, an optical recording medium capable of recording and reproducing the latter information, particularly an optical recording medium having a recording layer and a reflective layer on a substrate will be described. The optical recording medium of the present invention has a bonding structure as shown in FIG. That is, the recording layer 2 is formed on the substrate 1, the reflective layer 3 is provided in close contact with the recording layer 2, and the substrate 5 is further bonded thereto via the adhesive layer 4. However, another layer may be provided below or above the recording layer 2, and another layer may be provided above the reflective layer 3.

Basically, the material of the substrate should be transparent at the wavelengths of the recording light and the reproducing light. For example, a polymer material such as a polycarbonate resin, a vinyl chloride resin, an acrylic resin such as polymethylmethacrylate, a polystyrene resin, an epoxy resin, or an inorganic material such as glass is used.
These substrate materials are formed into a disc-shaped substrate by an injection molding method or the like. Guide grooves or pits may be formed on the surface of the substrate as needed. Such guide grooves and pits
Although it is desirable to apply it at the time of molding the substrate, it is also possible to apply it by using an ultraviolet curable resin layer on the substrate. When used as a normal DVD, it has a disk shape with a thickness of about 1.2 mm and a diameter of about 80 to 120 mm, and has a hole with a diameter of about 15 mm in the center.

In the present invention, a recording layer is provided on the substrate. The recording layer of the present invention has a λmax of 450 nm to 630.
It contains a dipyrromethene metal chelate compound of a metal ion with a dipyrromethene compound represented by the general formula (1) present in the vicinity of nm. Above all, an appropriate optical constant for a recording and reproducing laser wavelength selected from 520 nm to 690 nm (the optical constant is expressed by a complex refractive index (n + ki). In the formula, n and k are a real part n and an imaginary part. It is necessary to have a coefficient corresponding to k, where n is a refractive index and k is an extinction coefficient.

Generally, the organic dye has a refractive index with respect to the wavelength λ.
It is characterized by a large change in n and the extinction coefficient k. n is 1.8
When the value is smaller, the reflectance and the signal modulation required for accurate signal reading cannot be obtained, and even if k exceeds 0.40, the reflectance decreases and a good reproduced signal cannot be obtained. The signal is likely to change due to the reproduction light, which is not suitable for practical use.
In consideration of this feature, by selecting an organic dye having a preferable optical constant at a target laser wavelength and forming a recording layer, a medium having high reflectance and high sensitivity can be obtained. .

The dipyrromethene metal chelate compound of the general formula (1) used in the present invention and the metal ion of the dipyrromethene compound has a higher extinction coefficient than ordinary organic dyes, and the absorption wavelength depends on the selection of the substituent. Since the range can be arbitrarily selected, the optical constants required for the recording layer at the wavelength of the laser light (n is 1.8 or more and k is 0.04
To 0.40, preferably n is 2.0 or more, and k is 0.04 to 0.20), which is a very useful compound.

In the recording layer of the present invention, two or more dipyrromethene metal chelate compounds of the general formula (1) and metal ions are mixed in order to improve recording characteristics and the like. Is also good. The mixing ratio of the dipyrromethene metal chelate compound is not particularly limited, but for the above reason, the optical constant n is 1.8 or more, preferably 2.0 or more, and k is 0.04 to 0.4.
It is preferable to mix so as to be 0, preferably 0.04 to 0.20.

Further, it may be mixed with a dye other than the above which has an absorption maximum at a wavelength of 450 nm to 630 nm and has a large refractive index at 520 nm to 690 nm. Specifically, cyanine dyes, squarylium dyes, naphthoquinone dyes, anthraquinone dyes, porphyrin dyes, azaporphyrin dyes, tetrapyrporphyrazine dyes, indophenol dyes, pyrylium dyes, thiopyrylium dyes, Azurenium dyes, triphenylmethane dyes, xanthene dyes, indasulen dyes, indigo dyes, thioindigo dyes, merocyanine dyes, thiazine dyes, acridine dyes, oxazine dyes, etc. It may be mixed. The mixing ratio of these dyes is about 0.1 to 30%.

Further, when the dipyrromethene metal chelate compound of the dipyrromethene compound represented by the general formula (1) and a metal ion has a small k for a recording and reproducing laser wavelength selected from 520 nm to 690 nm,
Wavelength 600nm-900 for improving recording characteristics
You may mix with the light absorption compound which has an absorption maximum in nm. Specifically, cyanine dyes, squarylium dyes, naphthoquinone dyes, anthraquinone dyes, porphyrin dyes, azaporphyrin dyes, tetrapyrporphyrazine dyes, indophenol dyes, pyrylium dyes, thiopyrylium dyes, Azurenium dye, triphenylmethane dye, xanthene dye,
Induslen dye, indigo dye, thioindigo dye, merocyanine dye, thiazine dye, acridine dye, oxazine dye, phthalocyanine dye,
There are naphthalocyanine dyes and the like, and a mixture of a plurality of dyes may be used. The mixing ratio of these dyes is 0.1 to 3
It is about 0%.

The optical recording medium of the present invention is manufactured from 520 nm to 690 nm.
Reproduction with a laser beam selected from nm is basically possible if the reflectance is 20%.
% Or more is preferable.

When forming the recording layer, if necessary, a quencher, a dye decomposition accelerator, an ultraviolet absorber, an adhesive, an endothermic decomposition compound, or the like is mixed with the above dye, or It is also possible to introduce a compound having an effect as a substituent of the dye.

Specific examples of the quencher include acetylacetonate type, bisdithiol type such as bisdithio-α-diketone type and bisphenyldithiol type, thiocatechol type, salicylaldehyde oxime type and thiobisphenolate type metal. Complexes are preferred. Also, amines are suitable.

Examples of the thermal decomposition accelerator include metal compounds such as metal anti-knocking agents, metallocene compounds and acetylacetonate metal complexes.

Further, if necessary, a binder, a leveling agent, an antifoaming agent and the like can be used in combination. Preferred binders include polyvinyl alcohol, polyvinylpyrrolidone, nitrocellulose, cellulose acetate,
Examples thereof include ketone resin, acrylic resin, polystyrene resin, urethane resin, polyvinyl butyral, polycarbonate, polyolefin and the like.

When the recording layer is formed on the substrate, in order to improve the solvent resistance, reflectance, recording sensitivity, etc. of the substrate,
A layer made of an inorganic material or a polymer may be provided on the substrate.

Here, the content of the dipyrromethene metal chelate compound of the dipyrromethene compound represented by the general formula (1) and the metal ion in the recording layer is 30% or more, preferably 60% or more. It is also preferable that it is substantially 100%.

Examples of the method for providing the recording layer include a coating method such as a spin coating method, a spraying method, a casting method and a dipping method, a sputtering method, a chemical vapor deposition method and a vacuum vapor deposition method. The spin coating method is simple. Is preferred.

When a coating method such as spin coating is used, 1 to 4 dipyrromethene metal chelate compounds of the dipyrromethene compound represented by the general formula (1) and metal ions are used.
A coating solution which is dissolved or dispersed in a solvent so as to be 0% by weight, preferably 3 to 30% by weight is used.
It is preferable to select a solvent that does not damage the substrate. For example, alcohol solvents such as methanol, ethanol, isopropyl alcohol, octafluoropentanol, allyl alcohol, methyl cellosolve, ethyl cellosolve, tetrafluoropropanol, hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane. Aliphatic or alicyclic hydrocarbon solvents such as, toluene, xylene, aromatic hydrocarbon solvents such as benzene, halogenated hydrocarbon solvents such as carbon tetrachloride, chloroform, tetrachloroethane, dibromoethane, diethyl ether, Ether-based solvents such as dibutyl ether, diisopropyl ether and dioxane, ketone-based solvents such as acetone and 3-hydroxy-3-methyl-2-butanone, ethyl acetate and lactic acid Ester solvents such as Le, and water. These may be used alone or in combination of two or more.

If necessary, the dye in the recording layer may be dispersed in a polymer thin film or the like and used.

When a solvent that does not damage the substrate cannot be selected, sputtering, chemical vapor deposition, vacuum vapor deposition, etc. are effective.

The thickness of the dye layer is not particularly limited, but is preferably 50 nm to 300 nm. When the film thickness of the dye layer is less than 50 nm, recording cannot be performed because of large thermal diffusion, distortion occurs in the recording signal, and the signal amplitude becomes small. Further, when the film thickness is thicker than 300 nm, the reflectance is lowered and the reproduction signal characteristic is deteriorated.

Next, on the recording layer, preferably 50 nm-
A reflective layer having a thickness of 300 nm is formed. The material of the reflective layer has a sufficiently high reflectance at the wavelength of the reproduction light, for example, Au, Al, Ag, Cu, Ti, Cr, Ni, P.
The metals of t, Ta, Cr and Pd can be used alone or as an alloy. Among these, Au, Al,
Ag has a high reflectance and is suitable as a material for the reflective layer. Other than the above, the following may be included. For example, M
g, Se, Hf, V, Nb, Ru, W, Mn, Re, F
e, Co, Rh, Ir, Zn, Cd, Ga, In, S
Mention may be made of metals and metalloids such as i, Ge, Te, Pb, Po, Sn, Bi. Further, a material containing Au as a main component is preferable because a reflective layer having a high reflectance can be easily obtained. Here, the main component means that the content rate is 50% or more. It is also possible to stack a low refractive index thin film and a high refractive index thin film alternately with a material other than metal to form a multilayer film and use it as a reflective layer.

As a method of forming the reflective layer, for example,
Examples of the method include a sputtering method, an ion plating method, a chemical vapor deposition method, a vacuum vapor deposition method and the like. Further, a known inorganic or organic intermediate layer or adhesive layer may be provided on the substrate or below the reflective layer in order to improve the reflectance, the recording characteristics, and the adhesion.

Further, the material of the protective layer on the reflective layer is not particularly limited as long as it protects the reflective layer from external force. As the organic substance, a thermoplastic resin, a thermosetting resin,
Examples thereof include electron beam curable resins and ultraviolet curable resins. Further, as the inorganic substance, SiO ₂ , Si ₃ N
₄ , MgF ₂ , SnO _{2 and the} like. A thermoplastic resin, a thermosetting resin, etc. can be formed by dissolving in a suitable solvent, applying a coating solution, and drying.
The UV-curable resin can be formed as it is or by dissolving it in a suitable solvent to prepare a coating solution, applying the coating solution, and then irradiating it with ultraviolet rays to cure it. As the ultraviolet curable resin, for example, an acrylate resin such as urethane acrylate, epoxy acrylate, polyester acrylate can be used. These materials may be used alone or as a mixture, and may be used not only as one layer but also as a multilayer film.

As a method of forming the protective layer, a coating method such as a spin coating method and a casting method, a sputtering method, a chemical vapor deposition method and the like are used similarly to the recording layer, and the spin coating method is preferable among them.

The thickness of the protective layer is generally 0.1 μm to 1
Although it is in the range of 00 μm, in the present invention, 3 μm
It is 30 μm, and more preferably 5 μm to 20 μm.

Printing such as a label can be further performed on the protective layer. Alternatively, a protective sheet or substrate may be attached to the reflective layer surface, or two optical recording media may be attached such that the reflective layer surfaces face each other inside. In addition, an ultraviolet curable resin, an inorganic thin film, or the like may be formed on the mirror surface side of the substrate in order to protect the surface or prevent adhesion of dust or the like.

Wavelength referred to in the present invention is 520 nm to 690 nm
The laser is not particularly limited, but for example, a dye laser capable of wavelength selection in a wide range of visible light region or a wavelength 633.
helium neon laser of wavelength nm, recently developed high power semiconductor lasers of wavelengths 680, 650 and 635 nm, and harmonic conversion YAG laser of wavelength 532 nm. In the present invention, high-density recording and reproduction can be performed at one wavelength or a plurality of wavelengths selected from these.

[0104]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto.

Example 1 Synthesis of Dipyrromethene Metal Chelate Compound (D-1) In 150 ml of ethanol, 3.00 g of a compound represented by the following structural formula (2-a) and a compound represented by the following structural formula (3-a) Dissolve 1.31 g, 47% hydrobromic acid 1.9
After dropping 6 g, the mixture was stirred at room temperature for 2 hours. After concentration under reduced pressure, the residue was extracted with 200 ml of chloroform, washed with water, separated, and the solvent was distilled off to obtain 3.70 g of a compound represented by the following structural formula (1-1).

[0106]

[Chemical 10]

Next, the formula (1-
3.00 g of the compound represented by 1) is dissolved and copper acetate
86 g was added, and the mixture was stirred at reflux temperature for 2 hours. After concentration under reduced pressure, the precipitate was collected by filtration and washed with methanol and water to obtain 2.98 g of a compound represented by the following structural formula (D-1).

[0108]

[Chemical 11] From the following analysis results, it was confirmed to be the target product.

[0109]

[Table 21]

The compound thus obtained has a maximum absorption at 580 nm in a toluene solution and a gram extinction coefficient of 1.98 × 10 ⁵ ml / g. It was cm.

Example 2 Synthesis of dipyrromethene metal chelate compound (D-8) In 200 ml of ethanol, 5.00 g of a compound represented by the following structural formula (4-a) and a compound represented by the following structural formula (5-a) Dissolve 4.76 g, 47% hydrobromic acid 3.5
After dropping 2 g, the mixture was stirred at room temperature for 3 hours. After concentration under reduced pressure, the residue was extracted with 200 ml of chloroform, washed with water, separated, and the solvent was distilled off to obtain 8.27 g of a compound represented by the following structural formula (1-8).

[0112]

[Chemical 12]

Next, the formula (1-
7.00 g of the compound represented by 8) was dissolved and copper acetate 1.
63 g was added, and the mixture was stirred at reflux temperature for 4 hours. After concentration under reduced pressure, the precipitate was collected by filtration and washed with methanol and water to obtain 6.77 g of a compound represented by the following structural formula (D-8).

[0114]

[Chemical 13] From the following analysis results, it was confirmed to be the target product.

[0115]

[Table 22]

The compound thus obtained has a maximum absorption at 625 nm in a toluene solution and a gram extinction coefficient of 2.17 × 10 ⁵ ml / g. It was cm.

Example 3 Synthesis of dipyrromethene metal chelate compound (D-10) In 250 ml of ethanol, 5.00 g of a compound represented by the following structural formula (4-b) and a compound represented by the following structural formula (5-b) Dissolve 6.12g, 47% hydrobromic acid 3.3
After dropping 3 g, the mixture was stirred at reflux temperature for 3 hours. After concentration under reduced pressure, extraction with 300 ml of chloroform, washing with water, separation of liquids,
The solvent was distilled off to obtain 9.68 g of a compound represented by the following structural formula (1-10).

[0118]

[Chemical 14]

Next, the formula (1-1) was added to 400 ml of ethanol.
7.00 g of the compound represented by the formula (0) is dissolved and copper acetate 1.
33 g was added, and the mixture was stirred at reflux temperature for 2 hours. After concentration under reduced pressure, the precipitate was collected by filtration and washed with methanol and water to obtain 6.98 g of a compound represented by the following structural formula (D-10).

[0120]

[Chemical 15] From the following analysis results, it was confirmed to be the target product.

[0121]

[Table 23]

The compound thus obtained exhibits a maximum absorption at 605 nm in a toluene solution and has a Gram extinction coefficient of 2.03 × 10 ⁵ ml / g. It was cm.

Example 4 Synthesis of Dipyrromethene Metal Chelate Compound (D-27) In 250 ml of ethanol, 4.00 g of the compound represented by the structural formula (4-a) and the compound represented by the following structural formula (5-c) 2.65 g was dissolved and 47% hydrobromic acid 2.7
After dropping 8 g, the mixture was stirred at room temperature for 3 hours. After concentration under reduced pressure, the residue was extracted with 200 ml of chloroform, washed with water, separated, and the solvent was distilled off to obtain 5.58 g of a compound represented by the following structural formula (1-27).

[0124]

[Chemical 16]

Next, the formula (1-2
5.00 g of the compound represented by 7) was dissolved, and copper acetate 1.
49 g was added, and the mixture was stirred at reflux temperature for 2 hours. After concentration under reduced pressure, the precipitate was collected by filtration and washed with methanol and water to obtain 4.68 g of a compound represented by the following structural formula (D-27).

[0126]

[Chemical 17] From the following analysis results, it was confirmed to be the target product.

[0127]

[Table 24]

The compound thus obtained exhibits a maximum absorption at 589 nm in a toluene solution and a gram extinction coefficient of 1.87 × 10 ⁵ ml / g. It was cm.

Example 5 Synthesis of dipyrromethene metal chelate compound (D-39) In 250 ml of ethanol, 4.00 g of the compound represented by the following structural formula (4-c) and the compound represented by the following structural formula (5-d) Dissolve 1.84 g, 47% hydrobromic acid 2.1
After dropping 8 g, the mixture was stirred at room temperature for 4 hours. After concentration under reduced pressure, extraction with 400 ml of chloroform, washing with water, liquid separation, and evaporation of the solvent gave 5.30 g of the compound represented by the structural formula (1-39) below.

[0130]

[Chemical 18]

Next, the formula (1-3
9.00 g of the compound represented by 9) was dissolved, and copper acetate was added to 3.
33 g was added, and the mixture was stirred at reflux temperature for 2 hours. After concentration under reduced pressure, the precipitate was collected by filtration and washed with methanol and water to obtain 4.70 g of a compound represented by the following structural formula (D-39).

[0132]

[Chemical 19] From the following analysis results, it was confirmed to be the target product.

[0133]

[Table 25]

The compound thus obtained exhibits a maximum absorption at 590 nm in a toluene solution and a gram extinction coefficient of 1.88 × 10 ⁵ ml / g. It was cm.

Example 6 Dipyrromethene metal chelate compound (D-1) (0.2 g) was added to dimethylcyclohexane (10).
It was dissolved in ml to prepare a dye solution. The board is made of polycarbonate resin and has continuous guide grooves (track pitch:
0.74 μm) diameter 120 mm, thickness 0.6 m
A m-shaped disc was used.

The dye solution is spun on this substrate at a rotation speed of 1500r.
pm was spin-coated and dried at 70 ° C. for 3 hours to form a recording layer. 640 nm, 650 nm, 6 of this recording layer
The optical constants at each wavelength of 60 nm were as follows.

[0137]

[Table 26]

Au was sputtered on the recording layer using a sputtering apparatus (CDI-900) manufactured by Balzers Co., Ltd. to form a reflective layer having a thickness of 100 nm. Argon gas was used as the sputtering gas. The sputtering conditions are as follows: sputter power 2.5 kW, sputter gas pressure 1.33 Pa (1.0 × 1)
0 ^-2 Torr).

Furthermore, an ultraviolet curable resin SD-
After spin-coating 1700 (manufactured by Dainippon Ink and Chemicals, Inc.), it was irradiated with ultraviolet rays to form a protective layer having a thickness of 6 μm.

Further, an ultraviolet curable adhesive SD is formed on the protective layer.
-301 (manufactured by Dainippon Ink and Chemicals, Inc.) was spin-coated, and a polycarbonate resin was applied on it with a diameter of 120 m.
An optical recording medium was produced by placing a disc-shaped substrate having a thickness of m and a thickness of 0.6 mm and then irradiating it with ultraviolet rays.

An optical disk evaluation device (DDU-manufactured by Pulstec Industrial Co., Ltd.) equipped with a semiconductor laser head having a wavelength of 658 nm and a lens numerical aperture of 0.6 on the obtained optical recording medium.
1000) and a pulse generator manufactured by Pulstec Industrial Co., Ltd., and the shortest pit length is 0.1 at a linear velocity of 3.5 m / s.
It was recorded so as to be 40 μm. Recording sensitivity is 8.9mW
Met. After recording, a signal was reproduced using an evaluation device equipped with a 650 nm red semiconductor laser head (the numerical aperture of the lens was 0.6), and the reflectance, jitter, and degree of modulation were measured. The favorable values were 5%, jitter 7.5%, and modulation degree 0.60. Further, no change was observed after the light resistance test with a carbon arc for 100 hours and the humidity heat resistance test at 80 ° C., 85%, 100 hours. Further, even if the reproduction light of 0.7 mW was reproduced 1 million times, the change in jitter was 1% or less.

Furthermore, a linear velocity of 10.5 m / s (recording speed of 3
When the recording was performed so that the shortest pit length was 0.40 μm, the recording sensitivity was 12.5 mW. After recording,
A signal is reproduced using an evaluation device equipped with a 650 nm red semiconductor laser head (lens numerical aperture is 0.6).
As a result of measuring reflectance, jitter and modulation, 650
In the reproduction by nm, the reflectance was 47.5%, the jitter was 7.9%, and the degree of modulation was 0.68.

[Examples 7 to 21] An optical recording medium was prepared in the same manner as in Example 6 except that the dipyrromethene metal chelate compound shown in Table 1 was appropriately used.
Double speed recording was performed. The sensitivity, reflectance, jitter, and degree of modulation all showed good values. Also, the light resistance test with a carbon arc for 100 hours, and 80 ° C, 85%, 10
No change was observed even after the 0-hour moist heat resistance test. Also,
Even if the reproduction light of 0.7 mW was reproduced 1 million times, the change in jitter was 1% or less.

[Comparative Example 1] An optical recording medium was prepared in the same manner as in Example 6, except that 0.2 g of the dipyrromethene metal chelate compound represented by the following structural formula (A-1) was dissolved in 10 ml of dimethylcyclohexane and spin-coated. Was produced.

[0145]

[Chemical 20]

658n was applied to the produced medium in the same manner as in Example 6.
m Optical disk evaluation device equipped with semiconductor laser head (Pulstec Industrial Co., Ltd., trade name "DDU-1000")
Recording was performed at a linear velocity of 3.5 m / s and a laser power of 9.5 mW using a pulse generator manufactured by Pulstec Industrial Co., Ltd. After recording, a signal was reproduced using an evaluation device equipped with a 650 nm red semiconductor laser head, and the reflectance, jitter, and modulation degree were measured. As a result, at 650 nm reproduction, the reflectance was 62%, the jitter was 20% or more, and the modulation degree was 0. The jitter characteristic was 61, which was inferior.

The linear velocity of 10.5 m / s (recording speed of 3
When the recording was examined so that the shortest pit length would be 0.40 μm, the recording sensitivity was inferior (> 15 mW).
Good recording could not be performed.

Comparative Example 2 In Example 6, the pentamethine cyanine dye “NK-2929” (1,3,3,1 ′, 3 ′, 3 ′)
-Hexamethyl-2 ', 2'-(4,5,4 ', 5'-dibenzo) indodicarbocyanine perchlorate, manufactured by Japan Photosensitive Dye Research Institute)
An optical recording medium was prepared in the same manner except that 1 g was dissolved in 10 ml of tetrafluoropropanol and spin-coated. As in Example 6, a pulsed optical disk evaluation device (DDU-1000) manufactured by Pulstec Industrial Co., which has a 658 nm semiconductor laser head mounted on the manufactured medium, and a pulse generator manufactured by Pulstec Industrial Co., Ltd. were used to obtain a linear velocity of 3.5 m /
s, laser power was recorded at 10.0 mW. After recording,
A signal was reproduced using an evaluation device equipped with a 650 nm red semiconductor laser head, and the reflectance, jitter, and modulation were measured, and as a result, the reflectance was 10%, the jitter was 20% or more, and the modulation was 0.14 at 650 nm reproduction. Was there. Also, after the light resistance test with a carbon arc for 100 hours, the signal was deteriorated and could not be reproduced.

The linear velocity of 10.5 m / s (recording speed of 3
When the recording was examined so that the shortest pit length would be 0.40 μm, the recording sensitivity was inferior (> 15 mW).
Good recording could not be performed.

In Examples 6 to 21 and Comparative Examples 1 and 2 described above, Table 2 shows the sensitivity, reflectance, jitter and degree of modulation when each optical recording medium was recorded and reproduced at 1 × speed and 3 × speed. Shown together.

[0151]

[Table 27]

[0152]

EFFECT OF THE INVENTION By using the dipyrromethene metal chelate compound of the present invention as a recording layer, it is possible to record and reproduce with a laser having a wavelength of 520 to 690 nm, which is attracting a great deal of attention as a high density optical recording medium. It is possible to provide a write-once type optical recording medium suitable for high density and high speed recording.

[Brief description of drawings]

FIG. 1 is a sectional structural view showing a conventional optical recording medium and a layer structure of the present invention.

[Explanation of symbols]

1 substrate 2 recording layers 3 reflective layer 4 Adhesive layer 5 substrates

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G11B 7/24 522 B41M 5/26 Y (72) Inventor Shinobu Inoue 580-32 Nagaura, Sodegaura, Chiba Prefecture Mitsui Chemicals In-company (72) Inventor Misawa Denmi 580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals In-company F-term (reference) 2H111 EA03 EA12 EA22 EA25 FA12 FB42 FB60 4C050 AA01 BB04 CC16 EE01 FF02 FF05 GG02 HH04 4C071 AA01 BB01 CC01 CC21 DD04 EE13 FF03 GG05 JJ05 LL05 4H056 CA01 CC02 CC08 CE03 DD03 FA06 5D029 JA04 JC05

Claims (7)

[Claims] 1. A dipyrromethene metal chelate compound of a dipyrromethene compound represented by the following general formula (1) and a metal ion. [Chemical 1] [In the formula, R _{1 to} R ₅ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group,
Carboxyl group, sulfonic acid group, substituted or unsubstituted alkyl group having 20 or less carbon atoms, alkoxy group, alkylthio group, aryloxy group, arylthio group, alkenyl group, acyl group, alkoxycarbonyl group, carbamoyl group, acylamino group, aralkyl group, an aryl group or a heteroaryl group,, R ₆ is a halogen atom, of 20 or less substituted or unsubstituted aryl group having a carbon heteroaryl group, an alkoxy group, an alkylthio group, an aryloxy group or an arylthio group, Represents A, and represents a 2-pyrrolyl group in which a 5-membered ring containing a hetero atom is condensed. ] 2. A is the following general formula (a1) or (a
The dipyrromethene metal chelate compound according to claim 1, which is a 2-pyrrolyl group condensed with a 5-membered ring containing a hetero atom, which is selected from any of 2). [Chemical 2] [In the formula, R _{7 to} R ₁₁ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a substituted or unsubstituted group having 20 or less carbon atoms. Alkyl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, alkenyl group, acyl group, alkoxycarbonyl group, carbamoyl group, acylamino group, aralkyl group, aryl group,
Alternatively, it represents a heteroaryl group, and X ₁ represents an oxygen atom, a sulfur atom, or a substituted or unsubstituted nitrogen atom represented by the following general formula (d). —N (R ₁₅ ) — (d) (In the formula, R ₁₅ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 20 or less carbon atoms, an alkenyl group, an acyl group, an alkoxycarbonyl group, an aralkyl group, an aryl group, Or represents a heteroaryl group.)] 3. A 2-pyrrolyl group in which a 5-membered ring containing a hetero atom, which is selected from any of the following general formulas (b1), (b2) or (b3), is condensed: The described dipyrromethene metal chelate compound. [Chemical 3] [In the formula, R ₇ , R _{12 to} R ₁₄ are each independently a hydrogen atom,
Halogen atom, nitro group, cyano group, hydroxy group, amino group, carboxyl group, sulfonic acid group, substituted or unsubstituted alkyl group having 20 or less carbon atoms, alkoxy group, alkylthio group, aryloxy group, arylthio group, alkenyl group , An acyl group, an alkoxycarbonyl group, a carbamoyl group, an acylamino group, an aralkyl group, an aryl group, or a heteroaryl group, Y ₁ is an oxygen atom, a sulfur atom, or a substituent represented by the following general formula (d) or Represents an unsubstituted nitrogen atom. —N (R ₁₅ ) — (d) (In the formula, R ₁₅ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 20 or less carbon atoms, an alkenyl group, an acyl group, an alkoxycarbonyl group, an aralkyl group, an aryl group, Or represents a heteroaryl group.)] 4. A is the following general formula (c1) or (c
The dipyrromethene metal chelate compound according to claim 1, which is a 2-pyrrolyl group condensed with a 5-membered ring containing a hetero atom, which is selected from any of 2). [Chemical 4] [In the formula, R ₇ represents a hydrogen atom, a halogen atom, a nitro group,
Cyano group, hydroxy group, amino group, carboxyl group,
Sulfonic acid group, substituted or unsubstituted alkyl group having 20 or less carbon atoms, alkoxy group, alkylthio group, aryloxy group, arylthio group, alkenyl group, acyl group, alkoxycarbonyl group, carbamoyl group, acylamino group, aralkyl group, aryl Represents a group or a heteroaryl group, and Z ₁ represents an oxygen atom, a sulfur atom, or a substituted or unsubstituted nitrogen atom represented by the following general formula (d). —N (R ₁₅ ) — (d) (In the formula, R ₁₅ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 20 or less carbon atoms, an alkenyl group, an acyl group, an alkoxycarbonyl group, an aralkyl group, an aryl group, Or represents a heteroaryl group.)] 5. An optical recording medium having at least a recording layer and a reflective layer on a substrate, wherein the recording layer comprises
5. An optical recording medium containing at least one dipyrromethene metal chelate compound according to any one of 4 above. 6. The optical recording medium according to claim 5, wherein the recording layer has a refractive index of 1.8 or more and an extinction coefficient of 0.04 to 0.40 at a laser wavelength. 7. The optical recording medium according to claim 5, which is capable of recording and reproducing with respect to a laser beam selected from a wavelength range of 520 to 690 nm.