JP2002155076A - Diprromethene metal chelate compound and photorecording medium using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rewritable photorecording medium capable of carrying out good high-density recording and reproduction by using a laser having 520-690 nm wavelength and a diprromethene metal chelate compound used for the recording medium. SOLUTION: This photorecording medium comprises a diprromethene metal chelate compound represented by the following general formula (1) in a recording layer.

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, which can record and reproduce data at a higher density than 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 a DVD is a read-only medium, an optical recording medium capable of recording and reproducing data corresponding to the capacity is desired. Among them, the write-once type is called DVD-R.

[0003] In order to perform high-density recording in DVDs, the emission wavelength of laser light is 630 nm to 680 nm, which is shorter than that in CDs. Dyes of 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, JP-A-4-74690, JP-A-5-38878,
JP-A-6-40161, JP-A-6-40162, JP-A-6-199045, JP-A-6-33
6086, JP-A-7-76169, JP-A-7-125441, JP-A-7-262604, JP-A-9-156218, JP-A-9-193
544, JP-A-9-193545, JP-A-9-193747, JP-A-9-194748, JP-A-9-202052, JP-A-9-267
562, JP-A-9-274732 and the like, there is a problem of durability, especially a problem specific to a short wavelength application, for example, a place where a small pit should be opened with a narrowed laser beam has an influence on surroundings. Jitter is increased due to the formation of pits having a large distribution, the crosstalk in the radial direction is deteriorated, the degree of modulation is deteriorated due to the extremely small pits, or the target laser wavelength is not sufficient. At present, there is no solution to the decrease in reflectivity or the decrease in sensitivity caused by selecting an organic dye having an appropriate optical constant (refractive index, extinction coefficient) for the recording layer.

[0004]

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

[0005]

Means for Solving the Problems The present inventors have proposed an optical recording medium suitable for high-density recording capable of recording and reproduction using a dipyrromethene metal chelate compound as an organic dye (Japanese Patent Application Laid-Open No. Hei 10 (1999)). -226172). The present inventors have further studied the optical recording medium using the dipyrromethene metal chelate compound, and as a result, in the dipyrromethene metal chelate compound, by selecting a specific substituent, in addition to the recording characteristics, The inventors have found that an optical recording medium having excellent durability can be obtained, and have completed the present invention. That is, the present invention provides a dipyrromethene metal chelate compound represented by the following general formula (1).

[0006]

Embedded image

[Wherein, R ^{1 to} R ⁷ each independently represent 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, alkoxy, alkylthio, aryloxy, arylthio, alkenyl, acyl, alkoxycarbonyl, carbamoyl, acylamino, aralkyl,
Represents an aryl group or a heteroaryl group, R ¹ and R ² ,
At least one of R ⁶ and R ⁷ is bonded to form a saturated ring;
A and B each represent an aromatic ring or a heterocyclic ring having 20 or less carbon atoms;
Represents a transition element. An optical recording medium having at least a recording layer and a reflective layer on a substrate, wherein the recording layer contains the above-mentioned dipyrromethene metal chelate compound. An optical recording medium having at least a recording layer and a reflective layer on a substrate, wherein the recording layer contains the described dipyrromethene metal chelate compound and the dipyrromethene metal chelate compound represented by the following general formula (2). .

[0008]

Embedded image

[Wherein, R ^{8 to} R ¹⁵ each independently represent 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, alkoxy, alkylthio, aryloxy, arylthio, alkenyl, acyl, alkoxycarbonyl, carbamoyl, acylamino, aralkyl,
Represents an aryl group or a heteroaryl group, R ¹⁶ represents a halogen atom, an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, an aryloxy group, or an arylthio group, and M represents a transition element. The optical recording medium according to the above, 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. The optical recording medium according to the above, which is capable of recording and reproducing with respect to a laser beam selected from a wavelength range of 520 to 690 nm.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

In the dipyrromethene metal chelate compound represented by the general formula (1), specific examples of R ^{1 to} R ⁷ include:
Hydrogen atom; halogen atom such as fluorine, chlorine, bromine, iodine, etc .; 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, i
so-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,
2,2-trimethylbutyl group, 1,1,2-trimethylbutyl group, 1-ethyl-2-methylpropyl group, cyc
lo-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 ,
A substituted or unsubstituted alkyl group having 20 or less carbon atoms, such as a 5-tetramethylhexyl group, a 1-cyclo-pentyl-2,2-dimethylpropyl group, and a 1-cyclo-hexyl-2,2-dimethylpropyl group;

Methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-
Butoxy group, sec-butoxy group, t-butoxy group, n
-Alkoxy groups such as -pentoxy group, iso-pentoxy group, neo-pentoxy group, n-hexyloxy group, n-dodecyloxy group; 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-
Alkylthio groups such as pentylthio group, 2-methylbutylthio group, 1-methylbutylthio group, neo-pentylthio group, 1,2-dimethylpropylthio group and 1,1-dimethylpropylthio group; phenoxy group, 2-methyl Aryloxy groups such as phenoxy group, 4-methylphenoxy group, 4-t-butylphenoxy group, 2-methoxyphenoxy group, 4-iso-propylphenoxy group; phenylthio group, 4-methylphenylthio group, 2-methoxyphenyl Arylthio groups such as thio group and 4-t-butylphenylthio group; vinyl group, propenyl group, 1-butenyl group, i
so-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-methylcarboxylvinyl group, 2-cyano-2-methylsulfonevinyl group, 2
Alkenyl groups such as -phenyl-1-butenyl group; formyl group, acetyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso-butylcarbonyl group, se
c-butylcarbonyl group, t-butylcarbonyl group, n
Acyl groups such as -pentylcarbonyl group, iso-pentylcarbonyl group, neo-pentylcarbonyl group, 2-methylbutylcarbonyl group and nitrobenzylcarbonyl group; methoxycarbonyl group, ethoxycarbonyl group, isopropyloxycarbonyl group, 2,4- An alkoxycarbonyl group such as a dimethylbutyloxycarbonyl group;

Carbamoyl group; acylamino group such as acetylamino group, ethylcarbonylamino group, butylcarbonylamino group; benzyl group, nitrobenzyl group, cyanobenzyl group, hydroxybenzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group , Dichlorobenzyl, methoxybenzyl, ethoxybenzyl, trifluoromethylbenzyl, naphthylmethyl, nitronaphthylmethyl, cyanonaphthylmethyl, hydroxynaphthylmethyl, methylnaphthylmethyl, trifluoromethylnaphthylmethyl, etc. Aralkyl groups; phenyl, nitrophenyl, cyanophenyl, hydroxyphenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl Group, triethyl phenyl radical, 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-butyl Phenyl group, di (n-butyl) phenyl group, tri (n-butyl) phenyl group, iso-butylphenyl group, di (is
o-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,
Aryl groups such as chloronaphthyl group, bromonaphthyl group, iodonaphthyl group, methoxynaphthyl group, trifluoromethylnaphthyl group, N, N-dimethylaminonaphthyl group;

Hetero groups such as pyrrolyl, thienyl, furanyl, oxazoyl, isoxazoyl, oxadiazoyl, imidazoyl, benzoxazoyl, benzothiazoyl, benzoimidazoyl, benzofuranyl, indoyl and isoindoyl groups. Aryl group; and the like.

Specific examples of the case where R ¹ and R ² and R ⁶ and R ⁷ combine to form a saturated ring include —CH ₂ —CH ₂ — and —CH
_{2 -, - O -, -} S -, - C (CH 3) 2 -CH 2 -, - C
(CH ₃ ) _2- , and the like.

Specific examples of A and B include benzene, nitrobenzene, cyanobenzene, hydroxybenzene, methylbenzene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, triethylbenzene, n-propylbenzene, di (n-propyl) benzene , Tri (n-propyl) benzene, iso-propylbenzene, di (iso-propyl) benzene, tri (iso-propyl) benzene, n-butylbenzene,
Di (n-butyl) benzene, tri (n-butyl) benzene, iso-butylbenzene, di (iso-butyl) benzene, tri (iso-butyl) benzene, sec-butylbenzene, di (sec-butyl) benzene, Tri (sec-butyl) benzene, t-butylbenzene, di (t-butyl) benzene, tri (t-butyl) benzene, dimethyl-t-butylbenzene, phenylbenzene, carboxybenzene, fluorobenzene, chlorobenzene, bromobenzene, Iodobenzene, methoxybenzene, ethoxybenzene, iso-butoxybenzene, trifluoromethylbenzene, N, N-dimethylaminobenzene, naphthalene, nitronaphthalene, cyanonaphthalene, hydroxynaphthalene, methylnaphthalene, fluoronaphthalene, Aromatic rings such as lonaphthalene, bromonaphthalene, iodonaphthalene, methoxynaphthalene, trifluoromethylnaphthalene, N, N-dimethylaminonaphthalene; pyrrole, N-methylpyrrole, thiophene, methylthiophene, furan, oxazole, isoxazole, oxadi Heterocycles such as azole, imidazole, benzoxazole, benzothiazole, benzimidazole, benzofuran, indole and isoindole;

Specific examples of M are not particularly limited as long as they are transition elements having the ability to form a chelate with a dipyrromethene compound, but may be any of groups 8, 9, 10 (Group VIII), 11 (Ib), and 12 (IIb group), 3 group (IIIa group), 4 group (I
Va group), 5 group (Va group), 6 group (VIa group), 7 group (VIIa)
Group), and are preferably nickel, cobalt, iron, ruthenium, rhodium, palladium, copper, osmium, iridium, platinum, zinc and the like, and particularly preferably copper and cobalt from the viewpoint of light resistance.

The dipyrromethene metal chelate compound represented by the general formula (1) of the present invention is not limited.
Aust. J. Chem, 1965, 11, 1835-45, Heteroatom Chemi
stry, Vol. 1, 5, 389 (1990), USP-4,774,339, USP-5,4
It is produced according to the method described in 33,896 and the like. Typically, it can be produced by the following two-step reaction.

First, in the first step, a compound represented by the general formula (3) and a compound represented by the general formula (4), a compound represented by the general formula (5) and a compound represented by the general formula (6), or The compound represented by the general formula (4), the compound represented by the general formula (5) and the compound represented by the general formula (7) are mixed with a suitable solvent in the presence of an acid catalyst such as hydrobromic acid or hydrochloric acid. To give a dipyrromethene compound represented by the general formula (8). Next, in the second stage, the general formula (8)
A dipyrromethene compound represented by, nickel, cobalt,
The dipyrromethene metal chelate compound represented by the general formula (1) is obtained by reacting with a metal acetate or halide such as iron, ruthenium, rhodium, palladium, copper, osmium, iridium, platinum, and zinc.

[0020]

Embedded image

[0021]

Embedded image

[0022]

Embedded image

[0023]

Embedded image

[0024]

Embedded image

[0025]

Embedded image [In the formulas (3) to (8), R ^{1 to} R ⁷ , A and B represent the same meaning as described above. ]

In addition, the compounds represented by the general formulas (3) to (6), which are the raw materials giving the characteristic structure of the present compound, can be produced by the following reaction.

The compound represented by the general formula (4) and the compound represented by the general formula (5) include, but are not limited to, for example, Zhurnal Organicheskoj Khimii, 492-495 (1984), L.
iebigsAnn.Chem. 3847-3853 (1965), Chem. Ber. 110,
It is produced according to the method described in 491-499 (1977) and the like. Typically, a ketoxime derivative is obtained from a compound represented by the general formula (9) and a compound represented by the general formula (10), and then in a solvent such as dimethyl sulfoxide in the presence of a base catalyst such as potassium hydroxide. The presence of an alkoxide which reacts with dichloroethane, or a compound represented by the general formula (9), and a compound represented by the general formula (10) and 1-nitro-2-dimethylaminoethylene or glyoxal-mono (dimethylhydrazone) Under a suitable solvent, a 2-nitroethylidene-tetralone derivative or a 2- (dimethylhydrazone) ethylidene-tetralone derivative is obtained, which is then reduced with hydrosulfite or the like to obtain a compound represented by the general formula (4). And the compound represented by the general formula (5).

The compound represented by the general formula (3) and the compound represented by the general formula (6) are not limited. For example, the compounds represented by Organic Preparations and Procedures Int.
(2), 97-101 (1981), JOC 28, 3052-3058 (1963), Tet
It is produced by acylating the compound represented by the general formula (5) and the compound represented by the general formula (4), respectively, according to the method described in rahedron Letters 2411- (1989).

[0029]

Embedded image [In the formula (9), R ¹ , R ² and A represent the same meaning as described above. ]

[0030]

Embedded image [In the formula (10), R ⁶ , R ⁷ and B represent the same meaning as described above. ]

Table 1 shows specific examples of the dipyrromethene metal chelate compound represented by the general formula (1) of the present invention.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

[Table 4]

[0036]

[Table 5]

In the dipyrromethene metal chelate compound represented by the general formula (2), specific examples of R ^{8 to} R ¹⁵ include a hydrogen atom; a halogen atom such as fluorine, chlorine, bromine and iodine; a nitro group; a cyano group; A group; an 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 A 2-ethylbutyl group, a 1-ethylbutyl group,
1,2,2-trimethylbutyl group, 1,1,2-trimethylbutyl group, 1-ethyl-2-methylpropyl group, c
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-dimethylpropyl group, 1-cyclo
2 carbon atoms such as -hexyl-2,2-dimethylpropyl group
0 or less alkyl groups;

Methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-
Butoxy group, sec-butoxy group, t-butoxy group, n
-Alkoxy groups such as -pentoxy group, iso-pentoxy group, neo-pentoxy group, n-hexyloxy group, n-dodecyloxy group; 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-
Alkylthio groups such as pentylthio group, 2-methylbutylthio group, 1-methylbutylthio group, neo-pentylthio group, 1,2-dimethylpropylthio group and 1,1-dimethylpropylthio group; phenoxy group, 2-methyl Aryloxy groups such as phenoxy group, 4-methylphenoxy group, 4-t-butylphenoxy group, 2-methoxyphenoxy group, 4-iso-propylphenoxy group;

Arylthio groups such as phenylthio, 4-methylphenylthio, 2-methoxyphenylthio, 4-tert-butylphenylthio; vinyl, propenyl, 1-butenyl, iso-butenyl , 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
Alkenyl groups such as -methylcarboxylvinyl group, 2-cyano-2-methylsulfonevinyl group, 2-phenyl-1-butenyl 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, is
acyl groups such as o-pentylcarbonyl group, neo-pentylcarbonyl group, 2-methylbutylcarbonyl group and nitrobenzylcarbonyl group; methoxycarbonyl group, ethoxycarbonyl group, isopropyloxycarbonyl group and 2,4-dimethylbutyloxycarbonyl group Alkoxycarbonyl groups such as;

Carbamoyl group; acylamino group such as acetylamino group, ethylcarbonylamino group, butylcarbonylamino group; benzyl group, nitrobenzyl group, cyanobenzyl group, hydroxybenzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group , Dichlorobenzyl, methoxybenzyl, ethoxybenzyl, trifluoromethylbenzyl, naphthylmethyl, nitronaphthylmethyl, cyanonaphthylmethyl, hydroxynaphthylmethyl, methylnaphthylmethyl, trifluoromethylnaphthylmethyl, etc. Aralkyl groups; phenyl, nitrophenyl, cyanophenyl, hydroxyphenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl Group, triethyl phenyl radical, 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-butyl Phenyl group, di (n-butyl) phenyl group, tri (n-butyl) phenyl group, iso-butylphenyl group, di (is
o-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,
Aryl groups such as chloronaphthyl group, bromonaphthyl group, iodonaphthyl group, methoxynaphthyl group, trifluoromethylnaphthyl group, N, N-dimethylaminonaphthyl group;

Hetero groups such as pyrrolyl, thienyl, furanyl, oxazoyl, isoxazoyl, oxadiazoyl, imidazoyl, benzoxazoyl, benzothiazoyl, benzoimidazoyl, benzofuranyl, indoyl and isoindoyl groups. Aryl group; and the like.

Specific examples of R ¹⁶ include halogen atoms such as fluorine, chlorine, bromine and iodine; phenyl, nitrophenyl, cyanophenyl, hydroxyphenyl, methylphenyl, dimethylphenyl, trimethylphenyl, 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 (I
(so-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, nitro group Naphthyl group, cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl group,
Aryl groups such as fluoronaphthyl group, chloronaphthyl group, bromonaphthyl group, iodonaphthyl group, methoxynaphthyl group, trifluoromethylnaphthyl group, N, N-dimethylaminonaphthyl group;

Hetero groups such as pyrrolyl, thienyl, furanyl, oxazoyl, isoxazoyl, oxadiazoyl, imidazoyl, benzoxazoyl, benzothiazoyl, benzoimidazoyl, benzofuranyl, indoyl and isoindoyl groups. Aryl group; methoxy group, ethoxy group, n-propoxy group, i
so-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, t-butoxy group, n-pentoxy group, iso-pentoxy group, neo-pentoxy group, n-hexyloxy group, n-dodecyloxy Alkoxy groups such as a group; 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, 1,2-dimethylpropylthio group, 1,1-dimethylpropylthio group An alkylthio group such as

Phenoxy group, 2-methylphenoxy group,
Aryloxy groups such as 4-methylphenoxy group, 4-t-butylphenoxy group, 2-methoxyphenoxy group, 4-iso-propylphenoxy group; phenylthio group;
Arylthio groups such as a 4-methylphenylthio group, a 2-methoxyphenylthio group, and a 4-t-butylphenylthio group;

Specific examples of M include the same transition elements as M in the general formula (1).

Table 2 shows specific examples of the dipyrromethene metal chelate compound represented by the general formula (2) of the present invention.

[0047]

[Table 6]

[0048]

[Table 7]

[0049]

[Table 8]

The specific configuration of the present invention will be described below. The optical recording medium refers to both a read-only optical read-only medium on which information is recorded in advance and an optical recording medium capable of recording and reproducing information. Here, as an example, an optical recording medium capable of recording and reproducing the latter information, in particular, 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 bonded thereon 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.

As a material of the substrate, basically, it is sufficient that the substrate is transparent at the wavelength of the recording light and the reproducing light. For example, polymer materials such as acrylic resins such as polycarbonate resin, vinyl chloride resin and polymethyl methacrylate, polystyrene resins and epoxy resins, and inorganic materials such as glass are used.
These substrate materials are formed into a disk shape by injection molding or the like. If necessary, guide grooves or pits may be formed on the substrate surface. Such guide grooves and pits
It is desirable to apply it at the time of molding the substrate, but it can also be applied using an ultraviolet curable resin layer on the substrate. When used as a normal DVD, it is a disk having a thickness of about 1.2 mm and a diameter of about 80 to 120 mm, and a hole having a diameter of about 15 mm is formed in the center.

In the present invention, a recording layer is provided on a substrate, and the recording layer of the present invention has a λmax of 450 nm to 630 nm.
It contains a dipyrromethene metal chelate compound of a dipyrromethene-based compound represented by the general formula (1) and a metal ion present in the vicinity of nm. Above all, appropriate optical constants (optical constants are represented by complex refractive indices (n + ki) with respect to a recording and reproducing laser wavelength selected from 520 nm to 690 nm. 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. Here, n is a refractive index and k is an extinction coefficient.

Generally, an organic dye has a refractive index with respect to a wavelength λ.
There is a feature that n and the extinction coefficient k change greatly. n is 1.8
If the value is smaller, the reflectance and the signal modulation required for accurate signal reading may not be obtained, and k is 0.40.
Even if it exceeds, not only does the reflectivity decrease and it becomes difficult to obtain a good reproduction signal, but also the signal is easily changed by the reproduction light and 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 represented by the general formula (1) used in the present invention has a higher absorption coefficient than ordinary organic dyes, and the absorption wavelength range can be arbitrarily selected by selecting a substituent. 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).

In the recording layer of the present invention, a dipyrromethene metal chelate compound represented by the general formula (1) and a dipyrromethene metal chelate compound represented by the general formula (2) are further provided for improving recording characteristics and the like. May be used in combination of two or more. The mixing ratio of these dipyrromethene metal chelate compounds 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 0.40. And it is preferable to mix them so as to be preferably 0.04 to 0.20.

Further, it may be mixed with a dye other than the above dyes having an absorption maximum at a wavelength of 450 nm to 630 nm and having a large refractive index at 520 nm to 690 nm. Specifically, cyanine dyes, squarylium dyes, naphthoquinone dyes, anthraquinone dyes, porphyrin dyes, azaporphyrin dyes, tetrapyraporphyrazine dyes, indophenol dyes, pyrylium dyes, thiopyrylium dyes, There are azulenium dyes, triphenylmethane dyes, xanthene dyes, indathrene dyes, indigo dyes, thioindigo dyes, merocyanine dyes, thiazine dyes, acridine dyes, oxazine dyes, etc. It may be a mixture. The mixing ratio of these dyes is 0.1 to 3 with respect to the dipyrromethene metal chelate compound represented by the general formula (1).
It is about 0% by mass.

Further, when k of the dipyrromethene metal chelate compound represented by the general formula (1) is small with respect to a recording and reproducing laser wavelength selected from 520 nm to 690 nm, the recording characteristics and the like are improved. And a wavelength of 60
You may mix with the light absorption compound which has an absorption maximum in 0 nm-900 nm. Specifically, cyanine dyes, squarylium dyes, naphthoquinone dyes, anthraquinone dyes, porphyrin dyes, azaporphyrin dyes, tetrapyraporphyrazine dyes, indophenol dyes, pyrylium dyes, thiopyrylium dyes,
Azulenium dye, triphenylmethane dye, xanthene dye, indathrene dye, indigo dye,
There are thioindigo dyes, merocyanine dyes, thiazine dyes, acridine dyes, oxazine dyes, phthalocyanine dyes, naphthalocyanine dyes, and the like, and a mixture of a plurality of dyes may be used. The mixing ratio of these dyes is about 0.1 to 30% by mass based on the dipyrromethene metal chelate compound represented by the general formula (1).

The optical recording medium of the present invention has a thickness of 520 nm to 690.
Reproduction with a laser beam selected from nm is basically possible if the reflectivity is 20%.
% Is preferred.

When forming a recording layer, a quencher, a dye decomposition accelerator, an ultraviolet absorber, an adhesive or the like may be mixed with the above-mentioned dye, if necessary, or a compound having such an effect. Can be introduced as a substituent of the dye.

Specific examples of the quencher include metals such as acetylacetonate, bisdithio-α-diketone and bisphenyldithiol, bisdithiol, thiocatechol, salicylaldehyde oxime, and thiobisphenolate. Complexes are preferred. Amines are also suitable.

Examples of the thermal decomposition accelerator include metal antiknocking agents, metallocene compounds, and metal compounds such as 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,
Ketone resin, acrylic resin, polystyrene resin, urethane resin, polyvinyl butyral, polycarbonate, polyolefin and the like can be mentioned.

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

Here, the content of the dipyrromethene metal chelate compound represented by the general formula (1) or (2) in the recording layer is 30% or more, preferably 60% or more. In addition, it is also preferable that it is substantially 100%.

The method for providing the recording layer includes, for example, a coating method such as a spin coating method, a spray 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 a spin coating method is used, the dipyrromethene metal chelate compound represented by the general formula (1) or (2) is added in an amount of 1 to 40% by mass, preferably 3 to 30% by mass. A coating solution dissolved or dispersed in a solvent is used so that the solvent is preferably selected so as not to damage the substrate. For example, alcohol solvents such as methanol, ethanol, isopropyl alcohol, octafluoropentanol, allyl alcohol, methyl cellosolve, ethyl cellosolve, and tetrafluoropropanol, hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane Aliphatic or alicyclic hydrocarbon solvents such as, toluene, xylene, aromatic hydrocarbon solvents such as benzene, carbon tetrachloride, chloroform, tetrachloroethane, halogenated hydrocarbon solvents such as dibromoethane, diethyl ether, Ether solvents such as dibutyl ether, diisopropyl ether and dioxane; ketone solvents such as acetone and 3-hydroxy-3-methyl-2-butanone; Ester solvents such as methyl lactate, and water. These may be used alone, or
A plurality may be mixed.

It is to be noted that, if necessary, the dye of the recording layer can be used by dispersing it in a polymer thin film or the like.

When a solvent that does not damage the substrate cannot be selected, a sputtering method, a chemical vapor deposition method, a vacuum vapor deposition method, or the like is effective.

The thickness of the dye layer is not particularly limited, but is preferably 50 nm to 300 nm. If the thickness of the dye layer is less than 50 nm, recording cannot be performed due to large thermal diffusion, or a recording signal will be distorted and the signal amplitude will be small. On the other hand, when the film thickness is larger than 300 nm, the reflectivity decreases and the reproduction signal characteristics deteriorate.

Next, on the recording layer, preferably,
A reflective layer having a thickness of 300 nm is formed. As a material of the reflection layer, a material having sufficiently high reflectance at the wavelength of the reproduction light, for example, Au, Al, Ag, Cu, Ti, Cr, Ni, P
The metals t, Ta, Cr and Pd can be used alone or as an alloy. Among them, Au, Al,
Ag has a high reflectance and is suitable as a material for the reflective layer. In addition, 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
Metals and metalloids such as i, Ge, Te, Pb, Po, Sn, Bi and the like can be mentioned. Further, those containing Au as a main component are preferable because a reflection layer having high reflectance can be easily obtained. Here, the main component means a component having a content of 50% or more. It is also possible to form a multilayer film by alternately stacking low-refractive-index thin films and high-refractive-index thin films with a material other than a metal, and use it as a reflective layer.

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

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 organic substances, thermoplastic resins, thermosetting resins,
An electron beam curable resin, an ultraviolet curable resin, and the like can be given. Further, as the inorganic substance, SiO ₂ , Si ₃ N
₄ , MgF ₂ , SnO _{2 and the} like. A thermoplastic resin, a thermosetting resin, or the like can be formed by dissolving in a suitable solvent, applying a coating solution, and drying.
The ultraviolet curable resin can be formed by preparing a coating solution as it is or by dissolving it in an appropriate solvent, applying the coating solution, and irradiating ultraviolet rays to cure the resin. As the ultraviolet curable resin, for example, acrylate resins such as urethane acrylate, epoxy acrylate, and polyester acrylate can be used. These materials may be used alone or as a mixture, and may be used not only as a single layer but also as a multilayer film.

As a method of forming the protective layer, a coating method such as a spin coating method or a casting method, a sputtering method, a chemical vapor deposition method, or the like is used as in the case of the recording layer. Among them, the spin coating method is preferable.

The thickness of the protective layer is generally 0.1 μm to 1 μm.
In the present invention, the range is from 3 μm to
It is 30 μm, more preferably 5 μm to 20 μm.

A label or the like can be further printed on the protective layer. Further, a means such as bonding a protective sheet or a substrate to the reflective layer surface, or bonding two optical recording media with the reflective layer surfaces facing each other and facing each other may be used. Further, an ultraviolet curable resin, an inorganic thin film, or the like may be formed on the mirror surface of the substrate to protect the surface and prevent adhesion of dust and the like.

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

[0077]

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

Example 1 Synthesis of dipyrromethene metal chelate compound (1-1) 4.00 g of the compound represented by the following structural formula (5-a) and the compound represented by the following structural formula (6-a) in 400 ml of ethanol 4.66 g dissolved, 47% hydrobromic acid 4.2
After dropping 7 g, the mixture was stirred at room temperature for 2 hours. After concentration under reduced pressure, the residue was extracted with 400 ml of chloroform, washed with water and separated, and the solvent was distilled off to obtain 7.60 g of a compound represented by the following structural formula (8-a).

[0079]

Embedded image

Next, the formula (8-
Dissolve 3.50 g of the compound of a) and add copper acetate
12 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 3.10 g of a compound represented by the following structural formula (1-1).

[0081]

Embedded image

From the following analysis results, it was confirmed that the substance was the target substance.

[0083]

[Table 9]

The compound thus obtained exhibits an absorption maximum at 613.5 nm in a toluene solution, and has a gram extinction coefficient of 1.18 × 10 ⁵ ml / g. cm.

Example 2 Synthesis of Dipyrromethene Metal Chelate Compound (1-2) 6.00 g of the compound represented by the above structural formula (5-a) and the compound represented by the following structural formula (6-b) in 500 ml of ethanol Dissolve 8.40 g and add 47% hydrobromic acid 6.0
After dropping 0 g, the mixture was stirred at room temperature for 1 hour. After concentration under reduced pressure, extraction with 500 ml of chloroform, washing with water, and liquid separation, the solvent was distilled off to obtain 13.50 g of a compound represented by the following structural formula (8-b).

[0086]

Embedded image

Next, the formula (8-
6.00 g of the compound represented by b) was dissolved, and copper acetate 1.
38 g was added, and the mixture was stirred at reflux temperature for 3 hours. After concentration under reduced pressure, the precipitate was collected by filtration and washed with methanol and water to obtain 3.40 g of a compound represented by the following structural formula (1-2).

[0088]

Embedded image

From the following analysis results, it was confirmed that it was the target substance.

[0090]

[Table 10]

The compound thus obtained exhibits an absorption maximum at 589 nm in a toluene solution, and has a gram extinction coefficient of 1.12 × 10 ⁵ ml / g. cm.

Example 3 Synthesis of Dipyrromethene Metal Chelate Compound (1-3) 6.00 g of the compound represented by the above structural formula (5-a) and the compound represented by the following structural formula (6-c) in 600 ml of ethanol 9.80 g are dissolved and 47% hydrobromic acid 6.0
After dropping 0 g, the mixture was stirred at room temperature for 3 hours. After concentration under reduced pressure, the mixture was extracted with 500 ml of chloroform, washed with water and separated, and the solvent was distilled off to obtain 10.70 g of a compound represented by the following structural formula (8-c).

[0093]

Embedded image

Next, the formula (8-
9.00 g of the compound represented by c) was dissolved, and copper acetate 1.
90 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 8.60 g of a compound represented by the following structural formula (1-3).

[0095]

Embedded image From the following analysis results, it was confirmed that it was the target substance.

[0096]

[Table 11]

The compound thus obtained exhibits an absorption maximum at 590 nm in a toluene solution, and has a gram extinction coefficient of 0.97 × 10 ⁵ ml / g. cm.

Example 4 Synthesis of dipyrromethene metal chelate compound (1-4) 4.20 g of the compound represented by the above structural formula (5-a) and the compound represented by the following structural formula (6-d) in 400 ml of ethanol 5.00 g was dissolved, and 47% hydrobromic acid 4.2
After dropping 0 g, the mixture was stirred at room temperature for 2 hours. After concentration under reduced pressure, extraction with 200 ml of chloroform, washing with water, and liquid separation, the solvent was distilled off to obtain 7.70 g of a compound represented by the following structural formula (8-d).

[0099]

Embedded image

Next, the formula (8-
Dissolve 3.50 g of the compound of d) and add
90 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 3.50 g of a compound represented by the following structural formula (1-4).

[0101]

Embedded image From the following analysis results, it was confirmed that it was the target substance.

[0102]

[Table 12]

The compound thus obtained exhibits an absorption maximum at 589 nm in a toluene solution, and has a gram extinction coefficient of 1.17 × 10 ⁵ ml / g. cm.

Example 5 0.2 g of the dipyrromethene metal chelate compound (1-2) was added to dimethylcyclohexane 10
The dye solution was dissolved in the solution to prepare a dye solution. The substrate is made of a continuous guide groove made of polycarbonate resin (track pitch:
0.74 μm), diameter 120 mm, thickness 0.6 m
m was used.

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

[0106]

[Table 13]

Au was sputtered on the recording layer using a sputtering apparatus (CDI-900) manufactured by Balzers to form a reflective layer having a thickness of 100 nm. Sputter gas includes
Argon gas was used. The sputtering conditions were as follows: a sputtering power of 2.5 kW and a sputtering gas pressure of 1.33 Pa (1.0 ×
10 ⁻² Torr).

Further, an ultraviolet curable resin SD-
After spin-coating 1700 (manufactured by Dainippon Ink and Chemicals, Inc.), the layer was irradiated with ultraviolet rays to form a protective layer having a thickness of 6 μm. Further, an ultraviolet curable adhesive SD-301 is provided on the protective layer.
(Manufactured by Dainippon Ink and Chemicals, Inc.) and spin-coated thereon with a polycarbonate resin having a diameter of 120 mm and a thickness of 0.1 mm.
After placing a 6 mm disk-shaped substrate, the substrate was irradiated with ultraviolet rays to produce an optical recording medium bonded to the substrate.

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., at a linear velocity of 3.5 m / s and a laser power of 9.
Recording was performed so that the shortest pit length was 0.40 μm at 0 mW. After recording, the signal was reproduced using an evaluation apparatus equipped with a 650 nm red semiconductor laser head (the numerical aperture of the lens was 0.6), and the reflectance, jitter and modulation were measured. 5%, jitter 7.9% and modulation degree 0.60 all showed good values. No change was observed even after a light resistance test with a carbon arc for 100 hours and a moist heat test at 80 ° C., 85% and 100 hours. Further, the jitter change was 1% or less even when the reproduction was performed 1 million times with the reproduction light of 0.7 mW.

Example 6 0.2 g of the dipyrromethene metal chelate compound (1-3) was added to dimethylcyclohexane 10
An optical recording medium was prepared in the same manner as in Example 5 except that the dye solution was dissolved in the dye solution and a dye solution was prepared. 640 of this recording layer
The optical constants at each wavelength of nm, 650 nm, and 660 nm were as follows.

[0111]

[Table 14]

An optical disk evaluation device (DDU-1000) 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 in the same manner as in the fifth embodiment. Recording was performed using an industrial pulse generator at a linear velocity of 3.5 m / s and a laser power of 9.5 mW so that the shortest pit length was 0.40 μm. After recording, the signal was reproduced using an evaluation apparatus equipped with a 650 nm red semiconductor laser head (the numerical aperture of the lens was 0.6), and the reflectance, jitter and modulation were measured.
4%, jitter 7.8% and modulation degree 0.61 all showed good values. No change was observed even after a light resistance test with a carbon arc for 100 hours and a moist heat test at 80 ° C., 85% and 100 hours. Also, 0.7mW
1% change in jitter even when reproduced 1 million times
It was below.

Example 7 0.2 g of the dipyrromethene metal chelate compound (1-4) was added to dimethylcyclohexane 10
An optical recording medium was prepared in the same manner as in Example 5 except that the dye solution was dissolved in the dye solution and a dye solution was prepared. 640 of this recording layer
The optical constants at each wavelength of nm, 650 nm, and 660 nm were as follows.

[0114]

[Table 15]

An optical disc evaluation device (DDU- manufactured by Pulstec Industrial) equipped with a semiconductor laser head having a wavelength of 639 nm and a numerical aperture of a lens of 0.6 on the obtained optical recording medium.
1000) and a pulse speed of 3.5 m / s and a laser power of 8.5 using a pulse generator manufactured by Pulstec Industrial Co., Ltd.
Recording was performed so that the shortest pit length was 0.40 μm at mW. After recording, the 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 modulation were measured. 9%, jitter 7.7% and modulation degree 0.62 all showed good values. No change was observed even after a light resistance test with a carbon arc for 100 hours and a moist heat test at 80 ° C., 85% and 100 hours. Further, the jitter change was 1% or less even when the reproduction was performed 1 million times with the reproduction light of 0.7 mW.

Example 8 0.10 g of dipyrromethene metal chelate compound (1-1) and 1.0 g of dipyrromethene metal chelate compound (2-1) were added to dimethylcyclohexane 5
Example 5 except that the dye solution was dissolved in 5 ml to prepare a dye solution.
In the same manner as in the above, an optical recording medium was produced. 64 of this recording layer
The optical constants at the wavelengths of 0 nm, 650 nm and 660 nm were as follows.

[0117]

[Table 16]

An optical disk evaluation device (DDU-1000) 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 in the same manner as in the fifth embodiment. The shortest pit length is 0.40 μm at a linear velocity of 3.5 m / s, laser power of 11.0 mW using an industrial pulse generator.
It was recorded to be. After recording, the 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 modulation were measured.
7.1%, jitter 7.2% and modulation degree 0.61 all showed good values. No change was observed even after a light resistance test with a carbon arc for 100 hours and a moist heat test at 80 ° C., 85% and 100 hours. Also, 0.7
Even after 1 million reproductions with mW reproduction light, the change in jitter was 1% or less.

Example 9 A dye solution was prepared by dissolving 0.30 g of the dipyrromethene metal chelate compound (1-9) and 0.70 g of the dipyrromethene metal chelate compound (2-2) in 50 ml of dimethylcyclohexane. An optical recording medium was produced in the same manner as in Example 6. 6 of this recording layer
Optical constants at respective wavelengths of 40 nm, 650 nm, and 660 nm were as follows.

[0120]

[Table 17]

An optical disk evaluation device (DDU- manufactured by Pulstec Industrial Co., Ltd.) equipped with a semiconductor laser head having a wavelength of 639 nm and a numerical aperture of a lens of 0.6 on the obtained optical recording medium.
1000) and a pulse power of 3.5 m / s and a laser power of 10.
Recording was performed so that the shortest pit length was 0.40 μm at 0 mW. After recording, the signal was reproduced using an evaluation apparatus equipped with a 650 nm red semiconductor laser head (the numerical aperture of the lens was 0.6), and the reflectance, jitter and modulation were measured. 7%, jitter 7.7% and modulation degree 0.64 were all good values. No change was observed even after a light resistance test with a carbon arc for 100 hours and a moist heat test at 80 ° C., 85% and 100 hours. Further, the jitter change was 1% or less even when the reproduction was performed 1 million times with the reproduction light of 0.7 mW.

Comparative Example 1 An optical recording medium was prepared in the same manner as in Example 5, except that 0.2 g of the dipyrromethene metal chelate compound (2-3) was dissolved in 10 ml of dimethylcyclohexane and spin-coated. An optical disc evaluation device (DDU manufactured by Pulstec Industrial Co., Ltd.) equipped with a 658 nm semiconductor laser head on the produced medium in the same manner as in Example 5.
-1000) and a pulse speed of 3.5 m / s and a laser power of 1 using a pulse generator manufactured by Pulstec Industrial Co., Ltd.
Recorded at 1.0 mW. After recording, the signal was reproduced using an evaluation device equipped with a 650 nm red semiconductor laser head, and the reflectance, jitter and modulation were measured.
At a reproduction of 50 nm, the reflectance was 62%, the jitter was 20% or more, the modulation factor was 0.61, and the jitter characteristics were poor.

Comparative Example 2 In Example 5, 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 Photographic Dye Laboratories "1
g was dissolved in 10 ml of tetrafluoropropanol and spin-coated to prepare an optical recording medium in the same manner. In the same manner as in Example 5, a linear velocity of 3.5 m / m was measured by using a pulse medium manufactured by Pulstec Industrial Co., Ltd. (DDU-1000) and a pulse generator manufactured by Pulstec Industrial Co., Ltd.
s, recording was performed at a laser power of 10.0 mW. After recording,
The signal was reproduced using an evaluation device equipped with a 650 nm red semiconductor laser head, and the reflectance, jitter, and modulation were measured. As a result, the reflectance was 10%, the jitter was 20% or more, and the modulation was 0.14 at 650 nm reproduction. I was Also, after the light fastness test with a carbon arc for 100 hours, the signal deteriorated and could not be reproduced.

[0124]

By using the dipyrromethene metal chelate compound of the present invention as a recording layer, it is possible to record / reproduce information with a laser having a wavelength of 520 to 690 nm, which has been attracting much attention as a high-density optical recording medium, and to achieve additional durability. It is possible to provide a type optical recording medium.

[Brief description of the 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]

 DESCRIPTION OF SYMBOLS 1 Substrate 2 Recording layer 3 Reflective layer 4 Adhesive layer 5 Substrate

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C09B 23/00 B41M 5/26 Y (72) Inventor U Tsukahara 580-32 Nagaura, Sodegaura City, Chiba Prefecture Mitsui Inside Chemical Company (72) Inventor Shinobu Inoue 580-32 Nagaura, Sodegaura City, Chiba Prefecture Inside Mitsui Chemical Company (72) Inventor Akira Ogiso 580-32 Nagaura, Sodegaura City, Chiba Prefecture Inside Mitsui Chemical Company (72) Inventor Denmi Misawa 580-32 Nagaura, Sodegaura-shi, Chiba Prefecture Mitsui Chemicals Co., Ltd. (72) Inventor Masashi Koike 580-32 Nagaura, Sodegaura-shi, Chiba Prefecture Mitsui Chemicals Co., Ltd. 4C063 AA01 AA03 BB03 CC06 DD04 EE05 4H056 CA01 CC02 CC08 CE03 CE06 DD03 FA06 5D029 JA04 JB47 JC05 JC06

Claims (5)

[Claims] 1. A dipyrromethene metal chelate compound represented by the following general formula (1). Embedded image [Wherein, R ^{1 to} R ⁷ each independently represent 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 Represents an aryl group or a heteroaryl group, wherein at least one of R ¹ and R ² or R ⁶ and R ⁷ is bonded to form a saturated ring, and A and B each have 2 carbon atoms.
Represents an aromatic ring or a hetero ring of 0 or less, and M represents a transition element. ] 2. An optical recording medium having at least a recording layer and a reflective layer on a substrate, wherein the recording layer contains the dipyrromethene metal chelate compound according to claim 1. 3. An optical recording medium having at least a recording layer and a reflective layer on a substrate, wherein the dipyrromethene metal chelate compound according to claim 1 and a dipyrromethene metal chelate compound represented by the following general formula (2) in the recording layer: The optical recording medium according to claim 2, comprising: Embedded image [Wherein, R ^{8 to} R ¹⁵ each independently represent 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, 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, R ¹⁶ represents a halogen atom ,
Represents an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group,
M represents a transition element. ] 4. The optical recording medium according to claim 2, 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. 5. The optical recording medium according to claim 2, wherein recording and reproduction can be performed with respect to a laser beam selected from a wavelength range of 520 to 690 nm.