JPH11256056A - Benzopyrromethene-metal chelate compound and optical recording medium containing the sane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a benzopyrromethene-metal chelate compd. which comprises a benzopyrromethene compd. and a metal ion and is useful as an optical record ing medium which makes recording and reproduction with a short-wavelength laser possible and is suitable for high-density recording. SOLUTION: This benzopyrromethene-metal chelate compd. is represented by the formula (wherein R1 to R9 are each H, a halogen, nitro, cyano, hydroxyl, amino, carboxyl, sulfo, alkyl, halogenoalkyl, alkoxyalky, alkoxy, alkoxyalkoxy, aryloxy, dialkylaminoalkoxy, alkylthioalkoxy, acyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylcarbonylamino, or the like). A transition element such as Ni, Co, Fe, Ru, Rh, Pd, Cu, Os, Ir, Pt, Mn, or Zn and boron are pref. as metals for forming the chelate compd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel benzopyrromethene 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 oscillation wavelength of laser light is shorter than 630 nm to 680 nm as compared with 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. There is no solution to the problem of large pits with large distribution, increased jitter, worse crosstalk in the radial direction, or extremely small pits and insufficient modulation. Is the current situation.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel benzopyrromethene metal chelate compound which is suitable for high-density recording capable of recording and reproducing with a short wavelength laser having a wavelength of 520 to 690 nm. An optical recording medium is provided.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, completed the present invention. That is, the present invention provides a benzopyrromethene metal chelate compound of a benzopyrromethene compound represented by the following general formula (1) and a metal ion:

[0006]

Embedded image

[Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ ,
R ₇ , R ₈ and R ₉ 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, an alkyl group having 1 to 20 carbon atoms, a halogenoalkyl group, Alkoxyalkyl group, alkoxy group, alkoxyalkoxy group, aryloxy group, dialkylaminoalkoxy group, alkylthioalkoxy group, acyl group, alkoxycarbonyl group, alkylaminocarbonyl group, dialkylaminocarbonyl group, alkylcarbonylamino group, arylcarbonylamino group , Arylaminocarbonyl, aryloxycarbonyl, aralkyl, aryl, heteroaryl, alkylthio, arylthio, alkenyloxycarbonyl, aralkyloxycarbonyl, alkoxycarbonyl Alkoxycarbonyl group, alkylcarbonylalkoxycarbonyl group, mono (hydroxyalkyl) aminocarbonyl group, di (hydroxyalkyl) aminocarbonyl group, mono (alkoxyalkyl) aminocarbonyl group, di (alkoxyalkyl)
Represents an aminocarbonyl group or an alkenyl group having 2 to 20 carbon atoms. However, R ₂ and R ₃ may combine to form an aromatic ring. A benzopyrromethene metal chelate compound represented by the following general formula (2):

[0008]

Embedded image [Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ have the same meaning as in the general formula (1), and M represents nickel, cobalt, iron , Ruthenium, rhodium, palladium, copper, osmium, iridium, platinum, manganese or zinc. ]

A benzopyrromethene metal chelate compound represented by the following general formula (3):

[0010]

Embedded image

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ ,
R ₇ , R ₈ and R ₉ have the same meaning as in the above formula (1), and R ₁₀ and R ₁₁ each independently represent a halogen atom,
To 20 alkyl groups, aralkyl groups, aryl groups, heteroaryl groups, or alkoxy groups. ]

An optical recording medium having at least a recording layer and a reflective layer on a substrate, wherein the recording layer contains the benzopyrromethene metal chelate compound according to any of the above, and a wavelength of 520 to 690 nm. The present invention relates to an optical recording medium described in which recording and reproduction can be performed with respect to a selected laser beam.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Specific examples of a benzopyrromethene metal chelate compound of a benzopyrromethene compound represented by the general formula (1) and a metal ion contained in the recording layer of the present invention will be described below.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And R ₉ are, for example, a hydrogen atom; a nitro group; a cyano group; a hydroxy group; an amino group; a carboxyl group; a sulfone group; a halogen atom of fluorine, chlorine, bromine or iodine; 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-triethylpentyl group, 2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, 4-ethyloctyl Group, 4-ethyl-4,5-dimethylhexyl group, n-undecyl group, n-dodecyl group,
1,3,5,7-tetramethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, n-tridecyl group, 6-methyl-4-butyloctyl group, 6,6-
Diethyloctyl 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-cyc
a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms such as a lo-hexyl-2,2-dimethylpropyl group;

Halogenoalkyl groups such as chloromethyl group, dichloromethyl group, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group and nonafluorobutyl group; methoxyethyl group, ethoxyethyl group, iso-propyloxyethyl group; 3-methoxypropyl group, 2-
Alkoxyalkyl groups such as methoxybutyl 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, is
alkoxy groups such as o-pentoxy group, neo-pentoxy group, n-hexyloxy group, n-dodecyloxy group;
Methoxyethoxy group, ethoxyethoxy group, 3- (is
an alkoxyalkoxy group such as an o-propyloxy) propyloxy group; a phenoxy group, a 2-methylphenoxy group, a 4-methylphenoxy group, a 4-t-butylphenoxy group, a 2-methoxyphenoxy group, a 4-iso-propylphenoxy group Aryloxy group such as 2-dimethylaminoethoxy group and 2- (2-dimethylaminoethoxy)
Ethoxy group, 4-dimethylaminobutoxy group, 1-dimethylaminopropan-2-yloxy group, 3-dimethylaminopropoxy group, 2-dimethylamino-2-methylpropoxy group, 2-diethylaminoethoxy group, 2-
(2-diethylaminoethoxy) ethoxy, 3-diethylaminopropoxy, 1-diethylaminopropoxy, 2-di-iso-propylaminoethoxy, 2
A linear or branched dialkylaminoalkoxy group such as -di-n-butylaminoaminoethoxy group;

2-methylthioethoxy group, 2-ethylthioethoxy group, 2-n-propylthioethoxy group, 2-
alkylthioalkoxy groups such as iso-propylthioethoxy group, 2-n-butylthioethoxy group and 2-iso-butylthioethoxy group; formyl group, acetyl group, ethylcarbonyl group, n-propylcarbonyl group, iso
-Propylcarbonyl group, n-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; a methylaminocarbonyl group, an ethylaminocarbonyl group,
alkylaminocarbonyl groups such as n-propylaminocarbonyl group, n-butylaminocarbonyl group and n-hexylaminocarbonyl group; aryl groups such as phenylcarbonylamino group, 4-ethylphenylcarbonylamino group and 3-butylphenylcarbonylamino group Carbonylamino group; dimethylaminocarbonyl group, diethylaminocarbonyl group, di-n-propylaminocarbonyl group, di-n-butylaminocarbonyl group, N-methyl-
A dialkylaminocarbonyl group such as an N-cyclohexylaminocarbonyl group;

Alkylcarbonylamino groups such as acetylamino group, ethylcarbonylamino group and butylcarbonylamino group; phenylaminocarbonyl group, 4-methylphenylaminocarbonyl group, 2-methoxyphenylaminocarbonyl group and 4-n-propylphenyl An arylaminocarbonyl group such as an aminocarbonyl group; a phenoxycarbonyl group, a 2-methylphenoxycarbonyl group,
Aryloxycarbonyl groups such as 4-methoxyphenylcarbonyl group and 4-t-butylphenoxycarbonyl group; benzyl group, nitrobenzyl group, cyanobenzyl group, hydroxybenzyl group, methylbenzyl group, trimethylbenzyl group, dichlorobenzyl group, methoxy Benzyl group, ethoxybenzyl group, trifluorobenzyl group,
Aralkyl groups such as naphthylmethyl group, nitronaphthylmethyl group, cyanonaphthylmethyl group, trifluoromethylnaphthylmethyl group;

Phenyl, nitrophenyl, cyanophenyl, hydroxyphenyl, methylphenyl,
Dimethylphenyl, trimethylphenyl, dichlorophenyl, methoxyphenyl, ethoxyphenyl, trifluoromethylphenyl, N, N-dimethylaminophenyl, naphthyl, nitronaphthyl, cyanonaphthyl, hydroxynaphthyl, methyl Aryl groups such as naphthyl group and trifluoromethylnaphthyl group;
Pyrrolyl group, thienyl group, furanyl group, oxazoyl group, isoxazoyl group, oxadiazoyl group, imidazoyl group, benzoxazoyl group, benzothiazoyl group, imidazoyl group, benzooxazoyl group, benzothiazoyl group, benzimidazoyl group, benzofuranyl Groups, heteroaryl groups such as an indolyl 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 An alkylthio group such as an iso-pentylthio group, a 2-methylbutylthio group, a 1-methylbutylthio group, a neo-pentylthio group, a 1,2-dimethylpropylthio group, a 1,1-dimethylpropylthio group; a phenylthio group, 4-methylphenylthio Group, 2-methoxyphenyl thio group, an arylthio group such as 4-t-butylphenyl thio group;

Alkenyloxycarbonyl groups such as allyloxycarbonyl group and 2-butenoxycarbonyl group; aralkyloxycarbonyl groups such as benzyloxycarbonyl group and phenethyloxycarbonyl group; methoxycarbonylmethoxycarbonyl group and ethoxycarbonylmethoxycarbonyl group; alkoxycarbonylalkoxycarbonyl groups such as n-propoxycarbonylmethoxycarbonyl group and isopropoxycarbonylmethoxycarbonyl group; alkylcarbonylalkoxycarbonyl groups such as methylcarbonylmethoxycarbonyl group and ethylcarbonylmethoxycarbonyl group; hydroxyethylaminocarbonyl group and 2-hydroxy Mono (hydroxyamino) groups such as propylaminocarbonyl group and 3-hydroxypropylaminocarbonyl group; Kill) aminocarbonyl group; di (hydroxyethyl) aminocarbonyl group, di (2-hydroxypropyl) aminocarbonyl group, di (3-hydroxypropyl) di (hydroxyalkyl) aminocarbonyl group such as an amino group;

Mono (alkoxyalkyl) such as methoxymethylaminocarbonyl, methoxyethylaminocarbonyl, ethoxymethylaminocarbonyl, ethoxyethylaminocarbonyl, propoxymethylaminocarbonyl, ethoxyethylaminocarbonyl, propoxyethylaminocarbonyl, etc. ) Aminocarbonyl group; di (alkoxyalkyl) aminocarbonyl group such as di (methoxyethyl) aminocarbonyl group, di (ethoxymethyl) aminocarbonyl group, di (ethoxyethyl) aminocarbonyl group, di (propoxyethyl) aminocarbonyl group A vinyl group, a propenyl group, a 1-butenyl group, an iso-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 2-methyl-1-butenyl group, a 3-methyl-
1-butenyl group, 2-methyl-2-butenyl group, 2,2
Alkenyl having 2 to 20 carbon atoms such as -dicyanovinyl group, 2-cyano-2-methylcarboxylvinyl group, and 2-cyano-2-methylsulfonevinyl group.

Specific examples of R ₁₀ and R ₁₁ include a methyl group, an ethyl group, an n-propyl group, an 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-methyl Pentyl 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,
1,2-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-triethylpentyl group, 2,4-dimethylhexyl group,
2,2,4-trimethylpentyl group, n-nonyl group,
3,5,5-trimethylhexyl group, n-decyl group, 4
-Ethyloctyl group, 4-ethyl-4,5-dimethylhexyl group, n-undecyl group, n-dodecyl group,
3,5,7-tetramethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, n-tridecyl group, 6-methyl-4-butyloctyl group, 6,6-diethyloctyl 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
1 carbon atom such as hexyl-2,2-dimethylpropyl group
-20 linear, branched or cyclic alkyl groups;

Benzyl, nitrobenzyl, cyanobenzyl, hydroxybenzyl, methylbenzyl,
Aralkyl groups such as trimethylbenzyl, dichlorobenzyl, methoxybenzyl, ethoxybenzyl, trifluorobenzyl, naphthylmethyl, nitronaphthylmethyl, cyanonaphthylmethyl, trifluoromethylnaphthylmethyl; phenyl, nitro Phenyl, cyanophenyl, hydroxyphenyl, methylphenyl, dimethylphenyl, trimethylphenyl, dichlorophenyl, methoxyphenyl, ethoxyphenyl, trifluoromethylphenyl, N, N
An aryl group such as a dimethylaminophenyl group, a naphthyl group, a nitronaphthyl group, a cyanonaphthyl group, a hydroxynaphthyl group, a methylnaphthyl group, a trifluoromethylnaphthyl group;

A pyrrolyl group, a thienyl group, a furanyl group, an oxazoyl group, an isoxazoyl group, an oxadiazoyl group, an imidazoyl group, a benzoxazoyl group, a benzothiazoyl group, an imidazoyl group, a benzoxazoyl group;
Heteroaryl groups such as benzothiazoyl group, benzimidazoyl group, benzofuranyl group, indolyl 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, i
Alkoxy groups such as so-pentoxy group, neo-pentoxy group, n-hexyloxy group, n-dodecyloxy group; and halogen atoms of fluorine, chlorine, bromine and iodine.

The metal forming a chelate compound together with the benzopyrromethene compound represented by the general formula (1) is not particularly limited as long as it is generally a metal capable of forming a chelate compound with the benzopyrromethene compound. Cobalt, iron, ruthenium, rhodium,
Transition elements such as palladium, copper, osmium, iridium, platinum, manganese or zinc, and boron atoms are preferred.

The benzopyrromethene metal chelate compound of the present invention represented by the general formula (1) and a metal ion can be easily produced as follows. That is, typically, first, a compound represented by the general formula (4) and a compound represented by the general formula (5) or a compound represented by the general formula (6) in the presence of an acid catalyst such as hydrobromic acid or hydrogen chloride. ) Is reacted with a compound represented by the general formula (7) to produce a benzopyrromethene compound represented by the general formula (1). And the general formula (2)
In order to produce the benzopyrromethene metal chelate compound represented by the formula, nickel, cobalt, iron, ruthenium, rhodium, palladium, copper, osmium, iridium, platinum, manganese are added to the obtained benzopyrromethene compound represented by the general formula (1). , Zinc and other acetates and halides. In order to produce the benzopyrromethene metal chelate compound represented by the general formula (3), the obtained benzopyrromethene compound represented by the general formula (1) is reacted with boron trifluoride or boron trichloride. Further, the thus-obtained compound wherein R ₁₀ and R ₁₁ are a halogen atom may be added to alkoxides such as sodium methoxide and potassium ethoxide, sodium phenoxide,
Reaction of phenoxides such as sodium-2-methoxyphenoxide, butylmagnesium bromide, butyllithium, organometallic reagents such as phenylmagnesium bromide, methylmercaptan sodium, thiol salts such as 4-t-butylphenylthiol sodium salt, and the like, The desired compound can be obtained by substituting the halogen atom.

[0026]

Embedded image Wherein R ₁ , R ₂ , R ₃ and R ₄ are the same as above. 〉

[0027]

Embedded image Wherein R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are the same as above. 〉

[0028]

Embedded image Wherein R ₁ , R ₂ and R ₃ are the same as above. 〉

[0029]

Embedded image <In the formula, R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are the same as described above. 〉

Specific examples of the benzopyrromethene metal chelate compound of the benzopyrromethene compound represented by the general formula (1) and a metal ion include compounds having substituents and metals shown in Tables 1 and 2. Table 1
And the substituent shown in Table 2 has shown the substituent of said general formula (2) and (3), respectively.

[0031]

[Table 1]

[0032]

[Table 2]

The specific configuration of the present invention will be described below. 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.

Basically, the material of the substrate may be any material as long as it 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. The recording layer of the present invention has an absorption maximum of 450 nm or more.
It contains a benzopyrromethene metal chelate compound of a benzopyrromethene compound represented by the general formula (1) present at about 630 nm and a metal ion. Among them, 520 nm
It is necessary to have an appropriate optical constant for a recording and reproducing laser wavelength selected from ６690 nm.

The optical constant is represented by a complex refractive index (n + ki) (i represents an imaginary unit). N and k in the expression are coefficients corresponding to the real part n and the imaginary part k. Here, n is a refractive index, and k is an extinction coefficient.

In general, the refractive index and extinction coefficient of an organic dye show a large wavelength dependence. In consideration of this feature, by selecting an organic dye having a preferable optical constant at the target laser wavelength and forming a recording layer, it has a high reflectance, and can be a medium with high sensitivity. it can.

According to the present invention, the optical constant required for the recording layer is such that n is 1.8 or more at the wavelength of the laser light,
And k is 0.04 to 0.40, preferably n
Is 2.0 or more, and k is 0.04 to 0.20. If n is smaller than 1.8, the reflectance and signal modulation required for accurate signal reading cannot be obtained, and k is 0.4.
If the value exceeds 0, not only is the reflectance lowered and a good reproduction signal cannot be obtained, but also the signal is easily changed by 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 the target laser wavelength and forming a recording layer, having a high reflectance, and,
A medium with good sensitivity can be obtained. The benzopyrromethene metal chelate compound of the benzopyrromethene compound represented by the general formula (1) and a metal ion used in the present invention is:
All have the above preferred optical constants.

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.

In order to improve the recording characteristics and the like, the wavelength 4
It has an absorption maximum at 50 nm to 630 nm, and
It may be mixed with other dyes having a large refractive index at 690 nm. Specifically, cyanine dyes, squarylium dyes, naphthoquinone dyes, anthraquinone dyes, porphyrin dyes, tetrapyraporphyrazine dyes, indophenol dyes, pyrylium dyes, thiopyrylium dyes, azurenium dyes, tri There are phenylmethane dyes, xanthene dyes, indazulene dyes, indigo dyes, thioindigo dyes, merocyanine dyes, thiazine dyes, acridine dyes, oxazine dyes, etc. good. The mixing ratio of these dyes is about 0.1% to 30%.

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 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,
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 benzopyrromethene metal chelate compound of the benzopyrromethene compound represented by the general formula (1) and the metal ion in the recording layer is at least 30%, preferably at least 60%. In addition, substantially 100
% Is also preferable.

The method for providing the recording layer includes, for example, 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. Is preferred.

When a coating method such as a spin coating method is used, 1 to 40% by weight, preferably 3 to 30% by weight of a benzopyrromethene metal chelate compound of a benzopyrromethene compound represented by the general formula (1) and a metal ion is used. 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, methanol, ethanol,
Alcohol solvents such as isopropyl alcohol, octafluoropentanol, allyl alcohol, methyl cellosolve, ethyl cellosolve, and tetrafluoropropanol; aliphatics and fats such as hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, ethylcyclohexane, and dimethylcyclohexane Cyclic hydrocarbon solvents, toluene, xylene, aromatic hydrocarbon solvents such as benzene, carbon tetrachloride, chloroform,
Halogenated hydrocarbon solvents such as tetrachloroethane and dibromoethane, ether solvents such as diethyl ether, dibutyl ether, diisopropyl ether and dioxane; ketone solvents such as acetone and 3-hydroxy-3-methyl-2-butanone; acetic acid Examples include ester solvents such as ethyl and methyl lactate, and water. These may be used alone or in combination.

If necessary, the dye for the recording layer may be dispersed 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 50 nm
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 for 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. Of these, 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 surface of the reflective layer, or bonding two optical recording media with the surfaces of the reflective layers facing each other such that they face 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.

[0061]

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

Example 1 Synthesis of Benzopyrromethene Metal Chelate Compound (2-1) Under a nitrogen stream, 4.99 g of 2-benzoyl-3-phenylindole and 2,4-dimethyl-3-ethylpyrrole in 210 mL of methylene chloride. After dissolving 2.5 g of phosphorus oxychloride dropwise, the mixture was stirred at reflux temperature for 22 hours. After cooling to room temperature, discharge into 2 L of n-hexane and filter. The filtrate is concentrated to give the following structural formula (1-a)
3.38 g of the compound represented by were obtained.

[0063]

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Next, the formula (1-
3.38 g of the compound represented by a) was dissolved, 25.56 g of sodium acetate and 9.95 g of zinc (II) acetylacetonate monohydrate were added, and the mixture was stirred at the reflux temperature for 2 hours and 30 minutes. After concentration, extraction with toluene, washing with water, toluene was distilled off, and the residue was purified by alumina chromatography (chloroform) to obtain 61 mg of a compound represented by the following structural formula (2-1).

[0065]

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

[0067]

[Table 3]

The compound thus obtained exhibits a maximum absorption at 506.0 nm in a chloroform solution, and has a gram extinction coefficient of 1.411 × 10 ⁵ mL / g · c.
m.

Example 2 Synthesis of Benzopyrromethene Metal Chelate Compound (3-1) Under a nitrogen stream, 4.99 g of 2-benzoyl-3-phenylindole and 2,4-dimethyl-3-ethylpyrrole were placed in 210 mL of methylene chloride. After dissolving 2.5 g of phosphorus oxychloride dropwise, the mixture was stirred at reflux temperature for 22 hours. After cooling to room temperature, 8.86 g of N, N-diisopropylethylamine and 9.73 g of boron trifluoride diethyl ether complex were added, and the mixture was stirred at room temperature for 2 hours. After concentration, extraction with toluene, washing with water, distilling off toluene, crystallization with methanol, and the following structural formula (3-
0.77 g of the compound represented by 1) was obtained.

[0070]

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

[0072]

[Table 4]

The compound thus obtained exhibits a maximum absorption at 523.0 nm in a chloroform solution, and has a gram extinction coefficient of 0.915 × 10 ⁵ mL / g · c.
m.

Example 3 Synthesis of Benzopyrromethene Metal Chelate Compound (3-2) Under nitrogen stream, 140 mL of methylene chloride was added to 2-acetyl-
After 4.00 g of 3-methylindole and 6.95 g of 1- (4-methylphenyl) isoindole were dissolved, and 5.51 g of phosphorus oxychloride was added dropwise, the mixture was stirred at reflux temperature for 2 hours. After concentration, the residue was washed with 400 mL of n-heptane, 500 mL of toluene, 16.95 g of N, N-diisopropylethylamine and 17.74 g of boron trifluoride diethyl ether complex were added, and the mixture was stirred at room temperature for 1 hour and 30 minutes. After washing with water, toluene was distilled off, and the residue was purified by column chromatography (silica gel / toluene) to obtain 1.91 g of a compound represented by the following structural formula (3-2).

[0075]

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

[0077]

[Table 5]

The compound thus obtained showed a maximum absorption at 564.0 nm in a toluene solution.

Example 4 Synthesis of Benzopyrromethene Metal Chelate Compound (3-3) Under a nitrogen stream, 0.77 g of magnesium for Grignard reagent and 7.52 g of 4-n-hexylbromobenzene were added to 25 mL of tetrahydrofuran, and the Grignard reagent was added. Was prepared. There, the formula (3-
After adding 1.60 g of the compound represented by 2), the mixture was stirred at room temperature for 1 hour. Discharged in 200 mL of 2% hydrochloric acid, extracted with toluene, washed with water, distilled off toluene and purified by column chromatography (silica gel / toluene: hexane) to give a compound represented by the following structural formula (3-3) 1.
51 g were obtained.

[0080]

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From the following analysis results, the product was confirmed to be the target product.

[0082]

[Table 6]

The compound thus obtained exhibited a maximum absorption at 555.0 nm in a toluene solution, and had a gram extinction coefficient of 0.564 × 10 ⁵ mL / g · cm.

Example 5 0.2 g of the benzopyrromethene metal chelate compound (3-2) obtained in Example 3 was dissolved in 10 ml of dimethylcyclohexane to prepare a dye solution. The substrate is made of polycarbonate resin and has a continuous guide groove (track pitch: 0.8 μm) and a diameter of 1 μm.
A disc having a thickness of 20 mm and a thickness of 0.6 mm was used.

The dye solution was placed on the substrate at a rotational speed of 1500 r.
pm, and dried at 70 ° C for 3 hours to form a recording layer.

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 1.0 × 10 ⁻² Torr.
I went in.

Further, an ultraviolet-curable adhesive SD is applied on the reflective layer.
-301 (manufactured by Dainippon Ink and Chemicals) is spin-coated, and a polycarbonate resin having a diameter of 120 m is coated thereon.
After placing a disc-shaped substrate having a thickness of 0.6 mm and a thickness of 0.6 mm, the substrate was laminated by irradiating ultraviolet rays to produce an optical recording medium.

An optical disc evaluation device (DDU- manufactured by Pulstec Industrial Co., Ltd.) equipped with a semiconductor laser head having a wavelength of 635 nm and a lens numerical aperture of 0.6 on the obtained optical recording medium.
1000) and KENWOOD EFM encoder, linear velocity 3.8 m / s, laser power 10 mW
The recording was performed so that the shortest pit length was 0.40 μm.
After recording, the signal was reproduced using an evaluation device equipped with a 650 nm and 635 nm red semiconductor laser head (the numerical aperture of the lens was 0.6), and the reflectance, jitter and modulation were measured. 50%, jitter of 9.4%, modulation of 0.67, and reproduction at 635 nm showed excellent values of 49% for reflectance, 9.5% for jitter, and 0.66 for modulation. No change was observed even after the light resistance test with a carbon arc for 100 hours and the heat and humidity resistance test at 80 ° C. and 85%.

Examples 6 to 15 Optical recording media were prepared and recorded in the same manner as in Example 5, except that the benzopyrromethene metal chelate compounds described in Tables 1 and 2 were used. After recording, the signal was reproduced using an evaluation device equipped with 650 nm and 635 nm red semiconductor laser heads, and the reflectance, the jitter and the modulation were measured. No change was observed even after the light resistance test with a carbon arc for 100 hours and the heat and humidity resistance test at 80 ° C. and 85%.

In the above Examples 5 to 15, each optical recording medium was recorded at 635 nm, and was recorded at 650 and 635 nm.
Table 3 summarizes the reflectivity, jitter, and modulation factor when the data was reproduced by the above-mentioned method. The maximum absorption was measured in a state where the recording layer was formed.

Comparative Example 1 In Example 5, the benzopyrromethene metal chelate compound (3-2) and 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 Co., Ltd. A recording medium was produced. An optical disk evaluation device (DDU-1000) manufactured by Pulstec Industrial having a 635 nm semiconductor laser head mounted on the manufactured medium in the same manner as in Example 5, and an EFM manufactured by KENWOOD
Recording was performed at a linear velocity of 3.8 m / s and a laser power of 10 mW using an encoder. After recording, the signal was reproduced using an evaluation device equipped with 650 nm and 635 nm red semiconductor laser heads, and the reflectance, jitter, and modulation were measured. As a result, the reflectance was 9%, the jitter was 20% or more, and the modulation was 650 nm. The reflectivity was 9%, the jitter was 20% or more, and the modulation factor was 0.15 at 0.13 and 635 nm reproduction. Also, after the light fastness test with a carbon arc for 100 hours, the signal deteriorated and could not be reproduced.

[0092]

[Table 7]

[0093]

[Table 8]

[0094]

By using the benzopyrromethene metal chelate compound of the present invention as a recording layer, wavelengths of 520 to 690 n, which are attracting much attention as high-density optical recording media, can be obtained.
It is possible to provide a write-once optical recording medium that can be recorded and reproduced with a laser of m and has excellent durability.

[Brief description of the drawings]

FIG. 1 is a cross-sectional structural view showing a layer configuration of an optical recording medium of the related art and the present invention.

[Explanation of symbols]

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

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yojiro Kumagai 1-43, Yuge-cho Minami, Yao-shi, Osaka Yamamoto Kasei Co., Ltd. (72) Inventor Denmi Misawa 1190 Kasama-cho, Sakae-ku, Kanagawa Mitsui Chemicals, Inc. (72) Inventor Taizo Nishimoto 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Chemical Co., Ltd. (72) Inventor U. Tsukahara 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Inside Mitsui Chemicals, Inc.

Claims (5)

[Claims] 1. A benzopyrromethene metal chelate compound of a benzopyrromethene compound represented by the following general formula (1) and a metal ion. Embedded image [Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ each independently represent a hydrogen atom, a halogen atom, a nitro group,
Cyano group, hydroxy group, amino group, carboxyl group,
Sulfonic acid group, alkyl group having 1 to 20 carbon atoms, halogenoalkyl group, alkoxyalkyl group, alkoxy group, alkoxyalkoxy group, aryloxy group, dialkylaminoalkoxy group, alkylthioalkoxy group, acyl group, alkoxycarbonyl group, alkylamino Carbonyl group, dialkylaminocarbonyl group, alkylcarbonylamino group, arylcarbonylamino group, arylaminocarbonyl group, aryloxycarbonyl group,
Aralkyl, aryl, heteroaryl, alkylthio, arylthio, alkenyloxycarbonyl, aralkyloxycarbonyl, alkoxycarbonylalkoxycarbonyl, alkylcarbonylalkoxycarbonyl, mono (hydroxyalkyl) aminocarbonyl, di (hydroxy Represents an alkyl) aminocarbonyl group, a mono (alkoxyalkyl) aminocarbonyl group, a di (alkoxyalkyl) aminocarbonyl group, or an alkenyl group having 2 to 20 carbon atoms. Where R
₂ and R ₃ may combine to form an aromatic ring. ] 2. The benzopyrromethene metal chelate compound according to claim 1, represented by the following general formula (2). Embedded image [Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ have the same meaning as in the above general formula (1), and M is nickel, cobalt, iron , Ruthenium, rhodium, palladium, copper, osmium, iridium, platinum, manganese or zinc. ] 3. A benzopyrromethene metal chelate compound represented by the following general formula (3). Embedded image [Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ have the same meaning as in the general formula (1), and R ₁₀ and R
₁₁ is each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group, an aryl group, a heteroaryl group,
Or an alkoxy group. ] 4. An optical recording medium having at least a recording layer and a reflective layer on a substrate, wherein the recording layer comprises
An optical recording medium containing the benzopyrromethene metal chelate compound according to any one of the above. 5. The optical recording medium according to claim 4, wherein recording and reproduction can be performed with respect to a laser beam selected from a wavelength range of 520 to 690 nm.