JPH1143491A - Pyrromethene metallic chelate compound and optical recording medium using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound, comprising a specific pyrromethene metal chelate compound, capable of carrying out good high-density recording and reproducing with a laser at a wavelength within a specific range and usable in a recording layer of a write once type optical recording medium such as a compact disk. SOLUTION: This new pyrromethane type metallic chelate compound is represented by formula I (R1 to R7 are each H, a halogen, nitro, cyano, OH, amino, carboxyl, sulfonic acid, a 1-20C alkyl, an alkoxy, an aryl, a heteroaryl, a 2-20C alkenyl, etc.; X1 an X2 are each a 1-20C alkyl, a halogenoalkyl, an alkoxy, an alkylthio, an aryloxy, an arylthio, a heteroaryl or a halogen, with the proviso that X1 and X2 are not simultaneously the halogen) and is useful for an optical recording medium, etc., capable of carrying out the high-density recording and reproducing with a laser at a wavelength within the range of 520-690 nm. The compound is obtained by reacting pyrrole derivatives represented by formulae II and III in the presence of an acidic catalyst, then reacting the resultant compound with a boron trihalide and further reacting the obtained compound with a metallic alkoxide, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel pyrromethene 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 As a recordable optical recording medium conforming to the compact disk (hereinafter abbreviated as CD) standard, a CD-R is used.
(CD-Recordable) [for example, Nikkei Electronics No. 465
P. 107, January 23, 1989, OPTICAL DA
TA STORAGE DIGEST SERIES vol.1 P45, 1989 etc.]. In this CD-R, a recording layer 2, a reflective layer 3, and a protective layer 4 are laminated in this order on a transparent resin substrate 1 as shown in FIG.
By irradiating the recording layer with a high-power laser beam, the recording layer undergoes a physical or chemical change to record information in the form of pits. By irradiating a low-power laser beam to the formed pit portion and detecting a change in reflectance, pit information can be reproduced. For recording / reproducing such an optical recording medium, a wavelength of 770 to 83 is generally used.
Since it uses a near-infrared semiconductor laser of 0 nm and conforms to CD standards such as Red Book and Orange Book, it has the feature of being compatible with CD players and CD-ROM players.

However, the recording capacity of the above-mentioned conventional medium is 6
The capacity is about 50 MB, which is not sufficient when recording moving images, and the demand for higher density and larger capacity of information recording media is increasing with the dramatic increase in the amount of information.

Further, development of short-wavelength semiconductor lasers used for optical disk systems has been advanced, and wavelengths of 680 nm and 6 nm have been developed.
Red semiconductor lasers of 50 nm and 635 nm have been put into practical use [for example, Nikkei Electronics, No.
592, p. 65, October 11, 1993]. By shortening the wavelength of the recording / reproducing laser and increasing the numerical aperture of the objective lens, the beam spot can be reduced, and a high-density optical recording medium can be realized. In fact, a large-capacity optical recording medium capable of recording a moving image for a long time has been developed by shortening the wavelength of a semiconductor laser, increasing the numerical aperture of an objective lens, and using data compression technology [for example, Nikkei Electronics, No. 589, p. 55, August 30, 1993, No. 594, p. 169, 1993 11
8th issue]. Recently, a digital video disk (DVD) in which a moving image of two hours or more is digitally recorded has been developed. The DVD is a read-only medium having a recording capacity of 4.7 GB, and there is a further demand for the development of a recordable optical disc suitable for this capacity.

[0005] Further, a laser of 532 nm by harmonic conversion of a YAG laser has been practically used.

490 nm, a wavelength shorter than 532 nm
Blue / green semiconductor lasers have been studied, but have not yet reached the stage of practical use [for example, Applied
Physics Letter, P.C. 1272-12
74, Vol. 59 (1991) and “Nikkei Electronics” No. 552, p. 90, April 27, 1992].

When a short-wavelength laser is used, the linear recording density and the radial recording density of an optical disk can theoretically be increased to the same level, but at present, the recording density in the radial direction must be as large as the linear recording density. It is difficult. Since the laser beam is diffracted and scattered by the groove or the land, the signal detection light amount decreases as the track pitch decreases. Also, there is a molding limitation in reducing the track pitch while maintaining the depth at which a sufficient tracking signal can be obtained. If the groove is deep and narrow, it is difficult to form the recording layer uniformly. Furthermore, the edges of the grooves and lands are not smooth but have minute irregularities, which cause noise. Such an adverse effect occurs rapidly when the track pitch becomes narrow to some extent. Considering these, the wavelength 520n
At m and the numerical aperture of the objective lens is 0.6, the limit of the groove pitch is considered to be about 0.5 μm.

When pits are formed by irradiating a dye layer of a write-once optical recording medium with a laser beam to cause a physical change or a chemical change, it is important to determine whether pits having good optical constants and decomposition behavior of the dye can be formed. Element. Those that are difficult to decompose have reduced sensitivity, and those that decompose violently or are subject to change have a large effect on pits and lands in the radial direction, making reliable pit formation difficult. In a conventional CD-R medium, the refractive index of the dye layer is low and the extinction coefficient is not an appropriate value at a laser wavelength used at a high density, so that the reflectance is low and the modulation degree cannot be sufficiently obtained.
Furthermore, where a small pit should be opened with a narrowed beam, the influence on the surroundings is large and the pit has a large distribution, and crosstalk in the radial direction is deteriorated. Conversely, the pits became extremely small, and a sufficient degree of modulation could not be obtained. Therefore, the optical properties of the dye used in the recording layer,
It is necessary to select an appropriate decomposition behavior.

For example, Japanese Patent Application Laid-Open No. 6-199045 proposes an optical recording medium that can record and reproduce information with a semiconductor laser having a wavelength of 680 nm. Although this medium uses a cyanine dye in the recording layer and shows the possibility of high-density recording / reproduction, there is no description of actually recording at high density.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel pyromethene metal chelate compound and a high-density recording medium containing the same, which can be recorded and reproduced with a short wavelength laser having a wavelength of 520 to 690 nm. An optical recording medium is provided.

[0011]

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 pyrromethene metal chelate compound represented by the following general formula (I).

[0012]

Embedded image [Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and 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, 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, alkylaminocarbonyl group, dialkylaminocarbonyl group, alkylcarbonylamino group, arylcarbonylamino group, arylaminocarbonyl group, aryloxycarbonyl group, aralkyl group, aryl group, heteroaryl group, Alkylthio, arylthio, alkenyloxycarbonyl, aralkyloxycarbonyl, alkoxycarbonylalkoxycarbonyl, alkylcarbonylalkoxycarbonyl, mono (hydroxyalkyl) aminocarbonyl, di (hydroxyalkyl) aminocarbonyl, mono ( X ₁ and X ₂ represent an (alkoxyalkyl) aminocarbonyl group, a di (alkoxyalkyl) aminocarbonyl group or an alkenyl group having 2 to 20 carbon atoms.
Is an alkyl group having 1 to 20 carbon atoms, a halogenoalkyl group, an alkoxyalkyl group, an alkylthioalkyl group,
Dialkylaminoalkyl group, alkoxy group, alkoxyalkoxyalkoxy group, alkylthioalkoxy group, dialkylaminoalkoxy group, dialkylaminoalkoxyalkoxy group, alkylthio group, alkoxyalkylthio group, alkylthioalkylthio group, dialkylaminoalkylthio group, aryloxy group, aryl −
A ruthio group, a heteroaryl group, a heteroaryloxy group, a heteroarylthio group and a halogen atom. However, X ₁ and X ₂ are not simultaneously halogen atoms. ]

In an optical recording medium having at least a recording layer and a reflective layer on a substrate, an optical recording medium containing the pyromethene metal chelate compound described in the recording layer, a laser selected from the wavelength range of 520 to 690 nm An optical recording medium described in which recording and reproduction are possible with respect to light, a light described in which 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 present invention relates to the optical recording medium according to any one of-, wherein the recording medium has a reflectance of 20% or more measured from the substrate side with respect to a laser beam selected from the wavelength range of 520 to 690 nm.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION In the pyrromethene metal chelate compound represented by the general formula (I) of the present invention, R ₁ , R ₂ , R
_3, R _4, R _5, specific examples of R ₆ and R ₇ is a hydrogen atom; a nitro group; a cyano group; a hydroxy group; an amino group; a carboxyl group; a sulfonic group; fluorine, chlorine, bromine, halogen iodine Atoms: methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-
Butyl, tert-butyl, n-pentyl, iso-pentyl, 2-methylbutyl, 1-methylbutyl, neo-pentyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, cyclo -Pentyl, n-hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-
Methylpentyl, 3,3-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 1,2-dimethylbutyl, 1,1-dimethylbutyl Group,
3-ethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, 1,2,2-trimethylbutyl group, 1,1,2-trimethylbutyl 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-pentadecyl group, 3,5-dimethylheptyl group, 2,6-dimethylheptyl group, 2,4-dimethylheptyl group, 2,2,5,5 -A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms such as -tetramethylhexyl group, 1-cyclo-pentyl-2,2-dimethylpropyl group, 1-cyclo-hexyl-2,2-dimethylpropyl group ;
Chloromethyl group, dichloromethyl group, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group,
A halogenoalkyl group such as a nonafluorobutyl group; an alkoxyalkyl group such as a methoxyethyl group, an ethoxyethyl group, an iso-propyloxyethyl group, a 3-methoxypropyl group, a 2-methoxybutyl group;

Methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, t-butoxy, n-pentoxy,
Alkoxy groups such as iso-pentoxy group, neo-pentoxy group, n-hexyloxy group, n-dodecyloxy group; alkoxyalkoxy groups such as methoxyethoxy group, ethoxyethoxy group, 3- (iso-propyloxy) propyloxy group An aryloxy group such as 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; a 2-dimethylaminoethoxy group; 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 group, 3-diethylaminopropoxy group, 1-diethylaminopropoxy group, 2-
Linear or branched dialkylaminoalkoxy groups such as di-iso-propylaminoethoxy group, 2-di-n-butylaminoaminoethoxy group; 2-methylthioethoxy group, 2-ethylthioethoxy group, 2-n-propyl Thioethoxy group, 2-iso-propylthioethoxy group, 2-n-butylthioethoxy group, 2-
alkylthioalkoxy groups such as iso-butylthioethoxy group;

Formyl group, acetyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, n-pentylcarbonyl group, iso-pentylcarbonyl group, neo-pentylcarbonyl group, 2 Acyl groups such as -methylbutylcarbonyl group and nitrobenzylcarbonyl group; methoxycarbonyl group, ethoxycarbonyl group, isopropyloxycarbonyl group,
Alkoxycarbonyl groups such as 2,4-dimethylbutyloxycarbonyl group; alkylaminocarbonyl groups such as methylaminocarbonyl group, ethylaminocarbonyl group, n-propylaminocarbonyl group, n-butylaminocarbonyl group and n-hexylaminocarbonyl group Dimethylaminocarbonyl group, diethylaminocarbonyl group, di-n-propylaminocarbonyl group, di-n-butylaminocarbonyl group, dialkylaminocarbonyl group such as N-methyl-N-cyclohexylaminocarbonyl group; acetylamino group, Alkylcarbonylamino groups such as ethylcarbonylamino group and butylcarbonylamino group; phenylaminocarbonyl group, 4-methylphenylaminocarbonyl group,
Arylaminocarbonyl groups such as 2-methoxyphenylaminocarbonyl group and 4-n-propylphenylaminocarbonyl group; arylcarbonyl groups such as phenylcarbonylamino group, 4-ethylphenylcarbonylamino group and 3-butylphenylcarbonylamino group An amino group; an aryloxycarbonyl group such as a phenoxycarbonyl group, a 2-methylphenoxycarbonyl group, a 4-methoxyphenoxycarbonyl group, or a 4-t-butylphenoxycarbonyl group;

Benzyl, nitrobenzyl, cyanobenzyl, hydroxybenzyl, methylbenzyl,
Aralkyl groups such as dimethylbenzyl, trimethylbenzyl, dichlorobenzyl, methoxybenzyl, ethoxybenzyl, trifluorobenzyl, naphthylmethyl, nitronaphthylmethyl, cyanonaphthylmethyl, trifluoromethylnaphthylmethyl; Phenyl, nitrophenyl, cyanophenyl, hydroxyphenyl, methylphenyl, dimethylphenyl, trimethylphenyl, dichlorophenyl, methoxyphenyl, ethoxyphenyl, trifluoromethylphenyl, N, N-dimethylamino Aryl groups such as phenyl, naphthyl, nitronaphthyl, cyanonaphthyl, hydroxynaphthyl, methylnaphthyl, trifluoromethylnaphthyl; pyrrolyl, thienyl, furanyl, oxa Heteroaryl groups such as zoyl group, isoxazoyl group, oxadiazoyl group, imidazoyl group, benzoxazoyl group, benzothiazoyl group, benzimidazoyl group, benzofuranyl group and indoyl group;

Methylthio, ethylthio, n-propylthio, iso-propylthio, n-butylthio, iso-butylthio, sec-butylthio, t-butylthio, n-pentylthio, iso-pentylthio, 2 -Methylbutylthio group, 1-methylbutylthio group, neo-pentylthio group, 1,
Alkylthio groups such as 2-dimethylpropylthio group and 1,1-dimethylpropylthio group; arylthio groups such as phenylthio group, 4-methylphenylthio group, 2-methoxyphenylthio group and 4-t-butylphenylthio group Alkenyloxycarbonyl groups such as allyloxycarbonyl group and 2-butenoxycarbonyl group; aralkyloxycarbonyl groups such as benzyloxycarbonyl group and phenethyloxycarbonyl group; methoxycarbonylmethoxycarbonyl group, ethoxycarbonylmethoxycarbonyl group, n -Alkoxycarbonylalkoxycarbonyl groups such as -propoxycarbonylmethoxycarbonyl group and isopropoxycarbonylmethoxycarbonyl group; alkylcarbonylalkoxy groups such as methylcarbonylmethoxycarbonyl group and ethylcarbonylmethoxycarbonyl group Alkoxycarbonyl group;

Hydroxyethylaminocarbonyl group, 2-
Mono (hydroxyalkyl) aminocarbonyl groups such as hydroxypropylaminocarbonyl group and 3-hydroxypropylaminocarbonyl group; di (hydroxyethyl) aminocarbonyl group, di (2-hydroxypropyl) aminocarbonyl group, di (3-hydroxypropyl ) Di (hydroxyalkyl) aminocarbonyl groups such as aminocarbonyl group; mono (alkoxyalkyl groups such as methoxymethylaminocarbonyl group, methoxyethylaminocarbonyl group, ethoxymethylaminocarbonyl group, ethoxyethylaminocarbonyl group, propoxyethylaminocarbonyl group, etc. ) Aminocarbonyl group; di (methoxyethyl) aminocarbonyl group, di (ethoxymethyl) aminocarbonyl group, di (ethoxyethyl) aminocarbonyl group, di (propoxyethyl) Di (alkoxyalkyl) aminocarbonyl group such as minocarbonyl group; vinyl group, propenyl group, 1-butenyl group, iso-butenyl group, 1-pentenyl group, 2-pentenyl group, 2-methyl-1-butenyl group, 3 Alkenyl groups such as -methyl-1-butenyl group, 2-methyl-2-butenyl group, 2,2-dicyanovinyl group, 2-cyano-2-methylcarboxylvinyl group, and 2-cyano-2-methylsulfonevinyl group And the like.

Specific examples of X ₁ and X ₂ include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group,
iso-butyl group, sec-butyl group, tert-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-dimethylbutyl group, 3-ethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, 1,2,2-trimethylbutyl group,
1,1,2-trimethylbutyl 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-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-hexyl-2,2-dimethylpropyl group, etc. 20 linear, branched or cyclic alkyl groups;

Halogenoalkyl groups such as chloromethyl group, dichloromethyl group, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group and nonafluorobutyl group; methoxyethyl group, ethoxyethyl group, iso-propyloxyethyl group; Alkoxyalkyl groups such as 3-methoxypropyl group and 2-methoxybutyl group; 2-methylthioethyl group, 2-ethylthioethyl group, 2-n-propylthioethyl group, 2-iso-propylthioethyl group, 2- alkylthioalkyl groups such as n-butylthioethyl group and 2-iso-butylthioethyl group; 2-dimethylaminoethyl group, 2- (2-dimethylaminoethoxy) ethyl group, 4-dimethylaminobutyl group, 1
-Dimethylaminopropan-2-yl group, 3-dimethylaminopropyl group, 2-di-iso-propylaminoethyl group, 2-di-
a linear or branched dialkylaminoalkyl group such as an n-butylaminoethyl group;

Methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, t-butoxy, n-pentoxy,
iso-pentoxy group, neo-pentoxy group, n-hexyloxy group, n-dodecyloxy group, cyclohexyloxy group,
4-methylcyclohexyloxy group, 4-ethylcyclohexyloxy group, 2-n-propylcyclohexyloxy group,
4-t-butylcyclohexyloxy group, adamantane-1-
Alkoxy groups such as yloxy group and borneol group; 2-methoxyethoxy group, 1-methoxybutan-2-yloxy group, 1
-Methoxybutan-1-yloxy group, 1-methoxypropane
2-yloxy group, 2- (2-methoxyethoxy) ethoxy group, 2-ethoxyethoxy group, 2- (ethoxyethoxy) ethoxy group, 2-ethoxypropan-2-yloxy group, 2-iso-
Propoxyethoxy group, 2-butoxyethoxy group, 2-iso-
Butoxyethoxy group, 2-t-butoxyethoxy group, 2- (2-
Butoxyethoxy) a straight-chain or branched alkoxyalkoxy group such as an ethoxy group; 2-methylthioethoxy group, 2-ethylthioethoxy group, 2-n-propylthioethoxy group, 2-is
alkylthioalkoxy groups such as o-propylthioethoxy group, 2-n-butylthioethoxy group and 2-iso-butylthioethoxy group; 2-dimethylaminoethoxy group, 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 group, 3-diethylaminopropoxy group, 1-diethylaminopropoxy group, 2-
Linear or branched dialkylaminoalkoxy groups such as di-iso-propylaminoethoxy group, 2-di-n-butylaminoaminoethoxy group; phenoxy group, 2-methylphenoxy group, 4-methylphenoxy group, 4-t -Butylphenoxy group,
Aryloxy groups such as 2-methoxyphenoxy group and 4-iso-propylphenoxy group;

Methylthio, ethylthio, n-propylthio, iso-propylthio, n-butylthio, iso-butylthio, sec-butylthio, t-butylthio, n-pentylthio, iso-pentylthio, Alkylthio groups such as 1,2-dimethylpropylthio and 1,1-dimethylpropylthio; phenylthio, 2-methylphenylthio, 4-
Methylphenylthio group, 4-t-butylphenylthio group, 2-
Arylthio groups such as methoxyphenylthio group and 4-t-butylphenylthio group; and halogen atoms of fluorine, chlorine, bromine and iodine.

The pyrromethene metal chelate compound represented by the general formula (I) of the present invention can be easily produced as follows. That is, typically, first, the general formula (I
A compound represented by the formula (I) and a compound represented by the general formula (III), or a compound represented by the general formula (IV) and a compound represented by the general formula (V) are converted into, for example, hydrobromic acid, hydrogen chloride, phosphorus oxychloride Reaction in the presence of an acid catalyst such as
Alternatively, the compound represented by the general formula (VI) is reacted with the compound represented by the formula (II) or (IV). Then, the compound is reacted with boron trifluoride, boron trichloride or the like to synthesize a compound represented by the general formula (VII). Then sodium methoxide,
Alkoxides such as potassium ethoxide, phenoxides such as sodium phenoxide and sodium-2-methoxyphenoxide, organometallic reagents such as butylmagnesium bromide, butyllithium and phenylmagnesium bromide, sodium methylmercaptan, 4-t-butylphenylthio -Reacts with thiol salts such as sodium salt.

[0025]

Embedded image (In the formula, R ₅ , R ₆ and R ₇ are the same as described above.)

[0026]

Embedded image (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are the same as described above.)

[0027]

Embedded image (In the formula, R ₁ , R ₂ and R ₃ are the same as described above.)

[0028]

Embedded image (In the formula, R ₄ , R ₅ , R ₆ and R ₇ are the same as described above.)

[0029]

Embedded image (In the formula, R ₄ is the same as above. X ₃ represents chlorine or bromine.)

[0030]

Embedded image (In the formula, X ₄ and X ₅ represent fluorine, chlorine, bromine, and iodine.)

Specific examples of the pyrromethene metal chelate compound represented by the general formula (I) include compounds having a substituent shown in Table 1.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

[Table 4]

[0036]

[Table 5]

[0037]

[Table 6]

[0038]

[Table 7]

[0039]

[Table 8]

[0040]

[Table 9]

[0041]

[Table 10]

[0042]

[Table 11]

The specific structure of the recording medium 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. This optical recording medium has a four-layer structure in which a substrate, a recording layer, a reflective layer, and a protective layer are sequentially laminated as shown in FIG. 1, or has a laminated structure as shown in FIG. . That is, a recording layer 2 'is formed on a substrate 1', a reflective layer 3 'is provided in close contact with the recording layer 2', and a substrate 5 'is further laminated thereon via an adhesive layer 4'. ing. However, another layer may be provided below or above the recording layer 2 ', or another layer may be provided above the reflective layer.

As a material of the substrate, basically, any material may be used 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 are preferably provided at the time of molding the substrate, but may also be provided on the substrate using an ultraviolet curable resin layer. Normal C
When used as D, the thickness is about 1.2 mm and the diameter is 80
~ 120mm disc with 15mm diameter in the center
There is a hole of about mm.

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 to 630 nm.
It contains a pyromethene metal chelate compound represented by the general formula (I) present nearby. Among them, 520 nm to 69
Optical constant appropriate for the recording and reproducing laser wavelength selected from 0 nm (optical constant is complex refractive index (n + ki)
Is represented by 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, an organic dye is characterized in that the refractive index n and the extinction coefficient k greatly change with respect to the wavelength λ. n is 1.
If the value is less than 8, the reflectance and the signal modulation required for accurate signal reading cannot be obtained. Even if k exceeds 0.40, the reflectance is reduced and not only a good reproduced signal cannot be obtained. However, the signal tends to change due to the reproduction light, which is not suitable for practical use. In consideration of this feature, by selecting an organic dye having a preferable optical constant at a target laser wavelength and forming a recording layer, a medium having high reflectance and high sensitivity can be obtained. .

The compound represented by the general formula (I) of 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. Optical constants required for the recording layer at the wavelength (n is 1.8 or more and k is 0.04 to 0.40, preferably, n is 2.0 or more and k is 0.0
It is a very useful compound that satisfies 4-0.20).

The optical recording medium of the present invention has a thickness of 520 nm to 690.
When reproducing with a laser beam selected from nm, it is basically possible if the reflectance is 20% or more, but a reflectance of 30% or more is preferable.

In order to improve the recording characteristics, etc., it has an absorption maximum at a wavelength of 450 to 630 nm, and has an absorption maximum of 520 to 690 nm.
It may be mixed with other dyes having a large refractive index in nm. Specifically, cyanine dyes, squarylium dyes, naphthoquinone dyes, anthraquinone dyes, porphyrin dyes, tetrapyraporphyrazine dyes, indophenol dyes, pyrylium dyes, thiopyrylium dyes, azurenium dyes, triphenyl There are methane dyes, xanthene dyes, indazulene dyes, indigo dyes, thioindigo dyes, merocyanine dyes, thiazine dyes, acridine dyes, oxazine 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%.

When forming the recording layer, if necessary, a quencher, a dye decomposition accelerator, an ultraviolet absorber, an adhesive, or the like is mixed with the above-mentioned dye, 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, bisphenyldithiol, and other bisdithiols, thiocatechol, salicylaldehyde oxime, and thiobisphenolate. Complexes are preferred. Also, amines are suitable.

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

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

When the recording layer is formed on the substrate, a layer made of an inorganic substance or a polymer may be provided on the substrate in order to improve the solvent resistance, the reflectance, the recording sensitivity and the like of the substrate.
Here, the content of the pyrromethene metal chelate compound represented by the general formula (I) in the recording layer is 30% or more, preferably 60% or more. In addition, it is also preferable that it is substantially 100%.

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

When a coating method such as a spin coating method is used, the pyromethene metal chelate compound represented by the general formula (I) is dissolved in a solvent so as to be 1 to 40% by weight, preferably 3 to 30% by weight. A dispersed coating solution is used. At this time, it is preferable to select a solvent that does not 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, aromatic hydrocarbon solvents such as toluene, xylene and benzene, halogenated hydrocarbon solvents such as carbon tetrachloride, chloroform, tetrachloroethane and dibromoethane, diethyl ether, dibutyl ether, diisopropyl ether, Examples include ether solvents such as dioxane, ketone solvents such as acetone and 3-hydroxy-3-methyl-2-butanone, ester solvents such as ethyl acetate and methyl lactate, and water. These may be used alone or as a mixture of two or more.

If necessary, the dye of 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 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 thickness of 50
A reflective layer of ~ 300 nm is formed. As a material of the reflection layer, a material having a sufficiently high reflectance at the wavelength of the reproduction light, for example, A
u, Al, Ag, Cu, Ti, Cr, Ni, Pt, T
The metals a, Cr and Pd can be used alone or as an alloy. Among them, Au, Al and Ag have high reflectivity and are suitable as a material for the reflective layer. In addition, the following may be included. For example, Mg, S
e, Hf, V, Nb, Ru, W, Mn, Re, Fe, C
o, Rh, Ir, Zn, Cd, Ga, In, Si, G
Metals and metalloids such as e, Te, Pb, Po, Sn, and Bi 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 under 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, a UV curable resin, and the like can be given. As the inorganic substance, SiO ₂ , Si ₃ N ₄ ,
MgF ₂ , SnO _{2 and the} like can be mentioned. Thermoplastic resin, thermosetting resin, etc. are dissolved in an appropriate solvent and a coating liquid is applied,
It can be formed by drying. The UV 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 with UV light to cure the resin. UV
As the curable resin, for example, urethane acrylate,
Acrylate resins such as epoxy acrylate and polyester acrylate can be used. These materials may be used alone or as a mixture, or may be used as a multilayer film as well as a single layer.

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. Of these, the spin coating method is preferable.

The thickness of the protective layer is generally from 0.1 to 100.
μm, but in the present invention, 3 to 30 μm
And more preferably 5 to 20 μm.

A label or the like can be further printed on the protective layer.

Alternatively, a protective sheet or a substrate may be bonded to the reflective layer surface, or two optical recording media may be bonded with the reflective layer surfaces facing each other. 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 or prevent adhesion of dust and the like.

The laser having a wavelength of 520 to 690 nm referred to in the present invention is not particularly limited. For example, a dye laser capable of selecting a wavelength in a wide range of the visible region, a helium neon laser having a wavelength of 633 nm, and a recently developed wavelength of 68 can be used.
A high-power semiconductor laser near 0, 650, and 635 nm;
A harmonic conversion YAG laser having a wavelength of 532 nm may be used. According to the present invention, high-density recording and reproduction can be performed at one wavelength or a plurality of wavelengths selected from these.

[0068]

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

Example 1 Synthesis of Pyromethene Metal Chelate Compound (1) 2-Formyl-3,5 in 30 ml of dichloromethane under a nitrogen stream.
-Dimethyl-4-ethylpyrrole 5.0 g and 2,4-dimethyl
4.1 g of -3-ethylpyrrole was dissolved, 5.6 g of phosphorus oxytrichloride was added dropwise, and the mixture was stirred at 20 ° C for 1 hour. After concentration, washing with 200 ml of n-hexane,
After adding 18.4 g of N, N-diisopropylethylamine and stirring at room temperature for 30 minutes, 19.2 g of boron trifluoride ether complex was added, and the mixture was further stirred for 1 hour.
After washing with water, the toluene was distilled off and recrystallized with methanol.
4.5 g of a compound represented by the following structural formula (VII-a) was obtained.

[0070]

Embedded image

Next, n-butyl alcohol 3 was added under a nitrogen stream.
0.3 g of metallic sodium was added to 0 g, and
After stirring for hours to dissolve the metallic sodium, the formula (VII-
1.0 g of the compound shown in a) was added, and the mixture was stirred at 90 ° C for 5 hours. Drain into 100 ml of water and 200 ml of toluene
The solvent was distilled off after washing with water. Column chromatography (silica gel / toluene: ethyl acetate = 9:
Purification was performed in 1) to obtain 1.2 g of a compound represented by the following structural formula (1).

[0072]

Embedded image

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

[0074]

[Table 12]

The compound thus obtained exhibits a maximum absorption at 487 nm in a toluene solution, and has a gram extinction coefficient of 1.74 × 10 ⁵ ml / g. cm.

Example 2 Synthesis of Pyromethene Metal Chelate Compound (23) 2,4-Dimethyl-3 in 20 ml of dichloromethane under a nitrogen stream.
15.0 g of -ethylpyrrole was dissolved, 21.0 g of acetyl chloride was added dropwise, and the mixture was stirred at 40 ° C for 1 hour. After cooling to room temperature, concentrating, washing with 200 ml of n-hexane, adding 500 ml of toluene and 67.5 g of N, N-diisopropylethylamine, stirring at room temperature for 30 minutes, and then adding 70.2 g of a boron trifluoride ether complex. And further stirred for 1 hour. After washing with water, toluene was distilled off, and the residue was recrystallized from methanol to obtain 8.0 g of a compound represented by the following structural formula (VII-b).

[0077]

Embedded image

Next, 1.0 g of the compound represented by the formula (VII-b) was added to 50 ml of anhydrous tetrahydrofuran under a nitrogen stream.
And cooled under 5 ° C., n-hexylmagnesium bromide (1.0 mol / L: tetrahydrofuran) 3.1
4 ml was added dropwise and stirred for 30 minutes. 2% hydrochloric acid 100m
, extracted with 100 ml of toluene, washed with water,
The solvent was distilled off. Purification by column chromatography (silica gel / toluene: n-hexane = 5: 5) gave 0.77 g of a compound represented by the following structural formula (23).

[0079]

Embedded image

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

[0081]

[Table 13]

The compound thus obtained exhibits a maximum absorption at 518 nm in a toluene solution, and has a gram extinction coefficient of 2.25 × 10 ⁵ ml / g. cm.

Example 3 Synthesis of Pyromethene Metal Chelate Compound (24) Under a nitrogen stream, 1.0 g of the compound represented by the formula (VII-b) was dissolved in 20 ml of anhydrous tetrahydrofuran.
N-hexylmagnesium bromide (1.0
(mol / L: tetrahydrofuran) was added dropwise and stirred at 30 ° C. for 30 minutes. 100 ml of 2% hydrochloric acid
And extracted with 100 ml of toluene. After washing with water, the solvent was distilled off. Purification by column chromatography (silica gel / toluene: n-hexane = 3: 7) gave 1.15 g of a compound represented by the following structural formula (24).

[0084]

Embedded image

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

[0086]

[Table 14]

The compound thus obtained shows a maximum absorption at 511 nm in a toluene solution, and has a gram extinction coefficient of 2.07 × 10 ⁵ ml / g. cm.

Example 4 Synthesis of Pyromethene Metal Chelate Compound (27) Under a nitrogen stream, 1.0 g of the compound represented by the above formula (VII-b) was dissolved in 50 ml of anhydrous tetrahydrofuran.
Under cooling, phenylmagnesium bromide (2.0 mol
1 / L: tetrahydrofuran) 1.57 ml was added dropwise,
Stir for 1 hour. The mixture was discharged into 100 ml of 2% hydrochloric acid, extracted with 100 ml of toluene, washed with water, and the solvent was distilled off. Purified by column chromatography (silica gel / toluene: n-hexane = 35: 65), the following structural formula (27)
0.71 g of the compound represented by was obtained.

[0089]

Embedded image

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

[0091]

[Table 15]

The compound thus obtained shows a maximum absorption at 522 nm in a toluene solution, and has a gram extinction coefficient of 1.89 × 10 ⁵ ml / g. cm.

Example 5 Synthesis of Pyromethene Metal Chelate Compound (28) Under a nitrogen stream, 1.0 g of the compound represented by the above formula (VII-b) was dissolved in 20 ml of anhydrous tetrahydrofuran.
Phenylmagnesium bromide (2.0m
(ol / L: tetrahydrofuran) 4.71 ml was added dropwise and stirred at 30 ° C. for 30 minutes. 100 ml of 2% hydrochloric acid
And extracted with 100 ml of toluene. After washing with water, the solvent was distilled off. Purification by column chromatography (silica gel / toluene: n-hexane = 2: 8) gave 1.16 g of a compound represented by the following structural formula (28).

[0094]

Embedded image

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

[0096]

[Table 16]

The compound thus obtained exhibits a maximum absorption at 516 nm in a toluene solution, and has a gram extinction coefficient of 1.72 × 10 ⁵ ml / g. cm.

Example 6 Synthesis of Pyromethene Metal Chelate Compound (30) 0.5 g of the compound represented by the formula (VII-b) was dissolved in 25 ml of methanol, and 1.0 g of sodium methoxide was dissolved.
Was added and stirred at reflux temperature for 5 hours. The mixture was discharged into 100 ml of water, extracted with 150 ml of toluene, washed with water, and the solvent was distilled off. Column chromatography (silica gel /
Purification by toluene: ethyl acetate = 7: 3) gave 0.51 g of a compound represented by the following structural formula (30).

[0099]

Embedded image

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

[0101]

[Table 17]

The compound thus obtained exhibits a maximum absorption at 522 nm in a toluene solution, and has a gram extinction coefficient of 1.85 × 10 ⁵ ml / g. cm.

Example 7 Synthesis of Pyromethene Metal Chelate Compound (31) In a nitrogen stream, 0.072 g of sodium metal was added to 20 g of n-pentyl alcohol, and the mixture was stirred at 80 ° C. for 1 hour to dissolve the sodium metal. 1.0 g of the compound represented by the formula (VII-b) was added, and the mixture was stirred at 90 ° C for 5 hours. The mixture was discharged into 100 ml of water, extracted with 100 ml of toluene, washed with water, and the solvent was distilled off. Column chromatography (silica gel / toluene: ethyl acetate = 95: 5)
Then, 0.81 g of a compound represented by the following structural formula (31) was obtained.

[0104]

Embedded image

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

[0106]

[Table 18]

The compound thus obtained exhibits a maximum absorption at 523 nm in a toluene solution, and has a gram extinction coefficient of 1.37 × 10 ⁵ ml / g. cm.

Example 8 Synthesis of Pyromethene Metal Chelate Compound (33) In 10 ml of dioxane, 0.5 g of the compound represented by the formula (VII-b) was dissolved, and 2.43 g of a 15% aqueous solution of methyl mercaptan sodium was added. Stirred at C for 3 hours. Drain into 100 ml of water and 200 ml of ethyl acetate
The solvent was distilled off after washing with water. Column chromatography (silica gel / ethyl acetate: ethanol = 9
5: 5) to give 0.31 g of a compound represented by the following structural formula (33).

[0109]

Embedded image

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

[0111]

[Table 19]

The compound thus obtained shows a maximum absorption at 520 nm in a toluene solution, and has a gram extinction coefficient of 1.71 × 10 ⁵ ml / g. cm.

Example 9 Synthesis of Pyromethene Metal Chelate Compound (36) In a nitrogen stream, 0.5 g of the compound represented by the above formula (31) was dissolved in 20 ml of anhydrous tetrahydrofuran, and phenylmagnesium bromide (2. 0 mol
/ L: tetrahydrofuran) 0.65 ml is added dropwise and 3
Stirred for 0 minutes. The mixture was discharged into 100 ml of 2% hydrochloric acid, extracted with 100 ml of toluene, washed with water, and the solvent was distilled off. Purification by column chromatography (silica gel / toluene: n-hexane = 5: 5) gave 0.48 g of a compound represented by the following structural formula (36).

[0114]

Embedded image

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

[0116]

[Table 20]

The compound thus obtained shows a maximum absorption at 519 nm in a toluene solution, and has a gram extinction coefficient of 1.31 × 10 ⁵ ml / g. cm.

Example 10 Synthesis of Pyromethene Metal Chelate Compound (64) Under a nitrogen stream, 20 ml of dichloromethane was added to 2-isobarrel-
1.0 g of 3,5-dimethyl-4-ethylpyrrole and 0.46 g of 2,4-dimethylpyrrole were dissolved, and 0.81 g of phosphorus oxytrichloride was added dropwise. The mixture was stirred at 40 ° C. for 1 hour, concentrated, washed with 300 ml of n-hexane, and washed with 300 ml of toluene.
ml and 2.69 g of N, N-diisopropylethylamine were added, and the mixture was stirred at room temperature for 30 minutes. Then, 2.81 g of a boron trifluoride ether complex was added, and the mixture was further stirred for 1 hour.
After washing with water, toluene was distilled off, and the residue was purified by column chromatography (silica gel / toluene: ethyl acetate = 8: 2) to obtain a compound represented by the following structural formula (VII-c).
93 g were obtained.

[0119]

Embedded image

Next, 0.5 g of the compound represented by the formula (VII-c) was added to 20 ml of anhydrous tetrahydrofuran under a nitrogen stream.
2. Under cooling at 10 ° C., p-toluylmagnesium bromide (1.0 mol / L: tetrahydrofuran)
16 ml was added dropwise, and the mixture was stirred at 20 ° C. for 1 hour. The mixture was discharged into 100 ml of 2% hydrochloric acid, extracted with 100 ml of toluene, washed with water, and the solvent was distilled off. The product was purified by column chromatography (silica gel / n-hexane: toluene = 8: 2) to give the compound represented by the following structural formula (64) in 0.6.
3 g were obtained.

[0121]

Embedded image

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

[0123]

[Table 21]

The compound thus obtained shows a maximum absorption at 509 nm in a toluene solution, and has a gram extinction coefficient of 1.81 × 10 ⁵ ml / g. cm.

Example 11 Synthesis of Pyromethene Metal Chelate Compound (72) Under a nitrogen stream, 1.0 g of the compound represented by the above formula (VII-a) was dissolved in 20 ml of anhydrous tetrahydrofuran, and n-hexylmagnesium bromide (1.0 mol) was dissolved. / L: tetrahydrofuran) was added dropwise and stirred at 30 ° C for 1 hour. The mixture was discharged into 100 ml of 2% hydrochloric acid, extracted with 100 ml of toluene, washed with water, and the solvent was distilled off. The product was purified by column chromatography (silica gel / n-hexane) to give the compound represented by the following structural formula (72) in 1.
04 g was obtained.

[0126]

Embedded image

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

[0128]

[Table 22]

The compound thus obtained exhibits a maximum absorption at 517 nm in a toluene solution, and has a gram extinction coefficient of 1.92 × 10 ⁵ ml / g. cm.

Example 12 A dye solution was prepared by dissolving 0.2 g of the pyromethene metal chelate compound (1) in 10 ml of dimethylcyclohexane. The substrate is made of polycarbonate resin and has a continuous guide groove (track pitch: 0.8 μm) and a diameter of 120 m.
A disk having a diameter of mφ and a thickness of 1.2 mm 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. The absorption maximum of this recording layer is 552 nm, and the optical constants are n = 2.2 and k = 0.04 at 680 nm, and n = 2.2 and k = 0.2 at 650 nm.
06, n is 2.4 and k is 0.07 at 635 nm.
It is.

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 resin SD-
After spin-coating No. 17 (manufactured by Dainippon Ink and Chemicals), the layer was irradiated with ultraviolet rays to form a protective layer having a thickness of 6 μm, thereby producing an optical recording medium.

An optical disk evaluation device (DDU-D) manufactured by Pulstec Industrial Co., Ltd. equipped with a semiconductor laser head having a wavelength of 635 nm and a lens aperture of 0.6 on the obtained optical recording medium.
1000) and a KENWOOD EFM encoder so that the linear velocity was 3.5 m / s, the laser power was 8 mW, and the shortest pit length was 0.44 μm. After recording, the signals were reproduced using an evaluation device equipped with 650 nm and 635 nm red semiconductor laser heads (the aperture of the lens was 0.6), and the reflectance, error rate, and modulation were measured. The value was shown.

Next, an optical disk evaluation device (DDU) manufactured by Pulstec Industrial equipped with a 680 nm semiconductor laser head
-1000) and KENWOOD EFM encoder, linear velocity 1.4m / s, laser power 10m
W was recorded so that the shortest pit length was 0.60 μm.
The recorded medium was stored at 680 nm, 650 nm and 635 nm.
A signal was reproduced using an optical disk evaluation device (DDU-1000) manufactured by Pulstec Industrial equipped with a nm red semiconductor laser head, and the reflectance, the error rate, and the modulation were measured. All exhibited good values.

As described above, this medium was able to perform recording and reproduction satisfactorily with a plurality of laser wavelengths.

The error rate is a CD manufactured by Kenwood.
The measurement was performed using a decoder (DR3552), and the modulation was obtained by the following equation.

[0138]

(Equation 1)

Example 13 A substrate made of polycarbonate resin and having a continuous guide groove (track pitch: 0.8 μm) having a diameter of 120 mmφ was used.
Example 1 except that a disc having a thickness of 0.6 mm was used.
In the same manner as in Example 2, a coating and a reflection layer were formed.

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 is formed thereon and has a diameter of 120 mm.
An optical recording medium was prepared by placing a disc-shaped substrate having a diameter of 0.6 mm and then irradiating the substrate with ultraviolet rays.

An optical disk evaluation device (DDU-1000) manufactured by Pulstec Industrial and an EFM manufactured by KENWOOD were manufactured in the same manner as in Example 12 except that a 635 nm semiconductor laser head corresponding to a thickness of 0.6 mm was mounted on the manufactured medium.
Recorded 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, error rate, and modulation were measured.

Examples 14 to 23 Pyromethene metal chelate compounds [(2
3), (24), (27), (28), (30), (3)
1), (33), (36), (64), and (72)], except that the optical recording medium was manufactured in the same manner as in Example 13. 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 13, and KENWOO
Recording was performed using a D EFM encoder. After recording, 6
A signal was reproduced using an evaluation device equipped with a 50 nm and 635 nm red semiconductor laser head, and the reflectance, the error rate, and the modulation were measured. As a result, good values were obtained.

Example 24 Using a pyromethene metal chelate compound (30) and diacetone alcohol as a coating solvent, a continuous guide groove made of polycarbonate resin was used for a substrate (track pitch: 0.53 μm).
An optical recording medium was produced in the same manner as in Example 13 except that a disc having a diameter of 120 mmφ and a thickness of 0.6 mm having m) was used.

The absorption maximum of this recording layer is 528 nm, and the optical constants at 532 nm are n = 2.5 and k = 0.
Twelve.

Recording was performed on the prepared medium at a linear velocity of 3.8 m / s and a laser power of 7 mW using an optical disk evaluation apparatus equipped with a 532 nm YAG high frequency conversion laser head corresponding to a thickness of 0.6 mm and an EFM encoder manufactured by KENWOOD. After recording, the signal was reproduced using the same evaluation apparatus. As a result, the reflectance was about 50% and the error rate was 9c.
The ps and the degree of modulation were 0.66, all showing good values.

Comparative Example 1 In Example 13, a pentamethine cyanine dye NK-2929 was used instead of the pyrromethene metal chelate compound.
[1,3,3,1 ', 3', 3'-hexamethyl-2 ', 2'-(4,5,4 ', 5'-dibenzo) indodicarbocyanine perchlorate, manufactured by Japan Photographic Dye Laboratories ] Except that the optical recording medium was used. Using a Pulstec Industrial Optical Disk Evaluation System (DDU-1000) equipped with a 635 nm semiconductor laser head on the produced medium and a KENWOOD EFM encoder as in Example 12, at a linear velocity of 3.5 m / s and a laser power of 7 mW. Recorded. After recording, the signal was reproduced using an evaluation device equipped with 650 nm and 635 nm red semiconductor laser heads. As a result, the reflectance was low, the error rate was large, and the modulation was small. The signal was degraded when playing for a longer time.

Comparative Example 2 In Comparative Example 1, the methazine cyanine dye NK79 [1,3,3,1 ′, 3 ′, 3′-hexamethyl-
2 ′, 2′-Indodicarbocyanine iodide, manufactured by Japan Photographic Dye Laboratories Co., Ltd.]. 63 in the same manner as in Example 12
Pulstec Industrial Optical Disk Evaluation System (DDU-1000) equipped with a 5 nm semiconductor laser head and KE
2. Using an NWOOD EFM encoder, the linear velocity
Recording was performed at a laser power of 7 mW at 5 m / s. After recording,
When a signal was reproduced using an evaluation device equipped with 650 nm and 635 nm red semiconductor laser heads, the waveform was distorted, the error rate was large, and the modulation was small. The signal was degraded when playing for a longer time.

Examples 12 to 23 and Comparative Examples 1 and 2
In Table 2, the optical constants of the recording layer and the reflectance, error rate, and modulation factor when recording each medium at 635 nm and reproducing at 650 nm and 635 nm are shown in Table 2.

[0149]

[Table 23]

[0150]

[Table 24]

[0151]

The write-once optical recording medium which can be recorded and reproduced with a laser having a wavelength of 520 to 690 nm, which has been attracting much attention as a high-density optical recording medium, by using the pyrromethene metal chelate compound of the present invention in the recording layer. Can be provided.

[Brief description of the drawings]

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

FIG. 2 is a schematic sectional structural view showing a layer configuration of the optical recording medium of the present invention.

[Explanation of symbols]

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

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Dentsu Misawa, Inventor 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside of Mitsui Toatsu Chemical Co., Ltd. (72) Keisuke Takuma 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Chemical Co., Ltd.

Claims (5)

[Claims] 1. A pyrromethene metal chelate compound represented by the following general formula (I). Embedded image [Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and 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, 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, alkylaminocarbonyl group, dialkylaminocarbonyl group, alkylcarbonylamino group, arylcarbonylamino group, arylaminocarbonyl group, aryloxycarbonyl group, aralkyl group, aryl group, heteroaryl group, Alkylthio, arylthio, alkenyloxycarbonyl, aralkyloxycarbonyl, alkoxycarbonylalkoxycarbonyl, alkylcarbonylalkoxycarbonyl, mono (hydroxyalkyl) aminocarbonyl, di (hydroxyalkyl) aminocarbonyl, mono ( X ₁ and X ₂ represent an (alkoxyalkyl) aminocarbonyl group, a di (alkoxyalkyl) aminocarbonyl group or an alkenyl group having 2 to 20 carbon atoms.
Is an alkyl group having 1 to 20 carbon atoms, a halogenoalkyl group, an alkoxyalkyl group, an alkylthioalkyl group,
Dialkylaminoalkyl group, alkoxy group, alkoxyalkoxyalkoxy group, alkylthioalkoxy group, dialkylaminoalkoxy group, dialkylaminoalkoxyalkoxy group, alkylthio group, alkoxyalkylthio group, alkylthioalkylthio group, dialkylaminoalkylthio group, aryloxy group, aryl −
A ruthio group, a heteroaryl group, a heteroaryloxy group, a heteroarylthio group and a halogen atom. However, X ₁ and X ₂ are not simultaneously halogen atoms. ] 2. 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 comprising the pyromethene metal chelate compound as described in the above. 3. 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. 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 a reflectance of the laser light selected from the wavelength range of 520 to 690 nm measured from the substrate side is 20% or more.