JPH08176452A - Phthalocyanine compound and optical recording medium containing the same - Google Patents

Abstract

PURPOSE: To obtain an optical recording medium which shows high sensitivity even in high-speed recording and high-density recording and has good recording characteristics and light resistance by laying a recording layer containing a specified phthalocyanine compound on a substrate, laying a reflecting layer made of gold or aluminum on the recording layer, and laying a protective layer on the reflecting layer. CONSTITUTION: The phthalocyanine used is one represented by formula I [wherein M represents two H atoms, a bivalent metal atom, a monosubstituted trivalent metal atom, a disubstituted tetravalent metal atom, or an oxymetal group; L<1> is a group of formula II (wherein OR<1> is 1-20C linear or branched alkoxy; R<2> is 3-20C linear or branched alkyl substituted by 1-4 halogen atoms or 4-20C linear or branched alkenyl substituted by 1-2 halogen atoms; X is halogeno; and n is 0-2)] and has a sharp absorption at 650-900nm and a molecular extinction coefficient as high as 150000 or above. Examples of the central atoms represented by M in formula I include Pd, Cu, Si(Y)2 Sn(Y)2 and Ge(Y)2 (wherein Y is halogeno, alkoxy, aryloxy or the like).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel recording material for optical disks, information recording, a display sensor, a compound useful as a near-infrared absorber which plays an important role in optoelectronics related to protective glasses, and the recording thereof. The present invention relates to an optical recording medium such as an optical disc and an optical card formed by containing it in a layer.

[0002]

2. Description of the Related Art Laser light is used for writing and reading in optical disks, optical card devices and the like. In particular, as a recording method of an optical recording medium used in these devices, heat mode recording (thermal recording) through light / heat conversion is usually adopted as a practical level, and therefore, a low melting point metal as a recording layer, Various organic polymers and further organic dyes that undergo physical or chemical changes such as melting, evaporation, decomposition, or sublimation have been proposed. Among them, organic dyes having a low melting and decomposition temperature are preferable in terms of recording sensitivity, and therefore cyanine dyes, phthalocyanine dyes, naphthalocyanine dyes, azo dyes and the like have been developed as recording layers.

[0003] For example, in Japanese Patent Laid-Open No. 2-147286,
An optical recording medium containing a cyanine dye in the recording layer has been proposed. However, this medium system was inferior in long-term storage stability and light resistance, and further the recording characteristics were insufficient.

Anthraquinone dyes (for example, JP-A-58-2
24448), naphthoquinone dyes (see, for example, JP-A-58-
No. 224793) is also proposed, but all of them are inferior in long-term storability and light resistance like cyanine dyes, and also have insufficient recording characteristics.

In JP-A-61-25886, JP-A-2-43269 (USP 4960538), JP-A-2-296885 and the like, an optical recording medium containing a naphthalocyanine dye in a recording layer is proposed. There is. This medium system has excellent light resistance,
The reflectance of the recording layer was low and the recording characteristics were insufficient.

Further, a technique of utilizing a phthalocyanine dye, particularly an alkoxy-substituted phthalocyanine in a recording layer of an optical recording medium is disclosed in JP-A-61-154888 (EP 186404) and JP-A-61-154404.
197280, 61-246091, 62-39286
(USP 4769307), 63-37991, 63-39388 and the like. It has been difficult to say that the optical recording media using the phthalocyanine dyes disclosed in these patents have sufficient performance in terms of sensitivity, refractive index and recording characteristics. What improved it is JP-A-3-
62878 (USP 5124067), the improved compound also has a large error during high-speed recording and high-density recording by a laser beam and is not yet practically sufficient.

Alkoxy-substituted naphthalocyanines in JP-A-2-43269 (USP 4960538) and JP-A-2-296885, aliphatic hydrocarbon oxy-substituted phthalocyanines in JP-A-63-37991, JP-A-63-37991 Japanese Patent No. 39388 proposes the use of an alkenylthio-substituted phthalocyanine for an optical recording medium, but does not describe that it has an effect on sensitivity and recording characteristics.

It should be noted that no one having sufficient recording performance has been found in the recording characteristics of the optical recording medium using other known dyes.

Writing to and reading from an optical recording medium is 4
Since a laser beam having a wavelength of from 0 to 900 nm is used, it is important to control the absorption coefficient, the refractive index, and the like in the vicinity of the laser oscillation wavelength of the recording material and to form pits with high accuracy during writing. This is especially important in high-speed recording and high-density recording which have been recently desired. Therefore, it is necessary to develop a dye for an optical recording medium, which has high structural stability, a high refractive index for light in the vicinity of the laser oscillation wavelength, a good decomposition property, and a high sensitivity. However, conventionally developed dyes for optical recording media have drawbacks in sensitivity (C / N ratio, optimum recording power) and recording characteristics (jitter, deviation) particularly when used in recording media, for high speed recording and high density recording. There was a problem of having.

[0010]

DISCLOSURE OF THE INVENTION An object of the present invention is to improve the above-mentioned drawbacks, to provide an optical recording medium having high sensitivity even at high speed recording and high density recording, and having excellent recording characteristics and light resistance. Is to supply.

[0011]

The present inventors have completed the present invention as a result of extensive studies to solve the above-mentioned problems. That is, the present invention provides a phthalocyanine compound represented by the following general formula (1),

[0012]

Embedded image [In the formula (1), M is two hydrogen atoms, a divalent metal atom,
Represents a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or an oxymetal atom, and L ¹ is represented by the formula (2)

[0013]

[Chemical 4] (In the formula (2), OR ¹ represents a linear or branched alkoxy group having 1 to 20 carbon atoms, and R ² independently has 1 to 4 halogen atoms and 3 to 20 carbon atoms. A straight-chain or branched alkyl group or a straight-chain or branched alkenyl group having 4 to 20 carbon atoms in which a halogen atom is substituted by 1 to 2. X represents a halogen atom, and n is 0 to 2 independently. Represents a number].

In the general formula (1), the central metal represented by Met is Pd, Cu, Ru, Pt, Ni, C.
o, Rh, Zn, VO, TiO, Si (Y) ₂ , Sn
(Y) ₂ , Ge (Y) ₂ (Y is a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a hydroxy group, an alkyl group, an aryl group, an alkylthio group, an arylthio group, a trialkylsilyloxy group, a trialkyltin. An oxy group or a trialkylgermaniumoxy group)). An optical recording medium containing a phthalocyanine compound represented by the general formula (1). An optical recording medium has a structure in which a recording layer containing a phthalocyanine compound of the general formula (1), a reflective layer made of gold or aluminum, and a protective layer are further laminated on a substrate.

The phthalocyanine compound of the present invention is 650-9.
It has a sharp absorption at 00 nm and a molecular extinction coefficient of 150,000.
It is high as above and has excellent long-term stability and light resistance.
It is suitable as a recording material for an optical recording medium (optical disk, optical card, etc.) using a semiconductor laser. In addition, since the compound of the present invention has an alkenyl group substituted with an alkoxy group and a halogen atom or an alkenyl group substituted with a phthalocyanine ring, it is dissolved in a solvent used when applying a substrate by spin coating. Good property. Further, although the mechanism is not yet clear and is currently under investigation, the halogen atom substituted on the alkyl group or the alkenyl group, which is a feature of the phthalocyanine compound of the present invention, contributes to improvement in sensitivity during optical recording, It is effective in reducing the error of the formed signal. That is, the decomposition / melting of the dye is controlled during optical recording to form highly accurate pits, and the damage to the resin substrate of the recording medium is reduced. In the case of a recording medium having a reflective layer, the recording layer and the reflective layer are It is the improvement of the adhesion to a certain metal layer. Not only the conventional recording method, but also the high-speed recording or the high-density recording method as compared with the conventional recording method is effective in improving the sensitivity and recording characteristics of the optical recording medium.

The preferred embodiments of the present invention will be described in detail below.

In the general formula (2), specific examples of the linear or branched alkoxy group having 1 to 20 carbon atoms represented by OR ¹ include methoxy group, ethoxy group, n-propoxy group and iso-
Propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, iso-pentyloxy group, neo-pentyloxy group, 2-methylbutyl-3-oxy group, Pentyl-2-oxy group, pentyl-3-oxy group, n-hexyloxy group, cyclo-hexyloxy group, 2-methylpentyl-4-oxy group, 2-methylpentyl-
3-oxy group, 3-methylpentyl-4-oxy group, 4-methylpentyl-4-oxy group, n-heptyloxy group, hexyl-
3-oxy group, 2-methylhexyl-5-oxy group, 2,4-dimethylpentyl-3-oxy group, 2-methylhexyl-3-oxy group, heptyl-4-oxy group, n-octyloxy group, 2-ethylhexyl-1-oxy group, 2,5-dimethylhexyl-3-oxy group, 2,4-dimethylhexyl-3-oxy group, 2,2,4-trimethylpentyl-3-oxy group, n-nonyloxy Base, 3,5
-Dimethylheptyl-4-oxy group, 2,6-dimethylheptyl
-3-oxy group, 2,4-dimethylheptyl-3-oxy group, 2,2,
5,5-tetramethylhexyl-3-oxy group, 1-cyclo-pentyl-2,2-dimethylpropyl-1-oxy group, 1-cyclo-hexyl-2,2-dimethylpropyl-1-oxy group, etc. Can be mentioned.

In the general formula (2), a halogen atom represented by R ² is substituted by 1 to 4 and a linear or branched alkyl group having 3 to 20 carbon atoms or a halogen atom is substituted by 1 to 2. Specific examples of the linear or branched alkenyl group having 4 to 20 carbon atoms include 1-chloro-propyl group and 2-chloro-
Propyl group, 1-bromo-propyl group, 2-bromo-propyl group, 1-iodo-propyl group, 2-iodo-propyl group, 1-chloro-1-methyl-propyl group, 2-chloro-1-methyl- Propyl group, 1-bromo-1-methyl-propyl group, 2-bromo-1-methyl-propyl group, 1-iodo-1-methyl-propyl group, 2-iodo-1-methyl-propyl group, 1-chloro -1-ethyl-
Propyl group, 2-chloro-1-ethyl-propyl group, 1
-Brom-1-ethyl-propyl group, 2-Brom-1-
Ethyl-propyl group, 1-iodo-1-ethyl-propyl group, 2-iodo-1-ethyl-propyl group, 1-chloro-1-propyl-propyl group, 2-chloro-1-propyl-propyl group, 1 -Bromo-1-propyl-propyl group, 2-bromo-1-propyl-propyl group, 1-iodo-1-propyl-propyl group, 2-iodo-1-propyl-propyl group,

2-chloro-butyl group, 3-chloro-butyl group, 2-bromo-butyl group, 3-bromo-butyl group,
2-iodo-butyl group, 3-iodo-butyl group, 2-chloro-1-methyl-butyl group, 3-chloro-1-methyl-butyl group, 2-bromo-1-methyl-butyl group, 3-
Brom-1-methyl-butyl group, 2-iodo-1-methyl-butyl group, 3-iodo-1-methyl-butyl group, 2
-Chloro-2-methyl-butyl group, 3-chloro-2-methyl-butyl group, 2-bromo-2-methyl-butyl group,
3-bromo-2-methyl-butyl group, 2-iodo-2-
Methyl-butyl group, 3-iodo-2-methyl-butyl group, 2-chloro-3-methyl-butyl group, 3-chloro-
3-methyl-butyl group, 2-bromo-3-methyl-butyl group, 3-bromo-3-methyl-butyl group, 2-iodo-3-methyl-butyl group, 3-iodo-3-methyl-butyl group ,

2-chloro-2,3-dimethyl-butyl group, 3-chloro-2,3-dimethyl-butyl group, 2-bromo-2,3-dimethyl-butyl group, 3-bromo-2,
3-dimethyl-butyl group, 2-iodo-2,3-dimethyl-butyl group, 3-iodo-2,3-dimethyl-butyl group, 2-chloro-1,1-dimethyl-butyl group, 3-chloro- 1,1-dimethyl-butyl group, 2-bromo-1,
1-dimethyl-butyl group, 3-bromo-1,1-dimethyl-butyl group, 2-iodo-1,1-dimethyl-butyl group, 3-iodo-1,1-dimethyl-butyl group, 2-chloro- 1-ethyl-2-methyl-butyl group, 3-chloro-1-ethyl-2-methyl-butyl group, 2-bromo-1
-Ethyl-2-methyl-butyl group, 3-bromo-1-ethyl-2-methyl-butyl group, 2-iodo-1-ethyl-2-methyl-butyl group, 3-iodo-1-ethyl-2
-Methyl-butyl group,

2-chloro-pentyl group, 3-chloro-pentyl group, 2-bromo-pentyl group, 3-bromo-pentyl group, 2-iodo-pentyl group, 2-iodo-pentyl group, 2-chloro-1 -Methyl-pentyl group, 3-chloro-1-methyl-pentyl group, 2-bromo-1-methyl-pentyl group, 3-bromo-1-methyl-pentyl group,
2-iodo-1-methyl-pentyl group, 3-iodo-1
-Methyl-pentyl group, 2-chloro-2-methyl-pentyl group, 3-chloro-2-methyl-pentyl group, 2-bromo-2-methyl-pentyl group, 3-bromo-2-methyl-pentyl group, 2-iodo-2-methyl-pentyl group, 3-iodo-2-methyl-pentyl group, 2-chloro-3-methyl-pentyl group, 3-chloro-3-methyl-
Pentyl group, 2-bromo-3-methyl-pentyl group, 3
-Brom-3-methyl-pentyl group, 2-iodo-3-
Methyl-pentyl group, 3-iodo-3-methyl-pentyl group, 2-chloro-4-methyl-pentyl group, 3-chloro-4-methyl-pentyl group, 2-bromo-4-methyl-pentyl group, 3 -Bromo-4-methyl-pentyl group,
2-iodo-4-methyl-pentyl group, 3-iodo-4
-Methyl-pentyl group,

2-chloro-2,4-dimethyl-pentyl group, 3-chloro-2,4-dimethyl-pentyl group, 2-
Brom-2,4-dimethyl-pentyl group, 3-bromo-
2,4-dimethyl-pentyl group, 2-iodo-2,4-
Dimethyl-pentyl group, 3-iodo-2,4-dimethyl-pentyl group, 2-chloro-1,4-dimethyl-pentyl group, 3-chloro-1,4-dimethyl-pentyl group, 2
-Brom-1,4-dimethyl-pentyl group, 3-bromo-1,4-dimethyl-pentyl group, 2-iodo-1,4
-Dimethyl-pentyl group, 3-iodo-1,4-dimethyl-pentyl group,

2-chloro-1-ethyl-2-methyl-pentyl group, 3-chloro-1-ethyl-2-methyl-pentyl group, 2-bromo-1-ethyl-2-methyl-pentyl group, 3- Brom-1-ethyl-2-methyl-pentyl group, 2-iodo-1-ethyl-2-methyl-pentyl group, 3-iodo-1-ethyl-2-methyl-pentyl group, 2-chloro-hexyl group, 3-chloro-hexyl group, 2-bromo-hexyl group, 3-bromo-hexyl group, 2-iodo-hexyl group, 3-iodo-hexyl group,

2-chloro-1-methyl-hexyl group, 3
-Chloro-1-methyl-hexyl group, 2-bromo-1-
Methyl-hexyl group, 3-bromo-1-methyl-hexyl group, 2-iodo-1-methyl-hexyl group, 3-iodo-1-methyl-hexyl group, 2-chloro-3-methyl-hexyl group, 3 -Chloro-3-methyl-hexyl group,
2-bromo-3-methyl-hexyl group, 3-bromo-3
-Methyl-hexyl group, 2-iodo-3-methyl-hexyl group, 3-iodo-3-methyl-hexyl group,

2-chloro-heptyl group, 3-chloro-heptyl group, 2-bromo-heptyl group, 3-bromo-heptyl group, 2-iodo-heptyl group, 3-iodo-heptyl group, 2-chloro-2 -Methyl-heptyl group, 3-chloro-2-methyl-heptyl group, 2-bromo-2-methyl-heptyl group, 3-bromo-2-methyl-heptyl group,
2-iodo-2-methyl-heptyl group, 3-iodo-2
-Methyl-heptyl group,

2-chloro-3,4,4-trimethyl-2
-Heptyl group, 3-chloro-3,4,4-trimethyl-
2-heptyl group, 2-bromo-3,4,4-trimethyl-2-heptyl group, 3-bromo-3,4,4-trimethyl-2-heptyl group, 2-iodo-3,4,4-trimethyl -2-heptyl group, 3-iodo-3,4,4-trimethyl-2-heptyl group,

2-chloro-octyl group, 3-chloro-octyl group, 2-bromo-octyl group, 3-bromo-octyl group, 2-iodo-octyl group, 3-iodo-octyl group, 2-chloro-nonyl group Group, 3-chloro-nonyl group,
2-bromo-nonyl group, 3-bromo-nonyl group, 2-iodo-nonyl group, 3-iodo-nonyl group, 2-chloro-
2,5-dimethyl-5-heptenyl group, 3-chloro-
2,5-dimethyl-5-heptenyl group, 2-bromo-
2,5-dimethyl-5-heptenyl group, 3-bromo-
2,5-dimethyl-5-heptenyl group, 2-iodo-
2,5-dimethyl-5-heptenyl group, 3-iodo-
2,5-dimethyl-5-heptenyl group, 5-chloro-
2,5-dimethyl-2-heptenyl group, 6-chloro-
2,5-dimethyl-2-heptenyl group, 5-bromo-
2,5-dimethyl-2-heptenyl group, 6-bromo-
2,5-dimethyl-2-heptenyl group, 5-iodo-
2,5-dimethyl-2-heptenyl group, 6-iodo-
2,5-dimethyl-2-heptenyl group,

2-chloro-5-hexenyl group, 3-chloro-5-hexenyl group, 2-bromo-5-hexenyl group, 3-bromo-5-hexenyl group, 2-iodo-5- group.
Hexenyl group, 3-iodo-5-hexenyl group, 5-chloro-2-hexenyl group, 6-chloro-2-hexenyl group, 5-bromo-2-hexenyl group, 6-bromo-2-
Hexenyl group, 5-iodo-2-hexenyl group, 6-iodo-2-hexenyl group, 2-chloro-1-methyl-5
-Hexenyl group, 3-chloro-1-methyl-5-hexenyl group, 2-bromo-1-methyl-5-hexenyl group,
3-bromo-1-methyl-5-hexenyl group, 2-iodo-1-methyl-5-hexenyl group, 3-iodo-1-
Methyl-5-hexenyl group, 5-chloro-1-methyl-
2-hexenyl group, 6-chloro-1-methyl-2-hexenyl group, 5-bromo-1-methyl-2-hexenyl group, 6-bromo-1-methyl-2-hexenyl group, 5-
Iodo-1-methyl-2-hexenyl group, 6-iodo-
1-methyl-2-hexenyl group, 2-chloro-2-methyl-5-hexenyl group, 3-chloro-2-methyl-5-
Hexenyl group, 2-bromo-2-methyl-5-hexenyl group, 3-bromo-2-methyl-5-hexenyl group, 2
-Iodo-2-methyl-5-hexenyl group, 3-iodo-2-methyl-5-hexenyl group, 5-chloro-2-methyl-2-hexenyl group, 6-chloro-2-methyl-2
-Hexenyl group, 5-bromo-2-methyl-2-hexenyl group, 6-bromo-2-methyl-2-hexenyl group,
5-iodo-2-methyl-2-hexenyl group, 6-iodo-2-methyl-2-hexenyl group,

2-chloro-4-heptenyl group, 3-chloro-4-heptenyl group, 2-bromo-4-heptenyl group, 3-bromo-4-heptenyl group, 2-iodo-4-.
Heptenyl group, 3-iodo-4-heptenyl group, 4-chloro-2-heptenyl group, 5-chloro-2-heptenyl group, 4-bromo-2-heptenyl group, 5-bromo-2-
Heptenyl group, 4-iodo-2-heptenyl group, 5-iodo-2-heptenyl group,

1,2-dichloro-propyl group, 1,2-
Dibromo-propyl group, 1,2-diiodo-propyl group, 1,2-dichloro-1-methyl-propyl group, 1,
2-dibromo-1-methyl-propyl group, 1,2-diiodo-1-methyl-propyl group, 1,2-dichloro-1
-Ethyl-propyl group, 1,2-dibromo-1-ethyl-propyl group, 1,2-diiodo-1-ethyl-propyl group, 1,2-dichloro-1-propyl-propyl group,
1,2-dibromo-1-propyl-propyl group, 1,2
-Diiodo-1-propyl-propyl group,

2,3-dichloro-butyl group, 2,3-dibromo-butyl group, 2,3-diiodo-butyl group, 2,
3-dichloro-1-methyl-butyl group, 2,3-dibromo-1-methyl-butyl group, 2,3-diiodo-1-methyl-butyl group, 2,3-dichloro-2-methyl-butyl group, 2,3-dibromo-2-methyl-butyl group, 2,
3-diiodo-2-methyl-butyl group, 2,3-dichloro-3-methyl-butyl group, 2,3-dibromo-3-methyl-butyl group, 2,3-diiodo-3-methyl-butyl group, 2,3-dichloro-2,2-dimethyl-butyl group, 2,3-dibromo-2,3-dimethyl-butyl group,
2,3-diiodo-2,3-dimethyl-butyl group, 2,
3-dichloro-1,1-dimethyl-butyl group, 2,3-
Dibromo-1,1-dimethyl-butyl group, 2,3-diiodo-1,1-dimethyl-butyl group, 2,3-dichloro-1-ethyl-2-methyl-butyl group, 2,3-dibromo-1 -Ethyl-2-methyl-butyl group, 2,3-diiodo-1-ethyl-2-methyl-butyl group,

2,3-dichloro-pentyl group, 2,3-
Dibromo-pentyl group, 2,3-diiodo-pentyl group, 2,3-dichloro-1-methyl-pentyl group, 2,
3-dibromo-1-methyl-pentyl group, 2,3-diiodo-1-methyl-pentyl group, 2,3-dichloro-2
-Methyl-pentyl group, 2,3-dibromo-2-methyl-pentyl group, 2,3-diiodo-2-methyl-pentyl group, 2,3-dichloro-3-methyl-pentyl group,
2,3-dibromo-3-methyl-pentyl group, 2,3-
Diiodo-3-methyl-pentyl group, 2,3-dichloro-4-methyl-pentyl group, 2,3-dibromo-4-methyl-pentyl group, 2,3-diiodo-4-methyl-pentyl group, 2, 3-dichloro-2,4-dimethyl-pentyl group, 2,3-dibromo-2,4-dimethyl-pentyl group, 2,3-diiodo-2,4-dimethyl-pentyl group, 2,3-dichloro-1 , 4-dimethyl-pentyl group, 2,3-dibromo-1,4-dimethyl-pentyl group, 2,3-diiodo-1,4-dimethyl-pentyl group, 2,3-dichloro-1-ethyl-2- Methyl-pentyl group, 2,3-dibromo-1-ethyl-2-methyl-
Pentyl group, 2,3-diiodo-1-ethyl-2-methyl-pentyl group,

2,3-dichloro-hexyl group, 2,3-
Dibromo-hexyl group, 2,3-diiodo-hexyl group, 2,3-dichloro-1-methyl-hexyl group, 2,
3-dibromo-1-methyl-hexyl group, 2,3-diiodo-1-methyl-hexyl group, 2,3-dichloro-3
-Methyl-hexyl group, 2,3-dibromo-3-methyl-hexyl group, 2,3-diiodo-3-methyl-hexyl group, 2,3-dichloro-heptyl group, 2,3-dibromo-heptyl group, 2,3-diiodo-heptyl group, 2,
3-dichloro-2-methyl-heptyl group, 2,3-dibromo-2-methyl-heptyl group, 2,3-diiodo-2
-Methyl-heptyl group, 2,3-dichloro-3,4,4
-Trimethyl 2-heptyl group, 2,3-dibromo-3,
4,4-trimethyl-2-heptyl group, 2,3-diiodo-3,4,4-trimethyl-2-heptyl group, 2,3
-Dichloro-octyl group, 2,3-dibromo-octyl group, 2,3-diiodo-octyl group, 2,3-dichloro-nonyl group, 2,3-dibromo-nonyl group, 2,3-diiodo-nonyl group ,

2,3-dichloro-2,5-dimethyl-5
-Heptenyl group, 2,3-dibromo-2,5-dimethyl-5-heptenyl group, 2,3-diiodo-2,5-dimethyl-5-heptenyl group, 5,6-dichloro-2,5-
Dimethyl-2-heptenyl group, 5,6-dibromo-2,
5-dimethyl-2-heptenyl group, 5,6-diiodo-
2,5-dimethyl-2-heptenyl group, 2,5-dichloro-2,5-dimethyl-heptyl group, 2,6-dichloro-2,5-dimethyl-heptyl group, 3,5-dichloro-
2,5-dimethyl-heptyl group, 3,6-dichloro-
2,5-dimethyl-heptyl group, 2,5-dibromo-
2,5-dimethyl-heptyl group, 2,6-dibromo-
2,5-dimethyl-heptyl group, 3,5-dibromo-
2,5-dimethyl-heptyl group, 3,6-dibromo-
2,5-dimethyl-heptyl group, 2,5-diiodo-
2,5-dimethyl-heptyl group, 2,6-diiodo-
2,5-dimethyl-heptyl group, 3,5-diiodo-
2,5-dimethyl-heptyl group, 3,6-diiodo-
2,5-dimethyl-heptyl group,

2,3,5-trichloro-2,5-dimethyl-heptyl group, 2,3,6-trichloro-2,5-dimethyl-heptyl group, 3,5,6-trichloro-2,5
-Dimethyl-heptyl group, 2,5,6-trichloro-
2,5-dimethyl-heptyl group, 2,3,5-tribromo-2,5-dimethyl-heptyl group, 2,3,6-tribromo-2,5-dimethyl-heptyl group, 2,5,6-
Tribrom-2,5-dimethyl-heptyl group, 3,5
6-tribromo-2,5-dimethyl-heptyl group, 2,
3,5-triiodo-2,5-dimethyl-heptyl group,
2,3,6-triiodo-2,5-dimethyl-heptyl group, 2,5,6-triiodo-2,5-dimethyl-heptyl group, 3,5,6-triiodo-2,5-dimethyl-
Heptyl group,

2,3,5-trichloro-hexyl group,
2,3,6-trichloro-hexyl group, 2,5,6-trichloro-hexyl group, 3,5,6-trichloro-hexyl group, 2,3,5-tribromo-hexyl group, 2,
3,6-tribromo-hexyl group, 2,5,6-tribromo-hexyl group, 3,5,6-tribromo-hexyl group, 2,3,5-triiodo-hexyl group, 2,3,6
-Triiodo-hexyl group, 2,5,6-triiodo-
Hexyl group, 3,5,6-triiodo-hexyl group,
2,3,5-trichloro-1-methyl-hexyl group,
2,3,6-trichloro-1-methyl-hexyl group,
2,5,6-trichloro-1-methyl-hexyl group,
3,5,6-trichloro-1-methyl-hexyl group,
2,3,5-tribromo-1-methyl-hexyl group,
2,3,6-tribromo-1-methyl-hexyl group,
2,5,6-tribromo-1-methyl-hexyl group,
3,5,6-tribromo-1-methyl-hexyl group,
2,3,5-triiodo-1-methyl-hexyl group,
2,3,6-triiodo-1-methyl-hexyl group,
2,5,6-triiodo-1-methyl-hexyl group,
3,5,6-triiodo-1-methyl-hexyl group,
2,3,5-trichloro-5-methyl-hexyl group,
2,3,6-trichloro-5-methyl-hexyl group,
2,5,6-trichloro-5-methyl-hexyl group,
3,5,6-trichloro-5-methyl-hexyl group,
2,3,5-tribromo-5-methyl-hexyl group,
A 2,3,6-tribromo-5-methyl-hexyl group,
2,5,6-tribrom-5-methyl-hexyl group,
3,5,6-tribromo-5-methyl-hexyl group,
2,3,5-triiodo-5-methyl-hexyl group,
2,3,6-triiodo-5-methyl-hexyl group,
2,5,6-triiodo-5-methyl-hexyl group,
3,5,6-triiodo-5-methyl-hexyl group,
2,3,5-trichloro-2-methyl-hexyl group,
2,3,6-trichloro-2-methyl-hexyl group,
2,5,6-trichloro-2-methyl-hexyl group,
3,5,6-trichloro-2-methyl-hexyl group,
2,3,5-tribromo-2-methyl-hexyl group,
2,3,6-tribromo-2-methyl-hexyl group,
2,5,6-tribromo-2-methyl-hexyl group,
3,5,6-tribromo-2-methyl-hexyl group,
2,3,5-triiodo-2-methyl-hexyl group,
2,3,6-triiodo-2-methyl-hexyl group,
2,5,6-triiodo-2-methyl-hexyl group,
3,5,6-triiodo-2-methyl-hexyl group,

A 2,3,4-trichloro-heptyl group,
2,3,5-trichloro-heptyl group, 2,4,5-trichloro-heptyl group, 3,4,5-trichloro-heptyl group, 2,3,4-tribromo-heptyl group, 2,
3,5-tribromo-heptyl group, 2,4,5-tribromo-heptyl group, 3,4,5-tribromo-heptyl group, 2,3,4-triiodo-heptyl group, 2,3,5
-Triiodo-heptyl group, 2,4,5-triiodo-
Heptyl group, 3,4,5-triiodo-heptyl group,

2,3,5,6-tetrachloro-2,5-
Dimethyl-heptyl group, 2,3,5,6-tetrabromo-2,5-dimethyl-heptyl group, 2,3,5,6-tetraiodo-2,5-dimethyl-heptyl group, 2,3-
Dichloro-5-hexenyl group, 2,3-dibromo-5-
Hexenyl group, 2,3-diiodo-5-hexenyl group,
5,6-dichloro-2-hexenyl group, 5,6-dibromo-2-hexenyl group, 5,6-diiodo-2-hexenyl group, 2,3,5,6-tetrachloro-hexyl group,
2,3,5,6-tetrabromo-hexyl group, 2,3,3
5,6-tetraiodo-hexyl group,

2,3-dichloro-1-methyl-5-hexenyl group, 2,3-dibromo-1-methyl-5-hexenyl group, 2,3-diiodo-1-methyl-5-hexenyl group, 5, 6-dichloro-1-methyl-2-hexenyl group, 5,6-dibromo-1-methyl-2-hexenyl group, 5,6-diiodo-1-methyl-2-hexenyl group, 2,3,5,6 -Tetrachlor-1-methyl-hexyl group, 2,3,5,6-tetrabromo-1-methyl-
Hexyl group, 2,3,5,6-tetraiodo-1-methyl-hexyl group, 2,3-dichloro-2-methyl-5-
Hexenyl group, 2,3-dibromo-2-methyl-5-hexenyl group, 2,3-diiodo-2-methyl-5-hexenyl group, 5,6-dichloro-2-methyl-2-hexenyl group, 5, 6-dibromo-2-methyl-2-hexenyl group, 5,6-diiodo-2-methyl-2-hexenyl group,

2,3,5,6-tetrachloro-2-methyl-hexyl group, 2,3,5,6-tetrabromo-2-
Methyl-hexyl group, 2,3,5,6-tetraiodo-
2-methyl-hexyl group,

2,3-dichloro-5-methyl-5-hexenyl group, 2,3-dibromo-5-methyl-5-hexenyl group, 2,3-diiodo-5-methyl-5-hexenyl group, 5, 6-dichloro-5-methyl-2-hexenyl group, 5,6-dibromo-5-methyl-2-hexenyl group, 5,6-diiodo-5-methyl-2-hexenyl group,

2,3,5,6-tetrachloro-5-methyl-hexyl group, 2,3,5,6-tetrabromo-5-
Methyl-hexyl group, 2,3,5,6-tetraiodo-
5-methyl-hexyl group,

2,3-dichloro-4-heptenyl group,
2,3-dibromo-4-heptenyl group, 2,3-diiodo-4-heptenyl group, 4,5-dichloro-2-heptenyl group, 4,5-dibromo-2-heptenyl group, 4,5
-Diiodo-2-heptenyl group, 2,3,4,5-tetrachloro-heptyl group, 2,3,4,5-tetrabromo-heptyl group, 2,3,4,5-tetraiodo-heptyl group and the like. .

In the formula (2), X is a halogen atom such as chlorine, bromine or iodine.

Further, in the formula (1), divalent represented by Met.
Examples of metals include Cu, Zn, Fe, Co, Ni, R
u, Rh, Pd, Pt, Mn, Sn, Mg, Pb, H
g, Cd, Ba, Ti, Be, Ca, etc.
Examples of the alternative trivalent metal include Al-F, Al-Cl, and A.
1-Br, Al-I, Ga-F, Ga-Cl, Ga-B
r, Ga-I, In-F, In-Cl, In-Br, I
n-I, Tl-F, Tl-Cl, Tl-Br, Tl-
I, Al-C₆H_Five, Al-C₆H_Four(CH₃), In-C₆
H_Five, In-C₆H_Four(CH₃), Mn (OH), Mn (O
C₆H_Five), Mn [OSi (CH₃)₃], Fe-Cl, R
u-Cl and the like, and examples of the di-substituted tetravalent metal
Is CrCl₂, SiF₂, SiCl₂, SiBr₂, Si
I₂, SnF₂, SnCl₂, SnBr₂, ZrCl₂, G
eF₂, GeCl₂, GeBr₂, GeI ₂, TiF₂, T
iCl₂, TiBr₂, Si (OH)₂, Sn (OH)₂,
Ge (OH)₂, Zr (OH)₂, Mn (OH)₂, Ti
A₂, CrA₂, SiA₂, SnA₂, GeA₂[A is Al
Shows the kill group, phenyl group, naphthyl group and its derivatives.
], Si (OA ')₂, Sn (OA ')₂, Ge (O
A ')₂, Ti (OA ')₂, Cr (OA ')₂[A ’is
Alkyl group, phenyl group, naphthyl group, trialkyl group
Ryl group, dialkylalkoxysilyl group and derivatives thereof
Represents the body], Si (SA ”)₂, Sn (SA ")₂, Ge
(SA ”)₂[A] is an alkyl group, a phenyl group, a naphthyl group
Group and its derivatives] and the like, and oxygold
Examples of the genus include VO, MnO, TiO, and the like.
It Particularly preferable examples are Cu, Ni, Co and M.
g, Zn, Pd, Pt, VO, etc.

The synthetic method of the phthalocyanine compound represented by the general formula (1) includes the following formula (3) or (4)

[0047]

Embedded image [In the formulas (3) and (4), R ¹ has the same meaning as in the general formula (2), and R ′ represents an alkenyl group. ] The compound represented by the formula is, for example, 1,8-diazabicyclo [5,4,0]
In the presence of -7-undecene (DBU), the metal derivative is heated and reacted in alcohol. Alternatively, a metal derivative and a phthalocyanine compound having an alkoxy group and an alkenyl group are synthesized by heating and reacting in a high-boiling solvent such as chloronaphthalene, bromnaphthalene, and trichlorobenzene. It can be obtained by a method of reacting with a halogenating agent such as hydrogen fluoride, hydrobromic acid, bromine, hydrogen iodide, iodine or iodine monochloride.

The compound represented by the general formula (3) or (4) can be produced by the following route.

[0049]

[Chemical 6] 3-nitrophthalonitrile (A) in the presence of a base,
R'OH [R 'has the same meaning as described above. ] The alkoxy phthalonitrile (B) is obtained by making it react with the allyl alcohol derivative shown by these. Furthermore, after Claisen transfer reaction of (B), R ¹ X [R ¹ is an OR of the general formula (2) in the presence of a base.
¹ represents an alkyl group corresponding to the alkoxy group represented,
X represents a halogen atom. ] The objective compound shown by General formula (3) is manufactured by making it react with the alkyl halide derivative shown by these. The diiminoisoindoline compound represented by the general formula (4) can be obtained by reacting the compound represented by the general formula (3) with ammonia in alcohol using sodium methylate as a catalyst.

In the method for producing an optical recording medium using the phthalocyanine compound of the present invention, 1 to 3 compounds including the phthalocyanine compound of the present invention are coated or vapor-deposited on a transparent substrate in one layer or two layers. There is a method, and the coating method is 20% by weight or less of the binder resin, preferably 0%.
%, And the phthalocyanine compound of the present invention is 0.05 to 20% by weight, preferably 0.5 to 20% by weight, dissolved in a solvent and applied by a spin coater. The vapor deposition method is 10 ^-5 to 10 ^-7 torr, 100 to
There is a method of depositing a phthalocyanine compound on a substrate at 300 ° C.

The substrate may be any optically transparent resin. Examples thereof include acrylic resin, polyethylene resin, vinyl chloride resin, vinylidene chloride resin, polycarbonate resin, polyolefin copolymer resin, vinyl chloride copolymer resin, vinylidene chloride copolymer resin, and styrene copolymer resin. The substrate may be subjected to a surface treatment with a thermosetting resin or an ultraviolet curable resin.

When producing an optical recording medium (optical disk, optical card, etc.), a polyacrylate substrate or a polycarbonate substrate is used as the substrate and it is applied by a spin coating method in terms of cost and handling by the user. preferable.

Due to the solvent resistance of the substrate, the solvent used for spin coating is a halogenated hydrocarbon (eg, dichloromethane, chloroform, carbon tetrachloride, tetrachloroethylene, dichlorodifluoroethane, etc.), ethers (eg, tetrahydrofuran, diethyl ether, diether, etc.). Propyl ether, dibutyl ether, dioxane, etc.), alcohols (eg, methanol, ethanol, propanol, etc.), cellosolves (eg, methyl cellosolve,
Ethyl cellosolve, etc.), hydrocarbons (eg, hexane, cyclohexane, ethylcyclohexane, cyclooctane, dimethylcyclohexane, octane, benzene, toluene, xylene, etc.), or a mixed solvent thereof is preferably used.

In order to process it as a recording medium, it is covered with a substrate as described above, or is adhered to a substrate provided with two recording layers so as to face each other with an air gap, or a reflective layer is formed on the recording layer. (Aluminum or gold) is provided, and a protective layer of thermosetting or photocurable resin is laminated. As a protective layer, Al ₂ O ₃ , SiO ₂ , S
iO, may be used an inorganic compound of SnO ₂ or the like.

[0055]

EXAMPLES The present invention will be specifically described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 In a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube,
Structural formula (3-1) below

[0057]

[Chemical 7] 2- (2-Pentoxy) -4- (1-propenyl) phthalonitrile of 25.4 g (0.1 mol), DB
U (15.2 g, 0.1 mol) and n-amyl alcohol (125 g) were charged, and the temperature was raised to 100 ° C. under a nitrogen atmosphere. Next, 5.3 g of palladium chloride at the same temperature
(0.03 mol) was added and reacted at 95 to 100 ° C. for 20 hours. After completion of the reaction, the mixture was cooled and the insoluble matter was filtered off.
After the filtrate was concentrated under reduced pressure to recover the solvent, column purification (silica gel 500 g, solvent toluene) was performed, and the following structural formula (5
17.7 g (yield 63%) of a palladium tetra [α- (2-pentoxy) -β- (1-propenyl)] phthalocyanine compound represented by -1) was obtained.

[0058]

Embedded image The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 708 nm ε _g = 2.7 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

5 g (4.5 m) of the above phthalocyanine compound
(mol) was dissolved in 30 g of 1,1,2-trichloroethane, and 10 g of water was added. Then bromine 5.4 g (33.8
mmol) and 3 g of 1,1,2-trichloroethane were added dropwise at 50 to 55 ° C. in 30 minutes, and the same temperature was applied for 1 hour to complete the process. 10% aqueous sodium hydrogen sulfite solution 5
g and washed. 80 g of methanol was added dropwise to the organic layer, and the precipitated crystals were filtered and purified by column (silica gel 1
(00 g, solvent toluene) to obtain 8.0 g of a brominated phthalocyanine compound represented by the following structural formula (1-1). NM
From R, it was found that all of the side chain double bonds were replaced with bromine, and elemental analysis revealed that 11.5 bromine had been replaced. Therefore, it was found that 3.5 rings were substituted.

[0061]

[Chemical 9] The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 714 nm ε _g = 1.6 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

An n-octane solution (10 g / l) of the above phthalocyanine compound was added to spiral groove (pitch 1.
6 μm, groove width of 0.6 μm, groove depth of 0.18 μm), and a spin coat film was formed at 500 to 1000 rpm on a polycarbonate substrate for CD-R having an outer diameter of 120 mm and a thickness of 1.2 mm. A 30 nm gold layer is sputter-deposited thereon to form a reflective layer, and then a protective layer is formed by overcoating with a photo-curing polyacrylic resin and then photo-curing to form a CD-R.
A mold medium was prepared. When an EFM signal was written in this medium at a linear velocity of 1.4 m / s with a power of 5.5 mW using a semiconductor laser having a wavelength of 780 nm, the error rate was less than 0.2%. Also, linear velocity 2m / s, 0.8m
There was no change in recording even after reproducing 10 ⁵ times with W laser light.

Example 2 5 g (4.5 mmo) of the palladium tetra [α- (2-pentoxy) -β- (1-propenyl)] phthalocyanine compound represented by the structural formula (5-1) synthesized in Example 1
1) was dissolved in 30 g of 1,1,2-trichloroethane, and 10 g of water was added. Then 7.9 g of sulfuryl chloride
A mixed solution of (58.5 mmol) and 6 g of 1,1,2-trichloroethane was added dropwise at 50 to 55 ° C over 30 minutes, and the mixture was terminated at the same temperature for 1 hour. After 60 g of 10% aqueous sodium hydroxide solution was added for neutralization and liquid separation, the organic layer was added dropwise to 150 g of methanol, and the precipitated crystals were filtered and dried, followed by column purification (silica gel 100 g, solvent toluene). 8.0 g of a chlorinated phthalocyanine compound represented by 1-2) was obtained. From NMR, it was found that all side chain double bonds were replaced with chlorine, and elemental analysis revealed that 10.5 chlorine was replaced. Therefore, it was found that the ring had 2.5 substitutions.

[0065]

[Chemical 10] The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 705 nm ε _g = 1.7 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

A solution of the above phthalocyanine compound in ethylcyclohexane (10 g / l) was applied onto a polycarbonate substrate for CD-R by a spin coater in the same manner as in Example 1, and gold was sputter-deposited thereon, followed by UV curing resin. A protective layer was formed using to prepare a CD-R type medium. When an EFM signal was written on this medium at a linear velocity of 1.4 m / s with a power of 6.0 mW using a semiconductor laser of 780 nm, the error rate was less than 0.2%,
There was no change even after reproducing 1 million times with reproducing light of 0.5 mW. Recording / reproduction was not affected even after 1000 hours under the condition of 80 ° C./85%.

Example 3 The following structural formula (3-2) was placed in the same container as in Example 1.

[0069]

[Chemical 11] 3- (4-methyl-2-pentoxy) -4-
26.8 g (0.1-propenyl) phthalonitrile (0.1
Mol), 15.2 g (0.1 mol) of DBU and 120 g of n-amyl alcohol were charged, and 10
The temperature was raised to 0 ° C. Next, 5.3 g (0.03 mol) of palladium chloride was added at the same temperature, and the mixture was reacted at 95 to 100 ° C for 20 hours. After completion of the reaction, the mixture was cooled and the insoluble matter was filtered off. After the filtrate was concentrated under reduced pressure to recover the solvent, column purification (silica gel 500 g, solvent toluene) was carried out, and palladium tetra [α- (4
-Methyl-2-pentoxy) -β- (1-propenyl)] phthalocyanine compound 19.2 g (yield 65%)
I got

[0070]

[Chemical 12] The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 704 nm ε _g = 2.3 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

5.8 g of the above phthalocyanine compound (4.
5 mmol) was dissolved in 30 g of 1,1,2-trichloroethane, and 10 g of water was added. Next, 4.3 g of bromine (27
mmol) and 3 g of 1,1,2-trichloroethane were added dropwise at 50 to 55 ° C. in 30 minutes, and the same temperature was applied for 1 hour to complete the process. 15% sodium bisulfite aqueous solution 5
g and washed. The organic layer was added dropwise to 100 g of methanol, and the precipitated crystals were filtered, dried, and column-purified (silica gel 100 g, solvent toluene).
6.9 g of brominated phthalocyanine of 3) was obtained. It was found from elemental analysis that 10.1 bromine had been substituted, and from NMR that all side chain double bonds had been substituted with bromine.
Therefore, it was found that the ring had 2.1 substitutions.
The results of visible absorption spectrum and elemental analysis were as follows.

[0073]

[Chemical 13] Visible absorption: λ _max = 711 nm ε _g = 1.4 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

Dibutyl ether of the above phthalocyanine compound
A tellurium solution (10 g / l) was coated on a polycarbonate substrate for CD-R by a spin coater in the same manner as in Example 1, and gold was sputter-deposited on the substrate, followed by UV on the coated surface.
A protective layer was formed using a cured resin to produce a CD-R. 780nm, linear velocity 1.4m / s, 4mW in this medium
The error rate when the EFM signal was written by the semiconductor laser light of was less than 0.2%. Also, 0.5
It was possible to reproduce with mW laser light, and when the reproduction light stability was examined, it was possible to reproduce 10 ⁵ times. Furthermore 80
There was no problem in recording and reproduction even after 1000 hours under the condition of ° C / humidity of 85%.

Example 4 Palladium tetra [α- (4-methyl-2-pentoxy) -β- (1-) of the structural formula (5-2) synthesized in Example 3
Propenyl)] phthalocyanine compound 5.8 g (4.5
mmol) is dissolved in 40 g of 1,1,2-trichloroethane, and 9.2 g (68 m) of sulfuryl chloride at 50 to 55 ° C.
mol) is added dropwise. The reaction was carried out at the same temperature for 2 hours. 10%
It was neutralized with 80 g of sodium hydroxide. After separating the organic layer,
Crystals precipitated by dropping into 100 g of methanol were filtered and dried, followed by column purification (silica gel 100 g, solvent toluene).
Then, 7.2 g of chlorinated phthalocyanine represented by the following structural formula (1-4) was obtained. Elemental analysis showed that 10.8 chlorine was substituted, and NMR revealed that all side chain double bonds were substituted with chlorine. Therefore, it was found that the ring had 2.8 substitutions.

[0076]

Embedded image Visible absorption: λ _max = 699 nm ε _g = 1.7 × 10 ⁵ cm ² g ⁻¹ (solvent: toluene)

A solution of the phthalocyanine compound in ethylcyclohexane (20 g / l) was applied on a polycarbonate substrate for CD-R by a spin coater in the same manner as in Example 1, and gold was sputter-deposited on it, followed by UV curing resin. A protective layer was formed using to prepare a CD-R type medium. The error rate when an EFM signal was written at a power of 5.5 mW at a linear velocity of 2.8 m / s using a semiconductor laser of 780 nm on this medium was less than 0.2%,
There was no change even after reproducing 1 million times with reproducing light of 0.5 mW. Recording / reproduction was not affected even after 1000 hours under the condition of 80 ° C./85%.

Example 5 The following structural formula (3-3) was placed in the same container as in Example 1.

[0079]

[Chemical 15] 3 (g) of 3- (2-pentoxy) -4- (1,4-dimethyl-2-pentenyl) phthalonitrile represented by
(0.1 mol), DBU (15.2 g, 0.1 mol) and n-amyl alcohol (150 g) were charged, and the temperature was raised to 100 ° C. under a nitrogen atmosphere. Next, at the same temperature, 3.0 g (0.03 mol) of cuprous chloride was added, and the temperature was 95 to 100 ° C.
And reacted for 25 hours. After completion of the reaction, the mixture was cooled and the insoluble matter was filtered off. After the filtrate was concentrated under reduced pressure to recover the solvent, column purification (silica gel 500 g, solvent toluene) was performed, and copper tetra [α- (2-pentoxy) of the following structural formula (5-3) was used.
18.5 g (yield 55%) of -β- (1,4-dimethyl-2-pentenyl)] phthalocyanine compound was obtained.

[0080]

Embedded image The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 708 nm ε _g = 2.3 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

5.8 g of the above phthalocyanine compound (4.
5 mmol) was dissolved in 40 g of 1,1,2-trichloroethane, and 4.8 g (30 mmol) of bromine was added at 50 to 55 ° C.
Is dripped. The reaction was carried out at the same temperature for 2 hours. It was washed with 10 g of 10% sodium bisulfite. After separating the organic layer, the crystals were dropped into 80 g of methanol and the precipitated crystals were filtered and dried, followed by column purification (silica gel 100 g, solvent toluene) to obtain 7.2 g of brominated phthalocyanine of the following structural formula (1-5). . Elemental analysis revealed that 10.2 bromine had been substituted, and NMR revealed that all side chain double bonds had been substituted with bromine. Therefore, it was found that the ring had 2.2 substitutions.

[0083]

[Chemical 17] Visible absorption: λ _max = 725 nm ε _g = 16 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

An ethylcyclohexane solution of the above phthalocyanine compound (20 g / l) was applied on a polycarbonate substrate for CD-R by a spin coater in the same manner as in Example 1, and gold was sputter-deposited on it, followed by UV curing resin. A protective layer was formed using to prepare a CD-R type medium. The error rate when an EFM signal was written at a power of 5.5 mW at a linear velocity of 2.8 m / s using a semiconductor laser of 780 nm on this medium was less than 0.2%,
There was no change even after reproducing 1 million times with reproducing light of 0.5 mW. Recording / reproduction was not affected even after 1000 hours under the condition of 80 ° C./85%.

Example 6 As in Example 5, 3-represented by Structural Formula (3-3) was used.
(2-pentoxy) -4- (1,4-dimethyl-2-pentenyl) phthalonitrile 31.1 g (0.1 mol),
15.2 g (0.1 mol) of DBU and 150 g of n-amyl alcohol were charged, and the temperature was raised to 100 ° C under a nitrogen atmosphere. Next, 5.3 g of palladium chloride at the same temperature
(0.03 mol) was added, and the mixture was reacted at 95 to 100 ° C for 25 hours. After completion of the reaction, the mixture was cooled and the insoluble matter was filtered off.
After the filtrate was concentrated under reduced pressure to recover the solvent, column purification (silica gel 500 g, solvent toluene) was performed, and the following structural formula (5
-4) palladium tetra [α- (2-pentoxy)-
β- (1,4-Dimethyl-2-pentenyl)] phthalocyanine compound (18.5 g, yield 55%) was obtained.

[0086]

Embedded image The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 693 nm ε _g = 2.3 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

6.1 g of the above phthalocyanine compound (4.
5 mmol) was dissolved in 35 g of 1,1,2-trichloroethane, and 10 g of water was added. Next, at 50 to 55 ° C., 9.2 g (68 mmol) of sulfuryl chloride is added dropwise. The reaction was carried out at the same temperature for 2 hours. It was neutralized with 80 g of 10% sodium hydroxide. After separating the organic layer, the crystals were dropped into 100 g of methanol and the precipitated crystals were filtered and dried, followed by column purification (silica gel 100 g, solvent toluene), and the following structural formula (1-6).
7.0 g of chlorinated phthalocyanine represented by Elemental analysis showed that 10.8 chlorine was substituted, and NMR revealed that all side chain double bonds were substituted with chlorine. Therefore, it was found that the ring had 2.8 substitutions.

[0089]

[Chemical 19] The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 704 nm ε _g = 1.7 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

Using the above phthalocyanine compound, a CD-R type medium was prepared in the same manner as in Example 1. Using a laser with a wavelength of 780 nm for this medium, a linear velocity of 1.4 m
The error rate when the EFM signal was written at a power of 6.0 mW / s was less than 0.2%.

Example 7 6.1 g of palladium tetra [α- (2-pentoxy) -β- (1,4-dimethyl-2-pentenyl)] phthalocyanine compound of structural formula (5-4) synthesized in Example 5
(4.5 mmol) of 1,1,2-trichloroethane 4
Dissolve in 0g, bromine 5.8g (36mm at 50-55 ℃
ol) is added dropwise. The reaction was carried out at the same temperature for 2 hours. It was washed with 10 g of 10% sodium bisulfite. After separation of the organic layer, 80 g of methanol was added dropwise, and the precipitated crystals were filtered and dried, followed by column purification (silica gel 100 g, solvent toluene) to obtain 9.2 g of brominated phthalocyanine represented by the following structural formula (1-7). Obtained. Bromine is 11.5 from elemental analysis
It was found from FD-MS that all side chain double bonds were replaced by bromine. Therefore, it was found that 3.5 substitutions were made in the ring.

[0093]

Embedded image The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 717 nm ε _g = 2.1 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

Using the above phthalocyanine compound, a CD-R type medium was prepared in the same manner as in Example 1. Using a laser with a wavelength of 780 nm for this medium, a linear velocity of 1.4 m
The error rate when the EFM signal was written at a power of 6.0 mW / s was less than 0.2%.

Example 8 By the method of Example 1, the following structural formula (3-4)

[0097]

[Chemical 21] 3- (2,4-dimethyl-3-pentoxy) represented by
Structural formula (5-5) obtained in a similar manner except that -4- (1-propenyl) phthalonitrile was used.

[0098]

[Chemical formula 22] 5.5 g (4.5 mmol) of the palladium tetra [α- (2,4-dimethyl-3-pentoxy) -β- (1-propenyl)] phthalocyanine compound was dissolved in 40 g of 1,1,2-trichloroethane to give 50 Bromine at ~ 55 ° C 4.
8 g (30 mmol) was added dropwise, and the mixture was reacted at the same temperature for 2 hours. It was washed with 10 g of 10% sodium bisulfite. After separating the organic layer, the crystals were dropped into 100 g of methanol and the precipitated crystals were filtered and dried, followed by column purification (100 g of silica gel,
The solvent was changed to toluene) to obtain 8.0 g of brominated phthalocyanine represented by the following structural formula (1-8). From elemental analysis, it was found that 10.0 bromine atoms were substituted, and FD-MS revealed that all side chain double bonds were substituted with bromine atoms. Therefore, it was found that 2.0 rings were substituted.

[0099]

[Chemical formula 23] The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 715 nm ε _g = 2.4 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

Using the above phthalocyanine compound, a CD-R type medium was prepared in the same manner as in Example 1. Using a laser with a wavelength of 780 nm for this medium, a linear velocity of 1.4 m
The error rate when the EFM signal was written at a power of 6.0 mW / s was less than 0.2%. 0.5m
There was no change even after reproducing 1 million times with the reproducing light of W. Also recorded after 80 hours at 80 ° C / 85%.
There was no obstacle to regeneration.

Example 9 Palladium tetra [α- (2,4-
Dimethyl-3-pentoxy) -β- (1-propenyl)] phthalocyanine compound 5.5 g (4.5 mmo
l) was dissolved in 40 g of 1,1,2-trichloroethane,
Sulfuryl chloride 9.4g (70mmo at 50-55 ℃)
1) was added dropwise, and the mixture was reacted at the same temperature for 2 hours. It was neutralized with 80 g of 10% sodium hydroxide. After separating the organic layer, 100 g of methanol was added dropwise and the precipitated crystals were filtered and dried, and then column purified (silica gel 100 g, solvent toluene) to obtain 7.0 g of chlorinated phthalocyanine represented by the following structural formula (1-9). Obtained. Elemental analysis showed that 10.8 chlorine was substituted, and NMR revealed that all side chain double bonds were substituted with chlorine. Therefore, it was found that the ring had 2.8 substitutions.

[0103]

[Chemical formula 24] Visible absorption: λ _max = 705 nm ε _g = 1.6 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

Using the above phthalocyanine compound, a CD-R type medium was prepared in the same manner as in Example 1. Using a laser with a wavelength of 780 nm for this medium, a linear velocity of 1.4 m
The error rate when the EFM signal was written at a power of 6.0 mW / s was less than 0.2%. 0.5m
There was no change even after reproducing 1 million times with the reproducing light of W.

Example 10 The following structural formula (5-6) was obtained in the same manner as in Example 1.

[0106]

[Chemical 25] A copper tetra [α- (2,4-dimethyl-3-pentoxy) -β- (1-propenyl)] phthalocyanine compound represented by 5.4 g (4.5 mmol) was dissolved in 35 g of 1,1,2-trichloroethane. Bromine at 50-55 ° C 4.
8 g (30 mmol) are added dropwise. The reaction was carried out at the same temperature for 2 hours. It was washed with 10 g of 10% sodium bisulfite.
After separating the organic layer, the crystals were dropped into 100 g of methanol and the precipitated crystals were filtered and dried, followed by column purification (silica gel 100).
g, solvent toluene) to obtain 8.0 g of brominated phthalocyanine represented by the following structural formula (1-10). From elemental analysis, it was found that 10.0 bromine atoms were substituted, and FD-MS revealed that all side chain double bonds were substituted with bromine atoms. Therefore, it was found that 2.0 rings were substituted.

[0107]

[Chemical formula 26] The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 724 nm ε _g = 2.3 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

10 g of the phthalocyanine compound was dissolved in 500 ml of a mixed solvent of 3: 1 (volume ratio) of dibutyl ether and diisopropyl ether, and a spin coater was used to form a 100 nm-thick film on a polycarbonate optical card substrate.
Then, a protective layer was formed on the coated surface by using a UV curable resin to prepare an optical card. 780n on this medium
When recorded with a semiconductor laser beam of m, linear velocity of 2 m / s and 4 mW, the CN ratio was 60 dB. Also, linear velocity 2
It was possible to reproduce 10 ⁵ times with a laser beam of m / s and 0.8 mW.

Examples 11 to 32 Halogenated phthalocyanine compounds shown in Table 1 below were synthesized in the same manner as in Example 1, and CD-R was prepared in the same manner as in Example 1.
A medium was produced, the laser power (mW) required to write an EFM signal at a linear velocity of 1.4 m / sec was measured using a semiconductor laser of 780 nm, and the error rate at that time was evaluated. In the evaluation of the error rate, ◯ indicates that the error rate is less than 10, and x indicates that the error rate is 10 or more. As a comparative example, a medium prepared in the same manner as in Example 1 using the exemplified compound represented by the following structural formula (A) in JP-A-3-62878 (USP 5124067) was evaluated in the same manner, and the results are shown. It is shown in Table 1.

[0111]

[Chemical 27]

[0112]

[Table 1]

[0113]

[Table 2]

[0114]

[Table 3]

[0115]

[Table 4]

[0116]

[Table 5]

The optical recording medium using the phthalocyanine compound of the present invention showed good sensitivity and recording characteristics in the normal recording of 6.0 mW laser power and 3.6 mW low laser, high speed recording and high density recording.

[0118]

INDUSTRIAL APPLICABILITY The phthalocyanine compound of the present invention has a phthalocyanine ring substituted with an alkyl group or an alkenyl group substituted with an alkoxy group and a halogen atom. Has improved solubility. In addition, the substituted halogen atom controls the decomposition / melting of the dye during recording to form highly accurate pits, and the decrease in the amount of decomposition heat generated reduces damage to the resin substrate of the recording medium. In the case of a recording medium having a recording medium, it contributes to the improvement of the adhesion between the recording layer and the metal layer which is the reflection layer, and not only the conventional recording method but also the recording method which is faster than the conventional recording method or the high density recording method. In the above, the effect was also improved in improving the sensitivity and recording characteristics of the optical recording medium.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Taizo Nishimoto 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Takeshi Tsuda 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Keisuke Soma, 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (4)

[Claims] 1. The following general formula (1): [In the formula (1), M is two hydrogen atoms, a divalent metal atom,
Represents a trivalent mono-substituted metal atom, a tetravalent di-substituted metal atom, or an oxy metal atom, and L ¹ is represented by the formula (2): (In the formula (2), OR ¹ represents a linear or branched alkoxy group having 1 to 20 carbon atoms, and R ² represents a halogen atom of 1
~ 4 substituted linear or branched alkyl group having 3 to 20 carbon atoms, and 4 carbon atoms having 1 to 2 substituted halogen atoms
~ 20 represents a straight-chain or branched alkenyl group. X represents a halogen atom, and n independently represents a number of 0 to 2. ] The phthalocyanine compound shown by these. 2. In the general formula (1), the central metal represented by M is Pd, Cu, Ru, Pt, Ni, Co, R.
h, Zn, VO, TiO, Si (Y) ₂ , Sn (Y) ₂ ,
Ge (Y) ₂ (Y is a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a hydroxy group, an alkyl group, an aryl group, an alkylthio group, an arylthio group,
It represents a trialkylsilyloxy group, a trialkyltinoxy group, or a trialkylgermaniumoxy group. ) The phthalocyanine compound according to claim 1. 3. An optical recording medium containing the phthalocyanine compound according to claim 1 or 2. 4. A structure in which a recording layer containing the phthalocyanine compound according to claim 1 or 2 on a substrate, a reflective layer made of gold or aluminum thereon, and a protective layer further laminated thereon. 3. The optical recording medium according to 3.