JPH08193170A - Phthalocyanine compound and optical recording medium containing same - Google Patents

Abstract

PURPOSE: To provide an optical recording medium which is excellent in sensitivity, recording characteristics, regenerated light stability, storage stability, etc., not only in a conventional recording method but also in a recording method with a speed or density higher than that of a conventional method. CONSTITUTION: A phthalocyanine compd. represented by formula I [wherein M is two hydrogen atoms, a divalent metal atom, a monosubstd. trivalent metal atom, a disubstd. tetravalent metal atom, or an oxymetal atom; and L<1> is a group of formula II (wherein OR<1> is a 1-20C linear or branched alkoxy; R<2> and R<3> are each independently a 3-20C mono- to tetrahalogenated linear or branched alkyl group or a 3-20C non-, mono-, or dihalogenated linear or branched alkenyl group; and X is H or halogen)] is provided. An optical recording medium having a recording layer contg. the compd. is also provided.

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 using 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-61-1.
97280, 61-246091, 62-39286 (U
SP 4769307), 63-37991, 63-39388 and the like. In the optical recording medium using the phthalocyanine dye disclosed in these patents,
It was hard to say that it has sufficient performance in terms of sensitivity, refractive index, and recording characteristics. The improvement is JP-A-3-6287
No. 8 (USP 5124067), even the improved compound thereof has a large error in high-speed recording and high-density recording by laser light, and is still not practically sufficient. JP 2-4326
No. 9 (USP 4960538) and JP-A-2-296885, alkoxy-substituted naphthalocyanines, JP-A-63-37991, aliphatic hydrocarbon oxy-substituted phthalocyanines, JP-A-63-39388, alkenylthio. Although the use of substituted phthalocyanines for optical recording media has been proposed, it has not been described that they are effective in sensitivity and recording characteristics.

It is to be noted that none of the recording characteristics of the optical recording medium using other known dyes has sufficient performance.

Writing to and reading from the 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.

[0009]

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.

[0010]

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),

[0011]

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 represents the formula (a)

[0012]

[Chemical 4] (In the formula (a), OR ¹ represents a linear or branched alkoxy group having 1 to 20 carbon atoms, and R ² and R ³ each independently have ³ to 4 carbon atoms substituted with a halogen atom. 20 straight-chain or branched alkyl groups or halogen atoms are 0
~ 2 represents a linear or branched alkenyl group having 3 to 20 carbon atoms, which is substituted, and X represents a hydrogen atom or a halogen atom. ) Represents. ] The phthalocyanine compound shown by these.

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. ) Is a phthalocyanine compound. An optical recording medium containing a phthalocyanine compound represented by the general formula (1). The present invention relates to an optical recording medium having a structure in which a recording layer containing a phthalocyanine compound represented by the general formula (1), a reflective layer made of gold or aluminum, and a protective layer are further laminated on a substrate. The general formula (1) is
Hereinafter, it is abbreviated as the following structural formula (2).

[0014]

Embedded image

The phthalocyanine compound of the present invention is 650
It has sharp absorption at ~ 900nm, high molecular extinction coefficient of 150,000 or more, and excellent long-term stability and light resistance. It is suitable. 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 (1), 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, 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 (1), a linear or branched alkyl group having 3 to 20 carbon atoms in which 1 to 4 of the halogen atoms represented by R ² and R ³ are substituted, or a halogen atom of 0 to
Specific examples of the 2-substituted C 3-20 linear or branched alkenyl group include halogen-free substituents such as a propenyl group, a 1-methyl-propenyl group, and a 1-ethyl-propenyl group. , 1-propyl-propenyl group, 1,1-dimethyl-allyl group, 2-butenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 3-methyl-2-butenyl group, 2 , 3-dimethyl-2-butenyl group, 1,1-dimethyl-2-butenyl group, 1-ethyl-2-methyl-2-butenyl group, 2-
Pentenyl group, 1-methyl-2-pentenyl group, 2-methyl-2-pentenyl group, 3-methyl-2-pentenyl group, 4-methyl-2-pentenyl group, 2,4-dimethyl-2-pentenyl group, 1,4-dimethyl-2-pentenyl group, 1-ethyl-2-methyl-2-pentenyl group, 2
-Hexenyl group, 1-methyl-2-hexenyl group, 3-
Methyl-2-hexenyl group, 2-heptenyl group, 2-methyl-2-heptenyl group, 3,4,4-trimethyl-2
-Heptenyl group, 2-octenyl group, 2-nonanyl group,
2,5-dimethyl-2,5-heptadienyl group, 2,5
-Hexadienyl group, 1-methyl-2,5-hexadienyl group, 2-methyl-2,5-hexadienyl group, 5 methyl-2,5-hexadienyl group, 2,4-heptadienyl group and the like.

As the substituent having a halogen atom, 1-chloro-propyl group, 1-bromo-propyl group, 1-iodo-propyl group, 2-chloro-propyl group, 2-bromo-propyl group, 2 -Iodo-propyl group, 1,2-dichloro-propyl group, 1,2-dibromo-propyl group, 1,2-diiodo-propyl group, 1-chloro-1-methyl-propyl group, 1-bromo-1- Methyl-propyl group, 1-iodo-1-methyl-propyl group, 2-chloro-1-methyl-propyl group, 2-bromo-1-methyl-propyl group, 2-iodo-1-methyl-
Propyl group, 1,2-dichloro-1-methyl-propyl group, 1,2-dibromo-1-methyl-propyl group, 1,
2-diiodo-1-methyl-propyl group, 1-chloro-
1-ethyl-propyl group, 1-bromo-1-ethyl-propyl group, 1-iodo-1-ethyl-propyl group, 2-
Chlor-1-ethyl-propyl group, 2-bromo-1-ethyl-propyl group, 2-iodo-1-ethyl-propyl group, 1,2-dichloro-1-ethyl-propyl group, 1,
2-dibromo-1-ethyl-propyl group, 1,2-diiodo-1-ethyl-propyl group, 1-chloro-1-propyl-propyl group, 1-bromo-1-propyl-propyl group, 1-iodo- 1-propyl-propyl group, 2-chloro-1-propyl-propyl group, 2-bromo-1-propyl-propyl group, 2-iodo-1-propyl-propyl group, 1,2-dichloro-1-propyl- Propyl group, 1,2-dibromo-1-propyl-propyl group,
1,2-diiodo-1-propyl-propyl group, 2-chloro-1,1-dimethyl-propyl group, 2-bromo-
1,1-dimethyl-propyl group, 2-iodo-1,1-
Dimethyl-propyl group, 3-chloro-1,1-dimethyl-propyl group, 3-bromo-1,1-dimethyl-propyl group, 3-iodo-1,1-dimethyl-propyl group,
2,3-dichloro-1,1-dimethyl-propyl group,
2,3-dibromo-1,1-dimethyl-propyl group,
2,3-diiodo-1,1-dimethyl-propyl group,

2-chloro-butyl group, 2-bromo-butyl group, 2-iodo-butyl group, 3-chloro-butyl group,
3-bromo-butyl group, 3-iodo-butyl group, 2,3
-Dichloro-butyl group, 2,3-dibromo-butyl group,
2,3-diiodo-butyl group, 2-chloro-1-methyl-butyl group, 2-bromo-1-methyl-butyl group, 2-
Iodo-1-methyl-butyl group, 3-chloro-1-methyl-butyl group, 3-bromo-1-methyl-butyl group, 3
-Iodo-1-methyl-butyl group, 2,3-dichloro-
1-methyl-butyl group, 2,3-dibromo-1-methyl-butyl group, 2,3-diiodo-1-methyl-butyl group, 2-chloro-2-methyl-butyl group, 2-bromo-
2-methyl-butyl group, 2-iodo-2-methyl-butyl group, 3-chloro-2-methyl-butyl group, 3-bromo-2-methyl-butyl group, 3-iodo-2-methyl-butyl group A 2,3-dichloro-2-methyl-butyl group,
2,3-dibromo-2-methyl-butyl group, 2,3-diiodo-2-methyl-butyl group, 2-chloro-3-methyl-butyl group, 2-bromo-3-methyl-butyl group, 2
-Iodo-3-methyl-butyl group, 3-chloro-3-methyl-butyl group, 3-bromo-3-methyl-butyl group,
3-iodo-3-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-chloro-2,3-dimethyl-butyl group, 2-bromo-2,3-dimethyl-butyl group, 2-iodo-2,
3-dimethyl-butyl group, 3-chloro-2,3-dimethyl-butyl group, 3-bromo-2,3-dimethyl-butyl group, 3-iodo-2,3-dimethyl-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-chloro-1,1
-Dimethyl-butyl group, 2-bromo-1,1-dimethyl-butyl group, 2-iodo-1,1-dimethyl-butyl group, 3-chloro-1,1-dimethyl-butyl group, 3-bromo-1 , 1-dimethyl-butyl group, 3-iodo-1,
1-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-chloro-1-ethyl-2-methyl-butyl group, 2-bromo-1-ethyl-2-methyl-butyl group, 2-iodo-1-ethyl-2-methyl-butyl group,
3-chloro-1-ethyl-2-methyl-butyl group, 3-
Bromo-1-ethyl-2-methyl-butyl group, 3-iodo-1-ethyl-2-methyl-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-chloro-pentyl group, 2-bromo-pentyl group, 2-iodo-pentyl group, 3-chloro-pentyl group, 3-bromo-pentyl group, 3-iodo-pentyl group, 2,3-dichloro group -Pentyl group, 2,3-dibromo-pentyl group, 2,3-diiodo-pentyl group, 2-
Chlor-1-methyl-pentyl group, 2-bromo-1-methyl-pentyl group, 2-iodo-1-methyl-pentyl group, 3-chloro-1-methyl-pentyl group, 3-bromo-1-methyl- Pentyl group, 3-iodo-1-methyl-
Pentyl group, 2,3-dichloro-1-methyl-pentyl group, 2,3-dibromo-1-methyl-pentyl group, 2,
3-diiodo-1-methyl-pentyl group, 2-chloro-
2-methyl-pentyl group, 2-bromo-2-methyl-pentyl group, 2-iodo-2-methyl-pentyl group, 3-
Chlor-2-methyl-pentyl group, 3-bromo-2-methyl-pentyl group, 3-iodo-2-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-chloro-3-methyl-pentyl group, 2-bromo-3-methyl-pentyl group, 2-iodo- 3-methyl-pentyl group, 3-chloro-3-methyl-pentyl group, 3-bromo-3-methyl-
Pentyl group, 3-iodo-3-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-chloro-4-methyl-
Pentyl group, 2-bromo-4-methyl-pentyl group, 2
-Iodo-4-methyl-pentyl group, 3-chloro-4-
Methyl-pentyl group, 3-bromo-4-methyl-pentyl group, 3-iodo-4-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-chloro-2,4-dimethyl-pentyl group, 2- Bromo-2,4-dimethyl-pentyl group, 2-iodo-2,4-dimethyl-pentyl group, 3-
Chlor-2,4-dimethyl-pentyl group, 3-bromo-
2,4-dimethyl-pentyl group, 3-iodo-2,4-
Dimethyl-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-chloro-1,4-dimethyl-pentyl group, 2-bromo-1,4-dimethyl-pentyl group,
2-iodo-1,4-dimethyl-pentyl group, 3-chloro-1,4-dimethyl-pentyl group, 3-bromo-1,
4-dimethyl-pentyl group, 3-iodo-1,4-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-chloro-1-ethyl-2-methyl-pentyl group, 2-bromo-1-ethyl-2-methyl-pentyl group, 2-iodo-1-ethyl-2-methyl-pentyl group, 3-chloro-1-ethyl-2-methyl-pentyl group, 3-bromo-1-ethyl-2-methyl-pentyl group, 3-iodo-1-ethyl-2-methyl-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-chloro-hexyl group, 2-bromo-hexyl group, 2-iodo-hexyl group, 3-chloro-hexyl group, 3-bromo-hexyl group, 3-iodo-hexyl group, 2,3-dichloro group -Hexyl group, 2,3-dibromo-hexyl group, 2,3-diiodo-hexyl group, 2-
Chlor-1-methyl-hexyl group, 2-bromo-1-methyl-hexyl group, 2-iodo-1-methyl-hexyl group, 3-chloro-1-methyl-hexyl group, 3-bromo-1-methyl- Hexyl group, 3-iodo-1-methyl-
Hexyl group, 2,3-dichloro-1-methyl-hexyl group, 2,3-dibromo-1-methyl-hexyl group, 2,
3-diiodo-1-methyl-hexyl group, 2-chloro-
3-methyl-hexyl group, 2-bromo-3-methyl-hexyl group, 2-iodo-3-methyl-hexyl group, 3-
Chlor-3-methyl-hexyl group, 3-bromo-3-methyl-hexyl group, 3-iodo-3-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-chloro-heptyl group, 2-bromo-heptyl group, 2-iodo-heptyl group, 3-chloro-heptyl group, 3-bromo-heptyl group, 3-iodo-heptyl group, 2,3-dichloro group -Heptyl group, 2,3-dibromo-heptyl group, 2,3-diiodo-heptyl group, 2-
Chlor-2-methyl-heptyl group, 2-bromo-2-methyl-heptyl group, 2-iodo-2-methyl-heptyl group, 3-chloro-2-methyl-heptyl group, 3-bromo-2-methyl- Heptyl group, 3-iodo-2-methyl-
Heptyl group, 2,3-dichloro-2-methyl-heptyl group, 2,3-dibromo-2-methyl-heptyl group, 2,
3-diiodo-2-methyl-heptyl group, 2-chloro-
3,4,4-trimethyl-heptyl group, 2-bromo-
3,4,4-trimethyl-heptyl group, 2-iodo-
3,4,4-trimethyl-heptyl group, 3-chloro-
3,4,4-trimethyl-heptyl group, 3-bromo-
3,4,4-trimethyl-2-heptyl group, 3-iodo-3,4,4-trimethyl-2-heptyl group, 2,3-
Dichloro-3,4,4-trimethyl2-heptyl group,
2,3-dibromo-3,4,4-trimethyl-2-heptyl group, 2,3-diiodo-3,4,4-trimethyl-
2-heptyl group,

2-chloro-octyl group, 2-bromo-octyl group, 2-iodo-octyl group, 3-chloro-octyl group, 3-bromo-octyl group, 3-iodo-octyl group, 2,3-dichloro group -Octyl group, 2,3-dibromo-octyl group, 2,3-diiodo-octyl group,

2-chloro-nonyl group, 2-bromo-nonyl group, 2-iodo-nonyl group, 3-chloro-nonyl group,
3-bromo-nonyl group, 3-iodo-nonyl group, 2,3
-Dichloro-nonyl group, 2,3-dibromo-nonyl group,
2,3-diiodo-nonyl group,

2-chloro-2,5-dimethyl-5-heptenyl group, 2-bromo-2,5-dimethyl-5-heptenyl group, 2-iodo-2,5-dimethyl-5-heptenyl group, 3- Chlor-2,5-dimethyl-5-heptenyl group, 3-bromo-2,5-dimethyl-5-heptenyl group, 3-iodo-2,5-dimethyl-5-heptenyl group, 5-chloro-2,5 -Dimethyl-2-heptenyl group, 5-bromo-2,5-dimethyl-2-heptenyl group, 5-iodo-2,5-dimethyl-2-heptenyl group, 6-chloro-2,5-dimethyl-2- Heptenyl group, 6-bromo-2,5-dimethyl-2-heptenyl group, 6-iodo-2,5-dimethyl-2-heptenyl 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-
A 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- , 5-dimethyl -
Heptyl group, 2,5,6-trichloro-2,5-dimethyl-heptyl group, 3,5,6-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-tribromo-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, 2,3,5,6-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-chloro-5-hexenyl group, 2-bromo-5-hexenyl group, 2-iodo-5-hexenyl group, 3-chloro-5-hexenyl group, 3-bromo-5-
Hexenyl group, 3-iodo-5-hexenyl group, 5-chloro-2-hexenyl group, 5-bromo-2-hexenyl group, 5-iodo-2-hexenyl group, 6-chloro-2-
Hexenyl group, 6-bromo-2-hexenyl group, 6-iodo-2-hexenyl 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,

2,5-dichloro-hexyl group, 2,6-
Dichloro-hexyl group, 3,5-dichloro-hexyl group, 3,6-dichloro-hexyl group, 2,5-dibromo-hexyl group, 2,6-dibromo-hexyl group, 3,5
-Dibromo-hexyl group, 3,6-dibromo-hexyl group, 2,5-diiodo-hexyl group, 2,6-diiodo-hexyl group, 3,5-diiodo-hexyl group, 3,6
-Diiodo-hexyl 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, 2,3,5,6-tetrachloro-hexyl group,
2,3,5,6-tetrabromo-hexyl group, 2,3,3
5,6-tetraiodo-hexyl group,

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

2,5-dichloro-1-methyl-hexyl group, 2,6-dichloro-1-methyl-hexyl group, 3,
5-dichloro-1-methyl-hexyl group, 3,6-dichloro-1-methyl-hexyl group, 2,5-dibromo-1
-Methyl-hexyl group, 2,6-dibromo-1-methyl-hexyl group, 3,5-dibromo-1-methyl-hexyl group, 3,6-dibromo-1-methyl-hexyl group,
2,5-diiodo-1-methyl-hexyl group, 2,6-
Diiodo-1-methyl-hexyl group, 3,5-diiodo-1-methyl-1-methyl-hexyl group, 3,6-diiodo-1-methyl-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, 3,5,6-tetrachloro-1-methyl-hexyl group, 2,3,5,6-tetrabromo-1-methyl-hexyl group, 2,3,5,6-tetraiodo-1-methyl-hexyl group,

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

2,5-dichloro-2-methyl-hexyl group, 2,6-dichloro-2-methyl-hexyl group, 3,
5-dichloro-2-methyl-hexyl group, 3,6-dichloro-2-methyl-hexyl group, 2,5-dibromo-2
-Methyl-hexyl group, 2,6-dibromo-2-methyl-hexyl group, 3,5-dibromo-2-methyl-hexyl group, 3,6-dibromo-2-methyl-hexyl group,
2,5-diiodo-2-methyl-hexyl group, 2,6-
Diiodo-2-methyl-hexyl group, 3,5-diiodo-2-methyl-hexyl group, 3,6-diiodo-2-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, 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-chloro-5-methyl-5-hexenyl group, 2-bromo-5-methyl-5-hexenyl group, 2-
Iodo-5-methyl-5-hexenyl group, 3-chloro-
5-methyl-5-hexenyl group, 3-bromo-5-methyl-5-hexenyl group, 3-iodo-5-methyl-5-
Hexenyl group, 5-chloro-5-methyl-2-hexenyl group, 5-bromo-5-methyl-2-hexenyl group, 5
-Iodo-5-methyl-2-hexenyl group, 6-chloro-5-methyl-2-hexenyl group, 6-bromo-5-methyl-2-hexenyl group, 6-iodo-5-methyl-2
-Hexenyl 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,

2,5-dichloro-5-methyl-hexyl group, 2,6-dichloro-5-methyl-hexyl group, 3,
5-dichloro-5-methyl-hexyl group, 3,6-dichloro-5-methyl-hexyl group, 2,5-dibromo-5
-Methyl-hexyl group, 2,6-dibromo-5-methyl-hexyl group, 3,5-dibromo-5-methyl-hexyl group, 3,6-dibromo-5-methyl-hexyl group,
2,5-diiodo-5-methyl-hexyl group, 2,6-
Diiodo-5-methyl-hexyl group, 3,5-diiodo-5-methyl-hexyl group, 3,6-diiodo-5-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, 2,3,6-tribromo-5-methyl-hexyl group, 2, 5,6-tribromo-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, 2,3,5,6-tetrachloro-5- Methyl-hexyl group, 2,3,5,6-tetrabromo-5-methyl-
Hexyl group, 2,3,5,6-tetraiodo-5-methyl-hexyl group,

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

2,4-dichloro-heptyl group, 2,5-
Dichloro-heptyl group, 3,4-dichloro-heptyl group, 3,5-dichloro-heptyl group, 2,4-dibromo-heptyl group, 2,5-dibromo-heptyl group, 3,4
-Dibromo-heptyl group, 3,5-dibromo-heptyl group, 2,4-diiodo-heptyl group, 2,5-diiodo-heptyl group, 3,4-diiodo-heptyl group, 3,5
-Diiodo-heptyl group, 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, 2,3,4,5-tetrachloro-heptyl group,
2,3,4,5-tetrabromo-heptyl group, 2,3
A 4,5-tetraiodo-heptyl group and the like can be mentioned.

Examples of the halogen atom represented by X include chlorine, bromine and iodine.

Further, in the formula (1), a divalent metal represented by M
Examples of Cu, Zn, Fe, Co, Ni, Ru,
Rh, Pd, Pt, Mn, Sn, Mg, Pb, Hg, C
d, Ba, Ti, Be, Ca, etc., and one substitution of 3
Examples of the valent metal include Al-F, Al-Cl, Al-B.
r, Al-I, Ga-F, Ga-Cl, Ga-Br, G
a-I, In-F, In-Cl, In-Br, In-
I, Tl-F, Tl-Cl, Tl-Br, Tl-I, A
l-C₆H_Five, Al-C₆H_Four(CH₃), In-C₆H_Five,
In-C₆H_Four(CH₃), Mn (OH), Mn (OC₆H
_Five), Mn [OSi (CH₃)₃], Fe-Cl, Ru-
Cl and the like, and examples of the di-substituted tetravalent metal include C
rCl₂, SiF₂, SiCl₂, SiBr₂, SiI₂,
SnF₂, SnCl₂, SnBr₂, ZrCl₂, Ge
F₂, GeCl₂, GeBr₂, GeI ₂, TiF₂, Ti
Cl₂, TiBr₂, Si (OH)₂, Sn (OH)₂, G
e (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)

[0042]

[Chemical 6] [In the formulas (3) and (4), R ¹ is O in the general formula (1).
It represents an alkyl group corresponding to the alkoxy group represented by R ¹ , and R ′ ² and R ′ ³ represent an alkenyl group. ] The compound represented by the formula 1,8-diazabicyclo [5,4,4]
[0] -7-undecene (DBU) in the presence of a metal derivative in alcohol under heating. Alternatively, a phthalocyanine compound having an alkoxy group and an alkenyl group is synthesized by reacting a metal derivative with a chloronaphthalene, bromnaphthalene, trichlorobenzene or the like in a high boiling solvent, and thionyl chloride, sufuryl chloride, hydrobromic acid , Bromine, iodine, iodine monochloride and the like, and the like.

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

[0044]

[Chemical 7]

The presence of the commercially available 3-nitro-phthalonitrile (A) bases, R ^'2 OH [R' ² are as defined above. ] The alkoxy phthalonitrile (B) is obtained by making it react with the allyl alcohol derivative shown by these. Further, after the Claisen transfer reaction of (B), R ′ ³ X was added in the presence of a base.
[R ′ ³ has the same meaning as described above, and X represents a halogen atom. ] By reacting with an allyl halide derivative represented by
-Alkoxy-4-alkenylphthalonitrile (C) is obtained. Further, after (C) is subjected to Claisen rearrangement reaction and in the presence of a base, R ¹ X [R ¹ has the same meaning as described above and 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 compound represented by (4) can be obtained by reacting (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 kinds of compounds including the phthalocyanine compound of the present invention are coated or vapor-deposited on a transparent substrate. There is a method, and as a coating method, 20% by weight or less of a 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 manufacturing an optical recording medium (optical disk, optical card, etc.), a polyacrylate substrate or a polycarbonate substrate is used as the substrate and 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.

[0051]

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 introducing tube,
2- (2-Pentoxy) -4,6-bis (1-propenyl) phthalonitrile 29.4 g (0.1 mol), DBU
15.2 g (0.1 mol) and 125 g of n-amyl alcohol were charged, and the temperature was raised to 100 ° C. under a nitrogen atmosphere. Next, at the same temperature, 5.3 g of palladium chloride (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 20.2 g of a phthalocyanine compound represented by the following formula (1-1) (yield 63%).
I got The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 735 nm ε _g = 2.2 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

[0054]

Embedded image

5 g (3.9 m) of the above phthalocyanine compound
(mol) was dissolved in 30 g of 1,1,2-trichloroethane, and 10 g of water was added. Next, 5.0 g of bromine (31 mm
ol) and 5 g of 1,1,2-trichloroethane were added dropwise at 50 to 55 ° C. in 30 minutes, and the same temperature was reached for 1 hour to complete the process. 10% aqueous sodium hydrogen sulfite solution 8.6
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 8.7 g of a brominated phthalocyanine compound. Elemental analysis revealed that 15.8 bromine atoms were substituted, and FD-MS revealed that all bromine atoms were substituted in the side chain. The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 719 nm ε _g = 2.3 × 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 Phthalocyanine compound (1-1) 5 synthesized in Example 1
g (3.9 mmol) was dissolved in 30 g of 1,1,2-trichloroethane, and 10 g of water was added. Then bromine 9.6
A mixed solution of g (60.1 mmol) and 11 g of 1,1,2-trichloroethane was added dropwise at 50 to 55 ° C over 30 minutes, and the same temperature was added for 1 hour to complete the process. A 15% aqueous sodium hydrogen sulfite solution (8.6 g) was added for washing. 80 g of methanol was added dropwise to the organic layer, and the precipitated crystals were filtered and dried,
Column purification (silica gel 100 g, solvent toluene),
8.9 g of a brominated phthalocyanine compound was obtained. From NMR, it was found that all side chain double bonds were replaced with bromine, and from elemental analysis, 18.1 bromine was replaced.
Therefore, it was found that the ring had 2.1 substitutions. The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 727 nm ε _g = 2.1 × 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 In a container similar to that of Example 1, 3- (3-hexoxy)-
4,6-bis (1-propenyl) phthalonitrile 30.
8 g (0.1 mol), DBU 15.2 g (0.1 mol)
Then, 120 g of n-amyl alcohol was charged and the temperature was raised to 100 ° C. under a nitrogen atmosphere. Next, at the same temperature, 5.3 g (0.03 mol) of palladium chloride was added,
The reaction was carried out at 100 ° C for 20 hours. After the reaction is complete, cool down,
Insolubles were removed by filtration. The filtrate was concentrated under reduced pressure to recover the solvent, and then purified by column (silica gel 500 g, solvent toluene).
Then, 21.8 g (yield: 65%) of a phthalocyanine compound represented by the following formula (1-2) was obtained. The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 736 nm ε _g = 2.1 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

[0063]

[Chemical 9]

5.2 g of the above phthalocyanine compound (3.
9 mmol) was dissolved in 30 g of 1,1,2-trichloroethane, and 10 g of water was added. Next, 5.0 g (3
1.4 mmol) and 1,1,2-trichloroethane 5 g
The mixed solution of and was added dropwise at 50 to 55 ° C. in 30 minutes, and the operation was completed at the same temperature for 1 hour. A 15% aqueous sodium hydrogen sulfite solution (8.6 g) was added for washing. The organic layer is methanol 1
00 g was added dropwise, and the precipitated crystals were filtered, dried and column purified (silica gel 100 g, solvent toluene) to obtain 8.6 g of a brominated phthalocyanine compound. Elemental analysis revealed that 14.9 bromine atoms were substituted, and FD-MS revealed that all bromine atoms were substituted in the side chain. The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 721 nm ε _g = 2.1 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

Dibutyl ether of the above phthalocyanine compound
A tellurium solution (10 g / l) was applied onto a polycarbonate substrate for CD-R by a spin coater in the same manner as in Example 1, gold was sputter-deposited on the substrate, and then a protective layer was formed using a UV curable resin. , A CD-R type medium was produced.
When an EFM signal was written with a power of 5.0 mW at a linear velocity of 1.4 m / s on this medium using a semiconductor laser of 780 nm, the error rate was less than 0.2%.
There was no change even after performing reproduction 1 million times with reproduction light of 5 mW. Recording / reproduction was not affected even after 1000 hours under the condition of 80 ° C./85%.

Example 4 Phthalocyanine compound (1-2) synthesized in Example 3
5.2 g (3.9 mmol) was dissolved in 30 g of 1,1,2-trichloroethane, and 10 g of water was added. Next, a mixed solution of 9.7 g (60.5 mmol) of bromine and 11 g of 1,1,2-trichloroethane was added dropwise at 50 to 55 ° C over 30 minutes, and the operation was completed at the same temperature for 1 hour. A 15% sodium hydrogen sulfite aqueous solution 8.6 was added for washing. 80 g of methanol was added dropwise to the organic layer, and the precipitated crystals were filtered and dried, followed by column purification (silica gel 100 g, solvent toluene).
Then, 9.3 g of a brominated phthalocyanine compound was obtained. NM
From R, it was found that all of the side chain double bonds were replaced by bromine, and elemental analysis revealed that 19.5 bromine was replaced. Therefore, it was found that 3.5 rings were substituted. The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 736 nm ε _g = 2.3 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

Dibutyl ether of the above phthalocyanine compound
A tellurium solution (10 g / l) was applied onto a polycarbonate substrate for CD-R by a spin coater in the same manner as in Example 1, gold was sputter-deposited on the substrate, and then a protective layer was formed using a UV curable resin. , A CD-R type medium was produced.
0.5 m was recorded on this medium at a linear velocity of 1.4 m / s and a power of 5.0 mW using a semiconductor laser of 780 nm.
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 5 In a container similar to that of Example 1, 3- (2-pentoxy)-
4,6-bis (1-propenyl) phthalonitrile 29.
4 g (0.1 mol), DBU 15.2 g (0.1 mol), and 125 g of n-amyl alcohol were charged, and the temperature was raised to 100 ° C. under a nitrogen atmosphere. Next, 3.0 g (0.03 mol) of cuprous chloride was added at the same temperature, and
The reaction was carried out at -100 ° C for 10 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 to obtain 24.8 g (yield 80%) of a phthalocyanine compound represented by the following formula (1-3). The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 756 nm ε _g = 2.4 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

[0072]

[Chemical 10]

4.9 g of the above phthalocyanine compound (3.
9 mmol) was dissolved in 35 g of 1,1,2-trichloroethane, and 10 g of water was added. Next, 5.0 g of bromine (32 g
mmol) and 5.0 g of 1,1,2-trichloroethane were added dropwise at 50 to 55 ° C over 30 minutes, and the mixture was reacted at the same temperature for 2 hours. It was washed with 10 g of 10% sodium bisulfite. The organic layer was separated, 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 7.9 g of brominated phthalocyanine. Elemental analysis revealed that 15.3 bromine had been substituted, and FD-MS revealed that all bromine had been substituted in the side chain. The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 717 nm ε _g = 2.4 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

10 g of the above-mentioned 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 coat a polycarbonate optical card substrate with a thickness of 100 nm.
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 61 dB. Also, linear velocity 2
Reproduction was possible with a laser beam of m / s, 0.8 mW, and when the reproduction light stability was investigated, reproduction was possible 10 ⁵ times. Furthermore, this optical card also had good storage stability.

Example 6 4.9 g of the phthalocyanine compound (1-3) of Example 5
(3.9 mmol) was added to 1,1,2-trichloroethane 3
It was dissolved in 5 g and 10 g of water was added. Then 5.0 g of bromine
(32 mmol) and 1,1,2-trichloroethane 5.
A mixed solution with 0 g was added dropwise at 50 to 55 ° C over 30 minutes, and the mixture was reacted at the same temperature for 2 hours. 10% sodium bisulfite 1
It was washed with 0 g. After separating the organic layer, 80 g of methanol was added dropwise, and the precipitated crystals were filtered and dried, followed by column purification (100 g of silica gel, solvent toluene) to obtain 8.5 g of brominated phthalocyanine. Elemental analysis revealed that 18.2 bromine had been substituted, and FD-MS revealed that all side chain double bonds had been substituted with bromine. Therefore 2.2 in the ring
It turns out that they are replacing. The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption λ _max = 731 nm ε _g = 2.3 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

A solution of the above phthalocyanine compound in ethylcyclohexane (20 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. 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 7 A container similar to that used in Example 1 was charged with 3- (2,4-dimethyl-3).
-Pentoxy) -4,6-bis (1-propenyl) phthalonitrile 32.2 g (0.1 mol), DBU 15.2
g (0.1 mol) and 125 g of n-amyl alcohol
Was charged and the temperature was raised to 100 ° C. under a nitrogen atmosphere.
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 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 50
2 g of a phthalocyanine compound represented by the following formula (1-4) was obtained (60% yield). The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 736 nm ε _g = 2.4 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

[0081]

[Chemical 11]

5.1 g of the above phthalocyanine compound (3.
7 mmol) was dissolved in 35 g of 1,1,2-trichloroethane, and 10 g of water was added. Next, 4.7 g of bromine (30
mmol) and 5.0 g of 1,1,2-trichloroethane were added dropwise at 50 to 55 ° C over 30 minutes, 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, 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 brominated phthalocyanine 7.4 g. Elemental analysis revealed that 14.4 bromine had been substituted, and FD-MS revealed that all bromine had been substituted in the side chain. The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 723 nm ε _g = 2.2 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

10 g of the above-mentioned 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 coat a polycarbonate optical card substrate with a thickness of 100 nm.
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 61 dB. Also, linear velocity 2
Reproduction was possible with a laser beam of m / s, 0.8 mW, and when the reproduction light stability was investigated, reproduction was possible 10 ⁵ times. Furthermore, this optical card also had good storage stability.

Example 8 5.1 g of the phthalocyanine compound (1-4) of Example 7
(3.7 mmol) of 1,1,2-trichloroethane 3
It was dissolved in 5 g and 10 g of water was added. Next, 9.0 g of bromine
(57 mmol) and 1,1,2-trichloroethane 1
A mixed solution with 0.0 g was added dropwise at 50 to 55 ° C over 30 minutes, 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, methanol 8
The crystals precipitated by dropping in 0 g were filtered and dried, and then column purified (silica gel 100 g, solvent toluene) to obtain 8.7 g of brominated phthalocyanine. From elemental analysis, bromine was 18.
It was found that 7 substitutions were made, and FD-MS revealed that all side chain double bonds were replaced by bromine. Therefore, it was found that the ring had 2.7 substitutions. The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 735 nm ε _g = 2.0 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

A solution of the above phthalocyanine compound in ethylcyclohexane (20 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. 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 9 In a container similar to that of Example 1, 3- (3-methyl-butoxy) -4- (1-methyl-1-propenyl) -6- (1
30.8 g (0.1 mol) of -propenyl) phthalonitrile, 15.2 g (0.1 mol) of DBU, and 120 g of n-amyl alcohol were charged, and 10 were added under a nitrogen atmosphere.
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 15 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 21.8 g of a phthalocyanine compound represented by the following formula (1-5).
(Yield 65%) was obtained. The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 733 nm ε _g = 2.0 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

[0090]

[Chemical 12]

The above phthalocyanine compound (5.2 g, 3.
9 mmol) was dissolved in 35 g of 1,1,2-trichloroethane, and 10 g of water was added. Then sulfuryl chloride 4.
A mixed solution of 3 g (32 mmol) and 5.0 g of 1,1,2-trichloroethane was added dropwise at 50 to 55 ° C over 30 minutes, and the mixture was reacted at the same temperature for 2 hours. The solution was neutralized by adding 31 g of a 10% sodium hydroxide aqueous solution. The organic layer was separated, 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 7.7 g of chlorinated phthalocyanine. Elemental analysis revealed that 15.7 chlorine was substituted, and FD-MS revealed that all chlorine was substituted in the side chain. The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 716 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 61 dB. Also, linear velocity 2
Reproduction was possible with a laser beam of m / s, 0.8 mW, and when the reproduction light stability was investigated, reproduction was possible 10 ⁵ times. Furthermore, this optical card also had good storage stability.

Example 10 5.2 g of the phthalocyanine compound (1-5) of Example 9
(3.9 mmol) was added to 1,1,2-trichloroethane 3
It was dissolved in 5 g and 10 g of water was added. Then 9.4 g of bromine
(59 mmol) and 1,1,2-trichloroethane 1
A mixed solution with 0.0 g was added dropwise at 50 to 55 ° C over 30 minutes, 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, methanol 8
The crystals precipitated by dropping into 0 g were filtered and dried, and then column purified (silica gel 100 g, solvent toluene) to obtain 8.4 g of brominated phthalocyanine. Bromine was found to be 19.
Five substitutions were made, and it was found from FD-MS that the side chain double bonds were all substituted with bromine. Therefore, it was found that 3.5 rings were substituted. The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 731 nm ε _g = 2.1 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

A solution of the above phthalocyanine compound in ethylcyclohexane (20 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. 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%.

Examples 11 to 21 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. In addition, 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 similarly evaluated. The results are shown in Table 1.

[0098]

[Chemical 13]

[0099]

[Table 1]

[0100]

[Table 2]

[0101]

[Table 3]

[0102]

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, and therefore has a low solubility in a solvent used when coating a substrate by spin coating. Improved. In addition, the halogen atoms substituted on the alkyl or alkenyl groups and the phthalocyanine ring were used to control the decomposition and melting of the dye during recording to form highly accurate pits. Of the recording layer having a reflective layer, and in the case of a recording medium having a reflective layer, improved adhesion between the recording layer and the metal layer that is the reflective layer. Even in high-speed recording or high-density recording, the effect of improving the sensitivity and recording characteristics of the optical recording medium is improved.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kenichi Sugimoto 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 Kagaku 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 represents two hydrogen atoms, a divalent metal atom, a trivalent mono-substituted metal atom, a tetravalent di-substituted metal atom, and an oxy metal atom, and L ¹ is represented by the formula (a): Chemical 2] (In the formula (a), OR ¹ represents a linear or branched alkoxy group having 1 to 20 carbon atoms, and R ² and R ³ each independently have ³ to 4 carbon atoms substituted with a halogen atom. 20 straight-chain or branched alkyl groups or halogen atoms are 0
˜2 represents a linear or branched alkenyl group having 3 to 20 carbon atoms, and X represents a hydrogen atom or a halogen atom. ) Represents. ] 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.