JPH0790186A - Phthalocyanine compound and optical recording medium containing it - Google Patents

Abstract

PURPOSE:To obtain a phthalocyanine compound which gives an optical recording medium having excellent characteristics in, e.g. reflectance, sensitivity, recording characteristics, resistance to reproduction light, and shelf stability. CONSTITUTION:A phthalocyanine represented by the formula [wherein R<1>, R<2>, R<3> and R<4> are each 1-20C alkyl, 2-20C alkenyl or 2-20C alkynyl substituted by 0 to 5 halogen atoms, provided that at least one of them is a halogen- substituted group; X is halogen; k, l, m and n are each independently 0 to 3, and o, p, q and r are each independently 0, 1 or 2, except for the case where all of them are 0 at the same time and provided that the sams of k and o, land p, m and q, and n and r are each independently 0 to 4; and Met stands for two hydrogen atoms, a divalent metal atom, a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or an oxy metal atom].

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, protective glasses, and other compounds useful as a near-infrared absorber which plays an important role in optoelectronics related applications, and records the compound. The present invention relates to an optical recording medium such as an optical disk and an optical card formed by containing it in a layer, and a near-infrared absorber composed of these compounds.

[0002]

2. Description of the Related Art A technique of using a phthalocyanine dye in a recording layer of a recording medium such as an optical disk or an optical card is disclosed in Japanese Patent Laid-Open No.
1-154888 (EP 18646), 61
No. 1972280, No. 61-246091,
No. 62-39286 (USP 4,769,30).
7), No. 63-37991, and No. 63-39388.
Although widely known from Japanese Patent Laid-Open Publications, these phthalocyanines have been unsatisfactory for optical recording media in terms of sensitivity, refractive index, recording characteristics and the like. A compound obtained by improving them is disclosed in JP-A-3-62878, but it has not been practically sufficient due to a problem in recording characteristics when writing with a laser beam. In addition, JP-A-4-214388
JP-A-5-238150 and the like disclose that a phthalocyanine having fluorine introduced as a substituent improves solubility and adhesion to a resin, but the introduction of a fluorine group is a laser beam. Does not contribute to the improvement of sensitivity during writing.

[0003]

The above-mentioned phthalocyanines are sensitized (C / N ratio, optimum recording power), reflectivity, and recording characteristics (shape of signal during recording) when used in an optical recording medium.
Etc. do not have sufficient performance.

An object of the present invention is to satisfy the above performance,
That is, it is an object of the present invention to provide a dye having high sensitivity and reflectance and capable of forming an optical recording medium in which signal formation during recording is accurate.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies to achieve the above object and completed the present invention. That is, the present invention provides the following general formula (1)

[0006]

[Chemical 2] [In the formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently
C1-C20 alkyl group substituted with 0-5 halogen atoms, C2-C20 alkenyl group substituted with 0-5 halogen atoms, 0-5 halogen atoms substituted Is an alkynyl group having 2 to 20 carbon atoms,
At least one of R ¹ , R ² , R ³ , and R ⁴ is a group substituted with a halogen atom. X represents a halogen atom. k, l, m, and n each independently represent a number of 0 to 3. o, p, q, and r are independently 0, 1 or 2
And all cannot be 0 at the same time. The sums of k and o, l and p, m and q, and n and r are independently 0.
~ 4. Met represents two hydrogen atoms, a divalent metal atom, a trivalent mono-substituted metal atom, a tetravalent di-substituted metal atom, or an oxy metal atom. ] It is an optical recording medium formed by containing the phthalocyanine shown by these in a recording layer.

The phthalocyanine of the present invention comprises 650-90.
It has a sharp absorption at 0 nm and is suitable for a recording material of an optical recording medium using a semiconductor laser beam. The mechanism has not been clarified yet and it is currently under investigation. In particular, the halogen atom substituting the alkoxy group contributes to the improvement of the sensitivity at the time of recording and is effective in reducing the error of the formed signal.
That is, it controls the melting and decomposition of the dye during optical recording, reduces damage to the substrate of the recording medium, and improves the adhesion between the reflective layer and the recording layer in the case of a medium having a reflective layer.

The present invention will be described in detail below.

The characteristics of the phthalocyanine compound of the present invention are as follows:
That is, the α-position of the phthalocyanine ring is substituted with an alkyl group, an alkenyl group or an alkynyl group via an oxygen atom, and the substituent has at least one halogen atom. Here, the halogen atom is chlorine, bromine, or iodine, and these different kinds of halogen may be mixed in the same molecule. Of these, bromine and iodine are particularly preferable. Due to the halogen atom, in the optical recording medium using this compound, the signal at the time of optical recording can be correctly written, and the sensitivity and recording characteristics can be improved.

In the general formula (1), when o, p, q, and r each independently take the value of ² , OR ¹ , OR ² , OR ³ , and OR ⁴ existing on the same benzene ring are the same. But it can be different.

More preferably, R ¹ , R ² , R ³ and R ⁴ are each independently a C ⁵ to C 15 alkyl group substituted with 0 to 5 halogen atoms, and 0 to 5 halogen atoms. A substituted alkenyl group having 5 to 15 carbon atoms, an alkynyl group having 5 to 5 carbon atoms substituted with 0 to 5 halogen atoms, and at least one of R ¹ , R ² , R ³ , and R ⁴ ; One is a group in which a halogen atom is substituted, such as o, p,
A phthalocyanine in which both q and r are 1 and an optical recording medium formed by containing the phthalocyanine in the recording layer.

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

In the general formula (1), OR ¹ , OR ² , OR ³ ,
Among the substituents represented by OR ⁴ , the substituent having no halogen atom is an alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, or a carbon atom having 2 carbon atoms.
To 20 alkynyloxy groups, specifically, a methoxy group, an ethoxy group, a propoxy group, a butyloxy group,
Pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group , A heptadecyloxy group,
Octadecyloxy group, nonadecyloxy group, icosyloxy group,

Vinyloxy group, propenyloxy group, butenyloxy group, pentenyloxy group, hexenyloxy group, heptenyloxy group, octenyloxy group, nonanyloxy group, decenyloxy group, undecenyloxy group, dodecenyloxy group, tridecenyloxy group, Tetradecenyloxy group, pentadecenyloxy group, hexadecanyloxy group, heptadecenyloxy group, octadecenyloxy group, nonadecenyloxy group, icosenyloxy group,

Ethynyloxy group, propynyloxy group,
Butynyloxy group, pentynyloxy group, hexynyloxy group, heptynyloxy group, octynyloxy group, nonyloxy group, decynyloxy group, undecynyloxy group, dodecynyloxy group, tridecynyloxy group, tetradecynyloxy group, pentadecynyloxy group, hexadecyloxy group Examples thereof include a nyloxy group, a heptadecynyloxy group, an octadecynyloxy group, a nonadecynyloxy group and an icosinyloxy group.

Of these, a particularly preferred example is a branched alkoxy group having 5 to 15 carbon atoms, which is a group having a large steric hindrance and easily protruding in the vertical direction of the phthalocyanine ring.
An alkenyloxy group and an alkynyloxy group. Specifically, 2-methylbutane-1-oxy group, 3-methylbutane-1-oxy group, 4-methylpentane-3-oxy group, 4-methylpentane-2-oxy group, 2-methylpentane-3- Oxy group, 3-methylpentane-2-oxy group, 4-methylpentane-2-oxy group, 3-methylpentane-3-oxy group, 2-methylpentane-2-
Oxy group, 2-methylpentane-3-oxy group, 2,3
-Dimethylbutane-2-oxy group, 4-methylhexane-2-oxy group, 5-methylhexane-2-oxy group,
5-methylhexane-3-oxy group, 2,4-dimethylpentane-3-oxy group, 2-methylhexane-3-oxy group, 2-methyl-5-butylhexane-3-oxy group, 3-methylhexane -2-oxy group, 2,5-dimethylhexane-3-oxy group, 6-methylheptane-2
-Oxy group, 2-methylheptane-3-oxy group, 2,
2-dimethylheptane-3-oxy group, 5-methylheptane-4-oxy group, 6-methylheptane-3-oxy group, 4-methylheptane-3-oxy group, 3,5-dimethylheptane-4-oxy group Group, 2,5-dimethylheptane-4-oxy group, 2,4-dimethylheptane-1-oxy group, 2,5-dimethyl-5-hexene-3-oxy group, 2,5-dimethyl-1-hexene -3-oxy group,
And so on.

Also, a halogen atom having 1 to 20 carbon atoms.
Examples of the alkoxy group, the alkenyloxy group having 2 to 20 carbon atoms, or the alkynyloxy group having 2 to 20 carbon atoms include, for example, a chloromethyloxy group, a bromomethyloxy group, and a 2-chloroethyl-1-oxy group. ,
2-bromoethyl-1-oxy group, 2-iodoethyl-
1-oxy group, 2-chloropropyl-1-oxy group, 1
-Chloropropyl-2-oxy group, 2-bromopropyl-1-oxy group, 1-bromopropyl-2-oxy group,
2-iodopropyl-1-oxy group, 1-iodopropyl-2-oxy group, 2,3-dichloropropyl-1-oxy group, 2,3-dibromopropyl-1-oxy group,
2,3-diiodopropyl-1-oxy group, 3-chlorobutyl-1-oxy group, 3-bromobutyl-1-oxy group, 3-iodobutyl-1-oxy group,

3,4-dichloro-2-butyloxy group,
3,4-dibromo-2-butyloxy group, 3,4-diiodo-2-butyloxy group,

1-iodopentane-3-oxy group, 2-
Iodopentane-3-oxy group, 1-chloropentane-
3-oxy group, 2-chloropentane-3-oxy group, 1
-Bromopentane-3-oxy group, 2-bromopentane-3-oxy group, 1,2-diiodopentane-3-oxy group, 1,2-dibromopentane-3-oxy group, 5-
Iodohexane-2-oxy group, 6-iodohexane-
2-oxy group, 6-chlorohexane-2-oxy group,
1,2-dichloropentane-3-oxy group, 1,2-dibromopentane-3-oxy group,

5-iodohexane-2-oxy group, 6-
Iodohexane-2-oxy group, 5-chlorohexane-
2-oxy group, 6-chlorohexane-2-oxy group, 5
-Bromohexane-2-oxy group, 6-bromohexane-2-oxy group, 5,6-diiodohexane-2-oxy group, 5,6-dichlorohexane-2-oxy group, 5,
6-dibromohexane-2-oxy group,

1-iodohexane-3-oxy group, 2-
Iodohexane-3-oxy group, 1-chlorohexane-
3-oxy group, 2-chlorohexane-3-oxy group, 1
-Bromohexane-3-oxy group, 2-bromohexane-3-oxy group, 1,2-diiodohexane-3-oxy group, 1,2-dichlorohexane-3-oxy group, 1,
2-dibromohexane-3-oxy group,

5-iodohexane-1-oxy group, 6-
Iodohexane-1-oxy group, 5-chlorohexane-
1-oxy group, 6-chlorohexane-1-oxy group, 5
-Bromohexane-1-oxy group, 6-bromohexane-1-oxy group, 5,6-diiodohexane-1-oxy group, 5,6-dichlorohexane-1-oxy group, 5,
6-dibromohexane-1-oxy group, 3-iodohexane-1-oxy group, 4-iodohexane-1-oxy group, 3-chlorohexane-1-oxy group, 4-chlorohexane-1-oxy group, 3-bromohexane-1-oxy group, 4-bromohexane-1-oxy group, 3,4-diiodohexane-1-oxy group, 3,4-dichlorohexane-1-oxy group, 3,4-dibromo Hexane-1-
Oxy group, 5-iodohexane-1-oxy group, 5-chlorohexane-1-oxy group, 5-bromohexane-1
-Oxy group, 4,5-diiodohexane-1-oxy group, 4,5-dichlorohexane-1-oxy group, 4,5
-Dibromohexane-1-oxy group,

1-iodoheptane-4-oxy group, 1-
Chloroheptane-4-oxy group, 1-bromoheptane-
4-oxy group, 2-iodoheptane-4-oxy group, 2
-Chloroheptane-4-oxy group, 2-bromoheptane-4-oxy group, 1,2-diiodoheptane-4-oxy group, 1,2-dichloroheptane-4-oxy group, 1,
2-dibromoheptane-4-oxy group, 3-iodoheptane-4-oxy group, 3-chloroheptane-4-oxy group, 3-bromoheptane-4-oxy group, 2,3-diiodoheptane-4- An oxy group, a 2,3-dichloroheptane-4-oxy group, a 2,3-dibromoheptane-4-oxy group,

1-iodoheptane-3-oxy group, 1-
Chloroheptane-3-oxy group, 1-bromoheptane-
3-oxy group, 2-iodoheptane-3-oxy group, 2
-Chloroheptane-3-oxy group, 2-bromoheptane-3-oxy group, 1,2-diiodoheptane-3-oxy group, 1,2-dichloroheptane-3-oxy group, 1,
2-dibromoheptane-3-oxy group, 1-iodooctane-3-oxy group, 1-chlorooctane-3-oxy group, 1-bromooctane-3-oxy group, 2-iodooctane-3-oxy group, 2-chlorooctane-3-oxy group, 2-bromooctane-3-oxy group, 1,2-diiodooctane-3-oxy group, 1,2-dichlorooctane-3-oxy group, 1,2-dibromo Octane-3-
Oxy group,

1-iodooctane-4-oxy group, 1-
Chlorooctane-4-oxy group, 1-bromooctane-
4-oxy group, 2-iodooctane-4-oxy group, 2
-Chlorooctane-4-oxy group, 2-bromooctane-4-oxy group, 1,2-diiodooctane-4-oxy group, 1,2-dichlorooctane-4-oxy group, 1,
2-dibromooctane-4-oxy group, 3-iodooctane-4-oxy group, 3-chlorooctane-4-oxy group, 3-bromooctane-4-oxy group, 2,3-diiodooctane-4- Oxy group, 2,3-dichlorooctane-4-oxy group, 2,3-dibromooctane-4-oxy group,

1-iodononane-3-oxy group, 2-iodononane-3-oxy group, 1-chlorononane-3-oxy group, 2-chlorononane-3-oxy group, 1-bromononane-3-oxy group, 2- Bromononane-3-oxy group, 1,2-diiodononane-3-oxy group, 1,2-
Dichlorononane-3-oxy group, 1,2-dibromononane-3-oxy group,

3-iodo-2-methylbutane-1-oxy group, 3-chloro-2-methylbutane-1-oxy group,
3-bromo-2-methylbutane-1-oxy group, 4-iodo-2-methylbutane-1-oxy group, 4-chloro-
2-methylbutane-1-oxy group, 4-bromo-2-methylbutane-1-oxy group, 3,4-diiodo-2-methylbutane-1-oxy group, 3,4-dichloro-2-methylbutane-1-oxy group Group, 3,4-dibromo-2-methylbutane-1-oxy group, 2-iodo-3-methylbutane-1-oxy group, 2-chloro-3-methylbutane-
1-oxy group, 2-bromo-3-methylbutane-1-oxy group, 2,3-dibromo-3-methylbutane-1-oxy group, 4-iodo-3-methylbutane-1-oxy group, 4-chloro- 3-methylbutane-1-oxy group, 4
-Bromo-3-methylbutane-1-oxy group, 3-methyl-3,4-dibromobutane-1-oxy group,

1-iodo-4-methylpentane-3-oxy group, 2-iodo-4-methylpentane-3-oxy group, 1-chloro-4-methylpentane-3-oxy group,
2-chloro-4-methylpentane-3-oxy group, 1-
Bromo-4-methylpentane-3-oxy group, 2-bromo-4-methylpentane-3-oxy group, 1,2-diiodo-4-methylpentane-3-oxy group, 1,2-dichloro-4- Methyl pentane-3-oxy group, 1,2-
A dibromo-4-methylpentane-3-oxy group,

3-iodo-4-methylpentane-2-oxy group, 3-chloro-4-methylpentane-2-oxy group, 3-bromo-4-methylpentane-2-oxy group,
3,4-dibromo-4-methylpentane-2-oxy group, 1-iodo-2-methylpentane-3-oxy group,
1-chloro-2-methylpentane-3-oxy group, 1-
Bromo-2-methylpentane-3-oxy group, 1,2-
A dibromo-2-methylpentane-3-oxy group,

4-iodo-3-methylpentane-2-oxy group, 5-iodo-3-methylpentane-2-oxy group, 4-chloro-3-methylpentane-2-oxy group,
5-chloro-3-methylpentane-2-oxy group, 4-
Bromo-3-methylpentane-2-oxy group, 5-bromo-3-methylpentane-2-oxy group, 4,5-diiodo-3-methylpentane-2-oxy group, 4,5-dichloro-3- Methyl pentane-2-oxy group, 4,5-
Dibromo-3-methylpentane-2-oxy group, 5-iodo-4-methylpentane-2-oxy group, 5-bromo-4-methylpentane-2-oxy group, 4,5-dibromo-4-methylpentane -2-oxy group,

1-iodo-3-methylpentane-3-oxy group, 2-iodo-3-methylpentane-3-oxy group, 1-chloro-3-methylpentane-3-oxy group,
2-chloro-3-methylpentane-3-oxy group, 1-
Bromo-3-methylpentane-3-oxy group, 2-bromo-3-methylpentane-3-oxy group, 1,2-diiodo-3-methylpentane-3-oxy group, 1,2-dichloro-3- Methyl pentane-3-oxy group, 1,2-
A dibromo-3-methylpentane-3-oxy group,

4-iodo-2-methylpentane-2-oxy group, 5-iodo-2-methylpentane-2-oxy group, 4-chloro-2-methylpentane-2-oxy group,
5-chloro-2-methylpentane-2-oxy group, 4-
Bromo-2-methylpentane-2-oxy group, 5-bromo-2-methylpentane-2-oxy group, 4,5-diiodo-2-methylpentane-3-oxy group, 4,5-dichloro-2- Methyl pentane-3-oxy group, 4,5-
Dibromo-2-methylpentane-3-oxy group, 2,3
-Dimethyl-4-iodobutane-2-oxy group, 2,3
-Dimethyl-4-chlorobutane-2-oxy group, 2,3
-Dimethyl-4-bromobutane-2-oxy group, 2,3
-Dimethyl-3,4-dibromobutane-2-oxy group,
4-methyl-5-iodohexane-2-oxy group, 4-
Methyl-5-bromohexane-2-oxy group, 4-methyl-4,5-dibromohexane-2-oxy group, 5-methyl-6-iodohexane-2-oxy group, 5-methyl-6-chlorohexane -2-oxy group, 5-methyl-6
-Bromohexane-2-oxy group, 5-methyl-5,6
-Dibromohexane-2-oxy group,

5-methyl-6-iodohexane-3-oxy group, 5-methyl-6-chlorohexane-3-oxy group, 5-methyl-6-bromohexane-3-oxy group,
5-methyl-5,6-dibromohexane-3-oxy group, 1-iodo-2,4-dimethylpentane-3-oxy group, 1-chloro-2,4-dimethylpentane-3-oxy group, 1- Bromo-2,4-dimethylpentane-3-
Oxy group, 1,2-dibromo-2,4-dimethylpentane-3-oxy group, 2-methyl-5-iodohexane-
3-oxy group, 2-methyl-6-iodohexane-3-
Oxy group, 2-methyl-5,6-diiodohexane-3
-Oxy group, 2-methyl-5-chlorohexane-3-oxy group, 2-methyl-6-chlorohexane-3-oxy group, 2-methyl-5,6-dichlorohexane-3-oxy group, 2- Methyl-5-bromohexane-3-oxy group, 2-methyl-6-bromohexane-3-oxy group,
2-methyl-5,6-dibromohexane-3-oxy group, 2-methyl-4-iodohexane-3-oxy group,
2-methyl-4,5-diiodohexane-3-oxy group, 2-methyl-4-chlorohexane-3-oxy group,
2-methyl-4,5-dichlorohexane-3-oxy group, 2-methyl-4-bromohexane-3-oxy group,
2-methyl-4,5-dibromohexane-3-oxy group,

3-methyl-4-iodohexane-2-oxy group, 3-methyl-4-chlorohexane-2-oxy group, 3-methyl-4-bromohexane-2-oxy group,
3-methyl-3,4-dibromohexane-2-oxy group, 2,5-dimethyl-6-iodohexane-3-oxy group, 2,5-dimethyl-6-chlorohexane-3-oxy group, 2, 5-dimethyl-6-bromohexane-3-
Oxy group, 2,5-dimethyl-6,6-dibromohexane-3-oxy group, 1,6-diiodo-2,5-dimethylhexane-3-oxy group, 1,6-dichloro-2,5
-Dimethylhexane-3-oxy group, 1,2-dibromo-2,5-dimethyl-5-hexene-3-oxy group,
1,2-dichloro-2,5-dimethyl-5-hexene-
3-oxy group, 1,6-dibromo-2,5-dimethylhexane-3-oxy group, 5,6-dibromo-2,5-dimethyl-1-hexene-3-oxy group, 5,6-dichloro- 2,5-dimethyl-1-hexene-3-oxy group,
1,2,5,6-tetrabromo-2,5-dimethylhexane-3-oxy group, 1,2,5,6-tetrachloro-
2,5-dimethylhexane-3-oxy group,

5-iodo-6-methylheptane-2-oxy group, 5-bromo-6-methylheptane-2-oxy group, 5-chloro-6-methylheptane-2-oxy group,
5,6-dibromo-6-methylheptane-2-oxy group, 5,6-dichloro-6-methylheptane-2-oxy group, 1-iodo-2-methylheptane-3-oxy group, 1-chloro- 2-methylheptane-3-oxy group,
1-bromo-2-methylheptane-3-oxy group, 1,
2-dibromo-2-methylheptane-3-oxy group,
1,2-dichloro-2-methylheptane-3-oxy group, 2,2-dimethyl-5-iodoheptane-3-oxy group, 2,2-dimethyl-6-iodoheptane-3-oxy group, 2, 2-dimethyl-5-chloroheptane-3-
Oxy group, 2,2-dimethyl-6-chloroheptane-3
-Oxy group, 2,2-dimethyl-5-bromoheptane-
3-oxy group, 2,2-dimethyl-6-bromoheptane-3-oxy group, 2,2-dimethyl-5,6-diiodoheptane-3-oxy group, 2,2-dimethyl-5,6-
Dichloroheptane-3-oxy group, 2,2-dimethyl-
5,6-dibromoheptane-3-oxy group,

1-iodo-5-methylheptane-4-oxy group, 2-iodo-5-methylheptane-4-oxy group, 1,2-diiodo-5-methylheptane-4-oxy group, 1-chloro -5-methylheptane-4-oxy group, 2-chloro-5-methylheptane-4-oxy group,
1,2-dichloro-5-methylheptane-4-oxy group, 1-bromo-5-methylheptane-4-oxy group,
2-bromo-5-methylheptane-4-oxy group, 1,
2-dibromo-5-methylheptane-4-oxy group,

6-methyl-7-iodoheptane-3-oxy group, 6-methyl-7-chloroheptane-3-oxy group, 6-methyl-7-bromoheptane-3-oxy group,
6-methyl-6,7-dichloroheptane-3-oxy group, 6-methyl-6,7-dibromoheptane-3-oxy group, 1,2-diiodo-3,5-dimethylheptane-
4-oxy group, 1,6-diiodo-3,5-dimethylheptane-4-oxy group, 1,7-diiodo-3,5-dimethylheptane-4-oxy group, 2,6-diiodo-
3,5-dimethylheptane-4-oxy group,

6-iodo-3,5-dimethyl-1-heptene-4-oxy group, 7-iodo-3,5-dimethyl-
1-heptene-4-oxy group, 6,7-diiodo-3,
5-dimethyl-1-heptene-4-oxy group, 1,2-
Dibromo-3,5-dimethylheptane-4-oxy group,
1,6-dibromo-3,5-dimethylheptane-4-oxy group, 1,7-dibromo-3,5-dimethylheptane-4-oxy group, 2,6-dibromo-3,5-dimethylheptane-4 -Oxy group, 6-bromo-3,5-dimethyl-1-heptene-4-oxy group, 7-bromo-3,5
-Dimethyl-1-heptene-4-oxy group, 6,7-dibromo-3,5-dimethyl-1-heptene-4-oxy group, 1,2-dichloro-3,5-dimethylheptane-4
-Oxy group, 1,6-dichloro-3,5-dimethylheptane-4-oxy group, 1,7-dichloro-3,5-dimethylheptane-4-oxy group, 2,6-dichloro-3,
5-dimethylheptane-4-oxy group, 6-chloro-
3,5-dimethyl-1-heptene-4-oxy group, 7-
Chloro-3,5-dimethyl-1-heptene-4-oxy group, 6,7-dichloro-3,5-dimethyl-1-heptene-4-oxy group, 1,2,6,7-tetrachloro-
3,5-dimethylheptane-4-oxy group,

1-iodo-2,5-dimethylheptane-
4-oxy group, 1-bromo-2,5-dimethylheptane-4-oxy group, 2-bromo-2,5-dimethylheptane-4-oxy group, 1,2-dibromo-2,5-dimethylheptane- 4-oxy group, 1-chloro-2,5-dimethylheptane-4-oxy group, 2-chloro-2,5-dimethylheptane-4-oxy group, 1,2-dichloro-
2,5-Dimethylheptane-4-oxy group, 2,4-dimethyl-2-iodoheptane-1-oxy group, 2,4-
Dimethyl-3-iodoheptane-1-oxy group, 2,4
-Dimethyl-2,3-diiodoheptane-1-oxy group, 2,4-dimethyl-2,6-diiodoheptane-1
-Oxy group, 2,4-dimethyl-2,7-diiodoheptane-1-oxy group, 2,4-dimethyl-3,6-diiodoheptane-1-oxy group, 2,4-dimethyl-3,
7-diiodoheptane-1-oxy group, 2,4-dimethyl-6,7-diiodoheptane-1-oxy group, 2,4
-Dimethyl-2-iodo-6-heptene-1-oxy group, 2,4-dimethyl-3-iodo-6-heptene-1
-Oxy group, 2,4-dimethyl-2,3-diiodo-6
-Heptene-1-oxy group, 2,4-dimethyl-6-iodo-2-heptene-1-oxy group, 2,4-dimethyl-7-iodo-2-heptene-1-oxy group, 2,4-
Dimethyl-6,7-diiodo-2-heptene-1-oxy group,

2,4-dimethyl-2-bromoheptane-
1-oxy group, 2,4-dimethyl-3-bromoheptane-1-oxy group, 2,4-dimethyl-6-bromoheptane-1-oxy group, 2,4-dimethyl-7-bromoheptane-1- Oxy group, 2,4-dimethyl-2,3-dibromoheptane-1-oxy group, 2,4-dimethyl-3,
6-dibromoheptane-1-oxy group, 2,4-dimethyl-3,7-dibromoheptane-1-oxy group, 2,4
-Dimethyl-6,7-dibromoheptane-1-oxy group, 2,4-dimethyl-2-bromo-6-heptene-1
-Oxy group, 2,4-dimethyl-3-bromo-6-heptene-1-oxy group, 2,4-dimethyl-2,3-dibromo-6-heptene-1-oxy group, 2,4-dimethyl- 6-bromo-2-heptene-1-oxy group, 2,4-
Dimethyl-7-bromo-2-heptene-1-oxy group,
2,4-dimethyl-6,7-dibromo-2-heptene-
1-oxy group, 2,4-dimethyl-2,3,6,7-tetrachloro-2-heptene-1-oxy group,

2,4-dimethyl-2-chloroheptane-
1-oxy group, 2,4-dimethyl-3-chloroheptane-1-oxy group, 2,4-dimethyl-6-chloroheptane-1-oxy group, 2,4-dimethyl-7-chloroheptane-1- Oxy group, 2,4-dimethyl-2,3-dichloroheptane-1-oxy group, 2,4-dimethyl-3,
6-dichloroheptane-1-oxy group, 2,4-dimethyl-3,7-dichloroheptane-1-oxy group, 2,4
-Dimethyl-6,7-dichloroheptane-1-oxy group, 2,4-dimethyl-2-chloro-6-heptene-1
-Oxy group, 2,4-dimethyl-3-chloro-6-heptene-1-oxy group, 2,4-dimethyl-2,3-dichloro-6-heptene-1-oxy group, 2,4-dimethyl- 6-chloro-2-heptene-1-oxy group, 2,4-
Dimethyl-7-chloro-2-heptene-1-oxy group,
2,4-dimethyl-6,7-dichloro-2-heptene-
1-oxy group etc. are mentioned.

A particularly preferable example of the substituent having a halogen atom is a group having a large steric hindrance and easily protruding in the vertical direction of the phthalocyanine ring, specifically, 2,5-
Dimethyl-5-bromohexane-3-oxy group, 2,5
-Dimethyl-6-bromohexane-3-oxy group, 2,
5-dimethyl-5,6-dibromohexane-3-oxy group, 1-bromo-2,4-dimethylpentane-3-oxy group, 2-bromo-2,4-dimethylpentane-3-oxy group, 1, 2-dibromo-2,4-dimethylpentane-3-oxy group, 1-bromo-2,5-dimethylhexane-3-oxy group, 2-bromo-2,5-dimethylhexane-3-oxy group, 1, 2-dibromo-2,5-dimethylhexane-3-oxy group,

1-bromo-2,5-dimethyl-5-hexene-3-oxy group, 2-bromo-2,5-dimethyl-
5-hexene-3-oxy group, 1,2-dibromo-2,
5-dimethyl-5-hexene-3-oxy group, 2,5-
Dimethyl-5-bromo-1-hexene-3-oxy group,
2,5-Dimethyl-6-bromo-1-hexene-3-oxy group, 2,5-dimethyl-5,6-dibromo-1-hexene-3-oxy group, 1-bromo-3,5-dimethylheptane -4-oxy group, 2-bromo-3,5-dimethylheptane-4-oxy group, 1,2-dibromo-3,5
-Dimethylheptane-4-oxy group, 1,6-dibromo-3,5-dimethylheptane-4-oxy group, 1,7-
Dibromo-3,5-dimethylheptane-4-oxy group,
4-methyl-5-bromopentane-2-oxy group, 6-
Bromo-3,5-dimethyl-1-heptene-4-oxy group, 7-bromo-3,5-dimethyl-1-heptene-4
-Oxy group, 6,7-dibromo-3,5-dimethyl-1
-Heptene-4-oxy group,

4-methyl-4-bromopentane-2-oxy group, 4-methyl-5-bromopentane-2-oxy group, 4-methyl-4,5-dibromopentane-2-oxy group, 1-bromo -4-methylpentane-2-oxy group, 2-bromo-4-methylpentane-2-oxy group,
1,2-dibromo-4-methylpentane-2-oxy group, 1-bromo-2-methylpentane-3-oxy group,
2-bromo-2-methylpentane-3-oxy group, 1,
2-dibromo-2-methylpentane-3-oxy group, 5
-Methyl-5-bromopentane-3-oxy group, 5-methyl-6-bromopentane-3-oxy group, 5-methyl-5,6-dibromopentane-3-oxy group, 2,5-
Dimethyl-5-chlorohexane-3-oxy group, 2,5
-Dimethyl-6-chlorohexane-3-oxy group, 2,
5-dimethyl-5,6-dichlorohexane-3-oxy group,

1-chloro-2,4-dimethylpentane-
3-oxy group, 2-chloro-2,4-dimethylpentane-3-oxy group, 1,2-dichloro-2,4-dimethylpentane-3-oxy group, 1-chloro-2,5-dimethylhexane- 3-oxy group, 2-chloro-2,5-dimethylhexane-3-oxy group, 1,2-dichloro-2,
5-dimethylhexane-3-oxy group, 1-chloro-
2,5-dimethyl-5-hexene-3-oxy group, 2-
Chloro-2,5-dimethyl-5-hexene-3-oxy group, 1,2-dichloro-2,5-dimethyl-5-hexene-3-oxy group, 2,5-dimethyl-5-chloro-1
-Hexene-3-oxy group, 2,5-dimethyl-6-chloro-1-hexene-3-oxy group, 2,5-dimethyl-5,6-dichloro-1-hexene-3-oxy group,

1-chloro-3,5-dimethylheptane-
4-oxy group, 2-chloro-3,5-dimethylheptane-4-oxy group, 1,2-dichloro-3,5-dimethylheptane-4-oxy group, 1,6-dichloro-3,5-
Dimethylheptane-4-oxy group, 1,7-dichloro-
3,5-Dimethylheptane-4-oxy group, 4-methyl-5-chloropentane-2-oxy group, 6-chloro-
3,5-dimethyl-1-heptene-4-oxy group, 7-
Chloro-3,5-dimethyl-1-heptene-4-oxy group, 6,7-dichloro-3,5-dimethyl-1-heptene-4-oxy group,

4-methyl-4-chloropentane-2-oxy group, 4-methyl-5-chloropentane-2-oxy group, 4-methyl-4,5-dichloropentane-2-oxy group, 1-chloro -4-methylpentane-2-oxy group, 2-chloro-4-methylpentane-2-oxy group,
1,2-dichloro-4-methylpentane-2-oxy group, 1-chloro-2-methylpentane-3-oxy group,
2-chloro-2-methylpentane-3-oxy group, 1,
2-dichloro-2-methylpentane-3-oxy group, 5
-Methyl-5-chloropentane-3-oxy group, 5-methyl-6-chloropentane-3-oxy group, 5-methyl-5,6-dichloropentane-3-oxy group, and the like.

In the formula (1), examples of the divalent metal represented by Met include Cu, Zn, Mn, Fe, Co and N.
i, Ru, Rh, Pd, Pt, Pb, Mn, Mg, and the like, and examples of mono-substituted trivalent metals include Al-Cl,
Al-Br, In-Cl, In-Br, Ga-Cl, G
a-Br, and examples of the tetravalent metal 2-substituted, SiCl _2, SiBr _2, SiF _2, SnCl _2, Sn
_{Br 2, SnF 2, GeCl 2} , GeBr 2, GeF 2, S
i (OH) ₂ , Sn (OH) ₂ , Ge (OH) ₂ , Si
(OY) ₂ , Sn (OY) ₂ , Ge (OY) ₂ , Si (S
Y) ₂ , Sn (SY) ₂ , Ge (SY) ₂ [wherein Y represents an alkyl group, a phenyl group, a naphthyl group and derivatives thereof] and the like, and examples of the oxy metal include VO,
Examples thereof include MnO and TiO. Particularly preferable examples are Cu, Ni, Co, Pd, Pt, Mg and VO.

As a method for synthesizing the phthalocyanine compound represented by the general formula (1), the following formula (2) is used.

[0050]

[Chemical 3] [In Formula (2), R represents an unsaturated hydrocarbon group and s represents 0, 1 or 2. ] In the presence of 1 to 4 compounds (at least one of which is not 0) of 1,8-diazabicyclo [5,4,0] -7-undecene (DBU),
Heat-react with a metal derivative in alcohol, or heat-react with a metal compound in a high-boiling solvent such as chloronaphthalene, bromonaphthalene, and trichlorobenzene to synthesize a phthalocyanine having an unsaturated hydrocarbon oxy group. Examples thereof include a method of reacting with a halogenating agent such as thionyl, sulfuryl chloride, hydrobromic acid, bromine, iodine and iodine monochloride. Further, a method of reacting the compound represented by the formula (2) in the same manner with diiminoisoindoline represented by the formula (3) obtained by reacting sodium methylate with ammonia as a catalyst in an alcohol as an intermediate. Etc.

[0051]

[Chemical 4] [In Formula (3), R and s represent the same meaning as Formula (2). ]

In the present invention, a compound in which R in the formula (2) or (3) is a saturated hydrocarbon group is mixed with the compound of the formula (2) or (3) to synthesize a phthalocyanine compound. O of phthalocyanine
A phthalocyanine represented by the formula (1) containing a alkoxy group which is not substituted with a halogen atom by synthesizing a compound in which some of the R groups are saturated hydrocarbon groups, and reacting the compound with the above halogenating agent. The compound can also be obtained.

The compound represented by the formula (2) is synthesized by the method of the following formula (4).

[0054]

[Chemical 5] The starting material (3-) nitrophthalonitrile was obtained from Tokyo Kasei. The compound of formula (2) is synthesized from (3-) nitrophthalonitrile by NOUVEAU JOURNAL DECHIM
The method was described in IE Vol. 6, pages 653-658, 1982. That is, the alcohol was converted to sodium alkoxide with sodium hydride and subsequently reacted with (3-) nitrophthalonitrile at 0 to 100 ° C to obtain the target compound of the formula (2).

The method for producing an optical recording medium using the phthalocyanine compound of the present invention includes a method of coating or vapor depositing 1 to 3 compounds containing the phthalocyanine of the present invention on a transparent substrate in one layer or two layers. Yes, as a coating method,
The binder resin is 20% by weight, preferably 0%, and the phthalocyanine 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. is there. As the vapor deposition method, there is a method of depositing on a substrate at 10 ⁻⁵ to 10 ⁻⁷ Torr and 100 to 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 surface-treated with a thermosetting resin or an ultraviolet curable resin.

In the case of producing an optical recording medium (optical disk, optical card, etc.), the substrate is a polyacrylate substrate or a polycarbonate substrate and is applied by the spin coating method in view of cost and handling by the user. Is preferred.

Due to the solvent resistance of the substrate, solvents used for spin coating are halogenated hydrocarbons (eg dichloromethane, chloroform, carbon tetrachloride, tetrachloroethylene, dichlorodifluoroethane, etc.), ethers (eg tetrahydrolane, diethyl ether, diisopropyl). Ether, dioxane etc.), alcohols (eg methanol, ethanol, propanol etc.), cellosolves (eg methyl cellosolve, ethyl cellosolve etc.), hydrocarbons (eg hexane, octane, benzene, toluene, xylene etc.) It is preferably used.

In order to process it as a recording medium, it is covered with a substrate as described above, or a substrate provided with two recording layers is
An air gap is provided and it faces and is stuck. Or, providing a reflective layer (aluminum or gold) on the recording layer
There is a method of laminating a protective layer of a thermosetting (photocurable) resin.

[0061]

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

Example 1 In a container equipped with a stirrer, a reflux condenser and a nitrogen introducing tube,
60% sodium hydride (9.6 g, 0.24 mol) and N, N-dimethylformamide (150 ml) were charged, and the mixture was stirred under a nitrogen atmosphere, and 2,5-dimethyl-5-hexen-3-ol (32 g, 0) was added. 0.25 mol) for 20 to 30
The mixture was added dropwise at 1 ° C for 1 hour and stirred at the same temperature for 3 hours to prepare a sodium alcoholate solution. Next, in a container equipped with a stirrer, 34.6 g (0.2
mol) and N, N-dimethylformamide 150 m
1) was charged and dissolved, and a sodium alcoholate solution was added dropwise thereto at 0 ° C. or lower for 5 hours, and the temperature was adjusted to 20 after completion of the addition.
The temperature was raised to -30 ° C, and the reaction was terminated by stirring for 2 hours.
The reaction solution was discharged into 3 liters of water, stirred for 30 minutes, and added with toluene 50
0 ml was added, and the mixture was stirred for 30 minutes and allowed to stand, and the toluene layer was separated. After distilling off toluene under reduced pressure, n-hexane 500
Recrystallization with ml gave 3- (2,5-dimethyl-5-hexene-3-oxy) phthalonitrile 43.7 g (yield 86.0%).

[0063]

Then, the obtained 3- (2,5-dimethyl-) was placed in a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube.
25.4 g of 5-hexene-3-oxy) phthalonitrile
(0.1 mol), DBU 15.2 g (0.1 mol)
And 120 g of n-amyl alcohol were charged, the temperature was raised to 110 ° C. under a nitrogen atmosphere, 5.3 g (0.03 mol) of palladium chloride was added at the same temperature, and the temperature was increased to 1 at 120 ° C.
The reaction was allowed for 0 hours. After cooling, the insoluble matter was filtered off, the filtrate was concentrated under reduced pressure to recover the solvent, and then column purification (silica gel 3
(00 g, developed with toluene) to obtain a dark green crystal of a phthalocyanine palladium compound having an unsaturated hydrocarbon oxy group. The yield was 17.4 g (62.1% yield). The maximum absorption wavelength (λ _max ), gram extinction coefficient (ε _g ) and the result of elemental analysis are as follows.

Λ _max = 688.5 nm ε _g = 1.9 × 10 ⁵ g ⁻¹

5 g of palladium tetra α- (2,5-dimethyl-5-hexene-3-oxy) phthalocyanine
(4.50 mmol) was dissolved in 30 g of 1,1,2-trichloroethane, and 10 g of water was added. Then bromine 5.4
A mixed solution of g (33.79 mmol) and 6 g of 1,1,2-trichloroethane was added dropwise at 50 to 55 ° C., and 55 to 55
The reaction was carried out at 60 ° C. for 1 hour, and 5 g of a 15% aqueous sodium hydrogen sulfite solution was added for washing. The organic layer is methanol 80
The resulting crystals were filtered to obtain 8.0 g of brominated phthalocyanine. From NMR, it was found that all of the side chain double bonds were replaced with bromine, and from elemental analysis, 11.5 bromine was replaced. Therefore, it was found that 3.5 rings were substituted.

[0067] λ _max = 708.5 nm ε _g = 1.3 × 10 ⁵ g ^-1

Example 2 5 g of the brominated phthalocyanine obtained in Example 1 was dissolved in 500 ml of n-octane and spin-coated on a polycarbonate substrate, and gold was sputtered thereon to form a reflective layer on the CD- An R medium was prepared. The reflectance of this medium is 7
It was 1% (775 to 790 nm), and an EFM signal could be written with a power of 5.5 mW at a linear velocity of 1.3 m / sec using a semiconductor laser of 780 nm, and the error rate at that time was less than 10.

Example 3 Palladium tetra α- (2,5-dimethyl-5-hexene-3-oxy) phthalocyanine 5 synthesized in Example 1
g (4.50 mmol) was dissolved in 35 g of 1,1,2,2-tetrachloroethane, the temperature was raised to 50 to 60 ° C., and 3.1 g (18.01 mmol) of 47% hydrobromic acid at the same temperature.
Was dropped and reacted at 60 to 70 ° C. for 1 hour. After cooling to 20 ° C., 10% sodium hydrogen sulfite aqueous solution 10 g, 5%
It was washed with 10 g of an aqueous sodium hydrogen carbonate solution. After separating the organic layer, 90 g of methanol was added dropwise, and the precipitated crystals were filtered to obtain 5.8 g of brominated phthalocyanine. It was found from elemental analysis that four bromine atoms were substituted, and from FD-MS that all bromine atoms were substituted in the side chain.

[0070] λ _max = 688.5 nm ε _g = 1.5 × 10 ⁵ g ^-1

Example 4 An optical card was prepared by coating a solution of 5 g of brominated phthalocyanine synthesized in Example 3 in 500 g of dibutyl ether on a polycarbonate optical card substrate and providing a protective layer on the coated surface. This optical card has a linear velocity of 2 m / sec
Then, recording was possible with a semiconductor laser beam of 4 mW, and the CN ratio was 63 dB. In addition, linear velocity 2m / se
c, reproducible by 0.8 mW laser light, 10 ⁵
There was no change in the recording after replaying.

Example 5 A container equipped with a stirrer, a reflux condenser, and a nitrogen introducing tube was added,
60% sodium hydride (9.6 g, 0.24 mol) and N, N-dimethylformamide (150 ml) were charged, and the mixture was stirred under a nitrogen atmosphere, and 3,5-dimethyl-1,6-heptadien-4-ol (35 g) was added. (0.25 mol) to 2
The solution was added dropwise at 0 to 30 ° C over 1 hour and stirred at the same temperature for 3 hours,
A sodium alcoholate solution was prepared. Next, in a container equipped with a stirrer, 34.6 g of 3-nitrophthalonitrile
(0.2 mol) and N, N-dimethylformamide (150 ml) were charged and dissolved therein, and a sodium alcoholate solution was added dropwise thereto at 0 ° C or lower for 5 hours, and after the addition was completed, the temperature was raised to 20 to 30 ° C. The reaction was terminated by stirring for 3 hours. The reaction solution was discharged into 3 liters of water, stirred for 30 minutes, added with 500 ml of toluene, stirred for 30 minutes and allowed to stand, and the toluene layer was separated. After distilling off toluene under reduced pressure, the residue was recrystallized from 600 ml of n-hexane to give 3- (3,5-dimethyl-).
1,6-heptadiene-4-oxy) phthalonitrile 4
4.7 g was obtained (yield 84.0%).

[0073]

Then, the obtained 3- (3,5-dimethyl-) was placed in a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube.
1,6-heptadiene-4-oxy) phthalonitrile 2
6.6 g (0.1 mol), DBU 15.2 g (0.1
mol) and 125 g of n-amyl alcohol were charged, the temperature was raised to 110 ° C. under a nitrogen atmosphere, and 5.3 g (0.03 mol) of palladium chloride was added at the same temperature.
The reaction was carried out at 20 to 130 ° C for 9 hours. After cooling, the insoluble matter was filtered off, the filtrate was concentrated under reduced pressure to recover the solvent, and then column purification (silica gel 500 g, development with toluene) was performed to obtain a dark green crystal of a phthalocyanine palladium compound having an unsaturated hydrocarbon group. . The yield was 19.0 g (65% yield). The maximum absorption wavelength (λ _max ), gram extinction coefficient (ε _g ) and the result of elemental analysis were as follows.

Λ _max = 690.0 nm ε _g = 1.9 × 10 ⁵ g ⁻¹

Palladium tetra α- (3,5-dimethyl-1,6-heptadiene-4-oxy) phthalocyanine (10 g, 8.53 mmol) was added to dichloromethane (50 g).
It was added to a mixed solvent of 50 g of n-hexane and 100 g of water.
Bromine 4.8 g (30.03 mmol) was added dropwise at 40 ° C.
And reacted for 2 hours. After cooling to 20 ° C, toluene 50g
Was added and the layers were separated. Subsequently, the organic layer was washed with 100 g of a 10% aqueous sodium hydrogen sulfite solution and 100 g of a 5% aqueous sodium hydrogen carbonate solution. After distilling off the organic solvent, column purification (silica gel 500 g, development with toluene) was performed to obtain 11.0 g of brominated phthalocyanine. From elemental analysis and FD-MS, it was found that 6.6 bromine was substituted in the side chain.

[0077] λ _max = 691.5 nm ε _g = 1.2 × 10 ⁵ g ^-1

Example 6 10 g of the brominated phthalocyanine synthesized in Example 5 was n-
It was dissolved in 1000 g of octane and spin-coated on a polycarbonate substrate to prepare an optical recording medium. When recorded with a semiconductor laser of 780 nm, 60 m with a power of 7 mW
A CN ratio of B was obtained. No change was observed even after reproducing 10 ⁵ times with a reproducing light of 0.5 mW. Also, 80 ° C / 80% R
There was no change in recording even after 1000 hours under the condition of H.

Example 7 In a container equipped with a stirrer, a reflux condenser and a nitrogen introducing tube,
3- (3,5-dimethyl-1,6-, synthesized in Example 5
26.6 g of heptadiene-4-oxy) phthalonitrile
(0.1 mol), DBU 15.2 g (0.1 mo
1) and 120 g of n-amyl alcohol were charged, and the temperature was raised to 110 ° C. under a nitrogen atmosphere. At the same temperature, add 3.0 g (0.03 mol) of cuprous chloride, and add 1 at 135 ° C.
The reaction was allowed for 0 hours. After completion of the reaction, the mixture was cooled and insoluble matter was removed by filtration. After the filtrate was concentrated under reduced pressure to recover the solvent, column purification (silica gel 500 g, development with toluene) was performed.
Dark green crystals of a phthalocyanine copper compound having an unsaturated hydrocarbon oxy group were obtained. The yield was 21.4 g (76
%)Met. The maximum absorption wavelength (λ _max ), gram extinction coefficient (ε _g ) and the result of elemental analysis were as follows.

Λ _max = 706.0 nm ε _g = 1.6 × 10 ⁵ g ⁻¹ (solvent: toluene)

Copper tetra α- (3,5-dimethyl-1,6
-Heptadiene-4-oxy) phthalocyanine 10 g
(8.86 mmol) in 40 g of tetrahydrofuran, n
-Added to a mixed solvent of 40 g of hexane and 100 g of water. Bromine (5.5 g, 34.41 mmol) was added, and the mixture was added at 40 ° C.
Reacted for hours. After cooling to 20 ° C., 40 g of toluene was added and the layers were separated. Subsequently, the organic layer was washed with 80 g of 10% sodium hydrogen sulfite and 80 g of a 5% sodium hydrogen carbonate aqueous solution. After distilling off the organic solvent, column purification (silica gel 500 g, development with toluene) was performed to obtain 13.7 g of brominated phthalocyanine. It was found from elemental analysis and FD-MS that 7.4 side chains of bromine were substituted.

[0082] λ _max = 706.5 nm ε _g = 1.2 × 10 ⁵ g ^-1

Example 8 10 g of the brominated phthalocyanine synthesized in Example 7 was n-
Dissolved in 1000 g of octane, spin coated on a polycarbonate substrate, sputtered gold to provide a reflective layer,
A CD-R medium was made. The reflectance of this medium is 73%
(775-790 nm), an EFM signal could be written with a power of 6.0 mW at a linear velocity of 1.3 m / sec using a semiconductor laser of 780 nm, and the error rate at that time was less than 10.

Example 9 Palladium tetra α- (2,5-dimethyl-5-hexene-3-oxy) phthalocyanine 5 synthesized in Example 1
g (4.50 mmol) was dissolved in 30 g of 1,1,2-trichloroethane, and 10 g of water was added. Next, 6.4 g (45.0 mmol) of sulfuryl chloride (95 wt%) was added dropwise at 50 to 60 ° C, and the mixture was reacted at 60 to 70 ° C for 1 hour. After cooling to 30 ° C., a 10% aqueous sodium hydroxide solution was appropriately added until the pH of the aqueous layer portion reached about 7.0. After separating the organic layer, it was added dropwise to 180 g of methanol, and the precipitated crystals were filtered to obtain 6.8 g of chlorinated phthalocyanine. From elemental analysis, 12 chlorines were substituted. Further, it was found from NMR that all double bonds in the side chain were chlorinated.

[0085] λ _max = 702.0 nm ε _g = 1.3 × 10 ⁵ g ^-1

Example 10 5 g of the chlorinated phthalocyanine obtained in Example 9 was dissolved in 500 ml of dimethylcyclohexane, spin-coated on a polycarbonate substrate, and gold was sputtered thereon to form a reflective layer to form a CD-R. A medium was prepared. The reflectance of this medium is 74% (775 to 790 nm) and is 780
An EFM signal could be written with a power of 6 mW at a linear velocity of 1.3 m / sec using a semiconductor laser of nm, and the error rate at that time was less than 10.

Comparative Example 1 In a container equipped with a stirrer, a reflux condenser and a nitrogen introducing tube,
60% sodium hydride (9.6 g, 0.24 mol) and N, N-dimethylformamide (150 ml) were charged, and the mixture was stirred under aeration with nitrogen. 2-Fluoro-1-cyclohexanol (29.5 g, 0.25 mol) was added thereto. 20 ~ 30 ℃
At 1 hour, and the mixture was stirred at the same temperature for 3 hours to prepare a sodium alcoholate solution. Next, in a container equipped with a stirrer, 34.6 g of 3-nitrophthalonitrile (0.2 m
ol) and N, N-dimethylformamide 150 ml
Was charged and dissolved, and the above sodium alcoholate solution was added dropwise thereto at 0 ° C. or lower for 5 hours, and the temperature was adjusted to 2 after completion of the addition.
The temperature was raised to 0 to 30 ° C., and the reaction was terminated by stirring for 2 hours. The reaction solution was discharged into 3 liters of water, stirred for 30 minutes, added with 500 ml of toluene, stirred for 30 minutes and allowed to stand, and the toluene layer was separated. After distilling off toluene under reduced pressure, the residue was recrystallized from 600 ml of n-hexane to give 3- (2-fluoro-1)
-Cyclohexane-1-oxy) phthalonitrile 44.
0 g was obtained (yield 90.0%).

[0088]

Then, the obtained 3- (2-fluoro-1-) was placed in a container equipped with a stirrer, a reflux condenser and a nitrogen introducing tube.
Cyclohexane-1-oxy) phthalonitrile 22.4
g (0.1 mol), DBU 15.2 g (0.1 mo
1) and 120 g of n-amyl alcohol were charged, the temperature was raised to 110 ° C. under a nitrogen atmosphere, 3.0 g (0.03 mol) of cuprous chloride was added at the same temperature, and the mixture was heated to 1 ° C. at 135 ° C.
The reaction was allowed for 0 hours. After completion of the reaction, the mixture was cooled and insoluble matter was removed by filtration. After the filtrate was concentrated under reduced pressure to recover the solvent, column purification (silica gel 500 g, development with toluene) was performed.
Dark green crystals of a phthalocyanine copper compound having a fluorine-substituted hydrocarbon oxy group were obtained. The yield was 21.4 g (76% yield). The maximum absorption wavelength (λ _max ), gram extinction coefficient (ε _g ) and the result of elemental analysis were as follows.

Λ _max = 704.0 nm ε _g = 1.5 × 10 ⁵ g ⁻¹

Comparative Example 2 5 g of the fluorinated phthalocyanine obtained in Comparative Example 1 was added to n-
It was dissolved in 500 ml of octane, spin-coated on a polycarbonate substrate, and gold was sputtered on the polycarbonate substrate to provide a reflective layer, thereby producing a CD-R medium. The reflectance of this medium was 72% (775 to 790 nm), and a power of 10 mW was required to write an EFM signal at a linear velocity of 1.3 m / sec using a 780 nm semiconductor laser. The error rate at that time was 120.

Examples 11 to 20 and Comparative Examples 3 and 4 The phthalocyanine compounds shown in Table 1 below were synthesized in the same manner as in Example 1, and a CD-R medium was prepared in the same manner as in Example 2 to obtain a 780 nm film. Linear velocity using semiconductor laser 1.
The laser power (mW) required to write the EFM signal at 3 m / sec was measured, 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. The results are shown in Table 1.

[0093]

[Table 1]

[0094]

[Table 2]

[0095]

INDUSTRIAL APPLICABILITY The phthalocyanine compound of the present invention is substituted with an alkyl group, an alkenyl group or an alkynyl group at the α-position of the phthalocyanine ring via an oxygen atom, and the substituent has at least one halogen atom. This halogen atom enables the signal at the time of optical recording to be correctly written in the optical recording medium using this compound, and the sensitivity and recording characteristics can be improved.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G11B 7/24 516 7215-5D (72) Inventor Hideki Umehara 1190 Kasamacho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Kenichi Sugimoto 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Naoto Ito 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Chemical Co., Ltd. In the company

Claims (9)

[Claims] 1. The following general formula (1): [In the formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently
C1-C20 alkyl group substituted with 0-5 halogen atoms, C2-C20 alkenyl group substituted with 0-5 halogen atoms, and 0-5 halogen atoms substituted Is an alkynyl group having 2 to 20 carbon atoms,
At least one of R ¹ , R ² , R ³ , and R ⁴ is a group substituted with a halogen atom. X represents a halogen atom. k, l, m, and n each independently represent a number of 0 to 3. o, p, q, and r are independently 0, 1 or 2
And all cannot be 0 at the same time. The sums of k and o, l and p, m and q, and n and r are independently 0.
~ 4. Met represents two hydrogen atoms, a divalent metal atom, a trivalent mono-substituted metal atom, a tetravalent di-substituted metal atom, or an oxy metal atom. ] The phthalocyanine shown by these. 2. R ¹ , R ² , R ³ and R ⁴ are independently of each other,
C5-C15 alkyl group in which 0-5 halogen atoms are substituted, C5-C15 alkenyl group in which halogen atoms are substituted by 0-5, and 0-5 halogen atoms are substituted. Is an alkynyl group having 5 to 15 carbon atoms,
The phthalocyanine according to claim 1, wherein at least one of R ¹ , R ² , R ³ , and R ⁴ is a group substituted with a halogen atom, and o, p, q, and r are all 1. 3. The phthalocyanine according to claim 2, wherein X is chlorine, bromine or iodine. 4. The phthalocyanine according to claim 3, wherein the halogen atom substituting for R ¹ , R ² , R ³ and R ⁴ is chlorine, bromine or iodine. 5. The phthalocyanine according to claim 1, wherein R ¹ , R ² , R ³ and R ⁴ are branched alkyl groups, alkenyl groups or alkynyl groups. 6. Met is Cu, Pd, Co, Mg, VO
The phthalocyanine according to claim 5, which is 7. The phthalocyanine according to claim 6, wherein the halogen atom substituting for R ¹ , R ² , R ³ and R ⁴ is bromine or iodine, and X is bromine. 8. An optical recording medium formed by containing the phthalocyanine according to claim 1 in a recording layer. 9. A near-infrared absorber composed of the phthalocyanine according to claim 1.