JPH05222301A - New phthalocyanine compound and its production - Google Patents

Abstract

PURPOSE:To produce the title compd. which absorbs near-infrared rays and is excellent in solubility esp. in an alcoholic solvent by reacting a specific fluorine-contg. phthalocyanine compd. with an alcohol or thiol in an org. solvent. CONSTITUTION:A phthalocyanine compd. of formula I [wherein X is OR3 or SR4; R1, R2, R3, and R4 are each a 1-20C alkyl group or a phenyl, benzyl, or naphthyl group optionally substd. by halogen or by a 1-4C alkyl or 1-4C alkoxyl group provided that R1, R2, and R3 are different from each other; and M is a metal, a metal oxide, or a metal halide] is produced by reacting a compd. of formula II (wherein R1 and R2 are each as defined above) with a compd. of the formula: XH (wherein X is as defined above) in an org. solvent. Since the phthalocyanine compd. enables the control of the wavelengths of absorbed near-infrared rays in the range of 650-900nm and is excellent in solubility esp. in an alcoholic solvent, it is useful as a near-infrared-absorbing pigment.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phthalocyanine compound, a method for producing the same, and a near infrared absorbing material having absorption in the near infrared region. The novel phthalocyanine compound according to the present invention is 650-900 nm
Since it has absorption in the near-infrared region and excellent solubility, it is a near-infrared absorbing dye or near-infrared light for writing or reading in optical recording media using semiconductor lasers, liquid crystal display devices, optical character readers, etc. As a near-infrared absorbing material used as a sensitizer, heat-sensitive transfer, light-heat converting agent such as heat-sensitive paper and heat-sensitive stencil, near-infrared absorption filter, eye strain preventing agent, photoconductive material, or color separation used for an imaging tube. Filters, liquid crystal display elements, color cathode ray tube selective absorption filters, color toners, ink jet inks, tamperproof bar code inks, and microbial inactivating agents,
It exhibits an excellent effect when used as a photosensitive dye for tumor treatment.

[0002]

2. Description of the Related Art Recently, a semiconductor laser is used as a light source for writing or reading in an optical recording medium such as a compact disc, a laser disc, an optical memory disc, an optical card, a liquid crystal display device, and an optical character reader. In addition, a photoconductive material, a near-infrared absorption filter, an eye strain preventive agent, a heat-transfer agent such as heat-sensitive transfer / heat-sensitive paper, and heat-sensitive stencil, a substance that absorbs near-infrared rays as a near-infrared photosensitizer, so-called near-infrared rays. There is an increasing demand for development of infrared absorbing dyes.

Further, a color separation filter used for an image pickup tube,
Liquid crystal display element, color cathode ray tube selective absorption filter,
There is a demand for a dye that is more robust and can control the color tone even in a color toner, an inkjet ink, a tampering prevention barcode ink, a microbial inactivating agent, and a visible absorption dye used as a photosensitive dye for tumor treatment. .. Among them, many studies have been conducted on phthalocyanine compounds which are stable to light, heat, temperature and the like and have excellent fastness.

On the other hand, a phthalocyanine compound having a solubility which is practically advantageous has been recently disclosed. For example,
3,6-octaalkoxy phthalocyanine
No. 223056), but it has a problem that it is difficult to control the absorption wavelength, and the manufacturing process is complicated and an inexpensive phthalocyanine cannot be obtained.

JP-A-60-209583 and 61-
Nos. 152685, 63-308073, and 64-62361 disclose compounds in which a phthalocyanine skeleton is substituted with a large number of thioether groups or the like to improve solubility and lengthen absorption wavelength. Has been done.

Among them, JP-A-60-209583,
And JP-A-61-152685 disclose a synthesis example in which a thioether group is introduced at the phthalocyanine skeleton, especially at the 3,6-position. According to the method, a phthalocyanine compound having a chloro atom at the 3,6-position of a phthalocyanine skeleton and an organic thiol compound are heated in a quinoline solvent in the presence of KOH to obtain a phthalocyanine having a thioether group at the 3,6-position. However, the yield is 20 to 30% in each case.
However, there is a problem in manufacturing efficiency.

Further, JP-A-60-209583, JP-A-61-152685 and JP-A-64-62361 disclose synthetic examples in which a large number of 8 to 16 thioether groups are introduced into the phthalocyanine skeleton. .. The method is
A phthalocyanine compound having 8 to 16 chlorine atoms and / or bromine atoms in a benzene nucleus of a phthalocyanine skeleton and an organic thiol compound are mixed with KO in a quinoline solvent.
8 in the benzene nucleus of the phthalocyanine skeleton by heating in the presence of H
Phthalocyanine having ~ 16 thioether groups is obtained.

However, like the above-mentioned ones, the yield is about 20 to 30%, and there is a problem in production efficiency. That is, since the chloroether or bromine atom is poorly substituted with a thioether group, the yield is low, and for example, unreacted phthalocyanine in which the chloro atom is not completely substituted by the thioether group or a part of the chloro atom is a thioether group. To form unreacted phthalocyanine. Since it is practically difficult to separate the unreacted phthalocyanine and the target phthalocyanine from each other, in reality, only a mixture of phthalocyanines having various compositions can be obtained.

In fact, Japanese Unexamined Patent Publication (Kokai) No. 64-62361 describes a polythiol-substituted mixed condensation type phthalocyanine composition even after separation with a silica gel column, which shows that an unreacted type remains. When some of the chloro atoms remain, their solubility is significantly reduced, and it is disadvantageous to dissolve them as a near-infrared absorbing dye or for other applications, for example, as a visible absorption filter to form a thin film.

In JP-A-63-308073, monobromotetradecachlorophthalocyanine and an organic thiol mixture of 2-aminothiophenol and 4-methylphenylthiol are heated in the presence of KOH in a DMF solvent to remove thioether substituents. Introduced 42% phthalocyanine
Is obtained in a yield of.

However, in this method, different organic thiol mixtures are simultaneously added and reacted, so that a phthalocyanine mixture having a kind of combination of thioether substituents is obtained, and a single characteristic cannot be obtained. There is a problem that the application is limited when it is necessary to control the absorption wavelength, for example, as a cyan inkjet ink or a near infrared absorbing dye.

Japanese Patent Laid-Open Nos. 1-275664 and 2
No. -18462, a water-soluble phthalocyanine compound is obtained by sulfonating a phthalocyanine pigment and then sulfonamidating it. However, these are difficult to control the absorption wavelength, and therefore, cyan inkjet inks and color filter dyes. It is disadvantageous when used for etc.

In order to solve these drawbacks, the present inventors have proposed Japanese Patent Application Nos. 1-209599 and 2-125518.
In Japanese Patent Application No. 2-144292, the fluorine of octadecafluorophthalocyanine is selectively substituted with an alkylthio group or an arylthio group to try to extend the absorption wavelength and improve the solvent solubility, and to some extent the effect is obtained. It was

However, in order to apply a solvent onto a plastic substrate, it is necessary to dissolve it in alcohols which are generally used as a solvent that does not damage the plastic, but their solubility is not always satisfactory. Instead, there is a need for compounds with even greater solubility. It was also preferable that the absorption wavelength be further increased.

[0015]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances of the prior art. That is,
The object of the present invention is to control the absorption wavelength according to the purpose in the absorption wavelength region of 650 to 900 nm, and to improve the solubility,
In particular, it is to provide a novel phthalocyanine compound having excellent solubility in alcoholic solvents. Another object of the present invention is to provide a method for efficiently producing the phthalocyanine compound with high purity.

[0016]

DISCLOSURE OF THE INVENTION The inventors of the present invention have an alkoxy (aryloxy) group at the 3,6-position of a phthalocyanine compound having the same or different alkoxy (aryloxy) group at the 4,5-position of the phthalocyanine skeleton, or The present invention has been completed by finding that a compound satisfying the above object can be obtained by introducing an alkyl (aryl) thio group. That is, according to the present invention, the following general formula (I):

[0017]

[Chemical 3]

[Wherein, X's are mutually independent OR₃Or SR
_FourRepresents; R₁, R₂, R₃And R _FourAre independent of each other
And an alkyl group having 1 to 20 carbon atoms and 4 to 4 carbon atoms.
6 cycloalkyl group, or phenyl group, benzyl group
Or naphthyl group (the phenyl group, benzyl group and / or
Is a naphthyl group is an alkyl group having 1 to 4 carbon atoms, carbon
Alkoxyl group having 1 to 4 atoms and / or halogen atom
R), and R₁, R
₂And R₃Are not the same; and M is a metal, a metal oxide
Or represents a metal halide]
Phthalocyanine compounds are provided.

Such a fluorine-containing phthalocyanine compound
For example, R₁, R₂, R ₃And R_FourBut mutual
Independently of phenyl residue, tolyl residue, xylyl residue,
Benzyl residue, naphthyl residue, 1-2 fluorine
Is a phenyl group substituted with a chloro atom, having 1 to 2 carbon atoms
0 alkyl group or cycloalkyl group having 4 to 6 carbon atoms
And M is Cu, Zn, Pb, Fe, Ni, Co, A
lCl, AlI, InCl, InI, GaCl, Ga
I, TiCl₂, TiO, VCl₂, VO, SnCl₂
Or GeCl₂And a compound that is Before the present invention
Fluorine-containing phthalocyanine compound represented by the general formula (I)
The product is, for example, the following general formula (II):

[0020]

[Chemical 4]

[In the formula, R ₁ and R ₂ are, independently of each other, a linear or branched alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 4 to 6 carbon atoms, or a phenyl group, a benzyl group or a naphthyl group (the phenyl group, benzyl group and / or naphthyl group is an alkyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms). Alkoxyl group and /
Or optionally substituted by a halogen atom), and R ₁ and R ₂ are not the same], and the following general formula (III):

XH (III) [wherein, X represents OR ₃ or SR ₄ , and R ₃ and R ₄
Is a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, or a phenyl group, a benzyl group or a naphthyl group (the phenyl group,
The benzyl group and / or naphthyl group has 1 to 4 carbon atoms.
Which may be substituted by an alkyl group, an alkoxyl group having 1 to 4 carbon atoms and / or a halogen atom), and R ₃ is not the same as R ₁ and R ₂ at the same time] It can be produced by reacting a compound with an organic solvent.

The manufacturing method of the present invention will be described in detail below. In the fluorine-containing phthalocyanine represented by the general formula (I) used in the present invention, R ₁ , R ₂ , R ₃
And R ₄ are, independently of each other, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, or a phenyl group, a benzyl group or a naphthyl group (the phenyl group, The benzyl group and / or naphthyl group may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group and / or a halogen atom, and R ₁ , R ₂ and R ₃ are not the same at the same time. Specific examples thereof include the following compounds.

(4,5-Octakisphenoxy)-
(3,6-Octakisphenylthio) copper phthalocyanine (4,5-octakisphenoxy)-(3,6-octakisphenylthio) zinc phthalocyanine (4,5-octakisphenoxy)-(3,6-octa (Kisphenylthio) cobalt phthalocyanine (4,5-octakisphenoxy)-(3,6-octakisphenylthio) nickel phthalocyanine

(4,5-Octakisphenoxy)-
(3,6-Octakisphenylthio) iron phthalocyanine (4,5-octakisphenoxy)-(3,6-octakisphenylthio) oxyvanadium phthalocyanine (4,5-octakisphenoxy)-(3,6- Octakisphenylthio) oxytitanium phthalocyanine (4,5-octakisphenoxy)-(3,6-octakisphenylthio) chloroindium phthalocyanine

(4,5-Octakisphenoxy)-
(3,6-Octakisphenylthio) chloroaluminum phthalocyanine (4,5-octakisphenoxy)-(3,6-octakisphenylthio) dichlorotin phthalocyanine (4,5-octakisphenoxy)-(3,6 -Octakisphenylthio) dichlorogermanium phthalocyanine (4,5-octakisphenoxy)-(3,6-octakis-p-methylphenylthio) zinc phthalocyanine

(4,5-Octakisphenoxy)-
(3,6-Octakis-2,3-dimethylphenylthio) zinc phthalocyanine (4,5-octakisphenoxy)-(3,6-octakis-p-methoxyphenylthio) cobalt phthalocyanine (4,5-octakisphenoxy) )-(3,6-Octakis-α-naphthylthio) zinc phthalocyanine (4,5-octakisphenoxy)-(3,6-octakis-β-naphthylthio) lead phthalocyanine

(4,5-Octakisphenoxy)-
(3,6-Octakis-n-butylthio) cobalt phthalocyanine (4,5-octakisphenoxy)-(3,6-octakis-n-octylthio) zinc phthalocyanine (4,5-octakisphenoxy)-(3,6 -Octakis-n-propylthio) cobalt phthalocyanine (4,5-octakisphenoxy)-(3,6-octakis-iso-butylthio) iron phthalocyanine

(4,5-Octakisphenoxy)-
(3,6-Octakis-tert-butylthio) oxytitanium phthalocyanine (4,5-octakisphenoxy)-(3,6-octakis-o-chlorophenylthio) copper phthalocyanine (4,5-octakisphenoxy)-(3 , 6-Octakis-p-fluorophenylthio) zinc phthalocyanine (4,5-octakisphenoxy)-(3,6-octakisbenzylthio) oxyvanadium phthalocyanine

(4,5-Octakis-o-methylphenoxy)-(3,6-octakisphenylthio) lead phthalocyanine (4,5-octakis-o-methylphenoxy)-
(3,6-Octakis-o-methylphenylthio) copper phthalocyanine (4,5-octakis-p-fluorophenoxy)-
(3,6-Octakis-n-butylthio) copper phthalocyanine (4,5-octakis-α-naphthyl)-(3,6-octakisphenylthio) cobalt phthalocyanine

(4,5-Octakisbenzyloxy)-
(3,6-Octakisphenylthio) dichlorotin phthalocyanine (4,5-octakismethoxy)-(3,6-octakisphenylthio) copper phthalocyanine (4,5-octakismethoxy)-(3,6- Octakis-o-methylphenylthio) zinc phthalocyanine (4,5-octakisethoxy)-(3,6-octakisphenylthio) chloroaluminum phthalocyanine

(4,5-octakisethoxy)-(3,
6-Octakisethylthio) dichlorogermanium phthalocyanine (4,5-octakis-n-butoxy)-(3,6-octakis-p-methoxyphenylthio) oxytitanium phthalocyanine (4,5-octakis-n-butoxy)- (3,6-Octakisphenylthio) oxytitanium phthalocyanine (4,5-octakis-n-butoxy)-(3,6-octakisphenylthio) lead phthalocyanine

(4,5-Octakis-n-butoxy)-
(3,6-Octakis-n-butylthio) dichlorotin phthalocyanine (4,5-octakis-n-butoxy)-(3,6-octakis-n-octylthio) chloroindium phthalocyanine (4,5-octakis-n-octyl) Oxy)-(3
6-Octakisphenylthio) lead phthalocyanine (4,5-octakis-α-naphthyloxy)-(3,5
6-Octakis-α-naphthylthio) copper phthalocyanine

(4,5-Octakisbenzyloxy)-
(3,6-Octakisphenylthio) cobalt phthalocyanine (4,5-octakis-p-chlorophenoxy)-
(3,6-Octakis-p-methylphenylthio) copper phthalocyanine (4,5-octakis-p-fluorophenoxy)-
(3,6-Octakisphenylthio) cobalt phthalocyanine (4-tetrakisphenoxy)-(5-tetrakisethoxy)-(3,6-octakisphenylthio) copper phthalocyanine

(4-tetrakisphenoxy)-(5-tetrakis-n-butoxy)-(3,6-octakisphenylthio) copper phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-n
-Butoxy)-(3,6-octakisphenylthio) oxyvanadium phthalocyanine (4-tetrakis-p-fluorophenoxy)-(5-
Tetrakis-n-butoxy)-(3,6-octakisphenylthio) cobalt phthalocyanine (4-tetrakis-p-chlorophenoxy)-(5-tetrakis-p-fluorophenoxy)-(3,6-octakis-p- Chlorophenylthio) copper phthalocyanine

(4-tetrakisethoxy)-(5-tetrakisphenoxy)-(3,6-octakisphenylthio) cobalt phthalocyanine (4-tetrakis-n-butoxy)-(5-tetrakisphenoxy)-(3,6 -Octakisphenylthio) copper phthalocyanine (4-tetrakisbenzyloxy)-(5-tetrakis-n-butoxy)-(3,6-octakisphenylthio) cobalt phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis- p
-Fluorophenoxy)-(3,6-octakis-n-
Butylthio) copper phthalocyanine (4-tetrakis-n-octyloxy)-(5-tetrakis-n-hexyloxy)-(3,6-octakisethylthio) cobalt phthalocyanine

In the general formula (III) used in the present invention,
In the compounds represented, X is OR ₃Or SR_FourAnd
R₃And R_FourIs a straight or branched chain having 1 to 20 carbon atoms
Chain alkyl group, cycloalkyl having 4 to 6 carbon atoms
Group or phenyl group, benzyl group or naphthyl group
(The phenyl group, benzyl group and / or naphthyl group is charcoal.
Alkyl group having 1 to 4 elementary atoms, Al group having 1 to 4 carbon atoms
Substituted by coxyl radicals and / or halogen atoms
The following compounds may be specifically mentioned.
It

Phenol, o-methylphenol, m-
Methylphenol, p-methylphenol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,
6-dimethylphenol, o-fluorophenol, p
-Fluorophenol, 2,3,5,6-tetrafluorophenol, o-methoxyphenol, p-methoxyphenol, p-ethoxyphenol, benzyl alcohol,

Α-naphthol, β-naphthol, methanol, ethanol, n-propanol, iso-propanol, n-butanol, tert-butanol, n-
Pentanol, n-hexanol, n-hexanol,
n-octanol, n-nonyl alcohol, n-dodecyl alcohol, n-stearyl alcohol, methoxyethanol, ethoxyethanol, butoxyethanol,
(2-ethoxy) -ethoxyethanol, thiophenol,

O-Methylthiophenol, p-methylthiophenol, 2,3-dimethylthiophenol, 2,
4-dimethylthiophenol, 2,6-dimethylthiophenol, o-fluorothiophenol, p-fluorothiophenol, 2,3,5,6-tetrafluorothiophenol, o-methoxythiophenol, p-methoxythiophenol , P-ethoxythiophenol, benzyl mercaptan, α-thionaphthol, β-thionaphthol,

Methanethiol, ethanethiol, n-propanethiol, iso-propanethiol, n-butanethiol, tert-butanethiol, n-pentylmercaptan, n-hexylmercaptan, n-heptylmercaptan, n-octylmercaptan, n -Nonyl mercaptan, n-dodecyl mercaptan, 2-hydroxyethanethiol, 2-aminoethanethiol.

The organic solvent used in the present invention may be any inert solvent which does not react with the starting materials, for example, pyridine, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2. -Pyrrolidinone,
Basic solvents such as triethylamine and tri-n-butylamine, nitriles such as acetonitrile and benzonitrile, ethers such as diisopropyl ether, alcohols such as isopropyl alcohol and n-butyl alcohol, hydrocarbons such as benzene and toluene, Chloroform, 1,2-dichloroethane, 1,1,2,2-
A halogen solvent such as tetrachloroethane can be used, and a basic solvent and nitriles are preferable. Particularly preferred are pyridine, N, N-dimethylformamide, triethylamine and acetonitrile.

The present invention is preferably carried out in the presence of an alkaline substance. Examples of the alkaline substance to be used include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium fluoride, sodium fluoride and the like, and these can be used alone or in a mixture.

In the present invention, the fluorine-containing phthalocyanine represented by the general formula (II) is contained in an amount of 2 to 30 with respect to 100 parts of the organic solvent.
It is preferable to charge in the range of 1 part by weight, and 1 mol of the fluorinated phthalocyanine represented by the general formula (II) represents the general formula (II
The alcohol or thiol represented by I) is preferably charged in the range of 8.8 to 120 parts, particularly preferably 12 to 36 parts. Further, the alkaline substance is preferably used within a range of 0.9 to 3.0 mol, particularly preferably 1 to 1.5 mol, relative to 1 mol of alcohol or thiol.

The preferred reaction temperature in the present invention is preferably in the range of 30 to 250 ° C., particularly 80 to 20.
The range of 0 ° C is preferred. In the present invention, the starting material fluorine-containing phthalocyanine can be synthesized, for example, according to the first step, second step and third step of the following scheme. Then, in the present invention, the target substance can be obtained using these raw materials according to the following fourth step.

Where X is OR ₃ and R ₁ and R ₃
If the two are the same, the second step can be omitted. R _1, R ₂ in the scheme below, and X are the same as R _1, R _2, and X in the general formula I. Regarding the manufacturing method of the first step, the second step and the third step of the following scheme, Japanese Patent Application No. 63-65
806, 63-213830, Japanese Patent Application No. 1-10355.
4 and 1-103554.

[0047]

[Chemical 5]

[0048]

[Chemical 6]

[0049]

[Chemical 7]

The compound according to the present invention does not go through the above steps, for example, a method in which four substituents are introduced into a phthalonitrile compound as a raw material and then phthalocyanine is formed, or phthalocyanine is first formed and then the substituents are added. It can also be synthesized by the method of introduction.
However, since these methods have problems in the selectivity and yield of the substitution reaction, it is preferable to obtain the desired product via each of the above steps.

[0051]

According to the production method of the present invention, different substituents can be introduced site-selectively into the phthalocyanine skeleton. That is, according to the production method of the present invention, it is possible to design a molecule of a compound in which the absorption wavelength range of near-infrared rays or the solubility is changed according to the application, and fine characteristics can be controlled due to its high selectivity. Further, in that case, there is no need to go through a complicated manufacturing process, which is industrially advantageous.

Further, the novel phthalocyanine compound according to the present invention has an ether substituent having a high purity, and does not contain a chlorine atom or a bromine atom which deteriorates the solubility as disclosed in JP-A-63-295578. However, the fluorine atom in the novel compound of the present invention rather has the effect of increasing the solubility.

As mentioned above, the novel compounds of the present invention are
It has higher solubility in an organic solvent than conventionally known phthalocyanine compounds and has absorption in the near infrared region of 650 to 900 nm, and thus can be practically used as a near infrared absorbing dye or the like. Hereinafter, the present invention will be described more specifically by way of examples.

[0054]

EXAMPLES Example 1. 4,5-octakisphenoxy- (3,6-octakis
Phenylthio) oxyvanadium phthalocyanine [VO
_{Pc (PhO) 8 (PhS)} 8 ] thiophenol 4.52 g (41.0 mmol), potassium hydroxide 2.30 g (41.0 mmol), and pyridine 5
0 ml was placed in a 100 ml four-necked flask and reacted at 80 ° C. for 1 hour. Then, 3,6-octafluoro- (4,
5-Octakisphenoxy) oxyvanadium phthalocyanine [VOPc (PhO) ₈ F ₈ ] 5.00 g (3.
4 mmol) was added and the mixture was reacted under reflux conditions for 2 hours. After completion of the reaction, pyridine was distilled off, and the remaining solid content was washed with methanol to obtain 5.56 g of a target dark green cake (yield 74.5%).

Absorption wavelength 79 in chloroform
2.5 nm (ε = 1.47 × 10 ⁵ ) Coating film 796.0 nm Solubility Chloroform 11.5 wt% Toluene 5.8 wt% Elemental analysis value C (%) H (%) N (%) S (%) F ( Theoretical value 70.47 3.70 5.14 11.76 0.00 Analytical value 70.15 3.58 4.97 11.61 0.00 Infrared absorption spectrum The infrared absorption spectrum of this compound is shown in FIG.

Example 2. 4,5-octakisphenoxy- (3,6-octakis
Phenylthio) cobalt phthalocyanine [CoPc (P
3,6-octafluoro in Synthesis Example 1 of hO) ₈ (PhS) _8] - (4,5
3.85 g of 3,6-octafluoro- (4,5-octakisphenoxy) cobalt phthalocyanine instead of octakisphenoxy) oxyvanadium phthalocyanine
By operating in the same manner as in Example 1 except that (3.42 mmol) was used, 6.20 g of the target dark green cake was obtained (yield 83.4%).

Absorption wavelength in chloroform 71
2.0 nm (ε = 1.54 × 10 ⁵ ) Coating film 720.0 nm Solubility Chloroform 9.8 wt% Elemental analysis value C (%) H (%) N (%) S (%) F (%) Theoretical value 70.73 3.71 5.16 11.80 0.00 Analytical value 70.25 3.54 5.20 11.62 0.00 Infrared absorption spectrum The infrared absorption spectrum of this compound is shown in FIG.

Example 3. 4,5-octakisphenoxy- (3,6-octakis
Phenylthio) zinc phthalocyanine [ZnPc (Ph
O) ₈ (PhS) ₈ ], in the synthesis example 1, 3,6-octafluoro- (4,5-
A dark green cake of the target compound 5 was obtained by the same procedure as in Example 1 except that octafluoro- (octakisphenoxy) zinc phthalocyanine (4.60 g, 3.42 mmol) was used instead of octakisphenoxy) oxyvanadium phthalocyanine. 0.35 g was obtained (yield 71.8).
%).

Absorption wavelength in chloroform 73
9.5 nm (ε = 1.40 × 10 ⁵ ) Coating film 742.5 nm Solubility Chloroform 8.16 wt% Elemental analysis value C (%) H (%) N (%) S (%) F (%) Theoretical value 70.52 3.70 5.14 11.77 0.00 Analytical value 70.89 3.85 5.11 11.92 0.00 Infrared absorption spectrum The infrared absorption spectrum of this compound is shown in FIG.

Example 4. 4,5-octakisphenoxy- (3,6-octakis
-N-Butylthio) oxyvanadium phthalocyanine
Synthesis of [VOPc (PhO) ₈ (n-BuS) ₈ ] The same operation as in Example 1 except that 3.69 g (41.0 mmol) of n-butanethiol was used instead of thiophenol in Example 1. Thus, 4.77 g of the target dark green cake was obtained (yield 69.0%).

Absorption wavelength in chloroform 76
1.0 nm (ε = 2.03 × 10 ⁵ ) Coating film 764.5 nm Solubility Chloroform 14.8 wt% Elemental analysis value C (%) H (%) N (%) S (%) F (%) Theoretical value 66.54 5.58 5.54 12.69 0.00 Analytical value 65.98 5.43 5.28 12.55 0.00 Infrared absorption spectrum The infrared absorption spectrum of this compound is shown in FIG.

[Brief description of drawings]

FIG. 1 is a diagram showing an infrared absorption spectrum of the compound obtained in Example 1.

FIG. 2 is a diagram showing an infrared absorption spectrum of the compound obtained in Example 2.

FIG. 3 is a diagram showing an infrared absorption spectrum of the compound obtained in Example 3.

FIG. 4 is a diagram showing an infrared absorption spectrum of the compound obtained in Example 4.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C09K 3/00 105 9049-4H G03G 5/06 371 8305-2H 9/09 G03G 9/08 361

Claims (2)

[Claims] 1. The following general formula (I):[In the formula, X is mutually independent OR₃Or SR_FourRepresents;
R₁, R₂, R₃And R _FourIndependently of each other, the number of carbon atoms
1-20 alkyl group, cycloalkyl having 4-6 carbon atoms
Kill group, phenyl group, benzyl group and / or naphthyl group
Group (the phenyl group, benzyl group or naphthyl group
Is an alkyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms
Substituted with an alkoxyl group and / or a halogen atom of
May be present) and R₁, R₂And R₃Is
Not identical; and M is metal, metal oxide, or halogen
A new phthalocyanine compound represented by
object. 2. The following general formula (II): [In the formula, R ₁ and R ₂ independently of each other have 1 to 1 carbon atoms.
An alkyl group having 20 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, or a phenyl group, a benzyl group or a naphthyl group (the phenyl group, benzyl group and / or naphthyl group are
Which may be substituted by an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms and / or a halogen atom, and R ₁ and R ₂ are not the same] A phthalocyanine compound and the following general formula (III): XH (III) [wherein, X represents OR ₃ or SR ₄ , and R ₃ and R ₄
Is an alkyl group having 1 to 20 carbon atoms, 4 to 6 carbon atoms
Or a phenyl group, a benzyl group or a naphthyl group (wherein the phenyl group, the benzyl group and the naphthyl group are an alkyl group having 1 to 4 carbon atoms and a carbon atom having 1 carbon atom).
To 4) which may be substituted by an alkoxyl group and / or a halogen atom), and R ₃ is not the same as R ₁ and R ₂ ] in an organic solvent. The method for producing the novel phthalocyanine compound according to claim 1.