JPH05222047A - New phthalocyanine compound and its production - Google Patents

Abstract

PURPOSE:To obtain a new compound, having the absorption in the near infrared region, capable of controlling the absorption wavelength according to the purpose, excellent in solubility especially in alcoholic solvents and useful as a near infrared absorption material, etc. CONSTITUTION:The objective compound of formula I (X is OR3 or SR4; R1 to R4 are 1-20C alkyl, 4-6C cycloalkyl, phenyl, benzyl, naphthyl, etc.; M is metal, metallic oxide or halide), e.g. (4-tetrakisphenoxy)-(5-tetrakisphenylthio)-(3,6- octakis-n-butylthio)copper phthalocyanine. This compound of formula I is obtained by reacting a phthalocyanine compound of formula II with a compound of the formula XH, preferably in the presence of an alkaline substance (e.g. KOH) in an organic solvent (e.g. pyridine) at 30-250 deg.C. The compound of formula I has the absorption within the near infrared region and is useful as a near infrared absorption material, etc., used as optical recording media, liquid crystal display devices, photothermal converting agents, near infrared absorption filters, photoconductive materials, etc.

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 it is not possible to obtain inexpensive phthalocyanine.

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 No. 61-152685 disclose synthetic examples in which a thioether group is introduced at the phthalocyanine skeleton, particularly 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, in all cases, the yield is 20 to 3
It is about 0%, which causes 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 the 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 discloses 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, which is disadvantageous in dissolving them as a near-infrared absorbing dye or other uses, for example, as a dye for a color 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 a DMF solvent in the presence of KOH to give a thioether substituent. 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 as a near infrared absorbing dye or a cyan inkjet ink. However, there is a problem in that a single property cannot be obtained when using, and thus the application is limited.

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. The present inventors have proposed to solve these drawbacks in Japanese Patent Application No. 1-209.
599, Japanese Patent Application No. 2-125518, Japanese Patent Application No. 2-14
No. 4292, the fluorine of octadecafluorophthalocyanine was selectively substituted with an alkylthio group or an arylthio group to make the absorption wavelength longer and to improve the solvent solubility, and some effects were obtained.

However, in order to apply a solvent onto a plastic substrate, it is necessary to dissolve 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.

[0012]

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.

[0013]

That is, according to the present invention, the following general formula (I):

[0014]

[Chemical 3]

[In the formula, X is independently of each other OR ₃ or SR.
Represents R ₄ ; R ₁ , R ₂ , R ₃ and R ₄ are, independently of each other, 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 naphthyl group is an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms and / or Or optionally substituted by a halogen atom); and M represents a metal, a metal oxide, or a metal halide].

As such a fluorine-containing phthalocyanine compound, for example, R ₁ , R ₂ , R ₃ and R ₄ are independently of each other a phenyl residue, a tolyl residue, a xylyl residue,
Benzyl residue, naphthyl residue, phenyl group substituted by alkoxy group having 1 to 4 carbon atoms, phenyl group substituted by 1 to 2 fluorine or chloro atoms, alkyl group having 1 to 20 carbon atoms Or a cycloalkyl group having 4 to 6 carbon atoms, and M is Cu, Zn, Pb, F
e, Ni, Co, AlCl, AlI, InCl, In
I, GaCl, GaI, TiCl ₂ , TiO, VC
and compounds that are l ₂ , VO, SnCl ₂ or GeCl ₂ . The fluorine-containing phthalocyanine compound represented by the general formula (I) of the present invention is, for example, the following general formula (I
I):

[0017]

[Chemical 4]

[In the formula, R ₁ and R ₂ are independently of each other an 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 ( A phenyl group, a benzyl group and / or a naphthyl group represent an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms and / or a halogen atom). A phthalocyanine derivative 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 (the phenyl group, benzyl group and / or naphthyl group is an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms and / or The compound represented by the formula (which may be substituted with a halogen atom)] is reacted in 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, a phenyl group, a benzyl group or a naphthyl group (the phenyl group). , A benzyl group and / or a naphthyl group are an alkyl group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms.
Which may be substituted with an alkoxyl group and / or a halogen atom), and specific examples thereof include the following compounds.

(4-tetrakisphenoxy)-(5-tetrakisphenylthio)-(3,6-octakis-n-
Butylthio) copper phthalocyanine (4-tetrakisphenoxy)-(5-tetrakisphenylthio)-(3,6-octakis-n-butylthio)
Zinc phthalocyanine (4-tetrakisphenoxy)-(5-tetrakisphenylthio)-(3,6-octakis-n-butylthio)
Cobalt phthalocyanine (4-tetrakisphenoxy)-(5-tetrakisphenylthio)-(3,6-octakis-p-methylphenylthio) nickel phthalocyanine (4-tetrakisphenoxy)-(5-tetrakisphenylthio)-(3. 6-octakis-p-chlorophenylthio) iron phthalocyanine

(4-tetrakisphenoxy)-(5-tetrakisphenylthio)-(3,6-octakis-n-
Butylthio) oxyvanadium phthalocyanine (4-tetrakisphenoxy)-(5-tetrakisphenylthio)-(3,6-octakis-n-octylthio) oxytitanium phthalocyanine (4-tetrakisphenoxy)-(5-tetrakisphenylthio)-( 3,6-Octakisbenzylthio) -chloroindium phthalocyanine (4-tetrakisphenoxy)-(5-tetrakisphenylthio)-(3,6-octakis-α-naphthyl)-
Chloroaluminum phthalocyanine (4-tetrakisphenoxy)-(5-tetrakisphenylthio)-(3,6-octakis-α-naphthyl)-
Dichlorotin phthalocyanine

(4-tetrakisphenoxy)-(5-tetrakisphenylthio)-(3,6-octakis-n-
Dodecylthio) -dichlorogermanium phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-o
-Methylphenylthio)-(3,6-octakis-phenylthio) copper phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-o
-Methylphenylthio)-(3,6-octakis-phenylthio) cobalt phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-p
-Methylphenylthio)-(3,6-octakis-n-
Butylthio) zinc phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-
2,3-Dimethylphenylthio)-(3,6-octakis-o-methoxyphenylthio) zinc phthalocyanine

(4-tetrakisphenoxy)-(5-tetrakis-2,4-dimethylphenylthio)-(3,6
-Octakis-n-butoxy) copper phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-p
-Methoxyphenylthio)-(3,6-octakis-n
-Butoxy) cobalt phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-α
-Naphthylthio)-(3,6-octakis-phenylthio) zinc phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-β
-Naphthylthio)-(3,6-octakis-phenoxy) zinc phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-n
-Butylthio)-(3,6-octakis-phenylthio) cobalt phthalocyanine

(4-tetrakisphenoxy)-(5-tetrakis-n-butylthio)-(3,6-octakis-
n-Propylthio) zinc phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-n
-Butylthio)-(3,6-octakis-iso-propylthio) oxyvanadium phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-n
-Octylthio)-(3,6-octakis-n-butylthio) zinc phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-n
-Propylthio)-(3,6-octakis-o-methylphenylthio) cobalt phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-t
ert-Butylthio)-(3,6-octakis-phenylthio) iron phthalocyanine

(4-Tetrakisphenoxy)-(5-tetrakis-tert-butylthio)-(3,6-octakis-p-chlorophenylthio) oxytitanium phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-o
-Chlorophenylthio)-(3,6-octakis-n-
Octylthio) copper phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-p
-Fluorophenylthio)-(3,6-octakisbenzylthio) zinc phthalocyanine (4-tetrakisphenoxy)-(5-tetrakisbenzylthio)-(3,6-octakis-ethylthio) oxyvanadium phthalocyanine (4-tetrakis- o-methylphenoxy)-(5-tetrakisphenylthio)-(3,6-octakis-o-
Methoxyphenyl) lead phthalocyanine

(4-tetrakis-o-methylphenoxy)-(5-tetrakis-o-methylphenylthio)-
(3,6-Octakis-ethylthio) copper phthalocyanine (4-tetrakis-o-methylphenoxy)-(5-tetrakis-o-methylphenylthio)-(3,6-octakis-ethylthio) oxyvanadium phthalocyanine (4-tetrakis -O-methylphenoxy)-(5-tetrakis-n-butylthio)-(3,6-octakis-
o-Methylphenylthio) nickel phthalocyanine (4-tetrakis-o-methylphenoxy)-(5-tetrakis-o-chlorophenylthio)-(3,6-octakis-α-naphthyl) zinc phthalocyanine (4-tetrakis-p- Methylphenoxy)-(5-tetrakisphenylthio)-(3,6-octakis) oxyvanadium phthalocyanine

(4-tetrakis-p-fluorophenoxy)-(5-tetrakis-n-butylthio)-(3,6
-Octakis-p-fluorophenoxy) copper phthalocyanine (4-tetrakis-α-naphthyl)-(5-tetrakisphenylthio)-(3,6-octakis-n-hexylthio) cobaltphthalocyanine (4-tetrakisbenzyloxy)-( 5-tetrakisphenylthio)-(3,6-octakis-benzylthio) dichlorotin phthalocyanine (4-tetrakismethoxy)-(5-tetrakisphenylthio)-(3,6-octakis-n-octylthio)
Copper phthalocyanine (4-tetrakismethoxy)-(5-tetrakis-o-
Methylphenylthio)-(3,6-octakis-p-methylphenylthio) zinc phthalocyanine

(4-tetrakisethoxy)-(5-tetrakisphenylthio)-(3,6-octakis-p-fluorophenylthio) chloroaluminum phthalocyanine (4-tetrakisethoxy)-(5-tetrakisethylthio)-( 3,6-Octakis-phenylthio) dichlorogermanium phthalocyanine (4-tetrakis-n-butoxy)-(5-tetrakis-p-methoxyphenylthio)-(3,6-octakis-p-methylphenoxy) oxytitanium phthalocyanine (4 -Tetrakis-n-butoxy)-(5-tetrakisphenylthio)-(3,6-octakis-p-chlorophenyl) oxytitanium phthalocyanine (4-tetrakis-n-butoxy)-(5-tetrakisphenylthio)-(3 , 6-octakis-n- Butylthio) lead phthalocyanine

(4-tetrakis-n-butoxy)-(5
-Tetrakis-p-methylphenylthio)-(3,6-
Octakis-n-butylthio) copper phthalocyanine (4-tetrakis-n-butoxy)-(5-tetrakis-n-butylthio)-(3,6-octakis-phenylthio) zinc phthalocyanine (4-tetrakis-n-butoxy)-( 5-Tetrakis-n-butylthio)-(3,6-octakis-phenylthio) oxyvanadium phthalocyanine (4-tetrakis-n-butoxy)-(5-tetrakis-n-butylthio)-(3,6-octakis-phenylthio) Dichlorotin phthalocyanine (4-tetrakis-n-butoxy)-(5-tetrakis-n-octylthio)-(3,6-octakis-n-butylthio) chloroindium phthalocyanine

(4-tetrakis-n-octyloxy)
-(5-Tetrakisphenylthio)-(3,6-octakis-n-octylthio) lead phthalocyanine (4-tetrakis-n-octyloxy)-(5-tetrakis-o-phenylthio)-(3,6-octakis-
n-Dodecylthio) zinc phthalocyanine (4-tetrakis-α-naphthyloxy)-(5-tetrakis-α-naphthylthio)-(3,6-octakis-
Benzylthio) copper phthalocyanine (4-tetrakis-α-naphthyloxy)-(5-tetrakis-n-butylthio)-(3,6-octakis-phenylthio) chloroindium phthalocyanine (4-tetrakis-β-naphthyloxy)-(5 -Tetrakisphenylthio)-(3,6-octakis-p-methylphenylthio) iron phthalocyanine

(4-tetrakisbenzyloxy)-(5-
Tetrakisphenylthio)-(3,6-octakis-ethylthio) cobalt phthalocyanine (4-tetrakisbenzyloxy)-(5-tetrakis-
o-Methylphenylthio)-(3,6-octakis-benzylthio) oxyvanadium phthalocyanine (4-tetrakis-o-chlorophenoxy)-(5-tetrakisphenylthio)-(3,6-octakis-o-
Fluorophenylthio) nickel phthalocyanine (4-tetrakis-o-chlorophenoxy)-(5-tetrakis-n-hexylthio)-(3,6-octakis-phenylthio) oxytitanium phthalocyanine (4-tetrakis-p-chlorophenoxy)- (5-Tetrakis-p-methylphenylthio)-(3,6-octakis-p-methoxyphenylthio) copper phthalocyanine

(4-tetrakis-p-fluorophenoxy)-(5-tetrakisphenylthio)-(3,6-octakis-p-fluorophenylthio) cobalt phthalocyanine (3,4,6-dodecakisphenoxy)-( 5-Tetrakisphenylthio) copper phthalocyanine (3,4,6-dodecakisphenoxy)-(5-tetrakisphenylthio) oxyvanadium phthalocyanine (3,4,6-dodecakis-o-methylphenoxy)-
(5-Tetrakisphenylthio) cobalt phthalocyanine (3,4,6-dodecakisphenoxy)-(5-tetrakis-n-butylthio) nickel phthalocyanine

(3,4,6-dodecakisethoxy)-
(5-Tetrakisphenylthio) iron phthalocyanine (3,4,6-dodecakis-n-butoxy)-(5-tetrakisphenylthio) chloroindium phthalocyanine (4-tetrakis-phenoxy)-(3,5,6-dodecakis) Phenylthio) dichlorotin phthalocyanine (4-tetrakis-phenoxy)-(3,5,6-dodecaquis-n-hexylthio) iron phthalocyanine (4-tetrakis-p-methoxyphenoxy)-(3
5,6-Dodecamikis cyclohexylthio) oxytitanium phthalocyanine

(4-tetrakis-n-butoxy)-
(3,5,6-Dodecakisquis-n-butylthio) oxyvanadium phthalocyanine (4-tetrakis-n-butoxy)-(3,5,6-dodecakisquis-n-butylthio) cobalt phthalocyanine (4-tetrakis-n-) (Butoxy)-(3,5,6-dodecaquix phenylthio) dichlorotin phthalocyanine (4-tetrakis-n-butoxy)-(3,5,6-dodecaquixnaphthylthio) zinc phthalocyanine

In the compound represented by the general formula (III) used in the present invention, X is a linear or branched alkyl group having 1 to 20 carbon atoms, or 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 substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms and / or a halogen atom) The following compounds may be specifically mentioned.

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 fluorine-containing phthalocyanine represented by the general formula (II) is represented by the 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. The second step may be omitted when X is OR ₃ and R ₁ and R ₃ are the same, and when X is SR ₄ and R ₂ and R ₄ are the same. Is.

R in the scheme below₁, R₂, R₃，
R_Four, And X are R in the general formula I ₁, R₂, R₃, R
_Four, And X. The first scheme below
Step, second step and third step manufacturing method
Regarding Japanese Patent Application Nos. 63-65806 and 63-2138.
30 and Japanese Patent Application No. 1-103554.

[0046]

[Chemical 5]

[0047]

[Chemical 6]

[0048]

[Chemical 7]

The compound according to the present invention does not go through each of the above steps, for example, a method of introducing four substituents into a phthalonitrile compound as a raw material and then phthalocyanizing it, or first phthalocyanating and then substituting the substituents. 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.

[0050]

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 described above, the novel compound of the present invention 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. It can be used practically.

Hereinafter, the present invention will be described more specifically with reference to Examples.

EXAMPLES Example 1 4-tetrakis-n-butoxy- (3,5,6-dodeca
Kiss-n-butylthio) oxyvanadium phthalocyanine
[VOPc (BuO) ₄ (BuS) ₁₂ ] n-butanethiol 7.94 g (88.2 mmol), potassium hydroxide 4.94 g (88.2 mmol), and pyridine 50 ml were charged in a 100 ml four-necked flask at 80 ° C. In 1
Reacted for hours. Then, 3,5,6-dodeca Kiss fluoro - (4-tetrakis -n- butoxy) oxyvanadium phthalocyanine [VOPc (BuO) ₄ F _12] 5.
00 g (4.90 mmol) was added and reacted for 2 hours under reflux conditions. After completion of the reaction, pyridine was distilled off, and the remaining solid content was washed with methanol to obtain 7.44 g of a target dark green cake (yield 78.2%).

Absorption wavelength 799.0 nm in chloroform (ε = 1.19 × 10 ⁵ ) Coating film 807.0 nm Solubility Chloroform 18 wt% Toluene 11 wt% Elemental analysis value C H N S F theoretical value 59.38 7.47 5.77 19.81 0.00 Analysis value 59.87 7.85 6.01 19.85 0.00 Infrared absorption spectrum Figure 1 shows the infrared absorption spectrum of this compound.

Example 2 4-tetrakis-n-butoxy- (3,5,6-dodeca
Kiss-n-butylthio) cobalt phthalocyanine [Co
Synthesis of Pc (BuO) ₄ (BuS) ₁₂ ] In Example 1, 3,5,6-dodecamixfluoro-
(4-tetrakis-n-butoxy) oxyvanadium phthalocyanine was replaced by 3,5,6-dodecakisfluoro- (4-tetrakis-n-butoxy) cobalt phthalocyanine (5.00 g, 4.94 mmol). The same procedure as in Example 1 was carried out to obtain 7.71 g of the target dark green cake (yield 81.3%).

Absorption wavelength 746.5 nm in chloroform (ε = 5.43 × 10 ⁴ ) Coating film 753.5 nm Solubility Chloroform 16 wt% Toluene 11 wt% Elemental analysis value C H N S F Theoretical value 60.12 7.57 5.84 20.06 0.00 Analysis value 59.98 7.46 5.77 19.85 0.00 Infrared absorption spectrum Figure 2 shows the infrared absorption spectrum of this compound.

Example 3 4-tetrakis-n-butoxy- (3,5,6-dodeca
Kissphenylthio) oxyvanadium phthalocyanine
Synthesis of [VOPc (BuO) ₄ (PhS) ₁₂ ] By operating in the same manner as in Example 1 except that 9.70 g (88.2 mmol) of benzenethiol was used instead of n-butanethiol in Example 1, Thus, 8.16 g of a dark green cake was obtained (yield: 76.3%).

Absorption wavelength 793.5 nm in chloroform (ε = 1.11 × 10 ⁵ ) Coating film 798.5 nm Solubility Chloroform 10 wt% Toluene 6 wt% Elemental analysis value C H N S F theoretical value 66.55 4.47 5.17 17.76 0.00 Analysis value 66.38 4.28 5.02 17.68 0.00 Infrared absorption spectrum The infrared absorption spectrum of this compound is shown in FIG.

Example 4 4-Tetrakisphenoxy- (3,5,6-dodecakis
Phenylthio) zinc phthalocyanine [ZnPc (Ph
Synthesis of O) ₄ (PhS) ₁₂ ] In Example 1, dodecaquisfluoro- (tetrakis-
In place of (n-butoxy) oxyvanadium phthalocyanine, dodecakisfluoro- (tetrakisphenoxy) zinc phthalocyanine (5.00 g, 4.55 mmol), and in place of butanethiol, 9.01 g (81.
By operating in the same manner as in Example 1 except that (9 mmol) was used, 8.36 g of the target dark green cake was obtained (yield 83.1%).

Absorption wavelength 826.5 nm in chloroform (ε = 1.22 × 10 ⁵ ) Coating film 845.0 nm Solubility Chloroform 6 wt% Toluene 5 wt% Elemental analysis value C H N S F theoretical value 67.33 3.64 5.07 17.39 0.00 Analysis value 67.48 3.69 5.20 17.36 0.00 Infrared absorption spectrum Figure 4 shows the infrared absorption spectrum of this compound.

[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 front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area C07D 259: 00)

Claims (2)

[Claims] 1. The following general formula (I): [In the formula, X's each independently represent OR ₃ or SR ₄ ;
R ₁ , R ₂ , R ₃ and R ₄ are independently of each other an 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 group, benzyl group and / or naphthyl group is an alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms.
Optionally substituted by an alkoxyl group and / or halogen); and M represents a metal, a metal oxide, or a metal halide]. 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
A C1 to C4 alkyl group, a C1 to C4 alkoxyl group, a cycloalkyl group and / or a halogen atom may be substituted). (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 (the phenyl group, benzyl group and / or naphthyl group is an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms and / or A compound represented by the formula (which may be substituted with a halogen atom)] is reacted in an organic solvent.
A method for producing the novel phthalocyanine compound described.