JPH05222302A - New phthalocyanine compound and its production - Google Patents

Abstract

PURPOSE:To produce the title compd. which has an absorption band in the near-infrared region and an excellent solubility esp. in an alcoholic solvent by reacting a specific phthalonitrile compd. with a metal oxide or halide or a metal salt of an org. acid. CONSTITUTION:A phthalocyanine compd. of formula I [wherein X is F, OR2, or SR4; R1, R2, and R3 are each a 1-20C alkyl group, a 4-6C cycloalkyl group, or a phenyl, benzyl, or naphthyl group optionally substd. by halogen or by a 1-4C alkyl or 1-4C alkoxyl group; and M is a metal, a metal oxide, or a metal halide] is produced by reacting a phthalonitrile compd. of formula II (wherein X and R1 are each as defined above) with a metal oxide or halide or a metal salt of an org. acid of the formula: MmXn (wherein M is a metal or a metal oxide; X is O, halogen, or an org. acid group; and m and n are each 1-5). The phthalocyanine compd. has an absorption band in the near- infrared region of 650-900nm and an excellent solubility esp. in an alcoholic solvent.

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 to 1200.
Since it has absorption in the near infrared region of nm and has excellent solubility, it is a near infrared absorbing dye for writing or reading in optical recording media using semiconductor lasers, liquid crystal display devices, optical character readers, etc. Photosensitizer, thermal transfer, thermal paper
As a near-infrared absorbing material used as a photothermal conversion agent such as heat-sensitive stencil, near-infrared absorption filter, eye strain preventing agent, photoconductive material, etc., or as a color separation filter used for an image pickup tube, liquid crystal display element, 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 problems of insufficient absorption in the near infrared region, complicated manufacturing process, and inability 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 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, which is disadvantageous in dissolving them as a near infrared absorbing dye 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 can be obtained, and a single characteristic cannot be obtained, and the absorption wavelength is reduced. When it is used as an application that needs to be controlled, for example, as a cyan inkjet ink or a near infrared absorbing dye, there is a problem that the application is limited.

Japanese Unexamined Patent Publication 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 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.

[0014]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances of the prior art. That is,
An object of the present invention is to provide a novel phthalocyanine compound which has absorption in the near infrared region of 650 to 900 nm and is excellent in solubility, particularly in an alcoholic solvent.
Another object of the present invention is to provide a method for efficiently producing the phthalocyanine compound with high purity.

Another object of the present invention is to provide a near-infrared absorbing material containing a novel phthalocyanine compound which has absorption in the near-infrared region and is excellent in solubility (particularly in an alcohol solvent). is there. A further object of the present invention is to provide a near-infrared absorbing phthalocyanine compound whose absorption wavelength is controlled.

[0016]

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

[Chemical 3]

[Wherein X represents F, OR ₂ or SR ₃ independently of each other; R ₁ , R ₂ and R ₃ 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, benzyl group and / or naphthyl group has 1 to 4 carbon atoms; An alkyl group, an alkoxyl group having 1 to 4 carbon atoms and / or a halogen atom), and M is a metal,
Which represents a metal oxide or a metal halide].

As such a fluorine-containing phthalocyanine compound, for example, R ₁ , R ₂ and R ₃ are phenyl residue, tolyl residue, xylyl residue, benzyl residue, naphthyl residue and 1-2 A phenyl group substituted with a fluorine or chlorine atom, an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 4 to 6 carbon atoms, and M is C
u, Zn, Fe, Ni, Co, Pb, AlCl, Al
I, InCl, InI, GaCl, GaI, TiC
l ₂ , TiO, VCl ₂ , VO, SnCl ₂ or GeC
and the compound being l ₂ .

Specifically, the following compounds are used. (4-Tetrakisphenoxy)-(5-tetrakisphenylthio) -3,6-octafluorocopper phthalocyanine (4-Tetrakisphenoxy)-(5-tetrakisphenylthio) -3,6-octafluorozinc phthalocyanine (4-Tetrakis Phenoxy)-(5-tetrakisphenylthio) -3,6-octafluorocobalt phthalocyanine (4-Tetrakisphenoxy)-(5-tetrakisphenylthio) -3,6-octafluoronickel phthalocyanine

(4-Tetrakisphenoxy)-(5-tetrakisphenylthio) -3,6-octafluoroiron phthalocyanine (4-Tetrakisphenoxy)-(5-tetrakisphenylthio) -3,6-octafluorooxyvanadium phthalocyanine (4-Tetrakisphenoxy)-(5-tetrakisphenylthio) -3,6-octafluorooxytitanium phthalocyanine (4-Tetrakisphenoxy)-(5-tetrakisphenylthio) -3,6-octafluoro-chloroindium phthalocyanine

(4-Tetrakisphenoxy)-(5-tetrakisphenylthio) -3,6-octafluoro-chloroaluminum phthalocyanine (4-Tetrakisphenoxy)-(5-tetrakisphenylthio) -3,6-octafluoro- Dichlorotin phthalocyanine (4-tetrakisphenoxy)-(5-tetrakisphenylthio) -3,6-octafluoro-dichlorogermanium phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-o
-Methylphenylthio) -3,6-octafluorocopper phthalocyanine

(4-tetrakisphenoxy)-(5-tetrakis-2,4-dimethylphenylthio) -3,6-
Octafluorocopper phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-p
-Methoxyphenylthio) -3,6-octafluorocobalt phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-α
-Naphthylthio) -3,6-octafluorozinc phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-β
-Naphthylthio) -3,6-octafluorozinc phthalocyanine

(4-tetrakisphenoxy)-(5-tetrakis-n-butylthio) -3,6-octafluorocobalt phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-n
-Butylthio) -3,6-octafluorozinc phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-n
-Butylthio) -3,6-octafluorooxyvanadium phthalocyanine (4-tetrakisphenoxy)-(5-tetrakiscyclohexylthio) -3,6-octafluorooxyvanadium phthalocyanine

(4-tetrakisphenoxy)-(5-tetrakis-n-octylthio) -3,6-octafluorozinc phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-t
ert-Butylthio) -3,6-octafluoroiron phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-p
-Fluorophenylthio) -3,6-octafluorozinc phthalocyanine (4-tetrakisphenoxy)-(5-tetrakisbenzylthio) -3,6-octafluorooxyvanadium phthalocyanine

(4-tetrakis-o-methylphenoxy)-(5-tetrakisphenylthio) -3,6-octafluorocopper phthalocyanine (4-tetrakis-o-methylphenoxy)-(5-tetrakis-o-methylphenyl Thio) -3,6-octafluorocopper phthalocyanine (4-tetrakis-o-methylphenoxy)-(5-tetrakis-o-methylphenylthio) -3,6-octafluorooxyvanadium phthalocyanine (4-tetrakis-p- Methylphenoxy)-(5-tetrakisphenylthio) -3,6-octafluorooxyvanadium phthalocyanine

(4-tetrakis-p-fluorophenoxy)-(5-tetrakis-n-butylthio) -3,6-
Octafluorocopper phthalocyanine (4-tetrakis-α-naphthyl)-(5-tetrakisphenylthio) -3,6-octafluorocobalt phthalocyanine (4-tetrakismethoxy)-(5-tetrakis-o-
Methylphenylthio) -3,6-octafluorozinc phthalocyanine (4-tetrakisethoxy)-(5-tetrakisphenylthio) -3,6-octafluorochloroaluminum phthalocyanine

(4-tetrakisethoxy)-(5-tetrakisethylthio) -3,6-octafluorodichlorogermanium phthalocyanine (4-tetrakis-n-butoxy)-(5-tetrakis-p-phenylthio) -3,6 -Octafluorooxytitanium phthalocyanine (4-tetrakis-n-butoxy)-(5-tetrakisphenylthio) -3,6-octafluorooxytitanium phthalocyanine (4-tetrakis-n-butoxy)-(5-tetrakisphenylthio) -3,6-Octafluorolead phthalocyanine

(4-tetrakis-n-butoxy)-(5
-Tetrakis-p-phenylthio) -3,6-octafluorocopper phthalocyanine (4-tetrakis-n-butoxy)-(5-tetrakis-n-butylthio) -3,6-octafluorozinc phthalocyanine (4-tetrakis-n -Butoxy)-(5-tetrakis-n-butylthio) -3,6-octafluorooxyvanadium phthalocyanine (4-tetrakis-n-butoxy)-(5-tetrakis-n-butylthio) -3,6-octafluorodichloro Tin phthalocyanine

(4-tetrakiscyclohexyloxy)
-(5-Tetrakis-n-octylthio) -3,6-octafluorocopper phthalocyanine (4-Tetrakis-n-octyloxy)-(5-tetrakis-o-phenylthio) -3,6-octafluorozinc phthalocyanine (4 -Tetrakis-α-naphthyloxy)-(5-tetrakis-α-naphthylthio) -3,6-octafluorocopper phthalocyanine (4-tetrakis-α-naphthyloxy)-(5-tetrakis-n-butylthio) -3, 6-octafluorochloroindium phthalocyanine

(4-tetrakis-o-chlorophenoxy)-(5-tetrakisphenylthio) -3,6-octafluoronickel phthalocyanine (4-tetrakis-o-chlorophenoxy)-(5-tetrakis-n-hexylthio) -3,6-octafluorooxytitanium phthalocyanine (4-tetrakis-p-chlorophenoxy)-(5-tetrakis-p-phenylthio) -3,6-octafluorocopper phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis -Α
-Naphthyloxy) -3,6-octafluorocobalt phthalocyanine

(4-tetrakisphenoxy)-(5-tetrakis-o-chlorophenoxy) -3,6-octafluorocobalt phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-p
-Methoxyphenoxy) -3,6-octafluorooxytitanium phthalocyanine (4-tetrakisphenoxy)-(5-tetrakisethoxy) -3,6-octafluoronickel phthalocyanine (4-tetrakisphenoxy)-(5-tetrakis-n
-Butoxy) -3,6-octafluorodichlorotin phthalocyanine

(4-tetrakis-p-fluorophenoxy)-(5-tetrakis-p-chlorophenylthio)-
3,6-Octafluorocopper phthalocyanine (4-tetrakisbenzyloxy)-(5-tetrakisphenylthio) -3,6-octafluorochloroindium phthalocyanine (4-tetrakis-n-propyloxy)-(5-tetrakis-iso -Propyloxy) -3,6-octafluorocobalt phthalocyanine (4-tetrakis-n-butoxy)-(5-tetrakis-n-octyloxy) -3,6-octafluorozinc phthalocyanine (4-tetrakis-n-butoxy) )-(5-Tetrakis-n-dodecyloxy) -3,6-octafluorocopper phthalocyanine.

The fluorine-containing phthalocyanine compound represented by the general formula (I) of the present invention is, for example, the following general formula (I
I):

[0034]

[Chemical 4]

[Wherein, X represents F, OR ₂ or SR ₃ ; R ₁ , R ₂ and R ₃ independently of each other have 1 carbon atom;
˜20 alkyl group, C 4-6 cycloalkyl group, or phenyl group, benzyl group or naphthyl group (the phenyl group, benzyl group and / or naphthyl group are
A C1 to C4 alkyl group, a C1 to C4 alkoxyl group and / or a halogen atom may be substituted)], and the following general formula (III):

M _m X ′ _n (III) (wherein M represents a metal or a metal oxide, X ′ represents an oxygen atom, a halogen atom or an organic acid group, and m and n are integers of 1 to 5) It can be produced by reacting with a metal oxide, a metal halide or an organic acid metal salt.

The manufacturing method of the present invention will be described in detail below. The reaction between the phthalonitrile derivative and the metal oxide, metal halide or organic metal salt may be carried out in the absence of a solvent, but it is preferably carried out using an organic solvent. The organic solvent may be any inert solvent that is not reactive with the starting materials, such as benzene, toluene,
Inert solvent such as xylene, nitrobenzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, chloronaphthalene, methylnaphthalene, ethylene glycol, benzonitrile, or pyridine, N, N-dimethylformamide, N, N-dimethylacetamide,
An aprotic polar solvent such as N-methyl-2-pyrrolidinone, triethylamine, tri-n-butylamine, dimethyl sulfone or sulfolane can be used,
Preferably, chloronaphthalene, trichlorobenzene,
Nitrobenzene and benzonitrile.

In the present invention, the fluorine-containing phthalonitrile derivative represented by the general formula (II) is contained in the range of 2 to 30 parts by weight, the metal oxide represented by the general formula (III), and the metal halogen based on 100 parts by weight of the organic solvent. The compound or organic metal salt is charged in the range of 1 to 2 mol with respect to 4 mol of the phthalonitrile derivative and reacted at a reaction temperature of 30 to 250 ° C, preferably 80 to 200 ° C.

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 fluorinated phthalonitrile can be synthesized, for example, according to the first and second steps of the following scheme. R _1, R _2, R ₃ in the following scheme, and X are the same as the general formula R _1, R _2, R ₃ in the I, and X. Then, in the present invention, the target substance can be obtained using these raw materials according to the following third step. In addition,
The manufacturing method of the first step and the second step of the following scheme is described in Japanese Patent Application Nos. 63-65806 and 63-21.
3830, Japanese Patent Application Nos. 1-103554 and 1-10355.
4, etc.

[0040]

[Chemical 5]

[0041]

[Chemical 6]

[0042]

According to the production method of the present invention, it is possible to regioselectively introduce a substituent into the phthalocyanine skeleton. That is, according to the production method of the present invention, it is possible to molecular design of a compound having a near infrared absorption wavelength region or solubility changed according to the application, and at that time, industrially without the need for complicated production steps. It is advantageous. Further, it has an ether substituent of high purity, and it is disclosed in JP-A-63-295578.
As described in No. 3, the compound does not contain a chlorine atom or a bromine atom which deteriorates the solubility, and the fluorine atom in the novel compound of the present invention rather has the effect of enhancing the solubility.

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

[0044]

EXAMPLES Example 1. 4-tetrakisphenoxy- (5-tetrakisphenyl
Thio) -3,6-octakisfluorocobalt phthaloxy
Cyanine _{[CoPc (PhO) 4 (PhS)} 4 F 8 ] 4-phenoxy-5-phenylthio-3,6-difluoro phthalonitrile 5.00 g (13.7 mmol), anhydrous chloride cobaltous 5.54 g (4.12 mmol ) And benzonitrile (50 ml) were placed in a 100 ml four-necked flask and reacted at 175 ° C. for 4 hours. After the reaction was completed, the produced solid content was filtered off, and the remaining solid content was washed with methanol to obtain 4.49 g of a target dark green cake (yield 86.5%).

Absorption wavelength 709.5 nm in chloroform
(Ε = 7.92 × 10 ⁴ ) Coating film 719.5 nm Solubility Chloroform 1.2 wt% Toluene 0.8 wt% Elemental analysis value C (%) H (%) N (%) S (%) F (%) Theory Value 63.37 2.66 7.39 8.46 10.02 Analytical value 62.98 2.61 7.13 8.51 9.76 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.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location B41M 5/26 C09B 47/20 8619-4H C09D 11/00 PSZ 7415-4J C09K 3/00 105 9049 -4H

Claims (2)

[Claims] 1. The following general formula (I): [In the formula, X is independently of each other F, OR ₂ or SR ₃ ; R ₁ , R ₂ and R ₃ are independently of each other, having 1 carbon atom;
˜20 alkyl group, C 4-6 cycloalkyl group, or phenyl group, benzyl group or naphthyl group (the phenyl group, benzyl group and / or naphthyl group are
An alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms and / or a halogen atom may be substituted); and M represents a metal, a metal oxide, or a metal halide] A novel phthalocyanine compound represented by. 2. The following general formula (II): [In the formula, X represents F, OR ₂ or SR ₃ ; R ₁ , R
₂ and R ₃ 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, benzyl group and / or Naphthyl group has 1 carbon atom
May be substituted by an alkyl group of 4 to 4, an alkoxyl group having 1 to 4 carbon atoms and / or a halogen atom)
And a phthalonitrile compound represented by the following general formula (III): M _m X ′ _n (III) (wherein M represents a metal or a metal oxide, and X ′ represents an oxygen atom, a halogen atom or A novel phthalocyanine according to claim 1, characterized in that it is reacted with a metal oxide, a metal halide or an organic acid metal salt represented by an organic acid group, and m and n represent an integer of 1 to 5). Method for producing compound.