JPH06192584A - New phtalocyanine compound, its production and near infrared absorbing material containing the compound - Google Patents

Abstract

PURPOSE:To provide a new compound having an absorption band in a long wavelength range, a high solubility in an org. solvent and useful as near-infrared absorbing material, etc. CONSTITUTION:The compound of formula I [R<1> and R<2> are 3-10C alkyl or (substd.) phenyl] e.g. 4,5-octakis-anilino-(3,6-octakis-phenylthio) oxyvanadiumphthalocyanine. The compound is obtained by reacting a compound of formula II with a thiol compound of formula III.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel phthalocyanine compound, a method for producing the same, and 750 to 1500 nm.
The present invention relates to a near-infrared absorbing material having absorption in the near-infrared region and having high solubility in a solvent. The novel phthalocyanine compound according to the present invention is particularly excellent in absorption ability in the near infrared region of 900 to 1200 nm, excellent in solubility, and excellent in light resistance and heat resistance originally possessed by phthalocyanine. Therefore, it is necessary to satisfy all of these characteristics, such as near-infrared photosensitizer, heat-sensitive transfer, photothermal conversion agent such as heat-sensitive paper / heat-sensitive stencil, near-infrared absorption filter, eye strain preventive agent, or tampering prevention When used as a heat ray shielding agent for printed matter for automobiles or automobiles or building materials, it exerts an excellent effect.

[0002]

2. Description of the Related Art In recent years, many semiconductor lasers have been used as near-infrared light as a light source for writing or reading in optical recording media such as optical memory disks and optical cards, liquid crystal display devices, and optical character readers. Has been done. Near-infrared light occupies about half of solar energy, and has been greatly involved in human life as solar heat. for that reason,
Photoelectric materials, near-infrared absorption filters, which consist of effectively utilizing or adjusting or cutting these near-infrared light,
Various applications have been proposed, such as eye strain prevention agents, thermal transfer / thermal paper, photothermal conversion agents for thermal stencil, near-infrared photosensitizers, and heat ray shading agents for automobiles and building materials. Has been done.

However, carbon black, which is a typical heat ray absorbent used for some of those applications, is a black pigment that does not transmit visible light, and its applications are significantly limited. In addition, dyes such as nigrosine, naphthol green and cyanine compounds, polymethine compounds, aminium compounds, diimium compounds, which have been recently developed as near-infrared absorbers, and chelate compounds are light-resistant. , Has a problem in heat resistance.

On the other hand, phthalocyanine compounds, which are stable to light, heat, temperature and the like and have excellent fastness, have been widely used as pigments from the past, and in recent years due to their functional characteristics, particularly semiconductor lasers. Many compounds have been proposed as active materials for use in applications such as optical recording media and electrophotographic photoconductors that utilize.

For example, pigments such as metal-free phthalocyanine, titanyl phthalocyanine, and aluminum chloride phthalocyanine are generally well known as semiconductor laser-sensitive phthalocyanines.

Although these are insoluble in a solvent, attempts have been made to impart solubility. That is,
A solvent coating method such as a spin coating method can be considered as a practical method for forming a thin film of a dye without using a complicated process such as vapor deposition or dispersion in a resin. In this case, there is a demand for dyes that can be dissolved in a solvent that does not damage the substrate used as a device or be compatible with the resin that is used as a binder and that can be dissolved in a high concentration in various solvents according to each application. . However, the majority of phthalocyanine compounds were insoluble in solvents.

On the other hand, a phthalocyanine compound having a solubility that is practically advantageous has recently been disclosed. For example,
3,4-octaalkoxy phthalocyanine
No. 223056), but it has a problem that the control of the absorption wavelength is limited to the low wavelength side, and also has a problem that the manufacturing process is complicated and an inexpensive phthalocyanine cannot be obtained. ing.

A material having solubility and an absorption ability in the near infrared region has also been proposed. For example, Zhurnal Ob
shchei Khimii Vol. 51, No.
7, Jul. 1981, pp 1650 to 1656 describes a copper phthalocyanine compound having four dimethylamino groups introduced at the 3- or 6-positions. This compound has an absorption at 787 nm. Zhurnal O
bshchei Khimii Vol. 51, N
o. 10, October 1981, pp2319-
2324 describes a copper phthalocyanine compound having four phenylthio groups introduced at the 3- or 6-positions. This compound is 781 nm (in 1-chloronaphthalene solvent)
Has absorption. However, both are 700n
has a maximum absorption wavelength in the range of m to 860 nm,
Further, it has a problem that its use is limited due to its poor solubility in organic solvents.

Japanese Patent Publication No. 4-75916 and Dosho 61-
Nos. 152685, 63-308073, and 64-62361 disclose compounds in which a phthalocyanine skeleton is substituted with a large number of thioether groups to improve solubility and lengthen absorption wavelength. Has been done. Among them, JP-A-60-209583 discloses a synthetic example in which five or more thioether groups are introduced at the phthalocyanine skeleton, particularly at the 3,6-position. The method is to heat a phthalocyanine compound having a chlorine atom at the 3,6-position of a phthalocyanine skeleton and an organic thiol compound in a quinoline solvent in the presence of potassium hydroxide to give a phthalocyanine having a thioether group at the 3,6-position. It has gained. However, all of them have a yield of about 20 to 30%, which causes a problem in production efficiency. Moreover, the solubility is still insufficient, and the absorption wavelength range is in chloroform: 740 nm to 850 nm, in the film: 790 nm.
It has a maximum absorption wavelength at ˜860 nm and thus its range is limited.

As described above, the phthalocyanine compound currently proposed is not sufficient as a heat ray absorbing material. That is, there is no robust material having absorption ability in the near-infrared region of 900 nm or more, which has a main distribution in the heat ray absorption region of sunlight, and has solubility, and their development is required.

[0011]

DISCLOSURE OF THE INVENTION The object of the present invention is 90
It is an object of the present invention to provide a novel phthalocyanine compound having an effective absorption wavelength corresponding to the purpose in the absorption wavelength range of 0 nm or more and excellent in solubility in an organic solvent and having high light resistance and heat resistance. Another object of the present invention is to provide a method for efficiently producing the phthalocyanine compound with high purity.

[0012]

In order to achieve the above object, the inventors of the present invention have at least 8 or more anilino groups or alkylamino groups, which are substituents having a very strong electron donating property, on the benzene nucleus of phthalocyanine. We thought that it was necessary to replace them and conducted diligent studies.

An anilino group or an alkylamino group is added to 8
Japanese Patent Application Laid-Open No. 60-20958 which replaces more than one
No. 3 exemplifies octa (ethylamino) H ₂ Pc and hexadeca (ethylamino) H ₂ Pc. However, there is no description in the specification to prove its existence.

The inventors of the present invention disclosed in Japanese Patent Laid-Open No. 60-209583.
Attempts were made to introduce anilino and alkylamino groups according to the two methods suggested in the publication. One method is to use a phthalocyanine compound having 8 or more halogen atoms at the 3,4,5,6 positions of the phthalocyanine skeleton and an aniline compound or an alkylamine compound in the presence of KOH in a basically inert solvent such as quinoline. Another method is heating, in which tetrahalogenophthalonitrile is subjected to a nucleophilic substitution reaction with two or more aniline compounds or alkylamine compounds, and then converted to a phthalocyanine by a usual method. However, according to the method described above, it was found that up to about 4 anilino groups or alkylamino groups could be introduced into the phthalocyanine skeleton, but not 5 or more.

As a reason for this, it is a well-known fact among those skilled in the art that, in the nucleophilic substitution reaction, it is easy to introduce an electron-withdrawing group at the para-position or the ortho-position, but conversely. It is a well known fact to those skilled in the art that it is difficult to introduce an electron donating group at the para-position or the ortho-position. Therefore, it is difficult to carry out nucleophilic substitution of an aniline compound or an alkylamine compound at the ortho position after the introduction of an anilino group or an alkylaminino group having a strong electron donating property by a usual method, and therefore a phthalocyanine nucleus is It is possible to introduce up to 4 anilino groups or alkylamino groups, but it is difficult to introduce 5 or more substituents.

Thus, the present inventors considered that it would be difficult to introduce eight or more anilino groups or alkylamino groups into the phthalocyanine nucleus by the usual method, and studied earnestly whether there was a new method.

As a result, by reacting 1 mol of the phthalocyanine substituted with about 16 fluorine atoms with the aniline compound or the alkylamine compound in an amount of 35 mol times or more, without reacting with any other solvent, the reaction is carried out. It was found that about 8 anilino groups or alkylamino groups could be introduced. Solubility can be imparted by introducing 8 of these types, and the maximum absorption wavelength is 850 nm
Although the wavelength can be increased to some extent, the object of the present invention is 900
It was not possible to obtain a material having an absorption wavelength of nm or longer.
Therefore, the inventors of the present invention have made further studies to further improve the purpose of the present invention by further substituting these residues with a phenylthio group or an alkylthio group, and by particularly using oxyvanadium (VO) as a central metal. We have found what we can achieve.

That is, according to the present invention, 1 mol of hexadecafluorovanadyl phthalocyanine is represented by the general formula (2) R ¹ NH ₂ ... (2) [wherein R ¹ is a straight chain or a chain having 3 to 10 carbon atoms] Represents a chain alkyl group or a phenyl group (the phenyl group may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms and / or a halogen atom). ] The amine compound represented by
A phthalocyanine compound represented by the following general formula (3) is obtained by reacting hexadecafluorovanadyl phthalocyanine with an amine compound represented by the above general formula (2) by using as a substantial molar ratio solvent or more.

[0019]

[Chemical 3]

Then, a phthalocyanine compound represented by the above general formula (3) and the following general formula (4) SR ² H (4) [wherein R ² is a straight chain having 3 to 10 carbon atoms or Represents a branched alkyl group or a phenyl group (the phenyl group may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms and / or a halogen atom). . ] The phthalocyanine compound represented by the following general formula (1) can be produced by reacting it with a thiol compound represented by the following formula, and it was found that these compounds are compounds satisfying the above object, and the present invention was completed. .

According to the present invention, the following general formula (1)

[0022]

[Chemical 4]

[Wherein R ¹ and R ² have 3 to ¹ carbon atoms]
0 straight or branched chain alkyl or phenyl group (wherein the phenyl group is substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms and / or a halogen atom) Represents). ] The novel phthalocyanine compound shown by these is provided.

[0024]

In the present invention, the alkyl group having 1 to 4 carbon atoms means methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and tert.
-Means a butyl group. The alkoxy group having 1 to 4 carbon atoms is a methoxy group, an ethoxy group, an n-propoxy group,
Isopropoxy group, n-butoxy group, isobutoxy group,
And tert-butoxy groups. 3 carbon atoms
-10 alkyl groups mean n-propyl group, isopropyl group, n-butyl group, isobutyl group, and tert.
-Butyl group, linear or branched pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like.

Specific examples of the phthalocyanine skeleton of the general formula (1) include: 4,5-octakis (anilino) -3,6-octakis (phenylthio) phthalocyanine Abbreviation: Pc (PhNH) ₈ (PhS) ₈ 4,5 octakis (anilino) -3,6-octakis (o-methylphenylthio) phthalocyanine _{abbreviation: Pc (PhNH) 8 (o} -MePhS) 8 · 4,5- octakis (anilino) -3,6-octakis (p- ethoxyphenyl thio) phthalocyanine _{abbreviation: Pc (PhNH) 8 (p} -EtOPhS) 8 · 4,5- octakis (anilino) -3,6-octakis (p- chlorophenyl thio) phthalocyanine abbreviation: Pc (PhNH) _{8 (p-ClPhS) 8 ·} 4,5- octakis (anilino) -3,6-octakis (ethylthio) off Roshianin _{abbreviation: Pc (PhNH) 8 (EtS} ) 8 · 4,5- octakis (anilino) -3,6-octakis (n- butylthio) phthalocyanine _{Abbreviation: Pc (PhNH) 8 (BuS} ) 8 · 4,5- octakis (anilino) -3,6-octakis (n- dodecylthio) phthalocyanine _{abbreviation: Pc (PhNH) 8 (BuS} ) 8 · 4,5- octakis (o- methylanilino) 3,6
- octakis (phenylthio) phthalocyanine _{Abbreviation: Pc (o-MeOPhNH) 8} (PhS) 8 · 4,5- Okukisu (p- methoxyphenyl) -6-3,6
-Octakis (phenylthio) phthalocyanine Abbreviation: Pc (o-MePhNH) ₈ (PhS) ₈ · 4,5-octakis (cyclohexylamino) -3,
6-octakis (phenylthio) phthalocyanine Abbreviation: Pc (cy-HexNH) ₈ (PhS) ₈ · 4,5-octakis (n-butylamino) -3,6-
Octakis (phenylthio) phthalocyanine Abbreviation Pc (BuNH) ₈ (PhS) ₈ · 4,5-octakis (n-butylamino) -3,6-
Octakis (p-tert-phenylthio) phthalocyanine _{Abbreviation: Pc (BuNH) 8 (p} -tertPhS) 8 · 4,5- octakis (n- butylamino) -3,6
Octakis (n-butylthio) phthalocyanine Abbreviation: Pc (BuNH) ₈ (BuS) ₈ · 4,5-octakis (n-octylamino) -3,6
-Octakis (phenylthio) phthalocyanine Abbreviation: Pc (OctNH) ₈ (PhS) _{8 and the} like.

In the first step of the method for producing a novel phthalocyanine compound of the present invention, hexadecafluorophthalocyanine is reacted with an aniline compound or an alkylamino compound to introduce eight anilino groups or alkylamino groups. , 1 mol of hexadecafluorophthalocyanine, the anilineno compound or alkylamino compound represented by the general formula (2) is 3
It is preferable to charge 5 mol times or more, particularly 50 mol to 10 mol.
It is preferable to use 0 mol times.

Although an organic solvent which is inert under the use conditions can be used, it is preferable not to use it in the present invention because the reaction rate is lowered.

The reaction temperature is preferably 40 to 250 ° C, particularly preferably 60 to 200 ° C.

The aniline compound or the alkylamino compound is preferably liquid at normal pressure and has a boiling point in the range of 40 to 250 ° C. Those having a low boiling point cannot be reacted by the method of the present invention because they are not liquids. Further, those having a high boiling point are not preferable because the solubility of phthalocyanine is low and the reaction rate decreases.
Examples of the amine compound represented by the general formula (2) include aniline, o-toluidine, p-toluidine and p-toluidine.
Methoxyaniline, p-fluoroaniline, p-chloroaniline, 2,3,5,6-tetrafluoroaniline,
Examples include propylamine, butylamine, tert-butylamine, n-hexylamine, n-octylamine and the like.

Using a phthalocyanine having eight anilino groups or alkylamino groups of the general formula (3) introduced thereinto, a thiol compound of the general formula (4) is reacted to obtain a compound of the general formula (1), which is a target substance of the present invention. The organic solvent used in the production process of the novel phthalocyanine compound may be any inert solvent having no reactivity with the starting materials, for example, benzene, toluene, xylene, nitrobenzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, An inert solvent such as chloronaphthalene, methylnaphthalene, ethylene glycol, benzonitrile, or pyridine, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidine, triethylamine, tri-n-butylamine, Dimethyl sulfone, sulfolane Such as aprotic polar solvents can be used, preferably, benzonitrile, pyridine, N, N- dimethylformamide, N- methyl-2
Pyrrolidinone and the like.

The reaction temperature is preferably in the range of 50 ° C to 250 ° C, particularly preferably in the range of 100 ° C to 150 ° C.

In the method for producing a novel phthalocyanine of the present invention, the phthalocyanine represented by the general formula (3) is charged in an amount of 2 to 30 parts by weight, particularly preferably 5 to 15 parts by weight, based on 100 parts of the organic solvent. Is preferable, and 1 mol part to 1 mol of the thiol compound represented by the general formula (4) per 1 mol part of the phthalocyanine represented by the general formula (3).
It is preferable to charge in a range of 00 parts by mole, and particularly preferably in a range of 8 parts to 80 parts.

[0033]

EXAMPLES The present invention will be described in more detail below with reference to examples.

Example 1 First Stage Reaction 4,5-Octakisanilino- (3,6-octakisphenylthio) oxyvanadium phthalocyanine [VOP
Preparation of c (PhNH) ₈ (PhS) ₈ ] In a 100 ml four-necked flask, 5.19 g (6 mmol) of hexadecafluorooxyvanadium phthalocyanine and 26.82 g (288 mmol) of aniline were charged and reflux temperature (185 ° C.). And reacted for 4 hours. After the reaction was completed, the insoluble matter was filtered off to obtain 6.72 g of a target black cake (yield: 77.1%). As a result of analysis, it was found that this compound had 8 substituents.

Second Stage Reaction 4,5-Octakisanilino- (3,6-octakisphenylthio) oxyvanadium phthalocyanine [VOP
Preparation of c (PhNH) ₈ (PhS) ₈ ] 4.52 g (41.0 mmol) of thiophenol, 2.30 g (41.0 mmol) of potassium hydroxide, and 50 ml of pyridine were charged in a 100 ml four-necked flask,
The reaction was carried out at 80 ° C for 1 hour. After that, 3,94-octafluoro- (4,5-octylanilino) oxyvanadium phthalocyanine [vopc (PhNH) ⁸ F ⁸ ] 4.94 g (3.4 m
(ml) was added and the mixture was reacted under reflux conditions for 4 hours. After completion of the reaction, pyridine was distilled off, and the remaining solid content was washed with methanol to obtain 6.17 g of a target dark green cake. (Yield 83.5%) Absorption wavelength 905.5 nm in methyl ethyl ketone (ε
= 1.61 × 10 ⁵ ) Coating film 926.0 nm Solubility 8.8% by weight in methyl ethyl ketone Elemental analysis value C (%) H (%) N (%) S (%) F (%) Theoretical value 70.73 4.08 10.31 11.80 0.00 Analytical value 70.55 3.86 10.18 11.62 0.00 Infrared absorption spectrum The infrared absorption spectrum of this compound is shown in FIG.

Example 2 4,5-Octakisanilino- (3,6-octakisbutylthio) oxyvanadium phthalocyanine [VOPc
Synthesis of (PhNH) ₈ (BuS) _{8 In} both the first-step reaction and the second-step reaction except that 3.70 g of butanethiol was used in place of thiophenol in the second-step reaction of Example 1, By the same operation, 5.22 g of the target dark green cake was obtained.
(Yield 76.3%) Absorption wavelength 902.5 nm in methyl ethyl ketone
(Ε = 6.59 × 10 ⁴ ) Coating film 913.5 nm Solubility 26.0 wt% in methyl ethyl ketone Elemental analysis value C (%) H (%) N (%) F (%) Theoretical value 66.80 6.01 11.13 0.00 Analytical value 66.31 5.77 11.41 0.00 Infrared absorption spectrum The infrared absorption spectrum of this compound is shown in FIG.

Example 3 4,5-Octakisbutylamino- (3,6-tetrakisphenylthio) oxyvanadium phthalocyanine [V
_{OPc (BuNH) 8 (PhS)} 8] in the production first stage reaction octafluoro - octakis (n- butylamino) oxyvanadium phthalocyanine [VOPc (BuNH) 8
F8] production.

In the first stage reaction of Example 1, 21.10 g (288 mmol) of n-butylamine was used in place of aniline, and the reaction was carried out at the reflux temperature (78 ° C.). By carrying out the procedure described above, 7.02 g of a target black cake was obtained (yield 90.5%).
As a result of analysis, this compound was found to have 8 substituents in one molecule.

Second Stage Reaction 4,5-Octabutylbutylamino- (3,6-tetrakisphenylthio) oxyvanadium phthalocyanine [V
Production of ^{OPc (BuNH) 8 (PhS)} 8].

In the first stage reaction of Example 1, 3,6-
3.85 g (3.4 mmol) of 3,6-octafluoro- (4,5-octakisbutylamino) oxovanadium phthalocyanine instead of octafluoro- (4,5-octakisanilino) oxyvanadium phthalocyanine
By operating in the same manner as in Example 1 except that was used, 5.60 g of the target dark green cake was obtained. (Yield 8
1.7%) Absorption wavelength in methyl ethyl ketone 889.0 nm
(Ε = 4.96 × 10 ⁴ ) Coating film 903.5 nm Solubility 27.0 wt% in methyl ethyl ketone Elemental analysis value C (%) H (%) N (%) F (%) Theoretical value 66.80 6.01 11.13 0.00 Analytical value 66.97 5.95 11.23 0.00 Infrared absorption spectrum The infrared absorption spectrum of this compound is shown in FIG.

Example 4 4,5-Octakisbutylamino- (3,6-octakisbutylthio) oxyvanadium phthalocyanine [VO]
Production of Pc (BuNH) ₈ (BuS) ₈ ] In the second step reaction of Example 3, both the first step reaction and the second step reaction were carried out except that 3.70 g of butanethiol was used instead of thiophenol. The same operation as in 1 gave 4.91 g of the desired dark green cake.
(Yield 78.2%) Absorption wavelength 892.5 nm in methyl ethyl ketone
(Ε = 6.83 × 10 ⁴ ) Coating film 887.0 nm Solubility 35.0 t% in methyl ethyl ketone Elemental analysis value C (%) H (%) N (%) F (%) Theoretical value 62.47 7.86 12.14 0.00 Analytical value 62.36 7.72 14.03 0.00 Infrared absorption spectrum The infrared absorption spectrum of this compound is shown in FIG.

[0042]

The phthalocyanine compound according to the present invention is
Since it has an absorption wavelength of about 880 mm or more and has a high solubility in an organic solvent, it is extremely useful as a near infrared absorbing material.

Further, according to the method of the present invention, it is possible to introduce eight or more anilino groups or alkylamino groups into the benzene nucleus of phthalocyanine, which cannot be produced by the conventional method. There is an advantage that the compound of the present invention can be synthesized.

[Brief description of drawings]

1 shows an infrared absorption spectrum of the compound produced in Example 1. FIG.

FIG. 2 shows an infrared absorption spectrum of the compound produced in Example 2.

FIG. 3 shows an infrared absorption spectrum of the compound produced in Example 3.

FIG. 4 shows an infrared absorption spectrum of the compound produced in Example 4.

Claims (3)

[Claims] 1. A novel phthalocyanine compound represented by the following general formula (1). [Chemical 1] [Wherein R ¹ and R ² are a linear or branched alkyl group having 3 to 10 carbon atoms, or a phenyl group (the phenyl group is an alkyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms). It may be substituted with four alkoxy groups and / or halogen atoms). ] 2. A compound represented by the following general formula (2) R ¹ NH ₂ ... (2) with respect to 1 mol of hexadecafluorovanadyl phthalocyanine, wherein R ¹ is a linear or branched alkyl group having 3 to 10 carbon atoms. Or a phenyl group (the phenyl group may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms and / or a halogen atom). ] The amine compound represented by
A phthalocyanine compound represented by the following general formula (3) is obtained by reacting hexadecafluorovanadyl phthalocyanine with an amine compound represented by the above general formula (2) using as a substantial molar ratio solvent or more. And then a phthalocyanine compound represented by the above general formula (3) and the following general formula (4) SR ² H (4) [wherein R ² is a straight chain or branched chain having 3 to 10 carbon atoms]. An alkyl group or a phenyl group (the phenyl group may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms and / or a halogen atom). ] It reacts with the thiol compound shown by these, The manufacturing method of the novel phthalocyanine compound of Claim 1 characterized by the above-mentioned. 3. The 750 to 1500 nm according to claim 1.
A near-infrared absorbing material containing a novel phthalocyanine compound having absorption in the range.