JP2907624B2 - Novel fluorinated phthalocyanine compound, method for producing the same, and near-infrared absorbing material comprising them - Google Patents

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 and a method for producing the same, and a near-infrared absorbing material having absorption in the near infrared region and high solubility in a solvent. The novel phthalocyanine compound according to the present invention is excellent in solubility having absorption in the near infrared region of 650 to 900 nm, and also excellent in light resistance originally possessed by phthalocyanine. Optical recording media to be used, near-infrared absorbing dyes for writing or reading in liquid crystal display devices, optical character readers, etc. Excellent when used as an absorption filter, anti-eye strain agent, photoconductive material, etc., as well as a photosensitive dye for tumor treatment that absorbs light in the long wavelength region with good tissue permeability, and as a heat ray shielding agent for automobiles or building materials It has the effect.

Further, the present invention relates to a visible light absorbing material having a visible absorption, for example, a color separation filter used for an image pickup tube, a liquid crystal display device, a dye for a color CRT selective absorption filter, a color toner, an ink jet ink, and the like.
This is an excellent effect when used in a barcode ink for preventing falsification and forgery.

[0003]

2. Description of the Related Art In recent years, semiconductor lasers have been used as light sources for writing or reading in optical recording media such as compact disks, laser disks, optical memory disks, optical cards, liquid crystal displays, optical character readers, and the like. In addition, photoconductive materials, near-infrared absorbing filters, anti-eye strain agents, heat-transfer / heat-sensitive paper, light-to-heat converting agents such as heat-sensitive stencils, near-infrared light sensitizers, and long wavelength regions with good tissue permeability There is an increasing demand for a development of a near-infrared-absorbing dye, such as a photosensitive dye for treating tumors that absorbs light, or a substance that absorbs near-infrared light, such as a heat-light shielding agent for automobiles or building materials. Above all, phthalocyanine compounds, which are stable to light, heat, temperature, etc. and have excellent robustness, are required to control the absorption wavelength required according to the application, and to adjust the solvent required according to the application. Many studies have been made to dissolve it.

That is, with the recent diversification of devices,
Further, dyes having various absorption characteristics are required depending on the application, but it has been difficult to control the absorption wavelength of the phthalocyanine compound. In practice, a method of thinning a dye without using a complicated process such as vapor deposition or dispersion in a resin, using a solvent that does not attack the substrate used in the device, or dissolving in a resin used together, etc. Because of the need for a dye that is highly soluble in various solvents for each application is required,
However, most of the phthalocyanine compounds were solvent-insoluble.

On the other hand, a phthalocyanine compound having solubility which is practically advantageous has recently been disclosed. For example,
3,6-octaalkoxy phthalocyanine (JP-A-61
However, there is a problem that the control of the absorption wavelength is limited to the lower wavelength side, and there is a problem that the production process is complicated and an inexpensive phthalocyanine cannot be obtained. I have.

Japanese Unexamined Patent Publication Nos. 60-209583 and 61-1986
Nos. 152685, 63-308073, and 64-62361 disclose compounds in which the phthalocyanine skeleton is substituted with a large number of thioether groups and the like to improve the solubility and at the same time increase the absorption wavelength. Have been. Among them, Japanese Patent Application Laid-Open No. 60-209583
And No. 61-152885 disclose a synthesis example in which a thioether group is introduced into 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 was 20 to 3
This is about 0%, which has a problem in manufacturing efficiency. Moreover, the solubility is still insufficient and the range of the absorption wavelength is limited.

Further, JP-A-60-209584, JP-A-61-152885 and JP-A-64-62361 also disclose synthesis examples in which a large number of 8 to 16 thioether groups are introduced into a phthalocyanine skeleton. .

According to the method, 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 heated in a quinoline solvent in the presence of KOH to heat the benzene nucleus of the phthalocyanine skeleton. To obtain a phthalocyanine having 8 to 16 thioether groups. However, the yield is about 20 to 30% as in the case of the above, and there is a problem in the production efficiency.

That is, a poor yield of the thioether group on the chloro or bromo atom results in a low yield. For example, unreacted phthalocyanine in which the chloro atom is not completely substituted by a thioether group or some chloro atoms Is substituted with a thioether group to form an unreacted phthalocyanine. Since it is practically difficult to separate the unreacted phthalocyanine and the target substance phthalocyanine from each other, in fact, only a mixture of phthalocyanines having various compositions can be obtained.

In fact, JP-A-64-62361 describes a polythiol-substituted mixed condensed phthalocyanine composition even after separation with a silica gel column, indicating that unreacted type remains. If some of the chloro atoms remain, their solubility is significantly reduced, which is disadvantageous for dissolving 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 a DMF solvent in the presence of KOH to form a thioether substituent. Introduced, 42% phthalocyanine
In the yield. 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 property is not obtained, and the absorption wavelength is reduced. There is a problem that the use is limited when used as an application that needs to be controlled, for example, a cyan inkjet ink or a near-infrared absorbing dye. Although it has solubility, it is still at a low level and is insufficient in terms of thinning or solubility in resin.

Japanese Patent Application No. 64-42283 and JP-A-Hei 3
No. 62878 proposes a near-infrared absorbing dye in which an alkoxyl group and an alkylthio group are introduced into a phthalocyanine nucleus, but most of them have poor practicality and have starting materials having substituents at the 3 and 6 positions. There is a problem in practical use. In addition, there is a problem that phthalocyanine having a low solubility and a controlled absorption wavelength is limited. In addition, since a phthalocyanine is derived from a chlorinated compound at the 4- and 5-positions to introduce a substituent at the 4- and 5-positions, there is a problem that chlorine atoms remain which cause a decrease in solubility due to poor substitution. It also has a point.

On the other hand, phthalocyanines soluble in alcohols are disclosed in JP-A-63-295578.
According to this publication, hepta (4-methylphenylthio) -tetra (1- (1-methylphenylthio) -tetra (1-methyl) thiophene is obtained by reacting monobromotetradecachlorocopper phthalocyanine with an organic thiol mixture of 2-aminothiophenol and 4-methylphenylthiol. Amino-2-thiophenyl-1,2-ylene)-
A substituted thiocopper phthalocyanine mixture such as copper phthalocyanine is sulfonated with fuming sulfuric acid to obtain a phthalocyanine having an average of 10 sulfonic acid groups, and then treated with a basic substance such as tetrabutylamine to change to a sulfonamide group or the like. A phthalocyanine having solubility in a neutral solvent is obtained.

However, this method has the following problems. Some chloro atoms are likely to remain, and if some chloro atoms remain, their solubility is significantly reduced. Phthalocyanine is obtained as a mixture, and when used as a near-infrared absorbing dye, a single property cannot be obtained, thereby limiting its use. The steps are very complicated and the yield of each step is low. The sulfonation reaction is carried out in an aqueous system, and then the product is purified by dialysis, which is problematic as an industrial production method. The present inventors have made Japanese Patent Application No. Hei.
209599, Japanese Patent Application No. 2-125518, and Japanese Patent Application No. 2-144292, by increasing the wavelength of absorption and solvent solubility by selectively substituting fluorine of octadecafluorophthalocyanine with an alkylthio group or an arylthio group. Tried to improve the effect. Their solubility is not always satisfactory, and there is a need for compounds with improved solubility. Further, it is preferable to further increase the absorption wavelength.

[0015]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned 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 has excellent solubility, particularly excellent solubility in alcoholic solvents.
Another object of the present invention is to provide a method for producing the phthalocyanine compound efficiently and with high purity.

Still 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 with respect to alcohol solvents). is there. A further object of the present invention is to provide near-infrared absorbing phthalocyanine compounds controlled at various absorption wavelengths.

[0017]

Means for Solving the Problems The inventors of the present invention have an etheraryl group or a thioetheraryl group in at least one of the 4- and 5-positions of the phthalocyanine skeleton, and optionally have a fluorine atom or an etheraryl group in the remaining position. ,
The present invention has been found by sulfonating a phthalocyanine compound having any one of a thioetheraryl group, an etheralkyl group and a thioetheralkyl group and having a fluorine atom at the 3,6-position to obtain a compound satisfying the above object. Was completed.

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

Embedded image

Wherein X is independently a fluorine atom, O
R₁Za ~ d, SR_TwoZe ~ h, OR _ThreeOr SR
_Four(However, R₁And R_TwoAre independently a phenyl group or
Is a benzyl group, and the phenyl group or the benzyl group is
C1-C4 alkyl, alkoxyl, carboxyl
Substituted with a sil group, alkoxycarbonyl group or halogen
May be R_ThreeAnd R_FourAre independently C1-C
20 alkyl groups or C4-C6 cycloalkyl groups
And Z represents a sulfone group), and Y
OR independently_FiveZi ~ l or SR₆Zm-p (R_Fiveas well as
R₆Are each independently a phenyl or benzyl group.
The phenyl or benzyl group is an alkyl having 1 to 4 carbon atoms.
Kill group, alkoxyl group, carboxyl group, alkoxy
A carbonyl group or a halogen;
Represents a sulfone group), and a to p are integers of 0 to 7.
And the sum of a to p is 1 or more, M is metal-free, gold
Metal, metal oxide, metal carbonyl or metal halide
Fluorinated phthalocyanine represented by
A compound is provided.

Examples of such a fluorine-containing phthalocyanine include, for example, X is a fluorine atom, OR ₃ in X is a methoxy group, an ethoxy group, a butoxy group, an octyloxy group,
A cyclohexyloxy group; a phenoxy group in which OR ₁ is substituted with a phenoxy group, a carboxylphenoxy group, a methoxycarbonylphenoxy group, an ethoxycarbonylphenoxy group, a benzyloxy group, a tolyloxy group, a xylyloxy group, a fluorine or chlorine atom,

SR ₄ is methylthio, ethylthio, butylthio, octylthio, cyclohexylthio;
SR ₂ is a phenylthio group, a carboxylphenylthio group, a methoxycarbonylphenylthio group, an ethoxycarbonylphenylthio group, a benzylthio group, a tolylthio,
Xylylthio, a phenylthio group substituted with a fluorine or chlorine atom,

OR ₅ in Y is a phenoxy group,
Carboxylphenoxy group, methoxycarbonylphenoxy group, ethoxycarbonylphenoxy group, benzyloxy group, tolyloxy group, xylyloxy group, phenoxy group substituted by fluorine or chlorine atom; SR ₆
Is a phenylthio group, a carboxylphenylthio group, a methoxycarbonylphenylthio group, an ethoxycarbonylphenylthio group, a tolylthio, a xylylthio, a phenylthio group substituted with a fluorine or chlorine atom,

M is Cu, Zn, Fe, Ni, Co, Fe
Carbonyl, Ni carbonyl, Co carbonyl, AlC
1, AlI, InCl, InBr, GaCl, TiO,
VO, SnCl2, GeCl2, etc., and a compound in which 1 to 16 sulfone groups are introduced per 1 mol of a phthalocyanine molecule.

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

Embedded image

[Wherein X₁Is independently a fluorine atom,
OR₁, SR_Two, OR_ThreeOr SR_Four(However, R₁Passing
And R_TwoAre each independently a phenyl or benzyl group.
The phenyl or benzyl group is an alkyl having 1 to 4 carbon atoms.
Kill group, alkoxyl group, carboxyl group, alkoxy
May be substituted with a carbonyl group or halogen
K, R_ThreeAnd R_FourAre independently C1 to C20 alkyl
And a C4-C6 cycloalkyl group. )
And Y₁Are independently OR_FiveOr SR₆(R _FivePassing
And R₆Are each independently a phenyl or benzyl group.
The phenyl or benzyl group is an alkyl having 1 to 4 carbon atoms.
Kill group, alkoxyl group, carboxyl group, alkoxy
Carbonyl group or halogen)
Represents M, metal-free, metal, metal oxide, metal carbonyl
Or a metal halide. Phthalo
Using a sulfonating agent in an organic solvent
It can be produced by sulfonation.

Hereinafter, the production method of the present invention will be described in detail. The fluorine-containing phthalocyanine represented by the general formula (II) used in the present invention is, specifically, a phthalocyanine compound as shown below, preferably as a central metal,
It is preferable to use copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, chloroindium, chloroaluminum, dichlorotin, cobalt carbonyl, and iron carbonyl.

A) Type 4,5-octakis (phenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhS) 8 4,5-octakis (o-methylphenylthio) -3,
6-octafluorophthalocyanine Abbreviation: PcF8 (o-MePhS) 8 4,5-octakis (p-methylphenylthio) -3,
6-octafluorophthalocyanine Abbreviation: PcF8 (p-MePhS) 8 4,5-octakis (o-methoxyphenylthio)-
3,6-octafluorophthalocyanine Abbreviation: PcF8 (o-MeOPhS) 8

4,5-octakis (p-methoxyphenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (p-MeOPhS) 8 4,5-octakis (o-carboxylphenylthio)
-3,6-octafluorophthalocyanine Abbreviation: PcF8 (o-cPhS) 8 4,5-octakis (p-carboxylphenylthio)
-3,6-octafluorophthalocyanine Abbreviation: PcF8 (p-cPhS) 8

B) Type 4-tetrakis (phenoxy) -3,5,6-dodecafluorophthalocyanine Abbreviation: PcF12 (PhO) 4 4-tetrakis (o-methylphenoxy) -3,5,6
-Dodecafluorophthalocyanine Abbreviation: PcF12 (o-MePhO) 4 4-tetrakis (p-methylphenoxy) -3,5,6
-Dodecafluorophthalocyanine Abbreviation: PcF12 (p-MePhO) 4 4-tetrakis (o-methoxyphenoxy) -3,5
6-dodecafluorophthalocyanine Abbreviation: PcF12 (o-MeOPhO) 4

4-tetrakis (p-methoxyphenoxy) -3,5,6-dodecafluorophthalocyanine Abbreviation: PcF12 (p-MeOPhO) 4 4-tetrakis (o-carboxylphenoxy) -3,
5,6-dodecafluorophthalocyanine Abbreviation: PcF12 (o-cPhO) 4 4-tetrakis (p-carboxylphenoxy) -3,
5,6-dodecafluorophthalocyanine Abbreviation: PcF12 (p-cPhO) 4

C) Type 4-tetrakis (phenoxy) -5-tetrakis (phenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (PhS) 44-tetrakis (o-methylphenoxy) -5 Tetrakis (o-methylphenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (o-MePhO) 4 (o-MePh
S) 4 4-Tetrakis (o-methoxyphenoxy) -5-tetrakis (o-methoxyphenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (o-MeOPhO) 4 (o-MeOP
hS) 4 4-Tetrakis (o-carboxylphenoxy) -5
Tetrakis (o-carboxylphenylthio) -3,6
-Octafluorophthalocyanine Abbreviation: PcF8 (o-cPhO) 4 (o-cPhS) 4 4-tetrakis (o-methoxyphenoxy) -5-tetrakis (o-methylphenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (O-MeOPhO) 4 (o-MePh
S) 4

4-tetrakis (p-methoxyphenoxy) -5-tetrakis (o-methylphenylthio)-
3,6-octafluorophthalocyanine Abbreviation: PcF8 (p-MeOPhO) 4 (o-MePh
S) 4 4-Tetrakis (o-methylphenoxy) -5-tetrakis (o-methoxyphenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (o-MePhO) 4 (o-MeOPh
S) 4 4-Tetrakis (o-methylphenoxy) -5-tetrakis (p-methoxyphenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (o-MePhO) 4 (p-MeOPh
S) 4 4-Tetrakis (o-carboxylphenoxy) -5
Tetrakis (o-methylphenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (o-cPhO) 4 (o-MePhS)
4 4-tetrakis (o-carboxylphenoxy) -5
Tetrakis (p-methylphenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (o-cPhO) 4 (p-MePhS)
4

4-tetrakis (p-carboxylphenoxy) -5-tetrakis (o-methylphenylthio)-
3,6-octafluorophthalocyanine Abbreviation: PcF8 (p-cPhO) 4 (o-MePhS)
4 4-tetrakis (phenoxy) -5-tetrakis (o-
Methylphenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (o-MePhS) 4 4-tetrakis (phenoxy) -5-tetrakis (p-
Methylphenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (p-MePhS) 4 4-tetrakis (phenoxy) -5-tetrakis (m-
Methylphenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (m-MePhS) 4 4-tetrakis (phenoxy) -5-tetrakis (2,
4-dimethylphenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (2,4-MePhS) 4

4-tetrakis (phenoxy) -5-tetrakis (o-methoxyphenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (o-MeOPhS) 4 4-tetrakis (phenoxy) -5 Tetrakis (p-
Methoxyphenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (p-MeOPhS) 4 4-tetrakis (phenoxy) -5-tetrakis (o-
Fluorophenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (o-FPhS) 4 4-tetrakis (phenoxy) -5-tetrakis (p-
Fluorophenylthio) -3,6-octafluorophthalocyanine Abbreviation; PcF8 (PhO) 4 (p-FPhS) 4 4-tetrakis (phenoxy) -5-tetrakis (tetrafluorophenylthio) -3,6-octafluorophthalocyanine PcF8 (PhO) 4 (F4PhS) 4

4-tetrakis (phenoxy) -5-tetrakis (p-carboxylphenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (p-cPhS) 4 4-tetrakis (phenoxy) -5 Tetrakis (o-
(Carboxyphenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (o-cPhS) 4 4-tetrakis (phenoxy) -5-tetrakis (p-
Methoxycarbonylphenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (p-mcPhS) 4 4-tetrakis (phenoxy) -5-tetrakis (o-
Methoxycarbonylphenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (o-mcPhS) 4 4-tetrakis (phenoxy) -5-tetrakis (p-
Ethoxycarbonylphenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (p-ecPhS) 4

4-tetrakis (phenoxy) -5-tetrakis (o-ethoxycarbonylphenylthio) -3,
6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (o-ecPhS) 4 4-tetrakis (phenoxy) -5-tetrakis (m-
Ethoxycarbonylphenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (m-ecPhS) 4 4-tetrakis (phenoxy) -5-tetrakis (methylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (MeS) 4 4-tetrakis (phenoxy) -5-tetrakis (ethylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (EtS) 44-tetrakis (phenoxy) -5-tetrakis (Propylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (PrS) 4

4-tetrakis (phenoxy) -5-tetrakis (n-butylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (BuS) 4 4-tetrakis (phenoxy) -5-tetrakis (te)
rt-butylthio) -3,6-octafluorophthalocyanine Abbreviation; PcF8 (PhO) 4 (t-BuS) 4 4-tetrakis (o-methylphenoxy) -5-tetrakis (phenylthio) -3,6-octafluorophthalocyanine PcF8 (o-MePhO) 4 (PhS) 4 4-tetrakis (m-methylphenoxy) -5-tetrakis (phenylthio) -3,6-octafluorophthalocyanine Abbreviation; PcF8 (m-MePhO) 4 (PhS) 44 -Tetrakis (p-methylphenoxy) -5-tetrakis (phenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (p-MePhO) 4 (PhS) 4

4-tetrakis (o-fluorophenoxy) -5-tetrakis (phenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (o-FPhO) 4 (PhS) 4 4-tetrakis (p-fluorophenoxy)- 5-tetrakis (phenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (p-FPhO) 4 (PhS) 4 4-tetrakis (o-methoxyphenoxy) -5-tetrakis (phenylthio) -3,6-octafluoro Phthalocyanine Abbreviation: PcF8 (o-MeOPhO) 4 (PhS) 4 4-tetrakis (p-carboxylphenoxy) -5
Tetrakis (phenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (p-cPhO) 4 (PhS) 4 4-tetrakis (o-carboxylphenoxy) -5-
Tetrakis (phenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (o-cPhO) 4 (PhS) 4

4-tetrakis (m-carboxylphenoxy) -5-tetrakis (phenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (m-cPhO) 4 (PhS) 4 4-tetrakis (p-methoxycarbonylphenoxy)
-5-tetrakis (phenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (p-mcPhO) 4 (PhS) 4 4-tetrakis (o-methoxycarbonylphenoxy)
-5-tetrakis (phenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (o-mcPhO) 4 (PhS) 4 4-tetrakis (m-methoxycarbonylphenoxy)
-5-tetrakis (phenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (m-mcPhO) 4 (PhS) 44-tetrakis (p-ethoxycarbonylphenoxy)
-5-tetrakis (phenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (p-ecPhO) 4 (PhS) 4

4-tetrakis (o-ethoxycarbonylphenoxy) -5-tetrakis (phenylthio) -3,
6-octafluorophthalocyanine Abbreviation: PcF8 (o-mcPhO) 4 (PhS) 4 4-tetrakis (m-ethoxycarbonylphenoxy)
-5-tetrakis (phenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (m-mcPhO) 4 (PhS) 4 4-tetrakis (methoxy) -5-tetrakis (phenylthio) -3,6-octafluorophthalocyanine PcF8 (MeO) 4 (PhS) 4 4-tetrakis (ethoxy) -5-tetrakis (phenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (EtO) 4 (PhS) 44-tetrakis (n-butoxy) -5-tetrakis (phenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (BuO) 4 (PhS) 4

4-tetrakis (t-butoxy) -5-tetrakis (phenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (t-BuO) 4 (PhS) 44-tetrakis (n-hexyloxy) -5 -Tetrakis (phenylthio) -3,6-octafluorophthalocyanine Abbreviation; PcF8 (HxO) 4 (PhS) 44-tetrakis (n-octyloxy) -5-tetrakis (phenylthio) -3,6-octafluorophthalocyanine PcF8 (OxO) 4 (PhS) 4 4-tetrakis (n-decyloxy) -5-tetrakis (phenylthio) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (DeO) 4 (PhS) 4 4-tetrakis (n-hexa) (Decyloxy) -5-tetrakis (phenylthio) -3 6 octafluoro phthalocyanine abbreviation; PcF8 (HdO) 4 (PhS) 4 4- tetrakis (benzyloxy) -5-tetrakis (phenylthio) -3,6-octafluoro phthalocyanine abbreviation; PcF8 (BzO) 4 (PhS) 4

D) Type 4,5-octakis (phenoxy) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 8 4,5-octakis (o-methylphenoxy) -3,6
-Octafluorophthalocyanine Abbreviation: PcF8 (o-MePhO) 8 4,5-octakis (p-methylphenoxy) -3,6
-Octafluorophthalocyanine Abbreviation: PcF8 (p-MePhO) 8 4,5-octakis (o-methoxyphenoxy) -3,
6-octafluorophthalocyanine Abbreviation: PcF8 (o-MeOPhO) 8 4,5-octakis (p-methoxyphenoxy) -3,
6-octafluorophthalocyanine Abbreviation: PcF8 (p-MeOPhO) 8

4,5-octakis (o-carboxylphenoxy) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (o-cPhO) 8 4,5-octakis (p-carboxylphenoxy)-
3,6-octafluorophthalocyanine Abbreviation: PcF8 (p-cPhO) 8 4-tetrakis (phenoxy) -5-tetrakis (o-
Methylphenoxy) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (o-MePhO) 4 4-tetrakis (phenoxy) -5-tetrakis (p-
Methylphenoxy) -3,6-octafluorophthalocyanine Abbreviation: PcF84 (PhO) 4 (p-MePhO) 4 4-tetrakis (phenoxy) -5-tetrakis (o-
Methoxyphenoxy) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (o-MeOPhO) 4 4-tetrakis (phenoxy) -5-tetrakis (p-
Fluorophenoxy) -3,6-octafluoromphthalocyanine Abbreviation: PcF8 (PhO) 4 (p-FPhO) 4

4-tetrakis (phenoxy) -5-tetrakis (tetrafluorophenoxy) -3,6-octafluoromphthalocyanine Abbreviation: PcF8 (PhO) 4 (F4PhO) 4 4-tetrakis (p-carboxylphenoxy) -5
Tetrakis (phenoxy) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (p-cPhO) 4 4-tetrakis (m-carboxylphenoxy) -5
Tetrakis (phenoxy) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (m-cPhO) 4 4-tetrakis (o-methoxycarbonylphenoxy)
-5-tetrakis (phenoxy) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (o-mcPhO) 4 4-tetrakis (m-methoxycarbonylphenoxy)
-5-tetrakis (phenoxy) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (m-mcPhO) 4

4-tetrakis (p-ethoxycarbonylphenoxy) -5-tetrakis (phenoxy) -3,6
-Octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (p-ecPhO) 4 4-tetrakis (o-ethoxycarbonylphenoxy)
-5-tetrakis (phenoxy) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (o-ecPhO) 4 4-tetrakis (m-ethoxycarbonylphenoxy)
-5-tetrakis (phenoxy) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (m-ecPhO) 4 4-tetrakis (phenoxy) -5-tetrakis (methoxy) -3,6-octafluorophthalocyanine PcF8 (PhO) 4 (MeO) 4 4-tetrakis (phenoxy) -5-tetrakis (n-
Butoxy) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (BuO) 4

4-tetrakis (phenoxy) -5-tetrakis (n-octyloxy) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (OxO) 44 4-tetrakis (phenoxy) -5-tetrakis (benzyl) Oxy) -3,6-octafluorophthalocyanine Abbreviation: PcF8 (PhO) 4 (BzO) 4 and the like.

The fluorinated phthalocyanine represented by the general formula (1) of the present invention can be obtained by sulfonating the fluorinated phthalocyanine represented by the above general formula (II). As an agent,
Sulfuric acid, fuming sulfuric acid, sulfur trioxide, chlorosulfuric acid, fluorosulfuric acid, amidosulfuric acid, sulfur trioxide complex and the like, preferably sulfuric acid, fuming sulfuric acid, sulfur trioxide, sulfur trioxide complex,
Chlorosulfuric acid and fluorosulfuric acid are particularly preferred.

The organic solvent used in the present invention may be any solvent capable of dissolving or slurrying the starting materials, for example, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,2-trichloroethane. , 1,1,2,2-tetrachloroethane and the like; aromatic solvents such as nitrobenzene and benzonitrile; and carbon disulfide. Among them, halogenated solvents such as dichloromethane, 1,2,2-dichloromethane, chloroform, carbon tetrachloride, 1,1,2,2-tetrachloroethane are excellent in solubility of starting materials and can smoothly carry out a sulfonation reaction. Particularly preferred.

The reaction temperature is appropriately determined depending on the type of the raw material, the solvent, and other conditions.
Preferably, it is selected from the range of 40 ° C to 150 ° C.

The novel fluorinated phthalocyanine compound of the present invention has high solubility in organic solvents, especially alcoholic solvents. Examples of the alcoholic solvent include linear or branched alcohols having 1 to 12 carbon atoms, such as methanol, ethanol, and propanol; cellosolorubs, such as ethyl cellosolve; glycols, such as monoethylene glycol and diethylene glycol; diacetone alcohol; And the like.

In the present invention, the aryl group position in the raw material phthalocyanine is sulfonated so as to have an appropriate solubility in an alcoholic solvent. At this time, a sulfonic acid group is added to at least one phthalocyanine molecule per phthalocyanine molecule.
, Preferably 1 to 16, particularly preferably 1 to 1
It is preferable to introduce zero. In the present invention, the sulfonic acid group is simply introduced into the phthalocyanine, so that the solubility in an alcoholic solvent is high.However, the sulfonic acid group is further reacted with ammonia or an organic amine to form an ammonium salt or a sulfonamide group. Alternatively, solubility can be increased.

The fluorine-containing phthalocyanine compound of the present invention also has solubility in water. Then, in order to further increase the solubility in water, it is an effective means to react the sulfonic acid group with a metal such as an alkali metal to convert it to a metal salt of the sulfonic acid group.

The starting fluorinated phthalocyanine (general formula II) of the present invention can be synthesized, for example, according to any one of the following synthesis methods (1) to (4).
That is, the synthesis method (1) is a method in which the same or different substituents are introduced into the 4- and 5-positions in a two-step reaction, and then phthalocyanine is formed. ) Is a method of synthesizing a phthalocyanine in which 12 fluorine atoms remain in the skeleton by omitting the second step in the synthesis method (3) and (4). This is a method in which a phthalocyanine is formed after introducing a substituent. Of these synthesis methods, the first step (1), (2) and (4), the third step (1), the second step (2) and the second step (4) are described in the present invention. They have already filed Japanese Patent Application No. 63-
No. 65806, Japanese Patent Application No. 1-153554, Japanese Patent Application No.
No. 103555 and Japanese Patent Application No. 1-209599.

[0054]

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[0055]

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[0056]

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[0057]

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[0058] Incidentally, R _5, R ₆ and X ₁ is R ₅ in the general formula (II) of the structural formula at each step of the synthesis,
R ₆ and X ₁ (excluding the fluorine atom in X ₁ ). In the first and second steps of the synthesis method (1), the first step of the synthesis method (2), the first step of the synthesis method (3) and the first step of the synthesis method (4), nitriles such as acetonitrile are used as a reaction solvent. Further, potassium fluoride or the like can be used as a condensing agent. The reaction conditions in the second step of the synthesis method (1) are the same as those in the first step in the synthesis method (1) or the synthesis method (2). The reaction conditions in the first step of the synthesis method (3) are the same as those in the first step in the synthesis method (1), (2) or the synthesis method (4) except for the difference in the charging ratio between ROH and KF and tetrafluorophthalonitrile. The same is true. Similarly, the reaction conditions in the second step of the synthesis method (3) are the same as those in the third step of the synthesis method (1) or the second steps of the synthesis methods (2) and (4).

In the synthesis method (1), the reaction conditions in the first step are relaxed, and the one in which the 4-position is not completely substituted with OR and a fluorine atom remains in a part of the 4-position is used as a raw material for the second step. You can also. In the second step, the reaction conditions may be relaxed, and a material in which the 5-position is not completely substituted with OR or SR and a fluorine atom remains in a part of the 5-position may be used as a raw material in the third step.

Also in the synthesis methods (2), (3) and (4), the reaction conditions in the first step are relaxed and the 4-position or 5-position is reduced.
Those in which a fluorine atom is partially left without being completely substituted by OR or SR can be used as a raw material in the second step. In these cases, in the phthalocyanine as the final target, those containing an unsubstituted fluorine atom at the 4,5-position in addition to the fluorine atom at the 3-, 6-position exist.
This substance may be contained in a range that does not affect physical properties such as solubility.

[0061]

The novel phthalocyanine compound of the present invention is
Compared to a conventionally known phthalocyanine compound soluble in an alcoholic solvent (for example, the compound disclosed in JP-A-63-295578), the solubility in an alcoholic solvent can be improved without further sulfonamide-forming the sulfonated product. high. Of course, the compounds of the present invention can be further improved in solubility in alcoholic solvents by sulfonamidation. In addition, the compound of the present invention has a
It has absorption in the near infrared region of 900 nm.

These unique functions include two fluorine atoms at the 3- and 6-positions of the phthalocyanine ring and a fluorine atom at the 4-position, an etheraryl group, a thioetheraryl group, an etheralkyl group or a thioetheralkyl group, or 5 It is presumed that it was brought about by the co-operation of the etheraryl group or thioetheraryl group at the 1-position and the sulfonic acid group bonded thereto.

According to the production method of the present invention, it is possible to molecularly design a compound in which the near-infrared absorption wavelength range or the solubility is changed according to the intended use, and at that time, there is no need to go through a complicated production process and industrial design is possible. Is advantageous. That is, in the present invention, an ether substituent or a thioether substituent can be introduced into the phthalocyanine ring according to the purpose, and a phthalocyanine with high purity can be produced with high yield. Also, JP-A-63-2955
As described in No. 78, the compound does not contain a chloro atom or a bromo atom which deteriorates the solubility, and the fluorine atom in the novel compound of the present invention has an effect of enhancing the solubility. As described above, the novel compound of the present invention has high solubility in organic solvents, particularly alcoholic solvents, has solubility in water, and absorbs in the near infrared region of 650 to 900 nm. And thus can be practically used as a near-infrared absorbing dye.

[0064]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. A) PcF8 (RS) 8 type Example 1 ZnPcF8 (PhS) 8 (SO3H)
15 Synthesis example of starting material (1) ZnPcF8 (PhS)
8 In a 200 ml four-necked flask, 19.6 g (98 mmol) of tetrafluorophthalonitrile, thiophenol 2
1.6 g (196 mmol), potassium fluoride (17.
1 g (294 mmol) and 100 ml of acetonitrile
Was kept under stirring at 50 ° C. for 12 hours. After cooling to room temperature, the obtained yellow solid was filtered, and the obtained cake was purified by washing with methanol and then with warm water to give 3,6-difluoro-4,5-bisphenylthiophthalonitrile. 55 g were obtained.

In a 100 ml flask, the 3,3
6-difluoro-4,5-bisphenylthiophthalonitrile 10 g (26.2 mmol), zinc iodide 31.4
g (9.8 mmol) and α-chloronaphthalene 50
ml and then kept under stirring at 200 ° C. for 5 hours. After cooling, the reaction product was poured into 200 ml of ethanol, the obtained green solid was filtered, and then washed with Soxhlet in the order of methanol, benzene, and water to obtain 32.1 g of ZnPcF8 ( PhS ) 8 . Obtained.

ZnPcF8 (PhS) 8 (SO ₃ H) 1
Preparation of 1. In a 100 ml four-necked flask, 1.59 g (1 mmol) of octafluorooctakis (phenylthio) zinc phthalocyanine obtained in Synthesis Example 1 and 1,1,2,2-
Charge 20 ml of tetrachloroethane and stir with 80
C. Thereto, 3.12 g (24 mmol) of chlorosulfonic acid dissolved in 10 ml of tetrachloroethane was gradually added dropwise. After completion of the dropping, the temperature was raised to 140 ° C., and the reaction was further performed for 2 hours. After completion of the reaction, the mixture was cooled to room temperature and filtered. The resulting dark brown cake was washed with 100 ml of tetrachloroethane.
By washing twice, 2.09 g of the target sulfonated phthalocyanine was obtained. As a result of analysis, this phthalocyanine was found to have 15 sulfonic acid groups in one molecule.

Visible absorption spectrum Maximum absorption wavelength in methanol: 725.0 nm (ε
= 1.84 × 10 ⁵ ) In water; 700 nm (ε = 9.52 × 10 ⁴ ) Solubility Methanol: 10 wt% Ethyl cellosolve; 19 wt% water; 12 wt% Elemental analysis H CN NS F Theoretical value 1.98 34.28 4.00 26.31 5.42 Analytical value 2.01 35.67 4.11 25.05 5.62 The infrared absorption spectrum of this compound is shown in FIG.

Example 2 ZnPcF8 (PhS) 8
Preparation of (SO ₃ H) 5 In Example 1, 0.52 g of chlorosulfonic acid (4
(mmol) was used, and 1.81 g of the target sulfonated phthalocyanine was obtained in the same manner as in Example 1. As a result of analysis, this sulfonated phthalocyanine was found to have five sulfonic acid groups in one molecule.

Visible absorption spectrum Maximum absorption wavelength 698.5 nm in ethyl cellosolve (ε
= 1.14 × 10 ⁵ ) Solubility 10 wt% based on ethyl cellosolve Elemental analysis (assuming 5 sulfonic acid groups) H C N S F Theoretical 2.03% 48.35% 5.64% 20. 97% 7.65% Analytical value 2.18% 48.22% 5.48% 21.11% 7.58% The infrared absorption spectrum of this compound is shown in FIG.

Example 3 VOPcF8 (PhS) 8
Production of (SO ₃ H) 1 Except for using octafluorooctakis (phenylthio) vanadyl phthalocyanine in place of octafluorooctakis (phenylthio) zinc phthalocyanine in Example 1 and using 0.13 g (1 mmol) of chlorosulfonic acid. The same operation as in Example 1 was carried out to obtain 1.39 g of the target sulfonated phthalocyanine. As a result of analysis, this sulfonated phthalocyanine was found to have one sulfonic acid group in one molecule.

Visible absorption spectrum Maximum absorption wavelength 745.0 nm in ethyl cellosolve (ε
= 1.25 × 10 ⁵ ) Solubility Ethyl cell solvent; 8 wt% Elemental analysis (assuming one sulfonic acid group) H C N S F Theoretical value 2.42% 57.78% 6.71% 17.29% 9.11% Analytical value 2.59% 57.55% 6.57% 17.31% 8.94% The infrared absorption spectrum of this compound is shown in FIG.

Examples 4 to 10 In the same manner as in Example 1 except that phthalocyanine of Table 1 was used in place of octafluorooctakis (phenylthio) zinc phthalocyanine and chlorosulfonic acid was used in the amount shown in Table 1, By operation, phthalocyanines having the sulfonated numbers shown in Table 1 were obtained. Table 1 shows the absorption wavelengths and the solubility of the obtained sulfonated phthalocyanines in solvents.

[0073]

[Table 1]

Example 11 Fe (CO) 2 PcF 8
(PhS) 8 (SO ₃ H) 12 Synthesis Example of Starting Material (2) F8 (PhS) 8PcF
e (CO) 2 3,6-difluoro-4,
5 g of 5-bisphenylthiophthalonitrile (13.2 mm
ol) and methylnaphthalene (50 ml) and charged under N ₂ stream 20
It was kept under stirring at 0 ° C. So iron pentacarbonyl 0.7
20 ml of methylnaphthalene in which 1 g (3.6 mmol) is dissolved
Was added dropwise over about 30 minutes, and the temperature was kept at 200 ° C. for 4 hours. After cooling, the reaction product was put in 500 ml of ligroin, stirred, filtered, washed with benzene and acetone in that order, dried and 3.28 g of a deep green cake (vs. 3,6-difluoro-).
4,5-bisphenylthiophthalonitrile crude yield
9%).

Fe (CO) 2 PcF 8 (PhS) 8 (S
Production of O ₃ H) 12 In Example 1, 1.63 g (1 mmol) of octafluorooctakis (phenylthio) iron carbonyl phthalocyanine obtained in Synthesis Example 2 above was used instead of octafluorooctakis (phenylthio) zinc phthalocyanine. Using the same procedure as in Example 1 except that 1.04 g (8 mmol) of chlorosulfonic acid was used, 2.59 g of the target sulfonated phthalocyanine was obtained. As a result of analysis, these sulfonated phthalocyanines were found to have 1 / molecule per molecule.
It was found to have two sulfone groups.

Visible absorption spectrum Maximum absorption wavelength 699.5 nm in ethyl cellosolve (ε
= 1.01 × 10 ⁵ ) Solubility Ethyl cell solve; 19 wt% Elemental analysis (assuming 12 sulfonic acid groups) H C N S F Theoretical 1.54% 37.56% 4.32% 24.69% 5.86% Analysis 1.45% 38.20% 4.13% 24.17% 5.71% The infrared absorption spectrum of this compound is shown in FIG.

B) PcF12 (RO) 4 type Example 12 CuF12 (PhO) 4 (SO ₃ H)
4 Synthesis Example of Starting Material (3) CuF12 (PhO) 4 20.0 g (100 mmol) of tetrafluorophthalonitrile, 9.4 phenol in a 200 ml four-necked flask
g (100 mmol), KF (5.8 g) and acetonitrile (100 ml) were charged and kept under stirring at 5 ° C. for 3 hours. Thereafter, the solid was filtered, the filtrate was evaporated to dryness, and 3,4,6-trifluoro-5-phenoxyphthalonitrile was added in an amount of 22.5.
g was obtained.

In a 100 ml flask, the previously obtained 3,3
4,6-trifluoro-5-phenoxyphthalonitrile 5 g (18.4 mmol), cuprous chloride 0.95 g
(9.1 mmol) and N-methyl-2-pyrrolidone 5
0 ml was charged and then kept under stirring at 175 ° C. for 5 hours.
After cooling, the reaction product was poured into 500 ml of water, and the resulting purple solid was filtered and washed with methanol.
2.6 g of CuF12 (PhO) 4 was obtained.

For CuF 12 (PhO) 4 (SO ₃ H) 4
Preparation 1.16 g (1 mmol) of dodecakisfluorotetra (phenoxy) copper phthalocyanine and 20 ml of 1,1,2,2-tetrachloroethane were charged into a 100 ml four-necked flask and kept at 80 ° C. with stirring. There, 1.0 ml of chlorosulfonic acid dissolved in 10 ml of tetrachloroethane was added.
4 g (8 mmol) were slowly added dropwise. 14 after dropping
The temperature was raised to 0 ° C., and the reaction was further performed for 2 hours. After completion of the reaction, the resulting dark brown cake was cooled to room temperature and washed twice with 100 ml of tetrachloroethane to obtain 1.18 g of the target sulfonated phthalocyanine. As a result of analysis, this phthalocyanine was found to have 5 to 6 sulfonic acid groups in one molecule.

Visible absorption spectrum Maximum absorption wavelength 652.5 nm in ethyl cellosolve (ε = 6.55 × 10 ⁴ ) 636.5 nm in water (ε = 4.75 × 10 ⁴ ) Solubility 25 wt% element to ethyl cellosolve Analysis (assuming 8 sulfonic acid groups) HC N S F Theoretical 1.36% 45.43% 7.57% 8.66% 15.40% Analytical 1.64% 45.17% 7. 33% 8.48% 15.24% The infrared absorption spectrum of this compound is shown in FIG.

Example 13 VOF12 (PhO) 4
Preparation of (SO ₃ H) 5 Dodecakisfluorotetra (phenoxy) oxyvanadium phthalocyanine in a 100 ml four-necked flask.
16 g (1 mmol) and 20 ml of 1,1,2,2-tetrachloroethane were charged and maintained at 80 ° C. with stirring. Thereto, 1.04 g (8 mmol) of chlorosulfonic acid dissolved in 10 ml of tetrachloroethane was gradually added dropwise.
After completion of the dropping, the temperature was raised to 140 ° C., and the reaction was further performed for 2 hours. After completion of the reaction, the resulting dark brown cake was cooled to room temperature and washed twice with 100 ml of tetrachloroethane to obtain 1.32 g of the target sulfonated phthalocyanine.
As a result of analysis, this phthalocyanine was found to have 5 to 6 sulfonic acid groups in one molecule.

Visible absorption spectrum Maximum absorption wavelength 700.5 nm in methanol (ε = 5.38 × 10 ⁴ ) 668.0 nm in water (ε = 2.75 × 10 ⁴ ) Solubility 25% by weight based on methanol Based on ethyl cellosolve 23 wt% 15 wt% based on diacetone alcohol 18 wt% based on water Elemental analysis (assuming five sulfonic acid groups) HCNSF theoretical value 1.36% 45.33% 7.55% 8.64 % 15.36% Analytical value 1.58% 44.92% 7.08% 8.32% 14.98% The infrared absorption spectrum of this compound is shown in FIG.

Example 14 CuF12 (PhO) 4
Production of (SO ₃ H) 2 Example 13 was the same as Example 13 except that 1.16 g (1 mmol) of dodecakisfluorotetra (phenoxy) copper phthalocyanine was used and 0.26 g (2 mmol) of chlorosulfonic acid was used. The same operation was performed to obtain 0.92 g of the desired sulfonated phthalocyanine. As a result of the analysis, it was found that this sulfonated phthalocyanine had two sulfonic acid groups in one molecule.

Visible absorption spectrum Maximum absorption wavelength Ethyl cellosolve 648.5 nm (ε = 7.21 × 10 ⁴ ) Solubility 26 wt% with respect to ethyl cellosolve Elemental analysis (assuming two sulfonic acid groups) H C N S F Theoretical 1.53% 50.94% 8.49% 4.86% 17.27% Analytical 1.71% 51.19% 8.32% 5.28% 19.97% Infrared of this compound FIG. 7 shows the absorption spectrum.

Examples 15 to 19 In the same manner as in Example 13, except that phthalocyanine of Table 2 was used in place of dodecakisfluorotetra (phenoxy) oxyvanadium phthalocyanine, and that chlorosulfonic acid was used in the amounts shown in Table 2, To obtain a phthalocyanine having the sulfonated number shown in Table 2. Table 2 shows the absorption wavelengths of these obtained sulfonated phthalocyanines and the solubility in solvents.

[0086]

[Table 2]

C) PcF8 (RO) 4 (RS) 4 tie
StepExample 20 CoF8 (PhO) 4 (PhS) 4
(SO ₃ H) 4 Synthesis example of starting material (4) CoF8 (PhO) 4
(PhS) 4 3,5,6-trifluoro-4-phenoxyphthalonit
5.10 g (20 mmol) of ril, potassium fluoride 1.16
g (20 mmol) and 20 ml of acetonitrile in 100
Then, thiophenol was charged into a four-necked flask.
20 g (20 mmol) was added and reacted for 4 hours under reflux.
Was. After completion of the reaction, the potassium fluoride was filtered off and acetonitrile was removed.
The desired pale yellow cake 6.22 was distilled off.
g (85.3% yield).

4-phenoxy-5-phenylthio-3,
5.00 g of 6-difluorophthalonitrile (13.7 mm
ol), 5.54 g (4.12 mmol) of anhydrous cobaltous chloride
l) and 50 ml of benzonitrile were charged into a 100 ml four-necked flask and reacted at 175 ° C. for 4 hours. After completion of the reaction, the resulting solid was filtered off, and the remaining solid was washed with methanol to obtain the desired dark green cake 4.49.
g was obtained (86.5% yield).

Absorption wavelength 709.5 nm in chloroform (ε = 7.92 × 10 ⁴ ) Coating 719.5 nm Solubility Chloroform 1.2 wt% Toluene 0.8 wt%

CoF8 (PhO) 4 (PhS) 4 (SO
Preparation of ₃ H) 4 1.45 g of dodecakisfluorotetra (phenoxy) cobalt phthalocyanine in a 100 ml four-necked flask
(1 mmol) and 1,1,2,2-tetrachloroethane (20 ml) were charged and maintained at 80 ° C. with stirring. There,
1.04 g (8 mmol) of chlorosulfonic acid dissolved in 10 ml of tetrachloroethane was slowly added dropwise. After completion of the dropping, the temperature was raised to 140 ° C., and the reaction was further performed for 2 hours. After completion of the reaction, the resulting dark brown cake was cooled to room temperature and washed twice with 100 ml of tetrachloroethane to obtain 2.01 g of the target sulfonated phthalocyanine. As a result of analysis, this phthalocyanine was found to have 5 to 6 sulfonic acid groups in one molecule.

Visible absorption spectrum Maximum absorption wavelength Ethyl cellosolve 691.5 nm (ε = 3.04 × 10 ⁴ ) 678.0 nm in water (ε = 1.58 × 10 ⁴ ) Solubility 26 wt% based on methanol Elemental analysis (sulfone HC N S F theoretical 1.93% 45.92% 5.35% 12.26% 7.26% analytic 2.08% 45.50% 5.01% 11 8.87% 6.94% The infrared absorption spectrum of this compound is shown in FIG.

Examples 21 to 23 The procedure of Example 20 was repeated , except that the phthalocyanine shown in Table 3 was used instead of dodecafluorotetra (phenoxy) cobalt phthalocyanine, and the amount of chlorosulfonic acid was used in Table 3. Thus, a phthalocyanine having a sulfonation number shown in Table 3 was obtained. Table 3 shows the absorption wavelengths and the solubility of these sulfonated phthalocyanines in solvents.
Shown in

[0093]

[Table 3]

D) PcF8 (RO) 8 typeExample 24 CoPcF8 (PhO) 8 (SO
₃ H) 6 Synthesis example of starting material (5) CoPcF8 (PhO)
8 Tetrafluorophthalonite in a 200 ml four-necked flask
20.0 g (100 mmol) of ril, phenol 18.
8 g (100 mmol), 10.8 g KF and acetoacetate
100 ml of nitrile was charged and kept under stirring at 5 ° C. for 3 hours.
Thereafter, the solid product was filtered, and the filtrate was evaporated to dryness.
Fluoro-4,5-bisphenoxyphthalonitrile
7.4 g were obtained.

In a 100 ml flask, the previously obtained 3,
6-difluoro-4,5-bisphenoxyphthalonitrile 6.7 g (19.3 mmol), cobalt chloride 0.7
5 g (5.8 mmol) and 50 ml of benzonitrile were charged and then kept under stirring at 175 ° C. for 6 hours. After cooling, the reaction product was poured into 200 ml of acetone, and the resulting purple solid was filtered, washed with acetone, and washed with Co.
3.0 g of PcF8 (PhO) 8 was obtained.

CoPcF8 (PhO) 8 (SO ₃ H) 6
4 necked octafluoro oct kiss flask (phenoxy) cobalt phthalocyanine 1.45g of manufacturing 100ml
(1 mmol) and 1,1,2,2-tetrachloroethane (20 ml) were charged and maintained at 80 ° C. with stirring. There,
0.52 g (4 mmol) of chlorosulfonic acid dissolved in 10 ml of tetrachloroethane was slowly added dropwise. After completion of the dropping, the temperature was raised to 140 ° C., and the reaction was further performed for 2 hours. After completion of the reaction, the resulting dark brown cake was cooled to room temperature and washed twice with 100 ml of tetrachloroethane to obtain 1.26 g of the target sulfonated phthalocyanine. As a result of analysis, this phthalocyanine was found to have five sulfonic acid groups in one molecule.

Visible absorption spectrum Maximum absorption wavelength Ethyl cellosolve 690.0 nm (ε = 1.22 × 10 ⁵ ) Solubility 12 wt% based on ethyl cellosolve Elemental analysis (assuming five sulfonic acid groups) H C N S F Theoretical 2.34% 55.72% 6.50% 9.30% 8.81% Analytical 2.51% 55.89% 6.31% 9.58% 8.64% Infrared of this compound FIG. 9 shows the absorption spectrum.

Examples 25 to 27 In the same manner as in Example 24 except that phthalocyanine of Table 4 was used in place of octafluorooctakis (phenoxy) cobalt phthalocyanine and chlorosulfonic acid was used in the amount of Table 4 in Example 24, By operation, phthalocyanines having the sulfonated numbers shown in Table 4 were obtained. Table 4 shows the absorption wavelengths and solubility of these obtained sulfonated phthalocyanines in solvents.

[0099]

[Table 4]

[Brief description of the drawings]

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

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

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

FIG. 4 shows an infrared absorption spectrum of the compound obtained in Example 11.

FIG. 5 shows an infrared absorption spectrum of the compound obtained in Example 12.

FIG. 6 shows an infrared absorption spectrum of the compound obtained in Example 13.

FIG. 7 shows an infrared absorption spectrum of the compound obtained in Example 14.

FIG. 8 shows an infrared absorption spectrum of the compound obtained in Example 20.

FIG. 9 shows an infrared absorption spectrum of the compound obtained in Example 24.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G02F 1/13 500 B41M 5/26 Y (72) Inventor Miho Onozaki 1-25-25 Kannondai, Tsukuba-shi, Ibaraki Nippon Shokubai Co., Ltd. Within Tsukuba Research Laboratories (58) Field surveyed (Int.Cl. ⁶ , DB name) C07D 487/22 B41M 5/26 B41M 5/30 C09B 47/24 C09K 3/00 G02F 1/13 CA (STN) REGISTRY (STN )

Claims (3)

(57) [Claims] 1. The following general formula (I): Wherein X is independently a fluorine atom, OR ₁ Za 原子
d, SR ₂ Ze to h, OR ₃ , or SR ₄ (where R
₁ and R ₂ are each independently a phenyl group or a benzyl group, and the phenyl group or the benzyl group may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxyl group, a carboxyl group, an alkoxycarbonyl group or a halogen. Often,
R ₃ and R ₄ independently represent a C1 to C20 alkyl group or a C4 to C6 cycloalkyl group; Z represents a sulfone group); and Y independently represents OR ₅
Zi to l or SR ₆ Zm to p (R ₅ and R ₆ are each independently a phenyl group or a benzyl group, and the phenyl group or the benzyl group is an alkyl group having 1 to 4 carbon atoms, an alkoxyl group, May be substituted with a group, an alkoxycarbonyl group or a halogen, Z represents a sulfone group), a to p are integers of 0 to 7 and a to p
Is 1 or more, and M represents a metal-free, metal, metal oxide, metal carbonyl or metal halide.]
A novel fluorine-containing phthalocyanine compound represented by the formula: 2. The following general formula (II): [Wherein X ₁ is independently a fluorine atom, OR ₁ , SR
₂ , OR ₃ or SR ₄ (where R ₁ and R ₂ are each independently a phenyl group or a benzyl group, and the phenyl group or the benzyl group is an alkyl group having 1 to 4 carbon atoms, an alkoxyl group, a carboxyl group , An alkoxycarbonyl group or a halogen, and R ₃ and R ₄ are
Represents an alkyl group of 1 to C20 or a cycloalkyl group of C4 to C6), and Y ₁ is independently OR ₅ ,
Or SR ₆ (R ₅ and R ₆ are each independently a phenyl group or a benzyl group, and the phenyl group or the benzyl group is an alkyl group having 1 to 4 carbon atoms, an alkoxyl group, a carboxyl group, an alkoxycarbonyl group, or a halogen atom. And M represents a metal-free, metal, metal oxide, metal carbonyl or metal halide]
A method for producing a novel fluorine-containing phthalocyanine compound, characterized by obtaining the compound according to claim 1 by sulfonating the phthalocyanine derivative represented by the formula (1) in an organic solvent using a sulfonating agent. 3. A near-infrared absorbing material comprising the novel fluorine-containing phthalocyanine compound having an absorption in the range of 650 to 900 nm according to claim 1.