JPH0439361A - New phthalocyanine compound, production thereof and near infrared light absorbing material using the same compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I [R1 is alkyl, alkoxyalkyl, (substituted) phenyl, benzyl, etc.; at least one of R2 is alkoxy, alkoxyalkyloxy or (substituted) phenyloxy, etc., and the rest of R2 are F; M is Zn, Cu, Pb, VO, TiO, TiX2 (X is halogen), SnX2, AlX or InX]. EFFECT:Octakis(n-butylthio)octakis(ethoxy)vanadylphthalocyanine. USE:A far infrared light absorbing material, having absorption in a range of 700-1,500 nm. PREPARATION:A fluorine-containing phthalocyanine compound shown by formula II is reacted with alkoxide, an alchol or a phenol shown by the formula R3OA [R3 is alkyl, alkoxyalkyl, acyloxyalkyl, (substituted) phenyl, benzyl, etc.; A is H, Na or K] in an organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel phthalocyanine compound represented by the following general formula (1) and a method for producing the same.

R+ R \ / S S / \ RR ・ ・ ・ ・ (1) [In the formula, R3 is a linear or branched alkyl group, an alkoxyalkyl group, an acyloxyalkyl group, or an alkyl group, an alkoxy group, or a halogen substituted may represent a phenyl group, a --chloroalkyl group, or a hensyl group (wherein R may be the same or different), at least one of R2 is a linear or branched alkoxy group, a cycloalkyloxy group, alkoxyalkyloxy group, acyloxyalkyloxy group, hydroxyalkyloxy group, aminoalkyloxy group, cyanoalkyloxy group, alkoxycarbonylalkyloxy group, halogenated alkyloxy group, or alkyl group, alkoxy group, amino group, substituted Represents a possible secondary or tertiary amino group, sulfonic acid group, or phenyloxy group, cycloalkyloxy group, or benzyloxy group that may be substituted with halogen, where R2 may be the same or different. ), the remaining R2 represents F, and M represents Zn, Cu, Pb, VO, Tie, T
iX2.5nXz+ AI! , X, or InX (
Here, X represents a halogen atom].

The present invention also relates to a near-infrared absorbing material that absorbs in the near-infrared region. The novel phthalocyanine compound according to the present invention has absorption in the near-infrared region of 700 nm to 1,50 OnI11 and has excellent solubility, so it can be used in optical recording media using semiconductor lasers, liquid crystal display devices, optical character readers, etc. Demonstrates excellent effects when used as a near-infrared absorption dye for writing or reading, a photothermal conversion agent for thermal transfer, thermal paper, thermal stencils, etc., a near-infrared absorption filter, an eye strain prevention agent, or a photoconductive material. It is something to do.

[Prior Art] In recent years, optical recording media such as compact discs, laser discs, optical memory discs, and optical cards, liquid crystal display devices,
Semiconductor lasers are used as light sources for writing or reading in optical character readers, etc., and are also used in photoconductive materials, near-infrared absorption filters, anti-eye strain agents, and thermal transfer.

There is an increasing demand for the development of substances that absorb near-infrared light, so-called near-infrared absorbing dyes, as photothermal conversion agents for thermal paper, heat-sensitive stencils, etc. Among these, many phthalocyanine compounds have been studied because they are stable against light, heat, temperature, etc. and have excellent robustness.

However, the majority of them are solvent insoluble;
In order to make a dye into a thin film for practical purposes, processes such as vapor deposition or dispersion into resin were necessary.

On the other hand, phthalocyanine compounds having practically advantageous solubility have also been recently disclosed. For example, 3,6-octaalkoxyphthalocyanine (JP-A-61-223056
No.), but it has the problems of insufficient absorption in the near-infrared region and the complicated manufacturing process, making it impossible to obtain inexpensive phthalocyanine.

Also, JP-A-60-209583, JP-A-61-152
No. 685, No. 63-308073, and No. 64
No. 62361 discloses an example in which the solubility is improved and the absorption wavelength is made longer by substituting a large number of thioether substituents on the phthalocyanine skeleton. Among them, JP-A-60-209583 and JP-A-61-152685 disclose synthetic examples in which a thioether substituent is introduced at the 3°6-position of the phthalocyanine skeleton. The method involves heating a phthalocyanine compound having chlorine atoms at the 3 and 6 positions of the phthalocyanine skeleton and an organic thiol compound in a quinoline solvent in the presence of KO)I to obtain a phthalocyanine having a thioether substituent at the 3 and 6 positions. There is. However, in both cases the yield was 20
It is about ~30%, which poses a problem in manufacturing efficiency. JP 60-209583, JP 61-152685,
JP-A No. 64-62361 discloses a synthesis example in which 8 to 16 polythioether substituents are introduced into the phthalocyanine skeleton.

The method involves adding 8 to
A phthalocyanine compound having 16 chlorine atoms and/or bromine atoms and an organic thiol compound are heated in the presence of K in a quinoline solvent to obtain a phthalocyanine having 8 to 16 thioether substituents on the benzene nucleus of the phthalocyanine skeleton. ing. However, like the above-mentioned ones, the yield is about 20 to 30% and there is a problem in production efficiency. In other words, the yield is low due to the poor substitutability of chlorine or bromine atoms to thioether substituents.For example, unreacted phthalocyanine in which the chloro atom is not substituted with a thioether substituent or some chlorine atoms are converted into thioether substituents. Unreacted phthalocyanine substituted with a substituent is produced. Since it is practically difficult to separate these unreacted phthalocyanine and the target substance phthalocyanine from each other, the reality is that only a mixture of phthalocyanines of various compositions can be obtained. In fact, JP-A No. 64-62361 describes it as a polythiol-substituted mixed condensation type phthalocyanine composition even after separation using a silica gel column, indicating that unreacted phthalocyanine compositions remain. Furthermore, if some Rol atoms remain, their solubility is significantly reduced, which is disadvantageous for dissolving them as a near-infrared absorbing dye to form a thin film.

In JP-A No. 63-308073, monobromotetradecarylolophthalocyanine and an organic thiol mixture of 2-aminothiophenol and 4-methylphenylthiol are heated in the presence of KO)I in a DMFi medium to form a thioether substituent. phthalocyanine was obtained with a yield of 42%. However, in this method, different organic thiol mixtures are simultaneously added and reacted, so a phthalocyanine mixture having a certain combination of 1,000-onythyl substituents can be obtained, which can be used as a near-infrared absorbing dye. The problem is that uniform characteristics cannot be obtained, and therefore, the applications are limited.

[Problem to be solved by the invention]

The present invention has been made in view of the above-mentioned circumstances of the prior art. That is, the purpose of the present invention is to
The object of the present invention is to provide a novel phthalocyanine compound that has absorption in the near-infrared region of nm and has excellent solubility. Another object of the present invention is to provide a method for producing the phthalocyanine compound efficiently and with high purity. Furthermore, another object of the present invention is to provide a near-infrared absorbing material containing a novel phthalocyanine compound that absorbs in the near-infrared region and is soluble.

[Failure to resolve divisional issues]

The present inventors have achieved the above object by reacting a phthalocyanine compound having a fluorine atom at the 3.6-position of the phthalonanine skeleton and a thioether substituent at the 4.5-position with alkocites, alcohols, or phenols. The present invention was completed by discovering that a compound can be obtained. Specifically, the present invention relates to a fluorine-containing phthalocyanine compound represented by the following general formula (II) and R, R.

\7/ \ ・ ・ ・ ・ (It) [In the formula, R1 is a linear or branched alkyl group, an alkoxyalkyl group, an acyloxyalkyl group, or an alkyl group, an alkoxy group, or a phenyl group optionally substituted with a halogen. , cycloalkyl group, or benzyl group, where R may be the same or different), M is Zn, Cu.

Pb, Shi0. T+0. T+Xz, SnX,, A
It represents II-X or Inx (where X represents a halogen atom). ] General formula, OA (wherein R3 is a linear or branched alkyl group, an alkoxyalkyl group,
゛Acyloxyalkyl group, hydroxyalkyl group, aminoalkyl group, cyanoalkyl group, alkoxycarbonylalkyl group, halogenated alkyl group, or alkyl group, alkoxy group, amino group, substitutable secondary/tertiary amine group, sulfonic acid a phenyl group, a cycloalkyl group, or a benzyl group optionally substituted with a halogen, and A represents hydrogen, sodium, or potassium), alcohols, or phenols in an organic solvent. in a medium, preferably in at least one medium selected from the group consisting of aprotic polar solvents, benzonitrile, acetonitrile, quinoline and pyridine, preferably in the presence of an alkaline substance when A is hydrogen, more preferably KOH + KzC
In the presence of at least one selected from the group consisting of Oi, NaOH and Na2CO, preferably from 30°C to
The following general formula (I
) and a novel phthalocyanine compound are provided.

・ ・ ・ ・ (1) [In the formula, R4 is a linear or branched alkyl group, an alkoxyalkyl group, an acyloxyalkyl group, or an alkyl group, an alkoxy group, or a phenyl group or cycloalkyl group that may be substituted with a halogen. , or a benzyl group, where each R4 may be the same or different), at least one R2 is a linear or branched alkoxy group, an alkoxyalkyloxy group, an acyloxyalkyloxy group, a hydroxyalkyloxy group, An aminoalkyloxy group, a cyanoalkyloxy group, an alkoxycarbonylalkyloxy group, a halogenated alkyloxy group, an alkyl group, an alkoxy group, an amino group, a substitutable secondary/tertiary amino group, a sulfonic acid group, or a halogen. represents an optionally substituted phenyloxy group, cycloalkyloxy group, or benzyloxy group (wherein R2 may be the same or different), the remaining R2 represents F, and M is Zn, Cu ,
Pb, VO, Tie.

TiXz, SnX, AIX, or InX
(Here, χ represents a halogen atom).

The present invention will be explained in detail below.

In the fluorine-containing phthalocyanine represented by the general formula (II) used in the present invention, in the group represented by R and S,
Specific examples of linear or branched alkylthio groups include methylthio, ethylthio, n-propylthio, 1so-
Propylthio, n-butylthio, 1so-butylthio,
ter t-butylthio, n-pentylthio, 1,2-
dimethylpropylthio, hexylthio, heptylthio,
Examples include straight-chain or branched alkylthio groups having 1 to 20 carbon atoms, such as octylthio and nonylthio. Specific examples of the alkoxyalkylthio group include methoxymethylthio, ethoxymethylthio, methoxyethylthio, ethoxyethylthio, propoxyethylthio, butoxyethylthio, hexyloxyethylthio, 3-methoxybutylthio, phenoxyethylthio, and the like. . Examples of the acyloxyalkylthio group include acetyloxyethylthio, propionyloxyethylthio, and the like. Specific examples of the phenylthio group, cycloalkylthio group, or benzylthio group that may be substituted with an alkyl group, alkoxy group, or halogen include phenylthio, 0-methylphenylthio, p-methylphenylthio, 2,4-dimethyl Phenylthio, 2,3-
dimethylphenylthio, 26-dimethylphenylthio,
0-fluorophenylthio, p-fluorophenylthio, 2,3,5.6-tetrafluorophenylthio, 0-
Methoxyphenylthio, p-methoxyphenylthio, P
Specific examples of the -ethoxyphenylthio and cycloalkylthio groups include cyclohexylthio, 2-cyclohexylethylthio, and 3-cyclohexyl-2-methylpropylthio, and specific examples of the benzylthio group include benzylthio.

Specific examples of the alkoxides, alcohols, or phenols represented by the general 2 R30A used in the present invention include the following.

Alkoxides include sodium methoxide, sodium ethoxide, sodium propoxide, sodium iso-propoxide, sodium butoxide, sodium-1so-butoxide, sodium-ter
t-Butoxide, sodium pentyl oxide, sodium-1,2-dimethylpropoxide, sodium hexyl oxide, sodium hebutyl oxide, sodium pentyl oxide, sodium benzyl oxide, potassium methoxide, potassium ethoxide, potassium propoxide, potassium- 1so-propoxide, potassium butoxide, potassium-1so-butoxide, potassium-tert-butoxide, potassium pentyloxide,
Straight-chain or branched alkoxides having 1 to 20 carbon atoms, such as potassium-1,2-dimethylpropoxide, potassium hexyloxide, potassium hebutyloxide, potassium octyloxide, potassium rhamnonyloxide; sodium methoxymethoxide, sodium Ethoxyethoxide, sodium hexyloxyethoxide, sodium-
Alkoxyalkoxides such as 3-methoxybutoxide, sodium ethoxyethoxide, potassium methoxymethoxide, potassium ethoxyethoxide, potassium hexyloxyethoxide, potassium-3-methoxybutoxide, potassium phenoxyethoxide; sodium aminomethoxide, sodium-2 -aminoethoxide, sodium-3-aminobutoxide, potassium mitsume 1-
potassium-3-aminoethoxide, potassium-
Aminoalkoxides such as 3-aminobutoxide; sodium cyanomethoxide, sodium cyanoethoxide,
Cyanoalkoxides such as potassium cyanomethoxide and potassium cyanoethoxide; sodium acetyloxyethoxide, sodium propionyloxyethoxide,
Acyloxyalkoxides such as potassium acetyloxyethoxide and potassium propionyloxyethoxide;
Sodium hydroxymethoxide, sodium-2-hydroxypropoxide, potassium hydroxymethoxide,
Hydroxy alkoxides such as potassium-2-hydroxypropoxide; sodium methoxycarbonyl methoxide, sodium ethoxycarbonyl ethoxide, sodium butquine carbonyl propoxide, potassium methoxycarbonyl methoxide, potassium ethoxycarbonyl ethoxide, potassium butoxycarbonyl broboxoxide Alkoxycarbonyl alkoxides such as sodium trifluoromethoxide, potassium trifluoromethoxide; halogenated alkoxides such as sodium trifluoromethoxide, sodium cyclohexyl oxide, sodium-3-cyclohexylpropoxide, sodium benzyl oxide, potassium cyclohexyl oxide, potassium -3-cyclohexylpropoxide, potassium benzyl oxide and other alkyl groups,
Examples include an alkoxy group, an amino group, a substitutable secondary/tertiary amino group, or cyclohexyl oxide and hensyl oxide which may be substituted with a halogen.

Specific examples of alcohols or phenols include methanol, ethanol, n-propyl alcohol, 1s
o-propyl alcohol, n-butyl alcohol, 1s
o-butyl alcohol, ter heptyl alcohol,
1-2 carbon atoms such as n-pentyl alcohol, 1,2 dimethylpropyl alcohol, heptyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, etc.
0 linear or branched alkyl alcohols: alkoxyalkyl alcohols such as methoxymethyl alcohol, ethoxyethyl alcohol, hexyloxyethyl alcohol, phenoxyethyl alcohol; aminoethyl alcohol, 2-aminoethyl alcohol, 3-aminobutyl alcohol, etc. Aminoalkyl alcohols; cyanoalkyl alcohols such as cyanomethyl alcohol and cyanoethyl alcohol; acyloxyalkyl alcohols such as acetyloxyethyl alcohol and propionyloxyethyl alcohol; hydroxyalkyl alcohols such as hydroxymethyl alcohol, 2-hydroxyethyl alcohol, and 2-hydroxypropyl alcohol Alcohol; alkoxycarbonyl alkyl alcohol such as methoxycarbonyl methyl alcohol, ethoxy carbonyl ethyl alcohol, butoxycarbonyl propyl alcohol; halogenated alkyl alcohol such as trifluoromethyl alcohol; phenol, 0-methylphenol, p-methylphenol, 2.4- Dimethylphenol, 2,3-dimethylphenol, p-sulfenylphenol, 0-fluorophenol, p-fluorophenol, 2,35.6-tetrafluorophenol, 0-methoxyphenol, p
-methoxyphenol, p-ethoxyphenol, 0-
Aminophenol, p-aminophenol, 0-dimethylaminophenol, p-dimethylaminophenol,
Cyclohexyl alcohol, 3-cyclohexylpropyl alcohol, benzyl alcohol and other alkyl groups, alkoxy groups, amino groups, substitutable secondary and tertiary amino groups, or phenols which may be substituted with halogens, cycloalkyl alcohols, Examples include benzyl alcohol.

In the phthalocyanine represented by the general formula (1) which is the reaction product of the present invention, R2 is the same as R6 in the raw material phthalocyanine. In addition, in the group represented by R2,
Specific examples of linear or branched alkoxy groups include methoxy, ethoxy, n-propyloxy, 1so-propyloxy, n-butyloxy, 1so-butyloxy, tert-butyloxy, n-pentyloxy, 1
, 2-dimethylpropyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, etc. with 1 carbon number
to 20 straight-chain or branched alkoxy groups, and the like.

Specific examples of alkoxyalkyloxy groups include methoxymethyloxy, ethoxymethyloxy, methoxyethyloxy, ethoxyethyloxy, propoxyethyloxy, butoxyethyloxy, hexyloxyethyloxy, 3-methoxybutyloxy, phenoxyethyloxy, etc. can be mentioned. Examples of the acyloxyalkyloxy group include acetyloxyethyloxy and propionyloxyethyloxy. Specific examples of the cyanoalkyloxy group include cyanmethyloxy, cyanoethyloxy, etc., and specific examples of the hydroxyalkyloxy group include hydroxymethyloxy, 2-hydroxyethyloxy, 2-hydroxypropyloxy, etc. Specific examples of the aminoalkoxy group include aminomethoxy, 2-aminoethoxy, 3-aminobutoxy, and the like.

Specific examples of the alkoxycarbonylalkyloxy group include methoxycarbonylmethyloxy, ethoxycarbonylethyloxy, butoxycarbonylpropyloxy, and the like. Specific examples of halogenated alkyloxy groups include trifluoromethyloxy, and alkyl groups, alkoxy groups, amino groups,
Specific examples of substitutable secondary and tertiary amino groups, or phenoxy groups, cycloalkyloxy groups, and benzyloxy groups that may be substituted with halogens include phenoxy, 0-methylphenoxy, P-methylphenoxy, 2.4-dimethylphenoxy, 2.3-dimethylphenoxy, p-sulfonylphenoxy, 0-fluorophenoxy, p-fluorophenoxy, 2,3,
5.6-tetrafluorophenoxy, 0-methoxyphenoxy, P-methoxyphenoxy, p-ethoxyphenoxy, 0-aminophenoxy, p-aminophenoxy,
Examples include 〇-dimethylaminophenoxy, p-dimethylaminophenoxy, cyclohexyloxy, 3-cyclohexyl-2methylpropyloxy, henzyloxy, and the like.

Note that in the phthalocyanine represented by the above general formula (1), at least one R2 is an oxy compound shown in the above specific example, but in the present invention, R2 contains an unreacted fluorine atom as a residue. I don't mind.

The manufacturing method of the present invention is unique! Preferred organic solvents include aprotic polar solvents such as Ill, N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, dimethylsulfone, sulfolane, and N-methyl-2-pyrrolidone. , acetonitrile, benzonitrile, quinoline, pyridine, etc., and use of N,N-dimethylformamide, quinoline, and pyridine is particularly preferred. These solvents can be used alone or in combination of two or more.

In the production method of the present invention, the reaction is preferably carried out in the presence of an alkaline substance. Among these alkaline substances, potassium hydroxide, potassium carbonate, sodium hydroxide, and sodium carbonate are particularly preferred, and one or more of them can be used in combination.

In the present invention, the fluorine-containing phthalocyanine represented by the general formula (II) is preferably charged in a range of 2 to 30 parts per 100 parts of the solvent, and 1 mole part of the fluorine-containing phthalocyanine represented by the general formula (II) is used. It is preferable to use the alkoxylates, alcohols or phenols represented by the general formula R30A within the range of 8.8 to 80 mol parts, particularly preferably within the range of 12 to 24 mol parts. , and the alkaline substance is 0.9 to 3.0 per mole part of alkoxylates, alcohols, or phenols.
It is preferably used within the range of molar parts, particularly within the range of 1 to 1.5 molar parts.

In the present invention, the reaction temperature is preferably in the range of 30 to 250°C, particularly preferably in the range of 80 to 200°C.

In the present invention, the fluorine-containing phthalocyanine that is the starting material of the present invention can be synthesized, for example, according to the following scheme, that is, the first step and the second step. Thus, in the present invention, the target substance phthalocyanine can be synthesized using these raw materials according to the scheme of the third step below.

The present inventors have already disclosed the manufacturing methods of the following first and second steps in Japanese Patent Application No. 63-65806 and Japanese Patent Application No. 1999.
No. 403554, Japanese Patent Application No. 1-103555, and Japanese Patent Application No. 1-209599.

(first step) (Second step) metal halide to \ (Third step) ／　　　　＼ S ／　　＼ R,R.

(R2 represents R30 or F) [Effects of the Invention] By using the production method of the present invention, it becomes possible to introduce any number of ether groups into the 3 and 6 positions of the phthalocyanine skeleton, and the phthalonanine skeleton of the raw material It has a unique absorption wavelength region due to the joint action of the thioether group that existed at the 4 and 5 positions and the newly introduced ether group,
Furthermore, it has become possible to provide a new phthalocyanine with excellent solubility in solvents. In other words, the manufacturing method of the present invention has the feature that it is possible to design molecules of compounds with different near-infrared absorption wavelength ranges or solubility depending on the application. In addition, the fluorine atom at this position is easier to undergo nucleophilic substitution than the chlorine atom and the pro-hydrogen atom, so it has a good yield (
(approximately 70 to 95%) and can produce a phthalocyanine having an ether substituent with good purity. In addition, even if fluorine atoms remain, all fluorine atoms are substituted to ether positions because phthalocyanines with fluorine atoms have higher solubility than phthalocyanines with chlorine atoms and pro-hydrogen atoms. Its usefulness is not inferior to that of other phthalocyanines.

The novel phthalocyanine compound of the present invention has higher solubility in organic solvents such as dimethylformamide, tetrahydrofuran, ketones, and alcohols than conventionally known phthalocyanine compounds, and absorbs near infrared rays of 700 to 1500 nm*. Therefore, it can be used practically as a near-infrared absorbing dye.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 Octakis (n-butylthio) octakis (ethoxy)
Synthesis of vanadyl phthalocyanine [VOPc(n-BuS)s(EtO)e] 2.72 g (40 mmol) of sodium ethoxide and N,N-dimethylformamide (hereinafter abbreviated as DMF) 30Id! Pour into a 100cc Yotsuro flask,
The mixture was stirred at 80°C for 1 hour. Heoctakis(n-butylthio)octafluorobanadylphthalocyanine (hereinafter abbreviated as νOPc (n-J3uS) a Fe).
Add 1.43 g (1 mmol!) and boil at reflux temperature for 2 hours.
Allowed time to react. After the reaction is complete, the solid content is poured into water and neutralized with dilute hydrochloric acid, separated by a furnace, and washed with water and methanol to form a dark green cake ν0Pc (n-BuS).
)e(EtO)a 1.23g (yield 75.1%)
I got it.

Elemental analysis theory Direct C: 58.69% H: 6.89%
N: 5.97% S: 13.66% F: 0.
00% analysis direct C: 5B, 52% H: 6.60
%N: 5.59%S:13.51%F:0
．． 00% absorption wavelength D, MP λwax: 760
nm coating λwax: 820nm solubility DMF 1.5% acetone
0.6wt% isopropyl alcohol 0.
3wt% Example 2 Synthesis of octakis(n-butylthio)octakis(n-butoxy)vanadyl phthalocyanine [VOPc(n-BuS)s(n-BuO)s] Sodium butoxide 1,92g (20a+mo
l ) and DMF30d were charged into a 100 cc tetra-Solo flask and stirred at 80°C for 1 hour. Then VOPc (
After adding 1.43 g (1 mmof) of sFs (n-BuS), the mixture was reacted at reflux temperature for 2 hours. After the reaction is completed, a dark green cake VOP is obtained by performing the same operation as in Example 1.
c (n-BuS) 5(n-BuO)s 1.62g
(yield: 86.3%).

Elemental analysis theoretical values C: 61.94% H: 7.80% N:
6.02% S: 13.78% F: 0.00% analysis value C: 62.08% H: 8.01% N: 6.1
5%S: 14.02%F: 0.00% absorption wavelength
λwax in DMF: 778.5% m Solubility DMF 2.8wt% acetone
2.0wt% isopropyl alcohol 1
．． 1wt% Example 3 Octakis(n-butylthio)octakis(2methoxyethoxy)vanadyl phthalocyanine [VOPc(n-B
uS) ai(2-MeO)EtOla] In Example 2, 1.96 g (2-methoxy) ethoxide was used instead of sodium n-butoxide.
A black gooseberry C (n-BuS)* was obtained by the same operation as in Example 2 except that 0 mmo I2)
((2-MeO)EtO)s L31g (yield 7
8.9%).

Theoretical values of elemental analysis C: 56.30% H: 6.87% N: 5.
97% S: 13.66% F: 0.00% Analysis value C: 56.61% H: 6.92% N:
6.05%S:I3.78%F: 0.00% absorption wavelength in DMF λwax: 795.5
r++w Solubility DMF 4.2wt% Acetone 2.8wt% Isopropyl alcohol 1.5wt% Example 4 Octakis(n-butylthio)octakis(2hydroxyethoxy)vanadyl phthalocyanine [VOPc(n-
Synthesis of BuS)s(2-)10EtO)sJ In Example 2, 1.68 g of sodium-2-hydroxyethoxide was used instead of sodium n-butoxide, and N,N-dimethylacetamide was used instead of DMF as the reaction solvent. A black cake sheet c(n-BuS)e(2-HO
11.25 g (yield 7], 1%) of EtO) was obtained.

Elemental analysis burial* (Ba! C: 54.68% H: 5.9
7% N: 6.38% S: 14.60%
F: 0.00% Analysis value C: 54.19% H: 6.03% N:
6.50% S: 14.71% F: 0.00% Absorption wavelength in DMF λvnax: 791
%m coating λ'1aX: 830%w + solubility DMF 3.1i% acetone
3.3wt% isopropyl alcohol 1.8
14.t% Example 5 Octakis(phenylthio)octakis(ethoxy)zinc phthalocyanine [ZnPc(PhS)s(EtO)s
] 2.72 g of synthetic sodium ethoxide and 59 g of pyridine 2° fluorozinc phthalocyanine were added and reacted under reflux conditions for 4 hours. After the reaction, the solvent was distilled off and washed with water and methanol to obtain a dark green cake, ZnP.
C(PhS)s(EtO)s 1.40g (yield 85
．． 5%).

Elemental analysis theoretical value C: 64.22% + 4.49% N: 6
．． 24%S: 14.28%: 0.00% Analysis value C: 64.12%: 4.51% N:
6.21%S:]3.91%:0.00% Absorption wavelength in DMF λwax: 755%
m coating λ ship ax: 810%m solubility DMF 1.1wt% acetone
1.2ivt% isopropyl alcohol 0.5
111t% Example 6 Octakis (0=methylphenylthio) Octakis (1
, 2-dimethylpropoquine) lead phthalocyanine [PbP
c(o-TolS)e (1,2-(!1e)Proo
Synthesis of 1 sJ In Example 2, 2.20 g of sodium-1,2-dimethylpropoxide was used instead of sodium ethoxide, and VOPc(n-BuS) 11F
(o-methylphenylthio)octafluorolead phthalocyanine (PbPc(o-TolS) 5F
It is abbreviated as ll. ) Black cake PbPc (o-T
olS)s (1,2-(Me)ProO) sl, 4
0 g (yield 76.2%) was obtained.

Elemental analysis theoretical values C: 65.80% H: 5.85% N: 4.51%
S: 10.33% F: 0.00% Analysis value C: 66.03% H: S, 98% N:
4.52% S: 10.57% F: 0.00% Absorption wavelength in DMF λwax: 781n
a+ Coating film λwax: 830ns Meltability D MF 1.8wt% acetone
1.4 imt% isopropyl alcohol 0.8 wt% Example 7 Octakis (n-butyl) octakis (2-fluorophenoxy) titanyl phthalocyanine [TjOPc (n
-BuS)s(2-FPhO)Il] Synthesis of 0-fluorophenol 4.23g, sodium hydroxide 1.60g
and benzonitrile 20d were charged into a 100cc four-cylinder flask and reacted at 80''C for 1 hour. Then, octakis(butylthio)octafluorotitanyl phthalocyanine TiOPC(BuS)BFg, 0.54
g was added and reacted at 180°C for 4 hours.

After the reaction, the solvent was distilled off and washed with methanol to form a dark green cake, Ti0PC(Bus)s(2-FPhO).
sl, 21 g (yield 74.4%) was obtained.

Elemental Analysis Theory Direct C: 66.91% H: 5.21%
N: 5.57% S: 12.76% F: 0
．． 00% analysis value C: 66.72% H: 5.14%
N: 5.48% S: I2.50% F: 0.00
% Absorption wavelength λ1Iax in DMF: 782
Ni coating λmax: 830nm solubility DMF 1.6wt% acetone
1.0wt% isopropyl alcohol 0.3
wt% Example 8 Octakis(n-butylthio)octakis(2-aminoethoxy)copper phthalocyanine [CuPc(n-Bu
Synthesis of e(2-Nl(JtO)*) In Example 5, 3.96 g of potassium-2-aminoethoxide was used instead of sodium ethoxide, quinoline was used instead of DMF as the solvent, and the reaction temperature was A black cake CuPc(n-BuS) e(2-NHJtO) a, 1 was prepared in the same manner as in Example 5 except that the temperature was 180°C.
．． 18 g (yield 76.4%) was obtained.

Elemental Analysis Theory 4IIC: 58.52% H: 7.37% N
: 6.82% S: 15.62% F: 0. OO% Analysis value C: 58.43% H: 7.24% N:
6.69%S: 15.48%F 20.00%
Absorption wavelength λwax in DMF: 773.
Snm coating λwax: 81Snm solubility DMF 2.1wt% acetone
1.6wt% isopropyl alcohol 0.
4wt% Example 9 Octakis(2-acetylethylthio)octakis(octyloxy)dichlorotinphthalocyanine [SnCl
2Pc (2-AcEtS) 1l(Oct,) e
] In Synthesis Example 2, 3.06+ g of sodium normal octoxide was used instead of sodium butoxide, and 1.70 g of octakis(2-acetylethylthio)octafluorodichlorotinphthalocyanine was used instead of VOPc (n-BuS)@Fg. A black cake of 5nCf was prepared in the same manner as in Example 2 except that 5nCf! ,zPc(2-AcEtS)s(OctO)
1.38 g (yield 71.6%) of a was obtained.

Elemental analysis theoretical values C: 60.41% H: 7.60% N:
4.40% S: 10.08% F: 0.00% analysis value C: 60.09% H: 7.43% N:
4.21% S: 10.12% F: 0.00% Absorption wavelength λwax in DMF: 762n
m Coating film λo+ax: 810nm solubility DMF 1.3wt% acetone
1.4wt% isopropyl alcohol 0
．． 5ht% Example 10 Octakis(benzylthio)octakis(cyclohexyloxy)aluminumchlorophthalocyanine [AfCfPc
Synthesis of (BzS)s(c-HexO)s In Example 1, 4.84 g of sodium cyclohexide was used instead of sodium ethoxide, and VOPc(n-BuS)s
Black cake A was prepared in the same manner as in Example 1 except that 1.55 g of octakis(benzylthio)octafluoroaluminiumchlorophthalocyanine was used instead of Fs.
I CI Pc (BzS) a (c-HexO)
*1.37g) (yield 80.2%) was obtained.

Elemental analysis theory 41 C: 69.40% H: 6.17%N
: 4.76%S:10.90%F+0. OO% Analysis value C: 69.56% H: 6.23% N: 4.
91%S: 11.02% F: o, oo% Absorption wavelength λwax + 7641 in DMF
1111 coating λWax: 810n
+++ Solubility DMF 1.8wt% Acetone 1. , ht% isopropyl alcohol 0.7wt% Example 11 Octakis(tert-butylthio)octakis(2-
diethylaminoethoxy)indium chlorophthalocyanine [TnCnPc(tert-BuS)s (2-(Et
), NEto 1 e], 5.56 g of sodium-2-diethylaminoethoxide was used instead of sodium ethoxide, and octakis(tert-butylthio)octafluoro was used instead of VOPc(n-BuS) and Fll. A black cake InCfPc(tert-BuS)e (2-(Et
)2NEtO) e 1.24g (yield 72.8%) Elemental analysis theoretical values C: 58.76% J(: 8.10% N: 9
．． 79% S: 11.20% F: 0.00% analysis direct C: 59.02% H: 8.14% N
: 9.88% S: 11.29% F: 0.00
% Absorption wavelength λwax in DMF: 768n
Coating film λwax: 805%m Solubility DMF 1.2wt% Acetone
1. Owt% isopropylar]-ru 0.5
wt% Example 12 Octakis(n-butylthio)bis(n-butoxy)hexafluorovanadylphthalocyanine [VOPc(n-
Synthesis of n-BuS)s(n-BuO)zFa] 1.48 g of normal butanol, 1.12 g of potassium hydroxide, and
Pour DMF20d into a 100cc four-eye flask and add 80
The reaction was carried out at ℃ for 1 hour. After that, VOPc(n-BuS
) 1.43 g of sFe was added and the reaction was continued at reflux temperature for further 10 hours. After the reaction is completed, the same operation as in Example 1 is performed to obtain a black cake VOPc(n-BuS)*(n-BuO)Jb 1.3
2g (yield: 86.8%) was obtained.

Elemental analysis theoretical values C: 56.86% H: 5.96% S: 16
．． 86% F: 7.49% analysis value C: 56.59
% H: 6.01% S: 16.58% F: 7.2
7% absorption wavelength λwax in DMF Coating film λsilver ax Solubility DMF Acetone Isopropyl alcohol N: 7.37% N: 7.18%: 752.5%m: 795%m 1.2wt% 0.6wt% 0.1wt %

Claims (9)

[Claims] (1) New phthalocyanine compound represented by the following general formula (I) ▲ Numerical formula, chemical formula, table, etc. are available ▼... (I) [In the formula, R_1 is a straight chain or branched alkyl group, alkoxyalkyl group, acyloxyalkyl group] group, or an alkyl group, an alkoxy group, or a phenyl group, a cycloalkyl group, or a benzyl group optionally substituted with a halogen (herein, R_1 may be the same or different), and at least one of R_2 is a straight-chain or branched alkoxy group, an alkoxyalkyloxy group, an acyloxyalkyloxy group, a hydroxyalkyloxy group, an aminoalkyloxy group, a cyanoalkyloxy group, an alkoxycarbonylalkyloxy group, a halogenated alkyloxy group, or an alkyl group, alkoxy group,
Represents an amino group, a substitutable secondary/tertiary amino group, a sulfonic acid group, or a phenyloxy group, a cycloalkyloxy group, or a benzyloxy group that may be substituted with a halogen (herein, R_2 may be the same or the same). may be different), the remaining R_2 represents F, M is Zn,
Cu, Pb, VO, TiO, TiX_2, SnX_2,
represents AlX or InX (where X represents a halogen atom)]. (2) A fluorine-containing phthalocyanine compound represented by the general formula (II) below, and ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) [In the formula, R_1 is a linear or branched alkyl group, an alkoxyalkyl group M is Zn, Cu, Pb, VO, TiO,
Represents TiX_2, SnX_2, AlX, or InX (where X represents a halogen atom). ]General formula R_
3OA (wherein R_3 is a straight chain or branched alkyl group,
Alkoxyalkyl group, acyloxyalkyl group, hydroxyalkyl group, aminoalkyl group, cyanoalkyl group, alkoxycarbonylalkyl group, halogenated alkyl group, or alkyl group, alkoxy group, amino group,
Represents a substitutable secondary or tertiary amino group, a sulfonic acid group, or a phenyl group, a cycloalkyl group, or a benzyl group that may be substituted with a halogen, A is hydrogen,
The following general formula (representing sodium or potassium) is reacted with alcosides, alcohols or phenols represented by the formula (representing sodium or potassium) in an organic solvent medium.
A method for producing a phthalocyanine compound shown in I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) [In the formula, R_1 is a linear or branched alkyl group, an alkoxyalkyl group, an acyloxyalkyl group, or is substituted with an alkyl group, an alkoxy group, or a halogen. represents a phenyl group, a cycloalkyl group, or a benzyl group (herein, R_1 may be the same or different), and at least one of R_2 is a linear or branched alkoxy group, an alkoxyalkyloxy group, or an acyloxy group. Alkyloxy group, hydroxyalkyloxy group, aminoalkyloxy group, cyanoalkyloxy group, alkoxycarbonylalkyloxy group, halogenated alkyloxy group, or alkyl group, alkoxy group,
Represents an amino group, a substitutable secondary/tertiary amino group, a sulfonic acid group, or a phenyloxy group, a cycloalkyloxy group, or a benzyloxy group that may be substituted with a halogen (herein, R_2 may be the same or the same). may be different), the remaining R_2 represents F, M is Zn,
Cu, Pb, VO, TiO, TiX_2, SnX_2,
represents AlX or InX (where X represents a halogen atom)]. (3) The method according to claim (2), wherein when A is hydrogen, the reaction is carried out in the presence of an alkaline substance. (4) Claim (2) wherein the organic solvent is at least one selected from the group consisting of aprotic polar solvents, acetonitrile, benzonitrile, quinoline, and pyridine.
Method described. (5) The method according to claim (3), wherein the alkaline substance is at least one selected from the group consisting of potassium hydroxide, potassium carbonate, sodium hydroxide, and sodium carbonate. (6) Fluorine-containing phthalocyanine compound and alkoxides, alcohols or phenols at a concentration of 30 to 250
3. The method according to claim 2, wherein the reaction is carried out at a temperature in the range of .degree. (7) The aprotic polar solvent is at least one selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, dimethylsulfone, sulfolane, and N-methyl-2-pyrrolidone. The method according to claim (4). (8) The method according to claim (6), wherein the reaction is carried out at a temperature in the range of 80°C to 2000°C. (9) A near-infrared absorbing material having absorption in the range of 700 to 1500 nm and containing a novel phthalocyanine compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) [In the formula, R_1 is a linear or branched alkyl group, an alkoxyalkyl group, an acyloxyalkyl group, or a substituted with an alkyl group, an alkoxy group, or a halogen. represents a phenyl group, a cycloalkyl group, or a benzyl group which may be Acyloxyalkyloxy group, hydroxyalkyloxy group, aminoalkyloxy group, cyanoalkyloxy group, alkoxycarbonylalkyloxy group, halogenated alkyloxy group, or alkyl group, alkoxy group,
Represents an amino group, a substitutable secondary/tertiary amino group, a sulfonic acid group, or a phenyloxy group, a cycloalkyloxy group, or a benzyloxy group that may be substituted with a halogen (herein, R_2 may be the same or the same). may be different), the remaining R_2 represents F, M is Zn,
Cu, Pb, VO, TiO, TiX_2, SnX_2,
represents AlX or InX (where X represents a halogen atom)].