JPH0423868A - Novel phthalocyanine compound and near infrared light absorbent using the same - Google Patents

Abstract

NEW MATERIAL:A compound of formula I [R1 is alkyl, alkoxyalkyl, (substituted)phenyl, benzyl, etc.; R2 is alkyl, cycloalkyl, (substituted)phenyl, benzyl, etc.; M is Zn, Cu, Pb, VO, TiX2 (X is halogen), SnX2, AlX3, InX]. EXAMPLE:Octakis(butylthio)-octakis(phenylthio)vanadylphthalocyanine. USE:A near IR light absorbent having high solubility in organic solvents. PREPARATION:A fluorine-containing phthalocyanine compound of formula II is made to react with a thio-alcohol or thio-phenol of the formula: R2SH in an inactive organic solvent preferably in the presence of an alkaline substance at 80-200 deg.C.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a novel phthalocyanine compound represented by the following general formula (I).
) [In the formula, R1 represents a linear or branched alkyl group, an alkoxyalkyl group, an acyloxyalkyl group, or a phenyl group, a cycloalkyl group, or a benzyl group which may be substituted with an alkyl group, an alkoxy group, or a halogen. (where R1 may be the same or different), R8 is a straight chain or branched alkyl group, cycloalkyl group, alkoxyalkyl group, acyloxyalkyl group, hydroxyalkyl group, aminoalkyl group, cyanoalkyl group, alkoxy a carbonyl alkyl group, a halogenated alkyl group, an alkyl group, an alkoxy group, an amino group, a substitutable secondary/tertiary amino group, a sulfonic acid group, or a phenyl group that may be substituted with a halogen, a cycloalkyl group, or represents a benzyl group (wherein R2 may be the same or different (, and M different from R is Zn, Cu, Pb, V
O, TiO, TiXz, 5nXt +Aj! X,
or InX (where X represents a halogen atom)].

The present invention also relates to a near-infrared absorbing material containing the phthalocyanine compound of the general formula (1) and having absorption in the near-infrared region.

The novel phthalocyanine compound according to the present invention has 700
It absorbs in the near-infrared region of n- to 1.500 nm and has excellent solubility, so it can be used as an optical recording medium using a semiconductor laser.
Near-infrared absorption dyes for writing or reading in liquid crystal display devices, optical character readers, etc., photothermal conversion agents for thermal transfer, thermal paper, thermal stencils, etc., near-infrared absorption filters, eye strain prevention agents, or photoconductivity It exhibits excellent effects when used as a material, etc.

[Conventional technology]

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 and reading in optical character readers, etc., and they are also used for photoconductive materials, near-infrared absorption filters, eye strain prevention agents, thermal transfer/thermal paper, thermal stencils, etc. There is an increasing demand for the development of substances that absorb near-infrared light as photothermal conversion agents, so-called near-infrared absorbing dyes. Among these, many phthalocyanine compounds have been studied because they are stable against light, heat, temperature, etc. and have excellent robustness.

However, most of them are insoluble in solvents, and in order to practically form a thin film of the dye, a process such as vapor deposition or dispersion in a resin is required.

Phthalocyanine compounds with practically advantageous solubility have recently been disclosed. For example, 3,6-octaalkoxyphthalocyanine (Japanese Unexamined Patent Publication No. 61-223056) has been disclosed, but it has insufficient absorption in the near-infrared region. In addition, the manufacturing process is complicated and it is difficult to obtain inexpensive phthalocyanine.

Also, JP-A-60-209583, JP-A-61-152
No. 685, No. 63-308073, No. 64-62
No. 361 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, JP-A-61-
In No. 152685, the phthalocyanine skeleton, especially 3.6-
A synthetic example is disclosed in which a thioether substituent is introduced at the position.

In this method, a phthalocyanine compound having a chlorine atom at the 3.6-position of the 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 substituent at the 3.6-position. However, both have yields of about 20 to 30% and have problems in production efficiency.

JP-A-60-209583, JP-A No. 61-152685
No. 64-62361 discloses a synthetic example in which 8 to 16 polythioether substituents are introduced into a phthalocyanine skeleton.

The method involves heating a phthalocyanine compound and an organic thiol compound having 8 to 16 chloro and/or bromine atoms in a quinoline solvent in the presence of KOB to convert the benzene nucleus of the phthalocyanine skeleton into 8 Phthalocyanines with ~16 thioether substituents are obtained. However, like the above-mentioned ones, the yield is about 20 to 30% and there is a problem in production efficiency. That is, the yield is low due to poor substitutability of the chlorine atom or bromine atom to the thioether substituent.
For example, unreacted phthalocyanine in which no chlorine atoms are substituted with thioether substituents or unreacted phthalocyanine in which some chlorine atoms are substituted with thioether substituents is produced. It is practically difficult to separate these unreacted phthalocyanine and the target substance phthalocyanine from each other, and therefore, in reality, only a mixture of phthalocyanines of various compositions can be obtained. In fact, in JP-A No. 64-62361, it is described as a polythiol-substituted mixed condensation type phthalocyanine composition even after separation using a silica gel column, indicating that unreacted phthalocyanine compositions remain.

Note that if some chlorine 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-63-308073, a thioether substituent is introduced by heating monobromotetradecachlorophthalocyanine and an organic thiol mixture of 2-aminothiophenol and 4-methylphenylthiol in the presence of KOJI in a DMF solvent. Phthalocyanine is obtained with a yield of 42%. However, in these methods, different organic thiol mixtures are simultaneously added and reacted, so phthalocyanine mixtures having various combinations of thioether substituents are obtained, which makes it difficult to use a single product as a near-infrared absorbing dye. There is a problem that the properties are not 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, an object of the present invention is to provide a novel substituted phthalocyanine compound that has absorption in the near-infrared region and has excellent solubility.

[Means to solve the problem]

The present inventors have developed a compound that satisfies the above objectives by reacting a phthalocyanine compound having fluorine atoms at the 3 and 6 positions of the phthalocyanine skeleton and thioether substituents at the 4 and 5 positions with a thioalcohol or a thiophenol. The present invention was completed by discovering that the present invention can be obtained.

That is, the novel phthalocyanine compound of the present invention (the following general formula I) is, for example, a fluorine-containing phthalocyanine compound represented by the following general formula (If) and... (n) [wherein 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, an alkyl group, or a benzyl group which may be substituted with a halogen, where R1 may be the same or different) ,M
is Zn, Cu.

Pb, VO+ TiO+ TiXz r 5nXz
+A Represents IL or InX (where X represents a halogen atom),] general formula R, SR (wherein R2 is a linear or branched alkyl group, an alkoxyalkyl group, an acyloxyalkyl group, a hydroxyalkyl group, Substituted with an aminoalkyl group, a cyanoalkyl group, an alkoxycarbonylalkyl group, a halogenated alkyl group, or an alkyl group, an alkoxy group, an amino group, a substitutable secondary/tertiary amino group, a sulfonic acid group, or a halogen. thioalcohols or thiophenols represented by a phenyl group, a cycloalkyl group, or a benzyl group) in an inert organic solvent medium, preferably an aprotic polar solvent, benzonitrile, acetonitrile, quinoline and Pyridine (both in one medium, preferably in the presence of an alkaline substance, preferably KOH, KJO, etc.) selected from the group consisting of pyridine.

In the presence of at least one selected from the group consisting of NaOH and Hai, os, preferably from 30°C to 250°C
It can be efficiently produced by heating and reacting, more preferably at a temperature in the range of 80° to 200°C. still,
The method for synthesizing the novel phthalocyanine compound of the present invention is not limited to the above method.

Furthermore, the present invention provides a near-infrared compound containing a phthalocyanine compound represented by the following general formula (1), which has absorption in the near-infrared region of 700 nm to 1500 nm and has excellent solubility. Provide absorbent material.

・ ・ ・ ・ (1) [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 or cycloalkyl group that may be substituted with a halogen. , or a benzyl group (wherein R1 may be the same or different), R2 is a linear or branched alkyl group, an alkoxyalkyl group, an acyloxyalkyl group, a hydroxyalkyl group, an aminoalkyl group, a cyanoalkyl group, Alkoxycarbonylalkyl group, halogenated alkyl group or alkyl group, alkoxy group, amino group, substitutable 2
grade/tertiary amino group, sulfonic acid group, or phenyl group optionally substituted with halogen, cycloalkyl group,
or a benzyl group, where each 6 may be the same or different, and is different from R8), M is Zn
, Cu, Pb, VO.

TiOITiXz, SnX, , Aj! X, or InX (where X represents a halogen atom)].

In the novel phthalocyanine represented by the general formula (1), which is a compound of the present invention, specific examples of the linear or branched alkylthio group in the group represented by R and S 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 which may be substituted with an alkyl group, alkoxy group or halogen include phenylthio, 0-methylphenylthio, p-methylphenylthio, 2,4-dimethylphenyl Thio, 2,3-dimethylphenylthio, 2,6-dimethylphenylthio, 0
-Fluorophenylthio, methoxyphenylthio≠,
p-ethoxyphenylthio, 2-cyclohexylthio,
Examples include 3-cyclohexylpropylthio and benzylthio. Specific examples of linear or branched alkylthio groups in the group represented by R and S include methylthio, ethylthio, n-propylthio, iso-propylthio, n-butylthio, 1so-butylthio, ter
Examples include straight-chain or branched alkylthio groups having 1 to 20 carbon atoms, such as t-butylthio, n-pentylthio, 1,2-dimethylpropylthio, hexylthio, heptylthio, octylthio, and nonylthio. Specific examples of the cyanoalkylthio group include cyanomethylthio, cyanoethylthio, etc., and specific examples of the hydroxyalkylthio group include, for example, hydroxymethylthio, 2-hydroxypropylthio, and the like. Specific examples of aminoalkylthio groups include aminomethylthio, 2
-aminoethylthio, 3-aminobutylthio and the like. Specific examples of acyloxyalkylthio groups include:
Examples of acetyloxyethylthio, propionyloxyethylthio, etc., specific examples of alkoxycarbonylalkylthio groups include methoxycarbonylmethylthio, ethoxycarbonylethylthio, butoxycarbonylpropylthio, etc., and specific examples of halogenated alkylthio groups. Examples include trifluoromethylthio, and alkyl groups, alkoxy groups,
Specific examples of amino groups, substitutable secondary and tertiary amino groups, sulfonic acid groups, or phenylthio groups optionally substituted with halogen, cycloalkylthio groups, or benzylthio groups include phenylthio, 0-methylphenylthio, etc. , P-methylphenylthio, 2,4-dimethylphenylthio, 2,3-dimethylphenylthio, p
-sulfonylphenylthio, 0-fluorophenylthio, p-fluorophenylthio, 2.3.5.6-titrafluorophenylthio, 0-methoxyphenyl, p-
Methoxyphenylthio, P-ethoxyphenylthio, 0
-aminophenylthio, p-aminophenylthio, 0-
Dimethylaminophenylthio, p-dimethylaminophenylthio, 2-cyclohexylthio, 3-cyclohexyl-2methylpropylthio, benzylthio, and the like.

In the present invention, the fluorine-containing phthalocyanine (the above general formula (2)), which 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.
-103554, Japanese Patent Application No. 1-103555, and Japanese Patent Application No. 1-209599.

(First Step) (Second Step) (Third Step) [Effects of the Invention] Compared to conventionally known phthalocyanine compounds, the novel phthalocyanine compound of the present invention has a higher resistance to dimethylformamide, tetrahydrofuran, ketones, alcohols, etc. This is because it has high solubility in organic solvents and absorbs near infrared rays from TOO to 1500 nm.

Nakai Main Example 1 Octakis(butylthio)-octakis(phenylthio)vanadyl phthalocyanine (VOPc (BuS) m (PhS) s
) Synthesis of n-butanethiol 2.74 g (32 wm
3.58 g of potassium hydroxide (64smoj
and dimethylformamide (DMF) 30
wan was placed in a 100cc 4-turopor flask and reacted at 80°C for 1 hour.

Then octafluoro-octakis (phenylthio)
Vanadyl phthalocyanine (VOPc(PhS)sFs
) 3.18g (2smoffi) was added under reflux conditions (
ref) After the 11-hour reaction, the reaction product was placed in water, the resulting appetizer was heated, and then washed with methanol to obtain the target black cake VOPc (BuS).
Obtained 4.32 g of m(PhS)s (yield 86.8%)
Absorption wavelength in DMF 813 rv Coating film 860 nm Solubility DMF 1.5 kt% Acetone 1.2 kt% Elemental analysis value CIIN SF Theoretical value α) 62,57 5.25 5.21 23
．． 86 0.00 Analysis value (χ) 62.06 5.5
1 5.89 23.20 0.00 Examples 2 to 25 General formula R instead of n-butanethiol in Example 1
Using thiophenol or thioalcohol with R2 shown in Tables 1 and 2 in 15R, V in Example 1
In place of OPc (BuS) s (PhS) m, fluorine phthalocyanine containing R1 and the central metal shown in Tables 1 and 2 in the general formula (I) was used in the amounts shown in Tables 1 and 2, and the hydroxylation of Example 1 was carried out. The general formula (1 ) were obtained with the yields shown in Tables 1 and 2. R, , R, and phthalocyanines with central metals shown in Tables 1 and 2 were obtained in the yields shown in Tables 1 and 2.

Further, the physical properties of these obtained phthalocyanines are shown in Tables 3 and 4.

Examples 26-28 General formula R instead of n-butanethiol in Example 1
, SH using thiophenol or thioalcohol with R2 shown in Table 5, VOP in Example 1.
In place of c(PhS)aFsO, a fluorophthalocyanine containing R8 shown in Table 5 and a central metal in the general formula (It) was used in the amount shown in Table 5, and in place of potassium hydroxide in Example 1, an alkaline compound shown in Table 5 was used. The reaction conditions of Example 1 were changed to the reaction conditions shown in Table 5, except for changing the reaction conditions of Example 1 to the reaction conditions shown in Table 5. Phthalocyanine was obtained in the yield shown in Table 5.

Further, the physical properties of these obtained phthalocyanines are shown in Table 6.

Example 29 Synthesis of octakis(phenylthio)-octakis(0-aminophenylthio) vanadylgaphthalocyanine [VOPc(0-NHzPhS)a(PhS)s)
0-aminothiophenol 0.40 g (3,15m
n+ofI potassium hydroxide 0.35 g (6,3 mm
of ), and DMF 15 tar! 100c
The mixture was placed in a C4 Tulo flask and reacted at 80°C for 1 hour.

Then VOPc (PhS) Jsl g (0,63mm
of) and allowed to react under reflux conditions for 11 hours. After the reaction, the reaction mixture was poured into water, neutralized with dilute HCf aqueous solution, solids were filtered and washed with water and methanol to obtain a black cake (VOPc (0-NHzPhS)).
s(PhS)s ) 1.06 g (yield 75.5%)
I got it.

Absorption wavelength λ-, x in DMF: 910 nm Coating film λ-x: 11010n Solubility DMF 1.5 t% Acetone 1.2% 1t% Elemental analysis value CFIN SF Theoretical value (χ) 63.26 3.65 9.22 2
1.11 0.00 Analysis value (χ) 64.01 3.
92 9.02 20.98 0.00 Example 30-4
1 In place of 0-aminothiophenol in Example 29, thiophenol or thioalcohol with the general formula 1hSH changed to R2 shown in Table 7 was used, and in place of VOPc (PhS) *Fs in Example 29, general formula (I
In I), R and S shown in Table 7 and fluorine-containing phthalocyanine as a central metal were used in the amounts shown in Table 7, and Example 29
The reaction in general formula (1) was carried out in the same manner as in Example 29, except that the amount of potassium hydroxide charged was changed to the amount shown in Table 7, and the reaction conditions of Example were changed to the reaction conditions shown in Table 7. The R+, Rz and central metal phthalocyanine shown in Table 7 were obtained in the yield shown in Table 7.

Further, the physical properties of these obtained phthalocyanines are shown in Table 8.

Example 42 Octakis(benzylthio)octakis(
Synthesis of cyclohexylthio)zinc phthalocyanine 2.38 g of cyclohexyl mercaptan, 1.12 g of potassium hydroxide and 20s+j of pyridine! was charged into a Yotsuro flask and reacted at 80°C for 1 hour.

Then octafluorooctakis(benzylthio)zinc phthalocyanine (ZnPc(BzS)sFs) 1.
After the completion of the reaction, the mixture was poured into benzene to separate out the precipitated potassium hydroxide, and the solvent was distilled off and washed with methanol to form a black cake of the above compound. 1.25g (yield 73
．． 7%).

Absorption wavelength 768.5 nm in DMF Coating film 815 ns+ Solubility DMF 2.4 wt% Acetone 2.2 t% Elemental analysis value CHN SF Theoretical value (χ) 66.12 5.8? 4.54
20.76 0.00 Analysis value (χ) 65.58 6
．． 0B 4.24 20.18 0.00 Example 43
-48 In place of cyclohexyl mercaptan in Example 42, thiophenol or thioalcohol with general formula R, SH changed to R2 shown in Table 9 was used, and in place of ZnPc(BzS)sFs in Example 42, general formula ( II
), R3 shown in Table 9 and fluorine-containing phthalocyanine with a central metal were used in the amounts shown in Table 9, the pyridine of Example 42 was replaced with the solvent shown in Table 9, and Example 4
Except for changing the reaction conditions of 2 to the reaction conditions shown in Table 9, the same procedure as in Example 42 was carried out to prepare R1 + Rz shown in Table 9 and the central metal phthalocyanine in general formula (If) at the yield shown in Table 9. Obtained.

Further, the physical properties of these obtained phthalocyanines are shown in Table 1O.

Claims (2)

[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 which may be substituted with a halogen (here, R_1 may be the same or different), and R_2 is a straight chain or Branched alkyl group, cycloalkyl group, alkoxyalkyl group, acyloxyalkyl group, hydroxyalkyl group, aminoalkyl group,
cyanoalkyl group, alkoxycarbonylalkyl group,
A halogenated alkyl group, an alkyl group, an alkoxy group, an amino group, a substitutable secondary/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. Expression (here, R_2 may be the same or different, and R
_1), M is Zn. Cu, Pb, VO, TiO, TiX_2, SnX_2,
Represents AlX or InX (where X represents a halogen atom). ]. (2) Near-infrared absorbing material containing a new phthalocyanine compound represented by the following general formula (I) and having absorption in the range of 700 to 1500 nm ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ ... (I) [In the formula, R_1 represents a linear or branched alkyl group, an alkoxyalkyl group, an acyloxyalkyl group, or a phenyl group, a cycloalkyl group, or a benzyl group that may be substituted with an alkyl group, an alkoxy group, or a halogen ( Here, R_1 may be the same or different, respectively), R_2 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 (here, R_
2 may be the same or different and different from R_1), M is Zn, Cu, Pb, VO, TiO, TiX
_2, SnX_2, AlX, or InX (where X
represents a halogen atom). ].