JP2002114790A - Method for purifying phthalocyanine compound and naphthalocyanine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method capable of purifying a phthalocyanine compound and a naphthalocyanine compound into compounds having very small amounts of impurities which cause unnecessary absorptions except the maximum absorption and bring about reduction in mol absorptivity by effectively removing the impurities produced as by-products in a reaction process for producing a phthalocyanine compound and a naphthalocyanine compound. SOLUTION: This method for purifying a phthalocyanine compound and a naphthalocyanine compound comprises purifying a phthalocyanine compound and/or a naphthalocyanine compound with a mixed solution of a polar solvent having >=8 (cal.cm-3)1/2 solubility parameter at 25 deg.C and water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel method for purifying phthalocyanine compounds and naphthalocyanine compounds. In particular, the present invention relates to a method for purifying a phthalocyanine compound and a naphthalocyanine compound having high solubility in a solvent.

The phthalocyanine compound and the naphthalocyanine compound obtained by the method of the present invention have a small content of impurities which cause unnecessary absorption other than the maximum absorption and a decrease in the molar extinction coefficient. Since absorption is significantly suppressed and has a high molar extinction coefficient, near-infrared absorbing dyes for writing or reading in optical recording media using semiconductor lasers, liquid crystal display devices, optical character readers, etc. External sensitizer,
Light-to-heat conversion agents such as thermal transfer, thermal paper / thermosensitive stencil, near-infrared absorbing filter for plasma display (PDP), near-infrared absorbing material used as eye strain inhibitor, photoconductive material, etc. Color separation filters to be used, color filters for liquid crystal displays, color CRT selective absorption filters, color toners, dyes for flash fixing toners, inkjet inks, barcode inks for preventing tampering and counterfeiting, near infrared absorption inks, positioning of photographs and films Marking agents for use, goggle lenses and shielding plates, dyeing agents for sorting plastic recycling, preheating aids for PET bottle molding, microbial deactivators, photosensitive dyes for tumor treatment , Furthermore, heat ray shading agent for automobiles or building materials, and further resin classification It is intended to exhibit an excellent effect when used as a discrimination material.

[0003]

2. Description of the Related Art The need for near-infrared absorbing dyes has been increasing as their fields of use have expanded, and they have been required for writing or reading in optical recording media using semiconductor lasers, liquid crystal displays, optical character readers, and the like. Near-infrared absorbing dyes, near-infrared sensitizers, thermal transfer, light-to-heat conversion agents such as thermal paper / thermosensitive stencils, near-infrared absorbing filters, anti-eye strain agents, and near-infrared absorbing materials used as photoconductive materials Or color separation filters used in image pickup tubes, color filters for liquid crystal displays, color CRT selective absorption filters, color toners, inkjet inks, barcode inks for preventing tampering and counterfeiting, near infrared absorption inks, for positioning of photographs and films Marking agents, sorting of goggle lenses and shielding plates, and plastic recycling Dyes, preheating aids for PET bottle molding, microbial deactivators, photosensitive dyes for tumor treatment, and near-infrared absorbing dyes used as heat-ray shielding agents for automobiles or building materials. There is a strong demand for a material having a small amount of unnecessary absorption other than the maximum absorption and a high molar extinction coefficient, and many methods for producing materials such as compounds satisfying such characteristics have been reported.

[0004] For example, phthalocyanine compounds and naphthalocyanine compounds have long and complicated reaction steps in their production, so that it is difficult to prevent the contamination of impurities, and these impurities cause unnecessary absorption other than the maximum absorption. In addition, this causes a decrease in the molar extinction coefficient.

[0005] As described above, no effective purification method for obtaining such a material has been found, and as a result, a material which sufficiently satisfies the above-mentioned properties cannot be obtained.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention has been made in view of the above-mentioned problems, and has an effect of reducing impurities produced as a by-product during a reaction step in producing a phthalocyanine compound and a naphthalocyanine compound. It is intended to provide a method capable of purifying even a phthalocyanine compound and a naphthalocyanine compound, which cause unnecessary absorption other than the maximum absorption and thereby cause the reduction of the molar extinction coefficient, and contain very few impurities. .

Another object of the present invention is to provide an optical recording medium using a semiconductor laser, a liquid crystal display, a near-infrared absorbing dye, a near-infrared sensitizer, a light-to-heat converting agent for thermal transfer, a near-infrared absorbing filter, and the like. Near-infrared absorbing material, color separation filter, liquid crystal display color filter, optical color filter, plasma display color filter,
Color CRT selective absorption filter, color toner,
Phthalocyanine compounds and naphthalocyanine compounds having a high molar extinction coefficient with little unnecessary absorption other than maximum absorption, which can be used in various fields including ink-jet inks and the like, can be used on an industrial scale as well as on a laboratory scale. It is intended to provide a method which can be purified in a very low yield and in a substantially pure form.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above objects, and as a result, have been able to remove both oil-soluble and water-soluble impurities and to obtain a high yield of the target product. In order to obtain, a single organic solvent was found to be unsuitable as a solvent used in the purification of phthalocyanine compounds and naphthalocyanine compounds, and as a result of further intensive studies, it was found that the solubility parameter at 25 ° C. Is 8
A mixed solution containing a polar solvent and water (cal · cm ⁻³ ) ^1/2 or more has a solubility in water of phthalocyanine compound and naphthalocyanine compound, particularly 10 to 30 ° C. of 1.0.
It has been found that it is suitable for purification of a phthalocyanine compound and a naphthalocyanine compound having a content of not more than mass%. Based on these findings, the present invention has been completed.

That is, the present invention provides the following (1) to
This is achieved by (7).

(1) Purifying a phthalocyanine compound and / or a naphthalocyanine compound with a mixture containing a polar solvent and water having a solubility parameter at 25 ° C. of 8 (cal · cm ⁻³ ) ^1/2 or more. A method for purifying a phthalocyanine compound and a naphthalocyanine compound.

(2) The purification method according to (1), wherein the polar solvent is not separated from water when mixed with water but is mixed with water to give a uniform solution.

(3) The purification step according to (1) or (2), wherein the phthalocyanine compound and / or naphthalocyanine compound is mixed with a polar solvent, and then water is further added to the mixed solution. Purification method.

(4) The refining step comprises mixing a polar solvent miscible with water and water in advance and adding a phthalocyanine compound and / or a naphthalocyanine compound to the mixed solvent. The purification method according to (2).

(5) The phthalocyanine compound and / or naphthalocyanine compound has a solubility in water at 10 to 30 ° C. of 1.0% by mass or less.
The purification method according to any one of (4).

(6) The purification method according to (5), wherein the polar solvent is at least one selected from the group consisting of isopropyl alcohol, acetone, acetonitrile, methanol, ethylene glycol monoethyl ether and tetrahydrofuran.

(7) The purification method according to (6), wherein the polar solvent is at least one selected from the group consisting of isopropyl alcohol, acetone and acetonitrile.

(8) The above (1) to (7), wherein the volume ratio of water to the total volume of the polar solvent and water is 0.5 or less.
The purification method according to any one of the above.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION A method for purifying a phthalocyanine compound and a naphthalocyanine compound according to the present invention comprises a polar solvent having a solubility parameter at 25 ° C. of 8 (cal · cm ⁻³ ) ^1/2 or more (in the present specification, , A phthalocyanine compound and / or a naphthalocyanine compound are purified using a mixed solution containing water (hereinafter, also simply referred to as a “mixed solution”) containing water and a “polar solvent”. Things. The method of the present invention comprises dissolving a phthalocyanine compound and / or a naphthalocyanine compound in a polar solvent having a specific solubility parameter,
The phthalocyanine compound and / or naphthalocyanine compound is precipitated with almost no impurities in the coexistence of water, and is particularly preferably used for purification of a phthalocyanine compound and a naphthalocyanine compound having low solubility in water. Therefore, this method efficiently removes both oil-soluble and water-soluble impurities by-produced during each reaction in the industrial production process of useful phthalocyanine compounds and naphthalocyanine compounds that can be used for various applications. Thus, the desired phthalocyanine compound and naphthalocyanine compound can be obtained with high purity and high yield, and at an industrial level. In addition to the above advantages, the phthalocyanine compound and naphthalocyanine compound thus purified are:
Since it hardly contains impurities that cause unnecessary absorption other than the maximum absorption or lowers the molar absorption coefficient, it has little unnecessary absorption other than the maximum absorption and has a high molar absorption coefficient. Optical recording media using lasers, liquid crystal display devices, near-infrared absorbing dyes for writing or reading in optical character readers, near-infrared sensitizers, thermal transfer, photothermal conversion agents such as thermal paper and thermal stencils, Near infrared absorption filter for plasma display (PDP), near-infrared absorption material used as eye strain inhibitor, photoconductive material, or color separation filter used for image pickup tube, color filter for liquid crystal display, color cathode ray tube selection Absorption filter, color toner, dye for flash fixing toner, ink for ink jet, tamper Barcode ink for anti-fabrication, near-infrared absorbing ink, marking agent for photo and film positioning, goggle lens and shielding plate, dyeing agent for sorting plastic recycling, and pre-processing for PET bottle molding. It can be suitably used as a heating aid, a microbial deactivator, a photosensitive dye for treating tumors, a heat ray shielding agent for automobiles or building materials, and a resin classifier.

Hereinafter, the present invention will be described in detail.

The polar solvent that can be used in the purification method of the present invention is not particularly limited as long as it has a solubility parameter (25 ° C.) of 8 (cal · cm ⁻³ ) ^1/2 or more. Polar solvents can be used,
What mixes with water and does not separate at the time of mixing but presents a uniform solution is preferable. Considering the degree of mixing with water and purification (washing) efficiency, 8.5 to 15 (calcm)
^-3 ) ^1/2 , more preferably 9.0 to 14.6 (cal ·
It preferably has a solubility parameter (25 ° C.) of cm ⁻³ ) ^1/2 . At this time, if the solubility parameter (25 ° C.) of the polar solvent is less than 8 (cal · cm ⁻³ ) ^1/2 , the polar solvent and water do not mix well, impurities cannot be removed efficiently, and If the phthalocyanine compound and / or naphthalocyanine compound cannot be efficiently purified (washed) and the polar solvent and water are not mixed well, the phthalocyanine compound and / or naphthalocyanine compound dissolved in the polar solvent Since precipitation due to coexistence does not occur, the yield is significantly reduced, which is not preferable.

As such a polar solvent, for example, a
Seton (solubility parameter at 25 ° C .: 9.71 (c
al.cm^-3)^1/2), Acetonitrile (dissolved at 25 ° C)
Resolution parameter: 11.8 (cal · c)
m^-3)^1/2), Ethylene glycol monomethyl ether
(Solubility parameter at 25 ° C .: 10.8 (cal ·
cm^-3)^{1 / Two}), Ethylene glycol monoethyl ether
(Solubility parameter at 25 ° C .: 9.9 (cal ·
cm^-3)^1/2), Ethylene glycol diethyl ether
(Solubility parameter at 25 ° C .: 8.3 (cal · c
m^-3)^1/2), Methanol (solubility parameter at 25 ° C)
Tar: 14.5 (calcm)^-3)^1/2),ethanol
(Solubility parameter at 25 ° C .: 12.9 (cal ·
cm^-3)^1/2), Propanol (solubility para at 25 ° C)
Meter: 12.18 (calcm)^-3)^1/2), Iso
Propyl alcohol (solubility parameter at 25 ° C .:
11.5 (calcm^-3)^1/2), Tert-butano
(25 ° C. solubility parameter: 10.9 (ca)
lcm^-3)^1/2), Tetrahydrofuran (at 25 ° C)
Solubility parameter: 9.317 (calcm^-3)
^1/2), 1,4-dioxane (solubility parameter at 25 ° C)
Data: 10.13 (calcm)^-3)^1/2) And pil
Gin (solubility parameter at 25 ° C .: 10.62 (c
al.cm^-3)^1/2) And the like. These polar solvents
The medium may be used alone or as a mixture of two or more.
It may be used in the form of
In consideration of the process, it is preferable to use it alone. This
Of these, isopropyl alcohol, acetone,
Tonitrile, methanol, ethylene glycol monoethylene
Ether and tetrahydrofuran; especially isopropyl
Alcohol, acetone and acetonitrile are polar solvents
It is preferably used.

In the present invention, the water is not particularly limited, and includes tap water, pure water, ion-exchanged water, distilled water, deionized water, industrial water, and filtered water.
Of these, ion-exchanged water and distilled water are preferably used because it is easy to prevent contamination of impurities. However, even if tap water is used, there is no problem in cleaning efficiency and subsequent filterability. In consideration of the above, a method using tap water is also effective.

In the present invention, it is essential that the mixture contains a polar solvent and water, but other components may be used. At this time, the total mass concentration of the polar solvent and water in the mixture is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and most preferably
90 to 100% by mass.

In the purification method of the present invention, the mixing ratio of the polar solvent and water depends on the type of the polar solvent and water used, the desired properties of the phthalocyanine compound and the naphthalocyanine compound to be purified (for example, other than the maximum absorption). The optimum mixing ratio varies depending on the absorption, the molar extinction coefficient, the solubility in the polar solvent to be used, etc., and is not particularly limited, but the ratio of the volume of water to the total volume of the polar solvent and water is 0.1%. It is preferably 5 or less, more preferably 0.1 to 0.3, and most preferably 0.15 to 0.25. At this time, if the mixing ratio of water exceeds 0.5,
The efficiency of removing oil-soluble impurities is reduced. As a result, the purification (washing) efficiency of the target substance is reduced. Further, the target substance is purified with a mixed solution containing a polar solvent and water, and then filtered for separation. Although a step is provided, the filtration efficiency also decreases. If the ratio of water is too small, the efficiency of removing water-soluble impurities is reduced, and the phthalocyanine compound and the naphthalocyanine compound are dissolved in a large amount in the mixed solution. It is not preferable because it causes a reduction in the rate.

The purification method of the present invention essentially requires the use of a mixed solution containing a polar solvent and water. However, the step of purifying a phthalocyanine compound and / or a naphthalocyanine compound using a mixed solution containing a polar solvent and water is particularly required. There is no restriction. For example, (a) a step of mixing a phthalocyanine compound and / or a naphthalocyanine compound with a polar solvent and then adding and mixing water to the mixed solution or adding and mixing the mixed solution to water; Mixing a polar solvent miscible with water and water and adding and mixing a phthalocyanine compound and / or a naphthalocyanine compound to the mixed solvent or adding and mixing the mixed solvent to the phthalocyanine compound and / or the naphthalocyanine compound; And a step in which the above steps (A) and (A) are appropriately combined. In this case, the step (A) has an advantage that the particle diameter of the target purified compound becomes fine, and the washing efficiency can be improved. In the step (a), although the washing efficiency is slightly reduced, the particle size of the target purified compound is increased,
Therefore, the subsequent filtration step becomes easy and the filterability becomes very good, and this is an effective method in view of industrial efficiency.

In the purification (washing) steps (A) and (A), these steps may be repeated until a desired purity is obtained. The purification conditions in the process may be the same or different. In addition, the number of steps in such a case is not particularly limited as long as a desired purity can be achieved, and varies depending on the type and amount of the phthalocyanine compound, naphthalocyanine compound, polar solvent and water used, purification conditions, and the like, and is not particularly limited. No, but usually
It is 1 to 5 times, preferably 2 to 3 times. When the process is repeated, the process may be repeated as it is,
As the volume of the product to be purified increases, it is necessary to increase the size of equipment required for the next purification process, and the operation becomes complicated and complicated.
In consideration of efficiency, it is preferable to provide a filtration step between each step to remove impurities, and then perform any of the above-mentioned purification steps on the residue after filtration.

In any of the above (a) and (b) purification (washing) steps, the state of the phthalocyanine compound and / or naphthalocyanine compound mixed with the polar solvent or the mixed solution of the polar solvent and water is particularly limited. For example, (a) a phthalocyanine compound and / or
Or (b) filtering and centrifuging after synthesizing the phthalocyanine compound and / or the naphthalocyanine compound after the synthesis of the naphthalocyanine compound;
(C) converting the powdered phthalocyanine compound and / or naphthalocyanine compound obtained in (b) into a suitable solvent (eg, chloroform, toluene, etc.) , Tetrahydrofuran, benzonitrile, benzylamine, dimethylformamide, etc.). Of these, when the phthalocyanine compound and / or naphthalocyanine compound is in a powder state as in (b) above, the cleaning effect can be obtained only near the surface of the particles, and thus the above (a) and (c) ), The phthalocyanine compound and / or naphthalocyanine compound is preferably in a solution state.

In the purification (washing) step (a),
The method of mixing the polar solvent with the phthalocyanine compound and / or the naphthalocyanine compound is not particularly limited as long as the polar solvent and the phthalocyanine compound and / or the naphthalocyanine compound are mixed well. For example, when the phthalocyanine compound and / or naphthalocyanine compound is in a solution state as in the above (a) and (c), the phthalocyanine compound and / or
Alternatively, the naphthalocyanine compound solution may be added or mixed in the polar solvent all at once or continuously by dropping, or the polar solvent may be added to the phthalocyanine compound and / or
Alternatively, they may be added or mixed all at once or dropwise into the solution of the naphthalocyanine compound, and the order of adding the polar solvent and the phthalocyanine compound and / or the naphthalocyanine compound is not particularly limited. Considering the purification (washing) efficiency, the polar solvent is continuously added dropwise to the solution of the phthalocyanine compound and / or the naphthalocyanine compound, for example.
After mixing, a method of adding and mixing water into the mixed solution is particularly preferred because of its high washing effect. When the phthalocyanine compound and / or naphthalocyanine compound is in a powder state as in (b) above, the phthalocyanine compound and / or naphthalocyanine compound is added to the polar solvent all at once or continuously in small amounts. -Even after mixing, or after previously charging the phthalocyanine compound and / or naphthalocyanine compound in the washing container,
The polar solvent may be added and mixed, and the order in which the polar solvent and the phthalocyanine compound and / or naphthalocyanine compound are added is not particularly limited,
In consideration of purification (washing) efficiency, a method of continuously adding and mixing a small amount of a phthalocyanine compound and / or a naphthalocyanine compound in a polar solvent, and further adding and mixing water in the mixed solution, is a method of uniform washing. It is preferable because an effect can be obtained.

In the purification (washing) step (a), the polar solvent and the phthalocyanine compound and / or naphthalocyanine compound may be mixed with stirring so that the mixing can be performed better and more uniformly. desirable. In addition, the mixing time is not particularly limited as long as the time is such that the impurities can be efficiently removed by uniform mixing, but in the case of mixing with a polar solvent, 10 to 90 minutes, more preferably 30 to 60 minutes, In the case of the following mixing with water, the time is preferably 10 to 90 minutes, more preferably 30 to 60 minutes.

In the purification (washing) step (a),
The method of mixing the mixed solvent of the polar solvent and water and the method of mixing the phthalocyanine compound and / or the naphthalocyanine compound are not particularly limited, and the order of adding the mixed solvent and the phthalocyanine compound and / or the naphthalocyanine compound is not particularly limited. Specifically, when the phthalocyanine compound and / or naphthalocyanine compound is in a solution state as in the above (a) and (c), the solution of the phthalocyanine compound and / or naphthalocyanine compound is mixed with a polar solvent and water. It can be added or mixed all at once in a solvent or continuously by dropping, or a mixed solvent of a polar solvent and water can be continuously or batchwise dropped into a solution of a phthalocyanine compound and / or a naphthalocyanine compound. May be added or mixed. Among these, in consideration of purification (washing) efficiency, a method of continuously adding and mixing a solution of a phthalocyanine compound and / or a naphthalocyanine compound into a mixed solvent of a polar solvent and water by dropping or the like is preferable. When the phthalocyanine compound and / or naphthalocyanine compound is in a powder state as in the above (b), the phthalocyanine compound and / or naphthalocyanine compound are added together in a mixed solvent of a polar solvent and water or A phthalocyanine compound and / or a naphthalocyanine compound may be added and mixed in a small amount continuously, or a mixed solvent of a polar solvent and water may be added and mixed after a phthalocyanine compound and / or a naphthalocyanine compound are previously charged in a washing container. The order in which the phthalocyanine compound and / or the naphthalocyanine compound is added is not particularly limited. However, in consideration of purification (washing) efficiency, the phthalocyanine compound and / or the naphthalocyanine compound are mixed in a mixed solvent of a polar solvent and water. The method of continuously adding and mixing small amounts to Preferred for obtain a result.

In the purification (washing) step (a), the mixing is desirably carried out with stirring so that better and uniform mixing can be achieved. Also,
The mixing time is not particularly limited as long as it can uniformly mix and remove impurities efficiently, but is preferably 10 to 90 minutes, more preferably 30 to 60 minutes.

In the present invention, the concentration of the phthalocyanine compound and / or the naphthalocyanine compound depends on the type and composition of the mixed solution to be added (including the case of the polar solvent and water alone), the type of the phthalocyanine compound and / or the type of the naphthalocyanine compound. And purification conditions, etc.
There is no particular limitation as long as the concentration can remove impurities efficiently. However, when the phthalocyanine compound and / or naphthalocyanine compound is subjected to the purification step in a solution state as in the above (a) and (c), the concentration of the phthalocyanine compound and / or naphthalocyanine compound depends on the added polarity. The solvent, the solvent used to dissolve the phthalocyanine compound and / or the naphthalocyanine compound, water or a mixture thereof is usually 0.10 to 10.0% by mass, preferably 0.5 to 5% by mass. %, More preferably in the range of 1.0 to 2.5% by mass. Further, when the phthalocyanine compound and / or naphthalocyanine compound is subjected to the purification step in a powder state as in the above (b), the concentration of the phthalocyanine compound and / or naphthalocyanine compound is determined by adding a polar solvent, water Or 0.10 to 20.0 (w / v)%, preferably 1.0 to 10.0 (w / v)%, more preferably 2.0 to 5. 0 (w / v)%. On this occasion,
When the concentration of the phthalocyanine compound and / or the naphthalocyanine compound is lower than the lower limit of the above range, the phthalocyanine compound and / or the naphthalocyanine compound are dissolved in a large amount in the solution, and the dissolved component is excessively increased, and the yield is reduced. Alternatively, since a large amount of polar solvent and water are used for the phthalocyanine compound and / or naphthalocyanine compound, the subsequent separation step such as filtration is complicated, and the required filtration time is lengthened, and This is economically unfavorable, such as requiring large equipment. Conversely, when the concentration of the phthalocyanine compound and / or the naphthalocyanine compound exceeds the upper limit of the above range, the amount of the impurity is increased because the amount of the phthalocyanine compound and / or the naphthalocyanine compound is too large. Cannot be removed, purification (washing)
Because the efficiency decreases or the slurry property becomes strong,
In order to mix uniformly, strong stirring power is required,
After all, there is a fear that equipment for that is required.

In the purification method of the present invention, the purification conditions vary depending on the type and composition of the mixed solution to be added (including the case of using a polar solvent and water alone) and the type of the phthalocyanine compound and / or the naphthalocyanine compound. The conditions are not particularly limited as long as the impurities can be removed efficiently. For example, the temperature of the cleaning solution (polar solvent, water or a mixture thereof; hereinafter the same) during purification is usually from 0 to 50. C is appropriate, more preferably 1 ° C.
It is in the range of 0-30 ° C, most preferably 15-25 ° C. At this time, if the temperature of the cleaning liquid is less than 0 ° C., the dissolving ability of the phthalocyanine compound or the naphthalocyanine compound is insufficient, and impurities are precipitated, or the mixing ratio changes due to a difference in the freezing point between the polar solvent and water. However, there is a possibility that the purification efficiency and the yield may be reduced. Conversely, if the temperature of the washing liquid exceeds 50 ° C., the dissolving ability of the phthalocyanine compound and the naphthalocyanine compound will be increased, consequently, the yield will also decrease, or mixing will occur due to the difference in boiling point and vapor pressure between the polar solvent and water. The ratio may change, and purification efficiency and yield may be reduced.

In the purification method of the present invention, the type of the phthalocyanine compound and / or naphthalocyanine compound is not particularly limited, and known phthalocyanine compounds and naphthalocyanine compounds can be used. Purification method is to dissolve the phthalocyanine compound and / or naphthalocyanine compound in a polar solvent having a specific solubility parameter, and to precipitate the target compound in the coexistence of water, phthalocyanine compound and naphthalocyanine compound having low solubility in water, especially It is preferably used in the purification method of the present invention. Therefore, the phthalocyanine compound and / or naphthalocyanine compound preferably used in the method of the present invention include:
Solubility in water at 10 to 30 ° C. is 1.0% by mass or less;
More preferably 0.5% by mass or less, most preferably 0.1% by mass.
It is not more than 1% by mass. At this time, if the solubility of the purified phthalocyanine compound and / or naphthalocyanine compound in water at 10 to 30 ° C. exceeds 1.0% by mass, the phthalocyanine compound and / or naphthalocyanine compound dissolved in the polar solvent side is dissolved in water. Is not preferable because of the coexistence of Such phthalocyanine compounds and naphthalocyanine compounds include, for example, the following formula (1):

[0035]

Embedded image

(In the formula, A ^{1 to} A ¹⁶ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a hydroxysulfonyl group, an aminosulfonyl group, or a nitrogen atom, a sulfur atom, an oxygen atom or a halogen atom. And two adjacent substituents may be bonded via a linking group; and M ¹ is
Represents two hydrogen atoms or a divalent to hexavalent substituted metal atom. And a phthalocyanine compound represented by the following formula (2):

[0037]

Embedded image

(Wherein B ^{1 to} B ²⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a hydroxysulfonyl group, an aminosulfonyl group, or a nitrogen, sulfur, oxygen, or halogen atom) And two adjacent substituents may be bonded via a linking group; and M ² is 2
Represents one hydrogen atom or a divalent to hexavalent substituted metal atom. And the like. Among these, considering the solubility of the phthalocyanine compound and the naphthalocyanine compound involved in the cleaning efficiency, the types and properties of by-products and impurities that are expected to be by-produced during the synthesis, the following formula (3):

[0039]

Embedded image

(Where Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ ,
Z ₁₁ , Z ₁₄ and Z ₁₅ are each independently SR ¹ , O
R ² or a fluorine atom and at least one of them represents SR ¹ or OR ² ; Z ₁ , Z ₄ , Z ₅ , Z ₈ ,
Z ₉ , Z ₁₂ , Z ₁₃ and Z ₁₆ are each independently NH
R ³ , SR ¹ , OR ² or a fluorine atom and at least one of them represents NHR ³ ; at least one of Z _{1 to} Z ₁₆ represents a fluorine atom or OR ² ; R ¹ , R ² and R ³ is each independently a phenyl group which may have a substituent, an aralkyl group which may have a substituent or an alkyl having 1 to 20 carbon atoms which may have a substituent And M is a metal-free, metal,
Represents metal oxides or metal halides. The phthalocyanine compound represented by the formula (1) is preferably used, and more preferably the following formula (4):

[0041]

Embedded image

(Where Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ ,
Z ₁₁ , Z ₁₄ and Z ₁₅ are each independently SR ¹ , O
R ² or a halogen atom, and at least one of them represents SR ¹ or OR ² , Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z
₉ , Z ₁₂ , Z ₁₃ and Z ₁₆ are each independently NH
R ³ , SR ¹ , OR ² or a halogen atom, and at least one is NHR ³ and at least four are OR ² ; a plurality of R ¹ , R ² and R ³ are each independently a substituent Represents a phenyl group which may have a aralkyl group which may have a substituent or an alkyl group having 1 to 20 carbon atoms which may have a substituent; Represents a metal, metal, metal oxide or metal halide. The phthalocyanine compound represented by) is used in the present invention. In addition, in this specification, non-metal means that it is an atom other than a metal, for example, two hydrogen atoms.

Among these phthalocyanine compounds, those which are soluble in the polar solvent used in the present invention are particularly preferably used, and specific examples include the following compounds. In the following compounds, M in the phthalocyanine compound of the above formula (4) is metal-free, and the present invention is not limited to this. Needless to say, an oxide or a metal halide is also included. In the following compounds, positions 3 and 6 are at the α-position of the phthalocyanine nucleus (Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ ,
Z ₁₂ , Z ₁₃ , and Z ₁₆ ).
The 4- and 5-positions are the β-positions of the phthalocyanine nucleus (Z ₂ , Z ₃ , Z ₆ ,
Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ , and Z ₁₅ ). In the following compound abbreviations, Pc represents a phthalocyanine nucleus, represents eight substituents that substitute at the β-position immediately after Pc, and eight substituents that substitute at the α-position after the substituent that substitutes at the β-position. Represents a group. 4,5-octakis (phenoxy) -3,6- {tetrakis (phenoxy) -tris (anilino) -fluoro} phthalocyanine Abbreviation: Pc (PhO) ₈ (PhO) ₄ (PhNH) ₃ F (2,6-dichlorophenoxy)
-3,6- {tetrakis (2,6-dimethylphenoxy) -tris (DL-1-phenylethylamino) -fluoro} phthalocyanine Abbreviation: Pc (2,6-Cl ₂ PhO) ₈ ｛2,6- (CH
₃ ) ₂ PhO｝ ₄ ｛Ph (CH ₃ ) CHNH｝ ₃ F · 4,5-octakis (2,6-dichlorophenoxy)
-3,6- {tetrakis (2,6-dimethylphenoxy) -tris (benzylamino) -fluoro} phthalocyanine Abbreviation: Pc (2,6-Cl ₂ PhO) ₈ ｛2,6- (CH
₃ ) ₂ PhO｝ ₄ (PhCH ₂ NH) ₃ F • 4,5-octakis (2,6-dichlorophenoxy)
-3,6- {tetrakis (2,6-dibromo-4-methylphenoxy) -tris (DL-1-phenylethylamino) -fluoro} phthalocyanine Abbreviation: Pc (2,6-Cl ₂ PhO) ₈ {2 6- (B
_{r) 2 -4- (CH 3)} PhO} 4 {Ph (CH 3) CHN
H｝ ₃ F · 4,5-octakis (2,5-dichlorophenoxy)
3,6 {tetrakis (2,6-dimethylphenoxy) - tris (DL-1-phenyl-ethylamino) - fluoro} phthalocyanine _{abbreviation; Pc (2,5-Cl 2 PhO} ) 8 {2,6- (CH
₃ ) ₂ PhO｝ ₄ ｛Ph (CH ₃ ) CHNH｝ ₃ F · 4,5-octakis (2,5-dichlorophenoxy)
-3,6- {tetrakis (2,6-dimethylphenoxy) -tris (benzylamino) -fluoro} phthalocyanine Abbreviation: Pc (2,5-Cl ₂ PhO) ₈ {2,6- (CH
₃ ) ₂ PhO｝ ₄ (PhCH ₂ NH) ₃ F • 4,5-octakis (2,5-dichlorophenoxy)
-3,6- {tetrakis (2,6-dibromo-4-methylphenoxy) -tris (DL-1-phenylethylamino) -fluoro} phthalocyanine Abbreviation: Pc (2,5-Cl ₂ PhO) ₈ {2 6- (B
_{r) 2 -4- (CH 3)} PhO} 4 {Ph (CH 3) CHN
H｝ ₃ F · 4,5-octakis (2,5-dichlorophenoxy)
-3,6- {tetrakis (2,6-dibromo-4-methylphenoxy) -bis (DL-1-phenylethylamino) -difluoro} phthalocyanine Abbreviation: Pc (2,5-Cl ₂ PhO) ₈ } 2 6- (B
_{r) 2 -4- (CH 3)} PhO} 4 {Ph (CH 3) CHN
H} ₂ F ₂ · 4,5- octakis (4-cyanophenoxy) -3,
6- {Tetrakis (2,6-dimethylphenoxy) -tris (DL-1-phenylethylamino) -fluoro}
Phthalocyanine Abbreviation: Pc (4-CNPhO) ₈ {2,6- (CH ₃ ) _{2
PhO} 4 {Ph (CH 3} ) CHNH} 3 F · 4,5- octakis (4-cyanophenoxy) -3,
6- {tetrakis (2,6-dimethylphenoxy) -tris (benzylamino) -fluoro} phthalocyanine Abbreviation: Pc (4-CNPhO) ₈ {2,6- (CH ₃ ) _{2
PhO} 4 {PhCH 2 NH}} 3 F · 4,5- octakis (4-cyanophenoxy) -3,
6- {tetrakis (2,6-dibromo-4-methylphenoxy) -tris (DL-1-phenylethylamino)
-Fluorophthalocyanine Abbreviation: Pc (4-CNPhO) ₈ {2,6- (Br) _{2-
4- (CH 3) PhO} 4} {Ph (CH 3) CHNH} 3 F · 4,5- { tetrakis (butoxy) - tetrakis (2,6-dimethylphenoxy)} - 3,6 {tetrakis (2, 6-dimethylphenoxy) -tris (benzylamino) -fluoro {phthalocyanine Abbreviation: Pc (BuO) ₄ {2,6- (CH ₃ ) ₂ PhO} ₄
{2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₃ F • 4,5-octakis (phenylthio) -3,6- {tetrakis (2,6-dimethylphenoxy) -tris (benzylamino) -Fluorophthalocyanine Abbreviation; Pc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄
(PhCH ₂ NH) ₃ F • 4,5-octakis (phenylthio) -3,6- {tetrakis (2,6-dimethylphenoxy) -tris (anilino) -fluoro} phthalocyanine Abbreviation: Pc (PhS) ₈ } 2 6- (CH ₃ ) ₂ PhO｝ ₄
(PhNH) ₃ F • 4,5-octakis (butylthio) -3,6- {tetrakis (2,6-dimethylphenoxy) -tris (benzylamino) -fluoro} phthalocyanine Abbreviation: Pc (BuS) ₈ ｛2,6 − (CH ₃ ) ₂ PhO｝ ₄
(PhCH ₂ NH) ₃ F • 4,5- {tetrakis (butoxy) -tetrakis (phenylthio)}-3,6- {tetrakis (2,6-dimethylphenoxy) -tris (DL-1-phenylethylamino)- Fluorophthalocyanine Abbreviation: Pc (BuO) ₄ (PhS) ₄ ｛2,6- (C
_{H 3) 2 PhO} 4 {} Ph (CH 3) CHNH} 3 F · 4,5- octakis (phenoxy) -3,6 {tetrakis (phenoxy) - tris (benzylamino) - chloro} phthalocyanine abbreviation; Pc ( PhO) ₈ (PhO) ₄ (PhCH ₂ NH) ₃
Cl 4,4,5-octakis (2,5-dichlorophenoxy)
-3,6- {tetrakis (2,6-dimethylphenoxy) -tetrakis (DL-1-phenylethylamino)} phthalocyanine Abbreviation: Pc (2,5-Cl ₂ PhO) ₈ {2,6- (CH
_{3) 2 PhO} 4 {Ph} (CH 3) CHNH} 4 · 4,5- octakis (2,5-dichlorophenoxy)
-3,6- {tetrakis (2,6-dimethylphenoxy) -tetrakis (benzylamino)} phthalocyanine Abbreviation: Pc (2,5-Cl ₂ PhO) ₈ {2,6- (CH
_{3) 2 PhO} 4 (PhCH} 2 NH) 4 · 4,5- octakis (2,5-dichlorophenoxy)
-3,6- {tetrakis (2,6-dibromo-4-methylphenoxy) -tetrakis (DL-1-phenylethylamino)} phthalocyanine Abbreviation: Pc (2,5-Cl ₂ PhO) ₈ ｛2,6- (B
_{r) 2 -4- (CH 3)} PhO} 4 {Ph (CH 3) CHN
H} ₄ · 4,5-octakis (2,6-dichlorophenoxy)
-3,6- {tetrakis (2,6-dibromo-4-methylphenoxy) -tetrakis (DL-1-phenylethylamino)} phthalocyanine Abbreviation: Pc (2,6-Cl ₂ PhO) ₈ ｛2,6- (B
_{r) 2 -4- (CH 3)} PhO} 4 {Ph (CH 3) CHN
H} ₄ · 4,5-octakis (4-cyanophenoxy) -3,
6- {tetrakis (2,6-dimethylphenoxy) -tetrakis (DL-1-phenylethylamino)} phthalocyanine Abbreviation: Pc (4-CNPhO) ₈ {2,6- (CH ₃ ) _{2
PhO} 4 {Ph (CH 3} ) CHNH} 4 · 4,5- octakis (4-cyanophenoxy) -3,
6- {tetrakis (2,6-dimethylphenoxy) -tetrakis (benzylamino)} phthalocyanine Abbreviation: Pc (4-CNPhO) ₈ {2,6- (CH ₃ ) _{2
PhO} 4 (PhCH 2 NH)} 4 · 4,5- octakis (4-cyanophenoxy) -3,
6- {tetrakis (2,6-dibromo-4-methylphenoxy) -tetrakis (DL-1-phenylethylamino)} phthalocyanine Abbreviation: Pc (4-CNPhO) ₈ {2,6- (Br) _{2-
4- (CH 3) PhO} 4} {Ph (CH 3) CHNH} 4 · 4,5- { tetrakis (butoxy) - tetrakis (2,6-dimethylphenoxy)} - 3,6 {tetrakis (2,6 -Dimethylphenoxy) -tetrakis (benzylamino) {phthalocyanine Abbreviation: Pc (BuO) ₄ {2,6- (CH ₃ ) ₂ PhO} _{4
{2,6- (CH 3) 2 PhO} } 4 {PhCH 2 NH} 4 · 4,5- octakis (phenylthio) -3,6 {tetrakis (2,6-dimethylphenoxy) - tetrakis (benzylamino)} Phthalocyanine Abbreviation: Pc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄
(PhCH ₂ NH) ₄ · 4,5- octakis (phenylthio) -3,6 {tetrakis (2,6-dimethylphenoxy) - tetrakis (anilino)} phthalocyanine Abbreviation; Pc (PhS) ₈ {2,6- ( CH ₃ ) ₂ PhO｝ ₄
(PhNH) ₄ · 4,5- octakis (butylthio) -3,6 {tetrakis (2,6-dimethylphenoxy) - tetrakis (benzylamino)} phthalocyanine Abbreviation; Pc (BuS) ₈ {2,6- (CH ₃ ) ₂ PhO｝ _{4
(PhCH 2 NH) 4 · 4,5-} { tetrakis (butoxy) - tetrakis (phenylthio)} - 3,6 {tetrakis (2,6-dimethylphenoxy) - tetrakis (DL-1-phenyl-ethylamino)} phthalocyanine Abbreviation: Pc (BuO) ₄ (PhS) ₄ ｛2,6- (C
H ₃ ) ₂ PhO｝ ₄ ｛Ph (CH ₃ ) CHNH｝ ₄ The method for producing the phthalocyanine compound or naphthalocyanine compound used in the method of the present invention is not particularly limited, and is disclosed in the above publications and the like. Such a conventionally known method can be appropriately used. For example, in the case of a phthalocyanine compound, a method of cyclizing a phthalonitrile compound and a metal salt, preferably in a molten state or in an organic solvent, and then further reacting the cyclized reaction product with an amino compound can be particularly preferably used.

The phthalocyanine compound and naphthalocyanine compound according to the present invention may be used in the form of a reaction solution produced by the above-mentioned method or the like, or may be centrifuged, filtered, crystallized and evaporated to dryness. May be used in the form of a solid separated from the reaction solution by the known method of

The phthalocyanine compound and naphthalocyanine compound thus purified may be used, if necessary,
Further, it may be washed by pouring with a polar solvent, water or a mixture thereof. Further, the phthalocyanine compound and the naphthalocyanine compound thus purified, or a polar solvent, water or a mixed solution thereof, and the phthalocyanine compound and the naphthalocyanine compound washed by washing with a mixture thereof are vacuum-dried, hot-air dried,
It may be obtained as a solid by air drying or drying with a drying agent such as magnesium sulfate.

According to the purification method of the present invention as described above, in particular, after mixing the phthalocyanine compound and the naphthalocyanine compound with the polar solvent, and further adding and mixing water, the target compound having a fine particle diameter can be obtained with high purity and yield. Obtained at a rate. Also, for example, by adding and mixing a phthalocyanine compound and a naphthalocyanine compound in a mixed solution of a pre-mixed polar solvent and water,
Although the washing efficiency is slightly reduced, the target compound having a large particle size and hence easy to perform a subsequent filtration step can be obtained with high purity and yield.

[0047]

The present invention will now be described more specifically with reference to examples.

Synthesis Example 1: 4,5-octakis (2,5-
Dichlorophenoxy) -3,6- {tetrakis (2,6
-Dimethylphenoxy) -tris (DL-1-phenylethylamino) -fluorodivanadyl phthalocyanine [abbreviation: VOPc (2,5-Cl ₂ PhO) ₈ (2,6-
(CH ₃ ) ₂ PhO) ₄ {Ph (CH ₃ ) CHNH} ₃ F]
Synthesis of divanadium trioxide in a 300 ml four-necked flask
1.43 g (9.53 mmol), 3.64 g (19.1 mmol) of p-toluenesulfonic acid and 60 ml of benzonitrile were charged and then kept at 170 ° C. for about 3 hours with stirring. Thereafter, the temperature was raised to the reflux temperature, and 3- (2,
6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile 3
An additional 0 g (51.0 mmol) was added and kept at reflux for 4 hours under a nitrogen atmosphere. Then, the mixture was cooled to an air atmosphere, and 12.4 g of Ph (CH ₃ ) CHNH ₂ (102.3 g) was added.
Mmol) and 163 ml of benzonitrile, then kept at 60 ° C. for 6 hours and at 70 ° C. for 2 hours. After cooling, the reaction solution was filtered, and VOPc (2,5-Cl ₂ PhO) ₈ (2,
6- (CH ₃ ) ₂ PhO) ₄ {Ph (CH ₃ ) CHNH} ₃
240 ml of the reaction solution of F was obtained.

Synthesis Example 2: 4,5-octakis (2,5-
Dichlorophenoxy) -3,6- {tetrakis (2,6
-Dimethylphenoxy) -tetrakis (benzylamido)
V) Vanadyl phthalocyanine [VOPc (2,5-C
l_TwoPhO)₈(2,6- (CH _Three)_TwoPhO)_Four｛PhC
H_TwoNH｝_FourIn a 300 ml four-necked flask, divanadium trioxide was added.
1.24 g (8.29 mmol), p-toluenesulfo
Acid 3.15 g (16.6 mmol) and benzoni
60 ml of Toril is charged and then stirred at 170 ° C.
Hold for 3 hours. Thereafter, the temperature was raised to the reflux temperature, and 3- (2,
6-dimethylphenoxy) -4,5-bis (2,5-di
Chlorophenoxy) -6-fluorophthalonitrile 3
0 g (51.0 mmol) was added under nitrogen atmosphere.
The flow temperature was maintained for 10 hours. Then cool and under air atmosphere
And PhCH_TwoNH_Two 43.7 g (408.0 mmo
Le) and calcium carbonate (2.81 g, 28.0 mmol)
33), benzonitrile 33 ml, then 60 ° C
For 7 hours. After cooling, the reaction solution is filtered, and VOPc
(2,5-Cl_TwoPhO)₈(2,6- (CH_Three)_TwoPh
O)_Four｛PhCH_TwoNH｝_Four250 ml of a reaction solution was obtained.

Synthesis Example 3: 4,5-octakis (2,5-
Dichlorophenoxy) -3,6- {tetrakis (2,6
-Dimethylphenoxy) -tetrakis (benzylamino)｝ copper phthalocyanine [CuPc (2,5-Cl ₂ P
hO) ₈ (2,6- (CH ₃ ) ₂ PhO) ₄ (PhCH ₂ N
H) ₄ ] Synthesis of 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile 30 g (5
1.0 mmol), 1.52 g (15.3 mmol) of copper chloride, and 45 ml of n-octanol.
The temperature was maintained at 170 ° C. under nitrogen bubbling for about 4 hours with stirring. Thereafter, the atmosphere was changed to an air atmosphere, and PhCH ₂ NH ₂ 21.
9 g (204.0 mmol) and benzonitrile 180
ml and then kept at 90 ° C. for 5 hours. After cooling, the reaction solution was filtered, and CuPc (2,5-Cl ₂ PhO) ₈ (2,
6- (CH ₃ ) ₂ PhO) ₄ {PhCH ₂ NH} ₄ reaction solution
270 ml were obtained.

Synthesis Example 4: 4,5-octakis (phenylthio) -3,6- {tetrakis (2,6-dimethylphenoxy) -tetrakis (benzylamino)} vanadyl phthalocyanine [VOPc (PhS) ₈ (2,6- (C
Synthesis of H ₃ ) ₂ PhO) ₄ {PhCH ₂ NH} ₄ ] Vanadium trichloride was placed in a 300 ml four-necked flask.
2.61 g (16.58 mmol), 3- (2,6-dimethylphenoxy) -4,5-bis (phenylthio)-
30 g (62.2 mmol) of 6-fluorophthalonitrile and 60 ml of benzonitrile were charged.
C. and maintained at reflux temperature for 6 hours in an air atmosphere. After cooling, 100 ml of PhCH ₂ NH ₂ was added, and the mixture was kept at 100 ° C. for 7 hours. After cooling, the reaction solution was filtered and VOPc (PhS) ₈ (2,6- (CH ₃ ) ₂ Ph
O) ₄ {PhCH ₂ NH} ₄ Reaction liquid 200 ml was obtained.

EXAMPLE 1 900 ml of isopropyl alcohol and water were placed in a 2 L beaker.
Prepare a mixed solution with 260 ml, and under stirring conditions
VOPc (2,5-Cl) obtained by Synthesis Example 1_TwoPh
O)₈(2,6- (CH_Three)_TwoPhO)_Four｛Ph (CH_Three)
CHNH｝_ThreeDrop half amount (120 ml) of the reaction solution of F
The mixture was kept at 25 ° C. for about 30 minutes. afterwards
The washing liquid was filtered. Transfer the material on the filter paper into a 1L beaker
Isopropyl alcohol (solubility parameter at 25 ° C)
11.5 (calcm)^-3)^1/2) 450ml
And a mixed solution of 130 ml of water at 25 ° C for about 1 hour
The wash was then kept and filtered. Filter the filter paper onto isopropyl
Wash with 70 ml of alcohol, and vacuum dry,
VOPc (2,5-Cl_TwoPhO)₈(2,6- (C
H _Three)_TwoPhO)_Four｛Ph (CH_Three) CHNH｝_ThreeF1
2.25 g (vs. 3- (2,6-dimethylphenoxy)-
4,5-bis (2,5-dichlorophenoxy) -6-fu
Fluorophthalonitrile yield 70.5 mol%) was obtained.
Was.

The phthalocyanine compound [VOPc (2,5-Cl ₂ PhO) ₈ (2,6-
(CH ₃ ) ₂ PhO) ₄ {Ph (CH ₃ ) CHNH} ₃ F]
Weighed 0.010 g into a 3.5 ml sample bottle,
To this was added 1.000 g of water. Next, this liquid was stirred with a magnetic stirrer, dissolved at 30 ° C. for 1 hour under continuous stirring, and then allowed to stand. A large amount of the phthalocyanine compound that did not dissolve in water settled at the bottom of the sample bottle. Was observed.

Next, the absorption coefficient of the obtained dye at the maximum absorption wavelength in chloroform was measured using a spectrophotometer (UV-3100, manufactured by Shimadzu Corporation).

The obtained dye was placed in a quartz cell of 1 cm with a transmittance of 750 to 1050 nm having a minimum value of 8 to 10%.
, And the transmittance at that time was measured in the same manner using a spectrophotometer.
It was calculated according to the standard of IS R3106 (1985). The results are shown in Table 1 below.

Example 2 In a 2 L beaker, the VOPc (2,
5-Cl ₂ PhO) ₈ (2,6- (CH ₃ ) ₂ PhO)
Half of the reaction solution (125 ml) of ₄ {PhCH ₂ NH} ₄ was transferred and acetone (solubility parameter at 25 ° C .: 9.71 (cal · cm ⁻³ ) ^1/2 ) under stirring conditions.
1000 ml was added and kept at 23 ° C. for about 30 minutes. Then, 250 ml of water was added under continuous stirring, and the mixture was kept at 23 ° C. for about 15 minutes, and then the washing liquid was filtered. The material on the filter was transferred to a 1 L beaker, 500 ml of acetone was added, and the mixture was kept at 23 ° C. for about 1 hour with stirring. Subsequently, 125 ml of water was added under continuous stirring, and the mixture was kept at 23 ° C. for about 30 minutes, and then the washing liquid was filtered. Filter paper on acetone 40
The mixture was washed with a mixed solution of 10 ml of water and 10 ml of water, and dried under vacuum to obtain VOPc (2,5-Cl ₂ PhO) ₈ (2,6-
(CH ₃ ) ₂ PhO) ₄ {PhCH ₂ NH} ₄ 10.9 g
(Vs. 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile, yield 60.4 mol%).

The phthalocyanine compound [VOPc (2,5-Cl ₂ PhO) ₈ (2,6-
(CH ₃ ) ₂ PhO) ₄ {PhCH ₂ NH} ₄ ] to 3.5
0.010 g was weighed into a ml sample bottle, and 1.000 g of water was added thereto. Next, this liquid was stirred with a magnetic stirrer, dissolved at 30 ° C. for 1 hour under continuous stirring, and then allowed to stand. A large amount of the phthalocyanine compound that did not dissolve in water settled at the bottom of the sample bottle. Was observed.

The extinction coefficient and visible light transmittance of the obtained dye were measured in the same manner as in Example 1. Table 1 shows the results.

Example 3 In a 2 L beaker, the CuPc (2,
5-Cl ₂ PhO) ₈ (2,6- (CH ₃ ) ₂ PhO)
A half (135 ml) of the reaction solution of ₄ (PhCH ₂ NH) ₄ was transferred and acetonitrile (25 ° C.) was stirred under stirring conditions.
Solubility parameter at 11.8 (cal · cm ^-3 )
^1/2 ) 1200 ml was added and kept at 20 ° C. for about 30 minutes. Then, 130 ml of water was added while stirring was continued for 2 hours.
It was kept at 0 ° C. for about 15 minutes, after which the washings were filtered. The material on the filter paper is transferred to a 1 L beaker, and acetonitrile 60
After adding 0 ml, the mixture was kept at 20 ° C. for about 1 hour under stirring. Then, 65 ml of water was added while stirring was continued, and the mixture was kept at 20 ° C. for about 30 minutes, and then the washing solution was filtered. The material on the filter paper was washed with 100 ml of acetonitrile and dried under vacuum to obtain CuPc (2,5-Cl ₂ PhO) ₈ (2,6- (C
_{H 3) 2 PhO) 4 {} PhCH 2 NH} 4 10.4g ( vs. 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile yield 59.1 mol%).

The phthalocyanine compound [CuPc (2,5-Cl ₂ PhO) ₈ (2,6-
(CH ₃ ) ₂ PhO) ₄ {PhCH ₂ NH} ₄ ] to 3.5
0.010 g was weighed into a ml sample bottle, and 1.000 g of water was added thereto. Next, this liquid was stirred with a magnetic stirrer, dissolved at 30 ° C. for 1 hour under continuous stirring, and then allowed to stand. A large amount of the phthalocyanine compound that did not dissolve in water settled at the bottom of the sample bottle. Was observed.

The extinction coefficient and visible light transmittance of the obtained dye were measured in the same manner as in Example 1. The results are shown in Table 1 below.

Example 4 The VOPc (Ph) obtained in Synthesis Example 3 was placed in a 2 L beaker.
S) ₈ (2,6- (CH ₃ ) ₂ PhO) ₄ ｛PhCH ₂ N
A half amount (100 ml) of the reaction solution of H 移₄ was transferred and 900 m of acetonitrile (solubility parameter at 25 ° C .: 11.8 (cal · cm ⁻³ ) ^1/2 ) under stirring conditions.
1 and kept at 25 ° C. for about 30 minutes. Then, 100 ml of water was added under continuous stirring, and the mixture was kept at 25 ° C. for about 15 minutes, and then, the washing liquid was filtered. The material on the filter was transferred to a 1 L beaker, 450 ml of acetonitrile was added, and the mixture was kept at 25 ° C. for about 1 hour under stirring. Then, 50 ml of water was added under continuous stirring, and the mixture was kept at 25 ° C. for about 30 minutes.
Thereafter, the washing liquid was filtered. Filter material on acetonitrile 1
100 ml, and then dried under vacuum to obtain VOPc (P
hS) ₈ (2,6- (CH ₃ ) ₂ PhO) ₄ ｛PhCH ₂ N
8.5 g of H｝ ₄ (vs. 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy)-
6-Fluorophthalonitrile yield: 56.9 mol%).

The phthalocyanine compound [VOPc (PhS) ₈ (2,6- (CH ₃ ) ₂ Ph]
O) ₄ {PhCH ₂ NH} ₄ ] was weighed into a 3.5 ml sample bottle, and 0.010 g of water was added thereto. Next, this liquid is stirred with a magnetic stirrer,
After dissolving for 1 hour at 30 ° C. with continuous stirring, the mixture was allowed to stand, and it was observed that a large amount of the phthalocyanine compound that did not dissolve in water precipitated at the bottom of the sample bottle.

Further, the extinction coefficient and the visible light transmittance of the obtained dye were measured in the same manner as in Example 1. The results are shown in Table 1 below.

COMPARATIVE EXAMPLE 1 1160 ml of isopropyl alcohol was prepared in a 2 L beaker, and V was obtained according to Synthesis Example 1 under stirring conditions.
_{OPc (2,5-Cl 2 PhO)} 8 (2,6- (CH 3) 2
A half amount (120 ml) of a reaction solution of PhO) ₄ {Ph (CH ₃ ) CHNH} ₃ F was added dropwise, and the mixture was kept at 25 ° C. for about 30 minutes. Thereafter, the washing liquid was filtered. The material on the filter was transferred to a 1 L beaker, and isopropyl alcohol (solubility parameter at 25 ° C .: 11.5 (cal ·
cm ⁻³ ) ^1/2 ) 580 ml was added and the mixture was kept at 25 ° C. for about 1 hour, and then the washing solution was filtered. The material on the filter paper is washed with 70 ml of isopropyl alcohol and dried under vacuum.
VOPc (2,5-Cl ₂ PhO) ₈ (2,6- (C
7. H ₃ ) ₂ PhO) ₄ {Ph (CH ₃ ) CHNH} ₃ F
28 g (vs. 3- (2,6-dimethylphenoxy) -4,
5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile yield 47.7 mol%) was obtained.

The extinction coefficient and visible light transmittance of the obtained dye were measured in the same manner as in Example 1. The results are shown in Table 1 below.

Comparative Example 2 In a 2 L beaker, the VOPc (2,
5-Cl ₂ PhO) ₈ (2,6- (CH ₃ ) ₂ PhO)
Half of the reaction solution (125 ml) of ₄ {PhCH ₂ NH} ₄ was transferred and acetone (solubility parameter at 25 ° C .: 9.71 (cal · cm ⁻³ ) ^1/2 ) under stirring conditions.
1250 ml was added and kept at 23 ° C. for about 30 minutes. After that, the washing solution was filtered, but nothing was left on the filter paper.
_{Pc (2,5-Cl 2 PhO)} 8 (2,6- (CH 3) 2 P
hO) ₄ {PhCH ₂ NH} ₄ was not obtained. (Vs. 3
-(2,6-Dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile yield 0 mol%. Comparative Example 3 In a 2 L beaker, the CuPc (2,
5-Cl ₂ PhO) ₈ (2,6- (CH ₃ ) ₂ PhO)
Half of the reaction solution of ₄ (PhCH ₂ NH) ₄ (135 ml) was transferred, and hexane (solubility parameter at 25 ° C .: 7.423 (cal · c) under stirring conditions was used.
m- ³ ) ^1/2 ) 1350 ml was added and kept at 20 DEG C. for about 30 minutes. Thereafter, the washing liquid was filtered, and the material on the filter paper was transferred to a 1 L beaker. Hexane (665 ml) was added, and the mixture was kept at 20 ° C. for about 1 hour under stirring. After that, the washing liquid is filtered,
The material on the filter paper was washed with 100 ml of hexane and dried under vacuum to obtain CuPc (2,5-Cl ₂ PhO) ₈ (2,6-
(CH ₃ ) ₂ PhO) ₄ {PhCH ₂ NH} ₄ 12.1 g
(Vs. 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile yield: 68.4 mol%).

The extinction coefficient and visible light transmittance of the obtained dye were measured in the same manner as in Example 1. The results are shown in Table 1 below.

Comparative Example 4 The VOPc (Ph) obtained in Synthesis Example 4 was placed in a 2 L beaker.
S) ₈ (2,6- (CH ₃ ) ₂ PhO) ₄ ｛PhCH ₂ N
Half of the reaction solution (100 ml) of H｝ ₄ was transferred thereto, and acetonitrile (solubility parameter at 25 ° C .: 11.8 (cal · cm ⁻³ ) ^1/2 ) 1000 under stirring conditions.
ml and kept at 25 ° C. for about 30 minutes. Thereafter, the washing solution was filtered, the material on the filter paper was transferred to a 1 L beaker, 500 ml of acetonitrile was added, and the mixture was stirred at 25 ° C. for about 1 hour.
Time kept. Thereafter, the washing liquid was filtered, the material on the filter paper was washed with 100 ml of acetonitrile, and dried under vacuum to
OPc (PhS) ₈ (2,6- (CH ₃ ) ₂ PhO) ₄ ｛P
6.2 g of hCH ₂ NH｝ ₄ (vs. 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile yield 41.5 mol%) are obtained. Was done.

Further, the extinction coefficient and the visible light transmittance of the obtained dye were measured in the same manner as in Example 1. The results are shown in Table 1 below.

[0071]

[Table 1]

Comparative Example 5 Assuming that only water was used as the washing solvent, Synthesis Examples 1 to 4
A few drops of the reaction solution obtained in each step were collected in a 3 ml sample tube, and 1 ml of water was added and shaken well.
As a result, in each of the samples, the tar-like reaction liquid accumulated on the wall and the bottom of the sample tube, and was separated from water. Thereafter, even if filtration was attempted, the tar-like substance was clogged in the filter paper and filtration could not be performed, and the product in the reaction solution could not be isolated.

Synthesis Example 5 Octafluoro-octakisanilinooxyvanadium phthalocyanine [VOPc (P
Synthesis of [hNH) ₈ F ₈ ] In a 100 ml four-necked flask, 5.19 g (6 mmol) of hexadecafluorooxyvanadium phthalocyanine and 26.82 g (288 mmol) of aniline were charged and reacted at reflux temperature for 4 hours. After completion of the reaction, the insoluble matter was filtered off, aniline was distilled off, and the obtained solid was washed with 300 ml of n-hexane, filtered, and dried to obtain the desired product, octafluoro-octa. Kisanilinooxy vanadium phthalocyanine [VOPc (PhNH) ₈ F ₈ ] was obtained.

Synthesis Example 6 JP-A-9-111138 By the method described in Example 1, the phthalocyanine compounds shown in Example 6 in Table 2 below were synthesized. More specifically, Pigment Green 7 (trade name: Phthalocyanine Green) (10.0
g, 8.87 mmol), 2- (n-octylamino)
Thiophenol (33.7 g, 141.96 mmol,
16 equivalents), potassium carbonate (39.2 g, 283.6)
(3 mmol, 32 equivalents) in dimethylformamide (200 ml) at 120 ° C. for 5 hours. After cooling the reaction mixture to room temperature, methanol (500 ml)
During discharge. The precipitate was collected by suction filtration, washed with methanol, washed with water, and dried to obtain a desired phthalocyanine compound.

Synthesis Example 7 JP-A-11-152414 According to the method described in Example 1, the naphthalocyanine compounds shown in Table 2 and Example 7 below were synthesized. More specifically, the following compound (a) 4.0 g, copper chloride (I) 0.323 g, DBU
(1,8-diazabicyclo [5,4,0] undecene)
After mixing 1.63 ml and n-amyl alcohol 20 ml, the mixture was stirred under reflux for 6 hours. After cooling, methanol 10
The mixture was discharged to 0 ml, and the precipitate was separated by filtration to obtain 2.83 g of a nitronaphthalocyanine compound. Furthermore, 2.5 g of the obtained compound and 50 ml of N, N-dimethylformamide were mixed and heated to 70 ° C. To this, 20% NaS
5 g of H aqueous solution was added dropwise and stirred for 1 hour. After cooling, the mixture was discharged into 500 ml of water, neutralized with dilute sulfuric acid, and crystallized.
The desired naphthalocyanine compound was obtained by filtering the deposit.

[0076]

Embedded image

Examples 5 to 7 The three dyes obtained in Synthesis Examples 5 to 7 were
It is dissolved in chloroform so that the average transmittance of １０００1000 (nm) is 10 to 15%, and the transmittance at that time is measured with a spectrophotometer (manufactured by Shimadzu Corporation, UV-3100). JIS R3106 (1985)
Year)). The results are shown in Table 2 below.
Shown in

Next, 10 g of each of the three dyes obtained in Synthesis Examples 5 to 7 was weighed and placed in a 2 L beaker, and 800 ml of acetone (solubility parameter at 25 ° C .: 9.71 (cal · cm) ^-3 ) ^1/2 ) was added and the mixture was stirred at 25 ° C. for 1 hour. Then, with continuous stirring, add water 2
After adding 00 ml, the mixture was kept at 25 ° C. for about 30 minutes, and then the washing liquid was filtered. The material on the filter was transferred to a 1 L beaker, 400 ml of acetone was added, and the mixture was kept at 25 ° C. for about 1 hour under stirring. Then, while stirring continuously, 100 ml of water
Was added and kept at 25 ° C. for about 30 minutes, after which the washings were filtered. The material on the filter was washed with a mixed solution of 80 ml of acetone and 20 ml of water and dried under vacuum.

The visible light transmittance of the three dyes obtained was measured in the same manner as before the purification. These results are summarized in Table 2 below.

Each of the three kinds of dyes thus obtained was placed in a 3.5 ml sample bottle in an amount of 0.01 ml.
0 g was weighed, and 1.000 g of water was added thereto. Next, this liquid was stirred with a magnetic stirrer,
After dissolving at 0 ° C. for 1 hour and then standing, it was observed that a large amount of the dye not dissolved in water was precipitated at the bottom of the sample bottle for all the dyes.

[0081]

[Table 2]

[0082]

As described above, the method for purifying a phthalocyanine compound and a naphthalocyanine compound of the present invention purifies a phthalocyanine compound and / or a naphthalocyanine compound using a mixture of water and a polar solvent miscible with water. It is characterized by doing. According to the present method, both oil-soluble and water-soluble impurities which cause unnecessary absorption other than the maximum absorption and decrease in the molar extinction coefficient can be efficiently removed. Therefore, the phthalocyanine compound and / or naphthalocyanine compound obtained by the method can be efficiently removed. Is used for various purposes; for example, for writing or reading in an optical recording medium using a semiconductor laser, a liquid crystal display, an optical character reader, etc., because it has a small amount of unnecessary absorption other than the maximum absorption and has a high molar extinction coefficient. Near-infrared absorbing dyes, near-infrared sensitizers, thermal transfer, photothermal conversion agents such as thermal paper and thermal stencils, plasma displays (PD
P) and other near-infrared absorption filters, as near-infrared absorption materials used as anti-eye strain agents, photoconductive materials, or color separation filters used in image pickup tubes, color filters for liquid crystal displays, color CRT selective absorption filters, Color toners, dyes for flash fixing toners, inkjet inks, barcode inks for preventing tampering and counterfeiting, near-infrared absorbing inks, marking agents for photo and film positioning, goggle lenses and shielding plates, and plastic recycling Dyeing agent for sorting,
In addition, it can be suitably used as a preheating aid during molding of PET bottles, a microbial deactivator, a photosensitive dye for tumor treatment, a heat ray shielding agent for automobiles or building materials, and a resin classifier. it can.

In particular, by mixing the phthalocyanine compound and the naphthalocyanine compound with a polar solvent, and further adding and mixing water, the target compound having a fine particle diameter can be obtained with high purity and yield. By adding and mixing a naphthalocyanine compound in a mixed solution of a pre-mixed polar solvent and water,
Although the washing efficiency is slightly lowered, the target compound having a large particle size and therefore easy to perform a subsequent filtration step can be obtained with high purity and yield.According to the application, the most suitable phthalocyanine compound and naphthalocyanine compound are obtained. It can be obtained in high purity and yield without substantially containing both oil-soluble and water-soluble impurities that cause unnecessary absorption other than the maximum absorption and a decrease in the molar extinction coefficient.

Continued on the front page (72) Inventor Nobuaki Kitao 1-25-12 Kannondai, Tsukuba-shi, Ibaraki F-term (reference) in Nippon Shokubai Co., Ltd. 4C050 PA12 PA13 PA14 PA16 4C072 AA03 AA06 AA07 BB04 BB08 CC06 CC18 EE17 FF13 UU04

Claims (2)

[Claims] The solubility parameter at 25 ° C. is 8 (c
al · cm ⁻³ ) A method for purifying a phthalocyanine compound and / or a naphthalocyanine compound, comprising purifying a phthalocyanine compound and / or a naphthalocyanine compound with a mixed solution containing a polar solvent and water that are at least ^1/2 . 2. The purification method according to claim 1, wherein the volume ratio of water to the total volume of the polar solvent and water is 0.5 or less.