JP2002201194A - Amorphous body of phthalocyanine compound or its mixture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pigment capable of stably manufacturing a near infrared absorbing filter and an optical recording medium under conditions of having improved solvent solubility and free from trouble of precipitating crystals from a coating solution. SOLUTION: An amorphous body of a phthalocyanine compound or a mixture of phthalocyanine compounds are manufactured by heating a crystalline alkoxyphthalocyanine compound or a mixture of crystalline alkoxyphthalocyanine compounds in an organic solvent followed by removing the solvent by distillation or freeze drying.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an amorphous phthalocyanine compound or a mixture thereof having excellent solubility, which regulates the crystal form of the phthalocyanine compound or a mixture thereof, and a method for producing the same. The amorphous body of the phthalocyanine compound of the present invention or a mixture thereof is useful as a recording / memory material for a near-infrared absorbing filter, a liquid crystal display element, a write-once optical recording medium, and the like.

[0002]

2. Description of the Related Art A technique of using a phthalocyanine derivative, particularly an alkoxyphthalocyanine derivative, in a recording layer of a recording / storage material, particularly an optical recording medium such as an optical disk, is disclosed in Japanese Patent Application Laid-Open No. HEI 11-163,087.
No. 61-197280, No. 61-246091, No. 62-39286 (USP 4,769,307), No. 63-37991, No. 63-39388, etc. Poor solubility in organic solvents, especially hydrocarbon solvents with low polarity, making it difficult to form thin films by solution coating.

On the other hand, Japanese Patent Application Laid-Open Nos. 1-221461 and 3-50554
JP-A Nos. 3-50555 and 3-50555 disclose that crystallization of phthalocyanine is promoted by solvent treatment and heat treatment.

[0004]

In order to solve the above-mentioned problems, the present inventors have developed a recording material for an optical disk,
In particular, in order to develop an alkoxyphthalocyanine derivative described in JP-A-3-62878 as a recording material for CD-R, and to apply this alkoxyphthalocyanine derivative by a spin coating method which is one method of solution coating, a coating solution is required. 15g
It has been found that a concentration between / l and 90 g / l is optimal.
However, even the above-mentioned alkoxyphthalocyanine derivative may have low solubility depending on the crystal form, and may not dissolve to the optimum concentration, or may precipitate once in a short time even if dissolved once. It has been found that it may not be possible to prepare it.

[0005] The present inventors have found that the cause of the decrease in solubility is association of alkoxyphthalocyanine. That is, the association probably promotes crystallization and lowers the solubility in the solvent. Alternatively, it has been found that precipitation occurs from the dissolved state. In particular,
The presence of small amounts of aggregates nucleates larger associations and must be completely removed.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies on cutting the association state of the alkoxyphthalocyanine derivative, and as a result, after heating in an organic solvent, the solvent was distilled off to remove the solubility. The present inventors have found that an improved alkoxyphthalocyanine derivative can be obtained, and have reached the present invention. The present invention is disclosed in Japanese Patent Application Laid-Open Nos. 1-221461, 3-50554, and 3-50555, which is different from the methods disclosed in JP-A-3-50555. It is characterized by having obtained knowledge.

After the heat treatment, when the solvent is distilled off from the dye solution in a monomolecular dispersion state, if the state of the concentrated solution continues for a long time, the association of the dye starts to occur, so that the solvent is completely distilled off in a short time. There is a need to. The present inventors cut the association of the alkoxyphthalocyanine derivative, freeze the solution to immobilize it in a monomolecular state, and heat the frozen product under reduced pressure to sublimate the solvent by a vacuum freeze-drying method. The present inventors have found that an alkoxyphthalocyanine derivative in an amorphous state with improved solubility can be obtained, and the present invention has been achieved.

That is, the present invention provides the following general formula (1)

[0009]

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(In the formula (1), R represents a branched alkyl group, X represents a halogen atom, n represents the number of X, and is 0 to 4. Met is a divalent metal atom. A trivalent or tetravalent metal derivative or an oxymetal), or an amorphous form of alkoxyphthalocyanine, which is a mixture thereof, according to the production method described above.

The amorphous phthalocyanine derivative of the present invention has improved solvent solubility as compared with the untreated phthalocyanine derivative,
The precipitation of crystals from the coating liquid was eliminated, and it became possible to stably produce near-infrared absorbing filters and optical recording media.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The organic solvent used in the present invention is:
For the purpose of changing the crystalline state to an amorphous state, that is, to break the association, 1) dissolving the alkoxyphthalocyanine derivative, 2) a boiling point of 50 ° C. or higher, preferably 10 ° C.
It is preferable to satisfy the condition of 0 ° C. or higher,
Specific examples thereof include benzene, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,
1-trichloroethane, 1,1,2-trichloroethane, trichloroethylene, tetrahydrofuran, diisopropyl ether, dimethoxyethane, preferably toluene, ethylbenzene, isopropylbenzene, xylene, anisole, 1,1,2,2-tetrachloroethane, tetrachloroethylene, chlorobenzene, Dichlorobenzene, 1,3,5-trichlorobenzene, 1-chloronaphthalene, 2-chloronaphthalene, bromobenzene, difluorobenzene, 1-methylnaphthalene, 2-methylnaphthalene, 1,4-dioxane, di-n
-Butyl ether, diglyme and the like.

Further, when the phthalocyanine association is cleaved, 1) utilizing the π-π interaction and the coordination force of the solvent will further enhance the effect. 2) After the cleavage of the association, rapid re-association is prevented while preventing re-association. Considering two points that the solvent needs to be removed, an aromatic hydrocarbon having a boiling point of 100 ° C to 200 ° C is preferable, and examples thereof include toluene, ethylbenzene, and xylene.

The above-mentioned conditions 1) required for the organic solvent,
In order to remove the solvent by freeze-drying in addition to 2), it is preferable to satisfy the following three conditions: 3) the freezing point is -40 ° C or higher, preferably 0 ° C or higher and 40 ° C or lower;
Specific examples thereof include 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, iodobenzene, bromobenzene, 1-methylnaphthalene, m-chlorotoluene, o-xylene, and m- Dichlorobenzene, carbon tetrachloride, tetrachloroethylene, 1,6-dimethylnaphthalene,
2,4-dichlorobenzene, α, α-dichlorotoluene, 3,4-
Dichlorotoluene, 2,4-dichlorotoluene, α, α, α-
Trichlorotoluene, 1-chloronaphthalene, 1,2-dimethylnaphthalene, preferably benzene, p-xylene, 1-bromonaphthalene, p-chlorotoluene, p-dioxane and the like.

Considering that the effect of π-π interaction and coordination force of the solvent is further enhanced in cleaving the association of phthalocyanine, and the ease of freeze-drying after cleaving the association, the boiling point is 100 ° C. Aromatic hydrocarbons having a melting point of 0 to 200 ° C. and a freezing point of 0 ° C. or higher are preferable, and examples thereof include benzene and p-xylene.

The temperature of the heat treatment is 50 ° C. to 250 ° C., preferably 100 ° C. to 200 ° C., and the heat treatment time is 30 minutes to
10 hours, preferably 1 to 5 hours. The treatment concentration is 5 g / l to 500 g / l, preferably 10 g / l to 300 g / l.

Freeze-drying is performed by heating the solution at room temperature (15 to
After cooling to 25 ° C), put in a freeze dryer at -50 ° C or higher, preferably -40 ° C or higher and 0 ° C or lower at normal pressure, within 120 minutes, preferably within 60 minutes to freeze the solution and freeze the solution. After that, the pressure is reduced, and the heating medium for heating the shelf of the dryer is heated from -30 ° C to 70 ° C, preferably from -30 ° C to 40 ° C to sublimate and dry the frozen solvent while supplementing the latent heat of vaporization. . At this time, the internal pressure of the freeze dryer is approximately 133.32 Pa (1000 mtorr)
Hereinafter, it is preferably about 66.66 Pa (500 mtorr) or less, and is preferably about 26.66 Pa (200 mtorr) or less in the final stage of drying.

In the formula (1), the branched alkyl group represented by R is a hydrocarbon having 3 to 15 carbon atoms or a halogenated hydrocarbon, and a preferred branched alkyl group is a second, a third or a third alkyl group. 2 to 4 quaternary carbon atoms in total
It is a group containing. Specific examples include iso-propyl, sec-butyl, t-butyl, neo-pentyl, 1,2-
Dimethylpropyl, cyclo-hexyl, 1,3-dimethylbutyl, 1-iso-propylpropyl, 1,2-dimethylbutyl, 1,4-dimethylpentyl, 2-methyl-1-iso-propyl Propyl group, 1-ethyl-3-methylbutyl group, 3-methyl-1-iso-propylbutyl group, 2-methyl-1-iso-propylbutyl group, 1-t-butyl-2-methylpropyl group, etc. Examples include a halogenated alkyl group such as a hydrocarbon group and a 1,1,1,3,3,3-hexafluoro-2-propyl group.

Examples of the divalent metal atom represented by Met include Cu, Zn, Mn, Fe, Co, Ni, Ru, and R.
h, Pd, Pt, Pb, etc., and examples of trivalent or tetravalent metal derivatives include AlCl, AlBr, AlI,
AlOH, InCl, InBr, InI, InOH, S
_{iCl 2, SiBr 2, SiI 2} , Si (OH) 2, GeC
l ₂ , GeBr ₂ , GeI ₂ , SnCl ₂ , SnBr ₂ , S
Examples include nF ₂ and Sn (OH) _2, and examples of oxymetals include VO and TiO. Among these metals or derivatives thereof, Cu, Co, Ni, Rh,
When Pd and Pt are the central metals, the phthalocyanine represented by the above formula (1) usually easily associates as it is,
Crystallization and insolubility in a solvent and insolubility are easy, but those in which the crystal form is amorphous as in the present invention are less likely to be associated and the solubility is improved.

The conditions for synthesizing the phthalocyanine ring are as follows: 1 to 4 kinds of phthalonitrile (2) or diiminoisoindoline (3) as a raw material represented by the following formula are mixed with the above-mentioned metal or metal compound which can be a metal or a metal derivative. The reaction is carried out by heating in a solvent, preferably an alcohol, at a temperature in the range of 10 to 300 ° C. When the starting material is phthalonitrile represented by (2), the reaction temperature is preferably in the range of 80 to 160 ° C. When the raw material is diiminoisoindoline represented by (3), the reaction temperature is preferably in the range of 140 to 200 ° C. Also, as a catalyst for the ring formation reaction, 1,
8-diazabicyclo [5.4.0] -7-undecene (DBU), 1,
An auxiliary agent such as 5-diazabicyclo [4.3.0] -5-nonene (DBN) may be added.

[0021]

Embedded image In the formulas (2) and (3), R represents a branched alkyl group;
Represents a halogen atom, and n represents 0, 1, 2, or 3.

The halogenated alkoxyphthalocyanine synthesized under the above conditions is represented by the above formula (1).

Preferred halogenated alkoxyphthalocyanines are those represented by the following formulas (4) to (7).

[0024]

Embedded image In the formulas (4) to (7), R, X, n and Met have the same meanings as R, X, n and Met in the formula (1).

Particularly preferred halogenated alkoxyphthalocyanines include those having a branched alkyl group represented by R in the formulas (4) to (7) having a total of 2 to 4 carbon atoms of secondary, tertiary or quaternary. It is a group containing.

The alkoxyphthalonitrile (2) or alkoxydiiminoisoindoline (3) used in the present invention is synthesized by the method shown in the following reaction formula (8).

[0027]

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The starting material, 3-nitrophthalonitrile or 4-nitrophthalonitrile, was obtained from Tokyo Chemical Industry Co., Ltd. The first reaction from nitrophthalonitrile to alkoxyphthalonitrile is NOUVEAU JOURNAL DE CHIMIE, V
OL.6, NO.12, pp653-58, 1982. That is, an alcohol was reacted with sodium hydride to form a sodium alkoxide, and subsequently reacted with nitrophthalonitrile at 0 to 100 ° C. to obtain alkoxyphthalonitrile.

The synthesis of phthalonitrile halides is described in I.
T. HARRISON and S. HARRISON co-authored "COMPENDIUM OF ORGAN"
Alkoxyphthalonitrile was halogenated according to the method described in IC SYNTHETIC METHOD "Vol. Iodine, sulfuryl chloride, thionyl chloride, antimony chloride, iodine trichloride, iron (III) chloride,
Phosphorus pentachloride, phosphoryl chloride, t-butyl hypochlorite, N-
Preferred are chlorosuccinic imide, cuprous bromide, quaternary ammonium bromide, N-bromosuccinic imide, iodine monochloride, quaternary ammonium iodide, potassium iodide and the like. The amount of the halogenating agent used is appropriately 1 to 2 molar ratio.

The halogenated phthalocyanine mixture used in the present invention was synthesized as follows.

A mixture of the isomers represented by the following formulas (9) to (12) is mixed with an organic solvent and water at 20 ° C.
Reaction with a halogenating agent at 90 ° C.
A phthalocyanine mixture represented by (7) was synthesized.

[0032]

Embedded image In the formulas (9) to (12), R and Met are represented by the formula (4)
These are synonymous with R and Met in (7).

By reacting a phthalocyanine compound with a halogenating agent in a mixed solvent of an organic solvent and water,
Since the by-product hydrogen halide or the salt of the halogenating agent is dissolved in water, the phthalocyanine compound is prevented from being precipitated together with the by-product from the organic solvent which is a reaction solvent, and is efficiently halogenated. it is conceivable that.

As the halogenating agent, the following general formula (1)
3) XY (13) (in the formula (13), X represents a halogen atom;
Represents a halogenating agent residue. The compound represented by ()) can be used. X, H, F, Cl, B
r and I are preferable, and Br is preferable. As the halogenating agent residue of Y, Cl, Br, I, SO ₂ Cl, S
_{OCl, FeCl 2, PCl 2,} PCl 4, POCl 2, C
uBr, quaternary ammonium, and the like.

As the halogenating agent, chlorine, bromine, iodine, sulfuryl chloride, thionyl chloride, antimony chloride,
Iodine trichloride, iron (III) chloride, phosphorus pentachloride, phosphoryl chloride, t-butyl hypochlorite, N-chlorosuccinic imide, cuprous bromide, quaternary ammonium bromide, N-bromosuccinic imide, Iodine monochloride, quaternary ammonium iodide, potassium iodide and the like. Particularly, bromine is preferred. The amount of the halogenating agent to be used is appropriately 1 to 16 molar ratio depending on the desired amount of halogen to be introduced.

The reaction temperature is 20 to 90 ° C., preferably 40 to 70 ° C. If the reaction temperature is lower than 20 ° C., the reaction does not proceed well, and if it exceeds 90 ° C., it becomes difficult to control the halogenation rate.

The organic solvent is substantially immiscible with water, that is, one which forms two layers with water. Expressions (9) to (12)
Is a solvent capable of dissolving the phthalocyanine mixture of the above, and is preferably one or more selected from saturated hydrocarbons, ethers, and halogenated hydrocarbons. More preferably, n-hexane, n-pentane, n-octane, cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, tetrahydrofuran, n-butyl ether, n-propyl ether, isopropyl ether, carbon tetrachloride, chloroform, dichloromethane, 1 One or more selected from 1,1,1-trichloroethane, 1,1,2-trichloroethane, and 1,1,2,2-tetrachloroethane.

The amount of the organic solvent is 2 to 500 times by weight, preferably 3 to 200 times by weight, based on the phthalocyanine mixture as a raw material. It is necessary to dissolve the phthalocyanine mixture, but if it is less than 2 times by weight, solids are likely to precipitate during the reaction and hinder the reaction, while if it exceeds 500 times by weight, the reaction becomes too slow. Improper. In particular
When 1,1,2-trichloroethane or 1,1,2,2-tetrachloroethane is used, its amount is preferably 4 to 10 times by weight.

The amount of water is from 0.05 to
It is 10 times by weight, preferably 0.1 to 5 times by weight, and is preferably a ratio that forms many interfaces between water and the organic solvent. If the amount is less than 0.05 times by weight, the effect of mixing water will not be obtained, and a solid will easily precipitate during the reaction, thus hindering the reaction. On the other hand, if it exceeds 10 times by weight, the amount of the solvent becomes too large and the efficiency of the reaction is lowered, so that it is inappropriate.

The halogenated alkoxyphthalocyanine compound or mixture before the treatment of the present invention is often
It has a certain crystalline state, and therefore has low solvent solubility. That is, although the coating solution did not dissolve to a predetermined concentration, or even once dissolved in a solvent, a precipitate was formed in a short time. It becomes a state and the solubility is remarkably improved.

[0041]

EXAMPLES The present invention will be described below in detail with reference to examples, but the embodiments of the present invention are not limited thereto.

Examples 1 to 6, 8 to 12, 14 to 1
6, X-ray diffraction diagrams of the phthalocyanine compound or the mixture before and after the treatment are shown. The conditions of the X-ray diffraction are as follows.

Tube: Cu, tube voltage: 50 kV, tube current: 200 m
A, goniometer: wide-angle goniometer, sampling angle: 0.020 °, scan speed: 8.0 ° / min,
Scan axis: 2θ / θ, filter: Ni, divergence slit: 1
°, scattering slit: 1 °, fluorescent slit: 0.15 mm.

Example 1 The following formula (14)

[0045]

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37.56 g of diiminoisoindoline represented by
(145 mmol), 6.38 g (36 mmol) of palladium chloride, DBU2
After mixing 2.07 g (145 mmol) and 300 ml of 1-octanol at room temperature, the temperature was raised to the reflux temperature in 30 minutes. The mixture was reacted under reflux for 5 hours, cooled to room temperature, and then discharged into 1000 ml of methanol. The precipitated crystals are filtered, and methanol 300 ml
And washed. After drying at 60 ° C, the following formulas (15) and (1
35.8 g of a mixture of (6), (17) and (18) was obtained. Yield 92
%Met. The mixture has a maximum absorption wavelength λ _max = 692 nm, ε
_max = 2.7 × 10 ⁵ / toluene. The production ratio is (15) / (16) / (17) / (18) = 86 from the area ratio of the liquid chromatogram.
/ 9/3/2.

[0047]

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[0048]

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[0049]

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[0050]

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30 g of the resulting phthalocyanine mixture (27.89
mmol) was dissolved in 180 g (125 mmol) of 1,1,2-trichloroethane, and 60 g (60 ml) of water was added. Then 13.6 g of bromine (85.2
2 mmol) and a mixed solution of 38 g (26 ml) of 1,1,2-trichloroethane were added dropwise at 50 to 55 ° C, and reacted at 55 to 60 ° C for 1 hour.
Washing was performed by adding 30 g of a 15% aqueous sodium bisulfite solution. The organic layer was dropped into 480 g of methanol, and the precipitated crystals were filtered to obtain 35.9 g of a brominated phthalocyanine mixture represented by the following formulas (19), (20), (21) and (22).

[0052]

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[0053]

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[0054]

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[0055]

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The mixture has a maximum absorption wavelength λ _max = 711 nm,
ε _max = 1.6 × 10 ⁵ g ⁻¹ cm ² , melting point 215-45 ° C.

35 g of the above mixture (X-ray diffraction diagram, FIG. 1) was p-
Dissolve in 1 liter of xylene, heat and stir at 80 ° C for 2 hours, cool to room temperature, put into a Kyowa Vacuum Co., Ltd. Triomaster A freeze dryer, cool to -40 ° C, freeze the solution, The heating medium for heating the dryer shelf was heated to 30 ° C. below (40 Pa (300 mtorr)). The frozen p-xylene gradually sublimated, and the temperature of the frozen product increased to 25 ° C. and stabilized at 25 ° C. (at this time, the pressure was 26.7 Pa (200 mtorr)). The inside of the dryer was returned to normal pressure to obtain phthalocyanine from which p-xylene had been removed. This phthalocyanine was dissolved in ethylcyclohexane at a concentration of 30 g / l, and no precipitation occurred even after 10 hours. The X-ray diffraction pattern after the treatment is shown in FIG. The peak was broader than that before the treatment, and it was confirmed that the peak was amorphous. The phthalocyanine mixture before the treatment did not dissolve in ethylcyclohexane up to a concentration of 30 g / l.

Example 2 The following formula (23)

[0059]

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25.6 g of phthalonitrile represented by
(100 mmol), 15.2 g of DBU (100 m
mol) and 120 g of 1-hexanol were mixed at room temperature, and the temperature was raised to 110 ° C. Next, 5.3 g (30 mmol) of palladium chloride was added at the same temperature, and 110 ° C.
After reacting at ~ 120 ° C for 12 hours and cooling to room temperature, the insoluble matter was filtered off, the filtrate was concentrated under reduced pressure, and methanol 400m
The precipitated crystals were filtered and 100 ml of methanol was added.
l. After drying at 60 ° C., the following formula (2)
4) a mixture of (25), (26) and (27)
9 g were obtained. The yield was 92%. The mixture has a maximum absorption wavelength λ _max = 694 nm, ε _max = 2.2 × 1
0 ⁵ was g ^-1 cm ² (toluene). The formation ratio was determined from the area ratio of the liquid chromatogram as (24) / (25) /
(26) / (27) = 48/49/2/1.

[0061]

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[0062]

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[0063]

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[0064]

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10 g of the resulting phthalocyanine mixture (8.84
mmol) was dissolved in 56 g (39 mmol) of 1,1,2-trichloroethane, and 20 g (20 ml) of water was added. Then 4.94 g of bromine (30.91
mmol) and 12 g (8 ml) of 1,1,2-trichloroethane were added dropwise at 50 to 55 ° C, and reacted at 55 to 60 ° C for 1 hour.
Washing was performed by adding 20 g of a 10% aqueous sodium bisulfite solution. The organic layer was dropped into 135 g of methanol, and the precipitated crystals were filtered to obtain 12 g of a brominated phthalocyanine mixture represented by the following formulas (28), (29), (30) and (31).

[0066]

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[0067]

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[0068]

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[0069]

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The mixture has a maximum absorption wavelength λ _max = 705 nm,
ε _max = 1.7 × 10 ⁵ g ⁻¹ cm ² , melting point 268-86 ° C.

10 g of the above mixture (X-ray diffraction pattern, FIG. 3) was
Dissolved in 240 ml of xylene, heated and stirred at 100 ° C. for 2 hours, cooled to room temperature, put into the freeze dryer of Example 1,
Cool to 0 ° C, freeze the solution, and reduce pressure (33.3Pa (250 mt
In (orr)), the heating medium for heating the shelf of the dryer was heated to 30 ° C. The frozen p-xylene gradually sublimates, and the frozen material is 25 ° C
Temperature rises and stabilizes at 25 ° C (the pressure at this time is
20Pa (150 mtorr)). The inside of the dryer was returned to normal pressure to obtain phthalocyanine from which p-xylene had been removed. The phthalocyanine was dissolved in octane at a concentration of 30 g / l and no precipitation occurred after 24 hours. The X-ray diffraction pattern after the treatment is shown in FIG. The peak was broader than that before the treatment, and it was confirmed that the peak was amorphous. The phthalocyanine mixture before the treatment was dissolved in octane at a concentration of 30 g / l, but a precipitate was formed in 8 hours.

Example 3 The following formula (32)

[0073]

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24.2 g of phthalonitrile represented by
(100 mmol), 15.2 g of DBU (100 m
mol) and 100 g of n-amyl alcohol were mixed at room temperature and heated to 90 ° C. Next, 5.3 g (30 mmol) of palladium chloride was added at the same temperature, and 90 ° C.
The mixture was reacted at １００100 ° C. for 12 hours. After cooling to room temperature, insolubles were filtered off, and the filtrate was concentrated under reduced pressure.
The precipitated crystals were filtered and 100 ml of methanol was added.
l. After drying at 60 ° C., the above formula (1)
5) a mixture of (16), (17) and (18)
6 g were obtained. The yield was 92%. The mixture has a maximum absorption wavelength λ _max = 690 nm, ε _max = 2.8 × 1
0 ⁵ was g ^-1 cm ² (toluene). The production ratio was determined from the area ratio of the liquid chromatogram as (15) / (16) /
(17) / (18) = 48/48/2/2.

20 g of the above mixture (X-ray diffraction pattern, FIG. 5)
Was dissolved in 400 ml of benzene, heated and stirred at 80 ° C. for 3 hours, cooled to room temperature, put into the freeze dryer of Example 1, cooled to −40 ° C., frozen the solution, and reduced under reduced pressure (3
At 7.3 Pa (280 mtorr), the heating medium for heating the shelf of the dryer was heated to 30 ° C. The frozen benzene gradually sublimated, the temperature of the frozen product rose to 25 ° C., and the temperature became constant at 25 ° C. (at this time, the pressure was 18.7 Pa (140 ° C.).
mtorr)). The inside of the dryer was returned to normal pressure to obtain phthalocyanine from which benzene had been removed. This phthalocyanine is dissolved in ethylcyclohexane at a concentration of 30 g / l,
After 8 hours, no precipitation was observed. X after processing
The line diffraction diagram is shown in FIG. The peak was broader than that before the treatment, and it was confirmed that the peak was amorphous. The phthalocyanine mixture before the treatment was dissolved in ethylcyclohexane at a concentration of 30 g / l, but a precipitate was formed in 6 hours.

Example 4 The following formula (33)

[0077]

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9.8 of the diiminoisoindoline represented by
3 g (36 mmol), palladium chloride 1.59
g (9 mmol), DBU 5.47 g (36 mm
ol) and 50 ml of n-octyl alcohol were mixed at room temperature and reacted under reflux for 5 hours. After cooling to room temperature
Discharged in 200 ml of methanol. The precipitated crystals were filtered and washed with 100 ml of methanol. After drying at 60 ° C., the following formulas (34), (35), and (36)
12.0 g of a mixture of (37) and (37) were obtained. The yield was 92%. The mixture has a maximum absorption wavelength λ _max = 692
nm, ε _max = 2.5 × 10 ⁵ g ⁻¹ cm ² (toluene). The production ratio was (34) / (35) / (36) / (7) = 90 from the area ratio of the liquid chromatogram.
/ 5/3/2.

[0079]

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[0080]

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[0081]

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[0082]

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10 g of the resulting phthalocyanine mixture (8.84
mmol) was dissolved in 48 g (30 mmol) of 1,1,2,2-tetrachloroethane, and 20 g (20 ml) of water was added. Then 5.51 g of bromine (3
4.48 mmol) and 16 g (10 ml) of 1,1,2,2-tetrachloroethane
Was added dropwise at 50 to 55 ° C, reacted at 55 to 60 ° C for 1 hour, and washed by adding 25 g of a 10% aqueous sodium bisulfite solution. The organic layer was dropped into 158 g of methanol, and the precipitated crystals were filtered to obtain 12.5 g of a brominated phthalocyanine mixture represented by the following formulas (38), (39), (40) and (41).

[0084]

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[0085]

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[0086]

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[0087]

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The mixture has a maximum absorption wavelength λ _max = 709 nm,
ε _max = 1.4 × 10 ⁵ g ⁻¹ cm ² , melting point 201-28 ° C.

10 g of the above mixture (X-ray diffraction pattern, FIG. 7)
Dissolve in 100 ml of xylene, heat and stir at 100 ° C. for 2 hours, cool to room temperature, put into the freeze dryer of Example 1,
Cool to 0 ° C, freeze the solution, and reduce pressure (33.3Pa (250 mt
In (orr)), the heating medium for heating the shelf of the dryer was heated to 40 ° C. Frozen p-xylene gradually sublimates, frozen at 35 ° C
Temperature rises and stabilizes at 35 ° C (the pressure at this time is
20.0 Pa (150 mtorr)). The inside of the dryer was returned to normal pressure to obtain phthalocyanine from which p-xylene had been removed. This phthalocyanine was dissolved in ethylcyclohexane at a concentration of 30 g / l, and no precipitation occurred after 48 hours. FIG. 8 shows the X-ray diffraction pattern after the treatment. The peak was broader than that before the treatment, and it was confirmed that the peak was amorphous. The phthalocyanine mixture before the treatment was dissolved in ethylcyclohexane at a concentration of 30 g / l, but precipitation occurred in 8 hours.

Example 5 24.2 g of phthalonitrile represented by the above formula (32)
(100 mmol), DBU 15.2 g (100
mmol) and 130 g of n-amyl alcohol were mixed at room temperature and heated to 95 ° C. Next, 2.5 g (25 mmol) of copper (I) chloride was added at the same temperature,
The mixture was reacted at 105 ° C. for 10 hours, cooled to room temperature, filtered to remove insolubles, and the filtrate was concentrated under reduced pressure to give 500 ml of methanol.
The precipitated crystals were filtered and 100 ml of methanol was added.
And washed. After drying at 60 ° C., the following formula (4)
2) a mixture of (43), (44) and (45)
0 g was obtained. The yield was 93%. The mixture has a maximum absorption wavelength λ _max = 708 nm, ε _max = 2.8 × 10 ⁵
g ⁻¹ cm ² (toluene). The production ratio was calculated from the area ratio of the liquid chromatogram as (42) / (43) / (4
4) / (45) = 46/47/4/3.

[0091]

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[0092]

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[0093]

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[0094]

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20 g of the obtained phthalocyanine mixture (18.59
mmol) was dissolved in 120 g (83 mmol) of 1,1,2-trichloroethane, and 40 g (40 ml) of water was added. Then 9.1 g of bromine (56.81 m
mol) and 25 g (18 ml) of 1,1,2-trichloroethane were added dropwise at 50 to 55 ° C, and reacted at 55 to 60 ° C for 1 hour.
20 g of a 20% aqueous sodium bisulfite solution was added for washing.
The organic layer was dropped into 320 g of methanol, and the precipitated crystals were filtered to obtain 23.9 g of a brominated phthalocyanine mixture represented by the following formulas (46), (47), (48), and (49).

[0096]

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[0097]

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[0098]

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[0099]

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The mixture has a maximum absorption wavelength λ _max = 715 nm,
ε _max = 1.6 × 10 ⁵ g ⁻¹ cm ² , melting point 222-52 ° C.

20 g of the above mixture (X-ray diffraction pattern, FIG. 9)
Dissolve in 400 ml of xylene, heat and stir at 100 ° C. for 2 hours, cool to room temperature, put into the freeze dryer of Example 1,
After cooling to 0 ° C, the solution was frozen and the pressure was reduced (32.0 Pa (240 mto
In rr)), the heating medium for heating the shelf of the dryer was heated to 30 ° C.
The frozen p-xylene gradually sublimates, and the temperature of the frozen product rises to 30 ° C and stabilizes at 30 ° C (at this time, the pressure is 18.7 ° C).
Pa (140 mtorr)). The inside of the dryer was returned to normal pressure to obtain phthalocyanine from which p-xylene had been removed. The phthalocyanine was dissolved in octane at a concentration of 30 g / l and no precipitation occurred after 24 hours. The X-ray diffraction diagram after the treatment is shown in FIG. The peak was broader than that before the treatment, and it was confirmed that the peak was amorphous. The phthalocyanine mixture before the treatment was dissolved in octane at a concentration of 30 g / l, but a precipitate was formed in 9 hours.

Example 6 Diiminoisoindoline 4 represented by the above formula (33)
9.15 g (180 mmol), cuprous chloride 4.45
g (45 mmol), DBU 27.35 g (180
mmol) and 250 ml of n-octyl alcohol
Was mixed at room temperature and reacted under reflux for 5 hours. After cooling to room temperature, it was discharged into 1000 ml of methanol. The precipitated crystals were filtered and washed with 500 ml of methanol. After drying at 60 ° C., the following formulas (50) and (5)
52.8 g of a mixture of 1), (52) and (53) were obtained. The yield was 92%. The mixture maximum absorption wavelength _{λ ma x = 699 nm, ε} max = 2.1 × 10 5 g -1 c
m ² (toluene). The production ratio was calculated from the area ratio of the liquid chromatogram as (50) / (51) / (52) /
(53) = 90/5/3/2.

[0103]

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[0104]

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[0105]

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[0106]

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50 g of the obtained phthalocyanine mixture (44.2
mmol) was dissolved in 240 g (150 mmol) of 1,1,2,2-tetrachloroethane, and 100 g (100 ml) of water was added. Then bromine 27.5
5 g (172.4 mmol) and 80 g of 1,1,2,2-tetrachloroethane
(50 ml) was added dropwise at 50 to 55 ° C, and reacted at 55 to 60 ° C for 1 hour.
And washed. The organic layer was added dropwise to 790 g of methanol, and the precipitated crystals were filtered, and a brominated phthalocyanine mixture 62.5 represented by the following formulas (54), (55), (56) and (57) was obtained.
g was obtained.

[0108]

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[0109]

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[0110]

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[0111]

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The mixture has a maximum absorption wavelength λ _max = 712 nm,
ε _max = 1.4 × 10 ⁵ g ⁻¹ cm ² , melting point 210-32 ° C.

40 g of the above mixture (X-ray diffraction diagram, FIG. 11) was dissolved in 1000 ml of benzene, heated and stirred at 80 ° C. for 3 hours, cooled to room temperature, and placed in the freeze dryer of Example 1; Four
Cool to 0 ° C, freeze the solution, and reduce pressure (36.0 Pa (270 mt
The heating medium for heating the shelf of the dryer in (orr)) was heated to 30 ° C. The frozen benzene gradually sublimates, and the temperature of the frozen product rises to 28 ° C and stabilizes at 28 ° C.
5.3 Pa (190 mtorr)). The inside of the dryer was returned to normal pressure to obtain phthalocyanine from which benzene had been removed. This phthalocyanine is dissolved in ethylcyclohexane at a concentration of 30 g / l,
No precipitation occurred after 24 hours. FIG. 12 shows the X-ray diffraction pattern after the treatment. The peak was broader than that before the treatment, and it was confirmed that the peak was amorphous.
The phthalocyanine mixture before the treatment was dissolved in ethylcyclohexane at a concentration of 30 g / l, but a precipitate was formed in 9 hours.

Example 7 The ethylcyclohexane solution prepared in Example 1 was applied to a substrate to produce a CD-R medium. The produced optical disk had a reflectance of 71%, a linear velocity of 1.3 m / s and a sensitivity of 7.6 m.
W, the block error rate was 18, and satisfied the CD-R standard.

Example 8 30 g of the phthalocyanine mixture before the treatment in Example 1 was dissolved in 600 ml of toluene, heated and stirred at 100 ° C. for 2 hours, cooled to room temperature, and the solvent was distilled off with an evaporator. To dry the residue. The phthalocyanine thus treated was dissolved in ethylcyclohexane at a concentration of 30 g / l, and no precipitation occurred even after 10 hours. FIG. 13 shows the X-ray diffraction pattern after the treatment. The peak was broader than that before the treatment, and it was confirmed that the peak was amorphous.

Example 9 20 g of the phthalocyanine mixture before the treatment in Example 3 was dissolved in 350 ml of ethylbenzene, and the mixture was heated and stirred at 130 ° C. for 6 hours. After cooling to room temperature, the solvent was distilled off with an evaporator. The residue was dried. The phthalocyanine thus treated was dissolved in ethylcyclohexane at a concentration of 30 g / l, and no crystal precipitation was observed even after 12 hours. FIG. 14 shows an X-ray diffraction pattern after the treatment. The peak was broader than that before the treatment, and it was confirmed that the peak was amorphous.

Example 10 10 g of the phthalocyanine mixture before the treatment in Example 2 was dissolved in 240 ml of isopropylbenzene, heated and stirred at 150 ° C. for 2 hours, cooled to room temperature, and the solvent was distilled off with an evaporator. The residue was dried at C. The phthalocyanine thus treated was dissolved in octane at a concentration of 30 g / l, and no sedimentation change was observed even after 24 hours. The X-ray diffraction pattern after the treatment is shown in FIG. The peak was broader than that before the treatment, and it was confirmed that the peak was amorphous.

Example 11 10 g of the phthalocyanine mixture before the treatment in Example 4 was dissolved in 400 ml of xylene, and the mixture was heated and stirred at 135 ° C. for 2 hours. After cooling to room temperature, the solvent was distilled off with an evaporator. To dry the residue. The phthalocyanine treated in this way was dissolved in octane at a concentration of 30 g / l and no change was seen after 24 hours. FIG. 16 shows the X-ray diffraction pattern after the treatment. The peak was broader than that before the treatment, and it was confirmed that the peak was amorphous.

Example 12 20 g of the phthalocyanine mixture before the treatment in Example 5 was dissolved in 800 ml of xylene, heated and stirred at 135 ° C. for 2 hours, cooled to room temperature, and the solvent was distilled off with an evaporator. To dry the residue. The phthalocyanine treated in this way was dissolved in octane at a concentration of 30 g / l, and no precipitation was observed after 24 hours. FIG. 17 shows the X-ray diffraction pattern after the treatment. Compared to before processing
The peak was broad, and it was confirmed that the material was amorphous.

Example 13 The ethylcyclohexane solution prepared in Example 8 was applied to a polycarbonate substrate to prepare a CD-R medium. The produced medium had a reflectance of 71%, a linear velocity of 1.3 m / s, a sensitivity of 7.6 mW, a block error rate of 17, and a CD.
-R was satisfied.

Example 14 10 g of phthalonitrile represented by the following formula (58), 2 g of palladium chloride, 4 g of DBU and 200 g of n-amyl alcohol were mixed and reacted at 95 ° C. for 24 hours.

[0122]

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The reaction mixture is discharged into 1000 ml of methanol,
The precipitated tar was separated and purified by column chromatography to obtain the following formula (59): 2 g, (60): 2 g, (61): 0.5 g, and (62): 0.5 g. Each physical property value was as shown in Table 1 below.

[0124]

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[0125]

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[0126]

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[0127]

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[0128]

[Table 1]

2 g of the obtained compound of the formula (59) (X-ray diffraction pattern, FIG. 18) was dissolved in 50 ml of p-xylene, and the mixture was heated with stirring at 100 ° C. for 2 hours, cooled to room temperature, and cooled to room temperature. Put into a freeze dryer, cool to -40 ° C, freeze the solution, and heat the dryer shelf under reduced pressure (32.0 Pa (240 mTorr)) with 3 heat medium.
The temperature was raised to 0 ° C. The frozen p-xylene gradually sublimated, and the temperature of the frozen product rose to 30 ° C., and the temperature became constant at 30 ° C. (at this time, the pressure was 17.3 Pa (130 mTorr)). The inside of the dryer was returned to normal pressure to obtain phthalocyanine from which p-xylene had been removed. The treated phthalocyanine was dissolved in dimethylcyclohexane at a concentration of 30 g / l, and no precipitation was observed even after 24 hours. Fig. 1 shows the X-ray diffraction pattern after the treatment.
It is shown in FIG. It was confirmed that the peak was broader than that of the product before the treatment, and it was amorphous. The phthalocyanine before treatment was added to dimethylcyclohexane at 30 g /
Although dissolved at a concentration of 1 l, a precipitate formed in 8 hours.

Example 15 5 g of the mixture of (59) to (62) obtained in Example 14 (X-ray diffraction pattern, FIG. 20) was dissolved in 100 ml of toluene and heated at 100 ° C.
After heating and stirring for 2.5 hours and cooling to room temperature, the solvent was distilled off using an evaporator, and the residue was dried at 60 ° C. The treated phthalocyanine was dissolved in octane at a concentration of 30 g / l, and no precipitation was observed even after 24 hours. FIG. 21 shows an X-ray diffraction pattern after the treatment. It was confirmed that the peak was broader than that of the product before the treatment, and it was amorphous.

Example 16 5 g of a phthalonitrile represented by the above formula (58) was prepared by the following formula (63).
5 g of phthalonitrile, 2 g of palladium chloride, D
4 g of BU and 200 g of n-amyl alcohol were mixed and reacted at 95 ° C. for 24 hours.

[0132]

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The reaction mixture was discharged into 1000 ml of methanol,
The precipitated tar was separated and purified by column chromatography to obtain 0.1 g of the following formula (64), 0.1 g of (65), 0.5 g of (66) and 0.3 g of (67). Each physical property value was as shown in Table 2 below.

[0134]

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[0135]

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[0136]

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[0137]

[Of 60]

[0138]

[Table 2]

1 g of the above mixture (X-ray diffraction pattern, FIG. 22) was p-
Dissolve in 20 ml of xylene, heat and stir at 100 ° C. for 2 hours, cool to room temperature, and place in the freeze dryer of Example 1;
The solution was frozen by cooling to 0 ° C, and the solution was reduced under reduced pressure (34.7 Pa (260 m
(Torr)), the heating medium for heating the shelf of the dryer was heated to 30 ° C. Frozen p-xylene gradually sublimates, and frozen
The temperature rose to 8 ° C, and became constant at 28 ° C (at this time, the pressure was 17.3 Pa (130 mTorr)). The inside of the dryer was returned to normal pressure to obtain phthalocyanine from which p-xylene had been removed. The treated phthalocyanine was dissolved in dimethylcyclohexane at a concentration of 30 g / l, and no precipitation was observed even after 24 hours. FIG. 23 shows the X-ray diffraction pattern after the treatment.
It was confirmed that the peak was broader than that of the product before the treatment, and it was amorphous. The phthalocyanine before the treatment was dissolved in dimethylcyclohexane at a concentration of 30 g / l, but a precipitate was formed in 9 hours.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction diagram of phthalocyanine before treatment in Example 1.

FIG. 2 is an X-ray diffraction diagram of the phthalocyanine after the treatment in Example 1.

FIG. 3 is an X-ray diffraction diagram of phthalocyanine before treatment in Example 2.

FIG. 4 is an X-ray diffraction diagram of the phthalocyanine after the treatment in Example 2.

FIG. 5 is an X-ray diffraction diagram of phthalocyanine before treatment in Example 3.

FIG. 6 is an X-ray diffraction pattern of the phthalocyanine after the treatment in Example 3.

FIG. 7 is an X-ray diffraction diagram of phthalocyanine before treatment in Example 4.

FIG. 8 is an X-ray diffraction pattern of the phthalocyanine after the treatment in Example 4.

FIG. 9 is an X-ray diffraction diagram of phthalocyanine before treatment in Example 5.

FIG. 10 is an X-ray diffraction diagram of phthalocyanine after the treatment in Example 5.

FIG. 11 is an X-ray diffraction diagram of phthalocyanine before treatment in Example 6.

FIG. 12 is an X-ray diffraction diagram of the phthalocyanine after the treatment in Example 6.

FIG. 13 is an X-ray diffraction diagram of the phthalocyanine after the treatment in Example 8.

FIG. 14 is an X-ray diffraction diagram of the phthalocyanine after the treatment in Example 9.

FIG. 15 is an X-ray diffraction diagram of the phthalocyanine after the treatment in Example 10.

FIG. 16 is an X-ray diffraction pattern of the phthalocyanine after the treatment in Example 11.

FIG. 17 is an X-ray diffraction diagram of the phthalocyanine after the treatment in Example 12.

FIG. 18 is an X-ray diffraction diagram of phthalocyanine before treatment in Example 14.

FIG. 19 is an X-ray diffraction diagram of the phthalocyanine after the treatment in Example 14.

FIG. 20 is an X-ray diffraction pattern of the mixture obtained in Example 14 before processing.

FIG. 21 is an X-ray diffraction diagram of phthalocyanine after the treatment in Example 15.

FIG. 22 is an X-ray diffraction diagram of phthalocyanine before treatment in Example 16.

FIG. 23 is an X-ray diffraction pattern of the phthalocyanine after the treatment in Example 16.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G11B 7/24 516 B41M 5/26 Y (72) Inventor Kenichi Sugimoto 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Inside Chemical Co., Ltd. 2H048 CA04 CA12 2H111 EA03 EA22 FB45 GA07 4C050 PA12 5D029 JA04

Claims (14)

[Claims] [Claim 1] The following general formula (1) [In the formula (1), R represents a branched alkyl group, X represents a halogen atom, and n represents the number of X, and is 0 to 4. Met represents a divalent metal atom, a trivalent or tetravalent metal derivative, or an oxymetal. An amorphous body having improved solubility of an alkoxyphthalocyanine, which is a compound or a mixture represented by the formula, in an organic solvent for spin coating. 2. The method according to claim 1, wherein the amorphous body is produced by heating a crystalline phthalocyanine compound or a mixture thereof in an organic solvent and distilling off the organic solvent under reduced pressure. Amorphous body. 3. The amorphous body according to claim 2, which is produced by heating at a temperature of 50 to 250 ° C. in an organic solvent. 4. The amorphous material according to claim 2, wherein an aromatic organic solvent is used as the organic solvent. 5. The amorphous material according to claim 4, wherein the aromatic organic solvent is toluene, ethylbenzene, isopropylbenzene or xylene. 6. The amorphous body according to claim 1, wherein the amorphous body is produced by heating a crystalline phthalocyanine compound or a mixture thereof in an organic solvent, and then freeze-drying the organic solvent solution. 7. The organic solvent used for freeze-drying has a freezing point of-
The amorphous body according to claim 6, wherein the temperature is 40 to 40 ° C. 8. The amorphous body according to claim 6, wherein the heating temperature is 50 to 250 ° C. 9. The amorphous body according to claim 6, wherein the freezing temperature is from −50 to 0 ° C. 10. The method according to claim 6, wherein the temperature of the heating medium for heating the shelf of the dryer after freezing is from −30 to 70 ° C.
An amorphous body according to the item. 11. The amorphous body according to claim 10, wherein the temperature of the heating medium for heating the shelf of the dryer after freezing is 0 to 70 ° C. 12. The drying pressure is 133.32 Pa (1
000 mTorr) to 1.33 Pa (10 mTorr)
The amorphous body according to any one of claims 6 to 11, which is r). 13. The drying pressure is 133.32 Pa (1
000 mTorr) to 13.33 Pa (100 mTo
The amorphous body according to claim 12, which is rr). 14. The amorphous material according to claim 6, wherein the organic solvent is benzene or p-xylene.