JP2002363437A - Amorphous form of dipyrromethene metal chelate compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a dipyrromethene metal chelate compound improved in solubility. SOLUTION: The amorphous form of the dipyrromethene metal chelate compound of formula 1 [R<1> to R<8> are each H, a halogen atom, nitro, cyano, OH, amino, carboxy, sulfo, a <=20C (substituted) alkyl, alkoxy, alkylthio, aryloxy, arylthio, alkenyl, acyl, alkoxycarbonyl, carbamoyl, acylamino, aralkyl, aryl or heteroaryl; R<9> is a halogen atom, a <=20C (substituted) aryl, heteroaryl, alkoxy, alkylthio, aryloxy or arylthio, where R<1> and R<2> may form a ring via a linkage group; and M is a transition metal] is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an amorphous form of a dipyrromethene metal chelate compound having excellent solubility, which regulates the crystal form of the dipyrromethene metal chelate compound, and a method for producing the same. The amorphous body of the dipyrromethene metal chelate compound of the present invention is useful as a recording and storage material for a liquid crystal display device, an optical filter, a write-once optical recording medium and the like, particularly a recording material for an optical recording medium capable of high-density recording and reproduction. is there.

[0002]

2. Description of the Related Art Various organic dyes have been developed as recording and storage materials, and in particular, as recording materials for DVD-Rs, which have recently attracted attention as high-density optical recording media, and include cyanine, azo, benzopyran, benzodifuranone, and the like. Indigo, dioxazine, porphyrin dyes and the like have been proposed (JP-A-4-74690, JP-A-5-388).
No. 78, JP-A-6-40161, JP-A-6-401
40162, JP-A-6-199045, JP-A-6-336086, JP-A-7-76169, JP-A-7-125441, JP-A-7-26
2604, JP-A-9-156218, JP-A-9-193544, JP-A-9-193545, JP-A-9-193546, JP-A-9-19
4748, JP-A-9-20252, JP-A-9-267562, JP-A-9-274732, and the like.

However, the transmission wavelength of the laser light is 630 nm to 6
Problems caused by the wavelength being shorter than that of the CD when the wavelength is around 80 nm, for example, where a small pit should be opened with a focused laser beam, the influence on the surroundings is large, and the jitter due to the formation of a large distribution of pits is large. Deterioration, deterioration of crosstalk in the radial direction, deterioration of the degree of modulation due to extremely small pits, or inappropriate optical constants (refractive index,
At present, no solution has been made to the reduction of the reflectance or the deterioration of the sensitivity caused by selecting an organic dye having an extinction coefficient) for the recording layer.

[0004] Further, in recording, an optical recording medium capable of recording at a higher speed than a normal recording speed is desired. However, deterioration of the recording sensitivity and jitter due to the high speed recording can be solved. It is not at present.

In order to solve the above-mentioned problems, the present inventors have proposed an optical recording medium using a dipyrromethene metal chelate compound, which is disclosed in JP-A-10-226172 and JP-A-11-092682. Gazette, JP-A-11-
JP-A-165465, JP-A-11-227332, JP-A-11-227333, JP-A-11-3
No. 21098, Japanese Patent Application No. 13-052523, and the like. Examples of a method for providing a recording layer of an optical recording medium using a dipyrromethene metal chelate compound include spin coating, spraying, casting, coating such as dipping, sputtering, chemical vapor deposition, and vacuum vapor deposition. However, the spin coating method is simple and preferred. When preparing a coating solution for this spin coating method, the dipyrromethene metal chelate compound is used in a solvent in an amount of 1 to 40% by mass, preferably 3 to 40% by mass.
Although it dissolves at a concentration of 30% by mass, the above-mentioned dipyrromethene metal chelate compound does not dissolve to an optimum concentration, or precipitates in a short time even if dissolved once, so that the required concentration is applied. It has been found that the liquid cannot be adjusted in some cases.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an amorphous dipyrromethene metal chelate compound having improved solubility.

[0007]

Means for Solving the Problems The present inventors have made intensive studies on improving the solubility of the dipyrromethene metal chelate compound. As a result, after dissolving the dipyrromethene metal chelate compound in an organic solvent, the solution was frozen. The present inventors have found that an amorphous dipyrromethene metal chelate compound having improved solubility can be obtained by a vacuum freeze-drying method in which a frozen substance is heated under reduced pressure to sublime a solvent, thereby completing the present invention. That is, the present invention

An amorphous form of a dipyrromethene metal chelate compound represented by the following general formula (1).

[0009]

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[Wherein, R ^{1 to} R ⁸ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a substituent having 20 or less carbon atoms or Unsubstituted alkyl, alkoxy, alkylthio, aryloxy, arylthio, alkenyl, acyl, alkoxycarbonyl, carbamoyl, acylamino, aralkyl,
An aryl group or a heteroaryl group, R ⁹ represents a halogen atom, of 20 or less substituted or unsubstituted aryl group having a carbon heteroaryl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, R ¹
And R ² may form a ring via a linking group represented by formula (a), and M represents a transition element.

[0011]

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(A represents a substituted or unsubstituted aromatic or heterocyclic ring having 20 or less carbon atoms, and L ¹ includes a hetero atom which forms a ring together with the carbon atom to which it is bonded. Represents a substituted or unsubstituted residue)

A method for producing an amorphous form of a dipyrromethene metal chelate compound represented by the following general formula (1), comprising dissolving a crystalline dipyrromethene metal chelate compound in an organic solvent and freeze-drying the organic solvent solution.

[0014]

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[Wherein R ^{1 to} R ⁸ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a substituent having 20 or less carbon atoms or Unsubstituted alkyl, alkoxy, alkylthio, aryloxy, arylthio, alkenyl, acyl, alkoxycarbonyl, carbamoyl, acylamino, aralkyl,
An aryl group or a heteroaryl group, R ⁹ represents a halogen atom, of 20 or less substituted or unsubstituted aryl group having a carbon heteroaryl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, R ¹
And R ² may form a ring via a linking group represented by formula (a), and M represents a transition element.

[0016]

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(A represents a substituted or unsubstituted aromatic or heterocyclic ring having 20 or less carbon atoms, and L ¹ contains a hetero atom which forms a ring together with the carbon atom to which it is bonded. Represents a substituted or unsubstituted residue)

[0018] A production method in which the organic solvent used for freeze-drying has a freezing point of -40 to 40 ° C. The freezing temperature is-
The production method at 50 to 0 ° C. The temperature of the heating medium for heating the dryer shelf after freezing is -30.
-70 ° C. The temperature of the heating medium for heating the shelf of the dryer after freezing is 0 to 7
The production method at 0 ° C. The pressure during drying is 133.32 Pa (1000 mTo
rr) to 1.33 Pa (10 mTorr).

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The organic solvent used in the present invention is: 1) dissolving a dipyrromethene metal chelate compound to change the crystalline state to an amorphous state; 2) removing the solvent by freeze-drying; As described above, it is preferable that the condition of 0 ° C. or higher and 40 ° C. or lower be satisfied.
-Dichloroethane, 1,1,1-trichloroethane,
1,1,2-trichloroethane, iodobenzene, bromobenzene, 1-methylnaphthalene, m-chlorotoluene, o-xylene, m-dichlorobenzene, carbon tetrachloride, tetrachloroethylene, 1,6-dimethylnaphthalene, 1,2- Dichlorobenzene. α, α-dichlorotoluene, 3,4-dichlorotoluene, 2,4-dichlorotoluene, α, α, α-trichlorotoluene, 1-chloronaphthalene, 1,2-dimethylnaphthalene, diisopropyl ether, anisole, 1,1 , 2,2-tetrachloroethane, 1,3,5-trichlorobenzene, 1,3
-Dibromobenzene, 1,4-dibromobenzene, preferably benzene, p-xylene, 1-bromonaphthalene, p-chlorotoluene, 1,4-dioxane, 1,2
-Dibromoethane, 1,2-dibromobenzene, 2-methylnaphthalene and the like.

For drying by drying, the solution of the dipyrromethene metal chelate compound is put into a freeze dryer, and is heated at normal pressure at a temperature of -50 ° C or higher, preferably -40 to 0 ° C within 120 minutes, preferably 60 minutes. After cooling and freezing the solution, the pressure was reduced and the heating medium for heating the shelf of the dryer was heated from -30 to 70 ° C, preferably from -30 ° C to 40 ° C to freeze while supplementing the latent heat of vaporization. The solvent is sublimated and dried. At this time, the internal pressure of the freeze dryer was approximately 133.32 Pa.
(1000 mTorr) or less, preferably approximately 66.7
Pa (500 mTorr) or less, and approximately 26.7 Pa (200 mTorr) or less at the final stage of drying is preferable.

In the dipyrromethene metal chelate compound represented by the general formula (1), specific examples of R ^{1 to} R ⁸ include a hydrogen atom; a halogen atom such as fluorine, chlorine, bromine and iodine; a nitro group; a cyano group; Group; amino group; carboxyl group; sulfonic group; methyl group, ethyl group, n
-Propyl group, iso-propyl group, n-butyl group, i
so-butyl group, sec-butyl group, t-butyl group, n
-Pentyl group, iso-pentyl group, 2-methylbutyl group, 1-methylbutyl group, neo-pentyl group, 1,2
-Dimethylpropyl group, 1,1-dimethylpropyl group,
cyclo-pentyl group, n-hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,2-dimethylbutyl group, 1,1-dimethylbutyl group, 3-ethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group,
2,2-trimethylbutyl group, 1,1,2-trimethylbutyl group, 1-ethyl-2-methylpropyl group, cyc
lo-hexyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group,
5-methylhexyl group, 2,4-dimethylpentyl group,
n-octyl group, 2-ethylhexyl group, 2,5-dimethylhexyl group, 2,5,5-trimethylpentyl group,
2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group, 3,5,5-trimethylhexyl group, n-
Nonyl group, n-decyl group, 4-ethyloctyl group, 4-
Ethyl-4,5-dimethylhexyl group, n-undecyl group, n-dodecyl group, 1,3,5,7-tetraethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, n-tridecyl group , 6-methyl-4-butyloctyl group, n-tetradecyl group, n-pentadecyl group, 3,5-dimethylheptyl group, 2,6-dimethylheptyl group, 2,4-dimethylheptyl group, 2,2,5 ,
Substituted or unsubstituted with 20 or less carbon atoms, preferably 15 or less carbon atoms, such as a 5-tetramethylhexyl group, a 1-cyclo-pentyl-2,2-dimethylpropyl group, and a 1-cyclo-hexyl-2,2-dimethylpropyl group. An alkyl group of

Methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-
Butoxy group, sec-butoxy group, t-butoxy group, n
A substituted or unsubstituted alkoxy group having 20 or less, preferably 15 or less carbon atoms, such as -pentoxy group, iso-pentoxy group, neo-pentoxy group, n-hexyloxy group, n-dodecyloxy group; methylthio group, ethylthio group , N-propylthio group, iso-propylthio group, n
-Butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, i
so-pentylthio group, 2-methylbutylthio group, 1-
Methylbutylthio group, neo-pentylthio group, 1,2
A substituted or unsubstituted alkylthio group having 20 or less, preferably 15 or less carbon atoms, such as -dimethylpropylthio group and 1,1-dimethylpropylthio group; phenoxy group, 2-methylphenoxy group, 4-methylphenoxy group, -T-
Butylphenoxy group, 2-methoxyphenoxy group, 4-
a substituted or unsubstituted aryloxy group having 20 or less carbon atoms, preferably 15 or less carbon atoms, such as an iso-propylphenoxy group;

A substituted or unsubstituted arylthio group having a carbon number of 20 or less, preferably 15 or less, such as a phenylthio group, a 4-methylphenylthio group, a 2-methoxyphenylthio group and a 4-t-butylphenylthio group; Vinyl group, propenyl group, 1-butenyl group, iso-butenyl group, 1-pentenyl group, 2-pentenyl group, 2-methyl-1-butenyl group, 3-methyl-1-butenyl group, 2-methyl-2
-Butenyl group, 2,2-dicyanovinyl group, 2-cyano-2-methylcarboxylvinyl group, 2-cyano-2-
A substituted or unsubstituted alkenyl group having 20 or less, preferably 15 or less carbon atoms, such as a methylsulfone vinyl group and a 2-phenyl-1-butenyl group; formyl group, acetyl group, ethylcarbonyl group, n-propylcarbonyl group, iso
-Propylcarbonyl group, n-butylcarbonyl group, i
carbon such as so-butylcarbonyl group, sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, iso-pentylcarbonyl group, neo-pentylcarbonyl group, 2-methylbutylcarbonyl group, nitrobenzylcarbonyl group, etc. A substituted or unsubstituted acyl group having a number of 20 or less, preferably 15 or less; a carbon number of 20 or less, preferably 15 or less, such as a methoxycarbonyl group, an ethoxycarbonyl group, an isopropyloxycarbonyl group, and a 2,4-dimethylbutyloxycarbonyl group. A substituted or unsubstituted alkoxycarbonyl group; a carbamoyl group;

An acetylamino group, an ethylcarbonylamino group, a butylcarbonylamino group and the like having 20 or less carbon atoms;
Preferably 15 or less substituted or unsubstituted acylamino groups; benzyl group, nitrobenzyl group, cyanobenzyl group, hydroxybenzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, dichlorobenzyl group, methoxybenzyl group, ethoxybenzyl Group, trifluoromethylbenzyl group, naphthylmethyl group, nitronaphthylmethyl group, cyanonaphthylmethyl group, hydroxynaphthylmethyl group, methylnaphthylmethyl group, trifluoromethylnaphthylmethyl group and the like having 20 or less carbon atoms, preferably 15 or less. A substituted or unsubstituted aralkyl group;
Phenyl, nitrophenyl, cyanophenyl, hydroxyphenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, n-propylphenyl, di (n-propyl ) Phenyl, tri (n-propyl) phenyl, iso-propylphenyl, di (iso-propyl) phenyl, tri (is
o-propyl) phenyl group, n-butylphenyl group, di (n-butyl) phenyl group, tri (n-butyl) phenyl group, iso-butylphenyl group, di (iso-butyl) phenyl group, tri (iso- Butyl) phenyl group,
sec-butylphenyl group, di (sec-butyl) phenyl group, tri (sec-butyl) phenyl group, t-butylphenyl group, di (t-butyl) phenyl group, tri (t
-Butyl) phenyl group, dimethyl-t-butylphenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, iodophenyl group, methoxyphenyl group, ethoxyphenyl group, trifluoromethylphenyl group,
N, N-dimethylaminophenyl group, naphthyl group, nitronaphthyl group, cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl group, fluoronaphthyl group, chloronaphthyl group, bromonaphthyl group, iodonaphthyl group, methoxynaphthyl group, trifluoro A methylnaphthyl group, N,
A substituted or unsubstituted aryl group having 20 or less, preferably 15 or less carbon atoms, such as an N-dimethylaminonaphthyl group;

Carbon such as pyrrolyl, thienyl, furanyl, oxazoyl, isoxazoyl, oxadiazoyl, imidazoyl, benzoxazoyl, benzothiazoyl, benzoimidazoyl, benzofuranyl, indoyl, isoindoyl, etc. A substituted or unsubstituted heteroaryl group having a number of 20 or less, preferably 15 or less;

Specific examples of R ⁹ include halogen atoms such as fluorine, chlorine, bromine and iodine; phenyl, nitrophenyl, cyanophenyl, hydroxyphenyl, methylphenyl, dimethylphenyl,
Trimethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, n-propylphenyl, di (n-propyl) phenyl, tri (n-propyl) phenyl, iso-propylphenyl, di (iso- Propyl) phenyl group, tri (iso-propyl) phenyl group, n-butylphenyl group, di (n-butyl) phenyl group, tri (n-butyl) phenyl group, i
so-butylphenyl group, di (iso-butyl) phenyl group, tri (iso-butyl) phenyl group, sec-butylphenyl group, di (sec-butyl) phenyl group, tri (sec-butyl) phenyl group, t- Butylphenyl group, di (t-butyl) phenyl group, tri (t-butyl)
Phenyl group, dimethyl-t-butylphenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group,
Iodophenyl group, methoxyphenyl group, ethoxyphenyl group, trifluoromethylphenyl group, N, N-dimethylaminophenyl group, naphthyl group, nitronaphthyl group, cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl group, fluoronaphthyl group, Chloronaphthyl group,
A bromonaphthyl group, an iodonaphthyl group, a methoxynaphthyl group, a trifluoromethylnaphthyl group, an N, N-dimethylaminonaphthyl group, etc.
5 or less substituted or unsubstituted aryl groups;

Carbon such as pyrrolyl, thienyl, furanyl, oxazoyl, isoxazoyl, oxadiazoyl, imidazoyl, benzoxazoyl, benzothiazoyl, benzoimidazoyl, benzofuranyl, indoyl, isoindoyl and the like A substituted or unsubstituted heteroaryl group having a number of 20 or less, preferably 15 or less; a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-
Butoxy group, sec-butoxy group, t-butoxy group, n
A substituted or unsubstituted alkoxy group having 20 or less, preferably 15 or less carbon atoms, such as -pentoxy group, iso-pentoxy group, neo-pentoxy group, n-hexyloxy group, n-dodecyloxy group; methylthio group, ethylthio group , N-propylthio group, iso-propylthio group, n
-Butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, i
so-pentylthio group, 2-methylbutylthio group, 1-
Methylbutylthio group, neo-pentylthio group, 1,2
A substituted or unsubstituted alkylthio group having 20 or less carbon atoms, preferably 15 or less carbon atoms, such as -dimethylpropylthio group and 1,1-dimethylpropylthio group;

Phenoxy group, 2-methylphenoxy group,
A substituted or unsubstituted aryloxy group having 20 or less carbon atoms, preferably 15 or less carbon atoms, such as 4-methylphenoxy group, 4-t-butylphenoxy group, 2-methoxyphenoxy group, 4-iso-propylphenoxy group; phenylthio group , 4-methylphenylthio, 2-methoxyphenylthio, 4-t-butylphenylthio, etc.
Or less, preferably 15 or less substituted or unsubstituted allies.
A luthio group; and the like.

In the linking group represented by the formula (a) connecting R ¹ and R ² , specific examples of A include benzene, nitrobenzene, cyanobenzene, hydroxybenzene, methylbenzene, dimethylbenzene, trimethylbenzene,
Ethylbenzene, diethylbenzene, triethylbenzene, n-propylbenzene, di (n-propyl) benzene, tri (n-propyl) benzene, iso-propylbenzene, di (iso-propyl) benzene, tri (i
(so-propyl) benzene, n-butylbenzene, di (n-butyl) benzene, tri (n-butyl) benzene, iso-butylbenzene, di (iso-butyl) benzene, tri (iso-butyl) benzene, sec- Butylbenzene, di (sec-butyl) benzene, tri (sec-butyl) benzene, t-butylbenzene, di (t-butyl) benzene, tri (t-butyl) benzene, dimethyl-t-butylbenzene, fluorobenzene, Chlorobenzene, bromobenzene, iodobenzene, methoxybenzene, ethoxybenzene, trifluoromethylbenzene, N, N-dimethylaminobenzene,
20 carbon atoms such as naphthalene, nitronaphthalene, cyanonaphthalene, hydroxynaphthalene, methylnaphthalene, fluoronaphthalene, chloronaphthyl, bromonaphthyl, iodonaphthyl, methoxynaphthyl, trifluoromethylnaphthalene, N, N-dimethylaminonaphthalene, etc. Up to, and preferably up to 15 substituted or unsubstituted aromatic rings;

C20 or less carbon atoms such as pyrrole, N-methylpyrrole, thiophene, methylthiophene, furan, oxazole, isoxazole, oxadiazole, imidazole, benzoxazole, benzothiazole, benzimidazole, benzofuran, indole and isoindole; And preferably 15 or less substituted or unsubstituted heterocyclic rings; and the like.

L ¹ represents a substituted or unsubstituted residue which may contain a hetero atom, and forms a ring together with the carbon atom to which it is bonded.

Specific examples of the ring formed together with the carbon atom to which L ¹ is bonded include substituted or unsubstituted 5
A 6-membered ring, a 6-membered ring and a 7-membered ring can be mentioned, preferably a 5- or 6-membered ring substituted or unsubstituted, and more preferably a 6-membered ring substituted or unsubstituted. Can be mentioned.

Specific examples of L ¹ forming a 5-membered ring include:
_{-CH 2 -, - CH (F} ) -, - CH (Cl) -, - C
H (Br)-, -CH (I)-, -C (F) _2- , -C
(Cl) _2- , -C (Br) _2- , -C (I) _2- , -C
_{H (CH 3) -, -} C (CH 3) 2 -, - CH (OCH 3)
—, —C (OCH ₃ ) ₂ —, —O—, —S—, and the like.

Specific examples of L ¹ forming a 6-membered ring include:
_{-CH 2 CH 2 -, - CH} (F) CH 2 -, - CH (C
_{l) CH 2 -, - CH} (Br) CH 2 -, - CH (I) C
_{H 2 -, - CH (F} ) CH (F) -, - CH (Cl) C
H (Cl)-, -CH (Br) CH (Br)-, -CH
(I) CH (I) - , - C (F) 2 CH 2 -, - C (C
l) ₂ CH ₂ —, —C (Br) ₂ CH ₂ —, —C (I) ₂ C
_{H 2 -, - C (F} ) 2 C (F) 2 -, - C (Cl) 2 C (C
l) _2- , -C (Br) ₂ C (Br) _2- , -C (I) ₂ C
_{(I) 2 -, - CH} (CH 3) CH 2 -, - CH (CH 3)
_{CH (CH 3) -, -} C (CH 3) 2 CH 2 -, - C (CH
₃ ) ₂ C (CH ₃ ) _2- , -CH (OCH ₃ ) CH _2- , -C
_{H (OCH 3) CH (OCH} 3) -, - C (OCH 3) 2 C
H ₂ —, —C (OCH ₃ ) ₂ C (OCH ₃ ) ₂ —, —OCH ₂
-, -SCH _2- , and the like,

Specific examples of L ¹ forming a 7-membered ring include:
_{-CH 2 CH 2 CH 2 -,} - CH 2 CH (F) CH 2 -, -
_{CH 2 CH (Cl) CH 2} -, - CH 2 CH (Br) CH 2
_{-, - CH 2 CH (I} ) CH 2 -, - CH 2 C (F) 2 CH
_{2 -, - CH 2 C (} Cl) 2 CH 2 -, - CH 2 C (Br) 2
CH ₂ —, —CH ₂ C (I) ₂ CH ₂ —, —CH ₂ CH (C
_{H 3) CH 2 -, -} CH 2 C (CH 3) 2 CH 2 -, - CH 2
CH (OCH ₃ ) CH ₂ —, —CH ₂ C (OCH ₃ ) ₂ CH ₂
—, —CH ₂ OCH ₂ —, —CH ₂ SCH ₂ —, and the like.

Specific examples of M are not particularly limited as long as they are transition elements having the ability to form a chelate with a dipyrromethene compound, but may be any of groups 8, 9, 10 (Group VIII), 11 (Ib), and 12 (IIb group), 3 group (IIIa group), 4 group (IVa group), 5 group (Va group), 6 group (VIa group), 7 group (VII
Group a) metals are preferable, and nickel, cobalt, iron, ruthenium, rhodium, palladium, copper, osmium, iridium, platinum, zinc and the like are preferable, and copper and cobalt are particularly preferable in terms of light resistance.

The dipyrromethene metal chelate compound represented by the general formula (1) of the present invention is not limited.
Aust. J. Chem, 1965, 11, 1835-45, Heteroatom Chemi
stry, Vol. 1, 5,389 (1990), USP-4,774,339, USP-5,43
It is produced according to the method described in 3,896 and the like. Typically, it can be produced by the following two-step reaction.

First, in the first step, the compound represented by the general formula (2) and the compound represented by the general formula (3), or the compound represented by the general formula (4) and the compound represented by the general formula (5) In the presence of an acid catalyst such as hydrobromic acid or hydrochloric acid,
The reaction is performed in an appropriate solvent to obtain a dipyrromethene compound represented by the general formula (6). Next, in a second step, the dipyrromethene compound represented by the general formula (6) is reacted with an acetate or halide of a metal such as nickel, cobalt, iron, ruthenium, rhodium, palladium, copper, osmium, iridium, platinum, and zinc. To obtain a dipyrromethene metal chelate compound represented by the general formula (1).

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

Embedded image [In the formulas (2) to (6), R ^{1 to} R ⁹ represent the same meaning as described above. ]

[0045]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited by these examples.

In the examples, X-ray diffraction diagrams of the dipyrromethene metal chelate compound before and after the freeze-drying treatment are shown. The conditions of the X-ray diffraction are as follows.

Tube: Cu, tube voltage: 30 kV, tube current:
14 mA, goniometer: wide-angle goniometer, sampling angle: 0.020 °, scan speed: 8.
0 ° / min, scanning axis: 2θ / θ, filter: Ni, divergence slit: 1 °, scattering slit: 1 °, fluorescent slit:
0.15 mm.

Example 1 18.9 g of the compound represented by the following structural formula (4-a) and 13.1 g of the compound represented by the following structural formula (5-a) were dissolved in 600 ml of ethanol, and 47% bromide was dissolved. After dropwise addition of 10.1 g of hydrochloric acid, the mixture was stirred at room temperature for 2 hours. After concentration under reduced pressure, chloroform 500 ml
After extracting with water, washing and liquid separation, the solvent was distilled off to obtain 28.1 g of a compound represented by the following structural formula (6-a).

[0049]

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Next, the formula (6-) was added to 900 ml of ethanol.
26.7 g of the compound represented by a) were dissolved, and copper acetate was added.
1 g was added and the mixture was stirred at reflux temperature for 2 hours. After concentration under reduced pressure, the precipitate was collected by filtration and washed with methanol and water to obtain 25.0 g of a compound represented by the following structural formula (1-1).

[0051]

Embedded image From the following analysis results, it was confirmed that it was the target substance.

[0052]

[Table 1]

The compound thus obtained exhibits an absorption maximum at 584 nm in a toluene solution, and has a gram extinction coefficient of 0.73 × 10 ⁵ ml / g. cm.

Compound 2 represented by the above structural formula (1-1)
0.0 g (X-ray diffractogram, FIG. 1) in 500 ml of p-xylene
And stirred at 25 ° C. for 1 hour, put into a freeze dryer of Kyowa Vacuum Co., Ltd., cooled to −40 ° C. to freeze the solution,
The heating medium for heating the shelf of the dryer was heated to 30 ° C. under reduced pressure (2.67 Pa (20 mTorr)). The frozen p-xylene gradually sublimates, and the temperature of the frozen product rises to 25 ° C. and stabilizes at 25 ° C. (at this time, the pressure was 1.33 Pa).
(10 mTorr)). The inside of the dryer was returned to normal pressure to obtain a dipyrromethene metal chelate compound from which p-xylene had been removed.

The dipyrromethene metal chelate compound has 2
Dissolved in ethylcyclohexane at a concentration of 0 g / l,
No precipitation occurred after 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 dipyrromethene metal chelate compound before the treatment did not dissolve in ethylcyclohexane up to a concentration of 20 g / l.

Example 2 14.7 g of the compound represented by the following structural formula (4-b) and 10.2 g of the compound represented by the above-mentioned structural formula (5-a) were dissolved in 450 ml of ethanol, and 47% bromide was dissolved. After dropwise addition of 7.4 g of hydrochloric acid, the mixture was added at room temperature for 3 hours.
Stirred for hours. After concentration under reduced pressure, extraction with 500 ml of chloroform, washing with water, and liquid separation, the solvent was distilled off, and the following structural formula (6)
21.2 g of the compound represented by -b) were obtained.

[0057]

Embedded image

Next, 600 ml of ethanol and 3 parts of toluene
Compound 1 represented by Formula (6-b) in 00 ml of a mixed solvent
After dissolving 5.2 g, 2.9 g of copper acetate was added and the mixture was stirred at reflux temperature for 2 hours. After concentration under reduced pressure, the precipitate was collected by filtration and washed with methanol and water to obtain 15.2 g of a compound represented by the following structural formula (1-1).

[0059]

Embedded image From the following analysis results, it was confirmed that it was the target substance.

[0060]

[Table 2]

The compound thus obtained exhibits an absorption maximum at 586.4 nm in a toluene solution, and has a gram extinction coefficient of 0.77 × 10 ⁵ ml / g. cm.

Compound 1 represented by the above structural formula (1-2)
2.5 g (X-ray diffraction diagram, FIG. 3) was weighed to 500 m with p-xylene
and stirred at 25 ° C. for 1 hour.
The solution was put into a freeze dryer, cooled to −40 ° C. to freeze the solution, and the heating medium for heating the shelf of the dryer was heated to 30 ° C. under reduced pressure (20 mTorr). The frozen p-xylene gradually sublimates, and the temperature of the frozen product rises to 25 ° C. and stabilizes at 25 ° C. (The pressure at this time is 1.3.
3 Pa (10 mTorr)). Return the inside of the dryer to normal pressure,
A dipyrromethene metal chelate compound from which p-xylene was removed was obtained.

This dipyrromethene metal chelate compound has 2
Dissolved in ethylcyclohexane at a concentration of 5 g / l,
No precipitation occurred after 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 dipyrromethene metal chelate compound before the treatment did not dissolve in ethylcyclohexane up to a concentration of 25 g / l.

Example 3 60.8 g of the compound represented by the following structural formula (4-c) and 40.8 g of the compound represented by the following structural formula (5-b) were dissolved in 2400 ml of ethanol, and 47% bromide was dissolved. After dropwise addition of 35.6 g of hydrochloric acid, the mixture was stirred at room temperature for 2 hours. After concentration under reduced pressure, chloroform 1800m
After extracting with 1 and washing with water and liquid separation, the solvent was distilled off to obtain 89.1 g of a compound represented by the following structural formula (6-c).

[0065]

Embedded image

Next, the formula (6-) was added to 3500 ml of ethanol.
86.9 g of the compound shown in c) was dissolved, and copper acetate 2
0.2 g was added, and the mixture was stirred at reflux temperature for 3 hours. After concentration under reduced pressure, the precipitate was collected by filtration, washed with methanol and water,
82.0 g of a compound represented by the following structural formula (1-3) was obtained.

[0067]

Embedded image From the following analysis results, it was confirmed that it was the target substance.

[0068]

[Table 3]

The compound thus obtained exhibits an absorption maximum at 585.5 nm in a toluene solution, and has a gram extinction coefficient of 1.08 × 10 ⁵ ml / g. cm.

Compound 6 represented by the above structural formula (1-3)
0.0 g (X-ray diffraction diagram, FIG. 5) was added to 1,4-dioxane 1
Dissolve in 800 ml, stir at 25 ° C. for 1 hour, put into a freeze dryer of Kyowa Vacuum Co., Ltd., cool to −40 ° C., freeze the solution, and reduce the pressure (2.67 Pa (20 mTorr)).
The heating medium for heating the shelf of the dryer was heated to 30 ° C. The frozen 1,4-dioxane gradually sublimates, and the frozen
The temperature rose to 5 ° C. and stabilized at 25 ° C. (at this time, the pressure was 1.33 Pa (10 mTorr)). The inside of the dryer was returned to normal pressure to obtain a dipyrromethene metal chelate compound from which 1,4-dioxane had been removed.

This dipyrromethene metal chelate compound has 2
Dissolved in ethylcyclohexane at a concentration of 5 g / l,
No precipitation occurred after hours. FIG. 6 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 dipyrromethene metal chelate compound before the treatment did not dissolve in ethylcyclohexane up to a concentration of 25 g / l.

Example 4 15.8 g of the compound represented by the following structural formula (4-d) and 11.2 g of the compound represented by the following structural formula (5-c) were dissolved in 630 ml of ethanol, and 47% bromide was dissolved. After dropwise addition of 9.8 g of hydrochloric acid, 1
Stirred for hours. After concentration under reduced pressure, extraction with 500 ml of chloroform, washing with water, and liquid separation, the solvent was distilled off, and the following structural formula (6)
22.1 g of a compound represented by -d) were obtained.

[0073]

Embedded image

Next, the formula (6-) was added to 900 ml of ethanol.
21.4 g of the compound represented by d) was dissolved, and copper acetate was added.
8 g was added, and the mixture was stirred at reflux temperature for 2 hours. After concentration under reduced pressure, the precipitate was collected by filtration and washed with methanol and water to obtain 21.5 g of a compound represented by the following structural formula (1-4).

[0075]

Embedded image From the following analysis results, it was confirmed that it was the target substance.

[0076]

[Table 4]

The compound thus obtained shows an absorption maximum at 588.5 nm in a toluene solution, and has a gram extinction coefficient of 1.29 × 10 ⁵ ml / g. cm.

Compound 1 represented by the above structural formula (1-3)
7.9 g (X-ray diffraction diagram, FIG. 7) was added to p-xylene 1500
and stirred for 1 hour at 25 ° C.
The solution was placed in a freeze dryer, cooled to −40 ° C. to freeze the solution, and the heating medium for heating the shelf of the dryer was heated to 30 ° C. under reduced pressure (2.67 Pa (20 mTorr)). The frozen p-xylene gradually sublimates, and the temperature of the frozen product rises to 25 ° C. and stabilizes at 25 ° C. (The pressure at this time was 1.
33 Pa (10 mTorr). The inside of the dryer was returned to normal pressure to obtain a dipyrromethene metal chelate compound from which p-xylene had been removed.

This dipyrromethene metal chelate compound has 3
Dissolved in ethylcyclohexane at a concentration of 0 g / l,
No precipitation occurred after 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 dipyrromethene metal chelate compound before the treatment did not dissolve in ethylcyclohexane up to a concentration of 30 g / l.

Example 5 27.0 g of the compound represented by the formula (4-b) and 15.3 g of the compound represented by the formula (5-b) were dissolved in 1000 ml of ethanol, and 47% bromide was dissolved. After dropwise addition of 13.7 g of hydrochloric acid, the mixture was stirred at room temperature for 1 hour. After concentration under reduced pressure, chloroform 600 ml
After extraction, washing with water and liquid separation, the solvent was distilled off to obtain 36.8 g of a compound represented by the following structural formula (6-e).

[0081]

Embedded image

Next, the formula (6-) was added to 1700 ml of ethanol.
35.2 g of the compound shown in e) was dissolved, and copper acetate was added.
3 g was added, and the mixture was stirred at reflux temperature for 2 hours. After concentration under reduced pressure, the precipitate was collected by filtration and washed with methanol and water to obtain 34.2 g of a compound represented by the following structural formula (1-5).

[0083]

Embedded image From the following analysis results, it was confirmed that it was the target substance.

[0084]

[Table 5]

The compound thus obtained exhibits an absorption maximum at 587.5 nm in a toluene solution, and has a gram extinction coefficient of 0.93 × 10 ⁵ ml / g. cm.

Compound 3 represented by the above structural formula (1-5)
2.0 g (X-ray diffraction pattern, FIG. 9) was added to p-xylene 2240
and stirred for 1 hour at 25 ° C.
The solution was placed in a freeze dryer, cooled to −40 ° C. to freeze the solution, and the heating medium for heating the shelf of the dryer was heated to 30 ° C. under reduced pressure (2.67 Pa (20 mTorr)). The frozen p-xylene gradually sublimates, and the temperature of the frozen product rises to 25 ° C. and stabilizes at 25 ° C. (The pressure at this time was 1.
33 Pa (10 mTorr). The inside of the dryer was returned to normal pressure to obtain a dipyrromethene metal chelate compound from which p-xylene had been removed.

This dipyrromethene metal chelate compound has 3
Dissolved in dimethylcyclohexane at a concentration of 0 g / l,
No precipitation occurred after 4 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 dipyrromethene metal chelate compound before the treatment was dissolved in dimethylcyclohexane at a concentration of 30 g / l.
A precipitate formed in 8 hours.

Example 6 15.9 g of the compound represented by the structural formula (4-b) and 8.8 g of the compound represented by the following structural formula (5-d) were dissolved in 630 ml of ethanol.
After dripping 7.7 g of 47% hydrobromic acid, the mixture was stirred at room temperature for 1 hour. After concentration under reduced pressure, extraction with chloroform (600 ml), washing with water and liquid separation, the solvent was distilled off, and the following structural formula (6-
21.2 g of the compound shown in f) were obtained.

[0089]

Embedded image Next, 19.7 g of the compound represented by the formula (6-f) was dissolved in 800 ml of ethanol, and 4.8 g of copper acetate was added.
Stir at reflux temperature for 3 hours. After concentration under reduced pressure, the precipitate was collected by filtration, washed with methanol and water, and treated with the following structural formula (1-
18.3 g of the compound represented by 6) was obtained.

[0090]

Embedded image From the following analysis results, it was confirmed that it was the target substance.

[0091]

[Table 6]

The compound thus obtained exhibits an absorption maximum at 609.0 nm in a toluene solution, and has a gram extinction coefficient of 1.05 × 10 ⁵ ml / g. cm.

Compound 1 represented by the above structural formula (1-6)
Dissolve 4.2 g (X-ray diffraction diagram, FIG. 11) in 568 ml of 1,4-dioxane, stir at 25 ° C. for 1 hour, put into a freeze dryer of Kyowa Vacuum Co., Ltd., cool to −40 ° C. Is frozen under reduced pressure (2.67 Pa (20 mTorr).
In r)), the heating medium for heating the shelf of the dryer was heated to 30 ° C. The frozen 1,4-dioxane gradually sublimated, and the temperature of the frozen product rose to 25 ° C. and stabilized at 25 ° C. (at this time, the pressure was 1.33 Pa (10 mTorr)). The inside of the dryer was returned to normal pressure to obtain a dipyrromethene metal chelate compound from which 1,4-dioxane had been removed.

This dipyrromethene metal chelate compound has 2
Dissolved in ethylcyclohexane at a concentration of 5 g / l,
No precipitation occurred after 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. still,
The dipyrromethene metal chelate compound before the treatment was dissolved in ethylcyclohexane at a concentration of 25 g / l, but a precipitate was formed in 8 hours.

Example 7 14.1 g of the compound represented by the following structural formula (4-e) and 8.9 g of the compound represented by the above-mentioned structural formula (5-d) were dissolved in 700 ml of ethanol.
After dropping 8.0 g of 47% hydrobromic acid, the mixture was stirred at room temperature for 2 hours. After concentration under reduced pressure, extraction with chloroform (500 ml), washing with water and liquid separation, the solvent was distilled off, and the following structural formula (6-
20.2 g of the compound of the formula g) were obtained.

[0096]

Embedded image

Next, the formula (6-) was added to 570 ml of ethanol.
18.9 g of the compound of the formula
2 g was added, and the mixture was stirred at reflux temperature for 2 hours. After concentration under reduced pressure, the precipitate was collected by filtration and washed with methanol and water to obtain 19.3 g of a compound represented by the following structural formula (1-7).

[0098]

Embedded image From the following analysis results, it was confirmed that it was the target substance.

[0099]

[Table 7]

The compound thus obtained exhibits an absorption maximum at 599.0 nm in a toluene solution, and has a gram extinction coefficient of 1.72 × 10 ⁵ ml / g. cm.

Compound 1 represented by the above structural formula (1-7)
7.8 g (X-ray diffractogram, FIG. 13) was dissolved in 1068 ml of 1,4-dioxane, stirred at 25 ° C. for 1 hour, put in a freeze dryer of Kyowa Vacuum Co., Ltd., cooled to −40 ° C. Is frozen under reduced pressure (2.67 Pa (20 mTorr).
In r)), the heating medium for heating the shelf of the dryer was heated to 30 ° C. The frozen 1,4-dioxane gradually sublimated, and the temperature of the frozen product rose to 25 ° C. and stabilized at 25 ° C. (at this time, the pressure was 1.33 Pa (10 mTorr)). The inside of the dryer was returned to normal pressure to obtain a dipyrromethene metal chelate compound from which 1,4-dioxane had been removed.

This dipyrromethene metal chelate compound has 1
Dissolved in dimethylcyclohexane at a concentration of 5 g / l,
No precipitation occurred after 4 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.
The dipyrromethene metal chelate compound before the treatment did not dissolve in dimethylcyclohexane up to a concentration of 15 g / l.

Example 8 14.3 g of the compound represented by the following structural formula (4-f) and 9.0 g of the compound represented by the above-mentioned structural formula (5-d) were dissolved in 570 ml of ethanol.
After dropping 8.0 g of 47% hydrobromic acid, the mixture was stirred at room temperature for 3 hours. After concentration under reduced pressure, extraction with chloroform (500 ml), washing with water and liquid separation, the solvent was distilled off, and the following structural formula (6-
18.8 g of the compound of the formula h) were obtained.

[0104]

Embedded image

Next, the formula (6-) was added to 800 ml of ethanol.
16.7 g of the compound of the formula (h) was dissolved, and copper acetate was added.
8 g was added, and the mixture was stirred at reflux temperature for 2 hours. After concentration under reduced pressure, the precipitate was collected by filtration and washed with methanol and water to obtain 15.4 g of a compound represented by the following structural formula (1-8).

[0106]

Embedded image From the following analysis results, it was confirmed that it was the target substance.

[0107]

[Table 8]

The compound thus obtained exhibits an absorption maximum at 594.0 nm in a toluene solution, and has a gram extinction coefficient of 1.64 × 10 ⁵ ml / g. cm.

Compound 1 represented by the above structural formula (1-8)
Dissolve 0.2 g (X-ray diffraction diagram, FIG. 15) in 714 ml of 1,4-dioxane, stir at 25 ° C. for 1 hour, put in a freeze dryer of Kyowa Vacuum Co., Ltd., cool to −40 ° C. Is frozen under reduced pressure (2.67 Pa (20 mTorr).
In r)), the heating medium for heating the shelf of the dryer was heated to 30 ° C. The frozen 1,4-dioxane gradually sublimated, and the temperature of the frozen product rose to 25 ° C. and stabilized at 25 ° C. (at this time, the pressure was 1.33 Pa (10 mTorr)). The inside of the dryer was returned to normal pressure to obtain a dipyrromethene metal chelate compound from which 1,4-dioxane had been removed.

This dipyrromethene metal chelate compound has 2
Dissolved in ethylcyclohexane at a concentration of 0 g / l,
No precipitation occurred after 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. still,
The dipyrromethene metal chelate compound before the treatment did not dissolve in dimethylcyclohexane up to a concentration of 20 g / l.

Example 9 8.5 g of the compound represented by the structural formula (4-f) and 7.5 g of the compound represented by the following structural formula (5-e) were dissolved in 340 ml of ethanol.
After dropping 4.7 g of 7% hydrobromic acid, the mixture was stirred at room temperature for 1 hour. After concentration under reduced pressure, extracted with 300 ml of chloroform,
After washing with water and liquid separation, the solvent was distilled off to obtain the following structural formula (6-i)
14.1 g of a compound represented by the formula was obtained.

[0112]

Embedded image Next, 13.2 g of the compound represented by the formula (6-i) was dissolved in 530 ml of ethanol, and 2.6 g of copper acetate was added.
Stirred at reflux temperature for 1 hour. After concentration under reduced pressure, the precipitate was collected by filtration, washed with methanol and water, and treated with the following structural formula (1-
25.9 g of the compound represented by 9) was obtained.

[0113]

Embedded image From the following analysis results, it was confirmed that it was the target substance.

[0114]

[Table 9]

The compound thus obtained exhibits an absorption maximum at 592.5 nm in a toluene solution, and has a gram extinction coefficient of 1.22 × 10 ⁵ ml / g. cm.

Compound 2 represented by the above structural formula (1-9)
Dissolve 4.1 g (X-ray diffraction diagram, FIG. 17) in 240 ml of 1,4-dioxane, stir at 25 ° C. for 1 hour, put into a freeze dryer of Kyowa Vacuum Co., Ltd., cool to −40 ° C. Is frozen under reduced pressure (2.67 Pa (20 mTorr).
In r)), the heating medium for heating the shelf of the dryer was heated to 30 ° C. The frozen 1,4-dioxane gradually sublimated, and the temperature of the frozen product rose to 25 ° C. and stabilized at 25 ° C. (at this time, the pressure was 1.33 Pa (10 mTorr)). The inside of the dryer was returned to normal pressure to obtain a dipyrromethene metal chelate compound from which 1,4-dioxane had been removed.

This dipyrromethene metal chelate compound has 2
Dissolved in ethylcyclohexane at a concentration of 0 g / l,
No precipitation occurred after hours. FIG. 18 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. still,
The dipyrromethene metal chelate compound before the treatment did not dissolve in ethylcyclohexane to a concentration of 20 g / l.

[0118]

The dipyrromethene metal chelate compound before the treatment of the present invention is often in a certain crystalline state, and therefore has low solvent solubility. That is, the coating solution did not dissolve to a predetermined concentration, or even once dissolved in a solvent, precipitation occurred in a short time, but by performing the treatment of the present invention, the amorphous dipyrromethene metal chelate compound Is obtained, and the solubility is remarkably improved.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction diagram of a dipyrromethene metal chelate compound before treatment in Example 1.

FIG. 2 is an X-ray diffraction diagram of a dipyrromethene metal chelate compound after the treatment in Example 1.

FIG. 3 is an X-ray diffraction diagram of a dipyrromethene metal chelate compound before treatment in Example 2.

FIG. 4 is an X-ray diffraction diagram of a dipyrromethene metal chelate compound after the treatment in Example 2.

FIG. 5 is an X-ray diffraction diagram of a dipyrromethene metal chelate compound before treatment in Example 3.

FIG. 6 is an X-ray diffraction diagram of a dipyrromethene metal chelate compound after the treatment in Example 3.

FIG. 7 is an X-ray diffraction diagram of a dipyrromethene metal chelate compound before treatment in Example 4.

FIG. 8 is an X-ray diffraction diagram of the dipyrromethene metal chelate compound after the treatment in Example 4.

FIG. 9 is an X-ray diffraction diagram of a dipyrromethene metal chelate compound before treatment in Example 5.

FIG. 10 is an X-ray diffraction diagram of a dipyrromethene metal chelate compound after the treatment in Example 5.

FIG. 11 is an X-ray diffraction diagram of a dipyrromethene metal chelate compound before treatment in Example 6.

FIG. 12 is an X-ray diffraction diagram of a dipyrromethene metal chelate compound after the treatment in Example 6.

FIG. 13 is an X-ray diffraction diagram of a dipyrromethene metal chelate compound before treatment in Example 7.

FIG. 14 is an X-ray diffraction diagram of the dipyrromethene metal chelate compound after the treatment in Example 7.

FIG. 15 is an X-ray diffraction diagram of a dipyrromethene metal chelate compound before treatment in Example 8.

FIG. 16 is an X-ray diffraction diagram of the dipyrromethene metal chelate compound after the treatment in Example 8.

FIG. 17 is an X-ray diffraction diagram of a dipyrromethene metal chelate compound before treatment in Example 9.

FIG. 18 is an X-ray diffraction diagram of a dipyrromethene metal chelate compound after the treatment in Example 9.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Denmi Misawa, 580-32 Nagaura, Sodegaura City, Chiba Prefecture Mitsui Chemicals, Inc. (72) Inventor Youjiro Kumagai 1-443 Minami Yuge-cho, Yao-shi, Osaka Prefecture F-term in Yamamoto Kasei Co., Ltd.

Claims (7)

[Claims] 1. An amorphous form of a dipyrromethene metal chelate compound represented by the following general formula (1). Embedded image [Wherein, R ^{1 to} R ⁸ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group,
Carboxyl group, sulfonic acid group, substituted or unsubstituted alkyl group having 20 or less carbon atoms, alkoxy group, alkylthio group, aryloxy group, arylthio group, alkenyl group, acyl group, alkoxycarbonyl group, carbamoyl group, acylamino group, aralkyl Represents a group, an aryl group or a heteroaryl group, R ⁹ represents a halogen atom, a substituted or unsubstituted aryl group having 20 or less carbon atoms, a heteroaryl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group; R ¹ and R ² may form a ring via a linking group represented by the formula (a), and M represents a transition element. Embedded image (A represents a substituted or unsubstituted aromatic or heterocyclic ring having 20 or less carbon atoms, and L ¹ represents a substituted or unsubstituted heteroatom which forms a ring together with the carbon atom to which it is bonded. Or represents an unsubstituted residue)] 2. A method for producing an amorphous form of a dipyrromethene metal chelate compound represented by the following general formula (1), comprising dissolving a crystalline dipyrromethene metal chelate compound in an organic solvent and freeze-drying the organic solvent solution. . Embedded image [Wherein, R ^{1 to} R ⁸ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group,
Carboxyl group, sulfonic acid group, substituted or unsubstituted alkyl group having 20 or less carbon atoms, alkoxy group, alkylthio group, aryloxy group, arylthio group, alkenyl group, acyl group, alkoxycarbonyl group, carbamoyl group, acylamino group, aralkyl Represents a group, an aryl group or a heteroaryl group, R ⁹ represents a halogen atom, a substituted or unsubstituted aryl group having 20 or less carbon atoms, a heteroaryl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group; R ¹ and R ² may form a ring via a linking group represented by the formula (a), and M represents a transition element. Embedded image (A represents a substituted or unsubstituted aromatic or heterocyclic ring having 20 or less carbon atoms, and L ¹ represents a substituted or unsubstituted heteroatom which forms a ring together with the carbon atom to which it is bonded. Or represents an unsubstituted residue)] 3. The freezing point of an organic solvent used for freeze-drying is-
The method according to claim 2, wherein the temperature is 40 to 40C. 4. The freezing temperature is -50 to 0 ° C.
Manufacturing method. 5. The method according to claim 2, wherein the temperature of the heating medium for heating the shelf of the dryer after freezing is −30 to 70 ° C. 6. The method according to claim 5, wherein the temperature of the heating medium for heating the shelf of the dryer after freezing is 0 to 70 ° C. 7. The drying pressure is 133.32 to 1.33.
3. The method according to claim 2, wherein Pa is Pa.