JPH11269399A - Phthalocyanine compound, its intermediate, production of the compound and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound having absorption in wavelength area in a specific range, having high extinction coefficient and simultaneously, excellent in solubility to various kinds of organic solvents and resins and durability and useful for near infrared rays-absorbing materials such as near infrared rays-absorbing filters, photothermal conversion materials such as original print for laser direct printing. SOLUTION: This compound is represented by formula I (R is an alkyl or the like; X is halogen or the like; M is 2H or the like). The compound of formula I is obtained by reacting a diiminoisoincloline compound of formula II (R5 and R6 are each an alkyl or the like) [e.g. 5-(2-aminophenylthio)-6-chloro-1,3- diimino-4,7-diisopentoxyisoindoline] with a metal or a metal derivative (e.g. vanadium chloride), preferably in a solvent such as 2-n-butoxyethanol, in the presence (or absence) of 1,8-diazabicyclo[5.4.0]-7-undecene or the like, preferably at 130 to 220 deg.C. The compound has absorption in 800-1,200 nm wavelength.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phthalocyanine compound, and more particularly, to an optical card, an organic photoconductive compound, which has absorption in the near infrared region of 800 to 1200 nm and has excellent solubility in organic solvents. The present invention relates to a novel phthalocyanine compound useful for a body, near-infrared absorbing filter, heat ray shielding film, protective glasses, laser direct plate making (CTP), laser thermal transfer recording, laser thermal recording, and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Certain phthalocyanine compounds have excellent near-infrared absorption ability, so that optical cards, near-infrared absorption filters, heat ray shielding films, protective glasses, laser direct plate making, laser thermal transfer recording, laser thermal recording, laser printers In recent years, its application to organic photoconductors and the like has attracted attention.

[0003] As such a phthalocyanine compound, JP-A-8-176101 filed by the present inventors previously has an alkoxy group at the 3- and 6-positions and a 2-position at the 4-position.
A phthalocyanine compound obtained by reacting a phthalonitrile compound having an aminophenylthio group with a metal or a metal derivative is disclosed. However, when such phthalonitrile is used as an intermediate,
The obtained phthalocyanine compound was not sufficiently satisfactory in both the absorption coefficient and the absorption wavelength region. The reason is presumed to be that the phthalocyanine compound thus obtained is a mixture of a phthalocyanine compound having a different position and number of each substituent, a multimeric phthalocyanine compound, and the like.

Recently, the phthalocyanine compound has a longer wavelength than conventional phthalocyanine compounds for use as a near-infrared absorbing material or a light-to-heat converting material, such as a heat ray shielding film, a near-infrared absorbing filter of a plasma display, a laser direct plate making, a laser thermal transfer recording, and a laser thermal recording. Has absorption on the side,
In addition, a phthalocyanine compound having a high absorption coefficient is demanded.

[0005]

The problem to be solved by the present invention is as follows.
It is an object of the present invention to provide a phthalocyanine compound which has absorption in a wavelength range of 0 to 1200 nm and is useful as a near-infrared absorbing agent excellent in the above-mentioned various properties, a novel intermediate for producing the same, and a production method.

[0006]

As a result of various investigations to solve the above-mentioned problems, the present inventors have found that the phthalonitrile compound can be used to obtain 800-1
It has been found that a phthalocyanine compound having strong absorption in an absorption region of 200 nm and having excellent solubility in an organic solvent can be obtained.

The present invention firstly relates to a phthalocyanine compound represented by the general formula (I), a near-infrared absorbing material and a photothermal converting material containing the same.

[0008]

Embedded image (Wherein, R represents an alkyl group or an alkoxyalkyl group, X represents a halogen atom, an alkylthio group, an optionally substituted phenylthio group or an optionally substituted naphthylthio group, and M represents 2 A hydrogen atom, a divalent metal or a derivative of a trivalent or tetravalent metal.)

The present invention also relates to a phthalocyanine compound comprising at least one of the general formulas (II) to (V), a near-infrared absorbing material and a light-heat converting material containing the same.

[0010]

Embedded image

[0011]

Embedded image (Wherein, R _{1 to} R ₄ represent an alkyl group or an alkoxyalkyl group, and X represents a halogen atom, an alkylthio group, a phenylthio group which may have a substituent, or a naphthylthio group which may have a substituent. , M represents two hydrogen atoms, a divalent metal or a derivative of a trivalent or tetravalent metal.)

Further, the present invention is characterized in that a diiminoisoindoline compound represented by the general formula (VI) is reacted with a metal or a metal derivative. The present invention relates to a method for producing the represented phthalocyanine compound.

[0013]

Embedded image (Wherein, R ₅ and R ₆ represent an alkyl group or an alkoxyalkyl group, and X represents a halogen atom, an alkylthio group, a phenylthio group which may have a substituent, or a naphthylthio group which may have a substituent. Further, the present invention relates to a diiminoisoindoline compound represented by the general formula (VI) and a method for producing the same.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION (Phthalocyanine compound) The invention of the present application is a phthalocyanine compound comprising at least one of the following general formulas (I) or (II) to (V) (hereinafter referred to as a phthalocyanine compound of the present invention).

[0015]

Embedded image

[0016]

Embedded image

[0017]

Embedded image (Wherein (I) or (II) to (V), R, R ₁ to
R ₄ , X and M are the same as described above. )

In the phthalocyanine compound of the present invention,
When R or R _{1 to} R ₄ is an alkyl group, it has 1 to 1 carbon atoms.
A straight-chain or branched alkyl group having 12 carbon atoms is preferred, and a straight-chain or branched alkyl group having 1 to 8 carbon atoms is particularly preferred.
Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, neopentyl, n-heptyl, isoheptyl, sec -Heptyl group, n-octyl group and 2-ethylhexyl group.

When R or R _{1 to} R ₄ is an alkoxyalkyl group, those having 2 to 8 carbon atoms are preferred, and those having 3 to 6 carbon atoms are particularly preferred. Examples include methoxyethyl, methoxypropyl, methoxybutyl, ethoxyethyl, ethoxypropyl, ethoxybutyl,
Examples thereof include an n-propoxyethyl group and an iso-propoxyethyl group.

X is a halogen atom, an alkylthio group, a phenylthio group which may have a substituent or a naphthylthio group which may have a substituent, provided that X is a halogen atom, for example, chlorine atom, bromine An atom and a fluorine atom are preferred, and a chlorine atom is particularly preferred.

When X is an alkylthio group, an alkylthio group having 1 to 12 carbon atoms is preferable.
An alkylthio group of 8 is particularly preferred. Specific examples include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio, tert-butylthio, n-pentylthio,
Isopentylthio group, neopentylthio group, n-hexylthio group, isohexylthio group, sec-hexylthio group, cyclohexylthio group, n-heptylthio group, isoheptylthio group, sec-heptylthio group, n-octylthio group, 2-ethylhexyl Thio group, n-nonylthio group, n-decylthio group, n-undecylthio group, n-dodecylthio group and the like.

When X is a phenylthio group which may have a substituent, examples of such a substituent include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and further substituted with an alkyl group. Preferred are an amino group and a halogen atom. Specific examples of the phenylthio group which may have such a substituent include a phenylthio group, a p-methylphenylthio group, a p-ethylphenylthio group, a pn-butylphenylthio group, a pn-propylphenyl Thio group, pt
tert-butylphenylthio group, pn-octylphenylthio group, p-methoxyphenylthio group, p-ethoxyphenylthio group, pn-propoxyphenylthio group, p-iso-propoxyphenylthio group, p- n-
Butoxyphenylthio group, p-iso-butoxyphenylthio group, p-sec-butoxyphenylthio group, p-
n-pentoxyphenylthio group, pn-octylphenylthio group, 2,4-dimethylphenylthio group, p-dimethylaminophenylthio group, p-diethylaminophenylthio group, p-di-n-butylaminophenyl A thio group, a p-chlorophenylthio group, a p-bromophenylthio group, a p-fluorophenylthio group, a 2,4-dichlorophenylthio group, and the like. In particular, a phenylthio group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a dialkylamino group having 1 to 8 carbon atoms, or a phenylthio group having a halogen atom is preferable.

When X is a naphthylthio group which may have a substituent, such a substituent is preferably an alkyl group having 1 to 4 carbon atoms or a halogen atom. Specific examples of the naphthylthio group which may have such a substituent include a naphthylthio group, a methylnaphthylthio group, an n-propylnaphthylthio group, an iso-propylnaphthylthio group, an n-butylnaphthylthio group, a tert- Examples thereof include a butylnaphthylthio group, a chloronaphthylthio group, a bromonaphthylthio group, and a fluoronaphthylthio group. Particularly, a naphthylthio group and a naphthylthio group having an alkyl group having 1 to 4 carbon atoms are preferable.

When M is a divalent metal, C
u, Zn, Fe, Co, Ni, Ru, Pb, Rh, P
d, Pt, Mn, Sn, and Pb are preferable, and a derivative of a trivalent or tetravalent metal is Al.
Cl, InCl, FeCl, MnOH, SiCl ₂ , S
nCl ₂ , GeCl ₂ , Si (OH) ₂ , Sn (OH) ₂ ,
Ge (OH) ₂ , VO, and TiO are preferred. As M, particularly, Cu, Ni, Co, FeCl, Zn, VO, Pd,
MnOH is preferred.

The phthalocyanine compound of the present invention specifically includes phthalocyanine compounds of the following general formulas (II) to (V).
The compound of the general formula (II) is mainly produced easily.

[0026]

Embedded image

[0027]

Embedded image In the phthalocyanine compounds represented by the general formulas (II) to (V), the types of the substituents of R _{1 to} R ₄ are as follows.
It is particularly preferred that all of R _{1 to} R ₄ are the same substituent.

The compounds of the general formula (I) or (II) of the present invention
Table 1 shows preferred specific examples of the phthalocyanine compound represented by (V).

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

[Table 3]

[0032]

[Table 4]

[0033]

[Table 5]

[0034]

[Table 6]

(Diiminoisoindoline compound) The intermediate of the phthalocyanine compound of the present invention is a diiminoisoindoline compound represented by the general formula (VI).

[0036]

Embedded image (In the formula, R ₅ , R ₆ and X are the same as described above.)

In the diiminoisoindoline compound represented by the general formula (VI), R _{5 to} R ₆ are an alkyl group,
An alkoxyalkyl group, each of which represents R or R _{1 to} R ₄ of the phthalocyanine compound represented by the general formulas (I) and (V).
May be the same as X is a halogen atom, an alkylthio group, a phenylthio group which may have a substituent, or a naphthylthio group which may have a substituent, each of which is a phthalocyanine compound represented by any of the above general formulas (I) to (V). May be the same as X in the above.

Specific examples of the diiminoisoindoline compound of the present invention represented by the general formula (VI) are shown below.

VI- (1) 5- (2-aminophenylthio) -6-chloro-1,3-diimino-4,7-dimethoxyisoindoline VI- (2) 5- (2-aminophenylthio)- 6
-Bromo-1,3-diimino-4,7-dimethoxyisoindoline VI- (3) 5- (2-aminophenylthio) -6
-N-octylthio-1,3-diimino-4,7-dimethoxyisoindoline VI- (4) 5- (2-aminophenylthio) -6
-N-undecylthio-1,3-diimino-4,7-dimethoxyisoindoline VI- (5) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4,7-diethoxyisoindoline VI- (6) 5- (2-aminophenylthio) -6
-Fluoro-1,3-diimino-4,7-diethoxyisoindoline VI- (7) 5- (2-aminophenylthio) -6
-N-nonylthio-1,3-diimino-4,7-diethoxyisoindoline VI- (8) 5- (2-aminophenylthio) -6
-N-dodecylthio-1,3-diimino-4,7-diethoxyisoindoline VI- (9) 5- (2-aminophenylthio) -6
-(4-n-butylphenylthio) -1,3-diimino-4,7-diethoxyisoindoline VI- (10) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4,7-di-n-propoxyisoindoline

VI- (11) 5- (2-aminophenylthio) -6- (4-sec-heptylthio) -1,3
-Diimino-4,7-di-n-propoxyisoindoline VI- (12) 5- (2-aminophenylthio) -6
-(4-n-butoxyphenylthio) -1,3-diimino-4,7-di-n-propoxyisoindoline VI- (13) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4,7-di-iso-propoxyisoindoline VI- (14) 5- (2-aminophenylthio) -6
-N-pentylthio-1,3-diimino-4,7-di-
iso-propoxyisoindoline VI- (15) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4,7-di-n-butoxyisoindoline VI- (16) 5- (2-aminophenylthio) -6
-(4-di-n-butylaminophenylthio) -1,3
-Diimino-4,7-di-n-butoxyisoindoline VI- (17) 5- (2-aminophenylthio) -6
-Cyclohexylthio-1,3-diimino-4,7-di-n-butoxyisoindoline VI- (18) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4,7-di-sec-butoxyisoindoline VI- (19) 5- (2-aminophenylthio) -6
-Fluoro-1,3-diimino-4,7-di-sec-butoxyisoindoline VI- (20) 5- (2-aminophenylthio) -6
-Bromo-1,3-diimino-4,7-di-sec-butoxyisoindoline

VI- (21) 5- (2-aminophenylthio) -6-phenylthio-1,3-diimino-4,
7-di-sec-butoxyisoindoline VI- (22) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4,7-di-iso-butoxyisoindoline VI- (23) 5- (2-aminophenylthio) -6
-Tert-butylphenylthio-1,3-diimino-
4,7-di-iso-butoxyisoindoline VI- (24) 5- (2-aminophenylthio) -6
-Bromo-1,3-diimino-4,7-di-iso-butoxyisoindoline VI- (25) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4,7-di-n-pentoxyisoindoline VI- (26) 5- (2-aminophenylthio) -6
-Fluoro-1,3-diimino-4,7-di-n-pentoxyisoindoline VI- (27) 5- (2-aminophenylthio) -6
-(4-chlorophenylthio) -1,3-diimino-
4,7-di-n-pentoxyisoindoline VI- (28) 5- (2-aminophenylthio) -6
-Methylthio-1,3-diimino-4,7-di-n-pentoxyisoindoline VI- (29) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4,7-di-iso-pentoxyisoindoline VI- (30) 5- (2-aminophenylthio) -6
-Bromo-1,3-diimino-4,7-di-iso-pentoxyisoindoline

VI- (31) 5- (2-aminophenylthio) -6-fluoro-1,3-diimino-4,7-di-iso-pentoxyisoindoline VI- (32) 5- (2- Aminophenylthio) -6
-Ethylthio-1,3-diimino-4,7-di-iso
-Pentoxyisoindoline VI- (33) 5- (2-aminophenylthio) -6
-Iso-propylthio-1,3-diimino-4,7-
Di-iso-pentoxyisoindoline VI- (34) 5- (2-aminophenylthio) -6
-(4-methoxyphenylthio) -1,3-diimino-
4,7-di-iso-pentoxyisoindoline VI- (35) 5- (2-aminophenylthio) -6
-(Naphthylthio-2-yl) -1,3-diimino-
4,7-di-iso-pentoxyisoindoline VI- (36) 5- (2-aminophenylthio) -6
-(Naphthylthio-1-yl) -1,3-diimino-
4,7-di-iso-pentoxyisoindoline VI- (37) 5- (2-aminophenylthio) -6
-(4-Dimethylaminophenylthio) -1,3-diimino-4,7-di-iso-pentoxyisoindoline VI- (38) 5- (2-aminophenylthio) -6
-(4-ethoxyphenylthio) -1,3-diimino-
4,7-di-iso-pentoxyisoindoline VI- (39) 5- (2-aminophenylthio) -6
-(4-bromophenylthio) -1,3-diimino-
4,7-di-iso-pentoxyisoindoline VI- (40) 5- (2-aminophenylthio) -6
-(2,4-dichlorophenylthio) -1,3-diimino-4,7-di-iso-pentoxyisoindoline

VI- (41) 5- (2-aminophenylthio) -6-n-butylthio-1,3-diimino-
4,7-di-iso-pentoxyisoindoline VI- (42) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4,7-di-sec-pentoxyisoindoline VI- (43) 5- (2-aminophenylthio) -6
-Ethylthio-1,3-diimino-4,7-di-sec
-Pentoxyisoindoline VI- (44) 5- (2-aminophenylthio) -6
-N-propylthio-1,3-diimino-4,7-di-
sec-pentoxyisoindoline VI- (45) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4,7-di-neo-pentoxyisoindoline VI- (46) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4,7-di-n-hexyloxyisoindoline VI- (47) 5- (2-aminophenylthio) -6
-Bromo-1,3-diimino-4,7-di-n-hexyloxyisoindoline VI- (48) 5- (2-aminophenylthio) -6
-Fluoro-1,3-diimino-4,7-di-n-hexyloxyisoindoline VI- (49) 5- (2-aminophenylthio) -6
-Neo-pentylthio-1,3-diimino-4,7-
Di-n-hexyloxyisoindoline VI- (50) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4,7-di-iso-hexyloxyisoindoline

VI- (51) 5- (2-aminophenylthio) -6-iso-propylthio-1,3-diimino-4,7-di-iso-hexyloxyisoindoline VI- (52) 5- ( 2-aminophenylthio) -6
-Bromo-1,3-diimino-4,7-di-iso-hexyloxyisoindoline VI- (53) 5- (2-aminophenylthio) -6
-Fluoro-1,3-diimino-4,7-di-iso-hexyloxyisoindoline VI- (54) 5- (2-aminophenylthio) -6
-(4-methylphenylthio) -1,3-diimino-
4,7-di-iso-hexyloxyisoindoline VI- (55) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4,7-di-n-heptyloxyisoindoline VI- (56) 5- (2-aminophenylthio) -6
-(2,4-dimethylphenylthio) -1,3-diimino-4,7-di-n-heptyloxyisoindoline VI- (57) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4,7-di-iso-heptyloxyisoindoline VI- (58) 5- (2-aminophenylthio) -6
-N-pentylthio-1,3-diimino-4,7-di-
iso-heptyloxyisoindoline VI- (59) 5- (2-aminophenylthio) -6
-Fluoro-1,3-diimino-4,7-di-iso-heptyloxyisoindoline VI- (60) 5- (2-aminophenylthio) -6
-(4-Dimethylaminophenylthio) -1,3-diimino-4,7-di-iso-heptyloxyisoindoline VI- (61) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4,7-di-n-octyloxyisoindoline

VI- (62) 5- (2-Aminophenylthio) -6-fluoro-1,3-diimino-4,7-di-n-octyloxyisoindoline VI- (63) 5- (2- Aminophenylthio) -6
-Bromo-1,3-diimino-4,7-di-n-octyloxyisoindoline VI- (64) 5- (2-aminophenylthio) -6
-(4-Fluorophenylthio) -1,3-diimino-
4,7-di-n-octyloxyisoindoline VI- (65) 5- (2-aminophenylthio) -6
-Methylthio-1,3-diimino-4,7-di-n-octyloxyisoindoline VI- (66) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4,7-di (2-ethylhexyloxy) isoindoline VI- (67) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4,7-di-n-nonyloxyisoindoline VI- (68) 5- (2-aminophenylthio) -6
-Iso-pentylthio-1,3-diimino-4,7-
Di-n-nonyloxyisoindoline VI- (69) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4,7-di-n-decyloxyisoindoline VI- (70) 5- (2-aminophenylthio) -6
-Fluoro-1,3-diimino-4,7-di-n-decyloxyisoindoline VI- (71) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4,7-di-n-undecyloxyisoindoline

VI- (72) 5- (2-aminophenylthio) -6-chloro-1,3-diimino-4,7-di-n-dodecyloxyisoindoline VI- (73) 5- (2- Aminophenylthio) -6
-Chloro-1,3-diimino-4,7-di- (2-methoxyethoxy) isoindoline VI- (74) 5- (2-aminophenylthio) -6
-N-hexylthio-1,3-diimino-4,7-di-
(2-methoxyethoxy) isoindoline VI- (75) 5- (2-aminophenylthio) -6
-Iso-hexylthio-1,3-diimino-4,7-
Di-isoindoline VI- (76) 5- (2-aminophenylthio) -6
-Sec-hexylthio-1,3-diimino-4,7-
Di- (2-ethoxyethoxy) isoindoline VI- (77) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4,7-di- (2-ethoxyethoxy) isoindoline VI- (78) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4,7-di- (2-n-
Propoxyethoxy) isoindoline VI- (79) 5- (2-aminophenylthio) -6
-Bromo-1,3-diimino-4,7-di- (2-n-
Propoxyethoxy) isoindoline VI- (80) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4,7-di- (2-is
o-Propoxyethoxy) isoindoline VI- (81) 5- (2-aminophenylthio) -6
-N-heptylthio-1,3-diimino-4,7-di-
(2-iso-propoxyethoxy) isoindoline

VI- (82) 5- (2-aminophenylthio) -6- (2-ethylhexylthio) -1,3-
Diimino-4,7-di- (2-iso-propoxyethoxy) isoindoline VI- (83) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4,7-di- (3-ethoxypropoxy) isoindoline VI- (84) 5- (2-aminophenylthio) -6
-Bromo-1,3-diimino-4,7-di- (3-ethoxypropoxy) isoindoline VI- (85) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4,7-di- (4-ethoxybutoxy) isoindoline VI- (86) 5- (2-aminophenylthio) -6
-Fluoro-1,3-diimino-4,7-di- (4-ethoxybutoxy) isoindoline VI- (87) 5- (2-aminophenylthio) -6
-(4-ethylphenylthio) -1,3-diimino-
4,7-di- (4-ethoxybutoxy) isoindoline VI- (88) 5- (2-aminophenylthio) -6
-(4-n-propylphenylthio) -1,3-diimino-4,7-di- (4-ethoxybutoxy) isoindoline VI- (89) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4-n-octyloxy-7-iso-pentoxyisoindoline VI- (90) 5- (2-aminophenylthio) -6
-Chloro-1,3-diimino-4- (2-methoxyethoxy) -7-iso-pentoxyisoindoline VI- (91) 5- (2-aminophenylthio) -6
-Phenylthio-1,3-diimino-4- (2-methoxyethoxy) -7-iso-pentoxyisoindoline VI- (92) 5- (2-aminophenylthio) -6
-(4-tert-butylphenylthio) -1,3-diimino-4,7-di-iso-pentoxyisoindoline

(Production Method of Phthalocyanine Compound) In order to produce the phthalocyanine compound of the present invention, the diiminoisoindoline compound of the general formula (VI) is reacted with a metal or a metal derivative.

As the metal or metal derivative, Al, S
i, Ti, V, Mn, Fe, Co, Ni, Cu, Zn,
Examples include Ge, Ru, Rh, Pd, In, Sn, Pt, Pb, and halides, carboxylate, sulfate, nitrate, carbonyl compound, oxide, and complex thereof.
In particular, metal halides or carboxylates are preferably used, and examples thereof include copper chloride, copper bromide, copper iodide, nickel chloride, nickel bromide, nickel acetate, cobalt chloride, cobalt bromide, cobalt acetate, Iron chloride, zinc chloride, zinc bromide, zinc iodide, zinc acetate, vanadium chloride, vanadium oxytrichloride, palladium chloride, palladium acetate, aluminum chloride, manganese chloride, manganese acetate, acetylacetone manganese, manganese chloride, lead chloride, acetic acid Examples include lead, indium chloride, titanium chloride, tin chloride and the like.

The amount of the metal or metal derivative used is represented by the general formula
0.1 to the diiminoisoindoline compound of (VI)
The molar ratio is from 0.6 to mol, preferably from 0.20 to 0.5 mol.

The reaction temperature is 100 to 300 ° C., preferably 130 to 220 ° C.

In the reaction, the use of a solvent
preferable.

The solvent used in the reaction is a boiling point of 60 ° C.
Above, preferably an organic solvent of 80 ° C. or higher is preferable. Examples include methanol, ethanol, n-propyl alcohol, n-butyl alcohol, isobutyl alcohol,
t-butyl alcohol, n-amyl alcohol, n-hexanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 2-heptanol, 1
-Alcohol solvents such as octanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol, propylene glycol, ethoxyethanol, propoxyethanol, butoxyethanol, dimethylaminoethanol, diethylaminoethanol, trichlorobenzene, chloronaphthalene, sulfolane, nitrobenzene, quinoline and urea And high-boiling solvents.

The amount of the solvent used is 0.5 to 50 times, preferably 1 to 15 times the weight of the diiminoisoindoline compound of the general formula (VI).

The reaction proceeds in the presence or absence of a catalyst. Examples of the catalyst include inorganic catalysts such as ammonium molybdate and DBU (1,8-diazabicyclo [5.4.
0] -7-undecene) and DBN (1,5-diazabicyclo [4.3.0] -5-nonene). The addition amount is 0.01 to 10 mol, preferably 0.1 to 1 mol, per 1 mol of the diiminoisoindoline compound.
1 to 2 mol.

As the post-treatment, the desired product can be obtained by distilling off the solvent after the reaction or by discharging the reaction solution into a poor solvent for the phthalocyanine compound and collecting the precipitate by filtration. The phthalocyanine compound of the present invention thus obtained can be used as it is as a near-infrared absorbing material or light-to-heat conversion material.However, it is possible to obtain a higher-purity target product by further recrystallization or column chromatography. it can.

(Method for producing diiminoisoindoline compound) In order to produce diiminoisoindoline (VI), which is an intermediate of the phthalocyanine compound of the present invention, a phthalonitrile compound represented by the general formula (VII) and ammonia Is reacted in the presence of a metal alkoxide.

[0058]

Embedded image

[0059]

Embedded image (In the formulas (VI) and (VII), R ₅ , R ₆ and X are the same as described above.)

The details of the method for producing the diiminoisoindoline compound represented by the general formula (VI) will be described below.

Examples of the metal alkoxide include sodium or potassium methoxide, ethoxide, n-propoxide, n-butoxide, n-pentoxyside, n-hexyloxyside, n-heptyloxyside, n-octyloxyside and 2-methoxy. Ethoxyside, 2-ethoxyethoxide, 2-n-butoxyethoxide and the like are used. The amount of the metal alkoxide to be used is 0.01 to 5 mol, preferably 0.1 to 2.0 mol, relative to compound (VII).

In the reaction, it is preferable to use an organic solvent in combination. Usually, an alcohol solvent is used as the organic solvent.

Examples of alcohol solvents include methanol, ethanol, n-propanol, n-butanol,
n-pentanol, n-hexanol, n-heptanol, n-octanol, 2-methoxyethanol, 2-
Ethoxyethanol, 2-n-butoxyethanol and the like are used. The amount of the alcohol solvent used is determined according to the compound (V
II) It is 200 mL to 15 L, preferably 500 mL to 5 L per 1 mol.

In the production of the diiminoisoindoline compound represented by the general formula (VI), sodium alcohol or potassium metal is added to an alcohol as a reaction solvent to prepare an alcohol solution of a metal alkoxide, and then ammonia and a general alcohol are added. The phthalonitrile compound of the formula (VII) may be charged and reacted. Alternatively, ammonia, a phthalonitrile compound of the general formula (VII) and a separately prepared metal alkoxide may be charged into the reaction solvent. You may make it react. At this time, the amount of the metal to be used is 0.01 to 5.0 mol, preferably 0.1 to 2.0 mol, relative to compound (VII).

The amount of ammonia to be used was as follows: Compound (VII) 1
It is 1 to 20 mol, preferably 3 to 10 mol, per mol.

The reaction temperature is from 0 ° C. to the reflux temperature of the solvent,
The temperature is preferably from 20 ° C to the reflux temperature of the solvent.

The reaction time is preferably 30 minutes to 72 hours.

After the reaction, the solvent was distilled off, extracted with an aromatic organic solvent such as toluene, washed with water, and concentrated to obtain a compound of the formula (VI)
To obtain a diiminoisoindoline compound.

(Near-infrared absorbing material)
A near-infrared absorbing material containing the phthalocyanine compound.

The phthalocyanine compound of the present invention, as it is or together with a binder or an additive, is coated or kneaded on paper, a plastic sheet, a plastic film, glass, a resin, or the like, hard-coated, or polymerized with a monomer. Thereby, it can be used for various uses as a near-infrared absorbing material. That is, it can be used for near-infrared absorbing filters, protective glasses, agricultural films, heat ray blocking filters, light receiving elements, optical recording media for long-wavelength lasers, printing inks for preventing forgery, painting for camouflage, and the like.

In particular, the phthalocyanine compound of the present invention
What is mixed, dispersed or coated on a resin, or obtained by polymerizing a mixture with a monomer is preferably used as a near-infrared absorbing material.

The near-infrared absorbing material is obtained by mixing the phthalocyanine compound of the present invention with a transparent resin, for example, a polyacrylonitrile resin, a methacrylonitrile resin, a polymethyl methacrylate resin, an ABS resin, a polystyrene resin, a polyethylene terephthalate resin, or the like. It can be produced by dissolving or dispersing the phthalocyanine compound of the present invention in a solvent, immersing the resin and subjecting it to heat treatment, or applying the resin to the resin.

Further, the phthalocyanine compound of the present invention may be used as a monomer such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate,
4,4′-diphenylmethane diisocyanate, mesitylene triisocyanate, 1,4-bis (α, α′-dimethylisocyanatomethyl) benzene, 1,3,5-
Tris (3-thiopropyl) isocyanurate, 2,2 '
-A molded article can also be obtained by mixing with dimethylpropanediol bis (2-thioacetate) and then polymerizing.

As an example of manufacturing a lens for safety glasses,
There is a method of dissolving or dispersing the phthalocyanine compound of the present invention in a resin for a high refractive lens, followed by injection molding.

The near-infrared absorbing material containing the compound of the present invention has extremely high light fastness and does not lose its absorption ability even after a long time, so that it can be used in a wide range of fields which could not be used conventionally.

(Light-to-Heat Conversion Material) Still another invention of the present application is:
A photothermal conversion material containing the phthalocyanine compound.

The phthalocyanine compound of the present invention has a
Since the absorption coefficient of near-infrared light in the region of 1200 nm is high, laser direct plate making (CTP) is used as a photothermal conversion material for absorbing laser light in this region and converting it into heat.
It can be preferably used for a master plate, a laser thermosensitive recording material, a laser thermal transfer recording material, and the like.

The light-to-heat conversion material can be produced by the same method as that for the near-infrared ray absorbing material.

The photothermal conversion material of the present invention may contain a binder resin or the like in addition to the phthalocyanine compound of the present invention as a photothermal conversion agent.

As the photothermal conversion agent, various known near-infrared absorbing agents can be used in combination with the phthalocyanine compound of the present invention within a range not departing from the object of the present invention.

Examples of near-infrared absorbing agents that can be used in combination include pigments such as carbon black and aniline black, and “near-infrared absorbing dyes” of “Chemical Industry (May, 1986)” (P4
5-51) and "Development and market trends of functional dyes in the 1990s", CMC (1990), Chapter 2, 2.3, polymethine dyes (cyanine dyes), phthalocyanine dyes, and dithiol metal complex salt dyes , Naphthoquinone, anthraquinone dyes, triphenylmethane (similar) dyes, aminium, diimmonium dyes, etc .; azo dyes, indoaniline metal complex dyes, pigments such as intermolecular CT dyes, and dye dyes. .

The binder resin is not particularly limited. For example, homopolymers or copolymers of acrylic monomers such as acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, methyl cellulose, ethyl cellulose, cellulose acetate Cellulosic polymers such as polystyrene, vinyl chloride-vinyl acetate copolymer, polyvinylpyrrolidone, polyvinyl butyral, vinyl polymers such as polyvinyl alcohol and copolymers of vinyl compounds, polyesters, condensation polymers such as polyamides, Examples thereof include a rubber-based thermoplastic polymer such as a butadiene-styrene copolymer, and a polymer obtained by polymerizing and crosslinking a photopolymerizable compound such as an epoxy compound.

When the light-to-heat conversion material of the present invention is used as a recording material such as a laser heat transfer recording material or a laser heat-sensitive recording material, the light-to-heat conversion material may be used by mixing a coloring component or a coloring component. A layer containing a component or a coloring component may be separately provided. As a color-forming component or a coloring component, a sublimable dye or an electron-donating dye precursor and an electron-accepting compound, physically by heat of a polymerizable polymer, etc.
An image which is formed by a chemical change can be used.

For example, the coloring components of the laser thermal transfer recording material are not particularly limited, but pigment types such as titanium dioxide, carbon black, zinc oxide, Prussian blue, cadmium sulfide, iron oxide, and lead and zinc , Inorganic pigments such as barium and calcium chromates and azo-based, thioindigo-based, anthraquinone-based, anthranthrone-based, triphenedioxazine-based,
Organic pigments such as phthalocyanine and quinacridone are exemplified. Examples of the dye include an acid dye, a direct dye, a disperse dye, an oil-soluble dye, and a metal-containing oil-soluble dye.

The color forming component of the laser thermosensitive recording material is not particularly limited, but those conventionally used in thermosensitive recording materials can be used. The electron-donating dye precursor has a property of coloring by donating electrons or accepting a proton such as an acid, and has a partial skeleton of lactone, lactam, sultone, spiropyran, ester, amide, or the like. Compounds that have a partial skeleton ring-open or cleaved upon contact with an electron-accepting compound are used. For example, triphenylmethane compounds, fluoran compounds, phenothiazine compounds, indolylphthalide compounds, leuco auramine compounds, rhodamine lactam compounds, triphenylmethanephthalide compounds, triazene compounds, spiropyran compounds, Fluorene compounds and the like. Examples of the electron-accepting compound include a phenolic compound, an organic acid or a metal salt thereof, and an oxybenzoate.

The photothermal conversion material of the present invention can be suitably used for a lithographic printing original plate for direct plate making. The lithographic printing plate precursor for direct plate making comprises a light-to-heat conversion layer provided on a support. Further, a silicon rubber layer may be laminated on the light-to-heat conversion layer, or a protective layer or the like may be further laminated.

The components constituting the light-to-heat conversion layer include, in addition to the above-mentioned light-to-heat conversion materials, image forming components, binder resins and the like. Alternatively, a layer containing an image forming component may be provided by being laminated on the photothermal conversion layer.

As the image-forming components, those which form an image by physical or chemical change by heat and which have been conventionally studied variously can be used. For example, Japanese Unexamined Patent Publication
JP-A-108588, which contains a microencapsulated heat-fusible substance and a binder resin, etc., is active on a support having a hydrophilic surface disclosed in JP-A-62-164049. Those containing a blocked isocyanate or the like together with a hydrogen-containing binder;
A microcapsule containing a lipophilic component and a hydrophilic binder polymer disclosed in JP-1849, an acid precursor disclosed in JP-A-8-220755, a compound having a vinyl ether group, And those containing an alkali-soluble resin and the like, JP-A-9-59
No. 93, which contains a polymer compound having a hydroxyl group and an o-naphthoquinonediazide compound, etc .; Japanese Patent Application Laid-Open No. 9-131977; 1462
Examples include those containing a polymerization initiator and an ethylenically unsaturated monomer, oligomer, macromonomer, and the like disclosed in JP-A-64, and are not particularly limited. In some cases, JP-A-9-80745, JP-A-9-1319
No. 77, JP-A-9-146264, etc., as disclosed in the light-heat conversion layer (photosensitive layer or heat-sensitive recording layer)
An image portion may be formed by laminating a silicon rubber layer thereon and, after exposure, contacting or peeling off the silicon rubber layer.

The binder resin used in the light-to-heat conversion layer is not particularly limited, but may be, for example, a homopolymer or a copolymer of an acrylic acid monomer such as acrylic acid, methacrylic acid, an acrylic ester, a methacrylic ester, or the like. Methylcellulose, ethylcellulose, cellulose-based polymers such as cellulose acetate, polystyrene, vinyl chloride-vinyl acetate copolymer, polyvinylpyrrolidone, polyvinylbutyral, copolymers of vinyl-based polymers and vinyl compounds such as polyvinyl alcohol, polyester, polyamide Such a condensation polymer, a rubber thermoplastic polymer such as a butadiene-styrene copolymer, and a polymer obtained by polymerizing and crosslinking a photopolymerizable compound such as an epoxy compound can be exemplified.

As the support to be used, for example, paper, paper laminated with plastic (for example, polyethylene, polypropylene, polystyrene, etc.), for example, a metal plate such as aluminum (including aluminum alloy), zinc, copper, etc., for example, Cellulose diacetate, cellulose triacetate,
Plastic films such as cellulose butyrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., are mentioned. Typical examples are coated paper, metal plates such as aluminum, and plastics such as polyethylene terephthalate. Examples thereof include a film, a rubber, and a composite thereof, and preferred are aluminum, an aluminum-containing alloy, and a plastic film. The thickness of the support is 25 μm to 3 m
m, preferably 100 μm to 500 μm.

Usually, a light-to-heat conversion material, an image forming component, a binder resin and the like are dispersed or dissolved in an organic solvent or the like and applied to a support to prepare a lithographic printing original plate for printing.

A primer layer may be provided between the support and the light-to-heat conversion layer for improving the adhesion and the printing characteristics, or the support itself may be subjected to a surface treatment. Examples of the primer layer to be used include those obtained by exposing and curing various photosensitive polymers as described in JP-A-60-22903 before laminating a light-to-heat conversion layer. The epoxy resin disclosed in Japanese Patent Application Laid-Open No. 50760/1995 is obtained by thermosetting the epoxy resin disclosed in Japanese Patent Application Laid-Open No. 63-133151, the hardened gelatin disclosed in Japanese Patent Application Laid-Open Publication No. Using a urethane resin and a silane coupling agent.
And those using a urethane resin disclosed in JP-A-273248.

As a protective film for protecting the surface of the light-to-heat conversion layer or the silicone rubber layer, a transparent film, for example,
Polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene terephthalate, cellophane, etc. may be laminated or these films may be stretched for use.

[0094]

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

Example 1 5- (2-aminophenylthio) -6-chloro-1,3
Preparation of diimino-4,7-diisopentoxyisoindoline (compound (VI- (29))) A solution obtained by dissolving 0.7 g of metallic sodium in 200 mL of n-propyl alcohol at room temperature was supplied with ammonia gas at a flow rate of 120 mL / Minutes and then introduced for 1 hour.
22.8 g of (2-aminophenylthio) -5-chloro-3,6-diisopentoxyphthalonitrile were added, and 5
Stirred at 0-60 ° C for 20 hours. After cooling, n-propyl alcohol was distilled off, 200 mL of toluene was added to the residue, and the mixture was heated and dissolved at 30 to 40 ° C. Then, 500m of water
L was added, dispersed, allowed to stand, and separated. The same operation was repeated four times to wash the toluene layer. Next, toluene was distilled off from the toluene layer, 200 mL of n-heptane was added, and 60
After stirring at -65 ° C for 30 minutes, the mixture was cooled to room temperature. The crystals were collected by filtration and dried, and 20.3 g of 5- (2-aminophenylthio) -6-chloro-1,3-diimino-4,7-diisopentoxyisoindoline of the following structural formula (yield: 85. 8
%).

[0096]

Embedded image

The elemental analysis, mass analysis and melting point of the crystals were as follows. FIG. 1 shows the infrared absorption spectrum of this compound. Elemental analysis _{(C 24 H 31 ClN 4 O} 2 S): 475.05 M. W. CH N calculated (%) 60.68 6.58 11.79 found (%) 60.65 6.56 11.81 MS (m / e): 474 (M ⁺ ) Melting point: 174.8-176 .1 ℃

Example 2 5- (2-aminophenylthio) -6-chloro-1,3-diimino-4,7-di-n
-Octyloxyisoindoline (compound (VI- (6
Production of 1)) Ammonia gas was introduced at a flow rate of 120 mL / min for 1 hour at room temperature into a solution of 0.9 g of metallic sodium dissolved in 265 mL of n-propyl alcohol. Then, 4- (2-aminophenylthio) -5-chloro-
3,6-di-n-octyloxyphthalonitrile 35.
8 g was added, and the mixture was stirred at 50 to 60 ° C for 20 hours. After cooling, the same treatment as in Example 1 was performed to obtain 5-
16.4 g (44.4% yield) of (2-aminophenylthio) -6-chloro-1,3-diimino-4,7-di-n-octyloxyisoindoline was obtained.

[0099]

Embedded image The elemental analysis value, mass analysis value and melting point of this crystal were as follows. FIG. 2 shows the infrared absorption spectrum of this compound. Elemental analysis _{(C 30 H 43 ClN 4 O} 2 S): 559.21 M. W. CHN calculated (%) 64.43 7.75 10.02 found (%) 64.42 7.78 10.05 MS (m / e): 559 (M ⁺ ) Melting point: 97-99 ° C

Example 3 5- (2-aminophenylthio) -6-chloro-1,3
Preparation of -diimino-4,7-di- (2-ethoxyethoxy) isoindoline (compound (VI- (77))) A solution of 0.8 g of metallic sodium dissolved in 250 mL of n-propyl alcohol at room temperature under ammonia gas Was introduced at a flow rate of 120 mL / min for 1 hour.
27.6 g of (2-aminophenylthio) -5-chloro-3,6-di- (2-ethoxyethoxy) isoindoline
Was added and stirred at 50-60 ° C. for 20 hours. After cooling,
By performing the same processing as in Example 1, the following structural formula of 5- (2-
27.6 g (yield 96.2%) of (aminophenylthio) -6-chloro-1,3-diimino-4,7-di- (2-ethoxyethoxy) isoindoline was obtained.

[0101]

Embedded image The elemental analysis value, mass analysis value and melting point of this crystal were as follows. FIG. 3 shows the infrared absorption spectrum of this compound. Elemental analysis _{(C 22 H 27 ClN 4 O} 4 S): 478.99 M. W. CH N calculated (%) 55.16 5.68 11.70 found (%) 55.14 5.70 11.73 MS (m / e): 480 (M ⁺ ) Melting point: 114-116 ° C

Example 4 5- (2-aminophenylthio) -6- (4-tert)
-Butylphenylthio) -1,3-diimino-4,7-
Diisopentoxyisoindoline (compound (VI- (9
2)) Production of Ammonia gas was introduced at a flow rate of 120 mL / min for 1 hour at room temperature into a solution of 0.6 g of metallic sodium dissolved in 200 mL of n-propyl alcohol. Then, 4-
27.0 g of (2-aminophenylthio) -5- (4-tert-butylphenylthio) -3,6-diisopentoxyphthalonitrile was added, and the mixture was stirred at 50 to 60 ° C for 20 hours. After cooling, the same treatment as in Example 1 was carried out to give 5- (2-aminophenylthio) -6- (4-
tert-butylphenylthio) -1,3-diimino-
4,7-diisopentoxyisoindoline 20.9 g
(Yield 75.2%).

[0103]

Embedded image The elemental analysis value, mass analysis value and melting point of this crystal were as follows. FIG. 4 shows the infrared absorption spectrum of this compound. Elemental analysis _{(C 34 H 44 N 4 O} 2 S 2): 604.87 M. W. CHN calculated (%) 67.51 7.33 9.26 found (%) 67.49 7.35 9.28 MS (m / e): 605 (M ⁺⁺ 1) melting point: 198-199 [deg.] C

(Example 5) Production of phthalocyanine compound (compound (I- (31)) 15 mL of 2-n-butoxyethanol and 0.75 of DBU
g of the mixture was heated to 145 ° -155 ° C., and then the 5- (2-aminophenylthio) -6-chloro-
4.75 g of 1,3-diimino-4,7-diisopentoxyisoindoline and 0.47 g of vanadium chloride were added. Then, after stirring at 155 to 160 ° C. for 3 hours,
After cooling to 60-70 ° C, 300 ml of methanol was added. After cooling to room temperature, the precipitate was collected by filtration and dried to obtain 3.6 g of a blackish green powder. Purification by column chromatography [silica gel / toluene: n-hexane (1: 1)] gave 2.5 g of a purified product as a black-green powder. The product was confirmed to be the target by the following analysis results.

FIG. 5 shows the IR spectrum of the obtained compound. Elemental analysis (C ₇₆ H ₆₄ Cl ₄ N ₁₂ O ₅ S ₄ V): 1546.41 M.P. W. CHN calculated (%) 59.03 4.17 10.87 found (%) 59.05 4.21 10.85 MS (m / e): 1545 (M ⁺ ).

The toluene solution of the compound thus obtained showed a maximum absorption at 1004.5 nm and a gram extinction coefficient of 8.29 × 10 ⁴ ml / g · cm. FIG. 6 shows the absorption spectrum chart.

(Comparative Example 1) Production of phthalocyanine compound (compound disclosed in JP-A-8-176101) 4- (2-aminophenylthio) -5-chloro-3,
After mixing 12.6 g of 6-diisopentoxyphthalonitrile, 1.9 g of vanadium chloride, 7.8 g of DBU and 78 mL of n-pentyl alcohol, the mixture was stirred under reflux for 48 hours. After cooling, the mixture was discharged into 500 mL of methanol, and the precipitate was collected by filtration and dried to obtain 6.3 g of a crude product as a black powder.
This was purified by column chromatography (silica gel / toluene) to obtain 2.8 g of a purified product as a black powder.

The toluene solution of the compound thus obtained showed a maximum absorption at 943 nm, and the gram extinction coefficient was 4.76 × 10 ⁴ ml / g · cm.

(Example 6) Production of phthalocyanine compound (compound (I- (32)) 15 mL of 2-n-butoxyethanol and 0.75 of DBU
g of the mixture was heated to 145 ° -155 ° C., and then the 5- (2-aminophenylthio) -6-chloro-
4.75 g of 1,3-diimino-4,7-diisopentoxyisoindoline and 0.3 g of copper (I) chloride were added. Then, after stirring at 155 to 160 ° C. for 3 hours, 6
After cooling to 0-70 ° C, 300 ml of methanol was added. After cooling to room temperature, the precipitate was collected by filtration and dried to obtain 3.6 g of a blackish green powder. Purification by column chromatography [silica gel / toluene: n-hexane (3: 1)] gave 2.7 g of a purified product as a black-blue powder. The product was confirmed to be the target by the following analysis results.

FIG. 7 shows the IR spectrum of the obtained compound. Elemental analysis (C ₇₆ H ₆₄ Cl ₄ CuN ₁₂ O ₄ S ₄ ): 1543.02 W. CHN calculated (%) 59.16 4.18 10.89 found (%) 59.13 4.16 10.93 MS (m / e): 1543 (M ⁺ ).

The toluene solution of the compound thus obtained showed a maximum absorption at 938 nm, and the gram extinction coefficient was 8.23 × 10 ⁴ ml / g · cm. FIG. 8 shows this absorption spectrum chart.

(Comparative Example 2) Production of phthalocyanine compound (compound disclosed in JP-A-8-176101) 4- (2-aminophenylthio) -5-chloro-3,
After mixing 12.6 g of 6-diisopentoxyphthalonitrile, 1.2 g of copper (I) chloride, 7.8 g of DBU and 78 mL of n-pentyl alcohol, the mixture was stirred under reflux for 48 hours. After cooling, the mixture was discharged into 500 mL of methanol, and the precipitate was collected by filtration and dried to obtain 7.3 g of a crude product as a black powder.
This was purified by column chromatography (silica gel / toluene) to obtain 3.2 g of a purified product as a black powder.

The toluene solution of the compound thus obtained showed a maximum absorption at 896 nm, and the gram extinction coefficient was 2.71 × 10 ⁴ ml / g · cm.

(Example 7) Production of phthalocyanine compound (compound (I- (34)) 15 mL of 2-n-butoxyethanol and 0.75 of DBU
g of the mixture was heated to 145 ° -155 ° C., and then the 5- (2-aminophenylthio) -6-chloro-
4.75 g of 1,3-diimino-4,7-diisopentoxyisoindoline and 0.3 g of zinc chloride were added. Then, after stirring at 155 to 160 ° C. for 8 hours, Example 5 was performed.
3.3 g of a dark blue powder was obtained by the same treatment as described above. Purification by column chromatography [activated alumina / toluene: methanol (50: 1)] yielded 1.8 g of a purified product as a dark blue powder. The product was confirmed to be the target by the following analysis results.

The IR spectrum of the obtained compound is shown in FIG. Elemental analysis (C ₇₆ H ₆₄ Cl ₄ ZnN ₁₂ O ₄ S ₄ ): 1544.85 M.P. W. CHN calculated (%) 59.25 4.18 10.88 Found (%) 59.20 4.16 10.86 MS (m / e): 1544 (M ⁺ ).

The toluene solution of the compound thus obtained showed a maximum absorption at 873.5 nm, and the gram extinction coefficient was 7.26 × 10 ⁴ ml / g · cm. This absorption spectrum chart is shown in FIG.

(Example 8) Production of phthalocyanine compound (compound (I- (112)) 15 mL of 2-n-butoxyethanol and 0.61 of DBU
g of the mixture was heated to 145 ° -155 ° C., and then the 5- (2-aminophenylthio) -6-chloro-
3.79 g of 1,3-diimino-4,7-diisopentoxyisoindoline and 0.4 g of manganese chloride were added. Next, after stirring at 155 to 160 ° C. for 2 hours, the same treatment as in Example 5 was performed to obtain 2.8 g of a dark blue powder. Purification by column chromatography [silica gel / toluene: methanol (50: 1)], 1.6 g of purified product
Was obtained as a dark blue powder. The product was confirmed to be the target by the following analysis results.

Elemental analysis (C ₇₆ H ₆₅ Cl ₄ MnN ₁₂ O ₅ S ₄ ): 1551.42 W. CHN calculated (%) 58.84 4.22 10.83 found (%) 58.87 4.31 10.87

The toluene solution of the compound thus obtained showed a maximum absorption at 1047.0 nm, and the gram extinction coefficient was 7.36 × 10 ⁴ ml / g · cm. FIG. 11 shows this absorption spectrum chart.

Example 9 Production of phthalocyanine compound (compound (I- (137)) 15 mL of 2-n-butoxyethanol and 0.76 of DBU
g of the mixture was heated to 145 ° -155 ° C. and then the 5- (2-aminophenylthio) -6-chloro-
5.59 g of 1,3-diimino-4,7-di-n-octyloxyisoindoline and 0.3 g of nickel chloride were added. Next, after stirring at 155 to 160 ° C. for 9 hours, the same treatment as in Example 5 was performed to obtain 3.8 g of a dark blue powder.
I got Purification by column chromatography [activated alumina / toluene] yielded 2.7 g of a purified product as a dark blue powder. The product was confirmed to be the target by the following analysis results.

The IR spectrum of the obtained compound is shown in FIG.
Shown in Elemental analysis _{(C 88 H 88 Cl 4 N} 12 NiO 4 S 4): 1706.49 M. W. CHN calculated (%) 61.94 5.20 9.85 found (%) 62.12 5.24 9.80 MS (m / e): 1706 (M ⁺ ).

The toluene solution of the compound thus obtained showed a maximum absorption at 900.5 nm and a gram extinction coefficient of 7.10 × 10 ⁴ ml / g · cm. This absorption spectrum chart is shown in FIG.

(Example 10) Production of phthalocyanine compound (compound (I- (152)) 15 mL of 2-n-butoxyethanol and 0.76 of DBU
g of the mixture was heated to 145 to 155 ° C., and then the 5- (2-aminophenylthio) -6- (4-t prepared in Example 4 was heated.
tert-butylphenylthio) -1,3-diimino-
6.04 g of 4,7-diisopentoxyisoindoline and 0.4 g of vanadium chloride were added. Then 155
After stirring at -160 ° C for 8 hours, the same treatment as in Example 5 was performed to obtain 4.7 g of a dark green powder. Purification by column chromatography [silica gel / toluene: n-hexane (1: 2)] gave 3.1 g of a purified product as a dark green powder. The product was confirmed to be the target by the following analysis results.

The IR spectrum of the obtained compound is shown in FIG.
Shown in Elemental analysis (C ₁₁₆ H ₁₁₆ N ₁₂ O ₅ S ₈ V): 2065.69 M.P. W. CHN calculated (%) 67.45 5.66 8.14 found (%) 67.50 5.68 8.18 MS (m / e): 2065 (M ⁺⁺ 1).

The toluene solution of the compound thus obtained showed a maximum absorption at 1066.0 nm, and the gram extinction coefficient was 8.02 × 10 ⁴ ml / g · cm. FIG. 15 shows the absorption spectrum chart.

(Example 11) Production of phthalocyanine compound (compound (I- (159)) 15 mL of 2-n-butoxyethanol and 0.61 of DBU
g of the mixture was heated to 145 ° -155 ° C. and then the 5- (2-aminophenylthio) -6-chloro-
4.47 g of 1,3-diimino-4,7-di-n-octyloxyisoindoline and 0.3 g of vanadium chloride were added. Next, after stirring at 155 to 160 ° C. for 5 hours, the same treatment as in Example 5 was performed to obtain 3.1 g of a dark green powder.
I got Purification by column chromatography [silica gel / toluene: n-hexane (1: 2)]
6 g were obtained as a dark green powder. The product was confirmed to be the target by the following analysis results.

The IR spectrum of the obtained compound is shown in FIG.
Shown in Elemental analysis _{(C 88 H 88 Cl 4 VN} 12 O 5 S 4): 1714.73 M. W. CHN calculated (%) 61.64 5.17 9.80 found (%) 61.41 5.34 9.60 MS (m / e): 1712 (M ⁺ ).

The toluene solution of the compound thus obtained showed a maximum absorption at 1004.0 nm, and the gram extinction coefficient was 8.20 × 10 ⁴ ml / g · cm. FIG. 17 shows the absorption spectrum chart.

(Example 12) Production of phthalocyanine compound (compound (I- (164)) 15 mL of 2-n-butoxyethanol and 0.76 of DBU
g of the mixture was heated to 145 ° -155 ° C. and then prepared in Example 3 as 5- (2-aminophenylthio) -6-chloro-.
7.18 g of 1,3-diimino-4,7-di- (2-ethoxyethoxy) isoindoline and 0.1% of vanadium chloride.
6 g were added. Next, after stirring at 155 to 160 ° C. for 10 hours, the same treatment as in Example 5 was performed to obtain 5.1 g of a dark green powder. Purification by column chromatography [activated alumina / toluene: acetone (100: 1)] gave 3.8 g of a purified product as a dark green powder. The product was confirmed to be the target by the following analysis results.

The IR spectrum of the obtained compound is shown in FIG.
Shown in Elemental analysis (C ₇₂ H ₅₆ Cl ₄ N ₁₂ O ₉ S ₄ V): 1554.30 M.P. W. CHN calculated (%) 55.64 3.63 10.81 found (%) 55.60 3.97 10.55 MS (m / e): 1552 (M ⁺⁺ 1).

The toluene solution of the compound thus obtained exhibited a maximum absorption at 998.0 nm, and the gram extinction coefficient was 8.40 × 10 ⁴ ml / g · cm. FIG. 19 shows the absorption spectrum chart.

(Example 13) Production of near-infrared absorbing material 24.4 g of 1,4-bis (α, α-dimethylisocyanatomethyl) benzene, 23.4 g of 1,3,5-tris (3-thiopropyl) isocyanate, And Example 5
Phthalocyanine compound (I- (31)) 2 synthesized by
g, 0.06 g of dibutyltin dilaurate,
A homogeneous liquid was obtained. This solution was poured into a mold consisting of a glass mold and a PVC gasket surface-treated with a fluorine-based external release agent, and was heated at 70 ° C. for 4 hours, at 80 ° C. for 2 hours, and at 120 ° C.
, And then cooled and released. The obtained resin molded product is dark brown and has a characteristic absorption wavelength region of 900 to 110.
0 nm, and the near infrared ray of this wavelength was well absorbed.

Example 14 Production of Near-Infrared Absorbing Material The phthalocyanine compound (I-
A near-infrared absorbing material was produced in the same manner as in Example 13, except that the phthalocyanine compound (I- (32)) synthesized in Example 6 was used instead of (31)). The characteristic absorption wavelength region of the obtained resin molded product is 800 to 105.
0 nm, and the near infrared ray of this wavelength was well absorbed.

(Example 15) Production of near-infrared absorbing material The phthalocyanine compound (I-
A near-infrared absorbing material was produced in the same manner as in Example 13 except that the phthalocyanine compound (I- (34)) synthesized in Example 7 was used instead of (31)). The characteristic absorption wavelength region of the obtained resin molded product is 750 to 950.
nm, and the near infrared ray of this wavelength was well absorbed.

(Example 16) Production of near-infrared absorbing material The phthalocyanine compound (I-
Example 13 except that the phthalocyanine compound (I- (112)) synthesized in Example 8 was used instead of (31)).
By performing the same operation as described above, a near-infrared absorbing material was produced.
The characteristic absorption wavelength region of the obtained resin molded product is 950 to 12
00 nm, and the near infrared ray of this wavelength was well absorbed.

Example 17 Production of Near-Infrared Absorbing Material The phthalocyanine compound (I-
Example 13 was repeated except that the phthalocyanine compound (I- (137)) synthesized in Example 9 was used instead of (31)).
By performing the same operation as described above, a near-infrared absorbing material was produced.
The characteristic absorption wavelength region of the obtained resin molded product is 800 to 10
00 nm, and the near infrared ray of this wavelength was well absorbed.

Example 18 Production of Near-Infrared Absorbing Material The phthalocyanine compound (I-
Example 1 was repeated except that the phthalocyanine compound (I- (152)) synthesized in Example 10 was used instead of (31)).
By performing the same operation as in No. 3, a near-infrared absorbing material was produced. The characteristic absorption wavelength region of the obtained resin molded product is 950 to 950.
It was 1200 nm, and the near infrared ray of this wavelength was well absorbed.

(Example 19) Production of near-infrared absorbing material The phthalocyanine compound (I-
Example 1 was repeated except that the phthalocyanine compound (I- (159)) synthesized in Example 11 was used instead of (31)).
By performing the same operation as in No. 3, a near-infrared absorbing material was produced. The characteristic absorption wavelength region of the obtained resin molded product is 900 to
1100 nm, and the near infrared ray of this wavelength was well absorbed.

(Example 20) Production of near-infrared absorbing material The phthalocyanine compound (I-
Example 1 was repeated except that the phthalocyanine compound (I- (164)) synthesized in Example 12 was used instead of (31)).
By performing the same operation as in No. 3, a near-infrared absorbing material was produced. The characteristic absorption wavelength region of the obtained resin molded product is 850 to
It was 1000 nm, and the near infrared ray of this wavelength was well absorbed.

Example 21 Production of Near-Infrared Absorbing Filter 1 g of the phthalocyanine compound (I- (31)) synthesized in Example 5 was added to 100 g of polystyrene, and the mixture was heated and melted.
A filter was prepared by injection molding. The filter thus obtained shows good transmittance characteristics,
It had excellent durability.

(Examples 22 to 28) Production of near-infrared absorbing filter The phthalocyanine compound (I) used in Example 21
-(31)) A near-infrared absorbing filter was manufactured in the same manner as in Example 21 except that the phthalocyanine compounds synthesized in Examples 6 to 12 were used instead of (-31)). All of the filters thus obtained exhibited good transmittance characteristics and were excellent in durability.

Example 29 Production of Photothermal Conversion Material Polyethylene terephthalate (PE) having an average thickness of 5 μm
T) 10 g of Delpet 80N (Asahi Kasei Corporation; acrylic resin) and 0.1 g of the phthalocyanine compound (I- (31)) synthesized in Example 5 were put on a film in toluene / methyl ethyl ketone (1/1). A solution dissolved in 90 g of the mixed solution was applied to a dry film thickness of about 5 μm to obtain a sample.

A laser beam of a YAG laser (wavelength: 1064 nm) was condensed by a lens and arranged so as to have a beam diameter of 10 μm on the surface of the sample. The YAG laser was adjusted so that the power of the laser reaching the surface was 180 mW, and a single pulse was applied to the sample with a pulse width of 20 μs. Observation of the irradiated sample by an optical microscope confirmed that a through hole having a diameter of about 10 μm was formed.

Example 30 Production of Photothermal Conversion Material The phthalocyanine compound (I- (3
A light-to-heat conversion material was produced in the same manner as in Example 29 except that the phthalocyanine compound (I-112) synthesized in Example 8 was used instead of 1)).

Example 31 Production of Photothermal Conversion Material The phthalocyanine compound (I) used in Example 29
Example 29 except that the phthalocyanine compound (I-152) synthesized in Example 10 was used instead of-(31)).
By performing the same operation as described above, a light-to-heat conversion material was produced. Similar tests were performed with good results.

Example 32 Production of Photothermal Conversion Material The phthalocyanine compound (I) used in Example 29
Example 29 except that the phthalocyanine compound (I-159) synthesized in Example 11 was used instead of-(31)).
By performing the same operation as described above, a light-to-heat conversion material was produced. Similar tests were performed with good results.

Example 33 Production of Laser Thermal Recording Material Delpet 80N (Asahi Kasei Corporation; acrylic resin) on the surface of a commercially available thermal recording paper (Thermo Autochrome Paper A-20 manufactured by Fuji Photo Film Co., Ltd.) ) 10
g and the phthalocyanine compound (I-
(31)) A solution in which 0.1 g was dissolved in 90 g of a mixed solution of toluene / methyl ethyl ketone (1/1) was dried to a thickness of about 5 μm.
m to give a sample.

A single mode semiconductor laser (wavelength 980n)
The laser light of m) was condensed by a lens and arranged so that the beam diameter became 50 μm on the surface of the sample. The semiconductor laser was adjusted so that the power of the laser reaching the surface was 35 mW, and a single pulse was applied to the sample with a pulse width of 30 ms. When the irradiated sample was observed with an optical microscope, a black-brown portion having a diameter of about 50 μm was confirmed.

Example 34 Production of Laser Thermal Recording Material The phthalocyanine compound (I) used in Example 33
A photothermal conversion material was produced by performing the same operation as in Example 33 except that the phthalocyanine compound (I-112) synthesized in Example 8 was used instead of-(31)). Similar tests were performed with good results.

Example 35 Production of Laser Thermal Recording Material The phthalocyanine compound (I) used in Example 33
Example 33 except that the phthalocyanine compound (I-152) synthesized in Example 10 was used instead of-(31)).
By performing the same operation as described above, a light-to-heat conversion material was produced. Similar tests were performed with good results.

Example 36 Production of Laser Thermal Recording Material The phthalocyanine compound (I) used in Example 33
Example 33 except that-(31)) was replaced with the phthalocyanine compound (I-159) synthesized in Example 11.
By performing the same operation as described above, a light-to-heat conversion material was produced.

[0152]

The novel phthalocyanine compound of the present invention has an absorption at 800 to 1200 nm, has a high extinction coefficient, is excellent in solubility in various organic solvents and resins, and has excellent durability. It can be suitably used for various uses such as materials and light-to-heat conversion materials.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of 5- (2-aminophenylthio) -6-chloro-1,3-diimino-4,7-diisopentoxyisoindoline synthesized in Example 1.

FIG. 2 shows 5- (2-aminophenylthio) -6-chloro-1,3-diimino-4,7-di-synthesized in Example 2.
n-octyloxyisoindoline (compound (VI-
It is an infrared absorption spectrum of (61)).

FIG. 3 shows 5- (2-aminophenylthio) -6-chloro-1,3-diimino-4,7-di-synthesized in Example 3.
(2-ethoxyethoxy) isoindoline (compound (V
It is an infrared absorption spectrum of I- (77)).

FIG. 4 shows 5- (2-aminophenylthio) -6- (4-tert-butylphenylthio)-synthesized in Example 4.
4 is an infrared absorption spectrum of 1,3-diiminoisopentoxyisoindoline (compound (VI- (92)).

5 is an infrared absorption spectrum of a phthalocyanine compound (compound (I- (31))) synthesized in Example 5. FIG.

FIG. 6 is an absorption spectrum of a phthalocyanine compound (Compound (I- (31))) synthesized in Example 5 in a toluene solution.

FIG. 7 is an infrared absorption spectrum of a phthalocyanine compound (compound (I- (32))) synthesized in Example 6.

8 is an absorption spectrum of a phthalocyanine compound (compound (I- (32))) synthesized in Example 6 in a toluene solution. FIG.

9 is an infrared absorption spectrum of a phthalocyanine compound (compound (I- (34))) synthesized in Example 7. FIG.

10 is an absorption spectrum of a phthalocyanine compound (compound (I- (34))) synthesized in Example 7 in a toluene solution. FIG.

11 is an absorption spectrum of a phthalocyanine compound (compound (I- (112))) synthesized in Example 8 in a toluene solution. FIG.

FIG. 12 is an infrared absorption spectrum of a phthalocyanine compound (compound (I- (137))) synthesized in Example 9.

13 is an absorption spectrum of a phthalocyanine compound (compound (I- (137))) synthesized in Example 9 in a toluene solution. FIG.

FIG. 14 is an infrared absorption spectrum of a phthalocyanine compound (compound (I- (152))) synthesized in Example 10.

15 is an absorption spectrum of a phthalocyanine compound (compound (I- (152))) synthesized in Example 10 in a toluene solution. FIG.

FIG. 16 is an infrared absorption spectrum of a phthalocyanine compound (compound (I- (159))) synthesized in Example 11.

17 shows an absorption spectrum of a phthalocyanine compound (compound (I- (159))) synthesized in Example 11 in a toluene solution. FIG.

18 is an infrared absorption spectrum of a phthalocyanine compound (compound (I- (164))) synthesized in Example 12. FIG.

19 is an absorption spectrum of a phthalocyanine compound (compound (I- (164))) synthesized in Example 12 in a toluene solution. FIG.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] February 3, 1999

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0100

[Correction method] Change

[Correction contents]

Example 3 5- (2-aminophenylthio) -6-chloro-1,3
Preparation of -diimino-4,7-di- (2-ethoxyethoxy) isoindoline (compound (VI- (77))) A solution of 0.8 g of metallic sodium dissolved in 250 mL of n-propyl alcohol at room temperature under ammonia gas Was introduced at a flow rate of 120 mL / min for 1 hour.
27.6 g of (2-aminophenylthio) -5-chloro-3,6-di- (2-ethoxyethoxy) phthalonitrile
Was added and stirred at 50-60 ° C. for 20 hours. After cooling,
By performing the same processing as in Example 1, the following structural formula of 5- (2-
27.6 g (yield 96.2%) of (aminophenylthio) -6-chloro-1,3-diimino-4,7-di- (2-ethoxyethoxy) isoindoline was obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FIG02B 5/22 B41M 5/26 K (72) Inventor Shigeo Fujita 1-43, Yugecho Minami, Yao-shi, Osaka Yamamoto Kasei Co., Ltd. 72) Inventor Tsunehito Eda 1-443 Minami Yugecho, Yao City, Osaka Prefecture Inside Yamamoto Kasei Co., Ltd.

Claims (11)

[Claims] 1. A phthalocyanine compound represented by the general formula (I). Embedded image (Wherein, R represents an alkyl group or an alkoxyalkyl group, X represents a halogen atom, an alkylthio group, an optionally substituted phenylthio group or an optionally substituted naphthylthio group, and M represents 2 A hydrogen atom, a divalent metal or a derivative of a trivalent or tetravalent metal.) 2. The phthalocyanine compound according to claim 1, wherein R is an alkyl group having 1 to 12 carbon atoms or an alkoxyalkyl group having 2 to 8 carbon atoms. 3. General formulas (II) to (V): Embedded image (Wherein, R _{1 to} R ₄ represent an alkyl group or an alkoxyalkyl group, and X represents a halogen atom, an alkylthio group, a phenylthio group which may have a substituent, or a naphthylthio group which may have a substituent. , M represents a derivative of two hydrogen atoms, a divalent metal or a trivalent or tetravalent metal.). 4. The phthalocyanine compound according to claim 3, wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group having 1 to 12 carbon atoms or an alkoxyalkyl group having 2 to 8 carbon atoms. 5. M is Cu, Zn, Co, Ni, Pd, P
b, MnOH, AlCl, FeCl, InCl, SnC
l _2, a VO or TiO, a phthalocyanine compound according to any one of claims 1 to 4. 6. X is a chlorine, bromine or fluorine atom; an alkylthio group having 1 to 12 carbon atoms;
An alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group optionally substituted with an alkyl group or a phenylthio group optionally having a halogen atom; or an alkyl group having 1 to 4 carbon atoms as a substituent or The phthalocyanine compound according to any one of claims 1 to 5, which is a naphthylthio group optionally having a halogen atom. 7. The method for producing a phthalocyanine compound according to claim 1, wherein the diiminoisoindoline compound represented by the general formula (VI) is reacted with a metal or a metal derivative. Embedded image (Wherein, R ₅ and R ₆ represent an alkyl group or an alkoxyalkyl group, and X represents a halogen atom, an alkylthio group, a phenylthio group which may have a substituent, or a naphthylthio group which may have a substituent. .) 8. A diiminoisoindoline compound represented by the general formula (VI). Embedded image (Wherein, R ₅ and R ₆ represent an alkyl group or an alkoxyalkyl group, and X represents a halogen atom, an alkylthio group, a phenylthio group which may have a substituent, or a naphthylthio group which may have a substituent. .) 9. The diiminoisoindoline represented by the general formula (VI) according to claim 8, wherein the phthalonitrile compound represented by the general formula (VII) is reacted with ammonia in the presence of a metal alkoxide. A method for producing a compound. Embedded image (Wherein, R ₅ and R ₆ represent an alkyl group or an alkoxyalkyl group, and X represents a halogen atom, an alkylthio group, a phenylthio group which may have a substituent, or a naphthylthio group which may have a substituent. .) 10. A near-infrared absorbing material comprising the phthalocyanine compound according to claim 1. Description: 11. A photothermal conversion material comprising the phthalocyanine compound according to claim 1. Description: