JP2007169479A - Naphthalocyanine compound and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a naphthalocyanine compound useful for image-forming materials, optical film materials or the like, and its manufacturing method. <P>SOLUTION: The compound is represented by general formula (I). In general formula (I), R<SP>111</SP>, R<SP>121</SP>, R<SP>131</SP>and R<SP>141</SP>are each independently a group represented by general formula (II); R<SP>112</SP>, R<SP>122</SP>, R<SP>132</SP>and R<SP>142</SP>are each independently a substituent group; M<SP>1</SP>is two hydrogen atoms, two monovalent metal atoms, a bivalent metal atom, or a substituted metal atom comprising a trivalent or tetravalent metal atom, provided that M<SP>1</SP>is not bivalent zinc; and n112, n122, n132 and n142 are each independently an integer of 0-4. In general formula (II), R<SP>211</SP>is a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group linked by a carbon atom; R<SP>212</SP>and R<SP>213</SP>are each independently an aliphatic group, an aromatic group or a heterocyclic group linked by a carbon atom. The compound is represented, for example, by a sample compound (I-1). The manufacturing method of the naphthalocyanine compound comprises a reaction with a metal compound. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a naphthalocyanine compound useful for an image forming material, an infrared thermosensitive recording material, an optical recording element, an optical film material, and the like, and more particularly to a novel naphthalocyanine compound having excellent absorption characteristics. . The present invention also relates to a method for producing the naphthalocyanine compound.

  Phthalocyanines have been widely used as pigments. Among them, naphthalocyanine compounds do not substantially absorb visible light, but have been actively studied as near-infrared dyes that absorb infrared rays (see, for example, Patent Document 1). ).

Regarding the naphthalocyanine compound having a substituent on the naphthalene ring of the naphthalocyanine skeleton, various compounds have been known so far. Specifically, as a substituent on the naphthalene ring, a halogen atom, alkyl group, aryl group, hydroxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, amino group, alkylamino group, oxycarbonyl group, alkoxycarbonyl A group having a group, a cyano group or a nitro group (see, for example, Patent Document 1 and Non-Patent Document 1), a polymerization precursor having an acrylamide group (see, for example, Patent Document 2), an acylamino group and a precursor thereof ( For example, see Patent Documents 3 to 5).
However, there has been a demand for the development of naphthalocyanine compounds that exhibit even better performance in image forming materials, infrared thermosensitive recording materials, optical recording elements, optical film materials, and the like.

JP-A-2-29685 JP-A-7-118723 Japanese Patent Laid-Open No. 11-152413 Japanese Patent Laid-Open No. 11-152414 Japanese Patent Laid-Open No. 11-152415 Chinese Patent No. 1,367,173A Specification Journal of Chemical Society, Perkin Transaction, I, pp. 2453-2458 (1988)

  An object of the present invention is to provide a novel naphthalocyanine compound useful as an image forming material, an infrared thermosensitive recording material, an optical recording element, an optical film material and the like. Another object of the present invention is to provide a simple method for producing the naphthalocyanine compound.

  As a result of intensive studies, the present inventors have found that the above object of the present invention can be achieved by the following means.

(1) A naphthalocyanine compound represented by the following general formula (I).

In the general formula (I), R ¹¹¹ , R ¹²¹ , R ¹³¹ and R ¹⁴¹ each independently represents a group represented by the following general formula (II), and R ¹¹² , R ¹²² , R ¹³² and R ¹⁴² are each independently And M ¹ represents a substituted metal atom containing two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, or a trivalent or tetravalent metal atom. However, M ¹ is not divalent zinc. n112, n122, n132 and n142 each independently represents an integer of 0 to 4.

In the general formula (II), R ²¹¹ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group linked by a carbon atom, and R ²¹² and R ²¹³ are each independently an aliphatic group, an aromatic group or It represents a heterocyclic group linked by a carbon atom.
(2) The naphthalocyanine compound according to (1), wherein M ¹ is two hydrogen atoms or a divalent copper atom.
(3) The naphthalocyanine compound according to (1) or (2), wherein R ²¹¹ is a hydrogen atom.
(4) The naphthalocyanine compound according to any one of (1) to (3), wherein the n112, n122, n132, and n142 are all 0.
(5) A process for producing a compound represented by the following general formula (IA), comprising a step of reacting a compound represented by the following general formula (III) with a metal compound.

In the general formulas (III) and (IA), R ¹¹¹ , R ¹¹² , R ¹²¹ , R ¹²² , R ¹³¹ , R ¹³² , R ¹⁴¹ , R ¹⁴² , n112, n122, n132 and n142 in the general formula (I) As defined. M ² represents a divalent metal atom or a substituted metal atom containing a trivalent or tetravalent metal. However, M ² is not divalent zinc.
(6) The method according to (5), wherein the metal compound is acetate.

  According to the present invention, a novel naphthalocyanine compound useful as an image forming material, an infrared thermosensitive recording material, an optical recording element, an optical film material, or the like can be provided. Moreover, this naphthalocyanine compound can be easily manufactured by implementing the manufacturing method of this invention.

  Hereinafter, the compound of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

First, definitions of substituents and the like in this specification are described.
In the present specification, an aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. The alkyl group may have a branch and may form a ring (that is, a cycloalkyl group). The alkyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 18 carbon atoms. The alkyl part of the substituted alkyl group is the same as the above alkyl group. The alkenyl group may have a branch, or may form a ring (that is, a cycloalkenyl group). The alkenyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 18 carbon atoms. The alkenyl part of the substituted alkenyl group is the same as the above alkenyl group. The alkynyl group may have a branch and may form a ring (that is, a cycloalkenyl group). The number of carbon atoms in the alkynyl group is preferably 2-20, and more preferably 2-18. The alkynyl part of the substituted alkynyl group is the same as the above alkynyl group. The alkyl part of the aralkyl group and the substituted aralkyl group is the same as the above alkyl group. The aryl part of the aralkyl group and the substituted aralkyl group is the same as the following aryl group.

  Examples of the substituent of the alkyl part of the substituted alkyl group, substituted alkenyl group, substituted alkynyl group and substituted aralkyl group include a halogen atom (for example, chlorine atom, bromine atom, iodine atom), alkyl group [straight chain, branched, cyclic Represents a substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, eicosyl group, 2-chloroethyl group, 2-cyanoethyl group, 2-ethylhexyl group), cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group), Bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. For example, bicyclo [ 1.2.2] heptan-2-yl group, bicyclo [2.2.2] octane-3-yl group), It is intended to encompass such tricyclo structure having many cyclic structures into. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents such an alkyl group. ], An alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are an alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as a vinyl group, an allyl group, a prenyl group, a geranyl group, an oleyl group), a cycloalkenyl group (preferably a carbon number of 3 A substituted or unsubstituted cycloalkenyl group having ˜30, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, such as a 2-cyclopenten-1-yl group and 2-cyclohexene -1-yl group), a bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a hydrogen atom of a bicycloalkene having one double bond. For example, a bicyclo [2.2.1] hept-2-en-1-yl group, It is intended to include [2.2.2] oct-2-en-4-yl) group. An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as an ethynyl group, a propargyl group, a trimethylsilylethynyl group, an aryl group (preferably a substituted or unsubstituted group having 6 to 30 carbon atoms). An aryl group such as a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, an o-hexadecanoylaminophenyl group), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or It is a monovalent group obtained by removing one hydrogen atom from a non-aromatic heterocyclic compound, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. Furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano, hydroxyl, nitro, carboxy Group, alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy group, ethoxy group, isopropoxy group, tert-butoxy group, n-octyloxy group, 2-methoxyethoxy group ), An aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms such as phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2 -Tetradecanoylaminophenoxy group), silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy group, tert-butyldimethylsilyloxy group), heterocyclic oxy group (preferably having 2 carbon atoms) To 30 substituted or unsubstituted heterocyclic oxy groups, 1-phenyl te Razoru 5 group, 2-tetrahydropyranyloxy group),

Acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy group, acetyloxy group , Pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group), carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethyl) Carbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group), alkoxycarbonyloxy group (preferably 2 carbon atoms 30 substituted or unsubstituted alkoxycarbonyloxy groups, for example, methoxycarbonyloxy group, ethoxycarbonyloxy group, tert-butoxycarbonyloxy group, n-octylcarbonyloxy group), aryloxycarbonyloxy group (preferably having 7 to 7 carbon atoms) 30 substituted or unsubstituted aryloxycarbonyloxy groups, for example, phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxyphenoxycarbonyloxy group), amino group (preferably amino group, C1-C30 substituted or unsubstituted alkylamino group, C6-C30 substituted or unsubstituted anilino group, for example, amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino Group, Phenylamino group), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formyl Amino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group), aminocarbonylamino group (preferably having 1 to 30 carbon atoms) A substituted or unsubstituted aminocarbonylamino group such as carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group), alkoxycarbonylamino group (preferably having a carbon number) 2-30 Substituted or unsubstituted alkoxycarbonylamino group, for example, methoxycarbonylamino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group),

Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxycarbonylamino Group), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as a sulfamoylamino group, an N, N-dimethylaminosulfonylamino group, or an Nn group. -Octylaminosulfonylamino group), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino groups having 6 to 30 carbon atoms, for example, , Methylsulfonyl Mino group, butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group), mercapto group, alkylthio group (preferably a C1-C30 substitution) Or an unsubstituted alkylthio group, such as a methylthio group, an ethylthio group, an n-hexadecylthio group, an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, such as a phenylthio group, a p-chlorophenylthio group, m-methoxyphenylthio group), heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group ), Sulfamoyl group (preferably having 0 to 30 carbon atoms) Substituted or unsubstituted sulfamoyl groups such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N- Benzoylsulfamoyl group, N- (N′-phenylcarbamoyl) sulfamoyl group), sulfo group, alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, 6 to 30 A substituted or unsubstituted arylsulfinyl group, for example, a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, a p-methylphenylsulfinyl group), an alkyl or arylsulfonyl group (preferably a substituted or unsubstituted group having 1 to 30 carbon atoms) Alkylsulfonyl group of 6 -30 substituted or unsubstituted arylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, phenylsulfonyl group, p-methylphenylsulfonyl group), acyl groups (preferably formyl group, substituted or unsubstituted 2-30 carbon atoms) An unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, a heterocyclic carbonyl group bonded to the carbonyl group at a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms, for example, Acetyl group, pivaloyl group, 2-chloroacetyl group, stearoyl group, benzoyl group, pn-octyloxyphenylcarbonyl group, 2-pyridylcarbonyl group, 2-furylcarbonyl group), aryloxycarbonyl group (preferably carbon A substituted or unsubstituted aryloxy group of 7 to 30 Bonyl group, for example, phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, p-tert-butylphenoxycarbonyl group), alkoxycarbonyl group (preferably substituted or unsubstituted having 2 to 30 carbon atoms) An alkoxycarbonyl group, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, an n-octadecyloxycarbonyl group), a carbamoyl group (preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, for example, Carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (methylsulfonyl) carbamoyl group),

An aryl or heterocyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, such as a phenylazo group, a p-chlorophenylazo group, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group), imide group (preferably N-succinimide group, N-phthalimide group), phosphino group (preferably substituted or non-substituted having 2 to 30 carbon atoms) Substituted phosphino groups such as dimethylphosphino group, diphenylphosphino group, methylphenoxyphosphino group), phosphinyl groups (preferably substituted or unsubstituted phosphinyl groups having 2 to 30 carbon atoms such as phosphinyl group, dioctyl) Oxyphosphinyl group, diethoxyphosphinyl group), phosphinyloxy A group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as a diphenoxyphosphinyloxy group, a dioctyloxyphosphinyloxy group), a phosphinylamino group (preferably, A substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as a dimethoxyphosphinylamino group or a dimethylaminophosphinylamino group, a silyl group (preferably a substituted or unsubstituted group having 3 to 30 carbon atoms). Substituted silyl groups such as trimethylsilyl group, tert-butyldimethylsilyl group, and phenyldimethylsilyl group).

  Among the above functional groups, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.

  Examples of the substituent of the aryl moiety of the substituted aralkyl group include the substituents of the following substituted aryl group.

  In the present specification, the aromatic group means an aryl group and a substituted aryl group. These aromatic groups may be condensed with an aliphatic ring, another aromatic ring or a heterocyclic ring. 6-40 are preferable, as for the carbon atom number of an aromatic group, 6-30 are more preferable, and 6-20 are more preferable. Among them, the aryl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group.

  The aryl part of the substituted aryl group is the same as the above aryl group. Examples of the substituent of the substituted aryl group include the groups exemplified as the substituent of the alkyl moiety of the above-mentioned substituted alkyl group, substituted alkenyl group, substituted alkynyl group and substituted aralkyl group.

  In the present specification, the heterocyclic group preferably contains a 5-membered or 6-membered saturated or unsaturated heterocyclic ring. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring. Preferred examples of the ring-constituting hetero atom of the heterocyclic group include B, N, O, S, Se and Te, and more preferred examples include N, O and S. The heterocyclic group preferably has a valence (monovalence) in which the carbon atom is free. That is, the heterocyclic group has a carbon atom at the bonding position, and is preferably bonded at the carbon atom. The number of carbon atoms of a preferable heterocyclic group is 1-40, More preferably, it is 1-30, More preferably, it is 1-20. Examples of the saturated heterocyclic ring in the heterocyclic group include a pyrrolidine ring, a morpholine ring, a 2-bora-1,3-dioxolane ring, and a 1,3-thiazolidine ring. Examples of the unsaturated heterocyclic ring in the heterocyclic group include imidazole ring, thiazole ring, benzothiazole ring, benzoxazole ring, benzotriazole ring, benzoselenazole ring, pyridine ring, pyrimidine ring and quinoline ring. The heterocyclic group may have a substituent. Examples of such a substituent include those listed as substituents for the alkyl moiety of the aforementioned substituted alkyl group, substituted alkenyl group, substituted alkynyl group and substituted aralkyl group.

Next, the compound represented by formula (I) will be described.
In the general formula (I), R ¹¹² , R ¹²² , R ¹³² and R ¹⁴² each independently represent a substituent, and the substituent includes the above-mentioned substituted alkyl group, substituted alkenyl group, substituted alkynyl group and substituted aralkyl group alkyl. Examples include the groups listed as the substituent of the moiety. When R ¹¹² there are a plurality may be more R ¹¹² are bonded to each other to form a cyclic structure. The same ^{applies to} R ¹²² , R ¹³² , and R ¹⁴² . R ¹¹² , R ¹²² , R ¹³² and R ¹⁴² are preferably halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, alkoxy groups, aryloxy groups, silyloxy groups , Heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino Group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or aryl A sulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group, more preferably a halogen atom , Alkyl group, aryl group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, aminocarbonylamino Group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl , Sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, carbamoyl group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, more preferably a halogen atom Alkyl group, aryl group, hydroxyl group, alkoxy group, aryloxy group, amino group, mercapto group, alkylthio group, arylthio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, and A halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, and an arylthio group are preferable, and a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon number of 6 are more preferable. An aryl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and an arylthio group having 6 to 20 carbon atoms, more preferably 1-8 alkyl group, C6-C10 aryl group, C1-C8 alkoxy group, C6-C10 aryloxy group, C1-C8 alkylthio group, C6-C10 An arylthio group, more preferably an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 8 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, and an arylthio group having 6 to 8 carbon atoms.

  n112, n122, n132 and n142 are preferably 0 to 3, more preferably 0 to 2, still more preferably 0 or 1, and most preferably 0.

M ¹ represents a substituted metal atom including two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, or a trivalent or tetravalent metal atom.
Examples of the monovalent metal atom in M ¹ include alkali metals (for example, Li ⁺ , Na ⁺ , K ⁺ ), and examples of the divalent metal atom include Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Ti. ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Ru ²⁺ , Rh ²⁺ , Pd ²⁺ , Pt ²⁺ , Ba ²⁺ , Cd ²⁺ , Hg ²⁺ , Pb ^2+, Sn ^2+, and examples of the trivalent or tetravalent metal atom, Al, Ga, Mn, Fe , Ru, Cr, Si, Zr, Ge, Sn, Ti and the like. Examples of the substituent in the substituted metal atom include a halogen atom, a hydroxyl group, an oxygen atom, an aliphatic oxy group, an aromatic oxy group, an aliphatic thio group, and an aromatic thio group.

M ¹ is preferably 2 hydrogen atoms, 2 Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ and Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Ti ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Ru ²⁺ , Rh ²⁺ , Pd ²⁺ , Pt ²⁺ , Ba ²⁺ , Cd ²⁺ , Hg ²⁺ , Pb ²⁺ , Sn ²⁺ , Al-Cl, Al-Br, Al-F, Al-I, Ga-Cl, Ga-F, Ga-I, Ga-Br, In-Cl, In-Br, In-I, In-F, Tl -Cl, Tl-Br, Tl- I, Tl-F, Mn-OH, Fe-Cl, Ru-Cl, CrCl 2, SiCl 2, SiBr 2, SiF 2, SiI 2, ZrCl 2, GeCl 2, GeBr 2 _{, GeI 2, GeF 2, SnCl} 2, SnBr 2, SnI 2, SnF 2, TiCl 2, TiBr 2, TiF 2, Si (OH) 2, Ge (O _{) 2, Zr (OH) 2} , Mn (OH) 2, Sn (OH) 2, TiR 2, CrR 2, SiR 2, SnR 2, GeR 2, Si (OR) 2, Sn (OR) 2, Ge ( OR) ₂ , Ti (OR) ₂ , Cr (OR) ₂ , Sn (SR) ₂ , Ge (SR) ₂ [R represents an aliphatic group or an aromatic group], VO, MnO, TiO, and Preferably two hydrogen atoms, two Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ and Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Ti ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Ru ²⁺ , Rh ²⁺ , Pd ²⁺ , Pt ²⁺ , Ba ²⁺ , Sn ²⁺ , Al-Cl, Al-Br, Ga-Cl, Ga-F, Ga -I, Ga-Br, In- Cl, In-Br, Tl-Cl, Tl-Br, Mn-OH, Fe-Cl, Ru-Cl, CrCl 2, SiCl 2, SiBr 2, Z _{Cl 2, GeCl 2, GeBr 2} , SnCl 2, SnBr 2, TiCl 2, TiBr 2, Si (OH) 2, Ge (OH) 2, Zr (OH) 2, Mn (OH) 2, Sn (OH) 2 , TiR ₂ , CrR ₂ , SiR ₂ , SnR ₂ , GeR ₂ , Si (OR) ₂ , Sn (OR) ₂ , Ge (OR) ₂ , Ti (OR) ₂ , Cr (OR) ₂ , Sn (SR) ₂ , Ge (SR) ₂ [R represents an aliphatic group, an aromatic group], VO, MnO, TiO, more preferably two hydrogen atoms, two Li ⁺ , Na ⁺ , K ⁺ , And Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Ti ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Ru ²⁺ , Rh ²⁺ , Pd ²⁺ , Pt ^{2+, Ba 2+, Sn 2+,} Al-Cl, Ga-Cl, In-Cl, Tl-Cl, Mn-OH, Fe-Cl, Ru-Cl, Cr _{l 2, SiCl 2, ZrCl 2} , GeCl 2, TiCl 2, Si (OH) 2, Ge (OH) 2, Zr (OH) 2, Mn (OH) 2, TiR 2, CrR 2, SiR 2, GeR 2 , Si (OR) ₂ , Ge (OR) ₂ , Ti (OR) ₂ , Cr (OR) ₂ [R represents an aliphatic group or an aromatic group], VO, MnO or TiO. Further preferred M ¹ is two hydrogen atoms or Cu ²⁺ , most preferably Cu ²⁺ .

R ¹¹¹ , R ¹²¹ , R ¹³¹ and R ¹⁴¹ each independently represent a group represented by the general formula (II). In general formula (II), R ²¹¹ is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. Group, an alkynyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 6 to 6 carbon atoms. 10 is an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Most preferably, it is a hydrogen atom.

R ²¹² and R ²¹³ are preferably an alkyl group, an alkenyl group, an alkynyl group, and an aryl group, more preferably an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an alkynyl group having 2 to 20 carbon atoms. Group, an aryl group having 6 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms, and more preferably a carbon number. It is a C1-C8 alkyl group and a C6-C8 aryl group, More preferably, it is a C1-C4 alkyl group, More preferably, it is a C1-C3 alkyl group.

  Specific examples of the compound represented by formula (I) are shown below, but the compounds that can be employed in the present invention are not limited to these.

Next, the manufacturing method of the compound represented by general formula (I) is demonstrated.
The compound represented by the general formula (I) is a general formula having a metal at the center from the corresponding 2,3-naphthalenedicarboxylic acid or a derivative thereof (an acid anhydride, diamide, dinitrile, etc.) in the presence of a metal compound. The compound represented by (I) can be directly synthesized. For example, it can be synthesized with reference to Chemistry: A. European Journal, Vol. 9, pages 5123-5134 (2003). Alternatively, as described in Journal of Chemical Society, Parkin Transaction, I, pages 2453 to 2458 (1988), the above general formula (Na) is a metal-free form of naphthalocyanine once using a lithium compound ( After synthesizing the compound represented by III), it can be synthesized using a metal compound as described later, and this method is more preferred.

  In the case of synthesizing the compound represented by the general formula (I) using the compound represented by the general formula (III) and the metal compound, the ratio of the raw materials is 1 mol of the compound represented by the general formula (III). On the other hand, the preferable amount of the metal compound is 0.1 to 10 mol, more preferably 0.5 to 5 mol, and further preferably 1 to 3 mol. As the metal compound, inorganic and organic metal compounds can be used, and examples thereof include halides (for example, chlorinated products, brominated products), sulfates, nitrates, cyanides, acetates, metal acetylacetonates, and the like. . Preferred are chloride, sulfate, cyanide and acetate, more preferred are chloride and acetate, and most preferred is acetate.

  Examples of the solvent used in the reaction include amide solvents (eg, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone), sulfone solvents (eg, sulfolane), sulfoxide solvents (eg, dimethyl solvent). Sulfoxide), ether solvents (eg dioxane, cyclopentyl methyl ether), ketone solvents (eg acetone, cyclohexanone), hydrocarbon solvents (eg toluene, xylene), halogen solvents (eg tetrachloroethane, chlorobenzene), alcohol solvents (For example, 1-butanol, ethylene glycol, cyclohexanol) and pyridine solvents (for example, pyridine, γ-picoline, 2,6-lutidine) can be used alone or in combination. Of these, preferred are amide solvents, sulfone solvents, ether solvents, hydrocarbon solvents, halogen solvents, pyridine solvents, and more preferred sulfone solvents, ether solvents, hydrocarbon solvents, halogen solvents. More preferred are ether solvents, hydrocarbon solvents, halogen solvents, more preferred are halogen solvents, and chlorobenzene is most preferred.

  The reaction temperature is preferably -30 to 250 ° C, more preferably 0 to 200 ° C, still more preferably 20 to 150 ° C, still more preferably 50 to 100 ° C, and the reaction time is usually in the range of 5 minutes to 30 hours. Do.

  The features of the present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

Example 1 (Synthesis of Exemplified Compound (I-1))
Exemplified compound (I-1) was synthesized according to the following scheme.

In a three-necked flask, 35.4 g of compound (1), 21.8 g of anhydrous copper acetate (II) and 2000 ml of chlorobenzene were placed and stirred with heating at an internal temperature of 85 ° C. for 20 hours, and then cooled to an internal temperature of 20 ° C. Extraction operation was performed by adding 2000 ml. The obtained organic layer is dried over anhydrous magnesium sulfate, concentrated with a rotary evaporator, 600 ml of acetonitrile is added to the resulting residue and stirred, and the resulting crystals are collected by filtration and dried to obtain the target exemplified compound. 36.9 g of (I-1) was obtained (99% yield). When the mass spectrum of this product was measured, it was M ⁺ = 1,239 (main peak).

Example 2 (Synthesis of Exemplified Compound (I-1))
In Example 1, the reaction was carried out in the same manner except that anhydrous copper acetate (II) was changed to 12.1 g of copper (II) chloride to obtain 26.1 g of the target exemplified compound (I-1) (yield 70). %).

Example 3 (Synthesis of Exemplified Compound (I-1))
In Example 1, the reaction was carried out in the same manner except that chlorobenzene was changed to toluene at 85 ° C. for 20 hours by heating under reflux to obtain 31.3 g of the intended exemplified compound (I-1) (yield) 84%).

Example 4 (Synthesis of Exemplified Compound (I-1))
In Example 1, the reaction was carried out in the same manner except that chlorobenzene was changed to 1,2-dichloroethane, and the stirring under heating at 85 ° C. for 20 hours was changed to stirring under heating under reflux conditions for 30 hours. -1) 27.9 g was obtained (yield 75%).

Example 5 (Synthesis of Exemplified Compound (I-32))
Exemplified compound (I-32) was synthesized according to the following scheme.

38.7 g of compound (2), 21.8 g of anhydrous copper acetate (II) and 2000 ml of chlorobenzene were placed in a three-necked flask and heated and stirred at an internal temperature of 85 ° C. for 22 hours, then cooled to an internal temperature of 20 ° C. Extraction operation was performed by adding 2000 ml. The obtained organic layer is dried over anhydrous magnesium sulfate, concentrated with a rotary evaporator, 600 ml of acetonitrile is added to the resulting residue and stirred, and the resulting crystals are collected by filtration and dried to obtain the target exemplified compound. 39.8g of (I-32) was obtained (yield 98%). When the mass spectrum of this product was measured, it was M ⁺ = 1,351 (main peak).

Example 6 (Synthesis of Exemplified Compound (I-21))
Exemplified compound (I-21) was synthesized according to the following scheme.

Compound (3) 42.1 g, calcium acetate hydrate 16.6 g, and chlorobenzene 2000 ml were placed in a three-necked flask and the mixture was heated and stirred at an internal temperature of 85 ° C. for 26 hours, then cooled to an internal temperature of 20 ° C. Was added to perform extraction operation. The obtained organic layer is dried over anhydrous magnesium sulfate, concentrated with a rotary evaporator, 600 ml of acetonitrile is added to the resulting residue and stirred, and the resulting crystals are collected by filtration and dried to obtain the target exemplified compound. 40.7g of (I-21) was obtained (yield 94%). When the mass spectrum of this product was measured, it was M ⁺ = 1,440 (main peak).

Example 7
Other than using Exemplified Compounds (I-1), (I-21), (I-31) and (I-32) of the present invention instead of the phthalocyanine compound of Example 22 described in JP-A-9-316049 The same operation was performed to obtain a resin molded product. It was confirmed that the obtained resin molding effectively absorbs near infrared rays of 750 to 1100 nm.

  The compound of the present invention is useful for image forming materials, infrared thermosensitive recording materials, optical recording elements, optical film materials, and the like, and can be used effectively in the production of these materials and elements. Moreover, such a compound can be easily produced by carrying out the production method of the present invention. Therefore, the industrial applicability of the present invention is high.

Claims (6)

A naphthalocyanine compound represented by the following general formula (I).

[In the general formula (I), R ¹¹¹ , R ¹²¹ , R ¹³¹ and R ¹⁴¹ each independently represents a group represented by the following general formula (II), and R ¹¹² , R ¹²² , R ¹³² and R ¹⁴² each represents Independently represents a substituent, and M ¹ represents a substituted metal atom containing two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, or a trivalent or tetravalent metal atom. However, M ¹ is not divalent zinc. n112, n122, n132 and n142 each independently represents an integer of 0 to 4. ]

[In the general formula (II), R ²¹¹ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group linked by a carbon atom, and R ²¹² and R ²¹³ are each independently an aliphatic group or an aromatic group. Alternatively, it represents a heterocyclic group linked by a carbon atom. ] The naphthalocyanine compound according to claim 1, wherein M ¹ is two hydrogen atoms or a divalent copper atom. The naphthalocyanine compound according to claim 1, wherein R ²¹¹ is a hydrogen atom.   The naphthalocyanine compound according to any one of claims 1 to 3, wherein the n112, n122, n132, and n142 are all 0. A process for producing a compound represented by the following general formula (IA), comprising a step of reacting a compound represented by the following general formula (III) with a metal compound.

[In the general formula (IA), R ¹¹¹ , R ¹²¹ , R ¹³¹ and R ¹⁴¹ each independently represents a group represented by the following general formula (II), and R ¹¹² , R ¹²² , R ¹³² and R ¹⁴² each represents Independently represents a substituent, and M ² represents a divalent metal atom or a substituted metal atom containing a trivalent or tetravalent metal. However, M ² is not divalent zinc. n112, n122, n132 and n142 each independently represents an integer of 0 to 4. ]

[In the general formula (II), R ²¹¹ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group linked by a carbon atom, and R ²¹² and R ²¹³ are each independently an aliphatic group or an aromatic group. Alternatively, it represents a heterocyclic group linked by a carbon atom. ]

[In the general formula (III), R ¹¹¹ , R ¹¹² , R ¹²¹ , R ¹²² , R ¹³¹ , R ¹³² , R ¹⁴¹ , R ¹⁴² , n112, n122, n132 and n142 are as defined in the general formula (IA). It is. ]   The production method according to claim 5, wherein the metal compound is acetate.