JPH0776307B2 - Naphthalocyanine derivative, method for producing the same, optical information recording medium using the same, and method for producing the optical information recording medium - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel naphthalocyanine derivative, a method for producing the same, an optical information recording medium using the same, and a method for producing the optical information recording medium.

[Conventional technology]

In recent years, it has been proposed to use semiconductor laser light for writing or reading in compact disks, video disks, liquid crystal display devices, optical character readers, etc. and as a light source for electrophotography. For writing or reading with semiconductor laser light, a substance capable of absorbing semiconductor laser light, that is, near infrared light is indispensable.

As organic dyes that absorb near-infrared light, cyanine dyes are conventionally well known, and metal complexes of oximes and thiols and aminated quinone derivatives are also known as dyes that absorb near-infrared light. Journal of Organic Synthetic Chemistry, 43
Volume, p. 334 (1985), Journal of Coloring Materials, vol. 53, p. 197 (198
0), Journal of Coloring Materials, Vol. 58, p. 220 (1985)].

[Problems to be Solved by the Invention]

However, since cyanine dyes have extremely low light fastness, they are subject to many restrictions when used. Further, the metal complex of oxime or thiol also has a drawback that the metal is desorbed from the complex in a certain kind of medium and the absorption ability of near infrared light disappears. The aminated quinone derivative has a problem that its ability to absorb near infrared light is extremely low.

On the other hand, as a material capable of overcoming these problems, a naphthalocyanine derivative has been known recently, but a conventional unsubstituted metal naphthalocyanine (Zhurnal Obshchei Khimii), Vol. 39, p. 2554, 1969 ，
Mol.Cryst.Liq.Crys
t.) 112, 345, 1984] is extremely difficult to purify because it is insoluble in organic solvents. Further, recently, the synthesis of naphthalocyanine derivatives soluble in organic solvents has been reported (JP-A-60-23451, JP-A-60-184565, JP-A-61-215662, JP-A-61-215662). However, in these naphthalocyanine derivatives, the absorption varies greatly depending on the type, concentration, temperature, etc. of the solvent. Not only does it lose its ability to absorb,
When the reflected light is used to read the information recorded on the optical disk, the reflectance that is important is the semiconductor laser region (78
There was a problem that it was very low at 0-830 nm).

[Means for Solving the Problems]

The present invention has the general formula (I) [Wherein R ¹ is an alkyl group having 1 to 22 carbon atoms, a plurality of R ¹ may be the same or different, and n is the same or different integer of 1 to 4] Where M is a group Ib metal such as Cu, a group IIa metal such as Mg, a group IIb metal such as Zn, a group IIIa metal such as Al, ClAl, HOAl, In, ClIn, or a metal halide. Or metal hydroxide, Si, Cl ₂ Si, (HO) ₂
I, such as Si, Ge, Cl ₂ Ge, (HO) ₂ Ge, Sn, Cl ₂ Sn, (HO) ₂ Sn, Pb
Group Va metals, metal halides or metal hydroxides, Group IVb metals or metal oxides such as Ti and OTi, Group Vb group metal oxides such as OV, and VIb such as Cr and Mo. Group metals, Mn, C
Group VII b metals such as lMn or metal halides or F
e, ClFe, Co, Ni, Pt, Pd, and other group VIII metals or metal halides].

In addition, the present invention has the general formula (II) [Wherein R ¹ is an alkyl group having 1 to 22 carbon atoms, a plurality of R ¹ may be the same or different, and n is the same or different integer of 1 to 4] And Y ₁ and Y ₂ may be the same and are an aryloxyl group, an alkoxyl group, a trialkylsiloxyl group, a triarylsiloxyl group, a trialkoxysiloxyl group, a triaryloxysiloxyl group or a trityloxyl group. , M is Al, Ti, Si, Ge
Or Sn and M is Al, only Y ₁ is M, Ti, Si,
When Ge or Sn, Y ₁ and Y ₂ are covalently bonded to M. ]
And a naphthalocyanine derivative represented by

The naphthalocyanine derivatives represented by the general formulas (I) and (II) are aromatic, halogen-based, ether-based,
It is soluble in ketone and saturated hydrocarbon solvents, can be easily purified to improve its purity, and is extremely excellent in its ability to absorb semiconductor laser light.

Examples of the aromatic solvent include benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trimethylbenzene, 1-chloronaphthalene and quinoline, and examples of the halogen solvent include methylene chloride, chloroform, carbon tetrachloride and trichloroethane. The above ether solvents include diethyl ether, dibutyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether,
There are diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, etc., ketone solvents include acetone, methyl ethyl ketone, methyl propyl ketone, cyclopentanone, cyclohexanone, acetone alcohol, etc., and saturated hydrocarbon solvents include pentane, hexane, heptane, There are octane, nonane, decane, and undecane.

In the general formulas (I) and (II), examples of ¹ to 22 alkyl groups represented by R ¹ include methyl group, ethyl group, n-propyl group, sec-propyl group, n-butyl group, sec- Butyl group, t
-Butyl group, n-amyl group, t-amyl group, 2-amyl group, 3-
Amyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group,
Examples include octadecyl group, eicosyl group and docosyl group.

In the general formula (I), examples of M include Cu, Mg, Zn, and A.
l, ClAl, HOAl, In, ClIn, Si, Cl ₂ Si, (HO) ₂ Si, Ge, Cl ₂ Ge,
(HO) ₂ Ge, Sn, Cl ₂ Sn, (HO) ₂ Sn, Pb, Ti, OTi, OV, Cr, Mo, M
Examples include n, ClMn, Fe, ClFe, Co, Ni, Pt and Pd.

In the general formula (II), examples of M include Al, Ti, S
i, Ge, Sn, etc., and examples of Y ₁ and Y ₂ include phenoxyl group, tolyloxyl group, anisyloxyl group and the like as allureloxyl group, and amyloxyl group, hexyloxyl group, octyloxyl group as alkoxyl group. , Decyloxyl group, dodecyloxyl group, tetradecyloxyl group, hexadecyloxyl group, octadecyloxyl group, eicosyloxyl group, docosyloxyl group, etc., and the trialsiloxyl group includes trimethylsiloxyl group, triethylsiloxyl group. Group, tripropylsiloxyl group, tributylsiloxyl group, etc., and triarylsiloxyl group, such as triphenylsiloxyl group, trianisylsiloxyl group, tritolylsiloxyl group, trialkoxysiloxyl group. As the group, a trimethoxysiloxyl group, Triethoxysiloxyl group,
Examples thereof include a tripropoxysiloxyl group and tributoxysiloxyl group, and examples of the triaryloxysiloxyl group include a triphenoxysiloxyl group, a trianisiloxysiloxyl group, and a tritolyloxysiloxyl group.

In the general formula (I), M is Cu, Zn, ClAl, ClIn, Si, G
Na, phthalocyanine derivatives which are e, Sn, OV, Mn, Co, Ni or Pd are preferred.

In the general formula (I), a naphthalocyanine derivative in which n is 1 is preferable.

In the general formula (I), a naphthalocyanine derivative in which R ¹ is an alkyl group having 13 to 22 carbon atoms is preferable.

In the general formula (II), a naphthalocyanine derivative in which M is Ge is preferable.

In the general formula (II), a naphthalocyanine derivative in which n is 1 is preferable.

In the general formula (II), a naphthalocyanine derivative in which both Y ₁ and Y ₂ are trialkylsiloxyl groups is preferable.

In the general formula (II), naphthalocyanine derivatives in which both Y ₁ and Y ₂ are alkoxyl groups are preferred.

Specific examples of the naphthalocyanine derivative according to the present invention are shown below.

The present invention also provides a compound represented by the general formula (III) (Wherein R ¹ represents an alkyl group having 1 to 22 carbon atoms, and n is an integer of 1 to 4), and at least one kind of alkoxycarboxylic-2,3-dicyanonaphthalene represented by the general formula (IV-1) MXp (IV-1) (wherein X is a halogen atom or an acyloxyl group and p is 0 or a positive integer indicating the number of bonds of X to the metal M, and M is Cu or the like. Group Ib, group IIa such as Mg, group I such as Zn
Ib group, IIIa group such as Al, In, IVa such as Si, Ge, Sn, Pb group
Group, IV b group such as Ti, V b group such as V, VI b such as Cr, Mo
Group I, a metal of Group VII b such as Mn or a metal of Group VIII such as Fe, Co, Ni, Pt, Pd) or a metal salt represented by the general formula (I) [Wherein R ¹ , n and M have the same meanings as in the above general formula (I)] and relates to a method for producing a naphthalocyanine derivative.

The naphthalocyanine derivative represented by the general formula (I) is
Alkoxycarbonyl-2,3 represented by the general formula (III)
-To 1 mol of dicyanonaphthalene, the above general formula (IV-
It can be obtained by reacting with heating the metal or metal salt represented by 1) in the presence of 0.1 to 1 mol. In this case, the reaction temperature is preferably 150 to 300 ° C., and the reaction time is preferably 30 minutes to 10 hours. For this purpose, the reaction is carried out without a solvent, or as a solvent, urea, tetralin, quinoline, 1-chloronaphthalene, 1-bromonaphthalene, 1,
It is preferable to use 2,3-trimethylbenzene, dichlorobenzene, trichlorobenzene and the like. As the metal or metal salt, Mg, Zn, AlCl ₃ , InCl ₃ , SiCl ₄ , GeCl ₄ , SnCl
₂ , PbCl ₂ , TiCl ₄ , VCl ₃ , CrCl ₂ , MoCl ₂ , Mn (O ・ COCH ₃ ) ₂ , Fe
There are Cl ₃ , CoCl ₂ , NiCl ₂ , PtCl ₂ , PdCl _{2 and the} like.

Isolation and purification of the naphthalocyanine derivative from the reaction mixture is performed by washing the reaction mixture with dilute hydrochloric acid and then thoroughly washing with a poor solvent for the naphthalocyanine such as water, alcohol or acetone to prepare a halogen-based solvent or an aromatic solvent. It can be carried out by a method of concentrating the soluble material to be dissolved to dryness and collecting a solid.

Alkoxycarbonyl-2,3 represented by the general formula (III)
-Dicyanonaphthalene can be produced, for example, as follows.

That is, one of them is the general formula (IX) (Wherein R ¹ represents an alkyl group having 1 to 22 carbon atoms, and n represents an integer of 1 to 4) and an alkoxycarbonyl-o-xylene represented by the formula (X) A general formula (XI) obtained by irradiating an N-bromosuccinimide represented by (Wherein R ¹ represents an alkyl group having 1 to 22 carbon atoms, and n represents an integer of 1 to 4), and a compound represented by the formula (XII) Is a method of synthesizing an alkoxycarbonyl-2,3-dicyanonaphthalene represented by the general formula (III) by reacting with fumaronitrile represented by the formula under heating.

The other one is the general formula (III) (Wherein R ¹ and n have the same meanings as in the general formula (XI) above) can be represented by the general formula (XIII) R ⁴ OH (XIII) R ⁴ represents an alkyl group having 1 to 22 carbon atoms, which is different from R ^1, and is reacted with an alcohol represented by the general formula (III ′) (In the formula, R ⁴ represents an alkyl group having 1 to 22 carbon atoms, and n represents an integer of 1 to 4) and is a method for synthesizing alkoxycarbonyl-2,3-dicyanonaphthalene. .

Generally, the reaction of the alkoxycarbonyl-o-xylene represented by the general formula (IX) with the N-bromosuccinimide represented by the formula (X) is carried out by the alkoxycarbonyl-o-x-
4 mol of xylene and 0.8 mol of N-bromosuccinimide were irradiated with a high pressure mercury lamp in a solvent inert to light irradiation.
It can be carried out by heating under reflux for 12 hours. For the reaction, it is necessary to add a peroxide, which is a radical generator, as a photoreaction initiator. Examples of the peroxide include benzoyl peroxide, octanoyl peroxide, cyclohexanone peroxide, isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide and methyl ethyl ketone peroxide, and usually 500 mg to 2 g of solvent per 500 ml. Used in the range.
The solvent inert to light irradiation is appropriately selected from halogen solvents such as chloroform and carbon tetrachloride, or aromatic solvents such as benzene and chlorobenzene.

In addition, the compound represented by the following general formula (XI) and the formula (XI
The reaction with fumaronitol represented by I) can be carried out by the general formula (X
Fumaronitrile represented by the formula (XII) is allowed to coexist in a ratio of 1 to 2 mol with respect to 1 mol of the compound represented by I), the reaction temperature is preferably 70 ° C to 100 ° C, and the reaction time is 5 to 10
Time is preferred. As the solvent, polar organic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N, N-diethylformamide and N, N-diethylacetamide are preferable.

Alkoxycarbonyl-o-represented by the general formula (IX)
Xylene can be produced by the route of the following formula (A).

That is, hydroxycarbonyl-o-xylene (wherein n represents an integer of 1 to 4) [Formula (XIV)] 1 mol
Per alcohol [R ¹ OH, (where R ¹ is 1 carbon
~ 22 alkyl groups] in the presence or absence of a solvent in the presence or absence of a solvent, Lewis acid as a catalyst 25 to 50 mol% of hydroxycarbonyl-o-xylene
Alkoxycarbonyl-o-xylene [general formula (IX)] can be obtained by coexisting, heating and dehydration. Here, as the solvent, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trimethylbenzene, 1-chloronaphthalene and the like are preferable,
As the catalyst, sulfuric acid, p-toluenesulfonic acid, benzenesulfonic acid and the like are preferable, the reaction temperature is preferably 80 to 240 ° C., and the reaction time is preferably 1 to 10 hours.

1 mol of an alkoxycarbonyl-2,3-dicyanonaphthalene represented by general formula (III) (wherein R ¹ represents an alkyl group having 1 to 22 carbon atoms and n represents an integer of 1 to 4) In contrast, the alcohol represented by the general formula (XIII)
1 mol or more in the presence or absence of a solvent,
As a catalyst, Lewis acid is used as a raw material for alkoxycarbonyl-
Another alkoxycarbonyl-2,3-dicyanonaphthalene can be obtained by coexisting with 2,3-dicyanonaphthalene in an equimolar amount or more and heating under reflux to cause an ester exchange reaction. Here, the solvent is preferably benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trimethylbenzene, 1-chloronaphthalene, or the like, and the catalyst is preferably sulfuric acid, p-toluenesulfonic acid, benzenesulfonic acid, or the like. The temperature is 80
It is preferable to carry out in the range of ~ 240 ℃, the reaction time is 1-50
Time is preferable.

An alkoxycarbonyl group represented by the general formula (III) (wherein R ¹ represents an alkyl group having 1 to 22 carbon atoms)
Isolation and purification of 2,3-dicyanonaphthalene from the reaction mixture can be performed by extracting the reaction mixture with chloroform and then performing a recrystallization method, a column chromatography method, or the like.

In the general formula (IV-1), M is Cu, Zn, Al, In, Si, Ge,
Sn, V, Mn, Co, Ni or Pd, M in the general formula (I)
Are Cu, Zn, ClAl, ClIn, Si, Ge, OV, Mn, Co, Ni or Pd, respectively.
The method for producing a naphthalocyanine derivative which is

In the general formulas (III) and (I), n is 1
The method for producing a naphthalocyanine derivative which is

In the general formulas (III) and (I), a method for producing a naphthalocyanine derivative in which R ¹ is an alkyl group having 13 to 22 carbon atoms is preferable.

The present invention also provides a compound represented by the general formula (III) (Wherein R ¹ represents an alkyl group having 1 to 22 carbon atoms, and n is an integer of 1 to 4), and an alkoxycarbonyl-2,3-dicyanonaphthalene represented by the general formula (IV-
2) MXp (IV-2) (where X is a halogen atom and p is a positive integer indicating the number of bonds of X to the metal M, and M is Al, Ti, Si, Ge or Sn. ) Is reacted with a metal halide represented by the general formula (V) [Wherein R ¹ is an alkyl group having 1 to 22 carbon atoms, a plurality of R ¹ may be the same or different, and n may be the same or different. Is an integer, M has the same meaning as in formula (IV-2), X ₁ and X ₂ represent a halogen atom, and when M is Al, only X ₁ is M, Ti, Si,
In the case of Ge or Sn, X ₁ and X ₂ are covalently bonded to M], and the compound represented by the general formula (V) is hydrolyzed. (VI) [Wherein R ¹ is an alkyl group having 1 to 22 carbon atoms, a plurality of R ¹ may be the same or different, and n is the same or different integer of 1 to 4] And M has the same meaning as in the general formula (IV-2), Z ₁ and Z ₂ represent a hydroxyl group, and when M is Al, only Z ₁ or M is Ti, Si,
When Ge or Sn, Z ₁ and Z ₂ are covalently bonded to M]
A naphthalocyanine derivative represented by the following formula is obtained, and then the compound represented by the general formula (VI) is converted to the general formula (VII) (R ² ) ₃ SiOH (VII) [wherein R ² is an alkyl group or an aryl group. , An alkoxyl group or an aryloxyl group. Or a general formula (VIII) R ³ OH (VIII) [wherein R ³ is an alkyl group, an aryl group or a trityl group]. ] The general formula (II) characterized by reacting with an alcohol represented by [Wherein R ₁ , n, Y ₁ , Y ₂ and M have the same meaning as in the general formula (II)] and relates to a process for producing a naphthalocyanine derivative.

The naphthalocyanine derivative represented by the general formula (II) is
The compound represented by the general formula (VI) and a large excess of the general formula (VI
It can be obtained by heating the silanol represented by I) or the alcohol represented by the general formula (VIII) to cause a dehydration reaction. In this case, the reaction temperature is 80 to 250.
C is preferable, and the reaction time is preferably 30 minutes to 10 hours. This reaction is preferably carried out without a solvent, or benzene, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, tetralin, quinoline or the like is preferably used as a solvent.

Isolation and purification of the naphthalocyanine derivative represented by the general formula (II) from the reaction mixture is performed by separating the reaction mixture by column chromatography or thin layer chromatography, and then recrystallization. Method can be used.

The naphthalocyanine derivative represented by the general formula (VI) is
The compound represented by the general formula (V) can be obtained by performing a hydrolysis reaction with heating. In this case, the reaction temperature is preferably 50 to 150 ° C., and the reaction time is preferably 30 minutes to 10 hours. For this purpose, it is preferable to carry out the reaction in a mixed solvent such as pyridine / water, pyridine / ammonia water, methanol / ammonia water, ethanol / ammonia water, propanol / ammonia water.

The naphthalocyanine derivative represented by the general formula (V) is
Alkoxycarbonyl-2,3 represented by the general formula (III)
-General formula (IV-2) per mol of dicyanonaphthalene
It can be obtained by reacting the metal halide represented by the formula of 0.25 to 1 mol in a coexisting state with heating. in this case,
The reaction temperature is preferably 150 to 300 ° C, and the reaction time is 30 minutes to
5 hours is preferred. For this purpose, the reaction is carried out without a solvent, or as a solvent, urea, tetralin, quinoline, 1-chloronaphthalene, 1-bromonaphthalene, 1,
It is preferable to use 2,4-trimethylbenzene, 1,2,3-trimethylbenzene, dichlorobenzene, trichlorobenzene and the like. As the metal halide, AlCl
₃ , TiCl ₄ , SiCl ₄ , GeCl ₄ , GeBr ₄ , GeI ₄ , SnCl ₂ , SnI _{2 and the} like.

Alkoxycarbonyl-2,3 represented by the general formula (III)
-Dicyanonaphthalene can be produced by the method described in the above invention.

In the general formulas (IV-2), (V), (IV) and (II), a method for producing a naphthalocyanine derivative in which M is Ge is preferable.

In the general formulas (III), (V), (IV) and (II), a method for producing a naphthalocyanine derivative in which n is 1 is preferable.

In the general formula (VIII), R ² is an alkyl group,
In the general formula (II), a method for producing a naphthalocyanine derivative in which both Y ₁ and Y ₂ are trialkylsiloxyl groups is preferable.

In the general formula (VIII), R ³ is an alkyl group,
In the general formula (II), a method for producing a naphthalocyanine derivative in which both Y ₁ and Y ₂ are alkoxy groups is preferable.

Further, the present invention provides the following general formula (I) on the substrate surface. [Wherein R ¹ , n and M have the same meaning as in the general formula (I)], and a recording film layer containing a naphthalocyanine derivative as a main component is formed. The present invention relates to an information recording medium.

The present invention also provides a compound represented by the general formula (II) A recording film layer containing a naphthalocyanine derivative represented by the formula [wherein R ¹ , n, Y ₁ , Y ₂ and M have the same meaning as in the general formula (II)] is formed. And an optical information recording medium.

An optical information recording medium according to the present invention is one in which a recording layer containing a naphthalocyanine derivative represented by the general formula (I) of the present invention as a main component is provided on a substrate, and another optical information recording medium according to the present invention. The optical information recording medium is one in which a recording layer containing a naphthalocyanine derivative represented by the general formula (II) of the present invention as a main component is provided on a substrate. Other layers can be provided.

Further, the naphthalocyanine derivative represented by the general formula (I) and the general formula (II) can be used in combination.

The substrate material used is known to those skilled in the art,
It may be transparent or opaque to the laser light used. However, when writing and reading with laser light from the substrate side, it must be transparent to the laser light. On the other hand, when writing and reading are performed from the side opposite to the substrate, that is, the recording layer side, it is not necessary to be transparent to the laser light used. Substrate materials include inorganic materials such as glass, quartz, mica, ceramics, plate-shaped or foil-shaped metals, paper, polycarbonate, polyester, cellulose acetate, nitrocellulose, polyethylene, polypropylene, polyvinyl chloride,
Vinylidene chloride copolymer, polyamide, polystyrene,
Examples include, but are not limited to, plates of organic polymeric materials such as polymethylmethacrylate and methylmethacrylate copolymers. A support made of an organic polymer having a low thermal conductivity is desirable in the sense that heat loss is small during recording and sensitivity is increased, and a guide groove formed by unevenness may be provided on the substrate, if necessary.

In addition, a base film may be provided on the substrate as needed.

In the general formula (I), M is Cu, Zn, ClAl, ClIn, Si, G
An optical information recording medium in which a recording film layer containing a naphthalocyanine derivative which is e, Sn, OV, Mn, Co, Ni or Pd as a main component is formed is preferable.

In the general formula (I), an optical information recording medium in which a recording film layer containing a naphthalocyanine derivative in which n is 1 as a main component is formed is preferable.

In the general formula (I), an optical information recording medium in which a recording film layer containing a naphthalocyanine derivative whose R ¹ is an alkyl group having 13 to 22 carbon atoms as a main component is formed is preferable.

In the general formula (II), an optical information recording medium in which a recording film layer containing a naphthalocyanine derivative in which M is Ge as a main component is formed is preferable.

In the general formula (II), an optical information recording medium in which a recording film layer containing a naphthalocyanine derivative in which n is 1 as a main component is formed is preferable.

In the general formula (II), an optical information recording medium in which a recording film layer containing a naphthalocyanine derivative whose both Y ₁ and Y ₂ are trialkylsiloxyl groups as a main component is formed is preferable.

In the general formula (II), an optical information recording medium in which a recording film layer containing a naphthalocyanine derivative whose both Y ₁ and Y ₂ are an alkoxyl group as a main component is formed is preferable.

The present invention also provides a compound represented by the general formula (I) [Wherein R ₁ , n and M have the same meaning as in the above general formula (I)] and a recording film layer is formed on the surface of the substrate using a solution in which a naphthalocyanine derivative represented by the general formula (I) is mainly dissolved in an organic solvent. The present invention relates to a method for manufacturing an optical information recording medium.

The present invention also provides a compound represented by the general formula (II) [Wherein R ₁ , n, Y ₁ , Y ₂ and M have the same meaning as in the general formula (II)], and a solution of a naphthalocyanine derivative mainly dissolved in an organic solvent is applied to the substrate surface. The present invention relates to a method for manufacturing an optical information recording medium, which comprises forming a recording film layer.

Examples of the organic solvent include general formula (I) and general formula (II)
The solvent selected from the aromatic, halogen, ether, ketone and saturated hydrocarbon solvents that dissolves the naphthalocyanine derivative represented by the formula (1) may be a single solvent or a mixed solvent. However, it is preferable to use a solvent that does not soak the substrate used.

As a method of forming a recording film layer using a solution in which a naphthalocyanine derivative represented by the general formula (I) and / or (II) is dissolved in an organic solvent, there are a coating method, a printing method and a dipping method. Specifically, the dye is dissolved in the above solvent, sprayed,
Roller coating, spin coating, and dateing are used. When forming the recording medium, a binder such as a polymer binder and a stabilizer may be added as necessary. Examples of the binder include, but are not limited to, polyimide resin, polyamide resin, polystyrene resin, and acrylic resin.

The recording layer materials may be used singly or in a combination of two or more kinds, and in the case of a combination of two kinds or more, may have a laminated structure or a mixed single layer structure. The thickness of the recording layer
The range of 50 to 10000Å is preferable, and the range of 100 to 5000Å is particularly preferable.

In addition, reflected light is often used when optically reproducing a formed recorded image. In this case, as an effective method of increasing the contrast, when writing and reading from the substrate side, a metal layer showing a high reflectance can be provided on the surface of the recording layer on the side opposite to the substrate, which is opposite to the substrate. Side, that is, when writing and reading from the recording layer side,
It is also possible to provide a metal layer having a high reflectance between the substrate and the recording layer. The metals with high reflectivity include Al, Cr, Au, P
t, Sn, etc. are used. These films can be formed by known thin film forming techniques such as vacuum evaporation, sputtering, and plasma evaporation, and the film thickness is selected in the range of 100 to 10000Å.

However, among the naphthalocyanine derivatives, a compound represented by the general formula (I
The naphthalocyanine derivative represented by I) has high reflectance by itself, and it is not necessary to provide a metal reflection layer.

Further, when the surface smoothness of the substrate itself becomes a problem, it is preferable to provide a uniform film of an organic polymer on the substrate. Commercially available polymers such as polyester and polyvinyl chloride can be applied as these polymers.

Further, a protective layer may be provided on the outermost layer to increase stability and protective properties, and further, a layer may be provided for the purpose of increasing sensitivity by reducing surface reflectance. As materials used for such a protective layer, polyvinylidene chloride, polyvinyl chloride, vinylidene chloride and acrylonitrile copolymer, polyvinyl acetate, polyimide, polymethylmethacrylate, polystyrene, polyisoprene, polybutadiene, polyurethane, polyvinyl butyral, fluorine Raw rubber, polyester, epoxy resin, silicone resin, cellulose acetate, etc. These are used alone or as a blend. The presence of silicone oil, an antistatic agent, a crosslinking agent, etc. in the protective layer is preferable from the viewpoint of enhancing the membrane performance. Further, the protective layer may be laminated in two layers. The above-mentioned material for the protective layer can be applied by dissolving it in a suitable solvent and applying it or laminating it as a thin film. The thickness of such a protective layer is 0.1 to 1
The thickness is set to 0 μm, but preferably 0.1 to 2 μm is used.

In the general formula (I), M is Cu, Zn, ClAl, ClIn, Si, G
A method for producing an optical information recording medium using a naphthalocyanine derivative which is e, Sn, OV, Mn, Co, Ni or Pd is preferable.

In the general formula (I), a method for producing an optical information recording medium using a naphthalocyanine derivative in which n is 1 is preferable.

In the general formula (I), a method for producing an optical information recording medium using a naphthalocyanine derivative in which R ¹ is an alkyl group having 13 to 22 carbon atoms is preferable.

In the general formula (II), a method for producing an optical information recording medium using a naphthalocyanine derivative in which M is Ge is preferable.

In the general formula (II), a method for producing an optical information recording medium using a naphthalocyanine derivative in which n is 1 is preferable.

In the general formula (II), a method for producing an optical information recording medium using a naphthalocyanine derivative in which both Y ₁ and Y ₂ are trialkylsiloxyl groups is preferable.

In the general formula (II), a method for producing an optical information recording medium using a naphthalocyanine derivative in which both Y ₁ and Y ₂ are alkoxy groups is preferable.

〔Example〕

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

Synthesis Example 1 [Synthesis of methyl 3,4-dimethylbenzoate] 47.6 g (0.317 mol) of 3,4-dimethylbenzoic acid was added to methanol.
The mixture was added to 200 ml, and refluxed for about 4 hours while dehydrating with Molecule Sieves 3A (a drying agent manufactured by Wako Pure Chemical Industries, Ltd.) in the presence of about 6 ml of concentrated sulfuric acid. After allowing to cool, about 600 ml of water was added, and the mixture was extracted three times with about 200 ml of benzene. The benzene solution was washed 3 times with a saturated aqueous sodium hydrogen carbonate solution and then 3 times with water, and anhydrous sodium sulfate was added to dry the solution. After concentrating the Benzene solution and distilling under reduced pressure, the boiling point is 133-134 ℃ / 30m
49.4 g of colorless liquid was obtained at mHg. From the following analysis results, it was confirmed that this liquid was methyl 3,4-dimethylbenzoate.

(1) Elemental analysis value: C H calculated value (%) 73.15 7.37 Measured value (%) 73.13 7.46 (2) Nuclear magnetic resonance (NMR) spectrum value: CDCl ₃ solvent δ value 7.81 (1H, br-s) 7.76 ( 1H, dd, J = 7.93,1.53Hz) 7.18 (1H, d, J = 7.93Hz) 3.89 (3H, s) 2.30 (6H, s) (3) Infrared absorption (IR) spectrum (coating method) Shown in Figure 1. It has an absorption at about 1710 cm ^{-1 due} to the C = O stretching vibration of the ester.

Synthesis Example 2 [Synthesis of 6-methoxycarbonyl-2,3-dicyanonaphthalene] 33.8 g (0.2 mol) of methyl 3,4-dimethylbenzoate and N-
Bromosuccinimide 142.4g (0.8mol) carbon tetrachloride 50
Benzoyl peroxide (1 g) was added to the 0 ml solution, and light was irradiated with a high pressure mercury lamp (100 W) for 8 to 12 hours while refluxing in an internal irradiation tube. After standing to cool, the precipitated white crystals were removed by suction filtration,
The carbon tetrachloride solution of the mother liquor was concentrated under reduced pressure. The obtained solid was recrystallized from hexane / methylene chloride to give colorless crystals of methyl 3,4-bis (dibromomethyl) benzoate 79g.
Got The physical properties of methyl 3,4-bis (dibromomethyl) benzoate are shown below.

(1) Melting point 99.5-100.5 ° C (2) Elemental analysis value: C H Br calculated value (%) 25.03 1.68 66.62 Measured value (%) 25.07 1.54 65.72 (3) NMR spectrum value: CDCl ₃ solvent δ 8.29 (1H, br) -S) 8.03 (1H, dd, J = 8.24,1.53Hz) 7.81 (1H, d, J = 8.24Hz) 7.18 (1H, br-s) 7.09 (1H, br-s) 3.96 (3H, s) ( 4) IR spectrum (KBr method) is shown in FIG. About 1705c
It has absorption due to the C═O stretching vibration of ester near m ⁻¹ .

Next, 48 g (0.1 mol) of the obtained methyl 3,4-bis (dibromomethyl) benzoate and 13.5 g of fumaronitrile (0.173 mo
l) in a solution of 400 ml of anhydrous N, N-dimethylformamide while thoroughly stirring 100 g of sodium iodide (0.67 mol)
Was added and the mixture was stirred under a nitrogen atmosphere at about 75 ° C. for about 7 hours.
After the reaction, the content was poured out into about 2 kg of ice. Gradually add sodium bisulfite until the red and colored aqueous solution becomes pale yellow, then add a slight excess of sodium bisulfite,
After stirring for a while, the mixture was left overnight at room temperature. The precipitated pale yellow solid was suction filtered and washed thoroughly with water and then methanol. By recrystallizing the pale yellow solid from acetone / methanol, 13.9 g of colorless needle crystals were obtained. This crystal shows that 6-methoxycarbonyl-
It was confirmed to be 2,3-dicyanonaphthalene.

(1) Melting point 264 to 265 ° C (2) Elemental analysis value: CHN calculated value (%) 71.18 3.41 11.86 Measured value (%) 71.21 3.37 11.87 (3) NMR spectrum value: CDCl ₃ solvent δ value 8.72 (1H, br-s) 8.47 (1H, s) 8.41 (1H, s) 8.38 (1H, dd, J = 8.55,1.53Hz) 8.06 (1H, d, J = 8.55Hz) 4.04 (3H, s) (4) IR The spectrum (KBr method) is shown in FIG. About 1700c
It has absorption due to the C═O stretching vibration of ester near m ⁻¹ .

Synthesis Example 3 [Synthesis of n-amyl 3,4-dimethylbenzoate] 60 g (0.4 mol) 3,4-dimethylbenzoic acid, 43 ml (0.4 mol) n-amyl alcohol, p-toluenesulfonic acid monohydrate
Add 22 g (0.116 mol) to 15 ml of benzene, dehydrate with Dean Stark, and then Moreki Sieves 3A,
Refluxed for about 6 hours. After cooling, the reaction mixture was washed with 100 ml of a saturated aqueous solution of sodium hydrogen carbonate three times and then with water three times. A benzene solution of the reaction mixture was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The oily substance was distilled under reduced pressure to obtain 77 g of a colorless liquid at 145-148 ° C./8 mmHg. From the following analysis results, this liquid was found to be 3,4-dimethylbenzoic acid n-
I confirmed it was Amyl.

(1) Elemental analysis value: C H calculated value (%) 76.33 9.15 Measured value (%) 76.22 9.25 (2) NMR spectrum value: CDCl ₃ solvent δ value 7.81 (1H, br-s) 7.77 (1H, dd, J = 7.94, 1.98Hz) 7.18 (1H, d, J = 7.94Hz) 4.29 (2H, t, J = 6.72Hz) 2.30 (6H, s) 1.76 (2H, quintet, J = 6.72Hz) 1.40 (4H, m ) 0.93 (3H, t, J = 6.72Hz) (3) IR spectrum (coating method) is shown in FIG. About 1710
It has absorption due to the C = O stretching vibration of the ester near cm ^-1 .

Synthesis Example 4 [Synthesis of 6- (n-amyloxycarbonyl) -2,3-dicyanonaphthalene] n-amyl 3,4-dimethylbenzoate 44.1 g (0.2 mol) and N-bromosuccinimide 142.4 g (0.8 benzoyl peroxide (1 g) was added to a solution of carbon tetrachloride (500 mol) in an internal irradiation tube, and the mixture was irradiated with light from a high pressure mercury lamp (100 W) for 11 hours while refluxing. After allowing to cool, the precipitated white crystals were removed by suction filtration, and the carbon tetrachloride solution of the mother liquor was sufficiently concentrated under reduced pressure.
The pale and colored oil obtained was dissolved in 800 ml of anhydrous N, N-dimethylformamide and fumaronitrile 27 g (0.346 mol)
Then, while stirring well, 200 g of sodium iodide
(1.34 mol) was added, and the mixture was stirred under a nitrogen atmosphere at 75 ° C for about 7 hours. After the reaction, gradually add sodium bisulfite until the red and colored aqueous solution poured into about 4 kg of ice turns pale yellow, add a slight excess of sodium bisulfite, and stir for a while, then at room temperature. I left it overnight. The precipitated pale yellow solid was suction filtered, washed thoroughly with water, and then washed several times with methanol. About 500 ml of pale yellow solid
Was dissolved in chloroform, the chloroform layer was separated from the aqueous layer, and dried over anhydrous magnesium sulfate. Chloroform solution was concentrated under reduced pressure and then chloroform / ethanol was added to 2
By recrystallizing once, 20 g of colorless needle crystals were obtained. It was confirmed from the following analysis results that this crystal was 6- (n-amyloxycarbonyl) -2,3-dicyanonaphthalene.

(1) Melting point 150-152 ° C (2) Elemental analysis value: CHN calculated value (%) 73.95 5.52 9.52 Measured value (%) 73.82 5.38 9.51 (3) NMR spectrum value: CDCl ₃ solvent δ value 8.70 (1H, br-s) 8.49 (1H, s) 8.41 (1H, s) 8.38 (1H, dd, J = 8.55,1.53Hz) 8.06 (1H, d, J = 8.55Hz) 4.43 (2H, t, J = 6.72Hz) ) 1.84 (2H, quintet, J = 6.72Hz) 1.44 (1H, m) 0.96 (3H, t, J = 6.72Hz) (4) IR spectrum (KBr method) is shown in FIG. About 1700c
It has absorption due to the C═O stretching vibration of ester near m ⁻¹ .

Synthesis Example 5 [Synthesis of n-octyl 3,4-dimethylbenzoate] 40 g (0.27 mol) of 3,4-dimethylbenzoate, 100 ml (0.635 mol) of n-octanol, and 22 g of p-toluenesulic acid monohydrate
(0.116 mol) was added to 100 ml of benzene, and dehydrated with Dean Stark and then Molecule Sieves 3A,
Refluxed for about 6 hours. After cooling, the reaction mixture was treated in the same manner as in Synthesis Example 3 and distilled under reduced pressure to give a boiling point of 148 to 152 ° C / 3 mmHg.
To give 60.5 g of colorless liquid. From the following analysis results, it was confirmed that this liquid was n-octyl 3,4-dimethylbenzoate.

(1) Elemental analysis value: C H calculated value (%) 77.82 9.99 Measured value (%) 77.21 10.07 (2) NMR spectrum value: CDCl ₃ solvent δ value 7.81 (1H, br-s) 7.77 (1H, dd, J = 7.63,1.83Hz) 7.19 (1H, d, J = 7.63Hz) 4.29 (2H, t, J = 6.72Hz) 2.31 (6H, s) 1.76 (2H, quintet, J = 6.72Hz) 1.1 to 1.5 (10H , m) 0.88 (3H, t, J = 6.72Hz) (3) IR spectrum (coating method) is shown in FIG. About 1710
It has absorption due to the C = O stretching vibration of the ester near cm ^-1 .

Synthesis Example 6 [Synthesis of 6- (n-octyloxycarbonyl) -2,3-dicyanonaphthalene] n-octyl 3,4-dimethylbenzoate 52.5 g (0.2 mol) and N-bromosuccinimide 142.4 g (0.8 benzoyl peroxide (1 g) was added to a solution of carbon tetrachloride (500 ml) in an internal irradiation tube, and light was irradiated with a high pressure mercury lamp (100 W) for 11 hours while refluxing. After cooling, the reaction mixture was treated in the same manner as in Synthesis Example 4, treated with fumaronitrile, treated, and recrystallized several times from chloroform / ethanol to obtain about 7 g of colorless needle crystals. . It was confirmed from the following analysis results that this crystal was 6- (n-octyloxycarbonyl) -2,3-dicyanonaphthalene.

(1) Melting point 142-144 ° C (2) Elemental analysis value: CHN calculated value (%) 75.42 6.63 8.38 Measured value (%) 75.20 6.41 7.99 (3) NMR spectrum value: CDCl ₃ solvent δ value 8.70 (1H, 1H, br-s) 8.49 (1H, s) 8.42 (1H, s) 8.38 (1H, dd, J = 8.55,1.52Hz) 8.06 (1H, d, J = 8.55Hz) 4.42 (2H, t, J = 6.72Hz) ) 1.83 (2H, quintet, J = 6.72Hz) 1.2 to 1.6 (10H, m) 0.89 (3H, t, J = 6.72Hz) (4) IR spectrum (KBr method) is shown in FIG. About 1700c
It has absorption due to the C═O stretching vibration of ester near m ⁻¹ .

Synthesis Example 7 [Synthesis of 6- (n-octadecyloxycarbonyl) -2,3-dicyanonaphthalene] 6-methoxycarbonyl-2,3-dicyanonaphthalene 3.1
4 g (13.3 mol), 1-octadecanol 3.6 g (13.3 mol) in 40 ml of benzene p-toluenesulfonic acid monohydrate 2.
In the presence of 2 g (11.6 mol), the mixture was dehydrated with Molecular Sieves 3A and refluxed for about 6 hours while removing methanol. After cooling down,
About 150 ml of chloroform was added, and the chloroform solution was washed 3 times with a saturated aqueous sodium hydrogen carbonate solution and 3 times with water, and dried over anhydrous sodium sulfate. After the chloroform solution was concentrated, it was purified by silica gel column chromatography using benzene as a developing solvent. By recrystallizing the obtained colorless solid from ethanol / chloroform, 0.68 g of colorless needle crystals were obtained. From the following analysis results, this colorless needle crystal was found to be 6- (n-octadecyloxycarbonyl)
It was confirmed to be −2,3-dicyanonaphthalene.

(1) Melting point 139 to 140 ° C (2) Elemental analysis value: C H N calculated value (%) 78.44 8.92 5.90 Measured value (%) 78.52 9.05 5.87 (3) NMR spectrum value: CDCl ₃ solvent δ value 8.71 (1H, 1H, br-s) 8.49 (1H, s) 8.42 (1H, s) 8.38 (1H, dd, J = 8.55,1.53Hz) 8.06 (1H, d, J = 8.55Hz) 4.42 (2H, t, J = 6.72Hz) ) 1.83 (2H, quintet, J = 6.72Hz) 1.25 (30H, br-s) 0.88 (3H, t, J = 6.72Hz) (4) IR spectrum (KBr method) is shown in FIG. About 1700c
It has absorption due to the C═O stretching vibration of ester near m ⁻¹ .

Synthesis Example 8 [Synthesis of 6- (n-tetradecyloxycarbonyl) -2,3-dicyanonaphthalene] 6-methoxycarbonyl-2,3-dicyanonaphthalene 236
mg (1 mmol), 1-tetradecanol 10.7 g (50 mmol) in 100 ml of benzene, p-toluenesulfonic acid monohydrate 1.9
In the presence of 4 g (10.2 mmol), the mixture was refluxed for about 12 hours while dehydrating and removing methanol with Molecular Sieves 3A. After cooling, benzene was distilled off, and the residue was purified by silica gel column chromatography using toluene / chloroform (solvent having a volume ratio of 1: 1) as a developing solvent.

Further, recrystallization from acetone / methanol gave 103 mg of colorless crystals. From the following analysis results, this colorless crystal was found to be 6- (n-tetradecyloxycarbonyl)
It was confirmed to be −2,3-dicyanonaphthalene.

(1) Melting point 142-142.5 ° C (2) Elemental analysis value: C H N calculated value (%) 77.48 8.19 6.69 Measured value (%) 77.53 8.11 6.76 (3) NMR spectrum value: CDCl ₃ solvent δ value 8.68 (1H, br-s) 8.47 (1H, s) 8.39 (1H, s) 8.36 (1H, dd, J = 8.55,1.52Hz) 8.04 (1H, d, J = 8.85Hz) 4.40 (2H, t, J = 6.71Hz ) 1.81 (2H, quintet, J = 6.71Hz) 1.25 (22H, br-s) 0.87 (3H, t, J = 6.71Hz) (4) IR spectrum (KBr method) is shown in FIG. About 1710c
It has absorption due to the C═O stretching vibration of ester near m ⁻¹ .

Synthesis Example 9 [Synthesis of 6- (n-hexadecyloxycarbonyl) -2,3-dicyanonaphthalene] 6-methoxycarbonyl-2,3-dicyanonaphthalene 236
mg (1 mmol), 1-hexadecanol 12.1 g (50 mmol) in 100 ml of benzene p-toluenesulfonic acid monohydrate 1.9
In the presence of 4 g (10.2 mmol), the mixture was refluxed for about 12 hours while dehydrating and removing methanol with Molecular Sieves 3A. After cooling, benzene was distilled off, and the residue was purified by silica gel column chromatography using toluene / chloroform (solvent having a volume ratio of 1: 1) as a developing solvent. In addition, acetone /
247mg colorless crystals by recrystallization from methanol
Was obtained. From the following analysis results, this colorless crystal was 6-
It was confirmed to be (n-hexadecyloxycarbonyl) -2,3-dicyanonaphthalene.

(1) Melting point 141-142 ° C (2) Elemental analysis value: CHN calculated value (%) 77.99 8.58 6.27 Measured value (%) 78.07 8.51 6.19 (3) NMR spectrum value: CDCl ₃ solvent δ value 8.69 (1H, br-s) 8.47 (1H, s) 8.39 (1H, s) 8.37 (1H, dd, J = 8.55,1.53Hz) 8.04 (1H, d, J = 8.55Hz) 4.41 (2H, t, J = 6.72Hz) ) 1.81 (2H, quintet, J = 6.72Hz) 1.25 (26H, br-s) 0.87 (3H, t, J = 6.72Hz) (4) IR spectrum (KBr method) is shown in Fig. 10.

It has an absorption at about 1710 cm ^{-1 due} to the C = O stretching vibration of the ester.

Synthesis Example 10 [Synthesis of 6- (n-eicosyloxycarbonyl) -2,3-dicyanonaphthalene] 6-methoxycarbonyl-2,3-dicyanonaphthalene 236
mg (1 mmol), 1-eicosanol 15.6 g (50 mmol) in 100 ml of benzene p-toluenesulfonic acid monohydrate 1.94 g
In the presence of (10.2mmol), dehydration with Morekiura Sieves 3A,
The mixture was refluxed for about 28 hours while removing methanol. After allowing to cool, benzene was distilled off, and the residue was purified by silica gel column chromatography using toluene / n-hexane (a solvent having a volume ratio of 4/1) as a developing solvent. Further, by recrystallization from acetone / methanol, 166 mg of colorless crystals were obtained. From the following analysis results, this colorless crystal was confirmed to be 6- (n-eicosyloxycarbonyl) -2,3-dicyanonaphthalene.

(1) Melting point 138-138.5 ° C (2) Elemental analysis value: CHN calculated value (%) 78.84 9.22 5.57 Actual value (%) 78.89 9.31 5.52 (3) NMR spectrum value: CDCl ₃ solvent δ value 8.70 (1H, 1H, br-s) 8.48 (1H, s) 8.41 (1H, s) 8.38 (1H, dd, J = 8.85,1.52Hz) 8.05 (1H, d, J = 8.85Hz) 4.42 (2H, t, J = 6.71Hz) ) 1.83 (2H, quintet, J = 6.71Hz) 1.25 (34H, br-s) 0.88 (3H, t, J = 6.71Hz) (4) IR spectrum (KBr method) is shown in Fig. 11.

It has an absorption at about 1710 cm ^{-1 due} to the C = O stretching vibration of the ester.

Synthesis Example 11 [Synthesis of 6- (n-docosyloxycarbonyl) -2,3-dicyanonaphthalene] 6-methoxycarbonyl-2,3-dicyanonaphthalene 236
mg (1 mmol), 1-docosanol 16.3 g (50 mmol) in 100 ml of benzene, p-toluenesulfonic acid monohydrate 1.94 g
In the presence of (10.2mmol), dehydration with Morekiura Sieves 3A,
The mixture was refluxed for about 28 hours while removing methanol. After allowing to cool, benzene was distilled off, and the residue was purified by silica gel column chromatography using toluene / n-hexane (a solvent having a volume ratio of 4/1) as a developing solvent. Further, recrystallization from acetone / methanol gave 161 mg of colorless crystals. From the following analysis results, it was confirmed that the colorless crystal was 6- (n-docosyloxycarbonyl) -2,3-dicyanonaphthalene.

(1) Melting point 135-136.5 ° C (2) Elemental analysis value: CHN calculated value (%) 79.20 9.49 5.28 Measured value (%) 79.12 9.57 5.14 (3) NMR spectrum value: CDCl ₃ solvent δ value 8.70 (1H, br-s) 8.48 (1H, s) 8.41 (1H, s) 8.37 (1H, dd, J = 8.55,1.53Hz) 8.05 (1H, d, J = 8.55Hz) 4.42 (2H, t, J = 6.72Hz) ) 1.83 (2H, quintet, J = 6.72Hz) 1.25 (38H, br-s) 0.88 (3H, t, J = 6.72Hz) (4) IR spectrum (KBr method) is shown in FIG.

It has an absorption at about 1710 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 1 [Synthesis of tetrakis (n-amyloxycarbonyl) vanadyl naphthalocyanine [Exemplified Compound (1)] 6- (n-amyloxycarbonyl) -2,3-dicyanonaphthalene 1.46 g (5 mmol), vanadium trichloride 0.32g (2.0
1mmol), ammonium molybdate 10mg and urea 5g
Was reacted at about 220 ° C. for about 2.5 hours while stirring well.
After allowing to cool, 40 ml of 5% hydrochloric acid was added to the solidified reaction mixture, which was loosened to some extent and then thoroughly stirred at about 50 ° C. for 30 minutes.
After stirring, the insoluble matter was suction filtered and thoroughly washed with water, methanol, and then acetone. The obtained solid was subjected to Soxhlet extractor extraction of impurities for about 50 hours using a mixed solvent of methanol / acetone (1/1) as a solvent. Next, the solvent was changed to chloroform, and Soxhlet extraction was performed for 20 hours. The resulting dark green chloroform solution was subjected to absorption filtration under heating and then concentrated to dryness under reduced pressure to obtain 861 mg of glossy black crystals. This crystal shows tetrakis (n-amyloxycarbonyl) from the following analysis results.
It was confirmed to be vanadyl naphthalocyanine.

(1) Melting point> 300 ° C (stable at least below 300 ° C) (2) Elemental analysis value: C H N calculated value (%) 69.95 5.22 9.06 Measured value (%) 70.13 5.14 9.33 (3) Electronic spectrum value (CDCl ₃ Solution) is shown in FIG.

(4) IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1700 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 2 [Synthesis of tetrakis (n-amyloxycarbonyl) copper naphthalocyanine [Exemplified Compound (8)]] 6- (n-amyloxycarbonyl) -2,3-dicyanonaphthalene 1.46 g (5 mmol), second chloride Copper dihydrate 273mg
(1.6 mmol), 10 mg of ammonium molybdate and 5 g of urea were reacted at 220 ° C. for 2.5 hours with thorough stirring. After cooling, the reaction mixture was treated in the same manner as in Example 1 to obtain 987 mg of glossy black crystals. It was confirmed from the following analysis results that this crystal was tetrakis (n-amyloxycarbonyl) copper naphthalocyanine.

(1) Melting point> 300 ° C (stable at least below 300 ° C) (2) Elemental analysis value: C H N calculated value (%) 70.14 5.23 9.06 Measured value (%) 69.45 5.20 9.17 (3) Electronic spectrum value (CHCl ₃ Solution) is shown in FIG.

(4) IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1700 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 3 [Synthesis of tetrakis (n-amyloxycarbonyl) zinc naphthalocyanine [Exemplified Compound (13)]] 6 .- (n-Amyloxycarbonyl) -2,3-dicyanonaphthalene 1.46 g (5 mmol), powder zinc 105 mg (1.6 mmol),
Ammonium molybdate 10 mg and urea 5 g about 220 ℃
The mixture was stirred for about 2.5 hours to react. After cooling down,
By treating the reaction mixture as in Example 1,
937 mg of glossy black crystals were obtained. It was confirmed from the following analysis results that this crystal was tetrakis (n-amyloxycarbonyl) zinc naphthalocyanine.

(1) Melting point> 300 ° C (stable at least below 300 ° C) (2) Elemental analysis value: C H N calculated value (%) 70.04 5.22 9.08 Measured value (%) 69.35 5.22 9.08 (3) Electronic spectrum value (CHCl ₃ Solution) is shown in FIG.

(4) IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1700 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 4 [Synthesis of tetrakis (n-octyloxycarbonyl) vanadyl naphthalocyanine [exemplary compound (2)]] 6- (n-octyloxycarbonyl) -2,3-dicyanonaphthalene 1.67 g (5 mmol), vanadium trichloride 0.32g
(1.6 mmol), 10 mg of ammonium molybdate and 5 g of urea were reacted at 220 ° C. for 2.5 hours with thorough stirring. After cooling, the reaction mixture was treated in the same manner as in Example 1 to obtain 1.33 g of glossy black crystals. It was confirmed from the following analysis results that this crystal was tetrakis (n-octyloxycarbonyl) vanadyl naphthalocyanine.

(1) Melting point> 300 ° C (stable at least below 300 ° C) (2) Elemental analysis value: C H N calculated value (%) 71.83 6.31 7.98 Measured value (%) 71.99 6.18 8.29 (3) Electronic spectrum value (CHCl ₃ Solution) is shown in FIG.

(4) IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1700 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 5 [Synthesis of tetrakis (n-octyloxycarbonyl) copper naphthalocyanine [exemplary compound (9)]] 6- (n-octyloxycarbonyl) -2,3-dicyanonaphthalene 1.67 g (5 mmol), second chloride Copper dihydrate 273m
g (1.6 mmol), 10 mg of ammonium molybdate and 5 g of urea were reacted at 220 ° C. for 2.5 hours with thorough stirring. After cooling, the reaction mixture was treated in the same manner as in Example 1 to obtain 1.39 g of glossy black crystals. From the following analysis results, this crystal was confirmed to be tetrakis (n-octyloxycarbonyl) copper naphthalocyanine.

(1) Melting point> 300 ° C (stable at least below 300 ° C) (2) Elemental analysis value: C H N calculated value (%) 72.00 6.33 8.00 Measured value (%) 71.95 6.08 8.14 (3) Electronic spectrum value (CHCl ₃ Solution) is shown in FIG.

(4) IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1700 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 6 [Synthesis of tetrakis (n-octyloxycarbonyl) zinc naphthalocyanine [Exemplified Compound (14)]] 6- (n-octyloxycarbonyl) -2,3-dicyanonaphthalene 1.67 g (5 mmol), zinc powder 105 mg (1.6 mmol),
Ammonium molybdate 10 mg and urea 5 g about 220 ℃
The mixture was stirred for about 2.5 hours to react. After cooling down,
By treating the reaction mixture as in Example 1,
1.26 g of glossy black crystals were obtained. It was confirmed from the following analysis results that this crystal was tetrakis (n-octyloxycarbonyl) zinc naphthalocyanine.

(1) Melting point> 300 ℃ (Stable at least below 300 ℃) (2) Elemental analysis value: CHN calculated value (%) 71.89 6.32 7.98 Measured value (%) 71.90 6.20 8.02 (3) Electronic spectrum value (CHCl ₃ solution) is shown in FIG.

(4) IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1700 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 7 [Synthesis of tetrakis (n-amyloxycarbonyl) nickelnaphthalocyanine [Exemplified Compound (16)]] 6- (n-amyloxycarbonyl) -2,3-dicyanonaphthalene 1.46 g (5 mmol), nickel chloride. Hexahydrate 380m
g (1.6 mmol), 10 mg of ammonium molybdate and 5 g of urea were reacted at 220 ° C. for 2.5 hours with thorough stirring. After cooling, the reaction mixture was treated as in Example 1 to give tetrakis (n) as glossy black crystals.
-Amyloxycarbonyl) nickel naphthalocyanine
287 mg was obtained. The electronic spectrum (CHCl ₃ solution) is shown in FIG. 25. This compound is also stable at least at 300 ° C or lower. The IR spectrum (KBr method) is shown in FIG. About 1700c
It has absorption due to the C═O stretching vibration of ester near m ⁻¹ .

Example 8 [Synthesis of tetrakis (n-amyloxycarbonyl) palladium naphthalocyanine [Exemplified Compound (18)]] 6 .- (n-Amyloxycarbonyl) -2,3-dicyanonaphthalene 1.46 g (5 mmol), palladium chloride 284 mg (1.6 mm
ol), ammonium molybdate 10 mg and urea 5 g
The reaction was performed while stirring well at 220 ° C for about 2.5 hours. After cooling, the reaction mixture was treated in the same manner as in Example 1 to give 405 mg of tetrakis (n-amyloxycarbonyl) palladium naphthalocyanine as glossy black crystals.
Obtained. The electronic spectrum (CHCl ₃ solution) is shown in FIG. This compound is also stable at least below 300 ° C. The IR spectrum (KBr method) is shown in FIG. About 1700 cm
^It has absorption at around ^{-1 due} to the C = O stretching vibration of the ester.

Example 9 [Synthesis of tetrakis (n-octadecyloxycarbonyl) vanadylnaphthalocyanine [Exemplified compound (5)]] 6- (n-octadecyloxycarbonyl) -2,3-dicyanonaphthalene 650 mg (1.37 mmol), three Vanadium chloride 8
8 mg (1.6 mmol), ammonium molybdate 3 mg and urea 1.37 g were reacted while stirring well at about 220 ° C. for about 2.5 hours. After cooling, the reaction mixture was treated in the same manner as in Example 1 to obtain 556 mg of tetrakis (n-octadecyloxycarbonyl) vanadyl naphthalocyanine as glossy black crystals. This crystal shows tetrakis (n-octadecyloxycarbonyl) from the following analysis results.
It was confirmed to be vanadyl naphthalocyanine.

(1) Softening point 135-138 ℃ (2) Elemental analysis value: C H N calculated value (%) 75.77 8.61 5.70 Measured value (%) 75.25 8.51 6.17 (3) Electronic spectrum (CHCl ₃ solution) is shown in Fig. 29. Show.

(4) IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1700 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 10 [Synthesis of tetrakis (n-octadecyloxycarbonyl) copper naphthalocyanine [Exemplified compound (12)]] 6- (n-octadecyloxycarbonyl) -2,3-dicyanonaphthalene 200 mg (0.42 mmol), chloride Cupric dihydrate 23 mg (0.13 mmol), ammonium molybdate 1 mg
And 0.42 g of urea were reacted at about 220 ° C. for about 2.5 hours while stirring them well. After cooling, the reaction mixture was treated in the same manner as in Example 1 to obtain 160 mg of tetrakis (n-octadecyloxycarbonyl) copper naphthalocyanine as glossy black crystals. It was confirmed from the following analysis results that this crystal was tetrakis (n-octadecyloxycarbonyl) copper naphthalocyanine.

(1) Softening point 119-121 ° C (2) Elemental analysis value: C H N calculated value (%) 75.90 8.63 5.71 Measured value (%) 75.63 8.51 5.66 (3) Electronic spectrum (CHCl ₃ solution) is shown in FIG. 31. Show.

(4) IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1720 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 11 [Synthesis of tetrakis (n-tetradecyloxycarbonyl) vanadylnaphthalocyanine [Exemplified Compound (3)]] 6- (n-tetradecyloxycarbonyl) -2,3-dicyanonaphthalene 42 mg (0.1 mmol), three Vanadium chloride 6.4
mg (0.04 mmol), ammonium molybdate 0.2 mg, and urea 100 mg were reacted at about 220 ° C. for about 2.5 hours with thorough stirring. After cooling, the reaction mixture was treated in the same manner as in Example 1 to obtain 21 mg of glossy black crystals.
This crystal was confirmed to be tetrakis (n-tetradecyloxycarbonyl) vanadyl naphthalocyanine from the following analysis results.

(1) Softening point 210-212 ℃ (2) Elemental analysis value: C H N calculated value (%) 74.50 7.87 6.44 Measured value (%) 74.66 7.96 6.32 (3) Electronic spectrum (CHCl ₃ solution) is shown in FIG. 33. Show.

(4) IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1720 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 12 [Synthesis of tetrakis (n-tetradecyloxycarbonyl) copper naphthalocyanine [Exemplified compound (10)]] 6- (n-tetradecyloxycarbonyl) -2,3-dicyanonaphthalene 42 mg (0.1 mmol), chloride Cupric dihydrate 5.4 mg (0.03 mmol), ammonium molybdate 0.2 mg
Then, 100 mg of urea was reacted at about 220 ° C. for about 2.5 hours while stirring well. After cooling, the reaction mixture was treated in the same manner as in Example 1 to give 21 mg of shiny black crystals.
Obtained. It was confirmed from the following analysis results that this crystal was tetrakis (n-tetradecyloxycarbonyl) copper naphthalocyanine.

(1) Softening point 168-171 ° C (2) Elemental analysis value: CHN calculated value (%) 74.64 7.89 6.45 Measured value (%) 74.82 7.76 6.37 (3) Electronic spectrum (CHCl ₃ solution) is shown in Fig. 35. Show.

(4) IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1720 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 13 [Synthesis of tetrakis (n-hexadecyloxycarbonyl) vanadylnaphthalocyanine [Exemplified compound (4)]] 6- (n-hexadecyloxycarbonyl) -2,3-dicyanonaphthalene 45 mg (0.1 mmol), three Vanadium chloride 6.4
mg (0.04 mmol), ammonium molybdate 0.2 mg, and urea 100 mg were reacted at about 220 ° C. for about 2.5 hours with thorough stirring. After cooling, the reaction mixture was treated in the same manner as in Example 1 to obtain 13 mg of glossy black crystals.
It was confirmed from the following analysis results that this crystal was tetrakis (n-hexadecyloxycarbonyl) vanadyl naphthalocyanine.

(1) Softening point 151-154 ℃ (2) Elemental analysis value: CHN calculated value (%) 75.17 8.27 6.05 Measured value (%) 75.26 8.19 6.13 (3) Electronic spectrum (CHCl ₃ solution) is shown in FIG. 37. Show.

(4) IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1720 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 14 [Synthesis of tetrakis (n-eicosyloxycarbonyl) vanadylnaphthalocyanine [Exemplified compound (6)]] 6- (n-eicosyloxycarbonyl) -2,3-dicyanonaphthalene 52 mg (0.1 mmol), vanadium trichloride 6.4mg
(0.04 mmol), 0.2 mg of ammonium molybdate and 100 mg of urea were reacted at about 220 ° C. for about 2.5 hours with thorough stirring. After cooling, the reaction mixture was treated in the same manner as in Example 1 to obtain 26 mg of glossy black crystals. It was confirmed from the following analysis results that this crystal was tetrakis (n-eicosyloxycarbonyl) vanadyl naphthalocyanine.

(1) Softening point 83-85 ℃ (2) Elemental analysis value: C H N calculated value (%) 76.30 8.93 5.39 Measured value (%) 76.92 8.89 5.28 (3) Electronic spectrum (CHCl ₃ solution) is shown in FIG. 39. Show.

(4) IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1720 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 15 [Synthesis of tetrakis (n-eicosyloxycarbonyl) copper naphthalocyanine [Exemplified compound (11)]] 6- (n-eicosyloxycarbonyl) -2,3-dicyanonaphthalene 52 mg (0.1 mmol), second chloride Copper dihydrate
5.5 mg (0.03 mmol), ammonium molybdate 0.2 mg and urea 100 mg were reacted at about 220 ° C. for about 2.5 hours while stirring well. After cooling, the reaction mixture was treated in the same manner as in Example 1 to obtain 36 mg of glossy black crystals. This crystal shows that tetrakis (n
-Eicosiloxycarbonyl) copper naphthalocyanine was confirmed.

(1) Softening point 67-70 ℃ (2) Elemental analysis value: C H N calculated value (%) 76.43 8.94 5.40 Measured value (%) 76.62 8.78 5.61 (3) Electronic spectrum (CHCl ₃ solution) is shown in FIG. 41. Show.

(4) IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1720 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 16 [Synthesis of tetrakis (n-amyloxycarbonyl) cobalt naphthalocyanine [Exemplified Compound (20)]] 6- (n-amyloxycarbonyl) -2,3-dicyanonaphthalene 1.46 g (5 mmol), cobalt chloride. Hexahydrate 0.38
mg (1.6 mmol), ammonium molybdate 10 mg, and urea 5 g were reacted at about 220 ° C. for about 2.5 hours with thorough stirring. After cooling, the reaction mixture was treated in the same manner as in Example 1 to obtain 823 mg of glossy black crystals. It was confirmed from the following analysis results that this crystal was tetrakis (n-amyloxycarbonyl) cobalt naphthalocyanine.

(1) Melting point> 300 ° C (stable at least below 300 ° C) (2) Elemental analysis value: CHN calculated value (%) 70.41 5.25 9.12 Measured value (%) 69.54 5.02 9.36 (3) Electronic spectrum (CHCl ₃ solution) ) Is shown in FIG.

(4) IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1700 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 17 [Synthesis of tetrakis (n-amyloxycarbonyl) manganese naphthalocyanine [Exemplified Compound (22)]] 6- (n-amyloxycarbonyl) -2,3-dicyanonaphthalene 1.46 g (5 mmol), manganese acetate. Tetrahydrate 392m
g (1.6 mmol), 10 mg of ammonium molybdate and 5 g of urea were reacted at 220 ° C. for 2.5 hours with thorough stirring. After cooling, the reaction mixture was treated in the same manner as in Example 1 to obtain 605 mg of glossy black crystals. It was confirmed from the following analysis results that this crystal was tetrakis (n-amyloxycarbonyl) manganese naphthalocyanine.

(1) Melting point> 300 ° C (stable at least below 300 ° C) (2) Elemental analysis value: C H N calculated value (%) 70.64 5.27 9.15 Measured value (%) 70.79 5.19 9.66 (3) Electronic spectrum (CHCl ₃ solution) ) Is shown in FIG.

(4) IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1700 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 18 [Synthesis of tetrakis (n-octyloxycarbonyl) chloroindium naphthalocyanine [Exemplified Compound (27)]] 6- (n-octyloxycarbonyl) -2,3-dicyanonaphthalene 1.67 g (5 mmol), trichloride Indium tetrahydrate (470 mg, 1.6 mmol), ammonium molybdate (10 mg) and urea (5 g) were reacted at about 220 ° C. for about 2.5 hours with thorough stirring. After cooling, the reaction mixture was treated in the same manner as in Example 1 to obtain 1.32 g of glossy black crystals.
It was confirmed from the following analysis results that this crystal was tetrakis (n-octyloxycarbonyl) chloroindium naphthalocyanine.

(1) Melting point> 300 ° C (stable at least below 300 ° C) (2) Elemental analysis value: C H N Cl calculated value (%) 67.81 5.96 7.53 2.38 Measured value (%) 67.88 5.74 7.78 1.99 (3) Electronic spectrum ( CHCl ₃ solution) is shown in FIG.

(4) IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1700 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 19 [Synthesis of tetrakis (n-octyloxycarbonyl) chloroaluminum naphthalocyanine [Exemplified compound (24)]] 6- (n-octyloxycarbonyl) -2,3-dicyanonaphthalene 1.67 g (5 mmol), aluminum chloride 213 mg
(1.6 mmol), 10 mg of ammonium molybdate and 5 g of urea were reacted at 220 ° C. for 2.5 hours with thorough stirring. After allowing to cool, 40 ml of methanol was added to the solidified reaction mixture, the mixture was loosened to some extent, and then thoroughly stirred at about 50 ° C. for 30 minutes. After stirring, the insoluble matter was suction filtered and thoroughly washed with methanol and then acetone. Impurities were extracted from the obtained solid using a Soxhlet extractor for about 100 hours using methanol as a solvent and then for about 50 hours using acetone. Then, the solvent was changed to chloroform and Soxhlet extraction was performed for about 20 hours. The resulting dark green chloroform solution was suction filtered while hot and then concentrated to dryness under reduced pressure to obtain 243 mg of glossy black crystals. It was confirmed from the following analysis results that this crystal was tetrakis (n-octyloxycarbonyl) chloroaluminum naphthalocyanine.

(1) Melting point> 300 ° C (stable at least below 300 ° C) (2) Elemental analysis value: C H N Cl calculated value (%) 72.06 6.34 8.00 2.53 Measured value (%) 71.81 6.27 7.74 2.07 (3) Electronic spectrum ( CHCl ₃ solution) is shown in FIG.

(4) IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1700 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 20 [Synthesis of tetrakis (n-amyloxycarbonyl) silicon naphthalocyanine [exemplary compound (29)] 6- (n-amyloxycarbonyl) -2,3-dicyanonaphthalene 1.46 g (5 mmol), silicon tetrachloride 0.29 ml (2.5 mmo
l), ammonium molybdate 10 mg and urea 5 g about 2
The reaction was carried out at 20 ° C. for about 2.5 hours while stirring well. After allowing to cool, 40 ml of 5% hydrochloric acid was added to the solidified reaction mixture, which was loosened to some extent and then thoroughly stirred at about 50 ° C. for 30 minutes. After stirring, the insoluble matter was suction filtered and thoroughly washed with water, methanol, and then acetone. The solid thus obtained was subjected to Soxhlet extractor extraction using the solvent, first, methanol and then acetone, for about 100 hours. Then, the solvent was changed to chloroform and Soxhlet extraction was performed for about 20 hours. The resulting dark green chloroform solution was suction filtered while hot and then concentrated to dryness under reduced pressure to obtain 247 mg of glossy black crystals. It was confirmed from the following analysis results that this crystal was tetrakis (n-amyloxycarbonyl) silicon naphthalocyanine.

(1) Melting point> 300 ° C (stable at least below 300 ° C) (2) Elemental analysis value: C H N calculated value (%) 72.22 5.39 9.36 Measured value (%) 72.41 5.52 9.29 (3) Electronic spectrum value (CHCl ₃ Solution) is shown in FIG.

(4) FT-IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1716 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 21 [Synthesis of tetrakis (n-amyloxycarbonyl) germanium naphthalocyanine [Exemplified Compound (31)] 6- (n-amyloxycarbonyl) -2,3-dicyanonaphthalene 1.46 g (5 mmol), germanium tetrachloride 0.28 mg
(2.47 mmol), 10 mg of ammonium molybdate and 5 g of urea were reacted at 220 ° C. for 2.5 hours with thorough stirring. After cooling, the reaction mixture was treated in the same manner as in Example 20 to obtain 786 mg of glossy black crystals. It was confirmed from the following analysis results that this crystal was tetrakis (n-amyloxycarbonyl) germanium naphthalocyanine.

(1) Melting point> 300 ° C (stable at least below 300 ° C) (2) Elemental analysis value: C H N calculated value (%) 69.63 5.19 9.02 Measured value (%) 69.36 5.06 9.28 (3) Electronic spectrum value (CHCl ₃ Solution) is shown in FIG.

(4) FT-IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1716 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 22 [Synthesis of tetrakis (n-amyloxycarbonyl) tin naphthalocyanine [exemplary compound (33)] 6- (n-amyloxycarbonyl) -2,3-dicyanonaphthalene 1.46 g (5 mmol), stannous chloride 474 mg (2.5 mmo
l), ammonium molybdate 10 mg and urea 5 g about 2
The reaction was carried out at 20 ° C. for about 2.5 hours while stirring well. After cooling, the reaction mixture was treated in the same manner as in Example 20 to obtain 767 mg of glossy black crystals. It was confirmed from the following analysis results that this crystal was tetrakis (n-amyloxycarbonyl) tin naphthalocyanine.

(1) Melting point> 300 ° C (stable at least below 300 ° C) (2) Elemental analysis value: C H N calculated value (%) 67.14 5.01 8.70 Measured value (%) 66.82 4.74 8.33 (3) Electronic spectrum (CHCl ₃ solution) ) Is shown in FIG.

(4) IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1700 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 23 [Synthesis of bis (triethylsiloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine [Exemplified Compound (41)] 6- (n-amyloxycarbonyl) -2,3-dicyanonaphthalene 1.46 g ( 5 mmol), ammonium molybdate 10
mg and urea 5 g, 0.28 ml germanium tetrachloride (2.5 mmo
l) was added, and the mixture was reacted at about 220 ° C. for about 2.5 hours while stirring well. After allowing to cool, water was added to the solidified reaction mixture to thoroughly loosen it, and the black solid was suction filtered, and subsequently thoroughly washed with methanol. After drying, 3.06 g of a black solid was obtained. This black solid is a dichlorogermanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine (general formula (V)) according to the following analysis results: where R ¹ is all n-amyl group and n is 1, and M Is Ge and X is a chlorine atom), but this compound was used in the next reaction without further purification.

(1) Electronic spectrum (CHCl ₃ solution) is shown in FIG.

(2) IR spectrum (KBr method) is shown in FIG.

It has an absorption at about 1710 cm ^{-1 due} to the C = O stretching vibration of the ester.

Dichlorogermanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine obtained as described above
766 mg (0.58 mmol) of concentrated ammonia water 19 ml, ethanol 19
The mixture was refluxed for about 2 hours in a mixed solvent of water and 76 ml of water. After cooling down,
The reaction mixture was suction filtered, and the obtained solid was sufficiently washed with methanol and dried to obtain 213 mg of a black solid. This black solid is a dihydroxygermanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine (general formula VI) according to the following analysis results: where R ¹ is all n-aluminum group, n is 1 and M is Ge This compound was used in the next reaction without further purification.

(1) Electronic spectrum (CHCl ₃ solution) is shown in FIG. 59.

(2) IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1700 cm ^{-1 due} to the C = O stretching vibration of the ester.

Dihydroxygermanium-obtained as described above
After refluxing tetrakis (n-amyloxycarbonyl) naphthalocyanine 210 mg (0.16 mmol) in 15 ml of chlorobenzene in the presence of 0.6 ml of triethylsilanol for about 1 hour,
The reaction mixture was concentrated to about 5 ml. After cooling down, about 5 methanol
0 ml was added and the mixture was allowed to stand for a while, and the precipitated solid was suction filtered and thoroughly washed with methanol. The well-dried black solid was separated and purified by alumina thin layer chromatography using benzene as a developing solvent to obtain 18 mg of a dark green solid. This dark green solid was confirmed to be bis (triethylsiloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine [Exemplified Compound (41)] from the following analysis results.

(1) Melting point> 300 ° C (stable below 300 ° C) (2) Elemental analysis value: C H N calculated value (%) 67.06 6.30 7.45 Measured value (%) 66.84 6.27 7.44 (3) NMR spectrum value (NMR spectrum (Shown in Fig. 61): CDCl ₃ solvent δ value 10.27 (4H, br-s) 10.17 (4H, br-s) 9.45 (4H, br-s) 8.73 (4H, d, J = 8.70Hz) 8.53 (4H , dd, J = 8.70,1.53Hz) 4.58 (8H, t, J = 6.71Hz) 2.00 (8H, quintet, J = 6.71Hz) 1.59 (16H, m) 1.07 (12H, t, J = 7.02Hz) − 1.00 (18H, t, J = 7.94Hz) -2.01 (12H, q, J = 7.94Hz) (4) electronic spectrum (CHCl ₃ solution) is shown in FIG. 62.

(5) IR spectrum (KBr method) is shown in FIG. 63.

It has an absorption at around 1720 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 24 [Synthesis of bis (tributylsiloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine [Exemplified Compound (43)]] Dihydroxygermanium-tetrakis (n-amyloxy) synthesized by the method described in Example 23. Carbonyl)
Chlorobenzene 19 with naphthalocyanine 255 mg (0.2 mmol)
After refluxing for about 1 hour in the presence of 1 ml of tributylsilanol in ml, the reaction mixture was concentrated to about 5 ml. After cooling, about 50 ml of methanol was added and the mixture was allowed to stand for a while. The precipitated solid was suction filtered and thoroughly washed with methanol. A well-dried black solid was analyzed by alumina thin-layer chromatography.
Separation and purification using benzene as a developing solvent gave 13 mg of a dark green solid. This dark green solid was confirmed to be bis (tributylsiloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine [Exemplified Compound (43)] from the following analysis results.

(1) Melting point 280-290 ° C (decomposition) (2) Elemental analysis value CHN calculated value (%) 68.93 7.11 6.70 Measured value (%) 69.17 7.32 6.58 (3) NMR spectrum value (NMR spectrum is shown in FIG. 64) Shown): CDCl ₃ solvent δ value 10.19 (4H, s) 10.08 (4H, s) 9.39 (4H, br-s) 8.66 (4H, d, J = 8.70Hz) 8.46 (4H, dd, J = 8.70,1.53 Hz) 4.51 (8H, t, J = 6.70Hz) 1.93 (8H, quintet, J = 6.72Hz) 1.50 (16H, m) 1.00 (12H, t, J = 7.02Hz) -0.09 (30H, m) -0.99 (12H, quintet-like m) -2.08 (12H, t-like m) (4) Electronic spectrum (tetrahydrofuran solution)
Shown in Figure 65.

(5) IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1720 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 25 [Synthesis of bis (triethylsiloxy) germanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine [Exemplified Compound (44)] 6- (n-octyloxycarbonyl) -2,3-dicyanonaphthalene 1.67 g ( 5mmol), ammonium molybdate
0.28 ml (2.5 mmo) of germanium tetrachloride in 10 mg and 5 g of urea
l) was added, and the mixture was reacted at about 220 ° C. for about 2.5 hours while stirring well. After cooling, the reaction mixture was treated in the same manner as in Example 23 to obtain 3.35 g of a black-green solid. This black-green solid is dichlorogermanium-based on the following analysis results.
Tetrakis (n-octyloxycarbonyl) naphthalocyanine (general formula (V): where R ¹ is all n-octyl group, n is 1, M is Ge and X is chlorine atom) However, this compound was used in the next reaction without further purification.

(1) Electronic spectrum (CHCl ₃ solution) is shown in FIG. 67.

(2) IR spectrum (KBr method) is shown in FIG. 68.

It has an absorption at about 1710 cm ^{-1 due} to the C = O stretching vibration of the ester.

2 g (1.35 mmol) of dichlorogermanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine obtained as above was added to 50 ml of concentrated aqueous ammonia and 50 m of ethanol.
The mixture was refluxed for about 2 hours in a mixed solvent of 200 ml of water. After cooling down,
When the reaction mixture was treated in the same manner as in Example 23, 758 mg of a green solid was obtained. This green solid shows that dihydroxygermanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine (general formula (V
I): However, R ¹ is all n-octyl group, n is 1 and M is Ge), but this compound was used in the next reaction without further purification.

(1) Electronic spectrum (CHCl ₃ solution) is shown in FIG. 69.

(2) IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1700 cm ^{-1 due} to the C = O stretching vibration of the ester.

Dihydroxygermanium-obtained as described above
After 360 mg (0.25 mmol) of tetrakis (n-octyloxycarbonyl) naphthalocyanine was refluxed in 24 ml of chlorobenzene in the presence of 1.2 ml of triethylsilanol for about 1 hour, the reaction mixture was concentrated to about 5 ml. After cooling, about 50 ml of methanol was added, the mixture was allowed to stand for a while and the precipitated solid was suction filtered and thoroughly washed with methanol. A well-dried dark green solid was subjected to alumina thin layer chromatography using a mixed solvent of benzene / hexane (1/1) as a developing solvent.
By performing separation and purification, 47 mg of a dark green solid was obtained. It was confirmed from the following analysis results that this dark green solid was bis (triethylsiloxy) germanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine [Exemplified Compound (44)].

(1) Melting point to 280 ° C (decomposition) (2) Elemental analysis value: C H N calculated value (%) 68.93 7.11 6.70 Measured value (%) 68.85 7.03 6.71 (3) NMR spectrum value (NMR spectrum is shown in FIG. 71) Shown): CDCl ₃ solvent δ value 10.20 (4H, s) 10.09 (4H, s) 9.38 (4H, s) 8.65 (4H, d, J = 8.55Hz) 8.46 (4H, dd, J = 8.55,1.52Hz) 4.51 (8H, t, J = 6.41Hz) 1.91 (8H, quintet, J = 6.41Hz) 1.51 (40H, m) 0.89 (12H, t, J = 6.72Hz) -1.07 (18H, t, J = 7.94Hz) ) −2.08 (12H, q, J = 7.94Hz) (4) Electronic spectrum (tetrahydrofuran solution)
Shown in Figure 72.

(5) IR spectrum (KBr method) is shown in FIG. 73.

It has an absorption at around 1720 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 26 [Synthesis of bis (tributylsiloxy) germanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine [Exemplified Compound (45)]] Dihydroxygermanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine synthesized in Example 25 After 289 mg (0.2 mmol) was refluxed in 19 ml of chlorobenzene in the presence of 1 ml of tributylsilanol for about 1 hour, the reaction mixture was concentrated to about 5 ml. After cooling, about 50 ml of methanol
Was added and left for a while, and the precipitated solid was suction filtered,
It was thoroughly washed with methanol. The well-dried dark green solid was separated and purified by alumina thin layer chromatography using benzene as a developing solvent, and 41 mg of a dark green solid was obtained. It was confirmed from the following analysis results that this dark green solid was bis (tributylsiloxy) germanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine [Exemplified Compound (45)].

(1) Melting point 195 to 200 ° C (2) Elemental analysis value: C H N calculated value (%) 70.46 7.77 6.09 Measured value (%) 70.12 7.73 6.18 (3) NMR spectrum value (NMR spectrum is shown in FIG. 74) : CDCl ₃ solvent δ value 10.19 (4H, s) 10.08 (4H, s) 9.39 (4H, s) 8.66 (4H, d, J = 8.85Hz) 8.46 (4H, dd, J = 8.85,1.53Hz) 4.50 ( 8H, t, J = 6.71Hz) 1.92 (8H, quintet, J = 6.71Hz) 1.50 (40H, m) 0.09 (12H, t, J = 6.71Hz) −1.09 (30H, m) −0.99 (12H, quintet -Like m) -2.08 (12H, t-like m) (4) Electronic spectrum (tetrahydrofuran solution)
Shown in Figure 75.

(5) IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1720 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 27 [Synthesis of bis (n-dodecyloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine [Exemplified compound (53)]] Dihydroxygermanium-tetrakis (n-amyloxycarbonyl) obtained in Example 23 After 320 mg (0.25 mmol) of naphthalocyanine was refluxed in 25 ml of chlorobenzene in the presence of 1.4 g (7.5 mmol) of 1-dodecanol for about 1 hour, the reaction mixture was concentrated to about 5 ml. After cooling, about 50 ml of methanol was added and the mixture was allowed to stand for a while. The precipitated solid was suction filtered and thoroughly washed with methanol. A well-dried black solid is separated and purified by thin layer chromatography on alumina using benzene as a developing solvent.
12 mg of a dark green solid was obtained. This dark green solid is bis (n-dodecyloxy) germanium-
It was confirmed to be tetrakis (n-amyloxycarbonyl) naphthalocyanine [Exemplified compound (53)].

(1) Melting point 230-240 ° C (decomposition) (2) Elemental analysis value: CHN calculated value (%) 71.50 7.13 6.95 Measured value (%) 71.73 7.18 7.09 (3) Electronic spectrum value (CHCl ₃ solution) Shown in Figure 77.

(4) IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1720 cm ^{-1 due} to the C = O stretching vibration of the ester.

Example 28 [Synthesis of bis (n-octadecyloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine [Exemplified compound (54)]] Dihydroxygermanium-tetrakis (n) synthesized by the method described in Example 23. -Amyloxycarbonyl)
320 mg (0.25 mmol) of naphthalocyanine and chlorobenzene 2
After refluxing for about 1 hour in the presence of 2.03 g (7.5 mmol) of 1-octadecanol in 5 ml, the reaction mixture was concentrated to about 5 ml. After cooling, about 50 ml of methanol was added and the mixture was allowed to stand for a while. The precipitated solid was suction filtered and thoroughly washed with methanol. Well-dried black solid was separated by alumina thin-layer chromatography using benzene as a developing solvent.
Upon purification, 16 mg of dark green solid was obtained. It was confirmed from the analysis results below that this dark green solid was bis (n-octadecyloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine [Exemplified Compound (54)].

(1) Melting point 220 ° C-230 ° C (decomposition) (2) Elemental analysis value: CHN calculated value (%) 72.84 7.81 6.29 Measured value (%) 72.56 7.64 6.38 (3) Electronic spectrum (tetrahydrofuran solution) 79th Shown in the figure.

(4) IR spectrum (KBr method) is shown in FIG.

There is absorption due to the C = 0 stretching vibration of the ester around 1720 cm ^-1 .

Example 29 [Synthesis of bis (n-dodecyloxy) germanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine [Exemplified Compound (55)]] Dihydroxygermanium-tetrakis (n-octyl) obtained by the method described in Example 25. Roxycarbonyl) naphthalocyanine 360 mg (0.25 mmol) chlorobenzene 24 m
After refluxing for about 1 hour in the presence of 1.4 g (7.5 mmol) of 1-dodecanol in 1 l, the reaction mixture was concentrated to about 5 ml. After cooling, about 50 ml of methanol was added, the mixture was allowed to stand for a while and the precipitated solid was suction filtered and thoroughly washed with methanol. The well-dried dark green solid was separated and purified by thin layer chromatography on alumina using a mixed solvent of benzene / hexane (1/1) as a developing solvent, whereby 30 mg of a dark green solid was obtained. It was confirmed from the analysis results below that this dark green solid was bis (n-dodecyloxy) germanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine [Exemplified Compound (55)].

(1) Melting point 220 ℃ -230 ℃ (decomposition) (2) Elemental analysis value: CHN calculated value (%) 72.84 7.81 6.29 Measured value (%) 72.81 7.72 6.35 (3) Electronic spectrum (chloroform solution) Shown in the figure.

(4) IR spectrum (KBr method) is shown in FIG.

It has an absorption at around 1720 cm ^{-1 due} to the C = 0 stretching vibration of the ester.

Example 30 [Synthesis of bis (n-octadecyloxy) germanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine [Exemplified compound (56)]] Dihydroxygermanium-tetrakis (n-octyloxycarbonyl) synthesized in Example 25 ) Naphthalocyanine 360 mg (0.25 mmol) in 1 ml of chlorobenzene 1-
After refluxing for about 1 hour in the presence of 2.03 g (7.5 mmol) of octadecanol, the reaction mixture was concentrated to about 5 ml. After cooling, about 50 ml of methanol was added and the mixture was allowed to stand for a while. The precipitated solid was suction filtered and thoroughly washed with methanol. The well-dried dark green solid was separated and purified by alumina thin layer chromatography using benzene as a developing solvent, and 26 mg of a dark green solid was obtained. This dark green solid is
From the following analysis results, bis (n-octadecyloxy) germanium-tetrakis (n-octyloxycarbonyl)
It was confirmed to be naphthalocyanine [Exemplified Compound (56)].

(1) Melting point 220 ℃ -230 ℃ (decomposition) (2) Elemental analysis value: CHN calculated value (%) 73.94 8.37 5.75 Measured value (%) 73.78 8.16 5.62 (3) Electronic spectrum value (tetrahydrofuran solution) Figure 83 shows.

(4) IR spectrum (KBr method) is shown in FIG. 84.

There is absorption due to the C = 0 stretching vibration of the ester around 1720 cm ^-1 .

Test Example 1 Bis (triethylsiloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine [Exemplified Compound (41)] was dissolved in various solvents and the electronic spectrum was measured. Fig. 62, Fig. 85, Fig. 86, and Fig. 87 show the electron spectra in chloroform, tetrahydrofuran, acetone, and benzene, respectively. The change in the absorption waveform due to was never observed.

Test Example 2 Bis (n-dodecyloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine [Exemplified Compound (53)] was dissolved in various solvents and the electronic spectrum was measured. Figures 77, 88, and 89 show the electron spectra in chloroform, tetrahydrofuran, and benzene, respectively. The absorption waveform changes depending on the type of solvent and the absorption waveform changes depending on the solution concentration. It was never observed.

Comparative Example 1 Literature [Zhurnal Obshchei
Khimii), Vol. 42, p. 696, 1972], and an electron spectrum of tetra (t-butyl) vanadyl naphthalocyanine synthesized by the method described in Fig. 90 was measured in a benzene solution. As shown in Fig. 91, in this compound, when the type and concentration of the solvent changed, the absorption waveform changed, and as the concentration became higher, the absorption near 800 nm decreased and the absorption at 720 to 730 nm increased. Was observed.

Tetra (t-butyl) vanadyl naphthalocyanine Test Example 3 2 parts by weight of bis (tributylsiloxy) germanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine [exemplary compound (45)] and 1,1,2- A liquid consisting of 98 parts by weight of trichloroethane was applied by spin coating and dried at about 80 ° C for about 15 minutes to form an organic film. The transmission spectrum and 5 ° specular reflection spectrum of the organic film of this compound are shown in FIGS. 92 and 93, respectively. It has been found that the semiconductor laser region (780 to 830 nm) exhibits high light absorption capacity and high reflectance (to 47%).

Comparative Example 2 Tetra (t-butyl) used in Comparative Example 1 on a glass plate.
An organic film was formed from vanadyl naphthalocyanine in the same manner as in Test Example 2, and its transmission spectrum (Fig. 94) and 5 ° specular reflection spectrum (Fig. 95) were measured. In the semiconductor laser region (780 to 830 nm), it did not show very high light absorption ability and reflectance (<20%).

Test Example 4 The solubility of bis (tributylsiloxy) germanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine [Exemplified Compound (45)] was measured as follows. After adding 100 mg of bis (tributylsiloxy) germanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine and 0.5 ml of a solvent to a 2 ml sample tube, the container was sealed and ultrasonically shaken at 40 ° C for 15 minutes, and then left overnight at room temperature. , Filtered. The residue on the filter paper was collected, dried under reduced pressure, and the solubility was determined from the value obtained by subtracting the amount of residue from the amount used first.

Solubility of bis (tributylsiloxy) germanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine in various solvents Example 31 A solution of 4 parts by weight of tetrakis (n-octyloxycarbonyl) vanadyl naphthalocyanine [exemplified compound (2)] and 96 parts by weight of chloroform was spun on a polymethylmethacrylate 2P substrate having a thickness of 1.5 mm and a diameter of 150 mm. It was applied by a coating method and dried at about 80 ° C. for about 15 minutes to form a recording layer.
The thickness of this recording layer is about 20 as measured by Talisstep.
It was 00Å. An optical head equipped with a semiconductor laser having an oscillation wavelength of 830 nm and an output of 8 mW on the substrate surface was placed on a turntable with the recording layer facing upwards and rotated at a speed of 1000 rpm while the optical recording medium thus produced was placed on a turntable. While controlling the laser beam from the lower side of the optical recording medium, that is, the substrate side to focus on the recording layer through the polymethylmethacrylate resin plate using
A pulse signal of 1 MHz was recorded between the two. Next, using the same device, the recorded signal was reproduced while the output on the substrate surface of the semiconductor laser was 0.7 mW. The signal-to-noise ratio (S / N) at this time was 56 dB, and extremely good signal writing and reading could be performed.

Example 32 A chloroform solution of tetrakis (n-octyloxycarbonyl) copper naphthalocyanine [Exemplified compound (9)] was spin-coated on a polymethylmethacrylate 2P substrate having a thickness of 1.5 mm and a diameter of 150 mm in the same manner as in Example 31. It was applied to form a recording layer. The thickness of this recording layer was about 2500Å.
When recording and reproduction were performed on the optical recording medium thus manufactured in the same manner as in Example 31, the S / N ratio was 51 dB, and extremely good signal writing and reading could be performed.

Example 33 Tetrakis (n-octyloxycarbonyl) zinc naphthalocyanine [Exemplified Compound (14)] was spin-coated on a polymethylmethacrylate 2P substrate having a thickness of 1.5 mm and a diameter of 150 mm as a chloroform solution in the same manner as in Example 31. Apply
A recording layer was formed. The thickness of this recording layer was about 3000Å. When an optical recording medium thus produced was subjected to signal recording / reproduction in the same manner as in Example 31, the S / N ratio was 4
Very good signal writing and reading was possible at 9 dB.

Example 34 As in Example 31, tetrakis (n-amyloxycarbonyl) vanadyl naphthalocyanine [exemplary compound (1)] was spin-coated on a polymethylmethacrylate 2P substrate having a thickness of 1.5 mm and a diameter of 150 mm as a chloroform solution in the same manner as in Example 31. It was applied to form a recording layer. The thickness of this recording layer is approximately 2600Å
It was. The optical recording medium produced in this manner is used as an example.
When the signal was recorded / reproduced in the same manner as 31, the S / N ratio was 50 dB, and extremely good signal writing and reading could be performed.

Example 35 Tetrakis (n-amyloxycarbonyl) copper naphthalocyanine [Exemplified Compound (8)] was spin-coated on a polymethylmethacrylate 2P substrate having a thickness of 1.5 mm and a diameter of 150 mm as a chloroform solution in the same manner as in Example 31. It was applied to form a recording layer. The thickness of this recording layer was about 2300Å. When an optical recording medium thus produced was subjected to signal recording / reproduction in the same manner as in Example 31, the S / N ratio was 51d.
With B, extremely good signal writing and reading were possible.

Example 36 As in Example 31, tetrakis (n-amyloxycarbonyl) zinc naphthalocyanine [Exemplified Compound (13)] was spin-coated on a polymethylmethacrylate 2P substrate having a thickness of 1.5 mm and a diameter of 150 mm as a chloroform solution in the same manner as in Example 31. It was applied to form a recording layer. The thickness of this recording layer was about 2500Å. When an optical recording medium thus produced was subjected to signal recording / reproduction in the same manner as in Example 31, the S / N ratio was 52d.
With B, extremely good signal writing and reading were possible.

Example 37 Tetrakis (n-amyloxycarbonyl) nickelnaphthalocyanine [Exemplified Compound (16)] was applied on a polymethylmethacrylate 2P substrate having a thickness of 1.5 mm and a diameter of 150 mm in Example 31.
Similarly to, a chloroform solution was applied by spin coating to form a recording layer. The thickness of this recording layer is approximately 2100Å
It was. The optical recording medium produced in this manner is used as an example.
When the signal was recorded / reproduced in the same manner as 31, the S / N ratio was 54 dB, and extremely good signal writing and reading could be performed.

Example 38 Tetrakis (n-amyloxycarbonyl) palladium naphthalocyanine [Exemplified Compound (18)] was applied on a polymethylmethacrylate 2P substrate having a thickness of 1.5 mm and a diameter of 150 mm.
Similarly to 31, a chloroform solution was applied by spin coating to form a recording layer. The thickness of this recording layer is approximately 2300Å
It was. The optical recording medium produced in this manner is used as an example.
When the signal was recorded / reproduced in the same manner as 31, the S / N ratio was 51 dB, and extremely good signal writing and reading could be performed.

Example 39 Tetrakis (n-octyloxycarbonyl) chloroindium naphthalocyanine [Exemplified Compound (27)] was formed on a polymethylmethacrylate 2P substrate having a thickness of 1.5 mm and a diameter of 150 mm.
A liquid consisting of 2 parts by weight and 98 parts by weight of chloroform was applied by a spin coating method and dried at about 80 ° C. for about 15 minutes to form a recording layer. The thickness of this recording layer was about 1000Å. When the optical recording medium thus manufactured was recorded and reproduced in the same manner as in Example 31, the S / N ratio was 54 dB, and extremely good signal writing and reading could be performed.

Example 40 Tetrakis (n-octyloxycarbonyl) chloroaluminum naphthalocyanine on a polymethylmethacrylate 2P substrate having a thickness of 1.5 mm and a diameter of 120 mm [Exemplified compound (24)]
The chloroform solution of was applied by spin coating in the same manner as in Example 39 to form a recording layer. The thickness of this recording layer is approximately
It was 1500Å. When the optical recording medium thus produced was recorded and reproduced in the same manner as in Example 39, S / N
The ratio was 51 dB, and extremely good signal writing and reading could be performed.

Example 41 A chloroform solution of tetrakis (n-amyloxycarbonyl) cobalt naphthalocyanine [Exemplified compound (20)] was spin-coated on a polymethylmethacrylate 2P substrate having a thickness of 1.5 mm and a diameter of 150 mm in the same manner as in Example 39. Apply with
It was dried at about 80 ° C. for about 15 minutes to form a recording layer. The thickness of this recording layer was about 1100Å. When the optical recording medium thus produced was recorded and reproduced in the same manner as in Example 39, the S / N ratio was 49 dB, and extremely good signal writing and reading could be performed.

Example 42 A chloroform solution of tetrakis (n-amyloxycarbonyl) manganese naphthalocyanine [exemplary compound (22)] was spin-coated on a polymethylmethacrylate 2P substrate having a thickness of 1.5 mm and a diameter of 150 mm in the same manner as in Example 39. It was applied to form a recording layer. The thickness of this recording layer was about 1300Å. When the optical recording medium thus produced was recorded / reproduced in the same manner as in Example 39, the S / N ratio was 51 dB, and extremely good signal writing / reading could be performed.

Example 43 A chloroform solution of tetrakis (n-amyloxycarbonyl) silicon naphthalocyanine [Exemplified compound (29)] was spin-coated on a polymethylmethacrylate 2P substrate having a thickness of 1.5 mm and a diameter of 150 mm in the same manner as in Example 39. Apply with
It was dried at about 80 ° C. for about 15 minutes to form a recording layer. The thickness of this recording layer was about 1000Å.

When recording and reproduction were performed on the optical recording medium thus manufactured in the same manner as in Example 39, the S / N ratio was 52 dB, and extremely good signal writing and reading could be performed.

Example 44 As in Example 39, a chloroform solution of tetrakis (n-amyloxycarbonyl) germanium naphthalocyanine [Exemplified compound (31)] was spin-coated on a polymethylmethacrylate 2P substrate having a thickness of 1.5 mm and a diameter of 150 mm by the spin coating method. It was applied to form a recording layer. The thickness of this recording layer is approximately 900Å
It was. The optical recording medium produced in this manner is used as an example.
When recording and reproducing were performed in the same manner as 39, the S / N ratio was 5
Very good signal writing and reading was possible at 1 dB.

Example 45 Tetrakis (n-amyloxycarbonyl) tin naphthalocyanine [Exemplified compound (33)] was applied as a chloroform solution onto a polymethylmethacrylate 2P substrate having a thickness of 1.5 mm and a diameter of 150 mm by spin coating as in Example 39. Then, a recording layer was formed. The thickness of this recording layer was about 1100Å. When an optical recording medium thus produced was subjected to signal recording / reproduction in the same manner as in Example 39, the S / N ratio was 4
Very good signal writing and reading was possible at 9 dB.

Example 46 2 parts by weight of bis (triethylsiloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine [exemplary compound (41)] and 98 parts by weight of toluene on a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm. Part of the solution was applied by spin coating and dried at about 80 ° C. for about 15 minutes to form a recording layer. The thickness of this recording layer was about 1000Å as measured by Talisstep. An optical head equipped with a semiconductor laser having an oscillation wavelength of 830 nm and an output of 6 mW on the substrate surface is placed on a turntable with the recording layer facing up on a turntable and rotated at a speed of 900 rpm. While controlling the laser beam from the lower side of the optical recording medium, that is, the substrate side, through the polymethacrylate resin plate to focus on the recording layer, a pulse signal of 2 MHz was recorded within a radius of 40 to 60 mm from the center. . Next, using the same device, the recorded signal was reproduced while the output on the substrate surface of the semiconductor laser was 0.7 mW. The carrier / noise ratio (C / N) at this time is 5
Very good signal writing and reading was possible at 7 dB.

Example 47 On a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm, 2 parts by weight of bis (tributylsiloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine [Exemplified compound (43)] and 98 parts by weight of toluene. Part of the liquid by spin coating in the same manner as in Example 46,
A recording layer was formed. The thickness of this recording layer was about 700Å. When the optical recording medium thus manufactured was recorded and reproduced in the same manner as in Example 46, the C / N ratio was 55 dB, and extremely good signal writing and reading could be performed.

Example 48 2 parts by weight of bis (triethylsiloxy) germanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine [exemplary compound (44)] and 98 parts by weight of toluene on a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm. A part of the solution was applied by spin coating as in Example 46 to form a recording layer. The thickness of this recording layer was about 800Å. The optical recording medium thus prepared was used in Example 46.
When recording and reproducing were performed in the same manner as above, the C / N ratio was 56 dB, and extremely good signal writing and reading could be performed.

Example 49 2 parts by weight of bis (tributylsiloxy) germanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine [exemplary compound (45)] and 98 parts by weight of toluene on a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm. A part of the solution was applied by spin coating as in Example 46 to form a recording layer. The thickness of this recording layer was about 600Å. The optical recording medium thus prepared was used in Example 46.
When recording and reproducing were performed in the same manner as above, the C / N ratio was 57 dB and extremely good signal writing and reading could be performed.

Example 50 On a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm, 2 parts by weight of bis (n-dodecyloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine [exemplary compound (53)] and toluene 98 were used. A liquid consisting of parts by weight was applied by a spin coating method as in Example 46 to form a recording layer. The thickness of this recording layer was about 1000Å. When recording and reproduction were performed on the optical recording medium thus manufactured in the same manner as in Example 46, the C / N ratio was 52 dB, and extremely good signal writing and reading could be performed.

Example 51 On a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm, bis (n-octadecyloxy) germanium-
A liquid consisting of 2 parts by weight of tetrakis (n-amyloxycarbonyl) naphthalocyanine [Exemplified compound (54)] and 98 parts by weight of toluene was applied by a spin coating method as in Example 46 to form a recording layer. The thickness of this recording layer is approximately 700Å
It was. The optical recording medium produced in this manner is used as an example.
When recording and reproducing were performed in the same manner as in 46, the C / N ratio was 54 dB, and extremely good signal writing and reading could be performed.

Example 52 On a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm, 2 parts by weight of bis (n-dodecyloxy) germanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine [exemplary compound (55)] and toluene 98 A solution consisting of parts by weight was applied by spin coating in the same manner as in Example 46,
A recording layer was formed. The thickness of this recording layer was about 800Å. When the optical recording medium thus manufactured was recorded and reproduced in the same manner as in Example 46, the C / N ratio was 55 dB, and extremely good signal writing and reading could be performed.

Example 53 On a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm, bis (n-octadecyloxy) germanium-
A liquid consisting of 2 parts by weight of tetrakis (n-octyloxycarbonyl) naphthalocyanine [Exemplified compound (56)] and 98 parts by weight of toluene was applied by a spin coating method as in Example 46 to form a recording layer. The thickness of this recording layer was about 600Å. The optical recording medium thus prepared was used in Example 46.
When recording and reproducing were performed in the same manner as above, the C / N ratio was 53 dB, and extremely good signal writing and reading could be performed.

Example 54 Tetrakis (n-amyloxycarbonyl) exemplified above
Vanadyl naphthalocyanine [Exemplified Compound (1)] was dissolved in chloroform to prepare a 1% solution, and a 700 Å recording film layer was formed on a glass substrate having a thickness of 1.2 mm by a spin coating method. The recording medium thus formed has a wavelength of 830 nm.
The semiconductor laser was irradiated from the glass substrate side to evaluate the recording characteristics. The beam diameter was 1.6 μm, the linear velocity was 0.5 m / sec, and 6.4 mW.
It was possible to record at. On the other hand, in order to evaluate the stability against reproduction deterioration, 1 mW of reading light was repeatedly irradiated, but no change in reflectance occurred even after repeating 10 ⁶ times. The transmission spectrum is shown in FIG.

Comparative Example 3 A cyanine dye NK-2905 (manufactured by Japan Photosensitive Dye Research Institute) was dissolved in dichloroethane and a spin coating method was carried out to obtain a recording film layer having a thickness of 500 L on a glass substrate. When this recording medium was irradiated with laser light in the same manner as in Example 54, 4.8 mmW
It was possible to record at. However, when the stability against reproduction deterioration was evaluated, the reflectance started to decrease from the number of repeated irradiations of about 4 × 10 ⁴ times and decreased to 70% of the initial reflectance after 10 ⁶ times of irradiation.

Example 55 Tetrakis (n-octyloxycarbonyl) zinc naphthalocyanine [Exemplified Compound (14)] was dissolved in chloroform and a recording film layer having a thickness of 700Å was obtained on a glass substrate by a spin coating method. This recording medium was irradiated with a semiconductor laser having a wavelength of 780 nm from the glass substrate side and the recording characteristics were evaluated. As a result, recording was possible at a beam diameter of 1.6 μm, a linear velocity of 0.5 m / sec and 6.9 mW. On the other hand, in order to evaluate the stability against reproduction deterioration, 1 mW of reading light was repeatedly irradiated, but even if it was repeated 10 ⁶ times, the reflectance did not increase.

Example 56 Tetrakis (n-octyloxycarbonyl) chloroaluminum naphthalocyanine [Exemplified compound (24)] was dissolved in chloroform, and the solution was spin-coated on a glass substrate.
A recording film layer having a thickness of 900Å was obtained. Example 54 is recorded on this recording medium.
When laser light was irradiated in the same manner as in, recording was possible at 6.6 mW. When the stability against reproduction deterioration was evaluated in the same manner, no change in reflectance occurred even after repeated irradiation of 10 ⁶ times.

Example 57 Tetrakis (n-amyloxycarbonyl) on a glass substrate
Nickel naphthalocyanine [Exemplified compound (16)] and polystyrene were dissolved in chloroform at a ratio of 1: 1 and a 1500 Å-thick recording film layer was obtained by a spin coating method. When this recording medium was irradiated with laser light in the same manner as in Example 54, recording was possible at 9.6 mW. When the stability against reproduction deterioration was also evaluated in the same manner, no change in reflectance occurred even after repeated irradiation of 10 ⁶ times.

Example 58 Bis (trihexylsiloxane) tin-tetrakis (n-amyloxycarbonyl) naphthalocyanine [Exemplified Compound (64)] synthesized according to the method of Example 23 was dissolved in chloroform, and spin-coated. A 700 Å recording film layer was formed on a glass substrate having a thickness of 1.2 mm. This recording medium is irradiated with a semiconductor laser having a wavelength of 780 nm from the glass substrate side,
When the recording characteristics were evaluated, the beam diameter was 1.6 μm and the linear velocity was
Recording was possible at 0.5m / sec and 4.6mW. On the other hand, in order to evaluate the stability against reproduction deterioration, 1 mW of reading light was repeatedly irradiated, but no change in reflectance occurred even after repeating 10 ⁶ times.

Comparative Example 4 A cyanine dye NK-2873 (manufactured by Japan Photosensitive Dye Research Institute) was dissolved in dichloroethane, and a recording film layer having a thickness of 500Å was obtained on a glass substrate by a spin coating method. When this recording medium was irradiated with laser light in the same manner as in Example 54, the result was 5.2 mW.
It was possible to record at. However, when the stability against deterioration due to reproduction was evaluated, the reflectance began to decrease from the number of repeated irradiations of about 5 × 10 ⁴ times, and after 10 ⁶ times of irradiation, it decreased to 70% of the initial reflectance.

Example 59 Bis (tributylsiloxy) tin-tetrakis (n-octyloxycarbonyl) naphthalocyanine [Exemplified Compound (65)] synthesized according to the method of Example 23 was dissolved in dichloroethane, and a glass substrate was formed by spin coating. Top 500
A recording film layer of Å was obtained. When this recording medium was irradiated with laser light in the same manner as in Example 54, recording was possible at 4.4 mW. When the stability against reproduction deterioration was evaluated, the reflectance did not change even after repeated irradiation of 10 ⁶ times.

Example 60 The bis (triethylsiloxy) germanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine [Exemplified Compound (44)] synthesized in Example 25 was dissolved in chloroform, and the solution was spin-coated on a glass substrate to a thickness of
A recording film layer of 500Å was obtained. When this recording medium was irradiated with laser light in the same manner as in Example 54, recording was possible at 4.9 mW. When the stability against reproduction deterioration was evaluated, the reflectance did not change even after repeated irradiation of 10 ⁶ times.

Example 61 A bis (tributylsiloxy) titanium-tetrakis (methoxycarbonyl) naphthalocyanine [Exemplified Compound (68)] synthesized according to the method of Example 23 was dissolved in chloroform, and then applied on a glass substrate by a spin coating method to give a thick film. A recording film layer having a size of 400 Å was obtained. When this recording medium was irradiated with laser light in the same manner as in Example 54, recording was possible at 4.2 mW. Further, when the stability against reproduction deterioration was evaluated at the same time, no change in reflectance occurred even after repeated irradiation of 10 ⁶ times.

Example 62 Trihexylsiloxyaluminum-tetrakis (n-) synthesized according to the method of Example 23 on a 1.2 mm-thick polycarbonate substrate having a 10 nm Ti chelate surface protective layer.
A solution of amyloxycarbonyl) naphthalocyanine [Exemplified compound (69)] in toluene was spin-coated to give a thickness of 600
A recording film layer of Å was obtained. As in Example 54, linear velocity 5 m
When evaluated in / sec, recording was possible at 7.4 mW. Also, when the stability against reproduction deterioration was evaluated at the same time,
The reflectance did not change even after repeated irradiation of 10 ⁶ times.

Example 63 Of bis (n-octoxy) tin-tetrakis (n-amyloxycarbonyl) naphthalocyanine [Exemplified compound (74)] and polystyrene synthesized according to the method of Example 23
The 2: 1 mixture was dissolved in methyl ethyl ketone to obtain a recording film layer having a thickness of 600Å on a glass substrate. When evaluated in the same manner as in Example 54, a recording sensitivity of 4.8 mw and reproduction deterioration of 10 ⁶ times or more were obtained.

Example 64 Bis (tributylsiloxy) germanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine [Exemplified compound (45)] was dissolved in 1,1,2-trichloroethane to prepare a 0.8% by weight solution. Then, by a spin coating method, a recording layer having a thickness of 400 Å was obtained on a glass substrate having a thickness of 1.2 mm.
This recording medium was irradiated with a semiconductor laser having a wavelength of 830 nm from the glass substrate side, and the recording characteristics were evaluated. As a result, recording was possible with a 1 / e ² beam diameter of 1.6 μm, a linear velocity of 2.4 m / s and 7.8 mW. On the other hand, in order to evaluate the stability against regeneration deterioration, 0.
Irradiation with 8mW read light was repeated, but no change in reflectivity occurred even after repeating 10 ⁶ times.

Example 65 Bis (n-dodecyloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine [Exemplified compound (53)] was dissolved in 1,2-dichloroethane to prepare a 1.5 wt% solution, and the spin coating method was used. A recording layer of 600 Å was obtained on a 1.2 mm thick glass substrate. This recording medium has a wavelength of 8
When the recording characteristics were evaluated by irradiating 30 nm semiconductor laser light from the substrate side, 1 / e ² beam diameter 1.6 μm, linear velocity 2.5 m / s,
It was possible to record at 8.6mW. On the other hand, a read light of 0.8 mW was repeatedly irradiated to evaluate the stability against reproduction deterioration, but no change in reflectance occurred even after repeating 10 ⁶ times.

Example 66 Bis (tributylsiloxy) germanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine [Exemplified Compound (45)] and polystyrene in a 2: 1 mixture were mixed with 1,1,2-
It was dissolved in trichloroethane, and a recording layer having a thickness of 800 Å was obtained by spin coating on a glass substrate having a thickness of 1.2 mm. When this recording medium was irradiated with a semiconductor laser beam having a wavelength of 830 nm from the substrate side and the recording characteristics were evaluated, it was possible to record at a linear velocity of 2 m / s and 6 mW. Further, although the reading light of 1 mW was repeatedly irradiated, the reflectance did not change even if the irradiation was repeated 10 ⁶ times.

〔The invention's effect〕

According to the present invention, a novel naphthalocyanine derivative is provided, and this compound is useful as a recording layer material for an optical information recording medium.

[Brief description of drawings]

Fig. 1 is an IR spectrum of methyl 3,4-dimethylbenzoate, Fig. 2 is an IR spectrum of methyl 3,4-bis (dibromomethyl) benzoate, and Fig. 3 is 6-methoxy. FIG. 4 is an IR spectrum of carbonyl-2,3-dicyanonaphthalene, and FIG. 4 shows 3,4-dimethylbenzoic acid n-
FIG. 5 is an IR spectrum of amyl, and FIG. 5 shows an IR spectrum of 6- (n-amyloxycarbonyl) -2,3-dicyanonaphthalene.
FIG. 6 is a spectrum, and FIG. 6 shows 3,4-dimethylbenzoic acid n
Is an IR spectrum of octyl, and FIG. 7 shows 6- (n
Is an IR spectrum of -octyloxycarbonyl) -2,3-dicyanonaphthalene, and FIG. 8 shows I of 6- (n-octadecyloxycarbonyl) -2,3-dicyanonaphthalene.
Fig. 9 is an R spectrum, Fig. 9 is an IR spectrum of 6- (n-tetradecyloxycarbonyl) -2,3-dicyanonaphthalene, and Fig. 10 is 6- (n-hexadecyloxycarbonyl) -2, FIG. 11 is an IR spectrum of 3-dicyanonaphthalene, FIG. 11 is an IR spectrum of 6- (n-eicosyloxycarbonyl) -2,3-dicyanonaphthalene, and FIG. 12 is 6- (n-docosyloxycarbonyl). −
FIG. 13 is an IR spectrum of 2,3-dicyanonaphthalene, FIG. 13 is an electronic spectrum of tetrakis (n-amyloxycarbonyl) vanadylnaphthalocyanine, and FIG. 14 is an IR spectrum of tetrakis (n-amyloxycarbonyl) vanadylnaphthalocyanine. FIG. 15 is an electronic spectrum of tetrakis (n-amyloxycarbonyl) copper naphthalocyanine, FIG. 16 is an IR spectrum of tetrakis (n-amyloxycarbonyl) copper naphthalocyanine, and FIG. 17 is tetrakis. 2 is an electronic spectrum of (n-amyloxycarbonyl) zinc naphthalocyanine,
FIG. 18 is an IR spectrum of tetrakis (n-amyloxycarbonyl) zinc naphthalocyanine, FIG. 19 is an electronic spectrum of tetrakis (n-octyloxycarbonyl) vanadyl naphthalocyanine, and FIG. 20 is tetrakis (n-octyl). Is an IR spectrum of (roxycarbonyl) vanadylnaphthalocyanine, and FIG. 21 shows tetrakis (n-
22 is an IR spectrum of tetrakis (n-octyloxycarbonyl) copper naphthalocyanine, and FIG. 23 is a spectrum of tetrakis (n-octyloxycarbonyl) zinc naphthalocyanine. Electronic spectrum,
FIG. 24 is an IR spectrum of tetrakis (n-octyloxycarbonyl) zinc naphthalocyanine, FIG. 25 is an electronic spectrum of tetrakis (n-aminoxycarbonyl) nickelnaphthalocyanine, and FIG. 26 is tetrakis (n-amido). Is an IR spectrum of tetrakis (n-amyloxycarbonyl) palladium naphthalocyanine, and FIG. 28 is an IR spectrum of tetrakis (n-amyloxycarbonyl) palladium naphthalocyanine. FIG. 29 is an electronic spectrum of tetrakis (n-octadecyloxycarbonyl) vanadylnaphthalocyanine, and FIG. 30 is an IR spectrum of tetrakis (n-octadecyloxycarbonyl) vanadylnaphthalocyanine. Figure 31 shows Rakisu (n- octadecenyl siloxy carbonyl) an electronic spectrum of a copper naphthalocyanine, FIG. 32 is an IR spectrum of the tetrakis (n- octadecenyl siloxy carbonyl) copper naphthalocyanine,
FIG. 33 is an electronic spectrum of tetrakis (n-tetradecyloxycarbonyl) vanadyl naphthalocyanine, FIG. 34 is an IR spectrum of tetrakis (n-tetradecyloxycarbonyl) vanadyl naphthalocyanine, and FIG. 35 is 1 is an electronic spectrum of tetrakis (n-tetradecyloxycarbonyl) copper naphthalocyanine,
FIG. 36 is an IR spectrum of tetrakis (n-tetradecyloxycarbonyl) copper naphthalocyanine, and FIG. 37 is an electronic spectrum of tetrakis (n-hexadecyloxycarbonyl) vanadyl naphthalocyanine.
The figure shows tetrakis (n-hexadecyloxycarbonyl)
IR spectrum of vanadyl naphthalocyanine, 39th
The figure is an electronic spectrum of tetrakis (n-eicosyloxycarbonyl) vanadyl naphthalocyanine,
The figure is the IR spectrum of tetrakis (n-eicosyloxycarbonyl) vanadyl naphthalocyanine, FIG. 41 is the electron spectrum of tetrakis (n-eicosyloxycarbonyl) copper naphthalocyanine, and FIG. 42 is the tetrakis (n- FIG. 43 is an IR spectrum of eicosyloxycarbonyl) copper naphthalocyanine, and FIG. 43 shows tetrakis (n
-Amyloxycarbonyl) cobalt naphthalocyanine, FIG. 44 is an IR spectrum of tetrakis (n-amyloxycarbonyl) cobalt naphthalocyanine, and FIG. 45 is tetrakis (n-amyloxycarbonyl) manganese naphthalocyanine. FIG. 46 is an IR spectrum of tetrakis (n-amyloxycarbonyl) manganese naphthalocyanine,
FIG. 47 is an electronic spectrum of tetrakis (n-octyloxycarbonyl) chloroindium naphthalocyanine, FIG. 48 is an IR spectrum of tetrakis (n-octyloxycarbonyl) chloroindium naphthalocyanine, and FIG. 49 is tetrakis ( FIG. 50 is an electronic spectrum of (n-octyloxycarbonyl) chloroaluminum naphthalocyanine, and FIG. 50 shows IR of tetrakis (n-octyloxycarbonyl) chloroaluminum naphthalocyanine.
FIG. 51 is an electron spectrum of tetrakis (n-amyloxycarbonyl) silicon naphthalocyanine, FIG. 52 is an IR spectrum of tetrakis (n-amyloxycarbonyl) silicon naphthalocyanine, and FIG. 53 is Tetrakis (n-amyloxycarbonyl)
FIG. 54 is an electronic spectrum of germanium naphthalocyanine, and FIG. 54 shows tetrakis (n-amyloxycarbonyl).
It is an IR spectrum of germanium naphthalocyanine,
55 is an electronic spectrum of tetrakis (n-amyloxycarbonyl) tin naphthalocyanine, FIG. 56 is an IR spectrum of tetrakis (n-amyloxycarbonyl) tin naphthalocyanine, and FIG. 57 is dichlorogermanium-tetrakis ( FIG. 58 is an electronic spectrum of (n-amyloxycarbonyl) naphthalocyanine in a chloroform solution, and FIG. 58 shows IR of dichlorogermanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine.
FIG. 59 is an electronic spectrum of dihydroxygermanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine in a chloroform solution, and FIG. 60 is a spectrum of dihydroxygermanium-tetrakis (n-amyloxycarbonyl) na. FIG. 61 is an IR spectrum of phthalocyanine and FIG. 61 is an NMR spectrum of bis (triethylsiloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine.
The figure is an electronic spectrum of bis (triethylsiloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine in a chloroform solution.
The figure is an IR spectrum of bis (triethylsiloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine. FIG. 64 is an NMR spectrum of bis (tributylsiloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine,
Figure 65 shows bis (tributylsiloxy) germanium-
FIG. 66 is an electron spectrum of tetrakis (n-amyloxycarbonyl) naphthalocyanine in a tetrahydrofuran solution, and FIG. 66 is an IR spectrum of bis (tributylsiloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine. 67 is an electron spectrum of dichlorogermanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine in a chloroform solution, and FIG. 68 is an IR spectrum of dichlorogermanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine. FIG. 69 is an electronic spectrum of dihydroxygermanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine in a chloroform solution, and FIG. 70 is dihydroxygermanium-tetrakis (n-octyl). Roxycarbonyl) naphthalocyanine IR spectrum, FIG. 71 is an NMR spectrum of bis (triethylsiloxy) germanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine, and FIG. 72 is bis (triethylsiloxy) germanium. -Tetrakis (n-octyloxycarbonyl)
FIG. 73 is an electron spectrum of naphthalocyanine in a tetrahydrofuran solution, FIG. 73 is an IR spectrum of bis (triethylsiloxy) germanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine, and FIG.
The figure is an NMR spectrum of bis (tributylsiloxy) germanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine, and FIG. 75 is the tetrahydrofuran of bis (tributylsiloxy) germanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine. FIG. 76 shows an electronic spectrum in solution, and FIG. 76 shows bis (tributylsiloxy) germanium-tetrakis (n
-Octyloxycarbonyl) naphthalocyanine IR spectrum, FIG. 77 shows bis (n-dodecyloxy) germanium-tetrakis (n-amyloxycarbonyl)
FIG. 78 is an electron spectrum of naphthalocyanine in a chloroform solution, and FIG. 78 is an IR spectrum of bis (n-dodecyloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine. FIG. 79 is an electronic spectrum of bis (n-octadecyloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine in a tetrahydrofuran solution.
The figure shows an IR spectrum of bis (n-octadecyloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine, and FIG. 81 shows bis (n-dodecyloxy) germanium-tetrakis (n-octyloxycarbonyl). FIG. 82 is an electron spectrum of naphthalocyanine in a chloroform solution, and FIG. 82 is an IR spectrum of bis (n-dodecyloxy) germanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine.
FIG. 83 is an electron spectrum of bis (n-octadecyloxy) germanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine in a tetrahydrofuran solution, and FIG. 84 is bis (n-octadecyloxy) germanium- Tetrakis (n-octyloxycarbonyl)
FIG. 85 is an IR spectrum of naphthalocyanine, FIG. 85 is an electronic spectrum of bis (triethylsiloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine in a tetrahydrofuran solution, and FIG.
The figure shows an electronic spectrum of bis (triethylsiloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine in an acetone solution, and FIG. 87 shows bis (triethylsiloxy) germanium-tetrakis (n-amyloxycarbonyl). ) Is an electronic spectrum of naphthalocyanine in a benzene solution, and FIG. 88 shows
89 is an electronic spectrum of a solution of bis (n-dodecyloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine in tetrahydrofuran,
The figure is an electronic spectrum of bis (n-dodecyloxy) germanium-tetrakis (n-amyloxycarbonyl) naphthalocyanine in a benzene solution, and FIG. 90 is
Electron spectrum of tetra (t-butyl) vanadyl naphthalocyanine in chloroform solution, (a) shows 2.37 ×
The concentration is 10 ^-6 M, (b) is 1.89 × 10 ^-5 M concentration, and Fig. 91 shows the electron in the benzene solution of tetra (t-butyl) vanadyl naphthalocyanine (9.5 × 10 ^-6 M concentration). FIG. 92 is a transmission spectrum of a spin-coated film of bis (tributylsiloxy) germanium-tetrakis (n-octyloxycarbonyl) naphthalocyanine, and FIG. 93 is a spectrum of bis (tributylsiloxy) germanium-tetrakis ( FIG. 94 is a 5 ° specular reflection spectrum of a spin-coated film of n-octyloxycarbonyl) naphthalocyanine, and FIG. 94 is a transmission spectrum of a spin-coated film of tetra (t-butyl) vanadyl naphthalocyanine,
Fig. 95 is a 5 ° specular reflection spectrum of a spin coat film of tetra (t-butyl) vanadyl naphthalocyanine, and Fig. 96 is a transmission spectrum of a tetrakis (n-amyloxycarbonyl) vanadyl naphthalocyanine spin coat film. Is.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (31) Priority claim number Japanese Patent Application No. Sho 62-153959 (32) Priority date Sho 62 (1987) June 19 (33) Country of priority claim Japan (JP) (31) Priority right Claim number Japanese patent application Sho 62-201401 (32) Priority date Sho 62 (1987) August 12 (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese patent application Sho 62-258588 (32) Priority Nissho 62 (1987) October 14 (33) Priority claiming country Japan (JP) (72) Inventor Nobuyuki Hayashi 4-13-1 Higashimachi, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Ibaraki Research Institute (72 ) Inventor Yasushi Iwakabe 4026 Kuji Town, Hitachi City, Ibaraki Prefecture, Hitachi Research Laboratory, Hitachi Ltd. (72) Inventor Shunichi Numata 4026 Kuji Town, Hitachi City, Hitachi, Ibaraki Prefecture Hitachi Research Laboratory, Ltd. (72) Inventor Noriyuki Kaneshiro 4026 Kuji Town, Hitachi City, Ibaraki Prefecture Works Hitachi Research Laboratory (72) Inventor Susumu Era 4026 Kuji Town, Hitachi City, Ibaraki Prefecture Hitate Manufacturing Co., Ltd.Hitachi Research Laboratory (72) Inventor Setsuro Kobayashi 4026 Kuji Town, Hitachi City, Ibaraki Hitachi Research Co., Ltd. In-house (72) Inventor Akio Mukai 4026 Kuji-cho, Hitachi-shi, Ibaraki Prefecture Hitachi Research Laboratory, Hitachi, Ltd.

Claims (36)

[Claims] 1. A general formula (I) [Wherein R ¹ is an alkyl group having 1 to 22 carbon atoms, a plurality of R ¹ may be the same or different, and n may be the same or different 1 to 4 And M is a group IIb metal such as Cu, a group IIa metal such as Mg, a group IIb metal such as Zn, a group IIIa metal such as Al, ClAl, HOAl, In, ClIn, or a metal. Halides or metal hydroxides, Si, Cl ₂ Si, (HO) ₂
Si, Ge, Cl ₂ Ge, (HO) ₂ Ge, Sn, Cl ₂ Sn, (HO) ₂ Sn, Pb, etc.
Group IVa metal, metal halide or metal hydroxide, Group IVb metal or metal oxide such as Ti and OTi, Group Vb metal oxide such as OV, VIb such as Cr and Mo Group metals, Mn, C
Group VII b metals such as lMn or metal halides or F
Indicates one of group VIII metals such as e, ClFe, Co, Ni, Pt, and Pd, or metal halides. ] The naphthalocyanine derivative represented by these. 2. In the general formula (I), M is Cu, Zn, ClAl, C.
The naphthalocyanine derivative according to claim 1, which is lIn, Si, Ge, Sn, OV, Mn, Co, Ni or Pd. 3. The naphthalocyanine derivative according to claim 1, wherein in the general formula (I), n is 1. 4. In the general formula (I), R ¹ has 13 to 22 carbon atoms.
The naphthalocyanine derivative according to claim 1, 2 or 3, which is one alkyl group. 5. The general formula (II) [Wherein R ¹ is an alkyl group having 1 to 22 carbon atoms, a plurality of R ¹ may be the same or different, and n may be the same or different. It is an integer, and Y ₁ and Y ₂ may be the same or different, and are aryloxyl group, alkoxyl group, trialkylsiloxyl group, triarylsiloxyl group, trialkoxysiloxyl group, triaryloxysiloxyl group. Or a trityloxyl group, M is A
l, Ti, Si, Ge or Sn, and when M is Al, only Y ₁ is M
Is Ti, Si, Ge or Sn, Y ₁ and Y ₂ are covalently bonded to M]. 6. The naphthalocyanine derivative according to claim 5, wherein in the general formula (II), M is Ge. 7. The naphthalocyanine derivative according to claim 5, wherein n is 1 in the general formula (II). 8. The naphthalocyanine derivative according to claim 5, 6 or 7, wherein each of Y ₁ and Y ₂ in the general formula (II) is a trialkylsiloxyl group. 9. The naphthalocyanine derivative according to claim 5, 6 or 7, wherein Y ₁ and Y ₂ in the general formula (II) are both alkoxyl groups. 10. General formula (III) (Wherein R ¹ represents an alkyl group having 1 to 22 carbon atoms, and n is an integer of 1 to 4), and at least 1 of alkoxycarbonyl-2,3-dicyanonaphthalene
The species is represented by the general formula (IV-1) MXp (IV-1) (wherein X is a halogen atom or an acyloxyl group and p is 0 or a positive integer indicating the number of bonds of X to the metal M, and M is , Cu such as Ib group, Mg such as IIa group, Zn such as I
Group Ib, Group IIIa such as Al, In, IVa such as Si, Ge, Sn, Pb
Group, IV b group such as Ti, V b group such as V, VI b such as Cr, Mo
Group, VIIb group such as Mn or VIII such as Fe, Co, Ni, Pt, Pd
A metal represented by Group I) or a metal salt represented by the general formula (I) [Wherein R ¹ is an alkyl group having 1 to 22 carbon atoms, a plurality of R ¹ may be the same or different, and n may be the same or different 1 Is an integer of 4, M is a group Ib metal such as Cu, a group IIa metal such as Mg, or a group IIb such as Zn.
Group metals, Group IIIa metals such as Al, ClAl, HOAl, In, ClIn,
Metal halides or metal hydroxides, Si, Cl ₂ Si, (H
O) ₂ Si, Ge, Cl ₂ Ge, (HO) ₂ Ge, Sn, Cl ₂ Sn, (HO) ₂ Sn, Pb and other IVa group metals, metal halides or metal hydroxides, Ti , OTi or other IVb group metal or metal oxide, OV or other Vb group metal oxide, Cr, Mo or other VIb group metal, M
A group VII b metal or metal halide such as n or ClMn, or a group VIII metal or metal halide such as Fe, ClFe, Co, Ni, Pt, or Pd. ] The manufacturing method of the naphthalocyanine derivative represented by these. 11. In the general formula (IV-1), M is Cu, Zn,
Al, In, Si, Ge, Sn, V, Mn, Co, Ni or Pd, M in the general formula (I) is Cu, Zn, ClAl, ClIn, Si, Ge, S, respectively.
11. The method for producing a naphthalocyanine derivative according to claim 10, which is n, OV, Mn, Co, Ni or Pd. 12. The method for producing a naphthalocyanine derivative according to claim 10, wherein n is 1 in the general formulas (III) and (I). 13. A compound represented by the general formula (III) or (I) wherein R ¹ is an alkyl group having 13 to 22 carbon atoms.
Or the method for producing a naphthalocyanine derivative according to item 12. 14. General formula (III) (Wherein R ¹ represents an alkyl group having 1 to 22 carbon atoms, and n is an integer of 1 to 4), and at least 1 of alkoxycarbonyl-2,3-dicyanonaphthalene
The seed is represented by the general formula (IV-2) MXp (IV-2) (wherein X is a halogen atom and p is X to M).
Is a positive integer indicating the number of bonds of M, and M is Al, Ti, Si, Ge or S
(representing n) by reacting with a metal halide represented by the general formula (V) [Wherein R ¹ is an alkyl group having 1 to 22 carbon atoms, a plurality of R ¹ may be the same or different, and n is the same or different. Is an integer, M has the same meaning as in formula (IV-2), X ₁ and X ₂ represent a halogen atom, and when M is Al, only X ₁ is M, Ti, Si,
In the case of Ge or Sn, X ₁ and X ₂ are covalently bonded to M], and a compound represented by the general formula (V) is hydrolyzed to synthesize the naphthalocyanine derivative represented by the general formula (VI) [Wherein R ¹ is an alkyl group having 1 to 22 carbon atoms, a plurality of R ¹ may be the same or different, and n is the same or different. Is an integer, M has the same meaning as in formula (IV-2) above, Z ₁ and Z ₂ represent a hydroxyl group, and when M is Al, only Z ₁ and M are Ti, S
When i, Ge or Sn, Z ₁ and Z ₂ are covalently bonded to M]
A naphthalocyanine derivative represented by the following formula is obtained, and then the compound represented by the general formula (VI) is converted to the general formula (VII) (R ² ) ₃ SiOH (VII) [wherein R ² is an alkyl group or an aryl group. , An alkoxyl group or an aryloxyl group. Or a general formula (VIII) R ³ OH (VIII) [wherein R ³ is an alkyl group, an aryl group or a trityl group]. ] The general formula (II) characterized by reacting with an alcohol represented by [Wherein R ¹ is an alkyl group having 1 to 22 carbon atoms, a plurality of R ¹ may be the same or different, and n is the same or different. Is an integer, Y ₁ and Y ₂
May be the same or different, and is an aryloxyl group, an alkoxyl group, a trialkylsiloxyl group, a triarylsiloxyl group, a trialkoxysiloxyl group, a triaryloxysiloxyl group or a trityloxyl group, and M is , Al, Ti, Si, a Ge or Sn, when M is Al, only Y ₁ is M is Ti, Si, when the Ge or Sn Y ₁ and Y ₂ M
And a covalent bond] to the naphthalocyanine derivative. 15. The method for producing a naphthalocyanine derivative according to claim 14, wherein M in the general formulas (IV-2), (V), (VI) and (II) is Ge. 16. General formulas (III), (V), (VI) and (I)
16. The method for producing a naphthalocyanine derivative according to claim 14, wherein n is 1 in I). 17. The sodium group according to claim 14, 15 or 16, wherein R ² in the general formula (VII) is an alkyl group, and Y ₁ and Y ₂ in the general formula (II) are both trialkylsiloxyl groups. Process for producing phthalocyanine derivative. 18. The naphthalocyanine derivative according to claim 14, 15 or 16, wherein R ³ in the general formula (VIII) is an alkyl group, and Y ₁ and Y ₂ in the general formula (II) are both alkoxyl groups. Manufacturing method. 19. A substrate of the general formula (I) [Wherein R ¹ is an alkyl group having 1 to 22 carbon atoms, a plurality of R ¹ may be the same or different, and n is the same or different integer of 1 to 4] And M is a group Ib metal such as Cu, a group IIa metal such as Mg, a group IIb metal such as Zn, a group IIIa metal such as Al, ClAl, HOAl, In, ClIn, or a metal halogen. Or metal hydroxide, Si, Cl ₂ Si, (H
O) ₂ Si, Ge, Cl ₂ Ge, (HO) ₂ Ge, Sn, Cl ₂ Sn, (HO) ₂ Sn, Pb and other IVa group metals, metal halides or metal hydroxides, Ti , OTi or other IVb group metal or metal oxide, OV or other Vb group metal oxide, Cr, Mo or other VIb group metal, M
n, ClMn or other group VII b metal or metal halide or Fe, ClFe, Co, Ni, Pt, Pd or other group VIII metal or metal halide] An optical information recording medium having a recording film layer containing a derivative as a main component. 20. In the general formula (I), M is Cu, Zn, ClA.
20. The optical information recording medium according to claim 19, wherein a recording film layer containing a naphthalocyanine derivative which is l, ClIn, Si, Ge, Sn, OV, Mn, Co, Ni or Pd as a main component is formed. 21. The optical information recording medium according to claim 19 or 20, wherein a recording film layer containing a naphthalocyanine derivative in which n is 1 in the general formula (I) as a main component is formed. 22. In the general formula (I), R ¹ has 13 to 13 carbon atoms.
22. A recording film layer comprising a naphthalocyanine derivative which is 22 alkyl groups as a main component is formed.
The optical information recording medium described. 23. The compound of general formula (II) on the surface of a substrate. [Wherein R ¹ is an alkyl group having 1 to 22 carbon atoms, a plurality of R ¹ may be the same or different, and n is the same or different integer of 1 to 4] And Y ₁ and Y ₂ may be the same or different and each represents an aryloxyl group, an alkoxyl group, a trialkylsiloxyl group, a triarylsiloxyl group, a trialkoxysiloxyl group, a triaryloxysiloxyl group. Or a trityloxyl group, M is Al, Ti, Si, Ge or Sn, and when M is Al, Y
₁ only, when M is Ti, Si, Ge or Sn, Y ₁ and Y ₂ are covalently bonded to M], and a recording film layer containing a naphthalocyanine derivative as a main component is formed. An optical information recording medium characterized by: 24. The optical information recording medium according to claim 23, wherein in the general formula (II), a recording film layer whose main component is a naphthalocyanine derivative in which M is Ge is formed. 25. The optical information recording medium according to claim 23 or 24, wherein a recording film layer containing a naphthalocyanine derivative in which n is 1 in the general formula (II) as a main component is formed. 26. In the general formula (II), a recording film layer containing a naphthalocyanine derivative in which both Y ₁ and Y ₂ are trialkylsiloxyl groups as a main component is formed.
The optical information recording medium as described in 23, 24 or 25. 27. In the general formula (II), a recording film layer containing a naphthalocyanine derivative in which both Y ₁ and Y ₂ are alkoxyl groups as a main component is formed.
5. The optical information recording medium described in 5. 28. The general formula (I) [Wherein R ¹ is an alkyl group of 1 to 22 and a plurality of R ¹ may be the same or different, and n is an integer of 1 to 4 which may be the same or different. , M is I b such as Cu
Group metals, Group IIa metals such as Mg, Group IIb metals such as Zn, A
l, ClAl, HOAl, In, ClIn group IIIa metals, metal halides or metal hydroxides, Si, Cl ₂ Si, (HO) ₂ Si, Ge,
Cl ₂ Ge, (HO) ₂ Ge, Sn, Cl ₂ Sn, (HO) ₂ Sn, Pb and other group IVa metals, metal halides or metal hydroxides, Ti, O
Group IVb metals or metal oxides such as Ti, Vb group metal oxides such as OV, VIb group metals such as Cr and Mo, VIIb group metals or metal halides such as Mn and ClMn. Or Fe, ClFe, C
Forming a recording film layer on the surface of a substrate using a solution of a naphthalocyanine derivative represented by a group VIII metal such as o, Ni, Pt, or Pd or a halide of a metal] in an organic solvent A method for manufacturing an optical information recording medium, comprising: 29. In the general formula (I), M is Cu, Zn, ClA.
29. The method for producing an optical information recording medium according to claim 28, wherein a naphthalocyanine derivative which is 1, ClIn, Si, Ge, Sn, OV, Mn, Co, Ni or Pd is used. 30. The method for producing an optical information recording medium according to claim 28 or 29, wherein a naphthalocyanine derivative in which n is 1 in the general formula (I) is used. 31. In the general formula (I), R ¹ has 13 to 30 carbon atoms.
31. The method for producing an optical information recording medium according to claim 28, 29 or 30, wherein a naphthalocyanine derivative having 22 alkyl groups is used. 32. General formula (II) [Wherein R ¹ is an alkyl group having 1 to 22 carbon atoms, a plurality of R ¹ may be the same or different, and n is the same or different integer of 1 to 4] And Y ₁ and Y ₂ may be the same or different and each represents an aryloxyl group, an alkoxyl group, a trialkylsiloxyl group, a triarylsiloxyl group, a trialkoxysiloxyl group, a triaryloxysiloxyl group. Or a trityloxyl group, M is Al, Ti, Si, Ge or Sn, and when M is Al, Y
Only _1, M is Ti, Si, when the Ge or Sn is Y ₁ and Y ₂ are covalently bonded to M. ] A method for producing an optical information recording medium, characterized in that a recording film layer is formed on the surface of a substrate by using a solution in which a naphthalocyanine derivative represented by the following is mainly dissolved in an organic solvent. 33. The method for producing an optical information recording medium according to claim 32, wherein a naphthalocyanine derivative in which M is Ge in the general formula (II) is used. 34. The method for producing an optical information recording medium according to claim 32 or 33, wherein a naphthalocyanine derivative in which n is 1 in the general formula (II) is used. 35. The method for producing an optical information recording medium according to claim 32, 33 or 34, wherein a naphthalocyanine derivative in which Y ₁ and Y ₂ in the general formula (II) are both trialkylsiloxyl groups is used. . 36. The method for producing an optical information recording medium according to claim 32, 33 or 34, wherein a naphthalocyanine derivative in which both Y ₁ and Y ₂ in the general formula (II) are alkoxy groups is used.