JPH02663A - Naphthalocyanine derivative, its production, optical information recording medium produced by using same and production of the same medium - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] 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, compact discs and video discs.

It has been proposed to use semiconductor laser light for writing or reading in liquid crystal display devices, optical character readers, etc. and as a light source for electrophotography. For writing or reading using half-quadramid laser light, a material that can absorb semiconductor laser light, that is, near-infrared light, is essential.

Conventionally, cyanine dyes are well known as organic dyes that absorb near-infrared light, and metal complexes of oximes and thiols, and aminated quinone derivatives are also known as dyes that absorb near-infrared light. [Journal of the Society of Organic Synthetic Chemistry, 4]
Volume 3, page 334 (I985) 2 Journal of Color Materials Association, Volume 53,
197 pages (I980) 2 Color Materials Association Journal, Volume 58, 220
Page (I985)].

[Problem to be solved by the invention]

However, since cyanine dyes have extremely low fastness to light, their use must be subject to many restrictions. Furthermore, metal complexes of oximes and thiols also have the disadvantage that in certain media, the metal is desorbed from the complex and the ability to absorb near-infrared light is lost. Aminated quinone derivatives have extremely low ability to absorb near-infrared light.

On the other hand, naphthalocyanine derivatives have recently been known as materials that can overcome these problems, but conventional fil
Zhurnal 0bshchei Khimii
.

Vol. 39, p. 2554, 1969 Mo1.Cryst, Liq, Crys
t, Vol. 112, p. 345, 1984] is extremely difficult to purify because it is insoluble in organic solvents. Also,
Recently, the synthesis of naphthalocyanine derivatives soluble in organic solvents has been reported (JP-A-60-23451, JP-A-60-184565, JP-A-61-2156).
62, JP-A-61-215663), the absorption of these naphthalocyanine derivatives varies greatly depending on the type of solvent, concentration, temperature, etc. Not only is the ability to absorb semiconductor laser light extremely reduced, but the reflectance, which is important when using reflected light to read information recorded on an optical disc, is
There was a very low peak at 30 nm).

[Means to solve the problem]

The present invention is based on the general formula ([) Any IVb group metal or metal oxide, Vb group metal oxide such as Ov, Vb group metal such as Cr, Mo, Mn,
Group Vb metals or metal halides such as CQMn or Fe, CQFe, Co.

The present invention relates to a naphthalocyanine derivative represented by G, which is a type of group ① metal such as Ni, Pt, and Pd, or a metal halide.

The present invention also provides a compound of the general formula (II) [wherein R1 is an alkyl group having 1 to 22 carbon atoms, a plurality of R1's may be the same or different, and n is the same or different. M is an integer from 1 to 4 which may be
NB group metals such as AA.

Ha group metals such as CQAQ, HOAQ, In, CQIn, metal halides or metal hydroxides, Si, C
Q2Si, (HO)2Si, Ge.

CM□Ge, (HO)2G e , S n HCQzS
IVa group metals such as n r(HO)2Sn, Pb,
Metal halide or metal hydroxide, Ti, ○Ti
[However, in the formula, R1 is an alkyl group having 1 to 22 carbon atoms, multiple R1s may be the same or different, and n is 1 to 4, which may be the same or different. is an integer, and Y and Y2 may be the same or different and represent an aryloxyl group, an alkoxyl group, a trialkylsiloxyl group, a triarylsiloxyl group, a trialkoxysiloxyl group, a triaryloxysiloxyl group, or a trityl group. is an oxyl group, M is AQ, Ti, Si, Ge or Sn,
When M is AQ, only Y is used, and M is Ti and Si.

In the case of Ge or Sn, Y and Y2 are covalently bonded to M. This invention relates to a naphthalocyanine derivative represented by

It is a solute represented by the general formula (I) and the general formula (II), and not only can it be easily purified to improve its purity, but also has an extremely excellent ability to absorb semiconductor laser light.

Examples of the aromatic solvent include benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trimethylbenzene, and 1-talolonaphthalene.

Examples of the halogen-based solvents include methylene chloride, chloroform, carbon tetrachloride, trichloroethane, etc., and examples of the ether-based solvents include diethyl ether, dibutyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, Diethylene glycol monomethyl ether.

Examples include diethylene glycol dimethyl ether, ketone solvents include acetone, methyl ethyl ketone, methyl propyl ketone, cyclopentanone, cyclohexanone, acetone alcohol, etc., and saturated hydrocarbon solvents include pentane.

Hexane, heptane, octane, nonane, decane.

There are undecan etc.

In the general formulas (I) and (II), 1 to 2 of R1
An example of two alkyl groups is a methyl group.

Ethyl group, n-propyl group, 5ec-propyl group.

n-butyl group, 5ec-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, octadecyl group, eicosyl group, tocosyl group, etc. can be given.

In the above-formation (I), examples of M include C, Mg
, Zn, AQ, CQAQ, HOAQ.

In, CQIn, Sit CQ2Si, (HO)2Sl
lGe, CQ2Ge, (HO)2Ge, Sn, CQ2S
n.

(HO)2Sn, Pb, Ti, OTi+○V, Cr.

Mo, Mn, CQMn, Fe, CQFe, Go.

Examples include Ni, Pt, and Pd.

In the above-mentioned -formation (I1), as an example of M.

AQ, Ti, Sir Ge, Sn, etc. are mentioned, and examples of Y and Y2 include a phenoxyl group, tolyloxyl group, anitetradecyloxyl group, and hexadecyloxyl group as an aryloxyl group.

Ophtadecyloxyl group, Eiko''/A-order xyl group.

Tokomaki #xyl groups, etc.; trialkylsiloxyl groups include trimethylsiloxyl group, triethylsiloxyl group, tripropylsiloxyl group, tributylsiloxyl group, etc.; and triarylsiloxyl groups include,
There are triphenylsiloxyl groups, trianisylsiloxyl groups, tritolylsiloxyl groups, etc. Trialkoxysiloxyl groups include trimethoxysiloxyl groups, triethoxysiloxyl groups, tripropoxysiloxyl groups,
Examples of the triaryloxysiloxyl group include a tributoxysiloxyl group, and examples of the triaryloxysiloxyl group include a triphenoxysiloxyl group, a dorianisiloxysiloxyl group, and a tritolyloxysiloxyl group.

In the above-mentioned -formation (I), M is Cu or Zn.

CnAQ, CQ In, Si, Ge, Sn, ○■.

Preference is given to naphthalocyanine derivatives which are Mn, Co, Ni or Pd.

In the above-mentioned -formation (I), a naphthalocyanine derivative in which n is 1 is preferred.

In the -formation (I), R1 has 13 to 22 carbon atoms.
Naphthalocyanine derivatives having 2 alkyl groups are preferred.

In the above-mentioned -formation (II), a naphthalocyanine derivative 1 in which M is Ge is preferred.

In the above-mentioned -formation (II), a naphthalocyanine derivative in which n is 1 is preferred.

In the above-mentioned -formation (II), a naphthalocyanine derivative in which both Y and Y2 are trialkylsiloxyl groups is preferred.

In the above-mentioned -formation (II), a naphthalocyanine':/ derivative in which both Y□ and Y2 are alkoxyl groups is preferred.

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

(II-C, 6H33) to Oz COz (II-ct 6 H33) LCU2 (C2H5 le.

CO2 (II-C, o H21) [CO2(C21(S)]2 [C02 (C2H5).

CO2(II-C8H,7) COz (II-C5Hx x) CO2(II-(+4Hg) Also, The present invention is.

At least one alkoxycarbon-2,3-dicyanonaphthalene represented by the general formula (wherein R1 represents an alkyl group having 1 to 22 carbon atoms, and n is an integer of 1 to 4) Formula (TV-1)MXp
(IV-1) (However, in the formula, X is a halogen atom or an acyloxyl store, p is a positive integer indicating the number of bonds of rIa group, nb group such as Zn, AQ, I
In a group such as n, l such as Si, Ge, Sn, Pb
Va group, IVb group such as T, Vb group such as V, Cr.

■B group such as Mo, ■b group such as Mn, or Fe.

Group II metals such as Co, Ni, Pt, Pd, etc.)
The present invention relates to a method for producing a naphthalocyanine derivative represented by the formula (in which R', n and M have the same meanings as in general formula (I)).

The naphthalocyanine derivative represented by general formula (I) is
The alkoxy metal salt represented by the general formula (III) is 0
．． It can be obtained by heating reaction in the coexistence of 1 to 1 mo Q. In this case, the reaction temperature is 150-3
00'C is preferable, and the reaction time is preferably 30 minutes to 10 hours. For this purpose, the reaction may be carried out without a solvent or as a solvent such as urea, tetralin, quinoline, 1-chloronaphthalene, 1-bromonaphthalene, 1,2.3-
Preferably, trimethylbenzene, dichlorobenzene, trichlorobenzene and the like are used. Examples of the metal or metal salt include Mg, Zn, AQCQ, and InCJ.

5iCQ4. GeCQ4,5nCR2,PbCR2゜T
ic(I4, VCQ, CrCJ, MoCQ2゜M n
(○・C0CH,)2. FeCQ, , CoC11I2
゜N i CQ2. P t CQ2. PdCQ
There is a second prize.

Isolation and purification of naphthalocyanine derivatives from the reaction mixture: 1. Washing the reaction mixture with diluted hydrochloric acid, followed by water.

This can be carried out by thoroughly washing the naphthalocyanine with a poor solvent such as alcohol or acetone, and then concentrating and drying the soluble material in the halogenated solvent or aromatic solvent to collect the solid.

Alkoxycarbonyl-2 represented by general formula (m),
3-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 1 to 22 carbon atoms.
represents an integer of 4) and the formula (wherein R1 is a carbon number of 1 to 2)
(represents two alkyl groups, n represents an integer of 1 to 4)
The compound represented by the formula (XII) is reacted with fumaronitrile represented by the formula (XII) HCN \ / II (XII ) / \ NCR under heating to obtain alkoxycarbonyl-2,3 represented by the general formula (III).
-This is a radical for synthesizing dicyanonaphthalene.

The other is the general formula (X[) obtained by heating and irradiating the N-bromosuccinimide represented by the general formula (III) synthesized above (wherein R1 and n
represents the alkoxycarbonyl-2,3-dicyanonaphthalene represented by the general formula (X (represents an alkyl group having 1 to 22 carbon atoms) by heating to unreact with an alcohol represented by the general formula (■') (wherein R4 represents an alkyl group having 1 to 22 carbon atoms, and n is , an integer from 1 to 4)
-This is a radical for synthesizing dicyanonaphthalene.

Generally, the reaction between alkoxycarbonyl-0-xylene represented by the general formula (IX) and N-bromosuccinimide represented by the formula (X)
The reaction can be carried out by heating and refluxing 0.2 mo of -xylene (L) and 0.8 moQ of N-bromosuccinimide under irradiation with a high-pressure mercury lamp in a solvent inert to light irradiation for 4 to 12 hours. as a photoinitiator,
It is necessary to add peroxide, which is a radical generator.

Peroxides include benzoyl peroxide, octanoyl peroxide, cyclohexanone peroxide, imbutyryl peroxide,
Examples include 2,4-dichlorobenzoyl peroxide, methyl ethyl ketone peroxide, etc., and are usually used in an amount of 500 mg to 2 g per 500 ml of solvent. The solvent inert to light irradiation is appropriately selected from halogen solvents such as chloroform and carbon tetrachloride, and aromatic solvents such as benzene and clobenzene.

In addition, a compound represented by the following general formula (X[) and a compound represented by the formula (X
In the reaction with fumaronitrile represented by [l], fumaronitrile represented by formula (Xll) is reacted with 1 to 2 moQ of compound represented by general formula (X[).
The reaction temperature is preferably 70°C to 100°C, and the reaction time is preferably 5 to 10 hours. 7 The medium includes N,N-dimethylformamide, N,N-
Dimethylacetamide, dimethylsulfoxide, N, N
-Polar organic solvents such as diethylformamide and N,N-diethylacetamide are preferred.

Alkoxycarbonyl-0 represented by general formula (IX)
-Xylene can be produced by the route of the following formula (A).

(XN) (IX) (A) That is, hydroxycarbonyl-〇-xylene (in the formula, n represents an integer of 1 to 4) [Formula (Xlv)]
7/I/:l-/L/[R10H, (wherein R1 is an alkyl group having 1 to 22 carbon atoms] per 1 moQ is present in an amount of 1 moQ or more in the presence or absence of a solvent. Under the conditions, 25 to 50 mol% of hydroxycarbonyl-〇-xylene is coexisting with a Lewis acid as a catalyst, and by heating and dehydration, alkyoxycarbonyl-〇-xylene [general formula (mother)] can be obtained. Here, the above-mentioned solvents include benzene, toluene, xylene, and chlorobenzene.

Dichlorobenzene, trimethylbenzene, 1-chloronaphthalene, etc. are preferable, and as a catalyst, sulfuric acid, p-1-
Luenesulfonic acid, benzenesulfonic acid, etc. are preferred;
The reaction temperature is preferably 80 to 240°C, and the reaction time is preferably 1 to 10 hours.

A certain general formula (■) (in the formula, R1 has 1 to 22 carbon atoms)
1 mo +2 alkoxycarbonyl-2,3-dicyanonaphthalene represented by (n represents an integer of 1 to 4) an alcohol represented by general formula (XI) 1 mo Q or more, In the presence or absence of a solvent, a Lewis acid as a catalyst is allowed to coexist with the starting material alkoxycarbonyl 2,3-dicyanonaphthalene in an amount equal to or more than the same mole, and by heating and refluxing the transesterification reaction, another alkoxy carbonyl-2,
3-dicyanonaphthalene can be obtained. here,
As the above-mentioned solvent, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trimethylbenzene, 1-chloronaphthalene, etc. are preferable, and as the catalyst,
Sulfuric acid, P-toluenesulfonic acid, benzenesulfonic acid, etc. are preferred, the reaction temperature is preferably in the range of 80 to 240°C, and the reaction time is preferably about 1 to 50 hours.

General formula (■) (However, in the formula, R1 has a carbon number of 1 to 22 gA
Isolation and purification of alkoxycarbonyl-2,3-dicyanonaphthalene represented by (representing an alkyl group) from a reaction mixture can be performed by a recrystallization method, a column chromatography method, etc. after extracting the reaction mixture with chloroform. .

In the general formula (rV-1), M is Cu.

Zn, A(I, In, Si, Ge, Sn, V, Mn.

Co, Ni or Pd, and in the general formula (I), each M is Cu + Z n + CQ A Q+ CQ
I n + A method for producing a naphthalocyanine derivative in which n is 1 in the general formula (III) and general formula (I) is preferred.

In the general formula (I) and general formula (I), (wherein R1 represents an alkyl group having 1 to 22 carbon atoms, n
is an integer of 1 to 4) is an alkoxycarbonyl-2,3-dicyanonaphthalene represented by the general formula (IV-2
) M X p (rV-2) (where, in the formula,
Ge or Sn) is reacted with a metal halide represented by the general formula (III) [wherein R1 is an alkyl group having 1 to 22 carbon atoms, Multiple R1's are the same but have different tastes, and X
, and X2 represent a halogen atom, and when M is AQ(7), only x□ is present, and M is Ti or Si.

When Ge or Sn, xl and X2 are covalently bonded to M].
Next, the compound represented by general formula (V) may be hydrolyzed to form general formula (VI), where n is an integer from 1 to λ4, which may be the same or different, and M is an integer of 1 to λ4, which may be the same or different. It has the same meaning as the above general formula (IV-shi), Z and Z2 represent a hydroxyl group, and M
When is AQ, only Z work or M is Ti.

In the case of Si, Ge or Sn, Z2 and Z2 are covalently bonded to M], and then a compound represented by this general formula (Vl) is converted into a compound represented by the general formula (■) (R2 ) 3 SiOH (■) [However, in formula 1, R2 is an alkyl group or an aryl group.

It is an alkoxyl group or an aryloxyl group. ] Silanol or general formula (■) R30H (■) [wherein R3 is an alkyl group, an aryl group, or a trityl group. [However, in the formula, R1 is carbon S! 11 to 22 alkyl groups, and a plurality of R1s may be the same or different [wherein Ri+n+YlrI2 and M have the same meanings as in the above general formula (II)]; This invention relates to a method for producing phthalocyanine derivatives.

The naphthalocyanine derivative represented by the general formula (IT) can be obtained by heating the compound represented by the general formula (VI) and a large excess of the silanol represented by the general formula (■) or the alcohol represented by the general formula (■). It can be obtained by dehydration reaction. In this case, the reaction temperature is 80-2
50'C is preferable, and the reaction time is preferably 30 minutes to 10 hours. This reaction can be carried out without a solvent or with benzene, toluene, xylene, trimethylbenzene, chlorobenzene, or dichlorobenzene as a solvent.

Preference is given to using tritalolobenzene, 1-talolonaphthalene, te-1-larin, quinoline, and the like.

A single chick of the naphthalocyanine derivative represented by the general formula (H) can be purified from a reaction mixture by separating the reaction mixture into layers by column chromatography or thin layer talomadography, and then purifying it by recrystallization. This can be done by the following method.

The naphthalocyanine derivative represented by the general formula (VI) can be obtained by subjecting the compound represented by the general formula (V) to a hydrolysis reaction with heating. In this case 1
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, propatool/ammonia water, or the like.

The naphthalocyanine derivative represented by general formula (V) is
Alkoxycarbonyl represented by general formula (III)
General formula (I
0.25 to 1 of the metal halide represented by V-2)
It can be obtained by coexisting in a molar ratio and reacting under heating. In this case, the reaction temperature is preferably 150 to 300°C, and the reaction time is preferably 30 minutes to 5 hours. For this, you can react without a solvent or use urea as a solvent.

Tetralin, quinoline, 1-chloronaphthalene, 1-bromonaphthalene, 1,2,4-trimethylbenzene, 1
, 2,3-trimethylbenzene, dichlorobenzene, trichlorobenzene and the like are preferably used. The metal halides include AQCQs, TiC114,5
iCQ4. GeCQ+.

GeBr4. There are GeI4,5nCQz, SnI2, etc.

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

In the general formulas (TV-2), (V), (VI) and (II), a method for producing naphthalocyanine derivatives in which M is Ge is preferred.

In the general formulas (IIT), (V), (Vl) and (II), a method for producing a naphthalocyanine derivative in which n is 1 is preferred.

In the general formula (■), R2 is an alkyl group,
A method for producing a naphthalocyanine derivative in which Yl and I2 are both trialkylsiloxyl groups in general formula (II) is preferred.

In the general formula (VII), R3 is an alkyl group, and in the general formula (IT), Yt and I2 are both alkoxyl groups. A method for producing a naphthalocyanine derivative is preferred.

The present invention also provides a naphthalocyanine:yI derivative main component represented by the following general formula (T) [wherein R', n, and M have the same meanings as in the above-mentioned -formation (I)] on the substrate surface. The present invention relates to an optical information recording medium characterized in that a recording film layer is formed thereon.

The present invention also provides a record containing a naphthalocyanine derivative represented by -formation (II) [wherein R1, n, Yl, Y2 and M have the same meaning as the above-mentioned -formation (II)] as a main component. The present invention relates to an optical information recording medium characterized in that a film layer is formed.

The 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 the optical information recording medium according to another present invention The optical information recording medium is one in which a recording layer mainly composed of a naphthalocyanine derivative represented by the general formula (II) of the present invention is provided on a substrate. Other layers such as can be provided.

Moreover, the naphthalocyanine derivatives represented by -formation (I) and -formation (II) can be used together.

The substrate materials used are those known to those skilled in the art;
It may be transparent or opaque to the laser light used. However, when writing and reading are performed using 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, from the 8M side, it is not necessary to be transparent to the laser beam used. Substrate materials include inorganic materials such as glass, quartz, mica, ceramics, metal plates or foils, as well as paper, polycarbonate, polyester, cellulose acetate, nitrocellulose, polyethylene, and polypropylene.

Examples include, but are not limited to, plates of organic polymeric materials such as polyvinyl chloride, vinylidene chloride copolymer, polyamide, polystyrene, polymethyl methacrylate, and methyl methacrylate copolymer. In order to reduce heat loss during recording and increase sensitivity, a support made of an organic polymer with low thermal conductivity is preferable, and the substrate may be provided with guide grooves formed of unevenness, if necessary.

Further, a base film may be provided on the substrate as necessary.

In the above-mentioned - formation ([), M is Cu or Zn.

CD, AQ, CQIn, Si, Ge, Sn, ○V.

Preferably, an optical information recording medium is provided with a recording film layer containing a naphthalocyanine derivative such as Mn, Co, Ni, or Pd as a main component.

In the above-mentioned formation (I), an optical information recording medium is preferably formed, in which a film layer as described above is formed, the main component being a naphthalocyanine derivative in which n is 1.

In the above-mentioned -formation (I), an optical information recording medium is preferably formed with a recording film layer mainly composed of a naphthalocyanine derivative in which R1 is an alkyl group having 13 to 22 carbon atoms.

In the above-mentioned formation (II), an optical information recording medium is preferably formed with a recording film layer mainly composed of a naphthalocyanine derivative in which M is Ge.

In formation (II), an optical information recording medium on which a recording film layer mainly composed of a naphthalocyanine derivative in which n is 1 is preferable.

In the above-mentioned -formation (II), an optical information recording medium is preferably formed with a recording film layer mainly composed of a naphthalocyanine derivative in which both Y□ and Y2 are trialkylsiloxyl groups.

In the above-mentioned -formation (II), an optical information recording medium is preferably formed with a recording film layer mainly composed of a naphthalocyanine derivative in which both Y and Y2 are alkoxyl groups.

Further, the present invention provides a method for dissolving naphthalocyanine derivatives represented by -formation (I) in the following blanks [wherein R□, n and M have the same meanings as in -formation (I)] mainly in an organic solvent. The present invention relates to a method for manufacturing an optical information recording medium, which comprises forming a recording film layer on the surface of a substrate using a solution prepared by the above method.

Furthermore, the present invention provides a method for using a naphthalocyanine derivative represented by -formation (■) [wherein R1, n, Y□, Y2 and M have the same meaning as in the above-mentioned -formation (II)] mainly in an organic solvent. The present invention relates to a method of manufacturing an optical information recording medium, which comprises forming a recording film layer on the surface of a substrate using a dissolved solution.

The above-mentioned organic solvents include -formation (I) and -formation (II).
) The above-mentioned aromatic type, halogen type, and ether type which dissolve the naphthalocyanine derivative represented by.

The solvent may be selected from ketone-based solvents, saturated hydrocarbon-based solvents, etc., and may be a single solvent or a mixture of solvents. However, it is preferable to use a solvent that does not soak the substrate used.

A method for forming a recording film layer using a solution in which a naphthalocyanine derivative represented by general formula (I) and/or (II) is dissolved in an organic solvent is a coating method.

There are printing methods and dipping methods. Specifically, the dye is dissolved in the above solvent, sprayed, and roller coated.

Performed by spin coating and dipping. Incidentally, at the time of forming the recording medium, a binder such as a polymer binder, a stabilizer, etc. may be added as necessary. Examples of the binder include, but are not limited to, polyimide resin, polyamide resin, polystyrene resin, acrylic resin, and the like.

The recording layer materials may be used alone or in combination of two or more types, and in the case of a combination of two or more types, a laminated structure or a mixed single layer structure may be used. The thickness of the recording layer is 5
The range of 0 to 10,000 people is preferable, especially 100 to 50 people.
A range of 00 people is preferred.

Further, when optically reproducing the formed B image, reflected light is often used. In this case, as an effective method to increase the contrast, if writing and reading are performed from the substrate side, it is possible to provide a metal layer with high reflectance on the surface of the 9th layer on the opposite side of the substrate. When writing and reading are performed from the recording layer side, a metal layer exhibiting high reflectance may be provided between the substrate and the recording layer. AQ is a metal with this high reflectance.

Cr, Au, Pt, 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 1.
Selected from 00 to 10,000 people.

However, among the naphthalocyanine derivatives, formation (II
The naphthalocyanine derivative represented by ) itself has a high reflectance, and there is no need to provide a metal reflective layer.

Further, when the surface smoothness of the substrate itself is a problem, it is preferable to provide a uniform film of an organic polymer on the substrate. These polymers include polyester.

Commercially available polymers such as polyvinyl chloride are applicable.

Furthermore, a protective layer may be provided as the outermost layer to increase stability and protection, and a layer may also be provided for the purpose of increasing sensitivity by reducing surface reflectance. This kind of protection
Materials used for f1Jffi include polyvinylidene chloride, polyvinyl chloride, vinylidene chloride and acrylonitrile copolymer, polyvinyl acetate, polyimide, polymethyl methacrylate, polystyrene, polyisoprene,
Examples include polybutadiene, polyurethane, polyvinyl butyral, fluororubber, polyester, epoxy resin, silicone resin, and cellulose acetate. These may be used alone or as a blend. It is preferable to include silicone oil, an antistatic agent, a non-linking agent, etc. in the protective layer from the viewpoint of strengthening the film performance.

Moreover, the protective layer can also be stacked in two layers. The above-mentioned material for the protective layer can be applied by dissolving it in an appropriate solvent or by laminating it as a backing film. The thickness of such a protective layer is 0.1 to 10. It is provided at a thickness of cLm, preferably 0.1 to 2 μm.

In the general formula (I), M is Cu or Zn.

CQAQ, CQIn, Si, Ge, Sn, OV.

A method for producing an optical information recording medium using a naphthalocyanine derivative such as M n I Co , N x or Pd is preferred.

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

A method for producing an optical information recording medium using a naphthalocyanine derivative in which R1 is an alkyl group having 13 to 22 carbon atoms in the general formula (I) is preferred.

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

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

A method for producing an optical information recording medium using a naphthalocyanine derivative in which Yl and Y2 are both trialkylsiloxyl groups in the general formula (II) is preferred.

A method for producing an optical information recording medium using a naphthalocyanine derivative in which Yl and Y2 are both alkoxyl groups in the general formula (II) is preferred.

〔Example〕

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these in any way.

Synthesis Example 1 [Synthesis of methyl 3,4-dimethylbenzoate] 47.6 g of 3,4-dimethylbenzoic acid (0,317moQ,
) was added to 200 mQ of methanol, and the mixture was refluxed for about 4 hours in the presence of about 6 mQ of 1 sulfuric acid while being dehydrated using Molecular Sieves 3A (desiccant manufactured by Wako Pharmaceutical Industries, Ltd.). After cooling, about 600 mQ of water was added and extracted three times using about 200 mQ of benzene.

The benzene solution was diluted with saturated aqueous sodium bicarbonate solution three times.
Subsequently, after washing three times with water, anhydrous sodium sulfate was added to dry. After concentrating the benzene solution, distillation under reduced pressure yields a boiling point of 133-134°C/49.4 at 30 n+mHg.
g of a colorless liquid was obtained. From the analysis results below, it was confirmed that this liquid was methyl 3,4-dimethylbenzoate.

(I) Elemental analysis value: CH Calculated value (%) 73.15 7.37 Actual value (%
) 73.13 7.46 (2) Nuclear magnetic resonance (NM
R) Spectral value: CDCQ3 solvent δ value 7.81 (LH, b r-s) 7.76 (
IH, dd, J = 7.93゜1, 53 Hz) 7.18 (LH, d, J = 7.93 Hz) 3, 8
9 (3I-!, s)2.30 (6H,
5) (3) The infrared absorption (IR) spectrum (coating method) is shown in FIG. It has an absorption attributable to the C═O stretching vibration of the ester near about 1710<-1>.

Synthesis Example 2 [Synthesis of 6-medoxycarbonyl-2,3-dicyanonaphthalene] 33.8 g of methyl 3.4-dimethylbenzoate (0,
2mo(I) and N-bromosuccinimide 1-42.
1 g of benzoyl peroxide was added to a solution of 4 g (0.8 moQ) of carbon tetrachloride in 500 mQ, and the mixture was irradiated with light using a high-pressure mercury lamp (I00W) for 8 to 12 hours while refluxing in an internal irradiation tube. After cooling, remove the precipitated white crystals by suction filtration.
5. Add carbon tetrachloride solution of mother liquor under reduced pressure. ′! Shrunk. The obtained solid was recrystallized from hexane/methylene chloride to obtain 79 g of methyl 3°4-bis(dibromomethyl)benzoate as colorless crystals. 3,4-bis(dibromomethyl)
The physical properties of methyl benzoate were as shown below.

(I) Melting point 99.5-100.5°C (2) Elemental analysis value: HBr (3) NMR spectrum value: CDCQ, solvent δ 8.2
9 (LH, b r-s) 8.03 (IH, dd, J=8.24°1.53Hz
) 7.81 (LH, d, J=8.24Hz) 7.18
(LH,br-s) 7.09 (LH,br-s) 3.96 (3H,5) (4) The IR spectrum (KBr method) is shown in FIG.

It has an absorption attributable to the C=◯ stretching vibration of the ester near about 1705c+n-1.

Next, 48 g (0,1 mof2) of the obtained methyl 3,4-bis(dibromomethyl)benzoate and 13.5 g (0,173 moQ) of fumaronitrile were combined with anhydrous N,N-
Add 100 g (0.67 moQ) of sodium iodide to a 400 mΩ solution of dimethylformamide while stirring well.
was added and stirred at about 75°C for about 7 hours under a nitrogen atmosphere. After the reaction, the contents were poured into approximately 2 kg of ice. Sodium hydrogen sulfite was gradually added until the reddish-brown aqueous solution turned pale yellow, a slight excess amount of sodium hydrogen sulfite was added, and after stirring for a while, the mixture was allowed to stand overnight at room temperature.

The precipitated pale yellow solid was suction filtered and thoroughly washed with water and then with methanol. Recrystallization of the pale yellow solid from acetone/methanol yielded 13.9 g of colorless needles. This crystal was confirmed to be 6-medoxycarbonyl-2,3-dicyanonaphthalene from the following analysis results.

(I)￥! 2 points A 64-265 °C) Elemental analysis value HN (3) NMR spectrum value: CDCQ3 solvent δ value 8
．． 72 (IH, br-s) 8.47 (LH, s) 8.41 (LH, s) 8.38 (LH, dd, J=8.55°1.53Hz
) 8.06 (IH, d, J=8.55Hz) 4,04
(3H,s) (4) The IR spectrum (KBr method) is shown in FIG.

It has an absorption attributable to the C=0 stretching vibration of ester near about 1700 rho1.

Synthesis Example 3 [Synthesis of n-amyl 3,4-dimethylbenzoate] 3.4
- 60 g (0.4 moQ) of dimethylbenzoic acid.

n-amyl alcohol 43mQ (0.4moQ).

p-Toluenesulfonic acid superhydrate 22 g (0,1
16moQ) was added to 150mQ of benzene, and the mixture was refluxed for about 6 hours while dehydrating with Dean-Stark and then with Molecular Sieves 3A. After cooling, the reaction mixture was washed three times with 100 mQ of a saturated aqueous sodium bicarbonate solution, and then three times with water. The benzene solution of the reaction mixture was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. When the oil is distilled under reduced pressure, the temperature is 145-148°C/8 nyn Hg.
77 g of colorless liquid was obtained. From the analysis results below, it was confirmed that this liquid was n-amyl 3,4-dimethylbenzoate.

(I) Elemental analysis value: CH Calculated value (%) 76.33 9.15 Actual value (%
) 76.22 9.25 (2) NMR spectrum value: CDCQ, solvent δ value 7.81 (LH,br
-s) 7.77 (LH, dd, J=7.94゜1, 98
Hz) 7 r l 8 (I H, 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) I
The R spectrum (-1i cloth method) is shown in FIG.

Approximately 1.71. There is an absorption near Oc+n'' due to the C=O stretching vibration of the ester.

Synthesis Example 4 (Synthesis of 6-(II-amyloxycarbonyldicyanonaphthalene)) n-amyl 3,.1-dimethylbenzoate 44.IFC
(0.2 moQ) and N-bromosuccinimide 1
4 2,4 g (0.8 moQ.) of carbon tetrachloride 50
1 g of benzoyl peroxide was added to the 0 mQ solution, and the mixture was thoroughly concentrated under reduced pressure with a high-pressure mercury lamp (I00) for 11 hours under reflux in an internal irradiation tube.
, N-dimethylformamide 800m Q. Dissolve in
Fumaronitrile 27g (0.346mol1) Next, while stirring well, sodium iodide 200g
(I.34mofl) at 75° under nitrogen atmosphere.
The mixture was stirred at C for about 7 hours. After the reaction, the contents were poured into about 4 scoops of ice, and sodium bisulfite was gradually added until the red and colored aqueous solution turned pale yellow. After adding a slight excess of hydrogen sulfite and 1 helium, the mixture was stirred for a while. ,
The apparatus was kept overnight at room temperature. The precipitated pale yellow solid was suction-filtered, thoroughly washed with water, and then washed several times with methanol. The pale yellow solid was dissolved in about 500 mQ of chloroform, the chloroform layer was separated from the aqueous layer, and then dried over anhydrous magnesium sulfate. The chloroform solution was condensed 1, □'l under reduced pressure and then recrystallized twice from chloroform/ethanol to obtain 20 g of colorless needle-like crystals. From the analysis results below, this crystal is 6-(II-amyloxycarbonyl)
It was confirmed that it was -2.3-dicyanonaphthalene.

(I) FA point 150-152°C (2) Elemental analysis value: HN (3) NMR spectrum value: CDC13 solvent δ value 8.
70 (LH, br-s) 8, 49 (LH, s) 8, 41 (LH, s) 8, 38 (LH, dd, J=8.55.

1, 5 3 Hz) 8, 06 (LH, d, J = 8.55 Hz) 4, 43
(2H, t, J=6.72Hz) 1, 84 (2H,
quintet, J:=6.72Hz) 1, 44 (L
H, m) 0,96 (3H, t, J = 6.72Hz) (4)
Fig. 5 shows the mechanical R spectrum (KBr method).

It has an absorption attributable to the C=◯ stretching vibration of ester near about 1700 rho1.

Synthesis Example 5 [Synthesis of 3,4-dimethylbenzoyl mn-octyl] 3,
4-dimethylbenzoic acid 40 g (0.27 moQ).

n-octatool 100mQ (0.635+noQ)
.

p-Toluenesulfonic acid monohydrate 22 g (0.
+16 mob) was added to 100 mQ of benzene and allowed to flow for about 6 hours'a while dehydrating with Dean-Stark followed by Molecular Sieves 3A. After cooling, the reaction mixture was treated in the same manner as in Synthesis Example 3 and distilled under reduced pressure, resulting in a boiling point of 148
60.5 g of colorless liquid was obtained at −152° C./3 nrn HK. From the analysis results below, this liquid is 3,4
- It was confirmed that it was n-octyl dimethylbenzoate.

(I) Elemental analysis value: C H Calculated value (%) 77, 82 9.99 Actual value [%) 77, 21 10.07 (2) N M
R spectrum value: CDCQ. Solvent δ value 7.8 1
(LH, b r-s) 7, 77 (LH, dd, J=
7.63.

1,83Hz) 7,19 (LH, d, J=7.63Hz) 4.29
(2H, t, J=6.72Hz) 2.31 (6H
,s) 1,76 (2H, quintet, J =6.
72Hz) 1, 1~1, 5 (I0H, m)
0, 88 (3H, t, J = 6, 72
Hz) (3) The R spectrum (coating method) is shown in FIG.

It has an absorption attributable to the C=◯ stretching vibration of the ester near the 1710 mark -1.

Synthesis Example 6 (6-(II-octyloxycarbonyl)-2,3-
Synthesis of dicyanonaphthalene] 52.5 g of n-octyl 3.4-dimethylbenzoate (
Q, 2 moQ) and N-bromosuccinimide 142
．． 1 g of benzoyl peroxide was added to a solution of 4 g (0.8 moff) of carbon tetrachloride in 500 mQ, and the mixture was irradiated with light using a high-pressure mercury lamp (I00W) for about 11 hours while refluxing in an internal irradiation tube. After cooling, the reaction mixture was treated in the same manner as in Synthesis Example 4, reacted with fumaronitrile, and then recrystallized several times from chloroform/ethanol to obtain about 7 g of colorless needle crystals. From the analysis results below, this crystal is 6-(II-octyloxycarbonyl)-2,3
- Confirmed to be dicyanonaphthalene.

(I) Melting point 142-144°C (2) Elemental analysis value: CHN (3) NMR spectrum value 20 DCQ3 solvent δ value 8.
70 (LH,br-s)8,49 (LH,s
) 8.42 (LH, s) 8.38 (LH, dd, J=8.55゜1, 52
Hz) 8.06 (LH, d, J=8.55Hz) 4.42
(2H, t, J=6.72Hz) 1 , 83 (2H,
quintet, J = 6.72Hz) 1.2~1
．． 6 (I0H, m) 0.89 (3H, t, J=6.72Hz) (4) IR
The spectrum (KBr method) is shown in FIG.

It has an absorption attributable to the C=O stretching vibration of the ester near about 1700a++-1.

Synthesis Example 7 (6-(II-octadecyloxycarbonyl)-2゜3
-Synthesis of dicyanonaphthalene] 3.14 g of 6-medoxycarbonyl-2,3-dicyanonaphthalene (I3,3mo12) and 3.6 g of 1-octadecanol (I3,3moQ) were added to 40 m of benzene.
12, 2.2 g of P-toluenesulfonic acid monohydrate
(I1,6mmoQ), molecular sieves 3
The mixture was refluxed for about 6 hours while dehydrating and removing methanol using A. After cooling, about 150 mQ of chloroform was added, and the chloroform solution was washed three times with a saturated aqueous sodium bicarbonate solution and three times with water, and dried over anhydrous sodium sulfate. After concentrating the chloroform solution, it was purified by silica gel column chromatography using benzene as a developing solvent. The obtained colorless solid was recrystallized from ethanol/chloroform to obtain 0.68 g of colorless needle crystals. From the analysis results below, it was confirmed that the colorless needle crystals were 6-(II-octadecyloxycarbonyl)-2°-dicyanonaphthalene.

(I) Melting point 139-140°C (2) Elemental analysis value: CHN Calculated value (%) 78.44 8.92 5.90 Actual value (
%) 78.52 9.05 5.87(3)NM
R spectrum value: CDC1, solvent δ value 8.71 (I
H, br-s) 8.49 (LH, s) 8.42 (LH, s) 8.38 (LH, dd, J=8.55゜1, 53
Hz) 8.06 (LH, d, J=8.55Hz) 4.42
(2H, t, J = 6.72Hz) 1, 83 (2
H, quintet, J = 6.72Hz) 1.2
5 (30H, br-s) 0.88 (3H, t, J=6.72Hz) (4) IR
The spectrum (KBr method) is shown in FIG.

It has an absorption attributable to the C=◯ stretching vibration effect of the ester near about 1700 cm-'.

Synthesis Example 8 (6-(II-tetradecyloxycarbonyl)-2゜3
-Synthesis of dicyanonaphthalene] 6-medoxycarbonyl-2,3-dicyanonaphthalene 236 mg (ImmoQ), 1-tetradecanol 1
0.7 g (50 mmoQ) in 100 mQ of benzene in the presence of 1.94 g (I0,2 mmoQ) of p-toluenesulfonic acid, monohydrate, while dehydrating and removing methanol with molecular sieve 43A, about 12 Refluxed for an hour. After cooling, benzene was distilled off, and toluene/chloroform (volume ratio 1:1 solvent) was used as a developing solvent.
Purified by silica gel column chromatography.

Furthermore, 103 mg of A color crystals were obtained by recrystallization from acetone/methanol. the below described? From the analysis results, it was confirmed that the % colored crystals were 6-(II-tetradecyloxycarbonylphthalene).

(I) Melting point 142-14 2.5°C (2) Elemental analysis value: C HN Calculated value (%) 77, 48 8.19 6.6
9δ value 8.68 (LH, b r-s) 8, 47
(LH, s) 8, 3 9 (I H, s) 8, 36
(LH, dd, J=8.55.

1, 5 2 Hz) 8, 04 (LH, d, J=8.85Hz) 4, 40
(2H, t, J=6.71Hz) 1, 8 1
(2H, quintet, J = 6.71H
z ) 1, 25 (22H, b r-s) 0, 87 (3H, t, J=6.71Hz) (4) I
The R spectrum (KBr method) is shown in FIG.

It has an absorption attributable to the C=◯ stretching vibration of the ester near about 1710an-1.

Synthesis Example 9 (6-(II-hexadecyloxycarbonyl)-2
.

Synthesis of 3-dicyanonaphthalene] 236 mg of 6-methoxycarbonyl-2,3-dicyanonaphthalene (Immof2) and 12.1 g of 1-hexadecanol (50 mmoQ) were added to 100 mQ of benzene.
The mixture was refluxed for about 12 hours in the presence of 1.94 sg (I 0.2 mmoQ) of p-toluenesulfonic acid monohydrate while dehydrating and removing methanol with Molecular Sea 3A. After cooling, benzene #- and - were distilled off, and the mixture was purified by silica gel column chromatography using toluene/chloroform (solvent with a volume ratio of 1:1) as a developing solvent. Furthermore, 247 semg of Z color crystals were obtained by recrystallizing from acetone/methanol. From the analysis results below, this light-colored crystal is 6
It was confirmed that it was -(II-hexadecyloxycarbonyl)-2,3-dicyanonaphthalene.

(I) Melting point 141-142°C (2) Elemental analysis value: C HN Calculated value (%) 77, 99 8.58 6.2
7(3) NMR value: CDCQ3 solvent δ value 8.69 (LH, br-s) 8,47 (
LH, s) 8, 3 9 (LH, s) 8, 37
(LH, dd, J=8.55.

1,53Hz) 8,04 (IH, d, J =
8, 5 5 Hz) 4,, 41 (2H,
t. , J=6.72Hz) 1, 8 1 (2H, qu
intet, 6.7 2) (z) 1, 25 (26H
, b r-s) 0, 8 7 (3H, t, J=6.72Hz) (4)
The IR spectrum (KBr method) is shown in FIG.

It has an absorption attributable to the C=◯ stretching vibration of the ester near about 1710 an-'.

Synthesis example 10 (6-(II-eicosyloxycarbonyl)-2.

Synthesis of 3-dicyanonaphthalene] 6-medoxycarbonyl-2,3-dicyanonaphthalene 236 mg (ImmoQ), 1-eicosanol 1
5.6 g (50 mmoQ) in 100 mQ of benzene, 1.94 g of p-toluenesulfonic acid monohydrate (
IQ, 2mmoQ), molecular sieve, 3A
The mixture was refluxed for about 28 hours while dehydrating and removing methanol.

After cooling, benzene was distilled off, and I! 11 was made. Furthermore, 166 mg of bright colored crystals were obtained by recrystallizing from acetone/methanol or a spoon. From the analysis results below, this capsular crystal is 6-(II-
It was confirmed that it was eicosyloxycarbonyl)-2,3-dicyanonaphthalene.

(I) Melting point 138-138.5°C (2) Elemental analysis value: CHN Calculated value (%) 7g, 84 9.22 5.57 (
3) NMR value: CDCQ3 solvent δ value 8, 70 (L H, br -s) 8,
48 (L H, s) 8.41 (IH, s) 8.38 (LH, dd, J=8.85°1.52H
z) 8.05 (LH, d, J=8.85Hz) 4.42
(2H, t, J = 6.71Hz) 1, 83
(2H, quintet, J = 6.71Hz) 1
．． 25 (34H, b r-s) 0.88 (3H, t, J = 6.71Hz) (4)
The IR spectrum (KBr method) is shown in FIG.

It has an absorption attributable to the C=◯ stretching vibration of the ester near about 1710 an-'.

Synthesis Example 11 [6-(II-tocosyloxycarbonyl)-2,3-
Synthesis of dicyanonaphthalene] 236 mg of 6-medoxycarbonyl-2,3-dicyanonaphthalene (ImmoQ), 1-docosanol 16.
3 g (50 mmoQ) in 100 mQ of benzene, p
-Toluenesulfonic acid, monohydrate 1.94g (I0
, 2 mmon), and was refluxed for about 28 hours while dehydrating and removing methanol using molecular sieve 43A. After cooling, benzene camellia calyx was distilled off, and toluene/n-hexane (
The product was purified by silica gel force chromatography using a volume ratio of 4/1 solvent) as one volume of development. Further recrystallization from acetone/methanol yielded 161 mg of colored crystals. From the analysis results below, this green crystal is 6
It was confirmed that it was -(II-tocosyloxycarbonyl)-2<3>-dicyanonaphthalene.

(I) Melting point 135-136.5°C (2) Elemental analysis value: CHN Calculated value (%) 79.20 9.49 5.28 (
3) NMR value: CDCQ, solvent δ value 8.70
(LH, br-s) 8.48 (LH, s) 8.41 (LH, s) 8.37 (IH, dd, J=8.55°1.53H
z) 8.05 (LH, d, J = 8.55Hz) 4.4
2 (2H, t, J = 6.72Hz) 1, 83
(2H, quintet, J = 6.72Hz) 1
, 25 (38H, b r −s ) 0.88
(3H, t, J=6.72Hz) (4) The IR spectrum (KBr method) is shown in FIG.

It has an absorption attributable to the c=O stretching vibration of the ester near about 1710an-1.

Example 1 [Synthesis of tetrakis(II-amyloxycarbonyl)vanadylnaphthalocyanine [exemplified compound (I)]] 6-(
1.46 g (5 mmoQ) of (II-amyloxycarbonyl)-2,3-dicyanonaphthalene, 0.32 g (2,01 mmoQ) of vanadium trichloride, 10 mg of ammonium molybdate and 5 g of urea at about 220°C for about 2.
The reaction was allowed to proceed for 5 hours with thorough stirring. After cooling, 40 mQ of 5% hydrochloric acid was added to the solidified reaction mixture, and after stirring to some extent, the mixture was stirred well at about 5°C for 30 minutes. After stirring, insoluble matter was suction filtered and thoroughly washed with water, methanol, and then acetone. The obtained solid was extracted with a Soxhlet extractor using Z methanol/acetone (I/
Impurities were extracted using the mixed solvent of 1) for about 50 hours. Next, the solvent was changed to chloroform and Soxhlet extraction was performed for 20 hours. The resulting dark green chloroform solution was filtered under hot suction and then concentrated to dryness under reduced pressure to obtain 861 mg of glossy black crystals. This crystal was confirmed to be tetrakis(II-amyloxycarbonyl)vanadylnaphthalocyanine from the following analysis results.

(I) Melting point >300°C (stable at least below 300'C) (2) Elemental analysis value: CHN Calculated value (%) 69.95 5.22 9.06 Actual value (%) 70.13 5.14 9 .33(3
) The electronic spectrum values (CHCQ, solution) are shown in FIG.

(4) IR spectra 1 to 1 (KBr method) are shown in FIG.

It has an absorption attributable to the C=◯ stretching vibration of the ester near about 1700 cm-'.

Example 2 Synthesis of [Tetrakis(II-amyloxycarbonyl)coppernaphthalocyanine [Exemplary Compound (8)]] Corro n-amyloxycarbonyl)-2,3-dicyanonaphthalene 1
．． 46g (5mmofl), cupric chloride dihydrate 2
73 mg (I, 6 mmoQ), 10 mg ammonium molybdate and 5 g urea at about 220° C.
The reaction was allowed to take place while stirring well. After cooling, the reaction mixture was treated in the same manner as in Example 1 to obtain 987 mg of glossy black crystals. This crystal was confirmed to be tetrakis(II-amyloxycarbonyl)copper naphthalocyanine from the following analysis results.

(I) Melting point) 300°C (stable at least below 300°C) (2) Elemental analysis value: CHN Calculated value (%) 70.14 5.23 9.06 Actual value (%) 69.45 5.20 9. 17 (3
) The electronic spectrum values (CHCfl, solution) are shown in FIG.

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

About 1700C! It has an absorption near I+-1 that is attributable to the C=◯ stretching vibration of the ester.

Example 3 [Synthesis of tetrakis(II-amyloxycarbonyl)zinc naphthalocyanine [exemplified compound (I3)]] 6-(
II-amyloxycarbonyl)-2,3-dicyanonaphthalene 1.46g (5mmoQ), powdered zinc 105m
g(I,6mmoQ), ammonium molybdate 10
m g and 5 g of urea at about 220'C.
The reaction was allowed to take place while stirring well.

After cooling, the reaction mixture was treated in the same manner as in Example 1 to obtain 937 mg of glossy black crystals. This crystal was confirmed to be tetrakis(II-amyloxycarbonyl)zinc naphthalocyanine from the following analysis results.

(I) Melting point >300°C (stable at least below 300'C) (2) Elemental analysis value: CHN (3) Electronic spectrum (CHCQ, solution) is shown in Figure 17.

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

It has an absorption attributable to the C=O stretching vibration of the ester near about 1700 an-1.

Example 4 [Synthesis of tetrakis(II-octyloxycarbonyl)vanadylnaphthalocyanine [exemplified compound (2)]] 1.67 g (5 mmoQ) of 6-(II-octyloxycarbonyl)-2,3-dicyanonaphthalene, 3 0.32 g of vanadium chloride (I, 6 mmoα), 10 mg of ammonium molybdate and 5 g of urea at approx.
The mixture was allowed to react at 10°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 1.33 g of glossy black crystals. This crystal was confirmed to be tetrakis(II-octyloxycarbonyl)vanadylnaphthalocyanine from the following analysis results.

(I) Melting point >300°C (stable at least below 300°C) (2) Elemental analysis value: CHN (3) Electronic spectrum value (CHCQ, solution) is shown in Figure 19.

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

It has an absorption attributable to the C=◯ stretching vibration of the ester near about 1700■-1.

Example S [Tetrakis(II-octyloxycarbonyl)copper naphthalocyanine [Exemplary Compound (9)]] Synthetic Colour n-
octyloxycarbonyl)-2,3-dicyanonaphthalene 1.67 g (5 mmoΩ), cupric chloride, dihydrate 273 mg (I,6 mmoQ).

10 mg of ammonium molybdate and urea 5K 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 1.39 g of glossy black crystals. This crystal was confirmed to be tetrakis(II-octyloxycarbonyl)copper naphthalocyanine from the following analysis results.

(I) Melting point >300'C (stable at least below 300°C) (2) Elemental analysis value: CHN'#i# value (%) 71.95 6.08 8
．． 14(3) Electronic spectrum (CHCQ, solution) in the second
Shown in Figure 1.

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

It has an absorption attributable to the C=◯ stretching vibration of ester near about 1700 rho1.

Example 6 [Synthesis of tetrakis(II-octyloxycarbonyl)zinc naphthalocyanine [exemplified compound (I4)]] 6-
(II-octyloxycarbonyl)-2,3-dicyanonaphthalene 1.6'7 g (5mmoQ), zinc powder 1
05 mg (I, 6 mmo(I), 10 mg ammonium molybdate and 5 g urea at about 220°C for about 2.5
The reaction was allowed to take place while stirring well.

After cooling, the reaction mixture was treated in the same manner as in Example 1, and 1.26 g of shiny black crystals were confirmed to be cyanine.

(I) Melting point) 300°C (stable at temperatures below 300°C) (2) Elemental analysis values: CHN (3) Electronic spectrum values (CHCQ3 solution) are shown in Figure 23.

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

It has an absorption attributable to the C=◯ stretching vibration of the ester near about 1700 an-1.

Example 7 Synthesis of Tetrakis(II-amyloxycarbonyl)nickelnaphthalocyanine [Exemplary Compound (I6)] Coro-(II-amyloxycarbonyl)-2,3=dicyanonaphthalene 1.46 g (5mmoQ), nickel chloride , 380 mg of hexahydrate (I,6mmoQ).

10 mg of ammonium molybdate and 5 g 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 tetrakis (
287 mg of nickel naphthalocyanine (II-amyloxycarbonyl) was obtained.

Its electronic spectrum, 1 (CHCQ3 solution), is shown in FIG. This compound is also stable at least below 300'C. The IR spectrum (KBr method) is shown in FIG. It has an absorption attributable to the ester OC=O stretching vibration near about 1700 ■-''.

Example 8 Synthesis of [TeI-Rakis(II-amyloxycarbonyl)palladium naphthalocyanine [Illustrative Compound (Ig)] Coro-(II-amyloxycarbonyl)-2,3-dicyanonaphthalene 1.46 g (5 mmon) , 284 mg palladium chloride (I, 6 mmoQ), 10 mg ammonium molybdate and 5 g urea at about 220°C.
．． The reaction was allowed to proceed for 5 hours while stirring well. After cooling, the reaction mixture was treated in the same manner as in Example 1 to obtain 405 mg of tetrakis(II-amyloxycarbonyl)palladium naphthalocyanine as glossy black crystals. Its electronic spectrum (CHC (i, solution) is the 27th
As shown in the figure. This compound is also stable at temperatures below 300°C. The IR spectrum (KBr method) is shown in FIG. It has an absorption attributable to the C=◯ stretching vibration of the ester near about 1700 cm-1.

Example 9 [Synthesis of tetrakis(II-octadecyloxycarbonyl)vanadylnaphthalocyanine [exemplified compound (5)]] 6-(II-octadecyloxycarbonyl)-2゜3-
Dicyanonaphthalene 650mg (I, 37mmofl
), vanadium trichloride 88 mg (I, 6mmoQ).

3 mg ammonium molybdate and 1.37 g urea
The mixture was 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 556 mg of tetrakis(II-octadecyloxycarbonyl)vanadylnaphthalocyanine as glossy black crystals. This crystal was confirmed to be tetrakis(II-octadecyloxycarbonyldylnaphthalocyanine) from the following analysis results.

(I) Softening point: 135-138°C (2) Elemental analysis: C H N (3) The electronic spectrum (CHCQ3 solution) is shown in FIG.

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

It has an absorption attributable to the C=◯ stretching vibration of the ester near about 1700 cm-'.

Example 10 [Synthesis of tetrakis(II-octadecyloxycarbonyl)copper naphthalocyanine [exemplified compound (I2)]] 6
-(II-octadecyloxycarbonyl)-2.

3-dicyanonaphthalene 200mg (0.42mmo
Q), cupric chloride dihydrate 23mg (0.13mm
oQ), ammonium molybdate 1 mg and urea 0
．． 42 g 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 obtain tetrakis(II-octadecyloxycarbonyl) fi4 as glossy black crystals.
160 mg of naphthalocyanine was obtained. This crystal was confirmed to be tetrakis(II-octadecyloxycarbonyl)copper naphthalocyanine from the following analysis results.

(I) Softening point: 119-121°C (2) Elemental analysis: C H N (3) The electronic spectrum (CHCQ3 solution) is shown in FIG. 31.

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

It has an absorption attributable to the C=O stretching vibration of the ester near about 1720a++-'.

Example 11 [Synthesis of tetrakis(II-tetradecyloxycarbonyl)vanadylnaphthalocyanine [exemplified compound (3)]] 6-(II-tetradecyloxycarbonyl)-2゜3-
Dicyanonaphthalene 42 mg (0.1 mmon).

Vanadium trichloride 6.4 mg (0.04 mmoQ).

Ammonium molybdate 0.2 mg and urea 100
mg 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 obtain 21 mg of shiny black crystals.
Obtained. From the analysis results below, this crystal is tetrakis(I)
It was confirmed that it was vanadylnaphthalocyanine (I-tetradecyloxycarbonyl).

(I) Softening point 210-212°C (2) Elemental analysis value: CHN Calculated value (%) 74.50 7.87 6.44 Actual value (%) 74.66 7.96 6.32i4 (3 ) The electronic spectrum (CHCQ, solvent) is shown in FIG.

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

It has an absorption attributable to the C=◯ stretching vibration of the ester near about 1720an-1.

Example 12 [Synthesis of tetrakis(II-tetradecyloxycarbonyl)copper naphthalocyanine [exemplified compound (I0)]] 6
-(II-tetradecyloxycarbonyl)-2°3-dicyanonaphthalene 42 mg (0.1 mmoQ).

Cupric chloride dihydrate 5.4mg (0.03mmoQ)
.

Ammonium molybdate 0.2 mg and urea 1
00 mg 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 obtain 21 mg of shiny black crystals.
Obtained. According to the analysis results below, this crystal is tetrakis (
It was confirmed that it was copper naphthalocyanine (II-tetradecyloxycarbonyl).

(I) Softening point 168-171°C (2) Elemental analysis value: CHN Calculated value (%) 74.64 7.89 6.45 Actual value (%) 74.82 7.76 6.37 (3) Electron The spectrum (CHCQ, solvent) is shown in FIG.

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

It has an absorption attributable to the C=◯ stretching vibration of the ester near about 1720 cm-'.

Example 13 Synthesis of [Tetrakis(II-hexadecyloxycarbonyl)vanadylnaphthalocyanine [Exemplary Compound (4)] Coro-(II-hexadecyloxycarbonyl)-2゜3-
Dicyanonaphthalene 45 mg (0.1 mmoQ).

Vanadium trichloride 6.4 mg (0.04 mmoQ).

Ammonium molybdate 0.2 mg and urea 100
The reaction was carried out at about 220'C for about 2.5 hours with good stirring. After cooling, the reaction mixture was treated in the same manner as in Example 1 to obtain 1 glossy black crystal.
I got 3 mg. This crystal was confirmed to be tetrakis(II-hexadecyloxycarbonyl)vanadylnaphthalocyanine from the following analysis results.

(I) Softening point 151-154°C (2) Elemental analysis value: CHN Calculated value (%) 75.17 8.27 6.05 Actual value (%) 75.26 8.19 6.13-Funeral (3 ) The electronic spectrum (CHCQ3 solvent) is shown in FIG.

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

It has an absorption attributable to the C=◯ stretching vibration of the ester near about 1720 cm-1.

Example 14 [Synthesis of tetrakis(II-eicosyloxycarbonyl)vanadylnaphthalocyanine [exemplified compound (6)]] 6-(II-eicosyloxycarbonyl)-2°3-dicyanonaphthalene 52 mg (0.1 mmoQ,) .

Vanadium trichloride 6.4 mg (0.04 mmoQ).

Ammonium Q molybdate, 2 mg and urea 100
mg was reacted at about 220° C. for about 2.5 hours while stirring well. After cooling, one reaction mixture was treated in the same manner as in Example 1 to obtain 26 mg of glossy black crystals. From the analysis results below, this crystal is tetrakis(II)
- It was confirmed that it was vanadylnaphthalocyanine (eicosyloxycarbonyl).

(I) Softening point 83-85℃ (2) Elemental analysis value: CH Calculated value (%) 76.30 8.93 Actual value (%)
76.92 8.89 (3) Electronic spectrum (CHC
Q3 Shown in the figure.

(4) IR spectrum (KBr method) vinegar.

5.39 5, E8 Solvent layer) is shown in Fig. 40 and has an absorption attributable to the C═O stretching vibration of the ester in the vicinity of about 1720 -1.

Example 15 [Synthesis of tetrakis(II-eicosyloxycarbonyl)copper naphthalocyanine [exemplified compound (I1)′]] 6-
(II-eicosiloxycarbonyl)-2,3-dicyanonaphthalene 52 mg (0,1 mmoQ) + cupric chloride dihydrate 5.5 mg (0,03 mmoQ).

Ammonium Q molybdate, 2 mg and urea 100
mg 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 obtain 36 mg of shiny black crystals.
Obtained. According to the analysis results below, this crystal is tetrakis (
It was confirmed that it was II-eicosyloxycarbonyl)copper naphthalocyanine.

(I) Softening point 67-70'C (2) Elemental analysis value: CHN Calculated value (%) 76.43 8.94 5.40 Actual value (%) 76.62 8.78 5.61 Melon (3) The electronic spectrum (CHCQ, solvent) is shown in FIG.

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

It has an absorption attributable to the C=◯ stretching vibration of the ester near about 1720 cm-1.

Example 16 [Synthesis of tetrakis(II-amyloxycarbonyl)cobalt naphthalocyanine [exemplified compound (20)]] 6
-(II-amyloxycarbonyl)-2,3-dicyanonaphthalene 1.46 g (5mmoQ,), cobalt chloride hexahydrate 0.385g (I,6mmo12).

10 mg of ammonium molybdate and 5 g 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 823 mg of glossy black crystals.

From the analysis results below, this crystal is tetrakis(II-
It was confirmed that it was cobalt naphthalocyanine (amyloxycarbonyl).

(I) Melting point ) 300'C (stable at least below 300'C) (2) Elemental analysis value: CHN Calculated value (%) 70,41 5.25 9.12 Actual value (%) 69.54 5.02 9.36(3) The electronic spectrum (CHCQ3 solution) is shown in FIG.

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

It has an absorption attributable to the C=O stretching vibration of the ester near about 1700 cm-1.

Example 17 [Synthesis of Tetrakis(II-amyloxycarbonyl)manganese naphthalocyanine [Exemplary Compound (22)]]
(II-amyloxycarbonyl)-2,3-dicyanonaphthalene 1.46 g (5 mmofl), manganese acetate tetrahydrate 392 mg (I,6 mmoQ).

10 mg of ammonium molybdate and 5 g of urea were reacted at about 220'C for about 2.5 hours with good stirring. After cooling, the reaction mixture was treated in the same manner as in Example 1 to obtain 605 mg of glossy black crystals. From the analysis results below, this crystal is tetrakis(II)
-amyloxycarbonyl) manganese naphthalocyanine.

(I) Melting point >300°C (stable at least below 300'C) (2) Elemental analysis value: CHN Calculated value (%) 70.64 5,27 9.15 Actual value (%) 70.79 5.19 9 .66(3) The electronic spectrum (CHC1lt3 solution) is shown in Figure 45.

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

It has an absorption attributable to the C=◯ stretching vibration of ester near about 1700 rho1.

Example 18 [Tetrakis(II-octyloxycarbonyl)chloroindium naphthalocyanine [Exemplary Compound (27)]
Synthesis] 6-(II-octyloxycarbonyl)-2,3-
Dicyanonaphthalene 1.67 g (5mmoQ), indium trichloride tetrahydrate 470mg (I,6mmo
Q), 10 mg of ammonium molybdate and 5 g of urea 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 confirm that it was shiny carbonyl)chloroindium naphthalocyanine.

(I) Melting point 〉3oO℃ (stable at least below 300℃) (2) Elemental analysis value: HNCQ calculated value (%) 67.81 5,96 7,53 2
．． 38 Actual value (%) 67.88 5,74 7,7
8 1.99 (3) Electronic spectrum (CHCQ, solution)
is shown in FIG.

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

It has an absorption attributable to the C=0 stretching vibration of the ester near about 1700 an-'.

Example 19 [Tetrakis(II-octyloxycarbonyl)chloroaluminum naphthalocyanine l] [Exemplary compound (24)
) Synthesis of 6-(II-octyloxycarbonyl)-2,3-dicyanonaphthalene 1.67g (5mmoQ), aluminum chloride 213mg (I,6mmoQ), ammonium molybdate 1o and urea 5g at about 220°C. The reaction was allowed to proceed for about 2.5 hours while stirring well. After cooling, 40 mQ of methanol was added to the solidified reaction mixture, and after stirring to some extent, the mixture was stirred well at about 50° C. for 30 minutes.

After stirring, insoluble matter was suction filtered and thoroughly washed with methanol and then acetone. The obtained solid was first extracted with a Soxhlet extractor using methanol as a solvent for about 10 min.
Impurities were extracted for 0 hour and then for about 50 hours using acetone. Next, 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 quartz of glossy black crystals. This crystal was confirmed to be tetrakis(II-octyloxycarbonyl)chloroaluminum naphthalocyanine from the following analysis results.

(I) Melting point>300°C (stable at least below 300'C) (2) Elemental analysis value: CHN (,Q Calculated value (%) 72.06 6.34 8.00 2
．． 53 Actual value (%) 71.81 6.27 7.7
4 2.07 (3) Electronic spectrum (CHCQ, solution)
is shown in FIG.

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

It has an absorption attributable to the c=0 stretching vibration of the ester near about 1700<-1>.

Example 20 [Synthesis of tetrakis(II-amyloxycarbonyl)silicon naphthalocyanine [exemplified compound (29))] 6-
(II-amyloxycarbonyl)-2,3-dicyanonaphthalene 1.46 g (5 mmoQ), silicon tetrachloride 0.
29 mfl (j, 5 mmoQ), 10 mg ammonium molybdate and 5 g urea at about 220 °C
The reaction was allowed to take place while stirring well.

After cooling, 40 mQ of 5% hydrochloric acid was added to the solidified reaction mixture, and after stirring to some extent, the mixture was stirred well at about 50° C. for 30 minutes. After stirring, insoluble matter was suction filtered and thoroughly washed with water, methanol, and then acetone. Impurities were extracted from the obtained solid using a Soxhlet extractor using first methanol and then acetone as solvents for about 100 hours each. Next, the solvent was changed to chloroform and Soxhlet extraction was performed for 20 hours. The resulting dark green chloroform solution was filtered under hot suction and then concentrated to dryness under reduced pressure to obtain 247 mg of glossy black crystals. This crystal was confirmed to be tetrakis(II-amyloxycarbonyl)silicon naphthalocyanine from the following analysis results.

(I) Melting point >300'C (stable at least below 300'C) (2) Elemental analysis value: CHN Calculated value (%) 72,22 5.39 9.36 Actual value (%) 72,41 5.52 9.29(3) The electronic spectrum values (CHCQ, solution) are shown in FIG.

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

It has an absorption attributable to the C=O stretching vibration of the ester near about 1716(7)-1.

Example 21 Synthesis of Tetrakis(II-amyloxycarbonyl)germanium naphthalocyanine [Exemplary Compound (31)] Coro-(II-amyloxycarbonyl)-2,3'-dicyanonaphthalene 1.46g (5mmoQ), tetrachloride Germanium 0.28 mQ (2,47 mmoQ), ammonium molybdate 1101T1 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 786 mg of glossy black crystals. This crystal was confirmed to be tetrakis(II-amyloxycarbonyl)germanium naphthalocyanine from the following analysis results.

(I) Melting point >300°C (stable at least below 300°C) (2) Elemental analysis value: CHN Calculated value (%) 69.63 5.19 9.02 Actual value (%) 69.36 5.06 9, 28(3) electronic spectrum values (CHCfl, solution) are shown in FIG.

(4) FT-IR spectrum, (KBr method) Figure 54. Has absorption attributable to vibration.

Example 22 [Synthesis of tetrakis(II-amyloxycarbonyl)tinnaphthalocyanine [exemplified compound (33)]] 6-(I
I-amyloxycarbonyl)-2,3-dicyanonaphthalene 1.4f3g (5mmoQ), stannous chloride 47
4■ (2.5 mm included), ammonium molybdate 1
0.0 mm and 5 g 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 20 to obtain glossy black crystals 767I. This crystal was confirmed to be tetrakis(II-amyloxycarbonyl)tinnaphthalocyanine from the following analysis results.

(I) Melting point>300°C (stable at least below 300°C) (2) Elemental analysis value: CHN (3) Electronic spectrum (CHCQ, solution) is shown in Figure 55.

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

Approximately 1.700 (Has absorption attributable to C=◯ stretching vibration of ester near Il+-1.

Example 23 [Bis(triethylsiloxy)germanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine]
Synthesis of Exemplified Compound (41)] 6-(II-amyloxycarbonyl)-2,3-dicyanonaphthalene 1.46
g (5 mmoQ), 10 μm of ammonium molybdate and 5 g of urea, 0.28 m Q of germanium tetrachloride
(2.5mmoQ) and at about 220°C about 2.5
The reaction was allowed to take place while stirring well. After cooling, water was added to the solidified reaction mixture to loosen it well, and the black solid was suction-filtered and then thoroughly washed with methanol. After drying, 3.06 g of black solid was obtained. This black solid was found to be dichlorogermanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine (-formation (V)) according to the following analysis results: However, R1 = n-amyl group at , 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.

(I) The electronic spectrum (CHCQ3 solution) is shown in FIG.

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

It has an absorption attributable to the C═O stretching vibration of the ester near about 1710<-1>.

766 mg (0.58 mmoQ) of dichlorogermanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine obtained as described above was refluxed for about 2 hours in a mixed solvent of 19 mQ of concentrated ammonia water, 19 mQ of ethanol, and 76 rr+Q of water. After cooling, the reaction mixture was suction-filtered, and the resulting solid was thoroughly washed with methanol and dried to obtain 213 μm of a black solid. This black solid is dihydroxygermanium based on the analysis results below.
Tetrakis(II-amyloxycarbonyl)naphthalocyanine (-formation (■): However, R1゛ half is all n-
This compound was considered to be an aluminum group, n is 1, and M is Ge), but this compound was used in the next reaction without further purification.

(I) The electronic spectrum (CHCQ 3 solution) is shown in FIG.

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

It has an absorption attributable to the C=O stretching vibration of the ester near about 1700 cm-''.

210 mg (0.16 mmoQ) of dihydroxygermanium te-1-lakis(II-amyloxycarbonyl) naphthalocyanine obtained as above was added to 0.6 mQ of triethylsilanol in 15 mQ of glolobenzene.
After refluxing for about 11 hours in the presence of
Concentrated into After cooling, add about 50 mf2 of methanol,
After standing for a while, the precipitated solid was suction filtered and thoroughly washed with methanol.

The well-dried black solid was fractionated and purified by alumina thin layer chromatography using benzene as a developing solvent, yielding 18 μm of a dark green solid. This dark green solid was found to be bis(triethylsiloxy)germanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine [exemplified compound (41)] from the following analysis results.
It was confirmed that

(I) Melting point >300'C (stable below 300°C) (2
) Elemental analysis value: CHN (3) NMR spectrum value (NMR spectrum is 61st
): CDCQ3 solvent δ value Lo, 27 (4H, b r-s) 10.17
(4H, br-s) 9.45 (4H, br-s) 8.73 (4H, d, J=8.70Hz) 8.53
(4H, dd, J=8.710, 1.53Hz)4.
58 (8H, t, J=6.71Hz) 2.00
(8H, qujntet, J=6.7 1Hz) 1.5
9 (I6H, m) 1.07 (I2H, t, J=7.02Hz) -1,
00 (I8H, t, J = 7.94Hz) - 2,01 (I
2H, q, J = 7.94Hz) (4) Electronic spectrum (
CH(di, solution) is shown in FIG.

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

It has an absorption caused by C=O stretching vibration of ester near about 1720 mark -1.

Example 24 [Bis(tributylsiloxy)germanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine]
Synthesis of Exemplified Compound (43)] Dihydroxygermanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine 2 synthesized by the method described in Example 23
55rr1g (0.2mmoQ) of chlorobenzene 19
After refluxing for about 1 hour in the presence of 1 mQ of tributylsilanol in mQ, the reaction mixture was concentrated to about 5 mQ. After cooling, approximately 50 ml (l) of methanol 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 subjected to alumina three-layer chromatography using benzene as a developing solvent. As a result of separation and purification, 13μ of a dark green solid was obtained.This dark green solid was found to be bis(tributylsiloxy)germanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine [exemplified compound ( 43)).

(I) Melting point 280-290°C (decomposition) (2) Elemental analysis value CHN (3) NMR spectrum value (NMR spectrum
(shown in the figure): CDCD, solvent δ value 10.19 (4H, 5) 10.08 (4H, S) 9.39 (4H, b r-s) 8.66 (4H, d, J = 8.70Hz )8.46
(4H, dd, J=8.70, 1.53Hz) 4.51
(8H, t, J=6.72Hz) 1.93 (8H
, quintet, J = 6, 72Hz) 1.50(
I6H, m) 1.00 (I2H, t, J=7.02Hz) -0,0
9 (30H, m) 0.99 (I2H, quintet-1ike m
)-2,08(I2H,t-1ike m)(4)
The electronic spectrum (tetrahydrofuran solution) B is shown in FIG.

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

It has an absorption attributable to the C=O stretching vibration of the ester near about 1720c+n-1.

Example 25 Synthesis of [bis(I-ethylsiloxy)germanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine] [Exemplified Compound (44)] Coro-(II-octyloxycarbonyl)-2,3-dicyanonaphthalene 1
．． 67g (5mmoQ), ammonium molybdate! 0.28 mQ (2.5 mmoQ) of germanium tetrachloride was added to 10 mg of urea and 5 g of urea, and the mixture was 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 23 to obtain 3.35 g of a dark green solid. This black-green solid is dichlorogermanium te I lakis (II-octyloxycarbonyl) naphthalocyanine (-formation (■): However, R
1 are all n-octyl groups, n is 2, and M is G
e and X is a chlorine atom), but this compound was used in the next reaction without further purification.

(I) Electronic spectrum CCHCQ, 3 solution) is shown in FIG.

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

It has an absorption attributable to the C═O stretching vibration of the ester near about 1710 cm −1 .

2 g (I, 35 ml IoQ) of dichlorogermanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine obtained as above was added to 5 ml of concentrated ammonia water.
The mixture was refluxed for about 2 hours in a mixed solvent of 0 mQ, 50 mQ of ethanol, and 200 mQ of water. After cooling, the reaction mixture was treated in the same manner as in Example 23, resulting in a green solid of 7581TIg.
Obtained. This green solid was found to be dihydroxygermanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine (-formation (■); however, R1 = double nickel).

It is thought that all of the Kigyu E co≠ are n-octyl groups, n is 1, and M is Ge), but this compound was used in the next reaction without further purification.

(I) The electronic spectrum (CHCQ3 solution) is shown in FIG.

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

It has an absorption attributable to the C=◯ stretching vibration of the ester near about 1700■'''1.

Dihydroxygermanium obtained as above
360 mg (0.25 mmoQ) of tetrakis(II-octyloxycarbonyl)naphthalocyanine in 24 mQ of glorobenzene and 1.2 mg of triethylsilanol.
After refluxing for about 1 hour, the reaction mixture was concentrated to about 5 mQ. After cooling, about 50 mQ of methanol was added, and after being allowed to stand for a while, the precipitated solid was suction-filtered and thoroughly washed with methanol.

By separating and purifying a well-dried dark green solid by alumina thin layer chromatography using a mixed solvent of benzene/hexa, fi(I/1) as a developing solvent,
47 mg of a dark green solid was obtained. This dark green solid was confirmed to be bis(triethylsiloxy)germanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine [exemplified compound (44)'] from the following analysis results.

(I) Melting point ~ 280'C (decomposition) (2) Elemental analysis value: CHN Calculated value (%) 68.93 7.11 6.70 (3
) NMR spectrum values (NMR spectrum is shown in Figure 71): cocc, solvent δ value 10.20 (4H,5) 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 (88,t, J=6.41Hz)1.91 (
8H, quintet, J=6.41Hz) 1.51(
40H, m) 0.89 (I2H, t, J=6.72Hz)-1,,
07 (I8H, t, J=7.94Hz) 2.08 (I
2H, q, J = 7.94Hz) (4) Electronic spectrum (
(tetrahydrofuran solution) is shown in FIG.

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

It has an absorption attributable to the C=O stretching vibration of the ester near about 1720 mark -1.

Example 26 Synthesis of [bis(tributylsiloxy)germanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine] [Exemplified Compound (45)] Dihydroxygermanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine synthesized according to Example 25 289mg
After refluxing (0.2 mmoQ) in 19 mQ of chlorobenzene in the presence of 1 mQ of tributylsilanol for about 1 hour, the reaction mixture was concentrated to about 5 mQ. After cooling, about 50 mQ of methanol was added, and the mixture was allowed to stand for a while, and the precipitated solid was suction-filtered and thoroughly washed with methanol. When the well-dried dark green solid was separated and purified by alumina thin layer chromatography using benzene as a developing solvent, 41 mg of a dark green solid was obtained. This dark green solid was confirmed to be bis(tributylsiloxy)germanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine [exemplified compound (45)) from the following analysis results.

(I) Melting point 195-200°C (2) Elemental analysis value: CHN (3) NMR spectrum value (NMR spectrum is shown in Figure 74): cDcQ3 solvent δ value 10.19 (4H, 5) Lo, 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) 1.5
0 (40H, m) 0.90 (I2H, t, J=6.71Hz) -1,0
9 (30H, m, ) 0.99 (I2H, quintet-1ike m)
-2,08(I2H,"=-1ike m) (4) The electronic spectrum (tetrahydrofuran solution) is shown in FIG.

(5) IR spectrum (KBr method) A shown in FIG. 76.

It has an absorption attributable to the C=O stretching vibration of the ester near about 1720 cm-1.

Example 27 Synthesis of [bis(II-dobusyloxy)germanium-tetrakis(II-amyloxycarbonyl)cyanine [exemplified compound (53)]] Dihydroxygermanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine obtained in Example 23 320mg (0.25mm
oQ) in 25 mR of chlorobenzene, 1-dodecanol.

After refluxing for about 1 hour in the presence of 4 g (7.5 mmoQ),
The reaction mixture was concentrated to approximately 5 mQ. After cooling, about 50 mQ of methanol was added, the mixture was allowed to stand for a while, and the precipitated solid was suction-filtered, thoroughly washed with methanol, and separated and purified to obtain 12 μm of dark green solid. This dark green solid was confirmed to be bis(II-dobusyloxy)germanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine [exemplified compound (53)) from the following analysis results.

(I) Melting point: 230-240°C (decomposed) (2) Elemental analysis: CHN (3) The electronic spectrum (CHCQ3 solution) is shown in FIG.

(4) ■ The R spectrum (KBr method) is shown in FIG. 78.

Esther's C = ○ expansion and contraction vibration 3' near the ladle 1720■-1
．． Knee 5a has an absorption of A.

Example 28 [Synthesis of bis(II-octadecyloxy)germanium-tetra(II-amyloxycarbonyl)naphthalocyanine (exemplified compound (54))] Dihydro al-sigermanium synthesized by the method described in Example 23 -Tetrakis(II-amyloxycarbonyl)naphthalocyanine 32 Off 1 g (0.25 mmoQ) in chlorobenzene 2 S m Q, 1-octadecanol 2.03
After refluxing for about 1 hour in the presence of g (7.5 mmoQ),
The reaction mixture was concentrated to approximately 5 mQ. After cooling, about 50 mQ of methanol was added, and the mixture was allowed to stand for a while, and the precipitated solid was suction-filtered and thoroughly washed with methanol. Is the well-dried black solid alumina? By a-layer chromatography,
When separation and purification were performed using benzene as a developing solvent, 16rr1g of a dark green solid was obtained. According to the analysis results below, this dark green solid is bis(II octadecyloxy).
It was confirmed that it was germanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine [exemplified compound (54)].

(I) Melting point: 220°C-230'c (Division (2) Elemental analysis: C HN (3) The electronic spectrum (tetrahydrofuran solution) is shown in Figure 79.

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

It has an absorption attributable to the C=◯ stretching vibration of the ester near about 1720an''.

Example 29 [Synthesis of bis(II-dobusyloxy)germaniumtetrakis(II-octyloxycarbonyl)naphthalocyanine [exemplified compound (55)]] Dihydroxygermanium-tetrakis(II-) obtained by the method described in Example 25 octyloxycarbonyl) naphthalocyanine 360■ (0.25mff1oQ) to chlorobenzene 2
In 4mQ, 1.4g of 1-dodecanol (7,5mmoQ
), the reaction mixture was refluxed for about 1 hour in the presence of about 5 m
Concentrated in Q.

After cooling, about 50 mR of methanol was added, and after being 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 a mixed solvent of benzene/hexane (I/1) as a developing solvent to obtain 30 μm of a dark green solid. Based on the analysis results below, this dark green solid is bis(II-dobusyloxy)germanium-tetrakis(II-octyloxycarbonyl).
It was confirmed that it was naphthalocyanine [exemplified compound (55)].

(I) Melting point 220'C-230°C (decomposition) (2) Elemental analysis value: CHN (3) Electronic spectrum value (chloroform solution)
As shown in the figure.

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

It has an absorption attributable to the C=◯ stretching vibration of the ester near about 1720 cm-'.

Example 3゜Synthesis of [Bisya Kasuri Te(II-octadecyloxy)germanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine] [Exemplary Compound (56)] Example 25
Dihydroxygermanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine 3 synthesized by
60mg (0.25mmoQ) of chlorobenzene 2S
In mQ, 1-octadecanol 2.03# (7.5m
After refluxing for about 1 hour in the presence of moQ), the reaction mixture was concentrated to about 5 m fl.

After cooling, about 50 mQ of methanol 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 dark green solid was separated by alumina thin layer chromatography using benzene as the developing solvent.
When purified, 26 mg of a green solid was obtained.

This green solid a was confirmed to be bis(II-octadecyloxy)germanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine [exemplified compound (56)) from the following analysis results.

(I) Melting point 220'C-230'C (decomposition) (2) Elemental analysis value: CHN Calculated value (%) 73.94 8,38 5.75 (3
) electronic spectrum value (tetrahydrofuran solution)
Shown in Figure 3.

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

It has an absorption attributable to the C=O stretching vibration of the ester near about 1720<-1>.

Test Example 1 Bis(triethylsiloxy)germanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine [exemplified compound (41)) was dissolved in various solvents, and the electronic spectra were measured. Figure 62, Figure 85, Figure 86, Figure 8
Figure 7 shows the electronic spectra in chloroform, tetrahydrofuran, acetone, and benzene, respectively, and no change in the absorption waveform due to the type of solvent or change in the absorption waveform due to the concentration of the solution was observed.

Test Example 2 Bis(II-dobusyloxy)germanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine [exemplified compound (53)) was dissolved in various solvents, and the electronic spectra were measured. Figures 77 and 88.

Figure 89 shows the electronic spectra in chloroform, tetrahydrofuran, and benzene, respectively, but no change in the absorption waveform due to the type of solution or change in the absorption waveform due to the concentration of the solution was observed.

Comparative Example 1 Literature [Zhurnal Ovse Kimi (ZhurnalO
Tetra(t-
Figure 90 shows the electronic spectrum of (butyl)vanadylnaphthalocyanine in a chloroform solution, and Figure 91 shows the electron spectrum measured in a benzene solution. When the concentration changes, the absorption waveform changes, and it was observed that the higher the concentration, the lower the absorption near 800 nm, and the higher the absorption at 720 to 730 nm.

Tetra(t-butyl)vanadylnaphthalocyanine Test Example 3 Bis(tributylsiloxy)germanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine [exemplified compound (45)) 1 part of double ff and L on a glass plate
A liquid consisting of 98 parts by weight of L,2-)-lichloroethane was applied by a spin code method and dried at about 80'C for about 15 minutes to form an organic film. The transmission spectrum and 5-fold regular reflection spectrum of the organic film of this compound are shown in Figures 92 and 93.
Each is shown in the figure. Semiconductor laser area (780-83
0nm) and high light absorption capacity and high reflectance (~47%).
).

Comparative Example 2 Tetra (sheebutyl) used in Comparative Example 1 was placed on a glass plate.
An organic film was formed using vanadyl naphthalocyanine in the same manner as in Test Example 2, and its transmission spectrum (Figure 94) and quintuple specular reflection spectrum (Figure 95) were measured. It did not show very high light absorption ability and reflectance (20%) in the semiconductor laser region (780-830 nm).

Test Example 4 Bis(tributylsiloxy)germanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine%
[The solubility of exemplified compound (45)] was measured in the following manner. Add 100 mg of bis(tributylsiloxy)germanium-tetras off+kifp(II-<roxycarbonyl)naphthalocyanine and 0.5+nQ of solvent to a 2 mQ sample tube, and add 40' after sealing.
The mixture was subjected to ultrasonic shaking at C for 15 minutes, then left overnight at room temperature, and then filtered. After collecting the residue on the filter paper and drying it under reduced pressure, the solubility was determined from the value obtained by subtracting the amount of the residue from the amount originally used.

Solubility of tetrakis(II-goxycarbonylcyanine in various solvents) Example 31 Tetrakis(II-octyloxycarbonyl)vanadylnaphthalocyanine was deposited on polymethyl methacrylate 2Pl with a thickness of 1.5 mm and a diameter of 150 nm. [1st Listed Compound (2)] A solution consisting of 4 parts by weight of chloroform and 1 part by weight of 96 parts of chloroform was applied onto Spinco 1 using a method of approx.

It was dried at °C for about 15 minutes to form a recording layer. The thickness of this recording layer was about 2000 as measured by Talystep. The optical recording medium made in this way was placed on a turntable with the recording layer facing up, and while rotating at a speed of 11,000 rpm, an optical head equipped with a semiconductor laser having an oscillation wavelength of 830 nm and an output of 8 mW at the substrate surface was mounted. While controlling the laser beam to be focused on the recording layer from the bottom side of the optical recording medium, that is, from the substrate side, through the polymethyl methacrylate resin plate, a 1 MHz pulse signal was recorded within a radius of 40 to 60 mm from the center. went. Next, using the same device, the recorded signal was reproduced in the same manner, with the output of the semiconductor laser at the substrate surface being set to 0.7 mW. At this time, the signal-to-noise ratio (S/N
) was able to perform extremely good signal writing and reading at 56 dB.

Example 32 Te1-Rakis (II-Octylkis 7
'1 Dicarbonyl) copper naphthalocyanine [Exemplary compound (9)
] was coated using the spin code method in the same manner as in Example 31 to form a recording layer. The thickness of this recording layer was about 2,500 people. When recording and reproduction were performed on the optical recording medium thus prepared in the same manner as in Example 31, the S/N ratio was 51 dB, and very good signal writing and reading could be performed.

Example 33 Tetrakis(II-octyloxycarbonyl)zinc naphthalocyanine [Exemplary Compound (I4)
) was applied as a chloroform solution by the spin code method in the same manner as in Example 31 to form a recording layer. The thickness of this recording layer was about 3000 people.

↑ When signals were recorded and reproduced using the optical recording medium thus prepared in the same manner as in Example 31, the S/N ratio was 49.
Very good signal writing and reading was possible at dB.

Example 34 A chloroform solution of tetrakis(II-amyloxycarbonyl)vanadylnaphthalocyanine [exemplified by compound (I)] was placed on a polymethyl methacrylate-1-2P plate having a thickness of 1.5 mm and a diameter of 150 m in the same manner as in Example 31. 1Th was coated by a spin code method.

The thickness of this recording layer is approximately 2,600 people. When signals were recorded and reproduced using the optical recording medium thus produced in the same manner as in Example 31, the S/N ratio was 50 dB, and very good signal writing and reading could be performed.

Example 35 Te1-rakis(II-amyloxycarbonyl)coppernaphthalocyanine [Exemplary Compound (8)
)] was applied as a chloroform solution by the spin code method in the same manner as in Example 31 to form a recording layer.

The depth of this RM was approximately 2,300 people. When signals were recorded and reproduced using the optical recording medium thus produced in the same manner as in Example 31, the S/N ratio was 51 dB, and very good signal writing and reading could be performed.

Example 36 Tetrakis(II-amyloxycarbonyl)zinc naphthalocyanine [exemplified compound (I
3)) was applied as a chloroform solution by the spin code method in the same manner as in Example 31 to form a recording layer. The thickness of this recording layer was about 2,500 people.

When signals were recorded and reproduced using the optical recording medium thus prepared in the same manner as in Example 31, the S/N ratio was 5.
Very good signal writing and reading were possible at 2 dB.

Example 37 Tetrakis(II-amyloxycarbonyl)nickel naphthalocyanine [exemplified compound (
I6)) was applied as a chloroform solution by the spin code method in the same manner as in Example 31 to form a recording layer. The thickness of this recording layer was about 2100 people. When signals were recorded and reproduced using the optical recording medium thus produced in the same manner as in Example 31, the S/N ratio was 54 dB, and very good signal writing and reading could be performed.

Example 38 Tetrakis(II-amyloxycarbonyl)palladium naphthalocyanine [exemplified compound (I8)) was spin-coded as a chloroform solution in the same manner as in Example 31 on a polymethyl methacrylate 2PA plate with a thickness of 1.5 nvn and a diameter of 150 m. When the signal was recorded and reproduced in the same manner as in Recording Layer Example 31, the S/N ratio was 51 dB.
I was able to write and read signals very well.

Example 39 A solution consisting of 2 parts by weight of tetrakis(II-octyloxycarbonyl)chloroindium naphthalocyanine [exemplified compound (27)) and 98 parts by weight of chloroform was placed on a polymethyl methacrylate 2P plate having a thickness of 1.5 nvu and a diameter of 150 nwn. was applied using the spin code method, and the coating was applied at approximately 80℃ for approximately 1
It was dried for 5 minutes to form a recording layer.

The thickness of this record 8P:J was about 1000 people. When the optical recording medium thus produced was recorded and reproduced in the same manner as in Example 31, the soft S/Nl ratio was 54 dB.
I was able to write and read signals very well.

Example 40 A chloroform solution of tetrakis(II-octyloxycarbonyl)chloroaluminum naphthalocyanine [exemplified compound (24)] was spun on a polymethyl methacrylate 2P plate with a thickness of 1.5 m and a diameter of 150 m in the same manner as in Example 39. Coating was performed by a cord method to form the 8 layers described above. The thickness of this recording layer was approximately 1,500. When the optical recording medium thus produced was subjected to recording and reproduction in the same manner as in Example 39, the S/N ratio was 51 dB, and very good signal writing and reading could be performed.

Example 41 A chloroform solution of tetrakis(II-amyloxycarbonyl)cobalt naphthalocyanine [exemplified compound (20)] was applied on polymethyl methacrylate 2PFi having a thickness of 1.5 tn and a diameter of 150 m using the spin coding method in the same manner as in Example 39. The 8 layers were formed by drying at about 80° C. for about 15 minutes. The thickness of this recording layer is approximately 1100 mm.
It was a person. When the optical recording medium thus prepared was recorded and reproduced in the same manner as in Example 39, S/
The N ratio was 49 dB, and very good signal writing and reading could be performed.

Example 42 A chloroform solution of tetrakis(II-amyloxycarbonyl)manganese naphthalocyanine [exemplified compound (22)) was prepared in the same manner as in Example 39 on a polymethyl metahata creryl (2P) plate having a thickness of 1.5 mm and a diameter of 150 nn. A recording layer was formed by coating the film using a spin code method. This note @
The thickness of the layer was approximately 1,300 people.

↑ When the optical μ recording medium made in this way was recorded and reproduced in the same manner as in Example 39, the S/N ratio was 51 dB.
I was able to write and read signals very well.

Example 43 Tetrakis(II-amyloxycarbonyl)silicon naphthalocyanine [Exemplary Compound (2)
9)] was applied using the spin code method in the same manner as in Example 39, and dried at about 80° C. for about 15 minutes to form a recording layer. This recording layer roller S/N ratio is 52cl
With B, extremely good signal writing and reading were possible.

Example 44 A chloroform solution of tetrakis(II-amyloxycarbonyl)germanium naphthalocyanine [exemplified compound (31)) was spun on a polymethyl meta/Clichy 1-2P plate with a thickness of 1.5 mm and a diameter of 150 nyn in the same manner as in Example 39. A recording layer was formed by coating by a cord method. The depth of this recording layer is approximately 900 people, which is a treasure. Example 39 Optical 4 recording medium made in this way
When recording and playing back in the same manner as above, the S/N ratio was 5.
Very good signal writing and reading were possible at 1 dB.

Example 45 Dicarbonyl)tinnaphthalocyanine [Exemplary Compound (3)
3)) was applied as a chloroform solution using the spin code method in the same manner as in Example 39 to form a recording layer, and signals were recorded and reproduced in the same manner. The S/N14 ratio was 49 d.
With B, extremely good signal writing and reading were possible.

Example 46 A solution consisting of 2 parts by weight of germanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine [exemplified compound (41)) and 98 parts by weight of toluene was applied by a spin cord method and dried at about 80'C for about 15 minutes. Then, a recording layer was formed. The thickness of this recording layer was approximately 1000 mm as measured by a Talis chip. The optical recording medium thus produced was placed on a turntable with the recording layer facing up, and
While rotating at a speed of 0 rpm, a laser beam is passed through the polymethacrylate resin plate from below the optical recording medium, that is, from the substrate side, using an optical head equipped with a semiconductor laser having an oscillation wavelength of 830 nm and an output of 6 mW at the substrate surface. A 2 MHz pulse signal was recorded within a radius of 40 to 60 nn from the center while controlling the light to be focused on the B layer. Next, using the same device, the recorded signal was reproduced in the same manner, with the output of the semiconductor laser at the substrate surface being set to 0.7 mW. At this time, the carrier-to-noise ratio (C/N) was 57 dB, and very good signal writing and reading could be performed.

Example 47 2 parts by weight of bis(tributylsiloxy)germanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine [exemplified compound (43)) and 98% of toluene were placed on a polymethyl methacrylate 2P board with a thickness of 1.2 nn and a diameter of 130 m. A recording layer was formed by applying a liquid consisting of parts by weight using the spin code method in the same manner as in Example 46. The thickness of this recording layer was about 700 people. When the optical recording medium thus produced was recorded and reproduced in the same manner as in Example 46, the C/N ratio was 55 dB, and very good signal writing and reading could be performed.

Example 48 Bis(triethylsiloxy)germanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine [32 parts by weight of exemplified compound (44) and 98 parts by weight of toluene were placed on a polymethyl methacrylate 2P plate having a thickness of 1.2n+m and a diameter of 130nn+. A recording layer was formed by applying a liquid consisting of 30% by spin code method in the same manner as in Example 46. The thickness of this recording layer was approximately 800 mm. When recording and reproducing were performed using the light and the recording medium thus produced in the same manner as in Example 46, the C/N ratio was 56 dB, and very good signal writing and reading could be performed.

Example 49 Polymethyl methacrylate 2P having a thickness of 1.2 mm and a diameter of 130 mm was coated with 1 part of bis(tributylsiloxy)germanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine [exemplified compound (45) Tsuji] on a plate. A liquid containing 98 parts by weight of toluene and 98 parts by weight of toluene was applied by the spin code method in the same manner as in Example 46 to form a recording layer. The thickness of this recording layer was about 600 people. When the optical recording medium thus produced was recorded and reproduced in the same manner as in Example 46, the C/N ratio was 57 dB, and very good signal writing and reading could be performed.

Example 50 Bis(II-todecyloxy)germanium-tetrakis(II-amyloxycarbonyl) was deposited on a polymethyl methacrylate 2P plate with a thickness of 1.2 m and a diameter of 130 m.
A liquid consisting of 2 parts by weight of naphthalocyanine [exemplified compound (53): 1] and 98 parts by weight of toluene was applied by the spin code method in the same manner as in Example 46 to form a recording layer. The thickness of this recording layer was about 1000. When the optical recording medium thus produced was recorded and reproduced in the same manner as in Example 46, the C/N ratio was 52 dB, and very good signal writing and reading could be performed.

Example 51 Two weights of bis(II-ophtadecylquimene)germanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine [exemplified compound (54)) were placed on a polymethyl methacrylate 2P plate having a thickness of 1.2 nn+ and a diameter of 130 m+. A liquid consisting of 98 parts by weight and 98 parts by weight of toluene was prepared. The thickness of this recording layer was about 700. When the optical recording medium thus produced was recorded and reproduced in the same manner as in Example 46, the C/N ratio was 54 dB, and very good signal writing and reading could be performed.

Example 52 A liquid consisting of 2 parts by weight of germanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine [exemplified compound (55)) and 98 parts by weight of toluene was applied by the spin code method in the same manner as in Example 46 to form a recording layer. Formed. The thickness of this recording layer was about 800 people. When the optical recording medium thus produced was recorded and reproduced in the same manner as in Example 46, the C/N ratio was 55 dB, and very good signal writing and reading could be performed.

Example 53 Bis(II-octadecyloxy) was placed on a polymethylmethacrylate 2P board with a thickness of 1.2nwn and a diameter of 130mm.
Germanium te 1 herakis (II-octyloxycarbonyl) naphthalocyanine [Exemplary compound (56)) 2
A recording layer was formed by applying a liquid consisting of 98 parts by weight and 98 parts by weight of toluene by the spin code method in the same manner as in Example 46. The thickness of this layer B was approximately 600 people. When recording and reproducing were performed on the optical recording medium thus prepared in the same manner as in Example 46, the C/N ratio was 53 dB, and very good signal writing and reading could be performed.

Example 54 The previously exemplified tetrakis(II-amyloxycarbonyl)vanadylnaphthalocyanine [exemplified compound (I)] was dissolved in chloroform to prepare a 1% solution and coated with one rotation to a thickness of 1°2. A recording film layer of 700 people was formed on a glass substrate in the field. When the recording medium thus formed was irradiated with a semiconductor laser with a wavelength of 830 nm from the glass substrate side and the recording characteristics were evaluated, the beam diameter was 1.6 μm.
Recording was possible at a linear velocity of 0.5 m/sec and a power of 6.4 mW.

On the other hand, in order to evaluate the stability against playback deterioration,
Although the readout light was repeatedly irradiated, no change in reflectance occurred even after 10'' repetitions.The spectra of this issue after 1 lapse are shown in FIG.

Comparative example 3 Cyanine dye NK-2905 (Japanese photosensitive dye (manufactured by the Institute) in digloroethane and spin coating.

A recording film layer having a thickness of 500 mm was obtained on a glass substrate. When this recording medium was irradiated with laser light in the same manner as in Example 54, recording was possible at 4.8 nrnW. However, when we evaluated the stability against playback deterioration,
The reflectance begins to decrease from around 4 x 104 repeated irradiations, and after 106 irradiations, the initial reflectance is 70
%.

Example 55 Tetrakis(II-octyloxycarbonyl)zinc naphthalocyanine [exemplified compound (I4)] was dissolved in chloroform and coated on a glass substrate to a thickness of 700 mm by spin coating.
A human recording film layer was obtained. When this recording medium was irradiated with a semiconductor laser with a wavelength of 780 nm from the glass substrate side and the recording characteristics were evaluated, the beam diameter was 1.6 μm and the linear velocity was 0.5 m.
Recording was possible at 6.9 mW/second. On the other hand, in order to evaluate stability against reproduction deterioration, 1 mW readout light was repeatedly irradiated, but no change in reflectance occurred even after 106 repetitions.

Example 56 Tetrakis(II-octyloxycarbonyl)chloroaluminum naphthalocyanine [Exemplary Compound (24)] was dissolved in chloroform, and a recording film layer having a thickness of 900 mm was obtained on a glass substrate by spin coating. When this recording medium was irradiated with laser light in the same manner as in Example 54, 6
．． Recording was possible at 6 mW. Furthermore, when the stability against reproduction deterioration was similarly evaluated, no change in reflectance occurred even after repeated irradiation 10' times.

Example 57 Two--Tetrakis(II-amyloxycarbonyl)nickel naphthalocyanine [exemplified compound (I6)) and polystyrene were dissolved in chloroform at a ratio of 1=1, and a thickness of 1,500 mm was coated on a glass substrate by spin coating using MilL. A human recording film layer was obtained.

When this recording medium was irradiated with laser light in the same manner as in Example 54, recording was possible at 9.6 mW.

Furthermore, when the stability against reproduction deterioration was similarly evaluated, no change in reflectance occurred even after repeated irradiation 10' times.

Example 58 Bis(tri(64)) synthesized according to the method of Example 23
) was dissolved in chloroform and coated by spin coating to a thickness of 1.
A recording film layer of 700 people was formed on a 2 m glass substrate.

When 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, recording was possible at a beam diameter of 1.6 μm, a linear velocity of 0.5 m/sec, and 4.6 mW. On the other hand, in order to evaluate stability against reproduction deterioration, 1 mW readout light was repeatedly irradiated, but no change in reflectance occurred even after 106 repetitions.

Comparative Example 4 Cyanine dye NK-2873 (manufactured by Nippon Kanko Shikiki Mi-L Tsusho) was dissolved in dichloroethane, and by spin coating,
A recording film layer with a thickness of 500 mm was obtained on a glass substrate. When this recording medium was irradiated with laser light in the same manner as in Example 54, recording was possible at 5.2 mW. However, when we evaluated the stability against playback deterioration, we found that the reflectance began to decrease after the number of repeated irradiations was around 5x10'.
After irradiation 106 times, the reflectance decreased to 70% of the initial reflectance.

Example 59 Bis(tributylsiloxy)tin-tetrakis(II-octyloxycarbonyl)naphthalocyanine [exemplified compound (65): 1] synthesized according to the method of Example 23 was dissolved in dichloroethane and coated on a glass substrate by spin coating. The top 500 recording film layers were 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. Furthermore, when stability against reproduction deterioration was evaluated, no change in reflectance occurred even after repeated irradiation 106 times.

Example 60 Bis(triethylsiloxy) synthesized according to Example 25
Germanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine (the exemplified compound is compound (44)) was dissolved in chloroform and spin-coated to obtain a recording film layer with a thickness of 500 mm on a glass substrate. When this recording medium was irradiated with laser light in the same manner as in Example 54, recording was possible at 4.9 mW. Also,
When stability against reproduction deterioration was evaluated, no change in reflectance occurred even after repeated irradiation 106 times.

Example 61 Bis(tributylsiloxy)titanium pre-tetrakis(methoxycarbonyl) synthesized by the method of Example 23
4 naphthalocyanine [exemplified compound (68)] was dissolved in chloroform, and a recording film layer having a thickness of 400 mm was obtained on a glass substrate by spin coating.

When this BIX body was irradiated with laser light in the same manner as in Example 54, recording was possible at 4.2 mW. In addition, when we simultaneously evaluated the stability against playback deterioration, we found that
No change in reflectance occurred even after repeated irradiation 106 times.

Example 62 Thickness 1.2 with 10 nm Ti chelate surface protection layer
A toluene solution of trihexylsiloxyaluminum-tetrakis(II-amyloxycarbonyl)naphthalocyanine [exemplified compound (69)) synthesized according to the method of Example 23 was coated on a polycarbonate substrate with a thickness of A total of 600 recording film layers were obtained. When evaluated at a linear velocity of 5 m/sec in the same manner as the field test example, it was found to be 7.4
Recording was possible at mW. Furthermore, when stability against reproduction deterioration was simultaneously evaluated, no change in reflectance occurred even after repeated irradiation 106 times.

Example 63 A 2=1 mixture of bis(II-otatoxy)tin-tetrakis(II-amyloxycarbonyl)naphthalocyanine [exemplified compound (74)) synthesized according to the method of Example 23 and polystyrene was dissolved in methyl ethyl ketone. ,
A recording film layer with a thickness of 600 mm was obtained on a glass substrate. When evaluated in the same manner as Example>1, the recording sensitivity was 4.8 mw.
, the result was that the playback deterioration occurred more than 106 times.

Example 64 Bis(tributylsiloxy)germaniumate 1-rakis(II-octyloxycarbonyl)Natsuta was manufactured. Then, using a spin coating method, 4 coats were coated onto a glass substrate with a thickness of 1.2 m.
Obtained a record layer of 00 people. This recording medium has a wavelength of 83.0
When the recording characteristics were evaluated by irradiating the glass substrate side with a semiconductor laser of nm, it was found that the beam diameter was 1.6 μm and the linear velocity was 2.4 m/e2.
Recording was possible at sr7.8mW. On the other hand, in order to evaluate stability against reproduction deterioration, 0.8 mW readout light was repeatedly irradiated, but no change in reflectance occurred even after 10'' repetitions.

Example 65 Bis(II-dobusyloxy)germanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine [exemplified compound (53)) was dissolved in 1,2-dichloroethane to prepare a 1.5% by weight solution, and rotated. Thickness 1 by coating method
．． A recording layer of 600 people was obtained on a glass substrate of 2 rmI. When this recording medium was irradiated with semiconductor laser light with a wavelength of 830 nm from the substrate side and the recording characteristics were evaluated, it was found that 1/e
2 Beam diameter 1.6 μm, linear velocity 2.5 m/s, 8.6
Recording was possible at mW. On the other hand, in order to evaluate stability against reproduction deterioration, 0.8 mW readout light was repeatedly irradiated, but no change in reflectance occurred even after 106 repetitions.

Example 66 Bis(tributylsiloxy)germanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine [
A 2:1 mixture of exemplified compound (45)) and polystyrene was dissolved in 1,2-trichloroethane, and the thickness was 1,2.
A recording layer with a thickness of 800 mm was obtained on a 3.0 mm glass substrate by spin coating. When this recording medium was irradiated with semiconductor laser light with a wavelength of 830 nm from the substrate side and the recording characteristics were evaluated, recording was possible at a linear velocity of 2 m/s and 6 mW.

In addition, although the reading light of mW was repeatedly irradiated, the io'A
No change in reflectance occurred even after repeated irradiation.

〔Effect of the invention〕

The invention provides a novel naphthalocyanine derivative, and this compound is useful as a recording layer material of an optical information recording medium.

[Brief explanation of the drawing]

Figure 1 is the IR spectrum of methyl 3,4-dimethylbenzoate, Figure 2 is the IR spectrum of methyl 3,4-bis(dibromomethyl)benzoate, and Figure 3 is the IR spectrum of methyl 3,4-dimethylbenzoate. 4 is the IR spectrum of n-amyl 3,4-dimethylbenzoate, and FIG. 5 is the IR spectrum of 6-(II-amyloxycarbonyl). -2,3-dicyanonaphthalene IR spectrum, Figure 6 shows 3,
FIG. 7 is an IR spectrum of n-octyl 4-dimethylbenzoate, and shows the IR spectrum of n-octyl 4-dimethylbenzoate.
8 is the IR spectrum of 6-(II-octadecyloxycarbonyl)-2,3-dicyanonaphthalene, and FIG. 9 is the IR spectrum of 6-(II-octadecyloxycarbonyl)-2,3-dicyanonaphthalene. FIG. 10 is the IR spectrum of 6-(II-hexadecyloxycarbonyl)-2,3-dicyanonaphthalene, and FIG. 11 is the IR spectrum of 6-(II-hexadecyloxycarbonyl)-2,3-dicyanonaphthalene. 12 is an IR spectrum of 6-(II-eicosyloxycarbonyl)-2,3-dicyanonaphthalene, and FIG. 13 is an IR spectrum of 6-(II-tocosyloxycarbonyl)-2,3-dicyanonaphthalene. is an electronic spectrum of tetrakis(II-amyloxycarbonyl)vanadylnaphthalocyanine, FIG. 14 is an IR spectrum of tetrakis(II-amyloxycarbonyl)vanadylnaphthalocyanine, and FIG. 15 is an IR spectrum of tetrakis(II-amyloxycarbonyl)vanadylnaphthalocyanine. ) The electronic spec of copper naphthalocyanine is 1 hell,
Figure 16 shows tetrakis (II-amyloxycarbonyl)
Fig. 17 is an IR spectrum of copper naphthalocyanine, Fig. 17 is an electronic spectrum of tetrakis(II-amyloxycarbonyl)zinc naphthalocyanine, and Fig. 18 is an IR spectrum of tetrakis(II-amyloxycarbonyl)zinc naphthalocyanine. , FIG. 19 is an electronic spectrum of tetrakis(II-octyloxycarbonyl)vanadylnaphthalocyanine, FIG. 20 is an IR spectrum of tetrakis(II-octyloxycarbonyl)vanadylnaphthalocyanine, and FIG. -Octyloxycarbonyl) copper naphthalocyanine, and Figure 22 is an electronic spectrum of tetrakis (I
I-octyloxycarbonyl) copper naphthalocyanine I
Fig. 23 is the electronic spectrum of tetrakis(II-octyloxycarbonyl)zinc naphthalocyanine, Fig. 24 is the IR spectrum of tetrakis(II-octyloxycarbonyl)zinc naphthalocyanine, and Fig. 25 is the R spectrum. is an electronic spectrum of tetrakis(II-amyloxycarbonyl)nickel naphthalocyanine, FIG. 26 is an IR spectrum of tetrakis(II-amyloxycarbonyl)nickel naphthalocyanine, and FIG. 27 is an IR spectrum of tetrakis(II-amyloxycarbonyl)nickel naphthalocyanine. ) is the electronic spectrum of palladium naphthalocyanine, Figure 28 is the IR spectrum of tetrakis(II-amyloxycarbonyl)palladium naphthalocyanine, and Figure 29 is the electronic spectrum of tetrakis(II-octadecyloxycarbonyl)vanadylnaphthalocyanine. and Figure 30 shows the IR of tetrakis(II-octadecyloxycarbonyl)vanadylnaphthalocyanine.
FIG. 31 is an electronic spectrum of tetrakis(II-octadecyloxycarbonyl) copper naphthalocyanine, FIG. 32 is an IR spectrum of tetrakis(II-octadecyloxycarbonyl) copper naphthalocyanine, and FIG. Figure 33 is an electronic spectrum of tetrakis(II-tetradecyloxycarbonyl)vanadylnaphthalocyanine, and Figure 34 is an electronic spectrum of tetrakis(II-tetradecyloxycarbonyl)vanadylnaphthalocyanine.
Fig. 35 is an IR spectrum of vanadylnaphthalocyanine (tetradecyloxycarbonyl);
FIG. 36 is an IR spectrum of teI-lakis(II-tetradecyloxycarbonyl) copper naphthalocyanine, and FIG. 37 is an IR spectrum of tetradecyloxycarbonyl) FIG. 38 is an electronic spectrum of l-rakis(II-hexadecyloxycarbonyl)vanadylnaphthalocyanine, and FIG. 39 is an IR spectrum of tetrakis(II-hexadecyloxycarbonyl)vanadylnaphthalocyanine. This is an electronic spectrum of tetrakis(II-eicosyloxycarbonyl)vanadylnaphthalocyanine.
Figure 0 is an IR spectrum of tetrakis(II-eicosyloxycarbonyl)vanadylnaphthalocyanine,
FIG. 41 is an electronic spectrum of Tetrakis (II-eicosyloxycarbonyl) copper naphthalocyanine, and FIG. 42 is an IR spectrum of Tetrakis (II-eicosyloxycarbonyl) copper naphthalocyanine.
Figure 43 shows tetrakis (II-amyloxycarbonyl)
Figure 44 is an electronic spectrum of cobalt naphthalocyanine, and Figure 44 is an IR spectrum of tetrakis(II-amyloxycarbonyl) cobalt naphthalocyanine.
Figure 5 shows the electronic spectrum of tetrakis(II-amyloxycarbonyl)manganese naphthalocyanine, and the 46th
The figure shows the IR spectrum of tetrakis(II-amyloxycarbonyl)manganese naphthalocyanine, FIG. 47 shows the electronic spectrum of tetrakis(II-octyloxycarbonyl)thaloloindium naphthalocyanine, and FIG. FIG. 49 is an IR spectrum of tetrakis(II-octyloxycarbonyl)chloroindium naphthalocyanine, FIG. 50 is an electronic spectrum of tetrakis(II-octyloxycarbonyl)taloloaluminum naphthalocyanine, and FIG.
- IR spectrum of octyloxycarbonylchloroaluminum naphthalocyanine, FIG. 51 is an electronic spectrum of tetrakis(II-amyloxycarbonyl) silicon naphthalocyanine, and FIG. Figure 53 is the electronic spectrum of tetrakis(II-amyloxycarbonyl)germanium naphthalocyanine, and Figure 54 is the IR spectrum of tetrakis(II-amyloxycarbonyl)germanium naphthalocyanine. Figure 55 is the electronic spectrum of tetrakis(II-amyloxycarbonyl)tinnaphthalocyanine, Figure 56 is the IR spectrum of tetrakis(II-amyloxycarbonyl)tinnaphthalocyanine, and Figure 57 is the spectrum of tetrakis(II-amyloxycarbonyl)tinnaphthalocyanine. , dichlorogermanium-tetrakis (II-amyloxycarbonyl)
FIG. 58 is an IR spectrum of dichlorogermanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine, and FIG. 59 is an electronic spectrum of naphthalocyanine in a chloroform solution. Fig. 60 is an IR spectrum of dihydroxygermanium-tetrakis(II-amyloxycarbonyl) naphthalocyanine in a chloroform solution, and Fig. 61 is an IR spectrum of bis(triethylsiloxy) naphthalocyanine. Germanium-tetrakis (I
NMR of I-amyloxycarbonyl) naphthalocyanine
62 is an electronic spectrum of bis(triethylsiloxy)germanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine in a chloroform solution, and FIG. 63 is an electronic spectrum of bis(triethylsiloxy)germanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine. It is an IR spectrum of germanium-tetrakis (II-amyloxycarbonyl) naphthalocyanine. Figure 64 is the NMR spectrum of bis(tributylsiloxy)germanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine, and Figure 65 is the NMR spectrum of bis(tributylsiloxy)germanium-tetrakis(II-amyloxycarbonyl). 66 is an IR spectrum of bis(tributylsiloxy)germanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine, and FIG. 67 is an IR spectrum of dichlorogermanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine. FIG. 68 is an electronic spectrum of tetrakis(II-octyloxycarbonyl)naphthalocyanine in a chloroform solution, FIG. 68 is an IR spectrum of dichlorogermanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine, and FIG. 69 is
Dihydroxygermanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine in chloroform)
Figure 70 is an IR spectrum of dihydroxygermanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine, and Figure 71 is an IR spectrum of bis(triethylsiloxy)germanium-tetrakis(II-octyloxycarbonyl). FIG. 72 is an NMR spectrum of bis(triethylsiloxy)germaniumte1-lakis(II-octyloxycarbonyl)naphthalocyanine in a tetrahydrofuran solution; Figure 73 is an IR spectrum of bis(triethylsiloxy)germanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine, and Figure 74 is an IR spectrum of bis(tributylsiloxy)germanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine. FIG. 75 is an NMR spectrum, and FIG. 75 is an electronic spectrum of bis(tributylsiloxy)germanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine in a tetrahydrofuran solution, and FIG. 76 is
FIG. 77 is an IR spectrum of bis(tributylsiloxy)germanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine, and FIG. 77 shows a chloroform solution of bis(II-dobutylsiloxy)germanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine. FIG. 78 is an IR spectrum of bis(II-dobusyloxy)germanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine. Figure 79 is an electronic spectrum of bis(II-octadecyloxy)germaniumte-1-lakis(II-amyloxycarbonyl)naphthalocyanine in a tetrahydrofuran solution, and Figure 80 is an electronic spectrum of bis(II-octadecyloxy) FIG. 81 is an IR spectrum of germanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine, and FIG. 81 is an electronic spectrum of bis(II-dobusyloxy)germanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine in a chloroform solution. 82 is the IR spectrum of bis(II-dobucyloxy)germanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine, and FIG. 83 is the IR spectrum of bis(II-octadecyloxy)germanium-tetrakis(II-octyloxycarbonyl). FIG. 84 is an IR spectrum of bis(II-octadecyloxy)germanium-tetrakis(II-octyloxycarbonyl)naphthalocyanine in a tetrahydrofuran solution; FIG. 85 is an electronic spectrum of bis(triethylsiloxy)germanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine in a tetrahydrofuran solution, and FIG. 86 is an electronic spectrum of bis(triethylsiloxy)germanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine. Figure 87 is an electronic spectrum of bis(triethylsiloxy)germanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine in a benzene solution; Figure 88 is an electronic spectrum of bis(II-dobsiloxy)germanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine in tetrahydrofuran solution, and Figure 89 is an electronic spectrum of bis(II-dobsiloxy)germanium-tetrakis(II-amyloxycarbonyl)naphthalocyanine in tetrahydrofuran solution.
FIG. 90 is an electronic spectrum of tetra(t-amyloxycarbonyl)naphthalocyanine in a benzene solution;
Electron spectrum of (butyl)vanadylnaphthalocyanine in chloroform solution, (a) is 2.37 x 10
-6M; 13 degrees, (b) is 1.89 x 10-5M
Figure 91 shows that tetra(t-butyl)vanadylnaphthalocyanine in benzene solution (9,5X
Figure 92 is the transmission spectrum of the bis(tributylsiloxy)germanium-tetrakis (II-octyloxycarbonyl) cord film, and Figure 93 is the transmission spectrum of the bis(tributylsiloxy) germanium-tetrakis (II-octyloxycarbonyl) membrane. This is the 5° specular reflection spectrum of the spin coded film of (II-octyloxycarbonyl)naphthalocyanine, which is the 94th
The figure shows the 5° specular reflection spectrum of the spin code film of quinaphthalocyanine during the transmission of the spin code film of tetra(butyl)vanadylnaphthalocyanine≠-=≠during the season.
Figure 96 is Tor.

Claims (1)

[Claims] 1. General formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼(I) [However, in the formula, R^1 is an alkyl group having 1 to 22 carbon atoms, and multiple R^1 may be the same or different,
n is an integer of 1 to 4 which may be the same or different, and M
is a group Ib metal such as Cu, a group IIa metal such as Mg,
Group IIb metals such as Zn, Al, ClAl, HOAl, I
n, Group IIIa metals such as ClIn, metal halides or metal hydroxides, Si, Cl_2, Si, (HO)_
2Si, Ge, Cl_2Ge, (HO)_2Ge, Sn
, Cl_2Sn, (HO)_2Sn, group IVa metals such as Pb, metal halides or metal hydroxides, Ti
, IVb group metals or metal oxides such as OTi, Vb group metal oxides such as OV, VIb group metals such as Cr, Mo, VIIb group metals or metal halides such as Mn, ClMn, or Fe, ClFe, Co, Ni, Pt, Pd
A type of Group VIII metal or metal halide, such as ] A naphthalocyanine derivative represented by. 2. In general formula (I), M is Cu, Zn, ClA
l, ClIn, Si, Ge, Sn, OV, Mn, Co,
The naphthalocyanine derivative according to claim 1, which is Ni or Pd. 3. The naphthalocyanine derivative according to claim 1 or 2, wherein n is 1 in general formula (I). 4. In general formula (I), R^1 has 13 to 2 carbon atoms
The naphthalocyanine derivative according to claim 1, 2 or 3, which has two alkyl groups. 5. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) [However, in the formula, R^1 is an alkyl group having 1 to 22 carbon atoms, and multiple R^1s are the same But they can be different,
n is an integer from 1 to 4 that may be the same or different, and Y_
1 and Y_2 may be the same or different, and are an aryloxyl group, an alkoxyl group, a trialkylsiloxyl group,
It is a triarylsiloxyl group, a trialkoxysiloxyl group, a triaryloxysilokyl group, or a trityloxyl group, and M is Al, Ti, Si, Ge, or Sn, and when M is Al, only Y_1 is M However, 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 general formula (II), M is Ge. 7. The naphthalocyanine derivative according to claim 5 or 6, wherein n is 1 in general formula (II). 8. Claim 5, 6 or 7, wherein in general formula (II), Y_1 and Y_2 are both trialkylsiloxyl groups.
The naphthalocyanine derivatives described. 9. The naphthalocyanine derivative according to claim 5, 6 or 7, wherein in general formula (II), Y_1 and Y_2 are both alkoxyl groups. 10. General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) (However, in the formula, R^1 represents an alkyl group having 1 to 22 carbon atoms, and n is an integer of 1 to 4. At least one alkoxycarbonyl-2,3-dicyanonaphthalene represented by the general formula (IV-1) MXp (IV-1) (wherein, A positive integer indicating the number of bonds of X to M, M is a group Ib group such as Cu, a group IIa group such as Mg, Z
IIb group such as n, IIIa group such as Al, In, Si, G
IVa group such as e, Sn, Pb, IVb group such as Ti, Vb group such as V, VIb group such as Cr, Mo, VII such as Mn
A general formula (I) characterized by reacting with a metal or metal salt represented by group B or group VIII metals such as Fe, Co, Ni, Pt, Pd, etc. ▼(I) [However, R^1 in the formula is an alkyl group having 1 to 22 carbon atoms, and multiple R^1's may be the same or different,
n is an integer from 1 to 4 which may be the same or different,
M is a group Ib metal such as Cu, a group IIa metal such as Mg, a group IIb metal such as Zn, Al, ClAl, HOAl
, In, group IIIa metals such as ClIn, metal halides or metal hydroxides, Si, Cl_2Si, (H
O)_2Si, Ge, Cl_2Ge, (HO)_2Ge
, Sn, Cl_2Sn, (HO)_2Sn, Pb, etc.
Group IVa metals, metal halides or metal hydroxides, Group IVb metals or metal oxides such as Ti, OTi, O
Vb group metal oxides such as V, VIb group metals such as Cr, Mo, VIIb group metals such as Mn, ClMn, or metal halides, or Fe, ClFe, Co, Ni, Pt
, a group VIII metal such as Pd or a metal halide. ] A method for producing a naphthalocyanine derivative represented by 11. In general formula (IV-1), M is Cu, Zn, A
l, In, Si, Ge, Sn, V, Mn, Co, Ni or Pd, and in the general formula (I), M is C
u, Zn, ClAl, ClIn, Si, Ge, Sn, OV, Mn, Co, Ni
or Pd, the method for producing a naphthalocyanine derivative according to claim 10. 12. The method for producing a naphthalocyanine derivative according to claim 10 or 11, wherein n is 1 in general formula (III) and general formula (I). 13. In general formula (III) and general formula (I), R^1
is an alkyl group having 13 to 22 carbon atoms,
12. The method for producing a naphthalocyanine derivative according to 11 or 12. 14. General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) (However, in the formula, R^1 represents an alkyl group having 1 to 22 carbon atoms, and n is an integer of 1 to 4. At least one alkoxycarbonyl-2,3-dicyanonaphthalene represented by the general formula (IV-2) MXp(IV-2) (wherein,
is a positive integer indicating the number of bonds, M is Al, Ti, Si
, Ge or Sn), the general formula (V) ▲There are numerical formulas, chemical formulas, tables, etc.▼(V) [However, in the formula, R^1 is a carbon number of 1 to 22 alkyl groups, a plurality of R^1's may be the same or different, n is an integer of 1 to 4 which may be the same or different, and M represents the general formula (IV- 2) has the same meaning as X_1
and X_2 represent a halogen atom, and when M is Al, only X_1 is covalently bonded to M, and when M is Ti, Si, Ge, or Sn, X_1 and X_2 are covalently bonded to M]. synthesize, then this general formula (
By hydrolyzing the compound represented by V), the general formula (VI) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(VI) , multiple R^1s may be the same or different, n is an integer from 1 to 4 that may be the same or different, and M has the same meaning as the general formula (IV-2) above. Indicate, Z_1
and Z_2 represents a hydroxyl group, and when M is Al, only Z_1 is covalently bonded to M, and when M is Ti, Si, Ge, or Sn, Z_1 and Z_2 are covalently bonded to M]. Next, this general formula (
VI) is a compound represented by the general formula (VII) (R^2)_3SiOH(VII) [wherein R^2 is an alkyl group, an aryl group, an alkoxyl group, or an aryloxyl group. ] or the general formula (VIII) R^3OH(VIII) [wherein R^3 is an alkyl group, an aryl group, or a trityl group. General formula (II) characterized by reacting with an alcohol represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [However, in the formula, R^1 is an alkyl group having 1 to 22 carbon atoms. , a plurality of R^1s may be the same or different, n is an integer from 1 to 4 that may be the same or different, and Y_1 and Y_2 are the same or different. may also be 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
, Ge or Sn, and when M is Al, only Y_1 is present; when M is Ti, Si, Ge or Sn, Y_1 and Y
A method for producing a naphthalocyanine derivative represented by _2 is covalently bonded to M. 15. The method for producing a naphthalocyanine derivative according to claim 14, wherein M in general formulas (IV-2), (V), (VI) and (II) is Ge. 16. The method for producing a naphthalocyanine derivative according to claim 14 or 15, wherein n is 1 in general formulas (III), (V), (VI) and (II). 17. Production of a naphthalocyanine derivative according to claim 14, 15 or 16, wherein in general formula (VII), R^2 is an alkyl group, and in general formula (II), Y_1 and Y_2 are both trialkylsiloxyl groups. Law. 18. The method for producing a 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. 19. On the surface of the substrate, there are general formulas (I) ▲mathematical formulas, chemical formulas, tables, etc.▼(I) [However, in the formula, R^1 is an alkyl group having 1 to 22 carbon atoms, and multiple R^ 1 may be the same or different,
n is an integer from 1 to 4 which may be the same or different,
M is a group Ib metal such as Cu, a group IIa metal such as Mg, a group IIb metal such as Zn, Al, ClAl, HOAl,
Group IIIa metals such as In and ClIn, metal halides or metal hydroxides, Si, Cl, Si, (HO)_
2Si, Ge, Cl_2Ge, (HO)_2Ge, Sn
, Cl_2Sn, (HO)_2Sn, group IVa metals such as Pb, metal halides or metal hydroxides, Ti
, IVb group metals or metal oxides such as OTi, Vb group metal oxides such as OV, VIb group metals such as Cr, Mo, VIIb group metals or metal halides such as Mn, ClMn, or Fe, ClFe, Co, Ni, Pt, Pd
1. An optical information recording medium comprising a recording film layer mainly composed of a naphthalocyanine derivative represented by a group VIII metal or a metal halide such as VIII group metal or metal halide. 20. In general formula (I), M is Cu, Zn, Cl
Al, ClIn, Si, Ge, Sn, OVMn, Co,
20. The optical information recording medium according to claim 19, further comprising a recording film layer mainly composed of a naphthalocyanine derivative of Ni or Pd. 21. The optical information recording medium according to claim 19 or 20, further comprising a recording film layer mainly composed of a naphthalocyanine derivative in general formula (I), where n is 1. 22. In the general formula (I), R^1 has a carbon number of 13 to
Claims 19 and 20, wherein the recording film layer is formed mainly of a naphthalocyanine derivative having 22 alkyl groups.
Or the optical information recording medium according to 21. 23. On the surface of the substrate, there are general formula (II) ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (II) [However, in the formula, R^1 is an alkyl group having 1 to 22 carbon atoms, and multiple R^ 1 may be the same or different,
n is an integer from 1 to 4 which may be the same or different,
Y_1 and Y_2 may be the same or different, and are an aryloxyl group, an alkoxyl group, a trialkylsiloxyl group, a triarylsiloxyl group, a trialkoxysiloxyl group, a triaryloxy, a siloxyl group, or a trityloxyl group. Yes, M is Al, 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
is covalently bonded to M]. 1. An optical information recording medium comprising a recording film layer containing a naphthalocyanine derivative as a main component. 24. The optical information recording medium according to claim 23, wherein the recording film layer is formed mainly of a naphthalocyanine derivative in general formula (II), where M is Ge. 25. The optical information recording medium according to claim 23 or 24, wherein the recording film layer is formed mainly of a naphthalocyanine derivative in general formula (II), where n is 1. 26. The optical information according to claim 23, 24 or 25, wherein the recording film layer is formed mainly of a naphthalocyanine derivative in which Y_1 and Y_2 are both trialkylsiloxyl groups in general formula (II). recoding media. 27. Claims 23 and 24, wherein a recording film layer is formed whose main component is a naphthalocyanine derivative in which Y_1 and Y_2 are both alkoxyl groups in general formula (II).
Or the optical information recording medium according to 25. 28. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) n is an integer from 1 to 4 which may be the same or different, M is C
Group Ib metals such as u. Group IIa metals such as Mg, Group IIb metals such as Zn, Al,
Group IIIa metals such as ClAl, HOAl, In, ClIn, metal halides or metal hydroxides, Si,
Cl_2Si, (HO)_2Si, Ge, Cl_2Ge
, (HO)_2Ge, Sn, Cl_2Sn, (HO)_
Group IVa metals such as 2Sn and Pb, metal halides or metal hydroxides, Group IVb metals or metal oxides such as Ti and OTi, metal oxides of Group Vb such as OV, Cr
, VIb group metals such as Mo, V such as Mn, ClMn, etc.
Group IIb metals or metal halides or Fe, ClF
A recording film layer is formed on the surface of the substrate using a solution in which a naphthalocyanine derivative represented by the following formula is mainly dissolved in an organic solvent: 1. A method of manufacturing an optical information recording medium, the method comprising: forming an optical information recording medium. 29. In the general formula (I), M is Cu, Zn, C
nAl, ClIn, Si, Ge, Sn, OV, Mn, C
29. The method for producing an optical information recording medium according to claim 28, using a naphthalocyanine derivative which is O, Ni or Pd. 30. The method for producing an optical information recording medium according to claim 28 or 29, using a naphthalocyanine derivative in which n is 1 in general formula (I). 31. In the general formula (I), R^1 has a carbon number of 13 to
31. The method for producing an optical information recording medium according to claim 28, 29 or 30, using a naphthalocyanine derivative having 22 alkyl groups. 32. General formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) [However, in the formula, R^1 is an alkyl group having 1 to 22 carbon atoms, and multiple R^1s may be the same. It's okay to be different,
n is an integer from 1 to 4 which may be the same or different,
Y_1 and Y_2 may be the same or different, and are an aryloxyl group, an alkoxyl group, a trialkylsiloxyl group, a triarylsiloxyl group, a trialkoxysiloxyl group, a triaryloxysiloxyl group, or a trityloxyl group. Yes, M is Al, Ti, Si, Ge, or Sn, and when M is Al, only Y_1 is covalently bonded to M, and when M is Ti, Si, Ge, or Sn, Y_1 and Y_2 are covalently bonded to M. . ] A method for manufacturing an optical information recording medium, comprising forming a recording film layer on a substrate surface using a solution in which a naphthalocyanine derivative represented by the following is dissolved mainly in an organic solvent. 33. The method for producing an optical information recording medium according to claim 32, wherein a naphthalocyanine derivative in general formula (II) in which M is Ge is used. 34. The method for producing an optical information recording medium according to claim 32 or 33, using a naphthalocyanine derivative in which n is 1 in general formula (II). 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 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, using a naphthalocyanine derivative in which Y_1 and Y_2 are both alkoxyl groups in general formula (II).