JPH0726037B2 - Novel naphthalocyanine dye, method for producing the same, and optical information recording medium using the same - Google Patents

Description

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

(Prior Art) An optical information recording medium has a feature that the recording medium does not wear and deteriorate because a recording or reproducing head of the medium is not in contact, and various recording media have been researched and developed.
In particular, in the field of heat mode recording method which has an advantage of a semiconductor laser or the like, it has been proposed as a substance in which a low melting point metal, an organic polymer compound or a dye melts, evaporates or sublimes. The thin film is preferable in terms of recording sensitivity because it has a low thermal conductivity and a low melting or sublimation temperature.
Various substances such as squarylium dye have been proposed.

Conventionally, an optical information recording medium to which a dye is applied as a recording layer is known from JP-A-56-16948. However, in order to use this kind of dye thin film recording layer as a reflection type optical information recording medium, a metal reflection film is required, which complicates the medium structure and deteriorates information recording / reproducing characteristics. There's a problem. On the other hand, it has been proposed in JP-A-60-78787 to use a cyanine dye or the like having an appropriately high reflectance of the dye itself.
However, since cyanine dyes generally have low light resistance, there is a problem that when reading after writing, the dyes are decolorized by repeated irradiation of reading light, and the S / N ratio of reading decreases.

On the other hand, it has been proposed in JP-A-61-25886 and JP-A-61-177287 to use a naphthalocyanine compound as a dye having excellent light fastness in a recording layer. However, the reflectance of the naphthalocyanine dye shown in the former patent publication is generally lower than that of the cyanine dye, and it is not sufficiently satisfactory in terms of recording and reproducing characteristics. Also,
The latter patent publication proposes to use the substance similar to the naphthalocyanine dye of the present invention in an information recording medium, but shows an example in which its effectiveness as an optical information recording medium was confirmed. Therefore, it is impossible to judge whether the recording / reproducing characteristics are satisfactory or not, and the reflectance is sufficiently satisfactory.

(Problems to be Solved by the Invention) The present invention has been made in view of the above situation, and was earnestly studied to improve the above-mentioned conventional drawbacks, and a novel naphthalocyanine dye was produced and used. When an optical information recording medium was produced, it was found that the optical information recording medium had a reflectance equal to or higher than that of a cyanine dye and was excellent in reproduction deterioration characteristics, and thus completed the present invention.

That is, an object of the present invention is to provide a novel naphthalocyanine dye and a method for producing the same, and to use the same to provide an optical information recording medium having excellent recording / reproducing characteristics and improved reproducing deterioration characteristics. To provide.

(Means for Solving Problems) The first invention relates to a novel naphthalocyanine dye represented by the following general formula (I).

(In the formula, R represents an alkyl group or an aryl group having 1 to 22 carbon atoms, and three Rs may be the same group or different groups. M is Si, Al, Ti , Ge and Sn, and Y ₁ and Y ₂ are OR ′, OAr, OSi (R ′) ₃ , OSi (Ar) ₃ and O.
It is selected from the group consisting of C (Ar) ₃ and may be the same or different, but when M is Al, only Y ₁ is bonded to M. R'represents an alkyl group having 1 to 22 carbon atoms and Ar represents an aryl group or an aralkyl group.) The novel naphthalocyanine dye represented by the general formula (I) is an aromatic dye, a halogen dye or an ether dye. It is soluble in ketone solvents, can be easily purified to improve its purity, has no change in absorption due to the type and concentration of solvent, and has a high reflectance itself, and the ability to absorb semiconductor laser light. It is also extremely excellent in light resistance.

Examples of the aromatic solvent include benzene, toluene, xylene, chlorobenzene, 1-chloronaphthalene and quinoline, and examples of the ether solvent include diethyl ether, dibutyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, There are diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, etc., and the above ketone solvents include acetone, methyl ethyl ketone, methyl propyl ketone, cyclopentanone,
Examples include cyclohexanone and acetone alcohol.

In the general formula (I), examples of the alkyl group having 1 to 22 carbon atoms of R include a methyl group, an ethyl group, a propyl group,
Isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group,
Examples thereof include a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a heneicosyl group, and a docosyl group. Of these, a methyl group and an ethyl group are preferable. Examples of the aryl group of R include a phenyl group,
Examples thereof include a tolyl group, a xylyl group, a hydroxyphenyl group, a naphthyl group, an anthryl group and a pyrenyl group, and among them, a phenyl group is preferable. M is selected from the group consisting of Si, Al, Ti, Ge and Sn. Y ₁ and Y ₂ are OR ′, OAr, OSi
(R ′) ₃ , OSi (Ar) ₃ and OC (Ar) ₃ which may be the same or different, and among these, OR ′, OAr, OSi (R ′) ₃ and OSi (Ar) ₃ are preferred. When M is Al, Y ₁ is bonded, and in other cases, Y ₁ and Y ₂ are bonded. Examples of the alkyl group having 1 to 22 carbon atoms of R'in Y ₁ and Y ₂ include the 1 to 22 carbon atoms of R described above.
Examples of the alkyl group are the same as those described above, and among these, an alkyl group having 1 to 18 carbon atoms is preferable. Examples of the aryl group of Ar in Y ₁ and Y ₂ include the same as the aryl group of R described above, and among them, a phenyl group is preferable. Examples of the aralkyl group of Ar in Y ₁ and Y ₂ include a benzyl group, a phenylethyl group, a methylbenzyl group, a naphthylmethyl group and the like, and among these, a benzyl group and a methylbenzyl group are preferable.

The following can be given as examples of the novel naphthalocyanine dye.

(1) [(nC ₆ H _{13) 3} SiO] ₂ SINC [Si (CH _{3) 3] 4} bis (tri-hexyl-silyloxy) - tetrakis (trimethylsilyl) naphthalate Russian Nino - in silicon above formula, Nc naphthalocyanine Represents the skeleton.

(2) [(CH _{3) 3} SiO] ₂ SINC [Si (CH _{3) 3] 4} bis (trimethylsilyloxy) - tetrakis (trimethylsilyl) naphthalate Russian Nino - silicon (3) [(C ₂ H _{5) 3} SiO] ₂ GENC [Si (CH _{3) 3] 4} bis (triethylsilyl oxy) - tetrakis (trimethylsilyl) naphthalate Russian Nino - germanium (4) [(nC ₄ H _{9) 3} SiO] ₂ SnNc [Si (CH _{3) 3] 4-bis} (tri-butylsilyloxy) - tetrakis (trimethylsilyl) naphthalate Russia Nino - tin ₍₅₎ C ₆ H 5 OAlNc [Si (CH _{3) 3] 4} tetrakis (trimethylsilyl) naphthalate Russia Nino - phenoxyethanol aluminum (6) [ (nC ₃ H _{7) 3} SiO] ₂ TINC [Si (CH _{3) 3] 4} bis (tripropyl silyloxy) - tetrakis (trimethylsilyl) naphthalate Russian Nino - titanium (7) [(CH _{3) 3} SINC [Si ( CH _{3) 2} C ₆ H _{5] 4-bis} (trimethylsilyl Carboxymethyl) - tetrakis (dimethyl phenylalanine silyl) naphthalate Russian Nino - silicon _{(8) (C 2 H 5} O) 2 SiNc [Si (C ₆ H _{5) 3] 4} Bisuetokishi - tetrakis (triphenyl silyl) naphthalate Russian Nino - silicon (9) [(C ₆ H _{5) 3} SiO] ₂ SINC [Si (C ₂ H _{5) 3] 4} bis (triphenyl silyloxy) - tetrakis (triethylsilyl) naphthalate Russian Nino - silicon (10) [( nC ₄ H _{9) 3} SiO] ₃ SINC [Si (nC ₄ H _{9) 3] 4} bis (tri butylsilyloxy) - tetrakis (tributylsilyl) naphthalate Russian Nino - silicon (11) [(C ₂ H _{5) 3} SiO ] ₂ SiNc [Si (CH ₃ ) ₂ nC ₁₈ H ₃₇ ] ₄ Bis (triethylsilyloxy) -tetrakis (dimethyloctadecylsilyl) naphthalocyanino-silicon (12) [(C ₂ H ₅ ) ₃ SiO] ₂ SiNc [ _{Si (CH 3) 2 nC 10} H 21 ] _4-bis (triethylsilyl oxy) - tetra Scan (dimethyl decyl silyl) naphthalate Russian Nino - silicon (13) [(C ₂ H _{5) 3} SiO] ₂ GENC _{[Si (CH 3) 2 nC 14} H 29 ] _4-bis (triethylsilyl oxy) - tetrakis (dimethyl tetra Decylsilyl) naphthalocyanino-germanium Among these compounds, (1) and (3) are preferable.

The second invention is the following general formula (In the formula, R represents an alkyl group or an aryl group having 1 to 22 carbon atoms, and three Rs may be the same group or different groups.) Alternatively, triarylsilyl-2,3-dicyanonaphthalene (however, two or more kinds of these compounds may be used) is represented by the following general formula (III) MXn (III) (where M is Si, Al, Ti, Ge). And Sn, and X
Represents a halogen atom, n represents a positive integer representing the number of bonds of X to M), and is reacted with a metal halide represented by the following general formula (I
V) (Where R is the same as in formula (II), M and X are
Same as in I)), a dihalogenometal-tetrakis (trialkylsilyl or triarylsilyl) naphthalocyanine derivative represented by the following general formula is obtained by hydrolyzing the compound represented by the formula (IV). (V) (Wherein R is the same as in formula (II) and M is the same as in formula (III)) to obtain a dihydroxy metal-tetrakis (trialkylsilyl or triarylsilyl) naphthalocyanine derivative, and An alcohol represented by the following general formula (VI) R ″ OH (VI) or a halide represented by the following general formula (VII) R ″ Cl (VII) (formula (VI) And (VII), R ″ is R ′, Ar, Si (R ′) ₃ ,
Selected from the group consisting of Si (Ar) ₃ and C (Ar) ₃ , R ′ is an alkyl group having 1 to 22 carbon atoms, Ar is an aryl group,
R ′ and Ar may be the same or different) and a method for producing a novel naphthalocyanine-based dye represented by the following general formula (I).

(In the formula, R is the same as in formula (II), M is the same as in formula (III), and Y ₁ and Y ₂ are OR ′, OAr, OSi
(R ') ₃ , OSi (Ar) ₃ and OC (Ar) ₃ , which may be the same or different, but M is
When Al, only Y ₁ is bound to M.
R'represents an alkyl group having 1 to 22 carbon atoms, Ar represents an aryl group or an aralkyl group.) The novel naphthalocyanine dye represented by the general formula (I) is a compound represented by the general formula (V). It can be obtained by heating and reacting an excess of the alcohol represented by the general formula (VI) or the halide represented by the general formula (VII). In this case, the reaction temperature is preferably 80 to 250 ° C, and the reaction time is preferably 30 minutes to 10 hours. This reaction is carried out without a solvent, or as a solvent, benzene, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, 1
It is preferable to use -chloronaphthalene, tetralin, pyridine, β-picoline, quinoline and the like.

The isolation and purification of the novel naphthalocyanine dye represented by the general formula (I) from the reaction mixture is carried out by separating the reaction mixture by column chromatography or thin layer chromatography and then by recrystallization. It can be carried out by a method such as purification.

The dihydroxy metal-tetrakis (trialkylsilyl or triarylsilyl) naphthalocyanine derivative represented by the general formula (V) can be obtained by subjecting the compound represented by the general formula (IV) to hydrolysis reaction with heating. . In this case, the reaction temperature is preferably 50 to 150 ° C, and the reaction time is preferably 30 minutes to 10 hours. To do this,
Pyridine / water, pyridine / ammonia water, methanol /
It is preferable to carry out the reaction in a mixed solvent of ammonia water, ethanol / ammonia water, propanol / ammonia water or the like, or to treat with concentrated sulfuric acid and then with ammonia water.

In the metal halide represented by the general formula (III), examples of the halogen atom include Cl, Br, I and the like.

The trialkylsilyl- or triarylsilyl-2,3-dicyanonaphthalene represented by the general formula (II) is a known compound and can be produced, for example, as follows. That is, the following general formula (VIII) (In the formula, R represents an alkyl group or an aryl group having 1 to 22 carbon atoms) 2,3- or 3,4-dimethyltrialkylsilyl or triarylsilylbenzene represented by the formula (IX) A general formula (X) obtained by irradiating light with N-bromosuccinimide represented by In the formula, R represents an alkyl group having 1 to 22 carbon atoms or an aryl group. ) Is represented by the formula (XI) It is a method for synthesizing a trialkylsilyl- or triarylsilyl-2,3-dicyanonaphthalene represented by the general formula (II) by reacting with fumaronitrile represented by the formula under heating. In the present invention, two or more compounds represented by the general formula (II) may be optionally reacted with the metal halide represented by the general formula (III).

Generally, the reaction of 2,3- or 3,4-dimethyltrialkylsilyl or triarylsilylbenzene represented by the general formula (VIII) with N-bromosuccinimide represented by the formula (IX) is 2,3 -Or 3,4-dimethyltrialkylsilyl or triarylsilylbenzene (0.2 mol) and N-bromosuccinimide (0.8 mol) under high pressure mercury lamp irradiation in a solvent inert to light irradiation of 200 to 1000 ml, 4 to It can be carried out by heating under reflux for 12 hours. For the reaction, it is necessary to add a peroxide, which is a radical generator, as a photoreaction initiator. Examples of peroxides include benzoyl peroxide, octanoyl peroxide, cyclohexanone peroxide, isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, methyl ethyl ketone peroxide, etc., usually 500 ml of solvent
Used in the range of 500mg to 2g. The solvent inert to the light irradiation is appropriately selected from halogen solvents such as chloroform and carbon tetrachloride, or aromatic solvents such as benzene and chlorobenzene.

Further, the reaction between the compound represented by the general formula (X) and the fumaronitrile represented by the formula (XI) is performed by adding 1 mol of the fumaronitrile represented by the formula (XI) to 1 mol of the compound represented by the general formula (X). The reaction temperature is 70 ℃ ～ 100.
C is preferable, and the reaction time is preferably 5 to 10 hours. As the solvent, polar organic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N, N-diethylformamide and N, N-diethylacetamide are preferable.

A third invention relates to an optical information recording medium characterized in that an organic thin film containing a naphthalocyanine dye represented by the following general formula (I) as a main component is formed on a substrate.

(In the formula, R represents an alkyl group having 1 to 22 carbon atoms or an aryl group, which may be the same or different. M is S
selected from the group consisting of i, Al, Ti, Ge and Sn, Y ₁ and Y ₂ are O
R ′, OAr, OSi (R ′) ₃ , OSi (Ar) ₃ and OC (Ar) ₃ may be the same or different, but when M is Al , Y ₁ are only bound to M. R'represents an alkyl group having 1 to 22 carbon atoms, Ar
Represents an aryl group or an aralkyl group.) The optical information recording medium is one in which a recording layer containing the novel naphthalocyanine dye of the first invention as a main component is provided on a substrate. Other layers such as formations and protective layers can be provided.

The substrate material used is known to those skilled in the art and can be either transparent or opaque to the laser light used. However, when writing and reading with laser light from the substrate side, it must be transparent to the laser light. On the other hand, when writing and reading are performed from the side opposite to the substrate, that is, the recording layer side, it is not necessary to be transparent to the laser light used. The material of the substrate may be a commonly used recording material support such as glass, quartz, ceramics, plastic, paper, plate-shaped or foil-shaped metal. In addition, the substrate may be provided with a guide groove formed by unevenness, if necessary.

The recording layer can be formed by a coating method, a printing method or a vapor deposition method. In the optical information recording medium, it is economically advantageous to form the recording layer by a coating method or the like, and in the present invention, it is preferable to use the coating method or the printing method. When the coating method is used, a solvent such as toluene, chloroform, dichloroethane or methyl ethyl ketone can be used, and spraying, roller coating, spin coating, or dipping can be used.

The optical information recording medium should have an organic thin film containing a novel naphthalocyanine dye, which has a moderate absorption rate and reflectance in the wavelength range of laser light and is excellent in light resistance, as a recording layer. It has both excellent recording and reproducing characteristics and improved reproduction deterioration characteristics. Also,
The novel naphthalocyanine dye is excellent in solubility in various organic solvents and is superior to the conventional technique in the recording layer forming process.

(Examples) Hereinafter, the present invention will be described in more detail by showing specific examples of the present invention, but the present invention is not limited thereto.

Exemplified in Example 1 info [(nC ₆ H _{13) 3} SiO] ₂ SINC [Si (CH _{3) 3] 4} bis (tri-hexyl-silyloxy) - tetrakis (trimethylsilyl) naphthalate Russian Nino - silicon was dissolved in toluene The recording layer with a thickness of 50 nm was formed on the glass substrate by spin coating. This recording medium was irradiated with a semiconductor laser with a wavelength of 830 nm from the glass substrate side and the recording characteristics were evaluated. Recording was possible with a beam diameter of 1.6 μm, a linear velocity of 0.5 m / sec, and 4.2 mW. On the other hand, in order to evaluate the stability against reproduction deterioration, 1 mW of read light was repeatedly irradiated, but no change in reflectance occurred even after repeating 10 ⁶ times.

Comparative Example A cyanine dye NK-2905 (manufactured by Japan Photosensitive Dye Research Institute) was dissolved in dichloroethane and spin-coated to obtain a recording layer having a thickness of 50 nm on a glass substrate. Example 1 is recorded on this recording medium.
When the laser light was irradiated in the same manner as above, recording was possible at 4.8 mW. However, when the stability against regeneration deterioration was evaluated, it was found that the number of repeated irradiations was around 4 × 10 ⁴ times,
The reflectance started to decrease, and after 10 ⁶ irradiations, it decreased to 70% of the initial reflectance.

Example 2 [Synthesis of trimethylsilyl-o-xylene] To 14.4 g of well-dried shaving magnesium, a small amount of iodine crystals, and then 250 ml of ethyl ether were added. Under nitrogen atmosphere, a solution of 92.5 g of 4-bromo-o-xylene dissolved in 100 ml of ethyl ether was added dropwise over about 2 hours so that the reaction solution gently refluxed. After the dropping was completed, stirring was continued at room temperature for about 1 hour to prepare a Grignard reagent.

Next, 90 g of trimethylchlorosilane and 2 of ethyl ether
While refluxing 50 ml, the Grignard reagent was added dropwise over about 1 hour and then refluxed for another 1 hour. After allowing to cool, while cooling in an ice bath, a saturated aqueous solution of ammonium chloride was added dropwise to decompose the Grignard reagent, and the ether solution was separated from the reaction solution. The remaining aqueous solution was extracted with benzene three times, and the extracts were combined and dried over anhydrous magnesium sulfate. When this solution was concentrated and distilled under reduced pressure, the boiling point was 98
At ~ 103 ° C / 27-30 mmHg, 40 g of 4-trimethylsilyl-o-xylene was obtained as a colorless liquid.

[Synthesis of 6-trimethylsilyl-2,3-dicyanonaphthalene] 35.6 g of 4-trimethylsilyl-o-xylene and 142.4 g of N-bromosuccinimide were added to 1 g of benzoyl peroxide in 500 ml of carbon tetrachloride, and the mixture was placed in an internal irradiation tube It was irradiated with light from a high-pressure mercury lamp (100W) for about 12 hours while refluxing. After cooling, the precipitated white crystals were removed by suction filtration, and the carbon tetrachloride solution of the mother liquor was sufficiently concentrated under reduced pressure. The obtained pale and colored oily substance was dissolved in 800 ml of anhydrous N, N-dimethylformamide, and 27 g of fumaronitrile, and then 200 g of sodium iodide were added while stirring well, and the mixture was stirred at 75 ° C. for about 7 hours under a nitrogen atmosphere. After the reaction, pour the contents into about 4 kg of ice,
Sodium bisulfite was gradually added until the red and colored aqueous solution became pale yellow. A slight excess amount was added, the mixture was stirred for a while, and then left overnight at room temperature. The precipitated pale yellow solid was suction filtered, washed thoroughly with water, and then washed several times with methanol. The obtained solid was recrystallized from ethanol / acetone to give 6-trimethylsilyl-2,3 as colorless crystals.
16 g of dicyanonaphthalene were obtained.

[Synthesis of Bis (triethylsilyloxy) -tetrakis (trimethylsilyl) naphthalocyanino-germanium]

6-trimethylsilyl-2,3-dicyanonaphthalene 12.5
28 ml of germanium tetrachloride was added to 50 g of ammonium molybdate and 50 g of urea, and the mixture was heated at 240 ° C. for 2 hours and a half.
After cooling, water was added, the reaction mixture was suction filtered, and the mixture was thoroughly filtered with water and then methanol to give 0.68 black green crystals.
g got. The electronic spectrum (CHCl ₃ solution) of this crystal is shown in FIG. This crystal was considered to be tetrakis (trimethylsilyl) naphthalocyanino-dichlorogermanium and was used in the next reaction without further purification. 0.38 g of the above crystals was added to 39 ml of water, 10 ml of ethanol, and 10 ml of concentrated ammonia water.
Was added to the mixed solvent of and the mixture was refluxed for about 2 hours. After cooling, the reaction mixture was filtered, washed with methanol about 10 times, and dried to obtain 0.29 g of a black-green solid. The electronic spectrum (CHCl ₃ solution) of this solid is shown in FIG. This solid was considered to be tetrakis (trimethylsilyl) naphthalocyanino-dihydroxygermanium and was used in the next reaction without further purification. Chlorobenzene 2 of the above black green solid 0.21g
1 g of triethylsilanol was added to the 0 ml solution, and the mixture was refluxed for about 1 hour and then concentrated until the amount of the solution became about half. After cooling, about 100 ml of methanol was added, and the precipitated precipitate was filtered and thoroughly washed with methanol. The obtained solid was separated and purified by alumina column chromatography using benzene as a developing solvent, and 0.13 g of green crystals was obtained. From the following analysis results, it was confirmed that this crystal was bis (triethylsilyloxy) -tetrakis (trimethylsilyl) naphthalocyanino-germanium. The electronic spectrum (CHCl ₃ solution) is shown in FIG.
The elemental analysis values are as follows.

CHN calculated value (%) 66.93 6.71 8.67 Measured value (%) 67.18 6.85 8.41 [Recording test] Bis (triethylsilyloxy) -tetrakis (trimethylsilyl) naphthalocyanino-germanium [(C ₂ the H _{5) 3} SiO] ₂ GENC [Si (CH _{3) 3] 4} was dissolved in chloroform, by spin coating, on a glass substrate, to obtain a recording layer having a thickness of 70 nm. Example 1 is recorded on this recording medium.
When the laser light was irradiated in the same manner as above, recording was possible at 4.9 mW. When the stability against reproduction deterioration was evaluated in the same manner, no change in reflectance occurred even after repeated irradiation of 10 ⁶ times.

Example 3 Bis (tri butylsilyloxy) - tetrakis (trimethylsilyl) naphthalate Russian Nino - tin [(nC ₄ H _{9) 3} SiO]
₂ SnNc [Si (CH ₃ ) ₃ ] ₄ was spun onto the glass substrate for 8
A 0 nm recording film was obtained. When this recording medium was irradiated with laser light in the same manner as in Example 1, recording was possible at 5.8 mW. When the stability against reproduction deterioration was evaluated in the same manner, no change in reflectance occurred even after repeated irradiation of 10 ⁶ times.

Example 4 A recording layer having a thickness of 50 nm was formed on the polycarbonate substrate of the naphthalocyanine compound shown in the table below by a vapor deposition method. Recording / reproducing characteristics and reproducing deterioration characteristics were evaluated in the same manner as in Example 1. The results are listed in the table below.

Example 5 [(nC ₆ H _{13) 3} SiO] ₂ SINC [Si (CH _{3) 3] 4} and polystyrene
Dissolve a 2: 1 mixture in toluene and place it on a glass substrate with a thickness of 60n.
A recording layer of m was obtained. When evaluated in the same manner as in Example 1, a recording sensitivity of 4.8 mW and a reproduction deterioration characteristic of 10 ⁶ times or more were obtained.

(Effect of the invention) The optical information recording medium according to the third invention using the novel naphthalocyanine dye according to the first invention, which can be manufactured according to the second invention, exhibits excellent recording / reproducing information, and It can be seen that the reproduction deterioration characteristics are improved as compared with the conventional organic dye-based recording medium.

[Brief description of drawings]

FIG. 1 is an electron spectrum of tetrakis (trimethylsilyl) naphthalocyanino-dichlorogermanium in Example 2, and FIG. 2 is an electron spectrum of tetrakis (trimethylsilyl) naphthalocyanino-dihydroxygermanium in Example 2. The figure is the electronic spectrum of bis (triethylsilyloxy) -tetrakis (trimethylsilyl) naphthalocyanino-germanium in Example 2.

Claims (11)

[Claims] 1. A novel naphthalocyanine dye represented by the following general formula (I). (In the formula, R represents an alkyl group or an aryl group having 1 to 22 carbon atoms, and three Rs may be the same group or different groups. M is Si, Al, Ti , Ge and Sn, and Y ₁ and Y ₂ are OR ′, OAr, OSi (R ′) ₃ , OSi (Ar) ₃ and O.
It is selected from the group consisting of C (Ar) ₃ and may be the same or different, but when M is Al, only Y ₁ is bonded to M. R'represents an alkyl group having 1 to 22 carbon atoms, Ar represents an aryl group or an aralkyl group) 2. The novel naphthalocyanine dye according to claim 1, wherein both Y ₁ and Y ₂ in the general formula (I) are OR 'or OAr. 3. A novel naphthalocyanine dye according to claim 1, wherein Y ₁ and Y ₂ in the general formula (I) are both OSi (R ′) ₃ or OSi (Ar) ₃ . 4. The novel compound according to claim 1, wherein R in the general formula (I) is all methyl groups, M is Si, and Y ₁ and Y ₂ are trihexylsilyloxy groups. Naphthalocyanine dye. 5. The novel naphtha according to claim 1, wherein R in the general formula (I) is all methyl groups, M is Ge, and Y ₁ and Y ₂ are triethylsilyloxy groups. Phthalocyanine dye. 6. The following general formula (II) (In the formula, R represents an alkyl group or an aryl group having 1 to 22 carbon atoms, and three Rs may be the same group or different groups.) -Or triarylsilyl-2,3 dicyanonaphthalene (however, this compound
Or more) may be used in the following general formula (III) MXn (III) (wherein M is selected from the group consisting of Si, Al, Ti, Ge and Sn, and X
Represents a halogen atom, and n represents a positive integer representing the number of bonds of X to M) and is reacted with a metal halide represented by the following general formula (I
V) (Where R is the same as in formula (II), M and X are
Same as in I)), a dihalogenometal-tetrakis (trialkylsilyl or triarylsilyl) naphthalocyanine derivative represented by the following general formula is obtained by hydrolyzing the compound represented by the formula (IV). (V) (Wherein R is the same as in formula (II), M is the same as in formula (III)), and a dihydroxy metal-tetrakis (trialkylsilyl or triarylsilyl) naphthalocyanine derivative is obtained. The compound represented by the formula (V) is converted into an alcohol represented by the following general formula (VI) R ″ OH (VI) or a halide represented by the following general formula (VII) R ″ Cl (VII) (formulas (VI) and ( VII), R ″ is R ′, Ar, Si
Selected from the group consisting of (R ′) ₃ , Si (Ar) ₃ and C (Ar) ₃ .
R'is an alkyl group having 1 to 22 carbon atoms, Ar is an aryl group, and R'and Ar may be the same or different.) ) A method for producing a novel naphthalocyanine dye. (Where R is the same as in formula (II), M is the same as in formula (III), and Y ₁ and Y ₂ are OR ′, OAr, OSi (R ′)
₃ , OSi (Ar) ₃ and OC (Ar) ₃ , which may be the same or different, but when M is Al, only Y ₁ is bonded to M. Be present. R'represents an alkyl group having 1 to 22 carbon atoms, Ar represents an aryl group or an aralkyl group) 7. An optical information recording medium comprising an organic thin film containing a naphthalocyanine dye represented by the following general formula (I) as a main component, formed on a substrate. (In the formula, R represents an alkyl group having 1 to 22 carbon atoms or an aryl group, which may be the same or different. M is S
selected from the group consisting of i, Al, Ti, Ge and Sn, Y ₁ and Y ₂ are O
R ′, OAr, OSi (R ′) ₃ , OSi (Ar) ₃ and OC (Ar) ₃ may be the same or different, but when M is Al , Y ₁ are only bound to M. R'represents an alkyl group having 1 to 22 carbon atoms, Ar
Represents an aryl group or an aralkyl group) 8. The optical information recording medium according to claim 7, wherein Y ₁ and Y ₂ in the general formula (I) are both OR ′ or OAr. 9. The method according to claim 7, wherein Y ₁ and Y ₂ in the general formula (I) are both OSi (R ′) ₃ or OSi (Ar) ₃ .
An optical information recording medium according to the item. 10. The optical composition according to claim 7, wherein R in the general formula (I) is all methyl groups, M is Si, and Y ₁ and Y ₂ are trihexylsilyloxy groups. Information recording medium. 11. The optical information according to claim 7, wherein R in the general formula (I) is all methyl groups, M is Ge, and Y ₁ and Y ₂ are triethylsilyloxy groups. recoding media.