JPH0832836B2 - Tetranaphthoporphyrazine derivative and optical recording material containing the derivative - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel tetranaphthoporphyrazine derivative and an optical recording body containing the derivative as a light absorbing substance in a recording layer.

Optical recording using a laser, especially a semiconductor laser,
In order to enable high-density information recording storage and reproduction,
In recent years, this is a technology that is particularly desired to be developed. An optical disk can be mentioned as an example of such optical recording.

In general, an optical disc is one in which a thin recording layer provided on a circular substrate is irradiated with laser light focused to about 1 μm to perform high density information recording.

Recording is generated by thermal deformation such as decomposition, evaporation, and dissolution of the recording layer at that location by absorption of irradiated laser energy, and reproduction of recorded information is performed.
This is performed by reading the difference in reflectance between the portion where deformation has occurred and the portion where deformation has not occurred, using laser light.

Therefore, it is necessary for the recording medium to efficiently absorb the energy of the laser light, so that the absorption of the laser light of the specific wavelength used for recording is large, and in order to reproduce the information accurately, It is necessary that the reflectance with respect to the laser light of the wavelength is high.

[Conventional technology]

As such an optical recording material, various kinds of metals, materials using inorganic compounds such as metal compounds and chalcogenides have been proposed so far, but these thin films are susceptible to aerial oxidation and can be stored for a long period of time. There are problems that it is difficult, it is sensitive to light in the ultraviolet and visible parts, and it is weak to sunlight and other light. On the other hand, as an optical recording material using an organic compound instead of such an inorganic compound, one using a cyanine dye, a squarylium dye, a naphthoquinone dye, a phthalocyanine dye, or the like has been proposed.

[Problems to be Solved by the Invention]

However, among the organic compounds as described above, the phthalocyanine dyes are generally preferable because they have excellent weather resistance, and some of them are also suitable for the wavelength of the semiconductor laser (800 n
However, the absorption at the vicinity of 720 nm in the evaporated film of vanadyl phthalocyanine changes to 815 nm by heating (Molecular Crystals and Liquid Crystals 33 , 149).
~ 170 (1976)]. Further, the tetranaphthoporphyrazine-based compound also has absorption in the region near 800 nm, but those having no substituent on the naphthalene ring have extremely low solubility in a solvent, and therefore a recording layer cannot be formed by coating. , Has the problem.

It is an object of the present invention to provide a novel tetranaphthoporphyrazine derivative capable of solving the above conventional problems and an optical recording material using the derivative.

[Means for solving the problem]

The present inventors have arrived at the present invention as a result of intensive research to achieve such an object. That is, the present invention has the general formula [I] {In the formula, any one of X and Y is a --O (CH ₂ CH ₂ O) _n Z group (wherein Z is a tetrahydrofurfuryl group or a benzyl group which may have a substituent on the benzene ring). Shown, n is 0
Represents an integer of from 6 to 6. ), The other one represents a hydrogen atom, and A represents a VO or a metal atom of Cu, Ni or Co. } The tetranaphthoporphyrazine derivative shown by these,
Another object of the present invention is to provide an optical recording body comprising a substrate and a recording layer, the recording layer containing a tetranaphthoporphyrazine derivative represented by the general formula [I] shown above as a light absorbing substance. .

Such novel tetranaphthoporphyrazine derivatives of the present invention each have absorption in the near infrared region around 700 to 900 nm, have good light resistance and heat resistance, and as will be described later, a light-absorbing substance of an optical recording material. As is very useful. Above all,
A tetranaphthoporphyrazine derivative in which Z represents a tetrahydrofurfuryl group, n represents a number of 0, and A represents VO in the general formula [I] shown above is preferable.

Further, the optical recording medium of the present invention solves the problems of the conventional optical recording medium described above and improves its function by using the tetranaphthoporphyrazine derivative of the present invention as a light absorbing substance. It is a thing.

The tetranaphthoporphyrazine derivative represented by the general formula [I] shown above of the light-absorbing substance used in the optical recording material of the present invention has the following general formula [II] (In the formula, Z and n have the same meanings as in the above-mentioned general formula [I].) And a naphthalene-2,3-dicarboxylic acid derivative and a vanadium, copper, nickel or cobalt halide or oxide. In a quinoline or chloronaphthalene solvent in the presence of urea for about 1 to 5 hours, 200
It can be synthesized by heating to ℃ to 250 ℃. When nickel, cobalt or copper halide is used as the metal compound, it is preferable to add a small amount of ammonium molybdate as a catalyst because the yield is increased.

The optical recording medium of the present invention basically comprises a substrate and a recording layer, but if necessary, an undercoat layer may be provided on the substrate and a protective layer may be provided on the recording layer.

The substrate in the present invention may be transparent or opaque to the laser light used. As a material of the substrate, a support for a recording medium of this type such as glass, plastic, paper, plate-shaped or foil-shaped metal can be generally used, but plastic is preferable from various points. Examples of the plastic include acrylic resin, methacrylic resin, vinyl acetate resin, vinyl chloride resin, nitrocellulose, polyethylene resin, polypropylene resin, polycarbonate resin, polyimide resin, polysulfone resin and the like.

The thickness of the recording layer containing the light absorbing dye, which is the information recording layer in the optical recording material of the present invention, is 100Å to µm, preferably 500Å to 3 µm.

In order to form such a recording layer on the substrate surface in the present invention, a coating method is preferable. As a film forming method by coating, the above-mentioned general formula [I] used as a light absorbing substance is used.
In the tetranaphthoporphyrazine derivative of the present invention shown in, dissolved or dispersed in a solvent or a mixture of a solvent and a binder, such as a method of spin coating, and the like, the binder in such cases, a polyimide resin, polyamide Examples thereof include resins, polystyrene resins, acrylic resins, polyester resins, polycarbonate resins, cellulosic resins and the like. At that time, the ratio of the light absorbing substance to the resin is preferably 10 wt% or more. Also,
In this case, various solvents such as dimethylformamide, methyl ethyl ketone, methyl cellosolve, ethanol, tetrahydrofuran, dichloromethane, chlorobenzene can be used. As a substrate,
When a polycarbonate resin substrate or a methacrylic resin substrate manufactured by injection molding is used, the solvent is preferably ethyl cellosolve or ethanol.

The recording layer of the optical recording medium of the present invention may be provided on both sides of the substrate, or may be provided on only one side.

Recording on the optical recording material obtained as described above is performed by irradiating a laser beam, preferably a semiconductor laser beam, focused on a recording layer of about 1 μm provided on both sides or one side of the substrate. In the portion irradiated with laser light, thermal deformation of the recording layer such as decomposition, evaporation, and melting occurs due to absorption of laser energy.

The recorded information is reproduced by using a laser beam to read the difference in reflectance between the portion where thermal deformation has occurred and the portion where thermal deformation has not occurred.

As the light source, various lasers such as He-Ne laser, Ar laser, and semiconductor laser can be used,
A semiconductor laser is particularly preferable in terms of price and size.

As a semiconductor laser, the central wavelength is 830 nm and the central wavelength is 7
Lasers of 80 nm and shorter wavelengths can be used.

〔Example〕

Next, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples. In addition, "%" is "% by weight" unless otherwise specified.

Example 1 Synthesis of 5-tetrahydrofurfuryloxy-2,3-naphthalenedicarboxylic acid anhydride 5-hydroxy-2,3-naphthalenedicarboxylic acid (mp2
94-296 ° C.) 100 g was dispersed in methanol 1, 5% 97% sulfuric acid was added, and the mixture was stirred under reflux for 20 hours. After cooling, add to 4 liters of ice water, separate the precipitated crystals, wash with water, dry and mp
102 g of dimethyl 5-hydroxy-2,3-naphthalenedicarboxylate at 121 to 123 ° C was obtained. This 5-hydroxy-2,3
-Dimethyl naphthalene dicarboxylate (mp121-123 ℃) 26
g, 35 g of paratoluenesulfonic acid tetrahydrofurfuryl ester previously synthesized from p-toluenesulfonyl chloride and tetrahydrofurfuryl alcohol according to a conventional method and 9.0 g of potassium carbonate were mixed with chlorobenzene 500
It was added to the mixture and stirred under reflux for 10 hours. Then, after allowing to cool, the precipitated crystals were separated and chlorobenzene was removed from the liquid by distillation under reduced pressure to obtain 40 g of a pale brown tar-like substance.

The tar-like substance was dispersed in 500 ml of a 5% NaOH aqueous solution and stirred under reflux for 5 hours. After cooling, concentrated hydrochloric acid was added dropwise with ice cooling to adjust the pH to 3, and the precipitate was separated and dried to obtain 25 g of pale yellow crystals. The crystals were recrystallized from acetone to obtain 5-tetrahydrofurfuryloxy-2,3-naphthalenedicarboxylic acid anhydride having an mp of 186 to 188 ° C. The structure of this compound is represented by the following formula [III] Was confirmed by mass spectrum.

Synthesis of Tetranaphthoporphyrazine Derivative of the Present Invention 5-Tetrahydrofurfuryloxy-2,3-naphthalenedicarboxylic anhydride (mp186 obtained as described above
~ 188 ℃) 6.0g and 10.0g of urea after crushing and mixing in a mortar,
The reaction was carried out while stirring at 150 ° C to 180 ° C for 3 hours. Then, after cooling to about 100 ° C., 1.0 g of vanadium trichloride and 10 ml of quinoline were added, and the mixture was heated and stirred at 200 ° C. to 220 ° C. for 2 hours. After cooling to room temperature, methyl alcohol 10
0 ml was added and the mixture was stirred under reflux for 1 hr. Crystals obtained by heating this product were washed with 1% aqueous sodium hydroxide solution 10
The mixture was added to a mixed solution of 0 ml and 100 ml of ethyl alcohol, and the mixture was stirred under reflux for 2 hours. This was heated to obtain 5.4 g of dark green crystals. This crystal was dissolved in 200 ml of chloroform, and silica gel (Wako Pure Chemical Industries, Ltd., trade name Wakogel C
-200) as a packing material and purified by column chromatography (eluent: chloroform: methyl alcohol = 10: 1 mixture) to obtain 1.7 g of green crystals.

The substance (crystal) thus obtained is considered to contain isomers, and its typical structure is represented by the following formula [IV] The elemental analysis value is C69.21%, H4.78
%, Calculated with N9.50% (C69.21%, H4.76%, N9.50%)
Well matched. In addition, the λmax of this substance in a chloroform solution is 827 nm, and the molecular extinction coefficient ε is 13.8 × 10 ⁴
Met.

Examples 2 to 4 The following general formula [V] (In the formula, R is shown in Table 1 below.) Three examples of the tetranaphthoporphyrazine derivative of the present invention represented by the following were synthesized according to Example 1. Table 1 below shows the λmax and molecular extinction coefficient ε of each of the substances (crystals) obtained in Examples 2 to 4 in a chloroform solution together with the measurement results of Example 1 above.

Example 5 The following formula [VI] 5- (benzyloxy-ethoxy-ethoxy-ethoxy) -2,3-naphthalenedicarboxylic acid anhydride represented by the following was synthesized according to Example 1. 4.36 g (0.01 mol) of the obtained dicarboxylic acid anhydride (mp70-85 ° C) and urea 1
0 g was crushed and mixed in a mortar and reacted at 150 ° C to 180 ° C for 3 hours. After cooling to about 100 ° C, 1 g of cobalt chloride hexahydrate and 10 ml of quinoline were added, and the mixture was stirred at 200 ° C to 220 ° C for 3 hours, then cooled to room temperature, and then methyl alcohol 10
0 ml was added, and the mixture was heated and stirred under reflux for 3 hours. This was heated and the resulting solution was added to 300 ml of 1% hydrochloric acid. The precipitated solid was filtered and dried to obtain pale green crystals with a melting point of 50 ° C or lower. 1% sodium hydroxide solution
It was added to a mixture of 100 ml and 100 ml of ethyl alcohol, heated and stirred under reflux for 1 hour. After cooling, the crystals obtained by passing were washed with water and dried to obtain 1.1 g of green crystals.

The obtained substance (crystal) is considered to include isomers, and its typical structure is represented by the following formula [VII] Can be shown as The λmax of this substance in a chloroform solution was 770 nm, and the molecular extinction coefficient ε was 10.5 × 10 ⁴ .

Examples 6 to 8 According to Example 5, in Example 6, 5- (benzyloxy-ethoxy-ethoxy-ethoxy) -2,3-naphthalenedicarboxylic acid anhydride was used as a nickel compound, and in Example 7, the anhydride was used. Was reacted with a copper compound, and in Example 8, 5- (tetrahydrofurfuryloxy-ethoxy-ethoxy-ethoxy) -2,3-naphthalenedicarboxylic acid anhydride was reacted with a cobalt compound.

As a result, each of the obtained substances (crystals) is considered to contain isomers. As typical structures thereof, the substance of Example 6 has the following formula [VIII], and the substance of Example 7 has the following formula. The substance of formula [IX] and Example 8 can be represented by the following formula [X].

In addition, the measurement results of λmax and molecular extinction coefficient ε in the chloroform solution of each substance of Examples 6 to 8 are collectively shown in Table 2 below together with the measurement results of Example 5 described above.

Example 9 A 3% tetrachloroethane solution of the light-absorbing substance of the present invention having a typical structure represented by the structural formula [IV] synthesized based on Example 2 was prepared and spin-coated (rotation speed 1000 rp
m), the dry film thickness is 700Å ~ 8 on a 1.2 mm thick PMMA substrate.
It was applied so that it would be 00Å. The maximum absorption wavelength of the formed thin film was 840 nm, and its peak was broad.

When a laser beam having a center wavelength of 830 nm of the thin film was incident from the substrate side with an output mW beam diameter of about 1 μm, a very clear hole (pit) having a width of about 1 μm and a pit length of about 2 μm was formed.

〔The invention's effect〕

The novel tetranaphthoporphyrazine derivative of the present invention has absorption in the near infrared region around 700 to 900 nm, has good light resistance and heat resistance, and is unlikely to cause a change in absorption wavelength due to heating, and has an optical recording property. It has the industrially significant effect of being easy to apply to the substrate surface of the body.

Further, the optical recording material of the present invention contains such a novel tetranaphthoporphyrazine derivative of the present invention as a light-absorbing substance for the recording layer, and therefore not only is it excellent in light resistance and heat resistance, The peak of the maximum absorption wavelength of the thin film of the layer is wide, and when a laser beam is incident on this thin film, a remarkable effect that a hole (pit) having an extremely clear contour is formed is exhibited.

Claims (2)

[Claims] 1. A general formula [I] {In the formula, any one of X and Y is a --O (CH ₂ CH ₂ O) _n Z group (wherein Z is a tetrahydrofurfuryl group or a benzyl group which may have a substituent on the benzene ring). Shown, n is 0
Represents an integer of from 6 to 6. ), The other one represents a hydrogen atom, and A represents a VO or a metal atom of Cu, Ni or Co. } The tetranaphthoporphyrazine derivative shown by these. 2. An optical recording material comprising a substrate and a recording layer, the recording layer containing a tetranaphthoporphyrazine derivative represented by the general formula [I] shown above as a light absorbing substance.