JPH0713192B2 - Dioxadinaphthopentacene derivative and optical recording medium using the derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention provides 9,19-dioxadinaphtho- [3,2,1-de; 3,2,
The present invention relates to a 1-OP] pentacene derivative and an optical recording medium using the derivative. Specifically, the present invention is
The present invention relates to a novel dioxadinaphthopentacene derivative and an optical recording medium which uses the derivative and performs recording by utilizing a change in a material state by light energy having an oscillation wavelength of a semiconductor laser.

[Prior Art] As an optical recording medium for recording by utilizing a change in a material state by light energy of an oscillation wavelength of a semiconductor laser, various recording media have been known.

For example, JP-A-55-97033 discloses a substrate in which a single layer of a phthalocyanine dye is provided.
Further, JP-A-58-83344 discloses a phenalene dye, and JP-A-58-224793 discloses a naphthoquinone dye in a recording layer.

[Problems to be Solved by the Invention] Among the above conventional optical recording media, in the one using the phthalocyanine dye disclosed in JP-A-55-97033, the phthalocyanine dye has a low sensitivity and a decomposition point. It has a problem that it is high in vapor deposition and has a problem that it cannot be used for coating by coating because the solubility in an organic solvent is extremely low.

On the other hand, the dyes disclosed in JP-A-58-83344 and JP-A-58-224793 have the advantage of easy vapor deposition, but have the problem of low reflectance. If the reflectance is low, the contrast relating to the reflectance between the portion recorded by the laser beam and the unrecorded portion becomes low, and it becomes difficult to reproduce the recorded information. In addition, organic dyes generally have a problem of poor storage stability.

[Means for Solving Problems] The present invention solves the above-mentioned conventional problems, facilitates vapor deposition,
Novel dioxadinaphthopentacene derivative having high solubility in an organic solvent, coating by coating is possible, high reflectance, good contrast and excellent storage stability, and an optical recording medium using the same The following dye skeleton is provided for the purpose of providing (Where X is Or indicates O. ) 9,19-dioxadinaphtho- [3,2,1-de; 3,
An optical recording medium characterized in that a 2,1-OP] pentacene derivative and a recording layer containing the above derivative are provided.

Hereinafter, the present invention will be described in detail.

In the present invention, 9,19-dioxadinaphtho- [3,2,1-d
The e; 3,2,1-OP] pentacene derivative is preferably the following general formula [I] (Where X is Or O, R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms, alkyl groups,
It represents an alkoxy group, an alkoxyalkoxy group, a halomethyl group or a halogen atom, and R ⁵ and R ⁶ represent a hydrogen atom or a halogen atom. ) The dye represented by

In the dye represented by the above general formula [I], R ¹ , R ² ,
Examples of the alkyl group represented by R ³ and R ⁴ include C such as methyl group, ethyl group, linear or branched propyl group, butyl group, pentyl group, heptyl group, hexyl group and octyl group.
The alkyl group of _1-8 is mentioned. Examples of the alkoxy group include C such as methoxy group, ethoxy group, linear or branched propoxy group, butoxy group, pentyloxy group, heptyloxy group, hexyloxy group and octyloxy group.
The alkoxy group of _1-8 is mentioned. Examples of the alkoxyalkoxy group include methoxyethoxy group, ethoxyethoxy group, methoxypropoxy group, butoxyethoxy group and the like, and examples of the halomethyl group include chloromethyl group, bromomethyl group and the like. Examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom and an iodine atom.

Further, examples of the halogen atom represented by R ⁵ and R ⁶ include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom.

The dye represented by the general formula [I] is generally 700 to 900 nm.
Has absorption in the wavelength band of 10 to 1 and a molecular absorption coefficient of 10 ⁴ to 1
It is 0 ⁵ cm ^-1 .

The dioxadinaphthopentacene compound represented by the general formula [I] is, for example, the following general formula [II] (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same as defined above.) The compound represented by the following structural formula in chloroform in the presence of pyridine and titanium tetrachloride: It can be produced by reacting malonnitrile represented by

Next, the optical recording medium of the present invention using such a novel dioxadinaphthopentacene compound of the present invention will be described.

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

The substrate used in the present invention may be either transparent or opaque to the laser light used. Examples of the material of the substrate material include supports for general recording materials such as glass, plastic, paper, plate-shaped or foil-shaped metal, and among these, 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.

When the compound of the general formula [I] is used as the information recording layer in the optical recording medium of the present invention, the film thickness is 100Å to 5
It is preferable that the thickness is μm, preferably 1000 Å to 3 μm.

As the film forming method, a commonly used thin film forming method such as a vacuum vapor deposition method, a sputtering method, a doctor blade method, a casting method, a spinner method and a dipping method can be adopted.

When forming a film, a binder may be used if necessary. Known binders such as PVA, PVP, nitrocellulose, cellulose acetate, polyvinyl butyral, and polycarbonate are used, and the amount of the compound of the general formula [I] to these binder resins is 0.01 or more by weight. Is desirable. In order to improve the stability and light resistance of the recording material, a transition metal chelate compound (eg, acetylacetonate chelate, bisphenyldithiol, saltylaldehyde oxime, bisdithio-α-diketone, etc.) is used as a singlet oxygen quencher.
May be included. Further, other dyes can be used in combination, if necessary. Other dyes may be compounds of the same family of different types, triarylmethane dyes,
Other types of dyes such as azo dyes, cyanine dyes, squarylium dyes may be used.

Doctor blade method, casting method, spinner method, dipping method, in particular, as a coating solvent when forming the recording layer by a coating method such as a spinner method, bromoform, dibromoethane, tetrachloroethane, ethylsulosolve, xylene, chlorobenzene, Boiling point of cyclohexanone 120
Those having a temperature of up to 180 ° C are preferably used.

When the film is formed by the spinner method, the rotation speed is 500 to 500.
0 rpm is preferred, after spin coating, in some cases,
Processing such as heating or applying to solvent vapor may be performed.

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

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

A semiconductor laser is suitable as the laser beam used for recording or reproducing on the optical recording medium of the present invention from the viewpoints of light weight, easy handling, compactness and the like.

[Operation] 9,19-dioxazinanaphtho- [3,2,1 provided by the present invention
-De; 3,2,1-OP] Pentacene derivatives are easy to deposit, have high solubility in organic solvents, can be coated by coating, and have high reflectance, good contrast, and good storage stability. Are better.

Therefore, by using such a derivative, it is possible to easily and efficiently obtain a high-performance optical recording medium excellent in various characteristics such as recording and reproduction and having high stability.

[Examples] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Example 1 Synthesis The following structural formula 12.2 g of the compound represented by was dissolved in 125 ml of chloroform, and 6.9 ml of titanium tetrachloride was added. Then, the following structural formula A solution consisting of 16.5 g of malonnitrile represented by, 40.5 ml of pyridine and 125 ml of chloroform was added dropwise.

After the dropwise addition, the mixture was heated under reflux for 5 hours, allowed to cool to room temperature, and the reaction product was poured into 500 ml of water. The precipitated crystals were filtered, washed with water and suspended in methanol twice to obtain 10 g of black crystals. The black crystals were purified by silica gel column chromatography to obtain black crystals having the following physical properties and represented by the structural formula [III] below.

Molecular extinction coefficient (ε): 8.0 × 10 ⁴ λmax in chloroform solution: 790 nm Mass spectrum: 648 (M ⁺ ) Melting point: 270 to 275 ° C Formation film 1.0 g of the dye represented by the above structural formula [III] and 50 g of tetrachloroethane Was dissolved in the solution and filtered through a 0.22 μm filter to obtain a solution. 2 ml of this solution, depth 700 Å, width 0.7
Drop it on a PMMA resin substrate (120 mmφ) with a groove (μm) made of UV curable resin of 100 μm and use a spinner method to obtain 100
It was applied at a rotation speed of 0 rpm. After coating, it was dried at 60 ° C. for 10 minutes. It was 750 Å when it was applied to a glass plate under the same conditions and the film thickness was measured by the Taristep. The coating film had a maximum absorption wavelength of 760 nm and a reflectance of 24% (830 nm). The shape of the spectrum was wide. FIG. 1 shows the absorption and reflection spectra of the coating film.

Optical recording This coating film was irradiated with a semiconductor laser beam having a central wavelength of 830 nm at an output of 4 mW and a beam diameter of 1 μm. As a result, extremely clear bits having a width of about 1 μm and a bit length of about 2 μm were formed. C / N ratio was as high as 58 dB (8 mW) in the evaluation of dynamic characteristics, and storage stability (60 ° C, 80% RH) was also good.

Example 2 A film was formed in the same manner as in Example 1 except that the compound shown in Table 1 below was used instead of the compound represented by the structural formula [III]. A thin film substrate with the maximum absorption wavelength shown was obtained.

When writing was performed on the thin film thus obtained using a semiconductor laser as a light source, a bit with a uniform and clear shape was obtained, its C / N ratio was good, and its storage stability was also good. It was

Example 3 A dye represented by the following structural formula [IV] (molecular extinction coefficient (ε) and λmax in a chloroform solution are described below) was heated to about 80 to 150 ° C. under a vacuum of 1.6 × 10 ⁻⁵ Torr. It was heated and vacuum-deposited on a polycarbonate resin (hereinafter referred to as PC) substrate having a plate thickness of 1.2 mm and having a 1.6 μm pitch groove (group). As a result of measuring the vapor deposition film thickness by vacuum vapor deposition film thickness measurement with a crystal vibration type film thickness meter, it was 600Å. The maximum absorption wavelength measured by the spectrophotometer is 760 nm, and the reflectance is 28%.
(830 nm). The shape of the spectrum was broad.

Molecular extinction coefficient (ε): 8.0 × 10 ⁴ λmax in chloroform solution: 778 nm The thin film thus obtained has a central wavelength as a light source.
When writing was performed with a beam diameter of about 1 μm using a semiconductor laser of 830 nm, bits with a uniform and clear shape were obtained, and the C / N ratio was 55 dB (8 mW) in the dynamic characteristic evaluation, which was good.

This recording medium has a temperature of 60 ° C and a humidity of 90% in room light.
It exhibited good storage stability under the conditions of.

Example 4 Instead of the dye used in Example 1, the compounds shown in Table 2 below were used for vapor deposition to obtain a thin film substrate having the maximum absorption wavelength shown in Table 2 below.

When writing was performed on the obtained thin film using a semiconductor laser as a light source, bits having a uniform and clear shape were obtained. The C / N ratio was also good, and the storage stability was also good.

[Effects of the Invention] As described in detail above, the dioxadinaphthopentacene derivative of the present invention is easy to deposit, has high solubility in an organic solvent, can be coated by coating, and has high reflectance. Good contrast and excellent storability.

Therefore, the optical recording medium of the present invention provided with a recording layer containing such a derivative can be produced easily and efficiently, and has excellent characteristics such as recording and reproduction, and high stability. It is extremely useful industrially.

[Brief description of drawings]

FIG. 1 is an absorption and reflection spectrum diagram of the coating film obtained in Example 1.

Claims (4)

[Claims] 1. The following dye skeleton (Where X is Or indicates O. ) 9,19-dioxadinaphtho- [3,2,1-de; 3,
2,1-OP] Pentacene derivative. 2. The following general formula (Where X is Or O, R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms, alkyl groups,
It represents an alkoxy group, an alkoxyalkoxy group, a halomethyl group or a halogen atom, and R ⁵ and R ⁶ represent a hydrogen atom or a halogen atom. ) 9,19-dioxazinnaphtho- [3,2,1-de; 3,2,1-O according to claim 1, characterized in that
P] Pentacene derivative. 3. An optical recording medium for recording and reproducing by causing a state change by a laser beam, wherein the substrate has the following dye skeleton. (Where X is Or indicates O. ) 9,19-dioxadinaphtho- [3,2,1-de; 3,
An optical recording medium comprising a recording layer containing a 2,1-OP] pentacene derivative. 4. A 19,19-dioxadinaphtho- [3,2,1-de; 3,
The 2,1-OP] pentacene derivative is represented by the following general formula (Where X is Or O, R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms, alkyl groups,
It represents an alkoxy group, an alkoxyalkoxy group, a halomethyl group or a halogen atom, and R ⁵ and R ⁶ represent a hydrogen atom or a halogen atom. ) The optical recording medium according to claim 3, wherein the optical recording medium is represented by