JPH01105788A - Optical recording medium - Google Patents

Abstract

PURPOSE:To enable recording of high sensitivity which is chemically physically stable to be reproduced by laser beams, by forming an organic thin film layer containing one kind or not less than two kinds of specific naphthalocyanine compounds given by the formula on a substrate. CONSTITUTION:An organic thin film layer containing at least one kind or not less than two kinds of naphthalocyanine compounds given by the formula is formed as a recording layer on a substrate. In the formula, X represents a sulfur atom, a selenium atom, or a tellurium atom. A represents a substituted or nonsubstituted aliphatic hydrocarbon group, a substituted or nonsubstituted aromatic hydrocarbon group, or a substituted or nonsubstituted aromatic heterocyclic group. M represents a hydrogen atom, a halogen atom, or a metal atom which may contain an oxygen atom. Though k, l, m, and n respectively represent independently an integer of zero-four, all of them do not simultaneously become zero.

Description

[Detailed Description of the Invention] [Object of the Invention] (Industrial Application Field) The present invention provides a method for writing information using a laser beam,
The present invention relates to optical recording media that can be read and read.

(Prior Art) There are various types of media that record information using laser beams. One of them is to irradiate a recording layer on a substrate with a laser beam to locally heat the irradiated area.
Some materials record information by causing physical changes such as melting, evaporation, or decomposition.

Until now, As, Te, Se, T
Thin film layers of metals and alloys such as i have been used. Optical recording media having such a recording layer generally have relatively high writing sensitivity and can be applied to semiconductor lasers, which allow the optical system for recording and reproduction to be made compact; however, they have high thermal conductivity. 2. Due to reasons such as low reflectance, the energy of the laser beam cannot be used efficiently during recording,
High-speed scanning sometimes requires a high-power laser beam. Furthermore, these recording layers were chemically unstable and could deteriorate in the air.

For this reason, in recent years relatively long wavelengths (for example 78
Research has been carried out on optical recording media in which information is written to and read from an organic thin film layer on a substrate using a laser beam with a diameter of 0 nm or more.

Such an organic thin film layer has the advantage that small recesses (pits) can be easily formed by melting, evaporating, or decomposing using a semiconductor laser.

Optical recording media in which an organic thin film layer is formed on a substrate and information is recorded and reproduced using laser beams are disclosed in JP-A-57-82093, JP-A-58-56892, and JP-A-60- Publication No. 89842.

The one described in Japanese Patent Application Laid-open No. 150243/1983 is known. However, the reality is that a completely satisfactory optical recording medium that has a large absorption coefficient for semiconductor laser beams and high recording sensitivity has not been developed.

(Problems to be Solved by the Invention) The present inventors discovered that an optical recording medium having a recording layer containing a specific naphthalocyanine compound on a substrate had various excellent properties, and completed the present invention. The present invention is chemically and physically stable, and can be recorded and reproduced with high sensitivity using a laser beam. An object of the present invention is to provide an optical recording medium using an inexpensive specific naphthalocyanine compound.

[Structure of the invention]

(Means for Solving the Problems) The present invention includes, as a recording layer, an organic thin film layer containing at least one or two or more naphthalocyanine compounds represented by the following general formula (1) on a substrate. This is a characteristic optical recording medium.

[In the formula, X represents a sulfur atom, a selenium atom, or a tellurium atom.

A: Substituted or unsubstituted aliphatic hydrocarbon group.

Represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted aromatic heterocyclic group.

M: a hydrogen atom, a metal atom that may have a halogen atom or an oxygen atom, or (OR+)p, (OS i R2Rs Ra)q
.

(OS i Rt R5C0Rt)) represents a metal atom that may have -. Here, RI, R2゜R'l, R4
are each independently a hydrogen atom.

Substituted or unsubstituted aliphatic hydrocarbon group.

Substituted or unsubstituted aromatic hydrocarbon group.

or represents a substituted or unsubstituted aromatic heterocyclic group,
p and q represent integers from 0 to 2.

k, l, m, and n: Each independently represents an integer from O to 4, but not all of them are O at the same time. ] Next, to explain the substituents of the compound represented by the above general formula [I], A is a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic hydrocarbon group. Represents a substituted aromatic heterocyclic group, eg, phenyl group, naphthyl group.

anthonyl group, methyl group, ethyl group, propyl group.

pentyl group, hexyl group, octyl group, stearyl group,
Substituents include, but are not limited to, a pyridyl group, a carbazolyl group, a dibenzofuryl group, and a benzothiazolyl group. Also, these groups.

It may have substituents such as hydroxyl group, alkyl group, halogen atom, amino group, dialkylamino group, alkoxy group, nitro group, cyano group, aralkyl group, aryl group, but is limited to these substituents. isn't it.

M is H, Na, Li, Cu, Fe, Co, Ni.

Zn, Mn, pb, Si, Ge, Mg, Al-C
l.

In-Cl, Ti=O, V=O, or.

−(OR+)p + (OS t Rz Rx R
a) q, or (OS i Rz R3(ORi
)) Represents a metal atom that may have q. Here, R
i, Rz, R3, and R4.

Each independently represents a hydrogen atom or the same meaning as A in general formula (1), and p and q represent an integer from O to 2. k, 1. m and n each independently represent an integer from 0 to 4, but not all of them are 0 at the same time, and are preferably an integer from 0 to 2.

The naphthalocyanine compound represented by the above general formula [I] has large absorption in the visible to near-infrared region, and is suitable for recording and reproducing using a laser beam.

The naphthalocyanine compound represented by the above general formula (1) used in the present invention is generally represented by the following general formula (II).
It can be produced by heating one or more nitriles represented by and various metal salts (not used when producing metal-free naphthalocyanine), preferably in an organic solvent.

(wherein, X and A represent the same meanings as in general formula CI), k, It, m and n are O
represents an integer from 4 to 4) Furthermore, various naphthalocyanine compounds can be obtained by mixing and reacting nitriles having different substituents represented by the general formula (n). Also, general formula (1)
The naphthalocyanine compounds represented by can also be produced using naphthalic acids (general formula (nI)) and naphthalimides (general formula [■]) as starting materials.

General formula (III) 0 (wherein, X and A represent the same meanings as in general formula (1), and k, It, m and n are 0
(representing an integer from 4 to 4) for the production of these naphthalocyanine compounds.

Alcohols, glycols, xylene, quinoline.

α-Chlornaphthalene, nitrobenzene, sulfolane,
Common organic solvents such as N,N-dimethylformamide can be widely used, but it can also be obtained without a solvent.

Further, it may be preferable to use an alkali or an organic amine such as diazabicycloundecene or cyclohexylamine as a catalyst.

Moreover, two kinds of metal salts can be used as the raw material metal salts.

More specific representative examples of the naphthalocyanine compounds represented by the general formula [I] used in the present invention include di-ethylthiocopper naphthalocyanine, tributylthiovanadylnaphthalocyanine, tetra-n-pentylthiocopper naphthalocyanine, and tetra-n-pentylthiocopper naphthalocyanine. -n-hexylthiovanadylnaphthalocyanine, tetra-n-hexylthiotitanylnaphthalocyanine, tetra-n-octylthiozinc naphthalocyanine, tetra-n-stearylthio-vanadylnaphthalocyanine, tetra(2-ethylhexylthio)
Lead naphthalocyanine, hexa-n-propylthiocopper naphthalocyanine, hexa-n-butylthiomanganese naphthalocyanine, octaethylthiocopper naphthalocyanine, octa-n-butylthio-aluminum chlornaphthalocyanine, tetraphenylthio metal-free naphthalocyanine,
Tetraphenylthiocopper naphculocyanine, tetraphenythiovanadylnaphthalocyanine.

Tetraphenylthiotitanylnaphthalocyanine, tetraphenylselenocopper naphthalocyanine, tetra(2-chlorophenylthio)copper naphthalocyanine.

Tetra(2,4-dimethylphenylthio)vanadylnaphthalocyanine, Tetra(3-methoxyphenylthio)titanylnaphthalocyanine, Octaphenylthionicelnaphthalocyanine, Octa(2-methylphenylthio)
Copper naphthalocyanine, tetra(2-methoxyethylthio)copper naphthalocyanine, tetra(2-methoxyethylthio)titanylnaphthalocyanine, dihydroxysilicon tetraphenylthionapthalocyanine, bis[trimethylsiloxy]silicon tetraphenylthionapthalocyanine, dihexyloxysilicon tetraethyl Thionaphthalocyanine.

Bis[butoxytriethyleneoxydimethylsiloxy]
Silicon tetrahexylthionapthalocyanine.

Bis[hydroxyethyloxydiethylsiloxy]silicon tetraphenylthionaphthalocyanine and the like. Other dyes can also be used by mixing and dispersing or mixing and dissolving these naphthalocyanine compounds.

In the present invention, the substrate material on which the recording layer is provided includes various materials such as glass, plastic, paper, and metal plates. Plastics include vinyl chloride resin, acrylic resin, polyester resin, polyethylene resin, polyamide resin, polycarbonate resin, epoxy resin, methacrylic resin, vinyl acetate resin, nitrocellulose,
Polypropylene resin.

Examples include polyethylene terephthalate resin and phenol resin.

In the present invention, methods for forming the recording layer containing the natalocyanine compound represented by general formula [I] on the substrate include vacuum evaporation method, sputtering method, ion plate method, casting method, and spinner method.

There are chemical and mechanical methods such as the spray coating method, the blade coach ink method, and the LB method, but the spinner method is the most preferred. When coating using the spinner method.

A phthalocyanine compound is dispersed or dissolved in a common organic solvent such as alcohols, ketones, amides, sulfoxides, ethers, esters, aliphatic halogenated hydrocarbons, aromatic hydrocarbons, etc. and applied. At this time,
A polymer binder may be added if necessary. As a polymer/sl material, plastics such as those used for the substrate material can be used.

The thickness of the recording layer containing the naphthalocyanine compound formed on the substrate is 10 μm or less, preferably 500 μm to 2 μm.
It is less than μm. After application, the absorption wavelength of the thin film is shifted to longer wavelengths by exposing it to vapors of organic solvents such as lily, loloform, tetrahydrofuran, and toluene.
In some cases, sensitivity to laser light can be significantly improved.

In addition, in order to protect these recording layers, Al□0.
.

An inorganic compound such as SiO, SiO, SnO, etc. may be deposited to form a protective layer. As a protective layer, it is also possible to apply a polymer similar to that used for substrate materials).

The optical recording medium of the present invention can be written and read using various laser beams such as a) le-Ne laser beam as well as ruby, Ar, and semiconductor laser beams.

(Example) The present invention will be explained more specifically by examples.

The present invention is limited to the following examples and is not limitative.)

Note that 9% of the 9 examples is % by weight.

Synthesis Example 1 Synthesis of tetra-〇-hexylthiovanadylnaphthalocyanine To 30 parts by weight of n-amyl alcohol, 6-(n
-hexylthio)-2,3-dicyanonaphthalene 2.9
parts by weight, 0.5 parts by weight of vanadium trichloride, and 2.0 parts by weight of diazabicycloundecene (DBU).

After refluxing for 5 hours, it was diluted with 300 parts by weight of methanol, the product was filtered, washed with methanol, and then diluted with 1% hydrochloric acid and 1% hydrochloric acid.
% sodium hydroxide aqueous solution and water.

After drying, 2.0 parts by weight of tetra-n-hexylthiovanadylnaphthalocyanine was obtained.

Synthesis Example 2 Synthesis of tetraphenylthiotitanylnaphthalocyanine To 35 parts by weight of nitrobenzene, 6-phenylthio-2,
2.9 parts by weight of 3-dicyanonaphthalene and 2.5 parts by weight of titanium tetrachloride were added, heated and stirred at 180 to 200°C for 8 hours, diluted with 500 parts by weight of methanol, and the product was filtered and diluted with methanol. After washing, wash with 1% hydrochloric acid and 1% sodium hydroxide aqueous solution, and then wash with water.

After drying, 1.8 parts by weight of tetraphenylthiotitanylnaphthalocyanine was obtained.

Synthesis Example 3 Synthesis of tetra(2-chlorophenylthio)copper naphthalocyanine To 30 parts by weight of quinoline, 3.2 parts by weight of 6-(2-chlorophenylthio)-2,3-dicyanonaphthalene and 1.5 parts by weight of cuprous chloride. After adding 0 parts by weight and heating and stirring at 160 to 170°C for 5 hours, diluted with 500 parts by weight of methanol,
The product was filtered, washed with methanol, and then washed with 1% hydrochloric acid and 1%
Wash with aqueous sodium hydroxide solution.

Wash with water and dry, Tetra(2-chlorophenylthio)
2.6 parts by weight of copper naphthalocyanine was obtained.

Synthesis Example 4 Tetra(2-methoxyethoxyethylthio)
Synthesis of vanadylnaphthalocyanine 40 parts by weight of n-amyl alcohol, 3.2 parts by weight of 6-(2-methoxyethoxyethylthio)-2,3-dicyanonaphthalene, 0.5 parts by weight of vanadium trichloride, and
After adding 2.0 parts by weight of DBU and refluxing for 4 hours, the cooled 2.0 parts by weight reaction solution was added with 1.0 parts by weight of water. Pour into O1, filter out the precipitated crystals,
After washing with water and drying, it was recrystallized from ethanol to obtain 0.8 parts by weight of tetra(2-methoxyethoxyethylthio)copper naphthalocyanine.

Synthesis Example 5 Synthesis of dihydroxysilicon tetraethylthionaphthalocyanine To 50 parts by weight of quinoline, 2.4 parts by weight of 6-ethylthio-2,3-dicyanonaphthalene and 0.5 parts by weight of silicon tetrachloride.
After adding parts by weight and heating and stirring at 190 to 200°C for 4 hours, the mixture was diluted with 300 parts by weight of chloroform.

The product was filtered, washed with chloroform, and then dried under reduced pressure to obtain 1.2 parts by weight of dichlorosilicon tetraethylthionaphthalocyanine. 1.0 parts by weight of the obtained dichlorosilicon tetraethylthionaphthalocyanine was added to 300 parts by weight of 3% sodium hydroxide solution.

After stirring at room temperature for 2 hours, the mixture was filtered and washed with water to obtain 0.8 parts by weight of dihydroxysilicon tetraethylthionaphthalocyanine.

Synthesis Example 6 Synthesis of bis[trihexylsiloxy]silicon tetraphenylthionaphthalocyanine 6-ethylthio-
1.5 parts by weight of dihydroxysilicon tetraphenythionaphthalocyanine was prepared in the same manner as in Synthesis Example 5, except that 2.4 parts by weight of 2,3-dicyanonaphthalene was replaced with 3.1 parts by weight of 6-phenythio-2,3-dicyanonaphthalene. I got the department.

1.0 parts by weight of the obtained dihydroxysilicon tetraphenylthionaphthalocyanine and 1.5 parts by weight of trihexylsilanol were added to 50 parts by weight of benzene, and the mixture was refluxed for 4 hours.

After cooling, the product was filtered and washed with 20 parts by weight of n-hexane to obtain 1.2 parts by weight of bis[trihexylsiloxy]silicon tetraphenylthionaphthalocyanine.

Synthesis Example 7 Synthesis of bis[butoxytriethyleneoxydimethylsiloxy]silicon tetrahexylthionapthalocyanine 2.4 parts by weight of 6-ethylthio-2,3-dicyanonaphthalene was mixed with 3.2 parts by weight of 6-hexylthio-2,3-dicyanonaphthalene. 1.8 parts by weight of dihydroxysilicon tetrahexylthionapthalocyanine was obtained in the same manner as in Synthesis Example 5 except that the amount was changed to 1.8 parts by weight. 1.0 parts by weight of the obtained dihydroxysilicon tetrahexylthionapthalocyanine, 8 parts by weight of dichlorodimethylsilane, and 20 parts by weight of tri-n-butylamine were added to 50 parts by weight of dry pyridine,
Stir at room temperature for 18 hours.

After distilling off excess dichlorodimethylsilane and cooling,
30 weight of triethylene glycol monobutyl ether was added, and the mixture was stirred at 110 to 130 liters for 6 hours.

It was cooled to 100°C and filtered hot. The obtained filtrate,
Pour into 1000 parts by weight of ice water and filter the precipitate.

The product was washed with water, washed with a mixed solution of methanol/water (1/1 weight ratio), and dried to obtain 1.2 parts by weight of bis[butoxytriethyleneoxydimethylsiloxy]silicon tetrahexylthionaphthalocyanine.

Example 1 A solution obtained by dissolving 5 parts by weight of tetra-n-hexylthiovanadylnaphthalocyanine in 100 parts by weight of dichloromethane was placed on a polycarbonate resin substrate for 500 rpm.
After applying with pm spinner coating method, 80-90
The recording layer was dried at a temperature of 1 hour to obtain a recording layer having a thickness of about 8.0 mm.

The optical recording medium obtained in this way was attached to a turntable, and while the turntable was rotating at 1600 rpm, 5 mW, 8
Recording was performed by irradiating the recording layer with a MHz gallium-aluminum-arsenic semiconductor laser beam (830 nm) in the form of a track. Clear bits were observed under an electron microscope in the recording layer where recording was completed. Furthermore, when a low-power gallium-aluminum-arsenic semiconductor laser beam was applied to the obtained optical recording medium and the reflected light was detected, a waveform having a practically sufficient S/N ratio was exhibited.

Example 2 A solution obtained by dissolving 3 parts by weight of a commercially available nitrocellulose resin in 100 parts by weight of methyl ethyl ketone.

Furthermore, tetraphenylthiotitanylnaphthalocyanine 5
Parts by weight and 200 parts by weight of dichloromethane were mixed and dissolved. The resulting solution was coated with heat-resistant glass "Pyrex J"
(Manufactured by Corning Glass Works,
(trade name) by a 50 Orpm spinner coating method and dried at a temperature of 90° C. for 2 hours to obtain a recording layer with a thickness of about 800 nm.

When recording was performed on the optical recording medium thus obtained in the same manner as in Example 1, clear pits were observed under an electron microscope in the recorded layer.

Further, when the reflected light of the incident laser beam was detected in the same manner as in Example 1, a waveform having a practically sufficient S/N ratio was shown.

Example 3 Tetra(2-7yolphenylthio)copper naphthalocyanine was deposited on an acrylic resin substrate with a thickness of 1 fin kept at room temperature at a vacuum level of 10-7 Torr to form a deposited film with a thickness of 1,000 fins. .

When recording was performed on the optical recording medium thus obtained in the same manner as in Example 1, a sharp focus was observed on the recorded layer using an electron microscope.

Further, when the reflected light of the incident laser beam was detected in the same manner as in Example 1, a waveform having a practically sufficient S/N ratio was shown.

Example 4 A solution obtained by dissolving 3 parts by weight of tetra(2-methoxyethoxyethylthio)vanadylnaphthalocyanine in 100 parts by weight of ethanol was applied onto a polycarbonate resin substrate by a spinner coating method at 500 rpm.
It was dried at 80-90° C. for 30 minutes to obtain a recording layer with a thickness of about 700 mm. When recording was performed on the optical recording medium thus obtained in the same manner as in Example 1, clear pits were observed under an electron microscope in the recording layer after the recording was completed, and the same results as in Example 1 were observed. When the reflected light of the incident laser beam was detected, it showed a waveform with a practically sufficient S/N ratio.

Example 5 A solution obtained by dissolving 5 parts by weight of bis[trihexylsiloxy]silicon tetraphenylthionaphthalocyanine in 100 parts by weight of ethanol was applied onto a polycarbonate resin substrate using a spinner coating method at 500 rpm. Dry at ~90℃ for 30 minutes to a thickness of about 1000mm
Obtained a human record layer. When recording was carried out in the same manner as in Example 1, clear pits were observed under an electron microscope, and a practically sufficient S/N ratio was obtained.

Example 6 A solution obtained by dissolving 2 parts by weight of bis[butoxytriethyleneoxydimethylsiloxy]silicon tetrahexylthionapthalocyanine in 100 parts by weight of methyl cellosolve was coated on a polycarbonate resin substrate by a spinner coating method at 500 rpm. After that, 3 at 80-90℃
After drying for 0 minutes, a recording layer having a thickness of about 800 layers was obtained. When recording was carried out in the same manner as in Example 1, clear pits were observed under an electron microscope, and a practically sufficient S/N ratio was obtained.

〔Effect of the invention〕

The optical recording medium of the present invention has one or more configurations,
It is chemically and physically stable and can be recorded and reproduced with high sensitivity using laser beams.

Claims (1)

[Scope of Claims] 1. An optical recording medium characterized by having an organic thin film layer containing one or more naphthalocyanine compounds represented by the following general formula [I] on a substrate. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc. are available▼ [In the formula, X: represents a sulfur atom, selenium atom, or tellurium atom. A: Represents a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group. M: a metal atom that may have a hydrogen atom, a halogen atom, or an oxygen atom, or (OR_1)_p, (OSiR
_2R_3R_4)_g, [OSiR_2R_3(OR
_4)] Represents a metal atom that may have _g. Here, R_1, R_2, R_3, R_4 are each independently,
Represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group, and p and q represent an integer from 0 to 2. . k, l, m, and n: Each independently represents an integer from 0 to 4, but they cannot all be 0 at the same time. ]