JPH0313384A - Optical recording medium - Google Patents

Abstract

PURPOSE:To obtain an optical recording medium showing high absorption even to semiconductor laser having an oscillation wavelength within a region of 780nm or less and also having high reflectivity by forming a recording layer based on tetraazaporphin to the surface of a substrate and changing the recording layer by the irradiation with laser beam and reading recorded data on the basis of the difference in optical density between the irradiated part and non-irradiated part of the recording layer. CONSTITUTION:A recording layer based on tetraazaporphin represented by formula I is formed and changed by the irradiation with laser beam to record data and the recorded data is read on the basis of the difference in optical density between the irradiated part and part not irradiated with laser beam and not changed of the recording layer. In the formula, M is Si, Ge or Sn, Y is an aryloxy group, an alkoxyl group, a trialkylsiloxyl group, a triarylsiloxyl group, a trialkoxysiloxyl group, a triaryloxysiloxyl group, a trityloxyl group or an acyloxyl group and rings represented by A<1>, A<2>, A<3> and A<4> are an aromatic ring and at least one of them contains three or more nitrogen atoms.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an optical recording medium using a novel tetraazaporphine and a method for manufacturing the optical 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 disk devices, etc. and as a light source for electrophotography. In particular, optical recording media using semiconductor lasers have the characteristic that the recording medium does not deteriorate in impact resistance because there is no contact between the medium and the recording/reproducing head. It is being said. Particularly in the field of heat mode recording methods, low melting metals, organic polymer compounds, or dyes have been proposed as substances that melt, evaporate, or sublimate.

Organic thin films containing organic polymer compounds and dyes have low thermal conductivity and low melting or sublimation temperatures, so optical recording media in which various substances such as cyanine dyes and squarylium dyes are used as recording layer forming materials have been developed. It has been proposed (for example, Japanese Patent Laid-Open No. 16948/1983).

Among these conventional technologies, one that utilizes a cyanine dye, which has a moderately high reflectance of the dye itself, as an optical recording medium does not require a metal reflective film, and prevents the complexity of the medium configuration.
Proposals have been made to prevent deterioration of information recording and reproducing characteristics (for example, Japanese Patent Laid-Open No. 60-7878).

However, since known dyes such as cyanine dyes generally have low light fastness, when reading after writing, the dye fades due to repeated irradiation with read light, resulting in a decrease in the C/N ratio during read. It's called putting away.
There is a problem that so-called reproduction deterioration is large. Therefore,
It has been proposed to use naphthalocyanine compounds as dyes with excellent light fastness in recording layers (for example, US Pat. No. 4,725,525).

(Problem to be solved by the invention) Various methods are known, such as the coating method and the dipping method, but in general, the latter two methods are more effective than the former two methods, which use vacuum technology. The wet method is economically advantageous, so the solubility of the two dyes in the organic solvent plays an important role in the economics of the recording layer formation process.

On the other hand, semiconductor lasers are used in information recording and reproducing equipment to make them smaller and lighter.Recently, the oscillation wavelength of semiconductor lasers has been increased from around 780 nm to around 600 nm in order to improve recording density. The wavelength is becoming shorter. When using such a short wavelength semiconductor laser, there is a problem that conventional naphthalocyanine derivatives, which have an absorption maximum near 810 nm but have low absorption in the wavelength region below 780 nm and have a low reflectance of 1, cannot be used. was there. The present invention has been made in view of the above-mentioned current situation, and its purpose is to provide a semiconductor laser with high absorption and high reflectance even for semiconductor lasers having an oscillation wavelength in the region of 780 nm or less. The objective is to identify compounds that exhibit excellent properties of sensitivity and solubility in organic solvents, and to use them as optical recording media.

(Means for Solving the Problems) The present inventors conducted intensive studies to solve the above problems, and as a result, they arrived at the present invention.

The invention of claim 1 will be temporarily referred to as the first invention.

That is, the first invention is based on the general formula CI) [where M is Si,
represents Ge or Sn, Y is an aryloxyl group, alkoxyl Ml + alkyloxyl L
7-arylsiloxyl group, trialkoxysiloxyl group,
It represents a triaryloquine siloxyl group, a trityloxyl group, or an acyloxyl group, and the two Y's may be the same or different.

The ring represented by + A' + A'' and A4 represents an aromatic ring to which an organic substituent may be bonded, and + A' s A
9+ A" and A4 may be the same or different<, A"
, A'', A'' and A4 are nitrogen-containing aromatic rings containing three or more nitrogen atoms.

Information is recorded by changing the recording layer by irradiation with a laser beam, and the recorded information is read out based on the difference in optical density between the changed distribution area and the unchangeable recording layer area that is not irradiated with the laser beam. The present invention relates to an optical recording medium for an optical disc, characterized in that:

Tetraazaporphine represented by general f(I) is soluble in aromatic, halogen, ether, keto/saturated, and alicyclic hydrocarbon solvents, and can be easily purified to achieve purity. A'.

By selecting appropriate nitrogen-containing aromatic rings as the rings represented by A2, AM, and A4, the present invention can be applied to semiconductor lasers having an oscillation wavelength in the region of 800 nm or less.

It can be effectively applied to semiconductor lasers having an oscillation wavelength in the region of 780 nm or less.

It can be effectively applied to semiconductor lasers having an oscillation wavelength in the region of 740 nm or less.

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

Examples of the above-mentioned halogen-based solvents include quinoline.

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

Examples of ketone solvents include acetone, methyl ethyl ketone, methyl propyl ketone, cyclopentanone, cyclohexanone, and acetone alcohol; examples of saturated hydrocarbon solvents include hexane.

Examples of alicyclic hydrocarbon solvents include heptane, octane, nonane, decane, undecane, and dodecane, and fuchlorooctane is an alicyclic hydrocarbon solvent. Examples include cyclopentane, cyclohexane, and cyclohebutane.

In the general formula (I'), 9M is -8tsGe
and Sn, and Y includes aryloxyl groups such as phenoquinl group, tolyloxyl group, and acyloxyl group, and alkoxyl groups include amyloxyl group and hexyloxyl group.

There are ofthyloxyl groups, decyloxyl groups, dobusyloxyl groups, tetrazosiloxyl groups, hexadecyloxyl groups, octadecyloxyl groups, eicosiloxyl groups, tocosyloxyl groups, etc., and the 11-alkylsiloxyl groups include:
Trimethylsiloxyl group.

Triethylsiloxyl group, tripropylsiloxyl group, tributylsiloxyl group, trihexylsiloxyl group, tribenzylsiloxyl group, tricyclohexylsiloxyl group, dimethyl t-7'ylsiloxyl group, dimethyloctylsiloxyl group.

Dimethyloctadecylsiloxyl group, dimethylcyclohexylsiloxyl group, dimethylcyclopentylsiloxyl group, diethylcyclohexylsiloxyl group, diethylcyclopentylsiloxyl group.

Dipropylcyclohexylsiloxyl group, dipropylcyclopentylsiloxyl group, dibutylcyclohexylsiloxyl group, dibutylcyclopentylsiloxyl group, dicyclohexylmethylsiloxyl group, dicyclohexylethylsiloxyl group.

Dicyclohexylpropylsiloxyl group, dicyclohexylbutylsiloxyfur group, dicyclopentylmethylsiloxyl group, dicyclopentylethylsiloxyl group, dicyclopentylpropylsiloxyl group, dicyclopentylbutylsiloxyl group.

Dimethylphenylsiloxyl group, dimethylmethoxysiloxyl group, dimethyloctoxinroxyl group, dimethylphenoxysiloxyl group.

d3 H3 H3 H3 etc., and those with triarylsiloxyl groups.

There are triphenylsiloxyl groups, dorianisylsiloxyl groups, tritolylsiloxyl groups, etc. Trialkoxysiloxyl groups include trimethoxysiloxyl groups, triethoxysiloxyl groups, tripropoxysiloxyl groups,
Triaryloxysiloxyl groups include triphenoxysiloxyl groups, dorianisiloxysiloxyl groups, tritolyloxysiloxyl groups, etc., and acyloxyl groups include acetoxyl groups, Examples include propionyloxyl group, butyryloxyl group, valeryloxyl group, pivaloyloxyl group, hexanoyloxyl group, octanoyloxyl group, and the like.

In the general formula ('I), R in the organic substituent bonded to the aromatic ring represented by A'', A'' and A4, 1
The alkyl group of ~R11s is 1, for example, a methyl group,
Ethyl group, n-propyl group * 5ec-propyl group +
n-butyl group, 5ec-butyl group, t-butyl group, rhoamyl group, t-amyl group, 2-amyl group, 3-amyl J
L neo-pentyl group, hexyl group, heptyl group,
Octyl group, decyl group, dodecyl group, tetradecyl group,
Hexadecyl group, octadecyl group.

eicosyl group, tocosyl group, cyclooctyl group.

Cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group.

2-methylcyclopentyl group, 3-methylcyclopentyl group, 4-methylcyclohexyl group.

thyl group, 1,1-dicyclopentylmethyl group, cyclohexylmethyl group, cyclopropylmethyl group.

Examples include 2-cyclohexylethyl group, 2-cyclopentylethyl group, 2-cyclohexylpropyl group, and 3-cyclohexylethyl group.

Examples of the alkyl group having a substituent include an alkyl group having an ester group, an alkyl group having an amide group, and an alkyl group having a hydroxyl group.

Examples include an aralkyl group, an alkoxyalkyl group having a trialkylsilyl group, and a haloalkyl group.

Aryl groups include phenyl, tolyl, anisyl, and halophenyl groups, and halogen atoms represented by Xl include fluorine, chlorine, bromine, and iodine.

The length of the alkyl group in the organic substituent bonded to Y and the aromatic ring represented by A1 and A4 in the general formula (I) is such that the tetraazaporphine represented by the general formula (I) In addition to the solubility of this compound in a solvent, it is also important to consider the melting value of this compound, as well as the ability of an amorphous compound formed by dissolving this compound in an organic solvent and spin-coding the solution onto a suitable substrate such as a glass plate. Membrane spectrum (
absorption spectrum, transmission spectrum and reflection spectrum)
has a major impact on

In particular, the length of the alkyl group of the substituent Y bonded to the central metal M can finely adjust the spectrum of the spin code film.

Therefore, depending on the oscillation wavelength of the laser used,
(The shorter the alkyl chain length, the longer the wavelength shift of maximum absorption, minimum transmittance, and maximum reflectance, respectively).

On the other hand, the alkyl chain length in the organic substituent bonded to the aromatic ring represented by * A" * A' + A" and A4 is determined by the solubility of this compound in an organic solvent when the alkyl chain length of Y mentioned above is changed. and has a function to adjust the melting temperature.

In the general formula (I), + A"+ A" and A
Among the rings represented by 4, as aromatic rings.

etc., as nitrogen-containing aromatic rings containing three or more nitrogen atoms.

In particular, the type of nitrogen-containing aromatic ring containing three or more nitrogen atoms is useful for greatly changing the spectrum of the spin code film. Therefore, the type of nitrogen-containing aromatic ring having three or more nitrogen atoms can be appropriately selected according to the blind wavelength of the laser used.

Specific examples of tetraazaporphine according to the present invention are shown in Table 1 by formula.

Tetraazaporfin is represented by the general formula (■), and g
Types of aromatic rings represented by Aj, A', Aa and A4.

A large number of isomers exist depending on the direction of the ring condensation and the position of the organic substituent bonded thereto. General formula (I) includes all of these numerous isomers.

Alternatively, a mixture thereof may be used.

The tetraazaporphine used in the present invention is a novel tetraazaporphine represented by the general formula (■) [In the formula, M and the rings represented by AI, A9, AI and A4 have the same meanings as in the general formula (I)]. is the general formula (III)
(R”)38iCl (m
), a chlorosilane represented by the general formula (IV) (R1
7) 35iOH(IV) [I R1'' and R' in formulas (III) and (IV) are
Each.

an alkyl group, an aryl group, an alkoxyl group, or an aryloxyl group];
v) R,'OHfV) [In the formula, R18 is an alkyl group or an aryl group] or the general formula (■) RIICO, y
;s (■) [R13 in the formula
is a halogen atom, a hydroxyl group or an acyloxyl group]. In this case 1
The reaction mixture is preferably 80 to 250°C, and the reaction time is 30
Minutes to 40 hours are preferred. Can this reaction be performed without a solvent?

Or as a solvent, benzene, toluene, xylene,
Use trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, tetralin, pyridine, β-picoline, quinoli/etc., and add triethylamine, tripropylamine, tributylamine, trihentylamine, trihexyl as necessary. Preferably, the reaction is carried out in the presence of an aliphatic amine such as an amine.

Isolation and purification of tetraazaporphine represented by general formula (I) from a reaction mixture can be carried out by a method such as separating one reaction mixture by chromatography and then purifying by recrystallization.

Tetraazaporphine represented by general formula (II) is
General Formula (■) 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. Tetraazaporphine represented by the general formula (■) has the same meaning as in the general formula (Ml) [wherein M and the rings represented by AI, A''', AI and A4 have the same meanings as in the general formula 1'l). , Z represents a halogen atom and the two Z's may be the same or different] can be obtained by subjecting tetraazaporphine to a hydrolysis reaction under heating. ℃ is preferable, and one reaction time is preferably 30 minutes to 30 hours.

H or general formula (IX) [However, the ring represented by general formula (■) and general formula (IX), to which an organic substituent may be bonded, represents an aromatic ring or a nitrogen-containing aromatic ring] For 1 mole of the compound represented by the general formula (X) MZp (X ) [in the formula Z
is a halogen atom and p is a positive integer indicating the number of bonds of 2 to the metal M, and 2M indicates Si, Ge or Sn] are allowed to coexist in a ratio of 0.1 mole or more and heated to react. This can be obtained by In this case, one reaction temperature is preferably 150 to 300°C, and one reaction time is preferably 30 minutes to 10 hours. This reaction may be carried out without a medium, or using urea or tetralin as a solvent.

Quinoline, 1-chloronaphthalene, 1-bromonaphthalene, trimethylbenzene, dichlorobenzene, trichlorobenzene, etc. may be used. Further, this reaction may be carried out in the presence of amines, and the amine used is triethylamine.

Examples include tripropylamine, tributylamine, tripentylamine, trihexylamine, etc. The above metal Cf
As f-genides, S:C1*, SiBr4
.

SiL + GeCl< + GeBra + 5n
There are C1l, 5nlz, etc.

The compound represented by the general formula (■) is prepared by mixing the compound represented by the general formula (■) in methanol with ammonia gas in the presence of sodium methoxide as a catalyst, and
It can be obtained by heating under reflux for 10 hours.

The compound represented by the general formula (■) is described in 1 literature [Chemische Perichte (Chem, Ber, ) Vol. 108].

875 (1975) etc.].

The optical recording medium according to the present invention has the general formula (
Although a recording layer mainly composed of tetraazaporphine represented by 1) is provided, other layers such as an underlayer and a protective layer may be provided as necessary.

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 side of the recording layer, it is not necessary to be transparent to the laser beam used. As a substrate material.

Inorganic materials such as glass, quartz, mica, ceramics, sheet or foil metals, as well as 9 paper, polycarbonate, polyester, cellulose acetate, nitrocellulose, polyethylene, 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.

It is preferable to use an optical recording medium in which a recording layer containing tetraazaporphine as a main component, in which M is Si or Ge in the general formula (I), is formed.

It is preferable to use an optical recording medium in which a recording layer containing tetraazaporphine as a main component, in which two Y's in the general formula (I) are trialkylsiloxyfur groups, is formed.

The general formula (I) T/c Otnte A', A', A'
It is preferable to use an optical recording medium in which a recording layer containing tetraazaporphine as a main component, which is a nitrogen-containing aromatic ring in which all of the rings represented by A' and A'T contain three or more nine atoms, is preferable.

In the general formula (I), AL, A'1, A8
It is preferable to use an optical recording medium in which a recording layer containing tetraazaporphine as a main component, which is a nitrogen-containing aromatic ring in which the rings represented by and M all contain the same three or more nitrogen atoms, is preferable.

In the general formula 1'I), AI, A2, i,
The ring is represented by S and A4.

An optical recording medium is preferably formed with a recording layer containing tetraazaporphine as a main component, which is a ring selected from the group consisting of nitrogen-containing aromatic rings represented by:

A recording layer is formed whose main component is tetraazaporphine, which is a ring selected from the group consisting of nitrogen-containing aromatic rings represented by the general formula mniote A'', A'', A'' and A4te. Preferred is an optical recording medium that is

In the general formula (I), the organic substituent bonded to the aromatic ring represented by AI, AI, 88 and A4 is selected from the group consisting of the following substituents: -R-OR'S i R"R'R,'5O2NR'R,'-Co-R'-COOR'-O-CUR'' 100・N) (R11 N R1'l R1@sp,, 5a SO2RII' and I (wherein, R'~ R+" represents a hydrogen atom, an alkyl group, an alkyl group having a substituent, or an aryl group.

Xl represents a halogen atom), A'', A'', and A4
It is preferable to use an optical recording medium in which a recording layer mainly composed of tetraazaporphine substituted at least one aromatic ring at a substitutable position is formed.

The invention of claim 9 will be temporarily referred to as the second invention. That is, the second invention is an optical recording medium for an optical disc, characterized in that a recording layer is formed on the surface of a substrate using a solution in which a novel tetraazaporphine represented by general formula (I) is dissolved mainly in an organic solvent. Relating to a manufacturing method.

The above-mentioned organic solvent is the above-mentioned aromatic solvent that dissolves the tetraazaporphine represented by the general formula (1).

The solvent is selected from halogen-based, ether-based, ketone-based, saturated hydrocarbon-based and alicyclic hydrocarbon-based solvents, 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.

Methods for forming a solid film layer using a solution of tetraazaporphine represented by general formula (I) dissolved in an organic solvent include a coating method, a printing method, and a dipping method.

Specifically, the two dyes are dissolved in the above solvent, and the coating is carried out using spray roller coach ink, spin coating, tipping, or the like. In addition, when forming the recording film layer.

A binder such as a polymer binder, a stabilizer, etc. may be added as necessary. As the polymer binder, polycarbonate resin, polymethacrylate resin, polyimide resin, polyamide resin9. polystyrene resin,
Examples include, but are not limited to, epoxy resins, silicone resins, fluororesins, acrylic resins, 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.

Also, when optically reproducing the formed recorded image.

Often uses reflected light. 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 that exhibits high reflectance on the surface of the recording layer on the opposite side of the substrate. That is, 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. +AI for this highly reflective metal!
+Cr5Au*Pt*Sn etc. are used. These membranes.

It can be formed using known thin film forming techniques such as vacuum evaporation, sputtering, and plasma evaporation, and the film thickness is 100 mm.
-100OOA.

However, the tetraazaporphine itself has a high reflectance, so 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.

Further, 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 one surface reflectance. Materials used for such a protective layer include polysalts (?vinylidene,
Polyvinyl chloride, vinyl chloride/acrylonitrile copolymer, polyvinyl acetate, polyimide, polycargenate, polymethacrylate, 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 crosslinking agent, etc. in the protective layer from the viewpoint of enhancing membrane performance. Also,
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 thin film. The thickness of such a protective layer is preferably 0.1 to 10 μm.

The thickness is preferably 0.2 to 2 μm.

A method for producing an optical recording medium using tetraazaporphine in which M is Si or Ge in the general formula (■) is preferred.

A method for producing an optical recording medium using tetraazaporphine in which two Y's in the general formula (I) are trialkylsiloxyl groups is preferred.

A method for producing an optical recording medium using tetraazaporphine in which the rings represented by AI, AI, 8@, and A4 in the general formula (I) are all nitrogen-containing aromatic rings containing three or more nitrogen atoms is preferred.

A method for producing an optical recording medium using tetraazaporphine, in which the rings represented by A″+A″ and A4 in the general formula (I) are all nitrogen-containing aromatic rings containing the same three or more nitrogen atoms. is preferred.

In the general formula (I), the rings represented by A5, A''IA'', and A4 are rings, and a method for producing an optical recording medium using tetraazaporphine is preferred.

In the general formula CI), the rings are represented by AI, A2, Aa and A4.

A method for producing an optical recording medium using external tetraazaporphine is preferred.

In the general formula (I), the organic substituent bonded to the aromatic ring represented by +A″+A′ and A4 is selected from the group consisting of the following substituents: H, t −0FL′ −S i R″PL′ R,' 802N R'R' -Co-R@ -cooa" 10・COR10 100 -NHFLII NR1*R18 R14 SO2R" and Indicates an alkyl group or an alkyl group.

A method for producing an optical recording medium using tetraazaporphine substituted at least one substitutable position on the aromatic ring represented by A' l A' and A4 is preferred.

(Examples) The present invention will be explained below with reference to Examples, but the present invention is not limited to these.

Example 1 ~) Qρ A solution 'tL consisting of tetraazaporphine and an organic solvent with one exception was coated on a polymethyl methacrylate 2P substrate with a thickness of 1.2 mm and a diameter of 130 by a spin cord method, and then heated at about 80°C. It was dried for about 15 minutes to form a recording layer. The thickness of this recording layer was measured using DEKTAK3030 (manufactured by 5loan). The optical recording medium thus created was placed on a tar/table with the recording layer facing up, and
While rotating at a speed of 0 rpm, laser beams adjusted to various emission wavelengths using a combination of Nd:YAG lasers, dye lasers, etc. are sent through an optical head from below the optical recording medium, that is, from the substrate side. Light was focused on the recording layer through the methyl methacrylate substrate, while controlling the output at the substrate surface to be 10 mW.

A 2 MHz pulse symbol was recorded between a radius of 40 and 60 marks from the center. Next, using the same device, we weakened the output and played back the recorded signal with a laser beam controlled so that the output at the board surface was 0.5 mW, and measured the carrier/noise (C/N) at that time. did.

The obtained results are summarized in Table 2, and it was found that one example of tetraazaporphine exhibited a high C/N.

Table 2 continued Table 2 continued Table 2 continued Table 2 continued Table 2 continued Table 2 continued Table 2 continued Chiku 2 Table continued Table 2 continued Table 2 continued Table 2 continued Table 2 Table 2 continued Table 2 continued Table 2 continued Table 2 continued Table 2 continued Table 2 continued Table 2 continued Table 2 continued Table 2 continued Whistle 9 Back 15 points Vanadyl-tetra (t-butyl) Naphthalosia No. Table 2 continued Comparative Examples 1 to 4 On a polymethyl methacrylate 2P substrate with a thickness of 1.2 mm + diameter of 130 II + m
Zhurnal 0bshchei Khi
C/N of an optical recording medium formed in the same manner as in Examples 1 to 900 using vanadyl-tetra(t-butyl)naphthalocyanine synthesized by the method described in [Mii), Vol. 42, p. 696, 1972]. was measured. The obtained results are summarized in Table 3, and the C/N value of 1vanadyl-tetra(t-butyl)naphthalocyanine was only a small value under the present measurement conditions, and C1 Good Comparative Examples 5 to 8 Thickness 1 A typical compound bis(trihexylsiloxy)silicon-naphthalocyanine described in U.S. Pat. The C/N of the optical recording medium formed was measured. The obtained results are summarized in Table 4, and showed a low C/N value.

Bis(t+)hexylsiloxy) silicone naphthalocyanine Table 4 Examples 900 to 1150 A solution prepared by dissolving exemplified tetraazaporphine in an organic solvent was coated on a glass plate with a thickness of 1.2 pans by one rotation coating method. It was applied onto a plate to form a recording layer.

The recording characteristics of the recording medium thus formed were evaluated by irradiating laser light adjusted to various oscillation wavelengths using an Nd:YAG laser or the like from the glass substrate side. Recording and reproduction were performed with a beam diameter of 1.6 μm.

In order to evaluate the stability against reproduction light, the reflectance (R4) at the initial stage of reproduction was 106
The ratio R/FLo of the reflectance 1) after the second reproduction was measured. The results are summarized in Table 5, and the two examples of tetraazaporphine shown in Comparative Examples 9 to 12 have high safety against reproduction light. Example 90. After forming a recording layer in the same manner as in Examples 90f to 1150, the stability against reproduction light was evaluated in the same manner as in Examples 90f to 1150.

The results are summarized in Table 6, and the cyanine dyes had extremely poor stability against reproduction light.

The following Tanijiro-2 ~ NK-1760 2Hs NK-1805 NK-1841 Examples 1151 ~ 1320 A solution prepared by dissolving exemplary tetraazaporphine and a binder polymer in an organic solvent was coated with a spin coating method to a thickness of 1.2 mm. was coated on a glass plate to form a recording layer. Examples 900 to 1 of the recording medium thus formed
The stability against reproduction light was evaluated in the same manner as No. 150.

The results are summarized in Table 7, and the recording layer formed from the exemplified tetraazaporphine and binder exhibits high stability (effects of the invention). It has high absorption and high reflectance even for semiconductor lasers, so it is highly sensitive.

There is great latitude in its use.

The optical recording medium of the present invention is useful for use as a write-once type.

U.S. Patent Nos. 4,719,615 and 4,780,8
Application as a rewritable optical recording medium described in the specification of No. 67 is also possible.

Claims (1)

[Claims] 1. A recording layer containing a novel tetraazaporphin represented by general formula (I) as a main component is formed on the surface of a substrate, and the recording layer is changed by irradiation with a laser beam to record information. An optical recording medium for an optical disc, characterized in that recorded information is read out based on the difference in optical density between the changed recording layer portion and the unchangeable recording layer portion that is not irradiated with a laser beam. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, M represents Si, Ge or Sn, and Y represents an aryloxyl group, an alkoxyl group, a trialkylsiloxyl group, a triarylsiloxyl group, a trialkoxy Indicates a siloxyl group, triaryloxysiloxyl group, trityloxyl group, or acyloxyl group, and the two Y's may be the same or different, A^1, A^2, A^3, and A^4
The ring represented by represents an aromatic ring to which an organic substituent may be bonded, and A^1, A^2, A^3 and A^4 may be the same or different, and A^1, A^ 2. At least one of A^3 and A^4 is a nitrogen-containing aromatic ring containing three or more nitrogen atoms] 2. A novel tetraazaporph in which M is Si or Ge in the general formula (I) 2. The optical recording medium according to claim 1, further comprising a recording layer containing in as a main component. 3. The optical recording medium according to claim 1 or 2, further comprising a recording layer mainly composed of a novel tetraazaporphine in which two Y's in the general formula (I) are trialkylsiloxyl groups. 4. In general formula (I), A^1, A^2
, A^3, and A^4 are all nitrogen-containing aromatic rings containing three or more nitrogen atoms, and a recording layer is formed whose main component is novel tetraazaporphine. The optical recording medium according to item 1, 2 or 3. 5. A novel tetraaza in which the rings represented by A^1, A^2, A^3 and A^4 in general formula (I) are all nitrogen-containing aromatic rings containing the same three or more nitrogen atoms. Claim 1: A recording layer containing porphin as a main component is formed.
, 2 or 3. 6. In general formula (I), the rings represented by A^1, A^2, A^3, and A^4 are from the group consisting of nitrogen-containing aromatic rings represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 6. The optical recording medium according to claim 1, wherein the recording layer is formed mainly of a novel tetraazaporphine, which is the selected ring. 7. In the general formula (I), the rings represented by A^1, A^2, A^3 and A^4 are ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ The optical recording medium according to claim 1, 2, 3, 4 or 5, wherein the recording layer is formed mainly of a novel tetraazaporphin which is a ring selected from the group consisting of nitrogen-containing aromatic rings represented by: . 8. In general formula (I), the organic substituents of the aromatic rings represented by A^1, A^2, A^3 and A^4 are selected from the group consisting of the following substituents -R^1 - OR^2 -SiR^3R^4R^5 -SO_2NR^6R^7 -CO･R^8 -COOR^9 -O･COR^1^0 -CO･NHR^1^1 -NR^1^2R^ 1^3 -SR^1^4 -SO_2R^1^5 and -X^1 (wherein, R^1 to R^1^5 are a hydrogen atom, an alkyl group, an alkyl group having a substituent, or an aryl group and X
^1 indicates a halogen atom), A^1, A^2, A^3
Claims 1, 2, 3, wherein a recording layer is formed which mainly contains novel tetraazaporphine substituted at least one substituted position of the aromatic ring represented by and A^4.
7. The optical recording medium according to 4, 5, 6 or 7. 9. A method for producing an optical recording medium for an optical disc, comprising forming a recording layer on the surface of a substrate using an organic solvent solution containing a novel tetraazaporphine represented by the general formula (I). 10. The method for producing an optical recording medium according to claim 9, using a novel tetraazaporphine in which M in the general formula (I) is Si or Ge. 11. The method for producing an optical recording medium according to claim 9 or 10, using a novel tetraazaporphine in which two Y's in general formula (I) are trialkylsiloxyl groups. 12. In general formula (I), A^1, A^2, A^3
12. The method for producing an optical recording medium according to claim 9, 10 or 11, using a novel tetraazaporphine in which all rings represented by and A^4 are nitrogen-containing aromatic rings containing three or more nitrogen atoms. 13. In general formula (I), A^1, A^2, A^3
The production of an optical recording medium according to claim 9, 10 or 11, using a novel tetraazaporphine in which the rings represented by and A^4 are all nitrogen-containing aromatic rings containing the same three or more nitrogen atoms. Method. 14. In general formula (I), A^1, A^2, A^3
Claim 9, wherein the ring represented by and A^4 is a ring selected from the group consisting of nitrogen-containing aromatic rings represented by ▲mathematical formula, chemical formula, table, etc.▼
10, 11, 12 or 13. 15. In general formula (I), A^1, A^2, A^3
, and the ring represented by A^4 is a ring selected from the group consisting of nitrogen-containing aromatic rings represented by Claim 9 using tetraazaporphin,
10, 11, 12 or 13. 16. In general formula (I), A^1, A^2, A^3
, and the organic substituent of the aromatic ring represented by A^4 is selected from the group consisting of the following substituents -R^1 -OR^2 -SiR^3R^4R^5 -SO_2NR^6R^7 - CO・R^8 -COOR^9 -O・COR^1^0 -CO・NHR^1^1 -NR^1^2R^1^3 -SR^1^4 -SO_2R^1^5 and -X ^1 (In the formula, R^1 to R^1^5 represent a hydrogen atom, an alkyl group, an alkyl group having a substituent, or an aryl group. X^1 represents a halogen atom), A^1, A ^2, A^
Claim 9, 10, 11, 12, 13, 14 or 1 using a novel tetraazaporphin substituted at least one at a substitutable position of the aromatic ring represented by 3 and A^4.
5. The method for producing an optical recording medium according to 5.