JP2500969B2 - Write-once type optical disc compatible with recording material for optical disc and CD or CD-ROM - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical disk recording material used for an optical disk for recording and reproducing information by laser light, more specifically a compact disk (CD).
Or compact disc-ROM (CD-ROM)
The present invention relates to a corresponding write-once optical disc.

[0002]

2. Description of the Related Art Among information recording media using a condensed laser beam, a CD for reproducing music such as audio and a CD-ROM as a computer-ROM are widely used. Such a CD or CD-ROM is usually a CD or CD-ROM on a transparent substrate surface such as polycarbonate.
A pit string having a format signal is formed at the time of injection molding, aluminum or gold is provided as a reflective film by vapor deposition or sputtering, and a protective layer is coated on the pit string. The reproduction laser light (780 nm semiconductor laser light) is irradiated from the back surface of the substrate of the optical disc thus created, and each signal is read from the change in the reflectance due to the unevenness of the pits to reproduce the information. However, since such a CD or CD-ROM is for reproduction only and cannot be recorded, there is a disadvantage that it does not have an editing function such as a write-once optical disc or a rewritable magneto-optical disc. On the other hand, as a write-once optical disc or a magneto-optical disc having an editing function,
A recording film made of a chalcogenite compound such as e, a rare earth metal compound, or an organic compound such as cyanine has been put to practical use. However, these optical discs have a reflectance of 30 to 40% from the substrate surface, and have reached a reflectance of 70% or more from the substrate surface described in the current international standard for CD, Red Book. However, there is a problem that the signal cannot be reproduced by the reproducing device of the CD or the CD-ROM as it is. In order to solve such a problem, a reflective film made of gold or the like is provided on a recording film made of a cyanine compound or the like to secure a substrate surface reflectance of 70% or more, and a CD format or a CD at 780 nm.
-ROM format signal recorded, CD or CD-
Optical discs and methods have been proposed for reading information with a ROM playback device.

However, since the cyanine compound generally has poor photostability, it may cause a problem in the reliability of recording under a use condition such that a single plate structure such as a CD or a CD-ROM is directly exposed to sunlight. There is a nature. Therefore, attempts are being made to use a phthalocyanine compound having excellent chemical and physical stability in place of the cyanine compound as a recording film material.

In the case of this phthalocyanine compound, the recording sensitivity is low because it is thermally stable, and the absorption band is very sharp. Therefore, the allowable range of the oscillation wavelength of the semiconductor laser mounted in the pickup of the CD drive is large. It is difficult to obtain stable optical characteristics (reflectance and absorption) at (780 to 800 nm), the recording sensitivity has a large wavelength dependency, and it is difficult to form a general-purpose write-once optical disc. Therefore, at present, a CD or CD-RO having excellent stability and good recording characteristics is also provided.
M-compatible write-once optical discs are not provided.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the drawbacks of the conventional CD or CD-ROM having the write-once function and the edit function, is excellent in stability, and has good recording characteristics. In order to provide a corresponding write-once optical disc, low recording sensitivity and wavelength dependence of recording sensitivity that occur when a phthalocyanine compound having excellent chemical and physical stability is used as a recording film material is prevented, and a good reproduction signal is obtained. As a result of extensive studies on the obtained recording material, the present invention has been achieved.

[0006]

The present invention relates to a recording material for optical disks, which comprises a phthalocyanine compound represented by the general formula [1]. General formula [1]

[0007]

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[In the formula, each of the substituents X ^{1 to} X ⁴ independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Aralkyl group which may have, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylthio group which may have a substituent, and which may have a substituent It represents an arylthio group, a sulfonic acid group, a sulfonic acid amide group, a sulfonic acid ester group, a carboxylic acid group, a carboxylic acid ester group, a carboxylic acid amide group, an amino group, a nitro group, and a cyano group. n ^{1 to} n ⁴ are substituents X ^{1 to} X ⁴
Represents the integer of 0-4. The central metal M is Al,
It represents Ga, In, Si, Ge, Sn. The substituent Z is

[0009]

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Represents Here, R ¹ , R ² and R ³ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent, a substituent Represents an aralkyl group which may have. In addition, R ¹ and R ² may form an alicyclic ring or a heterocycle containing a hetero atom. m is an integer of 1 or 2> represents the number of the substituents Z. ]

Furthermore, the present invention is a write-once type optical disc comprising a transparent substrate / recording film / reflection film / protective film for recording CD format signals, the recording film being selected from compounds represented by the general formula [1]. A write-once optical disc compatible with a CD or a CD-ROM, which is composed of one or more phthalocyanine compounds. The feature of the phthalocyanine compound represented by the general formula [1] is that the phthalocyanine compound can be produced by the effect of the substituent (substituent Z in the general formula [1]) introduced from the central metal in the direction perpendicular to the molecular plane of the phthalocyanine ring. Since the decomposition temperature is largely shifted to the low temperature side, when these phthalocyanine compounds are used for the recording film, the recording sensitivity is significantly improved. In addition, the effect of the substituent Z increases the reflection level of the medium, and in addition, since good recording pits are formed, the contrast of the reproduced signal is good and a beautiful reproduced waveform can be obtained.

Alkoxy groups, siloxy groups and the like have so far been known as the substituents introduced from the central metal in the direction perpendicular to the molecular plane of the phthalocyanine ring. Since the decomposition temperature accompanied by weight reduction is 400 ° C. or higher, the low recording sensitivity has been a problem. In order to lower the decomposition point with these substituents, it was necessary to make the alkoxy group, siloxy group, etc. considerably bulky. Therefore, the decomposition point (or melting point) is lowered, but the edge of the recording pit rises. As a result, the shape of the recording pit is deteriorated, and it is difficult to obtain a clean reproduction signal.

The phthalocyanine compound of the present invention has a decomposition point of 400 ° C. or less accompanied by a large weight reduction even if the substituent Z in the general formula [1] is not bulky, and due to the effect of the substituent Z, it is recorded. In order to suppress the association of phthalocyanine molecules with each other on the film, it exhibits a high molecular extinction coefficient and the point of maximum reflectance approaches the emission wavelength region of the semiconductor laser. It has a feature that can secure the reflectance. Further, the effect of the substituent Z dramatically increases the solubility, and the solubility becomes high in a general-purpose organic solvent (for example, methanol or ethanol), which facilitates the production of the recording film by the spin coating method.

R ¹ in the substituent Z introduced into the phthalocyanine compound represented by the general formula [1] of the present invention,
Typical examples of the linear, branched or cyclic alkyl group R which may have a substituent of R ² and R ³ include a methyl group, an ethyl group, a hexyl group, a dodecyl group, an isopropyl group, a 2-ethylhexyl group, t-butyl group, neopentyl group, trichloromethyl group, 1,2-dichloroethyl group, trifluoromethyl group, heptafluoropropyl group, 2,2,2
There are 3,3-tetrafluoropropyl group, 2-methoxyethyl group, cyclohexyl group, adamantyl group and the like. Representative examples of the aryl group which may have a substituent in the substituent Z are a phenyl group, a naphthyl group, a 3-methylphenyl group, a 3-methoxyphenyl group, a 3-fluorophenyl group, a 3-trichloromethylphenyl group, 3-trifluoromethylphenyl group, pentafluorophenyl group, 3-
There is a nitrophenyl group etc. Representative examples of the aralkyl group which may have a substituent in the substituent Z include a benzyl group, a p-methoxybenzyl group, a p-diethylaminobenzyl group, an o-nitrobenzyl group, and 2-chloro-4-dimethylaminobenzyl. There are groups, etc.

Representative examples of the substituents X ^{1 to} X ⁴ introduced into the phthalocyanine compound represented by the general formula [1] of the present invention include a hydrogen atom corresponding to a case where no substituent is present, and a halogen atom as a halogen atom. Is chlorine, bromine, iodine, or fluorine, and as the alkyl group which may have a substituent,
Methyl group, n-butyl group, tert-butyl group, stearyl group, trichloromethyl group, trifluoromethyl group,
A 2-methoxyethyl group, a phthalimidomethyl group, and the like, an aryl group which may have a substituent, a phenyl group,
There are naphthyl group, p-nitrophenyl group, p-tert-butylphenyl group and the like, and typical examples of the aralkyl group which may have a substituent include a benzyl group, a p-methoxybenzyl group and a p-diethylaminobenzyl group. , An o-nitrobenzyl group, etc., and the alkoxy group which may have a substituent include a methoxy group, an ethoxy group, an n-butoxy group, a tert-butoxy group, a 2-ethylhexyloxy group, 2,2,2. 2-trichloroethoxy group, 2,2,2-
Trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,1,3,3,3-hexafluoro-2- Propoxy group, 2,2,3,4,4,4-hexafluorobutoxy group, 1H, 1H, 5H-octafluoropentoxy group, 1H, 1H, 7H-dodecafluoroheptoxy group, 1H, 1H, 9H- Hexadecafluorononyloxy group, 2- (perfluorohexyl) ethoxy group, 2- (perfluorooctyl) ethoxy group, 2
There are-(perfluorodecyl) ethoxy group, 2- (perfluoro-3-methylbutyl) ethoxy group, 6- (perfluoroethyl) hexyloxy group, 6- (perfluorohexyl) hexyloxy group, etc. As the aryloxy group which may be possessed, a phenoxy group, a p-nitrophenoxy group, a p-tert-butylphenoxy group, 3
-Fluorophenoxy group, pentafluorophenyl group,
There is a 3-trifluoromethylphenoxy group and the like, and the alkylthio group which may have a substituent includes a methylthio group, an ethylthio group, a tert-butylthio group, a hexylthio group, an octylthio group, a trifluoromethylthio group and the like. The arylthio group which may have a group is a phenylthio group, a p-nitrophenylthio group, a p-te.
Examples thereof include an rt-butylphenylthio group, a 3-fluorophenylthio group, a pentafluorophenylthio group, and a 3-trifluorophenylthio group, but are not limited thereto.

In the present invention, the compound represented by the general formula [1] can be produced, for example, by the following method.

That is, unsubstituted phthalonitrile, 3-position substituted phthalonitriles represented by the following general formula [2], 4
-Substituted phthalonitriles or unsubstituted 1,3-diiminoisoindoline represented by the following general formula [3], 4
Position-substituted 1,3-diiminoisoindoline compound, or 5-position-substituted 1,3-diiminoisoindoline compound,
Alternatively, by using the corresponding phthalic anhydrides, phthalimides and various metal salts of the metal represented by M in the general formula [1] as starting materials, the dihydroxy of the phthalocyanine compound represented by the general formula [4] is prepared by a conventional method. Can be manufactured.

General formula [2]

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[In the formula, X and n have the same meanings as X ^{1 to} X ⁴ and n ^{1 to} n ⁴ in the general formula [1], respectively. ]

General formula [3]

[Chemical 6]

[In the formula, X and n have the same meanings as X ^{1 to} X ⁴ and n ^{1 to} n ⁴ in the general formula [1], respectively. ]

General formula [4]

[Chemical 7]

[Wherein X ^{1 to} X ⁴ , n ^{1 to} n ⁴ , M, m
Are respectively X ^{1 to} X ⁴ and n ^{1 to} n in the general formula [1].
⁴ , has the same meaning as M and m. ]

Next, the obtained phthalocyanine compound represented by the general formula [4] is added to a halogenated thiocarboxylic acid,
By introducing a substituent represented by Z in the general formula [1] by reacting various reagents such as isocyanates, isothiocyanates or halogenated carbamic acids, the compound represented by the general formula [1] can be obtained. It is possible to produce a phthalocyanine compound.

Typical examples of the phthalocyanine compound represented by the general formula [1] used in the present invention include the phthalocyanine compounds (a) to (l) shown below, but the compounds are not limited thereto. Absent.

Phthalocyanine compound (a)

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Phthalocyanine compound (b)

[Chemical 9]

Phthalocyanine compound (c)

[Chemical 10]

Phthalocyanine compound (d)

[Chemical 11]

Phthalocyanine compound (e)

[Chemical 12]

Phthalocyanine compound (f)

[Chemical 13]

Phthalocyanine compound (g)

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Phthalocyanine compound (h)

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Phthalocyanine compound (i)

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Phthalocyanine compound (j)

[Chemical 17]

Phthalocyanine compound (k)

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Phthalocyanine compound (l)

[Chemical 19]

In the recording film using the phthalocyanine compound represented by the general formula [1] in the present invention, for the purpose of further improving the stability of the recording film such as light resistance and environment resistance, and the stability of repeated reproduction, You may add additives, such as an oxygen quencher and an ultraviolet absorber.

The recording film can be formed by a dry process such as vacuum deposition or sputtering, but a wet process such as spin coating, dipping, spraying, roll coating or LB. It is also possible by the (Langmuir-Blodgett) method. The recording film material of the present invention dissolves in a general-purpose organic solvent such as alcohol-based, ketone-based, cellosolve-based, halogenated hydrocarbon-based, freon-based, etc., so that spin coating can be performed from the viewpoint of productivity and uniformity of the recording film. The method of forming a film by is preferable.

As described above, when the film is formed by the so-called coating method, a polymer binder may be added if necessary. Examples of the polymer binder include acrylic resin, polycarbonate resin, polyester resin, polyamide resin, vinyl chloride resin, vinyl acetate resin, nitrocellulose, and phenol resin, but are not limited thereto. The mixing ratio of the polymer binder is not particularly limited, but it is 30% by weight with respect to the phthalocyanine compound.
The following are preferred.

The optimum film thickness of the recording film of the present invention is not particularly limited because it depends on the type and combination of recording film materials.
500 to 3000 angstroms is preferable, and 1000 to 2500 angstroms is the optimum film thickness range.

The reflective film material of the present invention includes gold, silver,
Metals such as copper, platinum, aluminum, cobalt, tin, and alloys containing these as the main components, MgO, ZnO, SnO
Examples thereof include metal oxides such as SiN ₄ , nitrides such as SiN ₄ , AlN, and TiN. Gold is most preferable because of its high absolute reflectance and excellent stability. In addition, an organic high reflection film can be used depending on the case.

As a method for forming such a reflection film, a dry process such as a vacuum deposition method or a sputtering method is most preferable, but the method is not limited to this. The optimum film thickness of the reflective film of the present invention is not particularly limited, but 400
The range of ˜1300 Å is preferred.

Furthermore, chemical deterioration of the disk, particularly the recording film and the reflective film, from above the reflective film (eg, oxidation, water absorption, etc.)
In addition, a protective film for protecting the disc is provided for the purpose of preventing physical deterioration (for example, scratches, slippage, etc.). As a material for the protective film, a method in which an ultraviolet curable resin is used and applied by spin coating and cured by ultraviolet irradiation is preferable, but the material is not limited to this.

Regarding the optimum thickness of the protective film, when it is thin, the effect of protection is lowered, and when it is thick, it causes deterioration of mechanical characteristics such as warpage of the disk due to shrinkage during curing of the resin. It is preferable to form a film in the range of 2 to 20 microns.

The disk substrate used in the present invention preferably has a light transmittance of 85% or more for writing and reading signals, and a small optical anisotropy. For example, glass, acrylic resin, polycarbonate resin, polyester resin, polyamide resin, vinyl chloride resin, vinyl acetate resin, polystyrene resin, polyolefin resin (poly-4-methylpentene, etc.), polyether sulfone resin, etc. A substrate made of a thermosetting resin such as a thermoplastic resin, an epoxy resin, or an allyl resin may be used. Among these, those made of a thermoplastic resin are preferable from the viewpoint of easiness of molding, provision of wobble signals for ATIP and guide grooves, and the like. Further, acrylic resins and acrylic resins are preferable in view of optical characteristics, mechanical characteristics and cost. Those made of polycarbonate resin are particularly preferable. The wobble signal for ATIP, the guide groove, and the like are preferably provided by using a stamper or the like when molding (injection molding, compression molding) a thermoplastic resin, but a so-called 2P method using a photopolymer resin is preferable. Can also be done by.

The shape of the guide groove of the present invention is not particularly limited and may be rectangular, trapezoidal or U-shaped. The optimum size of the guide groove varies depending on the type and combination of recording film materials, but the average groove width (width at half the groove depth) is 0.3 to 0.6 microns. The groove depth is preferably in the range of 800 to 2000 angstrom.

Since the disc form of the present invention needs to function as a CD or a CD-ROM after recording,
Or CD-ROM standard (Red Book) and R
-It is preferable to comply with the CD standard (Orange Book).

[0049]

EXAMPLES The present invention will be specifically described by the following examples, but the present invention is not limited to the following examples.
First, a method for producing a typical example of the phthalocyanine compound used in the present invention will be described.

Production Example 1: Production of phthalocyanine compound (b) 1,3-diiminoisoindoline 1 was added to 100 parts of quinoline.
Add 4.5 parts and 8.5 parts of silicon tetrachloride, and add 170-18
After heating and stirring at 0 ° C. for 3 hours, the mixture was cooled, and 1000
The precipitate was filtered, washed with methanol and acetone, and dried to obtain 10.8 parts of a blue powder. This powder was dissolved in 500 parts of concentrated sulfuric acid, poured into 10000 parts of ice water, and the deposited precipitate was filtered, washed with water and dried to obtain 8.2 parts of dark blue powder. This powder was analyzed by FD-MS,
It was confirmed to be dihydroxysilicon phthalocyanine corresponding to the general formula [4]. 5.0 parts of the dihydroxysilicon phthalocyanine obtained above was added to pyridine 10
After stirring and dissolving in 0 part, 5.0 parts of dimethylcarbamoyl chloride was added dropwise while cooling, stirred at room temperature for 1 hour, and then heated at 40 ° C. for 2 hours. After cooling, the reaction solution is cooled with ice water 2
It was poured into 000 parts, extracted with 500 parts of chloroform, dried over magnesium sulfate, and then the solvent was distilled off to obtain a green powder. Purification and isolation by alumina column chromatography gave 2.2 parts of green powder. As a result of FD-MS analysis, it was confirmed that this powder was the phthalocyanine compound (b).

Production Example 2: Production of phthalocyanine compound (d) 4- (2,2,3,3-tetrafluoro) propoxy-1,3-di was added to 200 parts of o-dichlorobenzene and 30 parts of tri-n-butylamine. Iminoisoindoline 13.8
And 3.4 parts of anhydrous aluminum chloride were added, and the mixture was heated and stirred at 160 to 170 ° C. for 3 hours under a nitrogen atmosphere. After cooling,
The reaction solution was washed and extracted with 1000 parts of hexane, the organic layer was removed, dispersed in 2000 parts of 3% hydrochloric acid water, boiled for 1 hour, filtered, washed with water, washed with a mixed solution of methanol / water (2: 1), and dried. Thus, 7.4 parts of green powder was obtained. This powder is F
As a result of D-MS analysis, it was confirmed to be hydroxyaluminum phthalocyanine corresponding to the general formula [4]. 7.0 parts of the hydroxyaluminum phthalocyanine obtained above was added to dimethyl sulfoxide (DMSO) 1
After stirring and dissolving in 20 parts and 1.0 part of pyridine, 5.0 parts of isocyanatoacetic acid ethyl ester was added dropwise while cooling, and the mixture was stirred at room temperature for 1 hour and then heated and stirred at 50 ° C. After cooling, the reaction solution was poured into 1000 parts of ice water, and chloroform 5
It was extracted with 00 parts and dried over magnesium sulfate, and then the solvent was distilled off to obtain a green powder. Purification and isolation by alumina column chromatography gave 4.3 parts of green powder. FD
As a result of -MS analysis, it was confirmed that this powder was the phthalocyanine compound (d).

Production Example 3: Production of Phthalocyanine Compound (f) In place of 13.8 parts of 4- (2,2,3,3-tetrafluoro) propoxy-1,3-diiminoisoindoline of Production Example 5, 5 -(2,2,3,3-tetrafluoro) propoxy-1,3-diiminoisoindoline 13.8 parts,
Instead of 3.4 parts of anhydrous aluminum chloride, 6.0 parts of silicon tetrachloride was used and treated in the same manner as in Production Example 2 to obtain 6.9 parts of green powder of dihydroxysilicon phthalocyanine corresponding to the general formula [4]. It was 6.0 parts of the dihydroxysilicon phthalocyanine obtained above was added to DMSO110.
Parts and 0.8 parts of pyridine with stirring, 3.0 parts of n-butyl isothiocyanate was added dropwise while cooling, and the mixture was stirred at room temperature for 1 hour and then heated with stirring at 70 ° C. After cooling, the reaction solution was poured into 1000 parts of ice water, extracted with 500 parts of chloroform, dried over magnesium sulfate, and the solvent was distilled off to obtain a green powder. Purification and isolation by alumina column chromatography gave 2.7 parts of green powder. FD-MS
As a result of the analysis, it was confirmed that this powder was the phthalocyanine compound (f).

Production Example 4: Production of phthalocyanine compound (g) To 100 parts of 1-chloronaphthalene, 9.2 parts of 4-tert-butylphthalonitrile and 3.0 parts of stannous chloride were added, and the mixture was heated at 170 to 180 ° C. for 4 hours. The mixture was heated and stirred for an hour. After cooling,
The reaction solution was poured into 1000 parts of methanol, the deposited precipitate was filtered, washed with a methanol / acetone mixed solution, the obtained green cake was dispersed in ammonia water, heated under reflux for 1 hour, filtered, washed with water and dried. As a result, 6.3 parts of green powder was obtained. As a result of FD-MS analysis, this powder was confirmed to be dihydroxytin phthalocyanine corresponding to the general formula [4]. 6.0 parts of the dihydroxytin phthalocyanine compound obtained above was dissolved in 150 parts of DMSO and 1.0 part of triethylamine with stirring, 2.0 parts of phenyl isocyanate was added while cooling, and the mixture was stirred at room temperature for 1 hour, then 70 The mixture was stirred at 0 ° C for 2 hours. After cooling, the reaction solution was poured into 1000 parts of ice water, extracted with 500 parts of chloroform, dried over magnesium sulfate, and then the solvent was distilled off to obtain a green powder. Purification and isolation by an alumina column chromatograph gave 3.0 parts of green powder. As a result of FD-MS analysis, it was confirmed that this powder was a phthalocyanine compound (g).

Production Example 5: Production of phthalocyanine compound (h) In place of 13.8 parts of 5- (2,2,3,3-tetrafluoro) propoxy-1,3-diiminoisoindoline of Production Example 3, 4 -(2,2,3,3-Tetrafluoro) propoxy-1,3-diiminoisoindoline 13.8 parts and treated in the same manner as in Production Example 3 to give dihydroxysilicone corresponding to general formula [4]. 6.2 parts of green powder of phthalocyanine was obtained. The dihydroxysilicon phthalocyanine (6.0 parts) obtained above was dissolved in 120 parts of DMSO and 1.0 part of triethylamine with stirring, 2.0 parts of phenylisothiocyanate was added while cooling, and the mixture was stirred at room temperature for 1 hour. The mixture was stirred at 0 ° C for 2 hours. After cooling, the reaction solution was poured into 1000 parts of ice water and extracted with 500 parts of chloroform,
After drying with magnesium sulfate, the solvent was distilled off to obtain a green powder. Purification and isolation by alumina column chromatography gave 2.6 parts of green powder. As a result of FD-MS analysis, it was confirmed that this powder was the phthalocyanine compound (h).

Production Example 6: Production of Phthalocyanine Compound (i) In place of 13.8 parts of 4- (2,2,3,3-tetrafluoro) propoxy-1,3-diiminoisoindoline of Production Example 5, 5 -(2,2,2-trifluoro) ethoxy-
1,2-Diiminoisoindoline was set to 12.2 parts and treated in the same manner as in Production Example 3 to obtain 5.8 parts of a green powder of dihydroxysilicon phthalocyanine corresponding to the general formula [4]. 5.0 parts of the dihydroxysilicon phthalocyanine obtained above was dissolved in 100 parts of DMSO and 1.0 part of triethylamine with stirring, 2.5 parts of p-nitrophenyl isocyanate was added while cooling, and after stirring at room temperature for 1 hour. The mixture was stirred at 70 ° C for 2 hours. After cooling, the reaction solution was poured into 1000 parts of ice water, extracted with 500 parts of chloroform, dried over magnesium sulfate, and then the solvent was distilled off to obtain a green powder. Purification and isolation by alumina column chromatography gave 2.9 parts of a green powder. As a result of FD-MS analysis, it was confirmed that this powder was the phthalocyanine compound (i).

Production Example 7: Production of Phthalocyanine Compound (j) In place of 13.8 parts of 4- (2,2,3,3-tetrafluoro) propoxy-1,3-diiminoisoindoline of Production Example 5, 4 -Butoxy-1,3-diiminoisoindoline was set to 10.9 parts and treated in the same manner as in Production Example 3 to obtain 7.4 parts of a green powder of dihydroxysilicon phthalocyanine corresponding to the general formula [4]. 7.0 parts of the dihydroxysilicon phthalocyanine obtained above was added to DMSO150.
And 1.3 parts of triethylamine with stirring, 4.0 parts of 1-naphthyl isothiocyanate was added with cooling, and the mixture was stirred at room temperature for 1 hour and then at 70 ° C. for 2 hours. After cooling, the reaction solution was poured into 1000 parts of ice water, extracted with 500 parts of chloroform, dried over magnesium sulfate, and then the solvent was distilled off to obtain a green powder. Purification and isolation by alumina column chromatography gave 3.6 parts of green powder.
As a result of FD-MS analysis, it was confirmed that this powder was the phthalocyanine compound (j).

Example 1 1200 angstrom deep, 0.50 micron wide,
1.20m thickness with guide grooves with pitch of 1.6 microns
m, an outer diameter of 120 mm, and an inner diameter of 15 mm, the phthalocyanine compound (b) was dissolved in diacetone alcohol at a concentration of 40 mg / ml, and 0.2 μm filtering was performed to prepare a coating liquid. Was used to form a film having a thickness of 1200 angstrom by a spin coater. Then, gold was deposited in a thickness of 800 angstrom on the recording film thus obtained by vacuum vapor deposition. Further, a protective film having a film thickness of 5 μm was formed thereon by an ultraviolet curable resin to prepare an optical disc. The reflectance of the optical disc thus created is 69
%Met. When an EFM-CD format signal was recorded at a linear velocity of 1.4 m / sec using a semiconductor laser having a wavelength of 785 nm using the optical disc thus prepared, the optimum recording laser power was 7.8 mW.
It was possible to record at. Next, when this signal was reproduced by a CD player with a laser power of 0.5 mW, the obtained signal was good, and the level was sufficiently high for a commercially available CD player.

Example 2 Depth 1500 Å, Width 0.52 μm,
1.20m thickness with guide grooves with pitch of 1.6 microns
m, an outer diameter of 120 mm, and an inner diameter of 15 mm, a phthalocyanine compound (d) was dissolved in ethyl cellosolve at a concentration of 50 mg / ml, and 0.2 μm filtering was performed to prepare a coating liquid. A spin coater was used to form a film having a thickness of 1400 angstroms. Next, gold was formed into a film having a thickness of 600 angstroms on the recording film thus obtained by sputtering. Further, a protective film having a film thickness of 5 μm was formed thereon by an ultraviolet curable resin to prepare an optical disc. The reflectance of the optical disk thus created is 72
%Met. When an EFM-CD format signal was recorded at a linear velocity of 1.4 m / sec using a semiconductor laser having a wavelength of 785 nm using the optical disc thus prepared, the optimum recording laser power was 6.7 mW.
It was possible to record at. Next, when this signal was reproduced by a CD player with a laser power of 0.5 mW, the obtained signal was good, and the level was sufficiently high for a commercially available CD player.

Example 3 Depth 1400 Å, Width 0.6 μm, Pitch 1.6 μm with guide grooves 1.20 m thick
m, an outer diameter of 120 mm, an inner diameter of 15 mm, a phthalocyanine compound (g) was dissolved in diacetone alcohol at a concentration of 45 mg / ml, and 0.2 μm filtering was performed to prepare a coating liquid. Was used to form a film having a thickness of 1500 angstrom by a spin coater. Next, gold was deposited in a thickness of 500 angstrom on the recording film thus obtained by vacuum vapor deposition. Further, a protective film having a film thickness of 5 μm was formed thereon by an ultraviolet curable resin to prepare an optical disc. The reflectance of the optical disk thus created is 72
%Met. When an EFM-CD format signal was recorded at a linear velocity of 1.4 m / sec using a semiconductor laser having a wavelength of 785 nm using the optical disc thus prepared, the optimum recording laser power was 5.8 mW.
It was possible to record at. Next, when this signal was reproduced by a CD player with a laser power of 0.5 mW, the obtained signal was good, and the level was sufficiently high for a commercially available CD player.

Example 4 Depth 1500 Angstroms, Width 0.8 micron, Thickness 1.6 mm with pitch 1.6 micron guide grooves
m, an outer diameter of 120 mm, an inner diameter of 15 mm, a phthalocyanine compound (h) was dissolved in ethyl cellosolve at a concentration of 60 mg / ml, and 0.2 μm filtering was performed to prepare a coating liquid. A spin coater was used to form a film having a thickness of 1400 angstroms. Next, gold was deposited on the recording film thus obtained by sputtering to have a film thickness of 500 angstrom. Further, a protective film layer having a film thickness of 5 μm was formed thereon with an ultraviolet curable resin to prepare an optical disk. The optical disk produced in this way has a reflectance of 7
4%. When an EFM-CD format signal was recorded at a linear velocity of 1.4 m / sec using a semiconductor laser having a wavelength of 785 nm using the optical disc thus prepared, the optimum recording laser power was 6.1 mW.
It was possible to record at. Next, when this signal was reproduced by a CD player with a laser power of 0.5 mW, the obtained signal was good, and the level was sufficiently high for a commercially available CD player.

Example 5 Depth 1300 Å, Width 0.6 μm, Pitch 1.6 μm with guide grooves 1.20 m thick
m, an outer diameter of 120 mm, an inner diameter of 15 mm, a phthalocyanine compound (i) was dissolved in ethyl cellosolve at a concentration of 55 mg / ml, and 0.2 μm filtering was performed to prepare a coating liquid. A spin coater was used to form a film having a thickness of 1450 Å. Next, gold was deposited in a thickness of 500 angstrom on the recording film thus obtained by vacuum vapor deposition. Further, a protective film having a film thickness of 5 μm was formed thereon by an ultraviolet curable resin to prepare an optical disc. The reflectance of the optical disc thus prepared was 73%. A linear velocity of 1.4 m is obtained by using a semiconductor laser having a wavelength of 785 nm using the optical disc thus prepared.
When the EFM-CD format signal was recorded at / sec, it was possible to record at the optimum recording laser power of 6.9 mW. Next, when this signal was reproduced by a CD player with a laser power of 0.5 mW, the obtained signal was good, and the level was sufficiently high for a commercially available CD player.

Examples 6-10 Depth 1300 Angstroms, Width 0.48 microns,
1.20m thickness with guide grooves with pitch of 1.6 microns
m, an outer diameter of 120 mm, and an inner diameter of 15 mm, the phthalocyanine compound shown in Table 1 was dissolved in diacetone alcohol at a concentration of 50 mg / ml to give 0.2
Micron filtering was performed to prepare a coating liquid, and the coating liquid was used to form a recording film with a film thickness of 1500 angstrom by a spin coater. Next, gold was deposited in a thickness of 500 angstrom on the recording film thus obtained by vacuum vapor deposition. Further, a protective film layer having a film thickness of 5 μm was formed thereon with an ultraviolet curable resin to prepare an optical disk. Table 1 shows the reflectance of the optical disc thus prepared and the optimum recording laser power when recording and reproducing are performed in the same manner as in Example 1.

[0063]

[Table 1]

[0064]

EFFECT OF THE INVENTION By creating an optical disk according to the structure of the present invention, a write-once type optical disk corresponding to a CD or a CD-ROM having a write-once function and an edit function showing stable recording / reproducing characteristics for a semiconductor laser of 770 nm to 800 nm is obtained. Can be provided.

Claims (2)

(57) [Claims] 1. A recording material for an optical disk comprising a phthalocyanine compound represented by the general formula [1], a general formula [1]: [In the formula, the substituents X ^{1 to} X ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group which may have a substituent,
An aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent,
Aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, a sulfonic acid group, a sulfonic acid amide group, a sulfonic acid ester group, a carboxylic acid Represents a group, a carboxylic acid ester group, a carboxylic acid amide group, an amino group, a nitro group, and a cyano group. n ^{1 to} n ⁴ are the numbers of substitutions of the substituents X ^{1 to} X ⁴ and represent an integer of 0 to 4. The central metal M represents Al, Ga, In, Si, Ge, Sn. The substituent Z has the following structure: Represents Here, R ¹ , R ² and R ³ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent, a substituent Represents an aralkyl group which may have. In addition, R ¹ and R ² may form an alicyclic ring or a heterocycle containing a hetero atom. m is an integer of 1 or 2 and represents the number of the substituents Z. ] 2. A write-once optical disc comprising a transparent substrate / recording film / reflection film / protective film for recording a CD format signal, the recording film being one kind selected from compounds represented by the general formula [1] or CD or CD comprising two or more phthalocyanine compounds
-Recordable type optical disc compatible with ROM.