JPH0596861A - Write-once optical disc for CD or CD-ROM - Google Patents

Abstract

(57) [Abstract] [Purpose] The present invention solves the drawbacks of a conventional CD or CD-ROM having a write-once function and an edit function.
Achieving stable optical characteristics in the wavelength range of ~ 810nm,
It is intended to provide an orange book compliant optical disc capable of being completely recorded and reproduced in this wavelength range. [Structure] Made of transparent substrate / recording film / reflection film, compact disc format or compact disc-
A write-once optical disc for recording a ROM format signal, wherein the recording film contains a phthalocyanine-based dye represented by the following general formula [I], for a compact disc or a compact disc-ROM. General formula [I]

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical disk for recording / reproducing information with a laser beam. More specifically, it relates to a write-once optical disc compatible with a CD or a CD-ROM.

[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 ROM for a computer are widely used. In such a CD or CD-ROM, a pit string having a CD or CD-ROM format signal is usually formed on the surface of a transparent substrate such as polycarbonate at the time of injection molding, and aluminum or gold is vapor-deposited or sputtered on the reflective film. And is coated with a protective layer. The reproduction laser light (780 nm semiconductor laser light) is irradiated from the back surface of the substrate of the optical disk 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 read-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 disk or a magneto-optical disk having an editing function, a recording film made of a chalcogenite compound such as Te, a rare earth metal compound or an organic dye such as cyanine has been put into 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 of gold or the like is provided on the recording film of cyanine or the like to secure a substrate surface reflectance of 70% or more.
An optical disc and method have been proposed in which a CD format or CD-ROM format signal is recorded at 0 nm and information is read out by a CD or CD-ROM reproducing device.

However, since cyanine dyes generally have poor photostability, under a use condition where they are directly exposed to sunlight in a single plate structure such as CD or CD-ROM,
There may be problems with the reliability of the records. for that reason,
Attempts have been made to use a phthalocyanine compound having excellent chemical and physical stability instead of a cyanine dye as a recording film material.

In the case of this phthalocyanine compound, the recording sensitivity is low because it is also thermally stable, and the absorption band is very sharp. Therefore, the oscillation of the semiconductor laser mounted in the pickup of the CD or CD-ROM drive is oscillated. It is difficult to obtain stable optical characteristics (reflectance and absorption) in the wavelength permissible range (780 to 800 nm), the wavelength dependence of recording sensitivity is large, and it is difficult to form a versatile write-once optical disc. There is a point. Therefore, at present, C, which has excellent stability and good recording characteristics, is used.
A write-once optical disc compatible with D or CD-ROM is not provided.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the drawbacks of a conventional CD or CD-ROM having a write-once function and an edit function, is excellent in stability, and has good recording characteristics. In order to provide an optical disk, a recording material that can prevent a low recording sensitivity and wavelength dependence of the recording sensitivity that occur when a phthalocyanine compound having excellent chemical and physical stability is used as a recording film material, and can obtain a good reproduction signal As a result of earnestly studying the above, the present invention has been achieved.

[0006]

A write-once type optical disc corresponding to a CD or a CD-ROM, which is excellent in stability and recording characteristics, is realized as follows.
A write-once type optical disc having a four-layer structure of a transparent substrate / recording film / reflection film / protective film for recording a CD format signal or a CD-ROM format signal, the recording film of which is a phthalocyanine compound represented by the following general formula [I]
A write-once optical disc compatible with a CD or a CD-ROM, characterized in that it is composed of one or more selected from General formula [I]

[0007]

[Chemical 2]

[In the formula, the substituents X ^{1 to} X ⁴ each independently represent a fluorine-substituted alkoxy group, and Y ^{1 to} Y ⁴ are each independently a hydrogen atom, a halogen atom, or an alkyl optionally having a substituent. Group, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, a substituent It represents an arylthio group, a nitro group, a cyano group, a sulfonic acid group, a sulfonic acid amide group, or a sulfonic acid ester group which may be possessed. n ^{1 to} n ⁴ are substituents X ¹ to
The substitution number of X ⁴ represents an integer of 0 to 4. The central metal M is A
It represents 1, Ga, In, and Ge. The substituent Z is -OC (=
O) R and -OC (= O) Ar. Here, R represents a linear, branched or cyclic alkyl group which may have a substituent, and Ar represents an aryl group which may have a substituent.
m is an integer of 1 or 2 and represents the number of substituents Z. ]

The above-mentioned problems have been solved by forming the recording film of the present invention from a phthalocyanine compound having a special structure represented by the general formula [I]. That is, the phthalocyanine compound represented by the general formula [I] is characterized by the effect of an acyl group (substituent Z in the general formula [I]) introduced from the central metal in the direction perpendicular to the molecular plane of the phthalocyanine ring. Since the decomposition temperature of the compound largely shifts to the low temperature side, the recording sensitivity is significantly improved when these phthalocyanine compounds are used in the recording film. 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 reproduction signal is good and a clear reproduction 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. However, phthalocyanine compounds having these substituents are large. Since the decomposition temperature accompanied by weight reduction is 400 ° C. or higher, the problem is that the recording sensitivity is low. 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 clear reproduction signal.

The phthalocyanine compound in the present invention is
Even when the substituent Z in the general formula [I] is not bulky, the decomposition point with a large weight reduction is 400 ° C. or lower, and the effect of the substituent Z causes the phthalocyanine molecules to associate with each other on the recording film. In order to suppress, the point where the maximum reflectance is shown is close to the emission wavelength region of the semiconductor laser while showing a high molecular extinction coefficient, so that it is possible to secure the reflectance of 65% or more, which is the standard of the Orange Book, as a write-once optical disc. It has the features that can.

Further, a fluorine-substituted alkoxy group introduced into the phthalocyanine ring (substituents X ^{1 to} X in the general formula [I]
^{By 4} ), the solubility is dramatically increased, and it becomes highly soluble in general-purpose organic solvents (for example, methanol and ethanol), which facilitates the production of recording films by spin coating. Further, due to the effect of the fluorine atoms introduced into the substituents X ^{1 to} X ⁴ (which is considered to be due to the relationship of the interface energy between the recording film and the substrate), the state of the recording pit is good and the contrast of the reproduced signal is good. , A beautiful reproduced waveform can be obtained.

Further, since the substituents X ^{1 to} X ⁴ influence the shift of the maximum absorption maximum depending on the introduction position, the absorption of the recording medium is adjusted to a position giving an appropriate recording sensitivity, and the thermal energy of the recording laser is effectively made. It can be utilized and the wavelength dependence of recording sensitivity can be adjusted.
Representative examples of the linear, branched or cyclic alkyl group R which may have a substituent in the substituent Z introduced into the phthalocyanine compound represented by the general formula [I] of the present invention are:
Methyl group, ethyl group, hexyl group, dodecyl group, isopropyl group, 2-ethylhexyl group, T-butyl group, neopentyl group, trichloromethyl group, 1,2-dichloroethyl group, trifluoromethyl group, heptafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2-
There are methoxyethyl group, cyclohexyl group, adamantyl group and the like. Representative examples of the aryl group Ar which may have a substituent in the substituent Z include a phenyl group, a naphthyl group,
3-methylphenyl group, 3-methoxyphenyl group, 3-
There are fluorophenyl group, 3-trichloromethylphenyl group, 3-trifluoromethylphenyl group, pentafluorophenyl group, 3-nitrophenyl group and the like.

Representative examples of the substituents X ^{1 to} X ⁴ introduced into the phthalocyanine compound represented by the general formula [I] of the present invention include 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, 1
H, 1H, 7H-dodecafluoroheptoxy group, 1H,
1H, 9H-hexadecafluorononyloxy group, 2-
(Perfluorohexyl) ethoxy group, 2- (perfluorooctyl) ethoxy group, 2- (perfluorodecyl) ethoxy group, 2- (perfluoro-3-methylbutyl) ethoxy group, 6- (perfluoroethyl) hexyloxy Group, 6- (perfluorohexyl) hexyloxy group and the like.

Typical examples of the atoms and organic substituents constituting Y ¹ to Y ⁴ introduced into the phthalocyanine compound represented by the general formula [I] of the present invention are hydrogen atoms corresponding to the case where no substituent is present. In addition, the halogen atom includes chlorine, bromine, iodine, and fluorine, and the alkyl group which may have a substituent includes a methyl group, an n-butyl group, and t.
An ert-butyl group, a stearyl group, a trichloromethyl group, a trifluoromethyl group, a 2-methoxyethyl group, a phthalimidomethyl group, and the like. Examples of the aryl group which may have a substituent are a phenyl group, a naphthyl group, and p- There are nitrophenyl group, p-tert-butylphenyl group, etc.,
Examples of 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 and a 2,2,2-trichloroethoxy group. Examples of the aryloxy group which may have a phenoxy group, a p-nitrophenoxy group, a p-tert-butylphenoxy group, a 3-fluorophenoxy group, a pentafluorophenyl group, a 3-trifluoromethylphenoxy group, etc. The alkylthio group which may have a group includes a methylthio group, an ethylthio group, a tert-butylthio group, a hexylthio group, an octylthio group and the like, and the arylthio group which may have a substituent includes a phenylthio group and p-nitro. Phenylthio group, p-tert-butylphenylthio group, 3-fluorophenylthio group Pentafluorophenylthio group, 3
Examples thereof include, but are not limited to, a trifluorophenylthio group and the like.

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

That is, an unsubstituted phthalonitrile represented by the following general formula [II], a 3-position-substituted phthalonitrile,
Alternatively, 4-position-substituted phthalonitriles, or unsubstituted 1,3-diiminoisoindoline represented by the following general formula [III], 4-position-substituted 1,3-diiminoisoindoline compound, or 5-position-substituted 1 , 3-diiminoisoindoline compound, or corresponding phthalic anhydrides and phthalimides and various metal salts of the metal represented by M in the general formula [I] are used as starting materials by a conventional method to give a compound of the general formula [IV ]
A phthalocyanine compound represented by can be produced.

General formula [II]

[Chemical 3]

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

General formula [III]

[Chemical 4]

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

General formula [IV]

[Chemical 5]

[Wherein X ^{1 to} X ⁴ , Y ^{1 to} Y ⁴ and n ¹ to
n ⁴ , M, and m are each X ^{1 to} X in the general formula [I].
⁴ , Y ^{1 to} Y ⁴ , n ^{1 to} n ⁴ , M and m have the same meaning.

Next, the phthalocyanine compound represented by the general formula [IV] is reacted with various acylating agents to produce the phthalocyanine compound represented by the general formula [I].

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

(A)

[Chemical 6]

(B)

[Chemical 7]

(C)

[Chemical 8]

(D)

[Chemical 9]

(E)

[Chemical 10]

(F)

[Chemical 11]

(G)

[Chemical formula 12]

(H)

[Chemical 13]

(I)

[Chemical 14]

(J)

[Chemical 15]

In the recording film using the phthalocyanine compound represented by the general formula [I] in the present invention, for the purpose of further improving the stability of the recording film such as light resistance and environmental resistance, and 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 the spin coating method can be used in view of productivity and recording film uniformity. The method of forming a film is preferred.

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 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 varies depending on the type and combination of recording film materials, and is not particularly limited.
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, and gold is most preferable because of its high absolute reflectance and excellent stability. Thus, gold is the most suitable material for the reflective film, but since gold is expensive, it is difficult to obtain an inexpensive write-once optical disc.
In order to solve this problem, the thickness of gold is reduced to the minimum, and the laminated film in which the insufficient thickness is compensated by another metal or metal oxide (eg, aluminum, silver, ZnO, etc.) is reflected. It can also be used in a membrane. In this case, in order to make the absolute reflectance almost equal to that of the gold single film, the gold film thickness of the lower layer (layer in contact with the recording film) must be at least 200 Å or more, and the thickness of the reflection film is 800. ~ 25
00 angstroms is optimal. In addition, an organic high reflection film may be used depending on the case.

As a method for forming such a reflective 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 to
The range of 1300 Angstroms 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.)
Further, 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, spin coating is applied, and curing is performed by ultraviolet irradiation is preferable, but the material is not limited thereto.

Regarding the optimum thickness of the protective film, when it is thin, the protective effect 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 can be used. Among these, those made of thermoplastic resin are preferable in view of ease of molding, provision of wobble signal for ATIP, and provision of guide grooves, etc. Further, acrylic resin and 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 angstroms.

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).

[0046]

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) 100 parts of quinoline was added to 4-butoxyphthalonitrile 10.
0 part, 3.4 parts of anhydrous aluminum chloride were added,
After heating and stirring at 170 ° C for 3 hours, the mixture is cooled and methanol 10
It was diluted with 00 parts, and the deposited precipitate was filtered, washed with methanol, and dried to obtain 7.8 parts of green powder. This powder was dissolved in 400 parts of concentrated sulfuric acid, poured into 8000 parts of ice water, and the deposited precipitate was filtered, washed with water and dried to give a green-blue powder 5.0.
I got a part. As a result of FD-MS analysis, this powder was confirmed to be hydroxyaluminum phthalocyanine corresponding to the general formula [IV]. 5.0 parts of the hydroxyaluminum phthalocyanine obtained above was added to picoline 30
After stirring and dissolving in 0 part and 50 parts of tri-n-butylamine, 5.0 parts of 2-ethylheptanoyl chloride was added dropwise while cooling, and the mixture was stirred at room temperature for 1 hour and then refluxed under heating for 3 hours. After cooling, the reaction solution was poured into 2000 parts of 5% hydrochloric acid water, extracted with 500 parts of chloroform, dried over magnesium sulfate, and then the solvent was distilled off to obtain a dark green Harz-like substance. Then, the product was purified and isolated by alumina column chromatography to obtain 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 (c) 4- (2,2,2-trifluoroethoxy) -1,1 in place of 10.0 parts of 4-butoxyphthalonitrile of Production Example 1
Using 3-diiminoisoindoline as 9.8 parts and treating in the same manner as in Production Example 1, 4.6 parts of a green powder of hydroxyaluminum phthalocyanine corresponding to the general formula [IV] was obtained. 4.0 parts of the hydroxyaluminum phthalocyanine obtained above was dissolved in 100 parts of pyridine with stirring, 3.0 parts of trifluoroacetic anhydride was added dropwise with cooling, and the mixture was stirred at room temperature for 1 hour and then refluxed under heating for 3 hours. After cooling, the reaction liquid was poured into 2000 parts of 5% hydrochloric acid water, the deposited precipitate was filtered, washed with water, washed with a mixed solution of methanol / water (3/1), and dried to obtain 4.2 parts of green powder. It was FD-MS
As a result of the analysis, it was confirmed that this powder was the phthalocyanine compound (c).

Production Example 3: Production of Phthalocyanine Compound (d) 4- (2,2,3,3-tetrafluoropropoxy) phthalonitrile 12.0 in place of 10.0 parts of 4-butoxyphthalonitrile of Production Example 1. And treated in the same manner as in Production Example 1 to obtain 5.7 parts of a green powder of hydroxyaluminum phthalocyanine corresponding to the general formula [IV]. After 5.0 parts of hydroxyaluminum phthalocyanine obtained above was dissolved in 100 parts of pyridine and 10 parts of tri-n-butylamine with stirring, 5.0 parts of heptafluoropropinoyl chloride was added dropwise while cooling, and at room temperature for 1 hour. After stirring, the mixture was heated and stirred at 60 ° C. for 4 hours. After cooling, the reaction solution was poured into 300 parts of 5% hydrochloric acid water, and the dark green viscous solid precipitated was dissolved in chloroform and dried over anhydrous sodium sulfate, and the solvent was distilled off, followed by column purification (alumina / chloroform). ) Gave 3.0 parts of a green powder. FD-
As a result of MS analysis, this powder was confirmed to be the phthalocyanine compound (d).

Production Example 4: Production of Phthalocyanine Compound (e) In place of 10.0 parts of 4-butoxyphthalonitrile of Production Example 1, 9.2 parts of 4-tert-butylphthalonitrile was used.
In place of 3.4 parts of anhydrous aluminum chloride of Production Example 1, 2.0 parts of gallium trichloride was used, and treated in the same manner as in Production Example 1,
2.4 parts of hydroxygallium phthalocyanine dark green powder corresponding to the general formula [IV] was obtained. 2.0 parts of hydroxygallium phthalocyanine obtained above was added to picoline 1
After stirring and dissolving in 100 parts of tri-n-butylamine (10.0 parts) and p-nitrobenzoic acid chloride while cooling, 5.
0 part was added dropwise, and the mixture was stirred at room temperature for 1 hour and then refluxed for 6 hours. After cooling, the reaction solution was poured into 2000 parts of 5% hydrochloric acid water, the deposited precipitate was filtered, washed with water, washed with methanol and dried to obtain 1.3 parts of a green powder. As a result of FD-MS analysis, it was confirmed that this powder was a phthalocyanine compound (e).

Production Example 5: Production of phthalocyanine compound (f) In place of 10.0 parts of 4-butoxyphthalonitrile of Production Example 1, 4- (2,2,3,3-tetrafluoropropoxy) -1,3- Diiminoisoindoline was adjusted to 13.0 parts and treated in the same manner as in Production Example 1 to obtain 2.4 parts of a dark green powder of hydroxyaluminum phthalocyanine corresponding to the general formula [IV]. 2.0 parts of the hydroxyaluminum phthalocyanine obtained above was dissolved in 100 parts of pyridine, 3.0 parts of trifluoroacetic anhydride was added dropwise while cooling, and the mixture was stirred at room temperature for 1 hour and then heated at 50 ° C. for 3 hours. It was stirred. The reaction solution was poured into 2000 parts of 5% hydrochloric acid water, and the deposited precipitate was filtered and washed with water, and then methanol / water (2 /
1) It was washed with the mixed solution and dried to obtain 1.2 parts of dark green powder. As a result of FD-MS analysis, this powder was confirmed to be the phthalocyanine compound (f).

Production Example 6: Production of Phthalocyanine Compound (h) In place of 10.0 parts of 4-butoxyphthalonitrile of Production Example 1, 4- (2,2,3,3-tetrafluoropropoxy) -1,3- Diiminoisoindoline was adjusted to 13.0 parts and treated in the same manner as in Production Example 1 to obtain 2.4 parts of a dark green powder of hydroxyaluminum phthalocyanine corresponding to the general formula [IV]. 2.0 parts of the hydroxyaluminum phthalocyanine obtained above was dissolved in 100 parts of pyridine, 3.0 parts of 2-ethylheptanoyl chloride was added dropwise while cooling, and the mixture was stirred at room temperature for 1 hour and then heated under reflux for 3 hours. did. The reaction solution was poured into 2000 parts of 5% hydrochloric acid water,
It was extracted with 500 parts of chloroform, dried over anhydrous sodium sulfate, the solvent was distilled off, and 0.7 parts of a green powder was obtained by column purification (alumina / chloroform). FD-
As a result of MS analysis, this powder was confirmed to be the phthalocyanine compound (h).

Example 1 Depth 1200 Å, Width 0.50 μm,
1.20m thickness with guide grooves with pitch of 1.6 microns
m, an outer diameter of 120 mm, an inner diameter of 15 mm, a phthalocyanine compound [c] was dissolved in diacetone alcohol at a concentration of 60 mg / ml, and 0.2 μm filtering was performed to prepare a coating liquid. Was used to form a film having a recording film thickness of 1300 angstroms by a spin coater. Next, 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 with an ultraviolet curable resin to prepare an optical disk. The optical disc thus prepared has a reflectance of 7
It was 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 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 2 1500 Angstroms deep, 0.52 microns 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, 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 recording film having a thickness of 1450 angstrom was formed by using 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 with an ultraviolet curable resin to prepare an optical disk.
The reflectance of the optical disc thus prepared was 72%. Using the optical disc thus prepared, a linear velocity of 1.4 is obtained by using a semiconductor laser having a wavelength of 785 nm.
When the EFM-CD format signal was recorded at m / sec, it was possible to record at the optimum recording laser power of 6.6 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.

Example 3 Depth 1250 Å, Width 0.48 μm,
1.20m thickness with guide grooves with pitch of 1.6 microns
m, outer diameter 120 mm, inner diameter 15 mm, a phthalocyanine compound [e] 2, 3,
A coating solution was prepared by dissolving in 3-terolafluoropropanol at a concentration of 45 mg / ml and filtering with 0.2 micron, and using this coating solution, a film having a recording film thickness of 1600 angstrom was formed 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 with an ultraviolet curable resin to prepare an optical disk. The reflectance of the optical disc thus prepared was 71%. Using the optical disk thus prepared, a semiconductor laser having a wavelength of 785 nm was used, and the linear velocity was 1.4 m / sec.
When a CD format signal was recorded, it was possible to record at an optimum recording laser power of 7.0 mW. next,
This signal is laser power 0.5 by CD player
When the signal was reproduced at mW, the obtained signal was good, and the level was sufficiently high for a commercially available CD player.

EXAMPLE 4 Depth 1300 Å, Width 0.5 μm, Pitch 1.6 μm, and Thickness 1.20 m
A phthalocyanine compound [f] was dissolved in ethyl cellosolve at a concentration of 65 mg / ml on a polycarbonate substrate having a diameter of m, an outer diameter of 120 mm, and an inner diameter of 15 mm, and 0.2 μm filtering was performed to prepare a coating liquid. A spin coater was used to form a film having a recording film thickness of 1700 angstroms. 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 with an ultraviolet curable resin to prepare an optical disk. The reflectance of the optical disc thus created is 71
%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 5.9 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 [h] was dissolved in ethyl cellosolve at a concentration of 60 mg / ml, and 0.2 μm of filtering was performed to prepare a coating liquid. A spin coater was used to form a film having a recording film 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 with an ultraviolet curable resin to prepare an optical disk. The reflectance of the optical disc thus created is 71
%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 5.9 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.

Examples 6-10 Depth 1250 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
50 mg / ml in 3,3-tetrafluoropropanol
Was dissolved at a concentration of 0.2 μm and filtered by 0.2 μm to prepare a coating liquid. Using this coating liquid, a recording film having a recording film thickness of 1300 Å was formed 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 with an ultraviolet curable resin to prepare an optical disk. Example 1 and the reflectance of the optical disk thus prepared
Table 1 shows the optimum recording laser power when recording and reproducing are performed in the same manner as in (1).

[0059]

[Table 1]

[0060]

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

Claims (4)

[Claims] 1. A transparent substrate / recording film / reflection film / protective film.
CD format signal or CD-R
In a write-once optical disc for recording an OM format signal, the recording film is composed of one or more selected from the following general formula [I] which is a phthalocyanine compound, a CD or a CD- A write-once optical disc compatible with ROM. General formula [I] [In the formula, each of the substituents X ^{1 to} X ⁴ independently represents a fluorine-substituted alkoxy group, and each of Y ^{1 to} Y ⁴ independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or a substituent. An aryl group which may have a group, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, and a substituent Good arylthio group, nitro group, cyano group,
It represents a sulfonic acid group, a sulfonic acid amide group, or a sulfonic acid ester group. n ^{1 to} n ⁴ are the number of substitutions of the substituents X ^{1 to} X ⁴ and represent an integer of 0 to 4. The central metal M is Al, Ga, I
represents n and Ge. The substituent Z is -OC (= O) R, -O.
Represents C (= O) Ar. Here, R represents a linear, branched or cyclic alkyl group which may have a substituent, and Ar represents an aryl group which may have a substituent. m is an integer of 1 or 2 and represents the number of substituents Z. ] 2. All of n ^{1 to} n ⁴ of the general formula [I] are 0.
The write-once optical disc for CD or CD-ROM according to claim ¹ , wherein Y ^{1 to} Y ⁴ are all hydrogen atoms. 3. The substitution position of X ^{1 to} X ⁴ of the general formula [I] is
X ¹ is at either the 2-position or 3-position in the formula, or both, X ² is at the 6-position or 7-position in the formula, or both, and X ³ is the 10-position or 11-position in the formula. 3. CD or CD according to any one of claims 1 to 2, wherein X ⁴ is necessarily substituted on either or both of the 14- and 15-positions in the formula in either or both of the above.
A write-once optical disc compatible with ROM. ^4. The substitution position of X ^{1 to} X ⁴ of the general formula [I] is
X ¹ is at either the 1-position or 4-position in the formula, or both, X ² is at the 5-position or 8-position in the formula, or both, and X ³ is at the 9-position or 12-position in the formula. 3. CD or CD according to any one of claims 1 to 2, wherein X ⁴ is substituted on either or both of the 13-position and 16-position in the formula, or both of them.
A write-once optical disc compatible with ROM.