JPH0596860A - Write-once read many optical disk for cd or cd-rom - Google Patents

Abstract

PURPOSE:To provide an optical disk in conformity with an orange book which can completely record/reproduce a wavelength range of 770-810nm by realizing optical characteristics stable in the range. CONSTITUTION:A recording film of a write-once read many optical disk having a transparent substrate/a recording film/a reflecting film/protective film for recording a compact disk format or compact disk ROM format signal contains phthalocyanine series colorant represented by a formula.

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 compact disk (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 formed by injection molding a pit train having a CD or CD-ROM format signal on the surface of a transparent substrate such as polycarbonate, and then providing aluminum or gold as a reflection film by vapor deposition or sputtering, and further coating a protective layer. To create. 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. But such a CD or CD
Since the ROM is exclusively for reproduction and cannot be recorded, there is an inconvenience that it does not have an editing function like 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 a recording film of cyanine or the like to secure a substrate surface reflectance of 70% or more, and a CD format or CD-ROM format signal at 780 nm is provided. There have been proposed optical discs and methods for recording data and reading information on a CD or CD-ROM playback device.

However, since cyanine dyes generally have poor photostability, there is a possibility that the reliability of recording may be deteriorated under a use condition such that a single plate structure such as CD or 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 instead of the 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, a write-once type optical disc corresponding to a CD or a CD-ROM which has excellent stability and good recording characteristics has not been provided.

[0006]

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.

[0007]

DISCLOSURE OF THE INVENTION CD or CD-ROM excellent in stability as described above and having good recording characteristics.
The corresponding write-once optical disc is realized as follows. A write-once optical disc having a four-layer structure of a transparent substrate / recording film / reflection film / protective film for recording CD or CD-ROM format signals, the recording film of which is selected from the following general formula [I], which is a phthalocyanine compound. 1
C, characterized by being composed of two or more species
It is a write-once optical disc compatible with D or CD-ROM.
General formula [I]

[0008]

[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} X
In substitution number of ⁴ represents an integer of 0-4. The central metal M is S
represents i and Sn. The substituent Z is -OC (= O) R, -O.
Represents C (= O) Ar. Here, R represents a fluorine-substituted linear, branched, or cyclic alkyl group, and Ar represents a fluorine-substituted aryl group. 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 greatest feature of the phthalocyanine-based dye represented by the general formula [I] is that an acyl group having a fluorine-substituted alkyl group or a fluorine-substituted aryl group introduced from the central metal in the direction perpendicular to the molecular plane of the phthalocyanine ring is introduced. Since the decomposition temperature of the phthalocyanine compound is largely shifted to the low temperature side due to the effect of the acyl group (substituent Z in the general formula [I]) having, when these phthalocyanine compounds are used for the recording film, the recording sensitivity is significantly increased. To improve. Further, due to the effect of the fluorine atom introduced into the substituent Z, the compound has high solubility in a general-purpose organic solvent, the shape of the recording pit is good, the contrast of the recording signal is large, and the reproduction waveform is To be clean. Furthermore, the effect of the substituent Z is to increase the reflection level of the medium.

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 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, but this lowers the decomposition point (melting point), but the shape of the recording pit becomes worse. However, the difficulty is that a clean reproduction signal cannot be obtained. The phthalocyanine compound of the present invention has a decomposition point of 400 ° C. or less accompanied by a large weight reduction even when the substituent Z in the general formula [I] is not bulky, and the substituent Z
Due to the effect of the fluorine atoms introduced in (1), the shape of the recording pit (which is considered to be due to the relation of the interface energy with the substrate) is improved, so that the reproduced signal has a good contrast and a clear reproduced waveform is provided. In addition, the steric and electrical effects of the substituent Z suppress the association of phthalocyanine molecules with each other on the recording film, so that the semiconductor laser has a high extinction coefficient and a maximum reflectance in the emission wavelength region of the semiconductor laser. Therefore, as a write-once optical disc, the reflectance of 65% or more, which is the standard of Orange Book, can be secured.

The second feature is that the fluorine-substituted alkoxy group (substituents X ^{1 to} X ⁴ in the general formula [I]) introduced into the phthalocyanine ring dramatically improves the solubility, and a general-purpose organic solvent (for example, It becomes highly soluble in (methanol or ethanol), which facilitates the production of a recording film by the spin coating method. Even in the case of this substituent, the substituent Z
The state of the recording pit becomes good due to the effect of the introduced fluorine atoms in the same manner as. Further, since the substituents X ^{1 to} X ⁴ influence the shift of the maximum absorption maximum depending on the introduction position, it is necessary to adjust the absorption of the recording medium to a position that gives an appropriate recording sensitivity and effectively utilize the thermal energy of the recording laser. In addition, the wavelength dependence of recording sensitivity can be adjusted.

Fluorine-substituted straight chain in the substituent Z introduced into the phthalocyanine compound represented by the general formula [I],
Typical examples of the branched or cyclic alkyl group R are trifluoromethyl group, 2,2,2-trifluoroethyl group, heptafluoropropyl group, pentadecafluoroheptyl group, 2,2,3,3-tetrafluoro group. Propyl group, 2,2,3,3,3-pentafluoropropyl group,
1,1,1,3,3,3-hexafluoroisopropyl group, 2,2,3,4,4,4-hexafluorobutyl group, 1H, 1H, 5H-octafluoropentyl group, 1
H, 1H, 7H-dodecafluoroheptyl group, 1H, 1
H, 9H-hexadecafluorononyl group, 2- (perfluorohexyl) ethyl group, 2- (perfluorooctyl) ethyl group, 2- (perfluorodecyl) ethyl group,
2- (perfluoro-3-methylbutyl) ethyl group, 6
There are a-(perfluoroethyl) hexyl group, a 6- (perfluorohexyl) hexyl 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] are:
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- (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 constituting Y ¹ to Y ⁴ and the organic substituent introduced into the phthalocyanine compound represented by the general formula [I] include a hydrogen atom corresponding to the case where no substituent is present, 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 a tert- group.
A butyl group, a stearyl group, a trichloromethyl group, a trifluoromethyl group, a 2-methoxyethyl group, a phthalimidomethyl group, and the like, and an aryl group which may have a substituent include a phenyl group, a naphthyl group, and p-nitrophenyl. Base,
There is a p-tert-butylphenyl group and the like, and the alkoxy group which may have a substituent includes a methoxy group, an ethoxy group, an n-butoxy group, a tert-butoxy group, a 2-ethylhexyloxy group, 2,2,2. There is a 2-trichloroethoxy group and the like, and examples of the aryloxy group which may have a substituent include a phenoxy group and a p-nitrophenoxy group p-t.
There are ert-butylphenoxy group, 3-fluorophenoxy group, pentafluorophenyl group, 3-trifluoromethylphenoxy group and the like, and examples of the alkylthio group which may have a substituent include a methylthio group, an ethylthio group and te.
There are rt-butylthio group, hexylthio group, octylthio group and the like, and the arylthio group which may have a substituent is a phenylthio group, p-nitrophenylthio group, p-t.
Examples thereof include an ert-butylphenylthio group, a 3-fluorophenylthio group, a pentafluorophenylthio group, and a 3-trifluorophenylthio group, but are not limited thereto.

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 obtained phthalocyanine compound represented by the general formula [IV] is mixed with an acylating agent having various fluorine-substituted linear, branched or cyclic alkyl groups, or an acyl group having a fluorine-substituted aryl group. By reacting the agent, the phthalocyanine compound represented by the general formula [I] can be produced.

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 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 dissolves in general-purpose organic solvents such as alcohols, ketones, cellosolves, halogenated hydrocarbons, and fluorocarbons, so it is formed by the spin coating method from the viewpoint of productivity and uniformity of the recording film. The method of doing 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 is 30% by weight with respect to the phthalocyanine compound.
The following are preferred.

The optimum film thickness of the recording film is not particularly limited because it varies depending on the type and combination of recording film materials, and is from 500 to
3000 Angstroms preferred, 1000 more
The optimum film thickness range is 2,500 Angstroms.

Materials for the reflective film include gold, silver, copper, platinum,
Examples include metals such as aluminum, cobalt, and tin, alloys containing these as the main components, metal oxides such as MgO, ZnO, and SnO, and nitrides such as SiN ₄ , AlN, and TiN, but high absolute reflectance and stability. Gold is the best because of its excellent properties. 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. ~ 2,500 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 is not particularly limited, but is preferably in the range of 400 to 1300 angstrom.

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 film thickness of the protective film, when it is thin, the protective effect is lowered, and when it is thick, it causes deterioration of mechanical properties such as warpage of the disk due to shrinkage during curing of the resin. It is preferable to form a film in the micron range.

The disk substrate is preferably one having 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. Also, A
The wobble signal for TIP and the guide groove 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 also possible. It can be carried out.

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

[0045]

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 (a) To 150 parts of quinoline, 14.5 parts of 1,3-diiminoisoindolenin and 5.7 parts of silicon tetrachloride were added to give 160 parts.
After heating and stirring at ~ 170 ° C for 3 hours, cool and methanol 1
It was diluted with 000 parts, and the deposited precipitate was filtered, washed with methanol and dried to obtain 8.3 parts of greenish blue powder. After dissolving this powder in 300 parts of concentrated sulfuric acid, poured into 6000 parts of ice water,
The deposited precipitate is filtered, washed with water and dried to give a greenish blue powder 7.
I got two copies. As a result of FD-MS analysis, this powder was confirmed to be dihydroxysilicon phthalocyanine corresponding to the general formula [IV]. 5.0 parts of the dihydroxysilicon phthalocyanine obtained above was added to pyridine 100
And 10 parts of tri-n-butylamine with stirring,
Heptafluorobutanoyl chloride 5.0 while cooling
Parts were added dropwise, and the mixture was stirred at room temperature for 1 hour and then heated and stirred at 50 ° C. for 3 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 a mixed solution of methanol / water (3/1), and dried to give a green powder 5.2.
I got a part. As a result of FD-MS analysis, it was confirmed that this powder was the phthalocyanine compound (a).

Production Example 2: Production of phthalocyanine compound (b) To 150 parts of quinoline, 14.5 parts of 1,3-diiminoisoindolenin and 4.2 parts of stannous chloride were added to give 160 parts.
After heating and stirring at ~ 170 ° C for 3 hours, cool and methanol 1
It was diluted with 000 parts, and the deposited precipitate was filtered, washed with methanol, and dried to obtain 7.6 parts of greenish blue powder. This powder is heated and stirred in 500 parts of ammonia water for 3 hours, and after cooling,
Filtration, washing with water and drying gave 6.5 parts of greenish blue powder. As a result of FD-MS analysis, this powder was confirmed to be dihydroxytin phthalocyanine corresponding to the general formula [IV]. After 5.0 parts of dihydroxytin phthalocyanine obtained above was dissolved in 100 parts of pyridine with stirring, 5.0 parts of trifluoroacetic anhydride was added dropwise while cooling, stirred at room temperature for 1 hour, and then heated at 50 ° C. for 3 hours. It was stirred. 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 3.8 parts of a green powder. It was FD
As a result of -MS analysis, it was confirmed that this powder was the phthalocyanine compound (b).

Production Example 3: Production of phthalocyanine compound (c) 50 parts of o-dichlorobenzene and 25 parts of tri-n-butylamine were added to 4- (2,2,2-trifluoroethyl) oxy-1,3-di. Add 7.8 parts of iminoisoindoline and 5.0 parts of silicon tetrachloride, heat and stir at 160 to 170 ° C. for 3 hours, cool, and dilute with 1000 parts of methanol,
The deposited precipitate was filtered, washed with a mixed solution of methanol / water (3/1) and dried to obtain 6.3 parts of a green powder. This powder was dissolved in 300 parts of concentrated sulfuric acid, poured into 6000 parts of ice water, and the deposited precipitate was filtered, washed with water and dried to obtain 5.0 parts of greenish blue powder. As a result of FD-MS analysis, this powder was confirmed to be dihydroxysilicon phthalocyanine corresponding to the general formula [IV]. 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 trifluoroacetic anhydride was added dropwise while cooling, and the mixture was stirred at room temperature for 1 hour and then heated and stirred at 60 ° C. for 3 hours. After cooling, the reaction solution was added with 5% hydrochloric acid water 20
It was poured into 00 parts, and the deposited precipitate was filtered, washed with water, washed with a mixed solution of methanol / water (2/1) and dried to obtain 4.9 parts of a green powder. As a result of FD-MS analysis, it was confirmed that this powder was the phthalocyanine compound (c).

Production Example 4: Production of Phthalocyanine Compound (d) 5- (4)-(2,2,2-trifluoroethyl) oxy-1,3-diiminoisoindoline in Production Example 3 was replaced with 5-7.8. (2,2,3,3-tetrafluoropropyl) oxy-1,3-diiminoisoindoline 7.6 parts,
3. A blue-green powder of dihydroxysilicon phthalocyanine corresponding to the general formula [IV], treated in the same manner as in Production Example 3.
6 parts were obtained. After 4.6 parts of dihydroxysilicon phthalocyanine obtained above was dissolved in 150 parts of picoline with stirring, 5.0 parts of heptafluorobutanoyl chloride was added dropwise while cooling, and the mixture was stirred at room temperature for 1 hour and then at 60 ° C. for 3 hours. Heated and stirred. After cooling, the reaction solution was added with 5% hydrochloric acid water 2000
And then extracted with 500 parts of chloroform. The organic layer was neutralized and washed with a sodium hydrogen carbonate solution, washed with water, dried over sodium sulfate, and the solvent was distilled off to obtain a green Harz-like substance. Next, column purification (silica gel / chloroform)
This gave 2.3 parts of a dark green powder. As a result of FD-MS analysis, it was confirmed that this powder was the phthalocyanine compound (d).

Production Example 5: Production of phthalocyanine compound (e) 80 parts of o-dichlorobenzene and 20 parts of tri-n-butylamine were added to 5- (2,2,2-trifluoroethyl) oxy-1,3-di. Iminoisoindoline (6.0 parts) and stannous chloride (4.8 parts) were added, and the mixture was heated with stirring at 150 to 160 ° C. for 3 hours, cooled, diluted with 1000 parts of hexane, and the hexane layer was removed by decantation. The mixture was washed with 500 parts of hexane and the Harz-shaped precipitate was washed with 5% hydrochloric acid water, and then heated and refluxed in 500 parts of ammonia water for 2 hours. After cooling, it was filtered, washed with water and dried to obtain 3.1 parts of a blue-green powder of dihydroxytin phthalocyanine corresponding to the general formula [IV]. After 3.0 parts of dihydroxysilicon phthalocyanine obtained above was dissolved in 100 parts of pyridine with stirring, 5.0 parts of trifluoroacetic anhydride was added dropwise while cooling, and the mixture was stirred at room temperature for 1 hour and then heated at 60 ° C. for 3 hours. It was stirred. After cooling, the reaction solution was poured into 2000 parts of 5% hydrochloric acid, extracted with 500 parts of chloroform, the organic layer was neutralized and washed with a sodium hydrogen carbonate solution, washed with water, dried over sodium sulfate, and the solvent was distilled off to give a greenish solution. A Hartz-like substance was obtained. Then, 2.2 parts of dark green powder was obtained by column purification (silica gel / chloroform). As a result of FD-MS analysis, it was confirmed that this powder was a phthalocyanine compound (e).

Production Example 4: Production of Phthalocyanine Compound (f) 5,4- (2,2,2-trifluoroethyl) oxy-1,3-diiminoisoindoline in Production Example 3 was replaced with 5,7 parts. Then, 7.2 parts of 8-di-n-butoxy-1,3-diiminoisoindoline was treated and treated in the same manner as in Production Example 3 to obtain 5.3 parts of a blue-green powder of dihydroxysilicon phthalocyanine corresponding to the general formula [IV]. Got 5.0 parts of the dihydroxysilicon phthalocyanine obtained above was added to picoline 1
After stirring and dissolving in 50 parts, while cooling, 3, 3, 4, 4
-5.0 parts of tetrafluorobutanoyl chloride was added dropwise, and the mixture was stirred at room temperature for 1 hour and then heated and stirred at 60 ° C for 3 hours. After cooling, the reaction solution was poured into 2000 parts of 5% hydrochloric acid water,
Extracted with 500 parts of chloroform, the organic layer was neutralized and washed with a sodium hydrogen carbonate solution, washed with water, and dried with sodium sulfate.
The solvent was distilled off to obtain a green Harz-like substance. Then
Column purification (silica gel / chloroform) gave 3.3 parts of a 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) 4- (2,2,2-trifluoroethyl) oxy-1,3-diiminoisoindoline of Production Example 3 was replaced by 4-instead of 7.8 parts. (2,2,3,3-tetrafluoropropyl) oxy-1,3-diiminoisoindoline 7.6 parts,
The same treatment as in Production Example 3 was carried out to obtain 3.0 parts of a blue-green powder of a dihydroxysilicon phthalocyanine compound corresponding to the general formula [IV]. 3.0 parts of the dihydroxysilicon phthalocyanine compound obtained above was dissolved in 100 parts of pyridine with stirring, 5.0 parts of trifluoroacetic anhydride was added dropwise while cooling, and the mixture was stirred at room temperature for 1 hour and then at 60 ° C. for 3 hours. Heated and stirred. After cooling, the reaction solution was poured into 2000 parts of 5% hydrochloric acid, extracted with 500 parts of chloroform, the organic layer was neutralized and washed with a sodium hydrogen carbonate solution, washed with water, dried over sodium sulfate, and the solvent was distilled off to give a greenish solution. A Hartz-like substance was obtained. Next, 1.7 parts of dark green powder was obtained by column purification (silica gel / chloroform). 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 (j) 4- (2,2,2-trifluoroethyl) oxy-1,3-diiminoisoindoline of Production Example 3 was replaced by 4-instead of 7.8 parts. (1H, 1H, 5H-perfluoroheptyl) oxy-1,3-diiminoisoindoline 9.2 parts,
The same treatment as in Production Example 3 was carried out to obtain 4.5 parts of a blue-green powder of a dihydroxysilicon phthalocyanine compound corresponding to the general formula [IV]. After 4.0 parts of the dihydroxysilicon phthalocyanine compound obtained above was dissolved in 200 parts of picoline with stirring, 7.0 parts of p-fluorobenzoic acid chloride was added dropwise while cooling, and the mixture was stirred at room temperature for 1 hour and then at 80 ° C. The mixture was heated and stirred for 3 hours. After cooling, the reaction solution was added with 5% hydrochloric acid water 2000
And then extracted with 500 parts of chloroform. The organic layer was neutralized and washed with a sodium hydrogen carbonate solution, washed with water, dried over sodium sulfate, and the solvent was distilled off to obtain a green Harz-like substance. Next, column purification (silica gel / chloroform)
This gave 1.7 parts of a dark green powder. As a result of FD-MS analysis, this powder was confirmed to be 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, a phthalocyanine compound [c] was added to a 2,2,3,2,3,2 substrate.
It was dissolved in 3-tetrafluoropropanol at a concentration of 50 mg / ml, and 0.2 micron filtering was performed to prepare a coating liquid. Using this coating liquid, a film having a recording film thickness of 1300 angstrom was formed 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 reflectance of the optical disc thus prepared was 76%. 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 6.1 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 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, an inner diameter of 15 mm, a phthalocyanine compound [d] was dissolved in diacetone alcohol at a concentration of 65 mg / ml, and 0.2 μm filtering was performed to prepare a coating liquid. Was used to form a recording film having 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 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 7%. 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 3 Depth 1250 Å, Width 0.48 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 [e] 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 recording film having a film thickness of 1400 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 70
%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 5.2 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 0.6 micron, Thickness 1.20 m with guide grooves with pitch 1.6 micron
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 recording film having a film thickness of 1600 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 disk thus created is 78
%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 5.6 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 5-10 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 was dissolved in ethyl cellosolve at a concentration of 50 mg / ml, and 0.2 μm filtering was performed to prepare a coating liquid. Was used to form a recording film having a recording film thickness of 1300 angstroms 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. Table 1 shows the reflectance of the optical disc thus prepared and the optimum recording laser power when recording and reproducing are performed by the same method as in Example 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.
In a write-once optical disc having a layered structure and recording a CD or CD-ROM format signal, the recording film is composed of one or more selected from the following general formula [I] which is a phthalocyanine compound. A write-once type optical disc compatible with a CD or a CD-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} are 0.
Represents an integer of 4; The central metal M represents Si and Sn.
Substituent Z represents -OC (= O) R or -OC (= O) Ar. Here, R represents a fluorine-substituted linear, branched, or cyclic alkyl group, and Ar represents a fluorine-substituted aryl group. 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.