JP3389677B2 - Optical recording material and write-once compact disc using the same - 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 recording medium on / from which information can be written / read by a laser beam. More specifically, it relates to a write-once compact disc (CD-R) and a recording film material thereof.

[0002]

2. Description of the Related Art Conventionally, a recording medium having a single film structure in which an organic dye is used as a recording film has been proposed, and a write-once optical disc for a filing system having an editing function has been put into practical use. This write-once optical disc has a reflectance of 20 to 30%.
In addition, since the recording / reproducing laser wavelength is 830 nm, there is no compatibility with a CD or CD-ROM that has already been popular. After that, by using a cyanine dye having a specific optical constant as a recording film and further providing a reflecting film on the recording film, the reflectance can be improved to 65% or more, and a CD format or CD-ROM format signal can be recorded. Alternatively, an optical disk and a method that can be reproduced by a CD-ROM reproducing device have been proposed (Japanese Patent Laid-Open Nos. 2-42652 and 2-147286),
It has already been put to practical use. However, since cyanine dyes generally have poor photostability, there may be a problem in the reliability of recording under use conditions such as direct exposure to sunlight. With a CD-R using a cyanine dye as a recording film, The same reliability as that of a read-only CD or CD-ROM has not been realized. Therefore, phthalocyanine dyes having excellent chemical and physical stability have been attracting attention, and studies have been conducted to apply them to CD-R recording film materials. The application of phthalocyanine dyes to optical recording media has been carried out since the time of study of write-once optical discs for filing systems, but it has not been possible to impart solubility to organic solvents, control optical characteristics, and improve recording sensitivity. It was a very difficult problem.

Among the studies on phthalocyanine dyes so far, phthalocyanine dyes having an optionally substituted alkoxy group have been introduced in JP-A-61-1154888, and fluorine-substituted alkoxy groups have been introduced in JP-A-64-14087. Phthalocyanine dyes have been proposed as optical recording materials. These phthalocyanine dyes impart solubility to organic solvents by introducing an alkoxy group and a fluorine-substituted alkoxy group, but suitable solvent species include halogenated hydrocarbons, aromatics, and fluorine-substituted ones. Since it is alcohol or the like, a substrate having high solvent resistance or an expensive special solvent must be used to form a recording film. Further, this proposal is intended for an optical recording medium having a substrate / recording film configuration, and optical characteristics and thermal characteristics adapted to a CD-R composed of a substrate / recording film / reflection film stack cannot be realized.

In recent years, as a recording film material for CD-R, an unsubstituted branched alkoxy group is introduced into each of four benzene rings of phthalocyanine in JP-A-3-62878, and one or more halogen atoms or A compound having a nitro group introduced has been proposed. This phthalocyanine dye has been conventionally prepared by introducing a halogen atom or a nitro group at the same time as an alkoxy group for the purpose of improving optical properties such as refractive index and thermal properties in order to form a recording film suitable for a CD-R structure. The signal characteristics have been clearly improved compared with the phthalocyanine dyes of the present invention, and have reached a practical level. However, when an unsubstituted branched alkoxy group is introduced into the phthalocyanine ring, the absorption wavelength becomes longer due to the effect of the electron donating property of the alkoxy group, and the absorption around 785 nm, which is the target for CD-R, tends to be too large. is there. Therefore, in the case where a compound in which one unsubstituted branched alkoxy group is introduced into each of the four benzene rings of phthalocyanine and one or more halogen atoms or nitro groups are introduced is applied to CD-R, it is around 785 nm. In order to realize the optimum optical characteristics, it is necessary to select a special central metal effective in shortening the absorption wavelength in terms of material.

Applying a material having a sulfonamide group introduced into a phthalocyanine skeleton to an optical recording medium is disclosed in Japanese Patent Publication No.
-78074. Further, application of a material having both an alkoxy group and a sulfonamide group introduced to a phthalocyanine skeleton to a write-once compact disc is proposed in JP-A-4-74691. However, in these inventions, regarding the substitution position of the alkoxy group, there is no specific description of the substitution at the α-position, nor is there any description about the fluorine-substituted alkoxy group.

[0006]

DISCLOSURE OF THE INVENTION Problem to be Solved by the Invention
As a D-R recording film, a phthalocyanine dye capable of wavelength control suitable for a CD-R, which is a phthalocyanine dye-based recording film excellent in durability conforming to the Orange Book standard and satisfying practical applicability. It provides the material.

[0007]

The present invention has the general formula [1]
Is composed of a phthalocyanine compound represented by
Optical recording material. General formula [1] MPc- (OR¹)_n(SO₂N-R²R³)_m [In the formula, Pc represents a phthalocyanine skeleton represented by Formula 2.
Where M is a hydrogen atom (H2) or oxygen, hydroxyl group, halogen
R represents a metal atom to which an atom may be bonded, R¹Has 1 carbon
To 20 optionally linear or branched substituents
Represents a kill group, R ²Is a hydrogen atom or 1 to 20 carbon atoms
Represents an alkyl group which may have a linear or branched substituent
And R³Is a linear or branched substituent having 1 to 20 carbon atoms
Represents an alkyl group which may have²And R³And with
It may have a substituent and may form an alkylene group.
Yes. ), N is an integer of 2 to 4, and m is 1 to 4
Represents the integer. However, the substituent (-OR¹) Replacement position
Is the 1 or 4 position, 5 or 8 position, 9 of the phthalocyanine skeleton
Alternatively, it is selected from the 12th, 13th or 16th positions. [Formula 2]

[Chemical 2]

The present invention further relates to the above optical recording material, wherein at least one of R ¹ is a fluorine-substituted linear or branched alkyl group. Further, the present invention provides a substituent (-SO
The substitution position of ^₂ NR ₂ R ³⁾ is 1 or 4-position of the phthalocyanine skeleton, 5 or 8, 9 or 12-position, regarding the optical recording material is a member selected from the 13 or 16 position. Furthermore,
The present invention relates to a write-once compact disc, which is composed of a laminated body of a bright substrate / recording film / reflection film / protective film and uses the above-mentioned optical recording material as the recording film.

Typical examples of the linear or branched alkoxy group which may have a substituent introduced into the phthalocyanine compound of the present invention include methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group and tert. -Butoxy group, 2,4-dimethyl-3-pentoxy group, 2-methyl-1-hexyloxy group, 4-methyl-cyclohexyloxy group, 2-methyl-1-iso-propylpropoxy group, 1,3-dimethylbutoxy group Group, 2,2-dimethyl-
1-iso-propylpropoxy group, 1,1,1-trifluoromethoxy group, ethoxyethoxy group, 2-diethylaminoethoxy group, 2,2,2-trichloroethoxy group, 2-methyl-2-nitro-1-propoxy group Base 1,
1,2,2-tetrafluoropropoxy group, 1,1,
1,3,3,3-hexafluoro-2-propoxy group,
2,2,2-trifluoroethoxy group, 2,2,3
3,3-pentafluoropropoxy group, 2,2,3
3,4,4-hexafluorobutoxy group, 1H, 1
H, 5H-octafluoropentyloxy group, 1H, 1
H, 7H-dodecafluoroheptyloxy group, 1H, 1
H, 9H-hexadecafluorononyloxy group, 2-
Examples thereof include (perfluorohexyl) ethoxy group, but not limited thereto.

The sulfonamide group (-
An amine (H that can be used for introducing SO ₂ NR ² R ³ )
Representative examples of NR ² R ³ ) include methylamine, ethylamine, butylamine, dibutylamine, isobutylamine, diisopropylamine, diisobutylamine, se.
c-butylamine, di-sec-butylamine, 1,2
-Dimethylpropylamine, n-hexylamine, cyclohexylamine, 2-ethylhexylamine, di-
(2-Ethylhexyl) amine, 2-methoxyethylamine, N, N-dimethylaminopropylamine, N, N
-Diethylaminopropylamine, N, N-dibutylaminopropylamine, N, N-diisopropylaminoethylamine, N-aminoethylpiperidine, N-aminoethylmorpholine, N-aminoethyl-4-pipecoline and the like can be mentioned. It is not limited.
Examples of the amine used for forming an alkylene group which may have a substituent with R ² and R ³ include piperidine,
Examples include, but are not limited to, 2-pipecoline, 2,4-lupetidine, 3-piperidinemethanol and the like.

Further, the phthalocyanine compound of the present invention may have a substituent such as a halogen atom, a nitro group, a cyano group or an amino group at an arbitrary position in addition to the above-mentioned substituents.

Typical examples of the central metal represented by M in the phthalocyanine dye of the present invention include protons in the case of no metal, Cu, Zn, Fe, Co, Ni, Ru,
Rh, Pd, Pt, Mn, Mg, Be, Ca, Ba, C
d, Hg, Al-Cl, Al-OH, Ca, In-C
l, In-OH, Ti = O, V = O, Cr, Zr, S
n, Si (OH) 2, Ge (OH) 2, etc. Also, 3
In the case of a valent or tetravalent metal, a substituent can be introduced also in the axial direction of the phthalocyanine ring, but when a bulky substituent is introduced in the axial direction, the packing of molecules during the film formation on the recording film. Is inhibited and the optical density is remarkably reduced.
The optimum film thickness as a D-R recording film tends to increase. Therefore, the volume change of pit formation at the time of recording becomes large, and the influence on adjacent tracks may appear and the signal quality may deteriorate. Furthermore, when an electron-withdrawing group such as a nitro group is introduced, the substituent introduced in the axial direction is likely to be eliminated, which may cause a decrease in durability.
Therefore, in the phthalocyanine dye of the present invention, the substituents that can be introduced in the axial direction are limited to relatively small substituents such as oxygen, hydroxyl group and halogen.

The phthalocyanine dye of the present invention can be produced, for example, by the following method. That is, using a mixture of phthalonitriles represented by the following general formulas [3] and [4] and various metal salts of the metal represented by M in the general formula [1] as starting materials, 1 to 4 are prepared by a conventional method. A phthalocyanine compound having a single linear or branched alkoxy group can be produced.

General formula [3]

[Chemical 3] [In the formula, R'is a hydrogen atom or -O of the general formula [1].
It has the same meaning as R ¹ . Also, instead of the phthalonitriles of the general formula [3] and the general formula [4], an indoline compound obtained by reacting ammonia with these phthalonitriles may be used to similarly obtain 1 to 4 linear or branched ones. A phthalocyanine compound having an alkoxy group can be produced.

Next, the obtained phthalocyanine compound having 1 to 4 linear or branched alkoxy groups is chlorsulfonated as described in JP-B-3-78074 and JP-A-4-74691, and then, The phthalocyanine compound of the present invention can be produced by introducing a sulfonamide group by reacting with an amine (HNR ² R ³ ).

Phthalocyanine compounds (a) to (k) shown below are typical examples of the phthalocyanine dye of the present invention.
However, the present invention is not limited to these.

[0017]

[Table 1]

[0018]

[Table 2]

The recording film layer using the phthalocyanine dye of the present invention contains an oxygen quencher and an ultraviolet absorber for the purpose of further improving the stability of the recording film such as light resistance and environmental resistance, and the stability of repeated reproduction. You may add additives, such as.

The recording film layer may 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 the like. It is also possible by the LB (Langmuir-Blodgett) method. The recording film material of the present invention is soluble in general-purpose organic solvents such as alcohol-based, ketone-based, cellosolve-based, halogen-based, hydrocarbon-based, freon-based, etc., and therefore spin-coated from the viewpoint of productivity and recording film uniformity. The method of forming a film by the method is preferable. When forming a film by this 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,
It is preferably 30 wt% or less with respect to the dye.

The optimum film thickness of the recording film layer of the present invention is not particularly limited because it varies depending on the type and combination of recording film materials, and is preferably 500 to 3000 A, and further 700 to
2500A 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 main components, MgO, ZnO, SnO
Examples thereof include metal oxides such as SiN4, nitrides such as SiN4, AlN, and TiN. Gold is most preferable because of its high absolute reflectance and excellent stability. In addition, an organic highly reflective film can 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 these. The optimum thickness of the reflective film of the present invention is not particularly limited, but is preferably in the range of 400 to 1300A.

Further, the disk is protected from above the reflective film in order to prevent chemical deterioration (eg, oxidation, water absorption, etc.) and physical deterioration (eg, scratches, scratches, etc.) of the disk, particularly the recording film layer and the reflective film layer. To provide a protective layer. As a material for the protective layer, 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 layer, 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.

Further, the disk substrate used in the present invention preferably has a light transmittance of 85% or more for writing and reading a signal 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-
Substrates made of a thermoplastic resin such as methylpentene) or a polyether sulfone resin, or a thermosetting resin such as an epoxy resin or an allyl resin can be given. Among these, those made of a thermoplastic resin are preferable from the standpoint of ease of molding and provision of wobble signals for ATIP and guide grooves, etc. Further, acrylic resin and polycarbonate are preferable in view of optical characteristics, mechanical characteristics and cost. Those made of resin are particularly preferable. The ATIP wobble signal and the guide groove are preferably provided by using a stamper or the like at the time of molding (injection molding, compression molding) a thermoplastic resin, but so-called 2P using a photopolymer resin is preferable.
It can also be carried out by the method by law.

The shape of the guide groove of the present invention is not particularly limited and may be 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 0.4 to 0.6 μm. ,
Further, the groove depth is preferably in the range of 700 to 2000A.
The disc form of the present invention is a CD or CD-R after recording.
CD or CD because it needs to function as an OM
-It is preferable to comply with the ROM standard (Red Book) and the R-CD standard (Orange Book).

[0026]

The present invention will be specifically described with reference to the following examples and comparative 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) 3- (1,1,2,2-tetrafluoropropoxy) phthalonitrile 10 in 100 parts of n-amyl alcohol and 30 parts of diazabicycloundecene (DBU) And 15 parts of cuprous chloride were added, and the mixture was heated with stirring at 130 to 135 ° C. for 3 hours, cooled, and diluted with 500 parts of methanol. The deposited precipitate was separated by filtration, washed with a mixed solution of methanol / water (4/1) and dried to obtain 10 parts of a blue powder. 5 parts of the copper phthalocyanine compound thus obtained was gradually added to 50 parts of chlorosulfonic acid to form a complete solution, and the temperature was raised to 7
The mixture was heated and stirred at 0 to 80 ° C for 4 hours. After cooling to 60 ℃,
Thionyl chloride (10 parts) was added dropwise, and the mixture was further heated at 70-80 ° C for 2
The mixture was heated and stirred for an hour. After cooling the reaction solution, it was poured into 500 parts of ice water, the deposited precipitate was quickly filtered, washed thoroughly with ice water, and dried under reduced pressure at room temperature to obtain 5.2 parts of a green chlorosulfonate. 5 parts of the chlorosulfonide thus obtained was added to 200 parts of methanol, and after sufficiently stirring, 3 parts of diisopropylamine was added, and after stirring at room temperature for 1 hour, the temperature was raised and the mixture was heated under reflux for 2 hours. After cooling, the reaction solution is poured into 2000 parts of a 10% aqueous acetic acid solution, the precipitate is filtered, and further washed with water. 10 water cakes of this sediment
% Aqueous sodium carbonate solution (1000 parts) and the mixture was stirred at room temperature for 2 hours. Thereafter, the reaction solution was filtered, washed sufficiently with water until it became neutral, and then dried to obtain 5.4 parts of the phthalocyanine compound (a).

Production Example 2: Production of phthalocyanine compound (b) In the same manner as in Production Example 1, 100 parts of n-amyl alcohol, D
3- (1,1,1,3,3,3-hexafluoro-2-propoxy) phthalonitrile and 15 parts of cuprous chloride are added to 30 parts of BU, and the mixture is heated and stirred at 130 to 135 ° C. for 3 hours and then cooled. , Diluted with 1000 parts of methanol, the deposited precipitate was filtered off, washed with a mixed solution of methanol / water (3/1),
After drying, 5.5 parts of blue powder was obtained. 5 parts of the copper phthalocyanine compound thus obtained was gradually added to 50 parts of chlorosulfonic acid to form a complete solution, which was then heated to 70-
The mixture was heated and stirred at 80 ° C. for 4 hours. After cooling to 60 ° C, 10 parts of thionyl chloride was added dropwise, and the mixture was further heated and stirred at 70 to 80 ° C for 2 hours. After cooling the reaction solution, it was poured into 500 parts of ice water, the deposited precipitate was quickly filtered, thoroughly washed with ice water, and then dried under reduced pressure at room temperature to give a green chlorosulfonate.
8 parts were obtained. 4.5 parts of the chlorosulfonate thus obtained was added to 180 parts of methanol and sufficiently stirred, then 3.2 parts of N-diisopropylaminoethylamine was added, and the mixture was stirred at room temperature for 1 hour and then heated to 2 Heated to reflux for hours. After cooling, the reaction solution is poured into 2000 parts of a 10% aqueous acetic acid solution, the precipitate is filtered, and further washed with water. The water cake of this precipitate was reslurried in 1000 parts of 10% sodium carbonate aqueous solution, and stirred at room temperature for 2 hours. Thereafter, the reaction solution was filtered, washed sufficiently with water until it became neutral, and then dried to obtain 4.2 parts of the phthalocyanine compound (b).

Production Example 3: Production of phthalocyanine compound (c) In the same manner as in Production Example 1, 100 parts of n-amyl alcohol, D
In 30 parts of BU, 3- (1,1,1,3,3,3-hexafluoro-2-propoxy) phthalonitrile and 3- (1,
10 parts of a mixture with 3-dimethylbutyl) oxyphthalonitrile in a molar ratio of 1: 1 and 5 parts of nickel chloride are added,
After heating and stirring at 130 to 135 ° C for 5 hours, the mixture is cooled to 200
Dilute with 0 parts methanol. The deposited precipitate was separated by filtration, washed with a mixed solution of methanol / water (4/1) and dried to obtain 8 parts of a green powder. 5 parts of the nickel phthalocyanine compound thus obtained was gradually added to 50 parts of chlorosulfonic acid to form a complete solution, and the temperature was raised to 70-80 ° C. for 4 hours.
The mixture was heated and stirred for an hour. After cooling to 60 ° C, 10 parts of thionyl chloride was added dropwise, and the mixture was further heated and stirred at 70 to 80 ° C for 2 hours. After cooling the reaction solution, it was poured into 500 parts of ice water, and the deposited precipitate was quickly filtered, washed thoroughly with ice water, and dried under reduced pressure at room temperature to obtain 5.1 parts of a green chlorosulfonate. 5 parts of the chlorosulfonate obtained in this way was added to 200 parts of methanol, and after sufficient stirring, 3 parts of cyclohexylamine was added, and after stirring at room temperature for 1 hour, the temperature was raised and the mixture was heated under reflux for 2 hours. After cooling, the reaction solution is poured into 2000 parts of a 10% aqueous acetic acid solution, the precipitate is filtered, and further washed with water. The water cake of this precipitate was reslurried in 1000 parts of 10% sodium carbonate aqueous solution, and stirred at room temperature for 2 hours. Then, the reaction solution was filtered, washed sufficiently with water until it became neutral, and then dried to obtain 5.8 parts of phthalocyanine compound (c).

Production Example 4: Production of phthalocyanine compound (d) In the same manner as in Production Example 1, 100 parts of n-amyl alcohol, D
To 30 parts of BU was added 10 parts of 3- (trifluoroethoxy) phthalonitrile and 5 parts of aluminum chloride to give 130
After heating and stirring at ~ 135 ° C for 5 hours, the mixture was cooled and diluted with 2000 parts of methanol. The deposited precipitate was separated by filtration, washed with a mixed solution of methanol / water (4/1) and dried to obtain 8 parts of a green powder. 5 parts of the aluminum phthalocyanine compound thus obtained was gradually added to 50 parts of chlorosulfonic acid to form a complete solution, which was then heated and stirred at 70 to 80 ° C. for 4 hours. After cooling to 60 ° C, thionyl chloride 1
0 part was added dropwise, and the mixture was further heated and stirred at 70 to 80 ° C. for 2 hours. After cooling the reaction solution, it was poured into 500 parts of ice water, the deposited precipitate was quickly filtered, washed thoroughly with ice water, and dried under reduced pressure at room temperature to obtain 5.2 parts of a green chlorosulfonate.
5 parts of the chlorosulfonide thus obtained was added to 200 parts of methanol and sufficiently stirred, then 3 parts of isopropylamine was added, and the mixture was stirred at room temperature for 1 hour, heated, and heated under reflux for 2 hours. After cooling, the reaction solution was added with a 10% acetic acid aqueous solution 2
It is poured into 000 parts, the precipitate is filtered, and further washed with water. The water cake of this precipitate was reslurried in 1000 parts of 10% sodium carbonate aqueous solution, and stirred at room temperature for 2 hours. Then, the reaction solution was filtered, washed sufficiently with water until it became neutral, and then dried to obtain 4.6 parts of the phthalocyanine compound (c).

Example 1 1200 Angstroms 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 (a) was dissolved in ethoxyethanol at a concentration of 50 mg / ml, and 0.2 micron filtering was performed to prepare a coating liquid. Was used to form a recording film having a recording film thickness of 650 angstroms using a spin coater. Next, gold was formed into a film having a thickness of 800 angstrom on the recording film thus obtained by sputtering. Further, a protective film layer having a film thickness of 5 μm was formed thereon by an ultraviolet curable resin to form an optical disk. Using the optical disk created in this way,
Linear velocity is 1. using a semiconductor laser with a wavelength of 785 nm.
When the EFM-CD format signal was recorded at 4 m / sec, the reflectance was 66% and the optimum recording laser power could be recorded at 6.2 mW, and the obtained recording control signal was good and the items described in Orange Book. All satisfied the standard values.

Example 2 1200 Angstroms deep, 0.50 micron wide,
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 (b) was dissolved in diacetone alcohol at a concentration of 60 mg / ml, and 0.2 micron filtering was performed to prepare a coating liquid. A spin coater was used to form a film having a recording film thickness of 700 Å. Next, gold was formed into a film having a thickness of 800 angstrom on the recording film thus obtained by sputtering. Further, a protective film layer having a film thickness of 5 μm was formed thereon by an ultraviolet curable resin to form an optical disk. 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 disk thus prepared, the reflectance was 68% and the optimum recording laser power was 6%. Recording was possible at 0.5 mW, the control signal of the obtained recording was good, and all the items described in the Orange Book satisfied the standard values.

Example 3 1200 Angstroms deep, 0.50 micron wide,
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 ethoxyethanol at a concentration of 50 mg / ml, and 0.2 micron filtering was performed to prepare a coating solution. Was used to form a recording film having a recording film thickness of 850 angstroms using a spin coater. Next, gold was formed into a film having a thickness of 800 angstrom on the recording film thus obtained by sputtering. Further, a protective film layer having a film thickness of 5 μm was formed thereon by an ultraviolet curable resin to form an optical disk. Using the optical disk created in this way,
Linear velocity is 1. using a semiconductor laser with a wavelength of 785 nm.
When the EFM-CD format signal was recorded at 4 m / sec, the reflectance was 71%, the optimum recording laser power was 6.4 mW, and it was possible to record. All satisfied the standard values.

Example 4 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, a phthalocyanine compound (d) was dissolved in ethoxyethanol at a concentration of 50 mg / ml, and a 0.2 μm filtering was performed to prepare a coating liquid. Was used to form a film having a recording film thickness of 700 angstroms by a spin coater. Next, gold was formed into a film having a thickness of 800 angstrom on the recording film thus obtained by sputtering. Further, a protective film layer having a film thickness of 5 μm was formed thereon by an ultraviolet curable resin to form an optical disk. Using the optical disk created in this way,
Linear velocity is 1. using a semiconductor laser with a wavelength of 785 nm.
When the EFM-CD format signal was recorded at 4 m / sec, the reflectance was 66% and the optimum recording laser power could be recorded at 6.2 mW, and the obtained recording control signal was good and the items described in Orange Book. All satisfied the standard values.

Comparative Example 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 and an inner diameter of 15 mm, and phthalocyanine compounds (1) and (m) shown in Table 3 in ethoxyethanol at 50 mg / m 2, respectively.
It was dissolved at a concentration of 1 and filtered by 0.2 micron to prepare a coating liquid. Using this coating liquid, a spin coater was used to form a film having a recording film thickness of 700 to 900 angstroms. Next, gold was formed into a film having a thickness of 800 angstrom on the recording film thus obtained by sputtering. Further, a protective film layer having a film thickness of 5 μm was formed thereon by an ultraviolet curable resin to form an optical disk. Using the optical disk created in this way, a wavelength of 785n
Linear velocity of 1.4 m / sec using a semiconductor laser of m
When an EFM-CD format signal was recorded with, the reflectance was 62% for (l), 68% for (m), and the optimum recording laser power was 8.5 mW for (l) and 9.5 mW for (m).
In terms of recording sensitivity and tracking error signal, the standard values of the items listed in Orange Book were not satisfied.

[0036]

[Table 3]

INDUSTRIAL APPLICABILITY In the phthalocyanine compound of the present invention, in order to control the effect of the electron donating property of the alkoxy group (O—R ¹ ), the effect of the fluorine-substituted alkoxy group having a weak electron donating property can be easily utilized. Moreover, it became possible to control the absorption wavelength range of the phthalocyanine compound. As a result, 7
It is easy to optimize the optical characteristics around 85 nm, and at the same time, it is economical because it is not necessary to use an expensive central metal. Further, the effect of the fluorine substitution markedly improves the solubility in an organic solvent, and becomes a material suitable for forming a recording film in a wet process. In addition, the effect of introducing the sulfonamide group (SO ₂ N—R ² R ³ ) lowers the decomposition temperature of the material molecule itself, effectively acting to improve the recording sensitivity, and at the same time, the sulfonamide group is changed to the para position of the alkoxy group. By introducing it, the effect of steric hindrance was increased, the stacking property of phthalocyanine molecules in the recording film was lowered, and the thermal decomposition temperature was lowered even in the molecular aggregation state, so that the recording sensitivity was improved.

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Claims (5)

(57) [Claims] 1. A phthalocyanine represented by the general formula [1]
An optical recording material comprising a compound. General formula [1] MPc- (OR¹)_n(SO₂N-R²R³)_m [In the formula, Pc represents a phthalocyanine skeleton represented by Formula 2.
Where M is a hydrogen atom (H2) or oxygen, hydroxyl group, halogen
R represents a metal atom to which an atom may be bonded, R¹Has 1 carbon
To 20 optionally linear or branched substituents
Represents a kill group, R ²Is a hydrogen atom or 1 to 20 carbon atoms
Represents an alkyl group which may have a linear or branched substituent
And R³Is a linear or branched substituent having 1 to 20 carbon atoms
Represents an alkyl group which may have²And R³And with
It may have a substituent and may form an alkylene group.
Yes. ), N is an integer of 2 to 4, and m is 1 to 4
Represents the integer. However, the substituent (-OR¹) Replacement position
Is the 1 or 4 position, 5 or 8 position, 9 of the phthalocyanine skeleton
Or selected from 12th, 13th or 16th place
It ] [Formula 2] [Chemical 1] 2. The optical recording material according to claim 1, wherein n is 4. 3. The optical recording material according to claim ¹ , wherein at least one of R ¹ is a fluorine-substituted linear or branched alkyl group. 4. The substitution position of the substituent (—SO ₂ NR ² R ³ ) is 1 or 4 position, 5 or 8 position, 9 position of the phthalocyanine skeleton.
The optical recording material according to claim 1, which is selected from the 12th, 13th and 16th positions. 5. A write-once compact disc comprising a laminate of a transparent substrate / recording film / reflection film / protective film, wherein the optical recording material according to claim 1 is used as the recording film.