JPH0453713B2 - - Google Patents

Description

[Detailed description of the invention]

[Object of the Invention] (Industrial Application Field) The present invention relates to an optical recording medium on which information can be written and read using a laser beam. (Prior Art) Various types of optical recording media have been known in the past for recording and reading information using laser beams. One of these methods is to record by irradiating a recording layer on a substrate with a laser beam and causing changes such as melting, evaporation, and decomposition in the irradiated area. The recording layer of such an optical recording medium is
Thin film layers of metals and alloys such as As, Te, Se, and Ti have been used. Optical recording media whose recording layer is a thin film layer of these metals or alloys generally have high writing sensitivity and can be used with semiconductor lasers that can miniaturize the recording/reproducing optical system, but they have high thermal conductivity. For several reasons, the laser beam energy could not be used efficiently during recording. Furthermore, these recording layers were chemically unstable and sometimes deteriorated. For this reason, Japanese Patent Application Laid-open No. 57-82093, Japanese Patent Application Laid-open No. 58
-56892 Publication, JP-A-60-89842, JP-A-Sho
No. 60-150243, etc., proposed an optical recording medium in which an organic thin film layer is used as a recording layer and information is written and read using a laser beam having a relatively long wavelength, for example, 780 nm or more. In such optical recording media, minute recesses (pits) can be easily formed in the organic thin film layer by melting, evaporation, decomposition, etc. using a semiconductor laser, which enables miniaturization of the recording/reproducing optical system. However, there were drawbacks such as a low extinction coefficient for semiconductor laser beams and insufficient recording sensitivity. (Problems to be Solved by the Invention) The present invention improves various hair spots of conventional optical recording media having an organic thin film recording layer, is chemically and physically stable, and can be recorded with high sensitivity by laser beams.
The present invention provides a reproducible optical recording medium using a specific phthalocyanine compound. [Structure of the Invention] (Means for Solving the Problems) The present invention provides an optical recording device comprising, on a substrate, an organic thin film layer containing at least one phthalocyanine compound represented by the following general formula []. It is a medium. General formula [] [In the formula, rings A ¹ to ^{A 4} each independently represent a benzene ring, a naphthalene ring, or an anthracene ring. M represents Al, Ga, In, Si, Ge, or Sn. X may be the same or different from each other, and is an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic residue that may have a substituent. , a phthalimidomethyl group which may have a substituent, a halogen atom, a nitro group, a cyano group, a sulfonic acid group, -OR ¹ , -SR ² , -COOR ³ ,

【formula】 【formula】

【formula】

[Formula] -NHCOR ¹² , -N=NR ¹³ , or -N=CHR ¹⁴
represents. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ may be the same or different from each other, and may include hydrogen atoms and substituents. represents an alkyl group, aryl group, acyl group, cycloalkyl group, or polyether group that may have
R ⁶ and R ⁷ , R ⁸ and R ⁹ , or R ¹⁰ and R ¹¹ may form a 4- to 7-membered ring, and these 4- to 7-membered rings may further contain a nitrogen atom. , an oxygen atom, or a heterocyclic ring containing a sulfur atom. R ¹² , R ¹³ and R ¹⁴ may be the same or different and represent an alkyl group, a cycloalkyl group, or an aryl group having a substituent. Y is

【formula】

【formula】

[Formula] or -O-Se-R ²³ . Z is hydrogen, a halogen atom, a hydroxyl group, an alkyl group that may have a substituent,

【formula】

【formula】

[Formula] or represents -O-Se-R ³² . R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ ,
R ²⁷ and R ³² may be the same or different and are an alkyl group which may have a substituent, an aryl group which may have a substituent, an acyl group, a cycloalkyl group, an alkoxy group, allyloxy group, polyether group, hydroxyl group, or halogen atom. R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²⁸ , R ²⁹ , R ³⁰ and
R ³¹ may be the same or different from each other, and may have a substituent(s) such as an alkyl group, an aryl group, an acyl group, a cycloalkyl group, an alkoxy group, an allyloxy group, a polyether group, a hydroxyl group, Represents a halogen atom or a hydrogen atom. W represents O, S, Se or Te. k, l, m, and n each independently represent an integer of 0 to 8. p represents 0 or 1. ] In the compound represented by the general formula [ ] related to the present invention, representative examples of atoms and groups constituting X, Z, and R ¹ to R ³² include chlorine atom, bromine atom, iodine atom as halogen atom. , and the alkyl group which may have a substituent for the fluorine atom include a methyl group, n-butyl group, tert-
Butyl group, stearyl group, trichloromethyl group,
Aryl groups which may have substituents such as 2-methoxyethyl group include phenyl group, chlorophenyl group, tolyl group, naphthyl group, anthryl group, dimethylaminophenyl group, hydroxyphenyl group, diethylaminonaphthyl group. , hydroxynaphthyl group, etc., as a cycloalkyl group,
Examples of acyl groups that may have substituents include acetyl groups, trifluoroacetyl groups, etc.; examples of polyether groups include diethylene glycol monoethyl groups, triethylene glycol monobutyl groups, etc. , heterocyclic groups include pyridyl group, furyl group,
Thiazolyl group, piperazinyl group, morpholyl group, etc., and phthalimidomethyl group which may have a substituent include phthalimidomethyl group, nitrophthalimidomethyl group, tert-butylphthalimidomethyl group, methoxyphthalimidomethyl group,
Examples include dichlorophthalimidomethyl group, but are not limited to these groups. In the present invention, the compound represented by the general formula [] can be produced, for example, by the following method. That is, the isoindolenine compound represented by the following general formula [] and various metal salts, or by a conventional method using carboxylic acid anhydrides, imides, or nitriles as starting materials, Manufacture phthalocyanine compounds. General formula [] [In the formula, ^A1-4 , X, k, l, m, and n represent the same meaning as in the general formula []. ] General formula [ ] [In the formula, rings ^A1-4 , M, X, k, l, m, n and p have the same meanings as in the general formula []. ] Next, by reacting the obtained phthalocyanine compound represented by the general formula [] with various phosphorus compounds or selenium compounds, the phthalocyanine compound represented by the general formula [] can be produced. Representative examples of the phthalocyanine compounds represented by the general formula [] used in the present invention include:
The following phthalocyanine compounds (a) to (s) can be mentioned. What, phthalocyanine compound (a)?
Ph in (s) represents a phenyl group, and Me represents a methyl group. The substrate used in the present invention preferably has a light transmittance of 85% or more for writing and reading signals, and has small optical anisotropy. For example, thermal Examples include substrates made of thermosetting resins such as plastic resins, epoxy resins, and allyl resins. Among these, those made of thermoplastic resin are preferred due to ease of molding and ease of providing guide grooves, address signals, etc., and those made of acrylic resin or polycarbonate resin due to optical and mechanical properties. is desirable. In the present invention, the thickness of these transparent substrates is not particularly limited and may be plate-like or film-like. Moreover, the shape may be circular or card-like, and there is no particular restriction on the size. In addition, substrates usually have guide grooves for position control during recording and reading, and unevenness for preformatting address signals and various marks, but these unevenness are formed by molding thermoplastic resin as described above. It is preferable to apply using a stamper or the like during injection molding, compression molding, etc. In the optical recording medium of the present invention, methods for forming an organic thin film layer containing a phthalocyanine compound on a substrate include a vacuum evaporation method, a sputtering method, an ion plate method, and an LB method (Langmiure-Blodget method). Although there are methods, these methods require complicated operations and have low productivity.Furthermore, the phthalocyanine compound represented by the general formula [] is used in conventional optical recording media having an organic thin film layer. Since the solubility in ordinary organic solvents is much higher than that of organic dyes, a coating method using a spin coater or the like is most advantageous. When forming an organic thin film layer, which is a recording layer, by a coating method, phthalocyanine compounds may be mixed with alcohols, ketones, amides, sulfoxides, ethers, esters, aliphatic halogenated hydrocarbons, or aromatic compounds. It is applied by dispersing or dissolving it in a common organic solvent such as group hydrocarbons. At this time, a polymer binder may be added if necessary. Examples of the polymer binder include vinyl chloride resin, acrylic resin, polyester resin, polyamide resin, polycarbonate resin, epoxy resin, methacrylic resin, vinyl acetate resin, nitrocellulose, and phenol resin. When using a polymeric binder, the ratio of the polymeric binder to the phthalocyanine compound is preferably 10% by weight or less. Further, in the present invention, other pigments may be mixed and dispersed or mixed and dissolved in the phthalocyanine compound. Examples of dyes that can be used in combination include known ones, such as aromatic or unsaturated aliphatic diamine metal complexes, aromatic or unsaturated aliphatic dithiol metal complexes, phthalocyanine complexes, naphthalocyanine complexes, and squalium-based complexes. Examples include dyes, naphthoquinone complexes, anthraquinone dyes, and polymethine dyes. The thickness of the recording layer containing the phthalocyanine compound formed on the substrate is 10 μm or less, preferably
500〓~2μm. In addition, by exposing the organic thin film layer to the vapor of an organic solvent such as chloroform, tetrahydrofuran, or toluene after coating, the absorption wavelength of the organic thin film layer shifts to longer wavelengths, significantly increasing the sensitivity to light in the oscillation wavelength range of semiconductor lasers. In some cases, it can be improved. In addition, to protect these recording layers,
An inorganic compound such as Al ₂ O ₃ , SiO ₂ , SiO, SnO or the like may be deposited as a protective layer. Further, a polymer may be applied as a protective layer. In addition, in order to increase the reflection level of the recording layer,
On the recording layer, metals such as gold, silver, copper, platinum, aluminum, cobalt, tin, MgO, ZnO,
A reflective film made of a metal oxide such as SnO ₂ , a nitride such as SiN ₄ , AlN, or TiN, or a chalcogen compound containing Te, Se, S, or the like may be provided. Recording on the obtained recording medium is carried out by irradiating the recording layer provided on the substrate with laser light, preferably semiconductor laser light, focused to about 1 μm. The portion of the recording layer irradiated with the laser beam undergoes thermal state changes such as decomposition, evaporation, and melting due to absorption of laser energy. Reproduction is performed by reading the difference in reflectance between a portion that has undergone thermal changes and a portion that has not. The phthalocyanine compound represented by the general formula [] has a very large difference in reflectance before and after recording, and is therefore extremely advantageous compared to organic dyes used in conventional optical recording media having organic thin film layers. In addition, the lasers include He-Ne laser,
Although various lasers such as Ar laser and semiconductor laser can be used, semiconductor laser is particularly preferable in terms of cost and size. As the semiconductor laser, a laser having a center wavelength of 830 nm, 780 nm, or a shorter wavelength can be used. (Examples) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples. In addition, in the examples, parts represent parts by weight. Production Example 1 Production of phthalocyanine compounds (a) to (k) and (r) 7.8 parts of 1,3-diiminobenziisoindoline and 5.0 parts of silicon tetrachloride were added to 50 parts of quinoline, and the mixture was heated at 180 to 200°C. After heating and stirring for 3 hours, it was cooled, diluted with 500 parts of methanol, filtered, washed with methanol and dimethylformamide, and dried to obtain dihydroxysilicon naphthalocyanine.
Got 7.0 copies. 110 parts of the obtained dihydroxysilicon naphthalocyanine, 50 parts of chlorodiphenylphosphine, 50 parts of tri-n-butylamine, and 300 parts of pyridine.
After heating and stirring at ℃ for 2 hours, cool and add methanol.
The mixture was diluted with 1000 parts and filtered to obtain a filtrate, and methanol was distilled off under reduced pressure and heating from the obtained filtrate. The entire amount of the product thus obtained was diluted with dilute hydrochloric acid.
Add 500 parts, filter the precipitate, wash with water,
Dry at 80℃ to obtain phthalocyanine compound (a) 3.0
I got the department. Phthalocyanine compounds (b) to (k) and (r) were obtained by a method similar to the method for producing phthalocyanine compound (a). Production Example 2 Production of phthalocyanine compounds (l) to (n) 5.0 parts of dihydroxysilicon naphthalocyanine obtained in Production Example 1, 50 parts of benzene selenenyl chloride, 50 parts of tri-n-butylamine, and 300 parts of pyridine were heated at 110°C. After heating and stirring for 2 hours, the mixture was cooled, diluted with 1000 parts of ethanol, and filtered to obtain a filtrate, from which methanol was distilled off under reduced pressure under heating. The entire amount of the product thus obtained was diluted with dilute hydrochloric acid.
Add 500 parts, filter the precipitate, wash with water,
Dry at 80℃ to obtain 2.5 phthalocyanine compounds (l)
I got the department. Phthalocyanine compounds (m) and (n) were obtained by a method similar to the method for producing phthalocyanine compound (l). Production Example 3 Production of phthalocyanine compounds (o) and (p) 5.0 parts of dihydroxysilicon naphthalocyanine obtained in Production Example 1, 50 parts of diphenyl phosphate, 50 parts of tri-n-butylamine, and 300 parts of pyridine were heated at 110°C. After heating and stirring for 2 hours, the mixture was cooled, diluted with 1000 parts of methanol, and filtered to obtain a filtrate, from which methanol was distilled off under reduced pressure under heating. The entire amount of the product thus obtained was diluted with dilute hydrochloric acid.
Add 500 parts, filter the precipitate, wash with water,
Dry at 80℃ to obtain 2.8 phthalocyanine compounds (o)
I got the department. The phthalocyanine compound (p) was obtained by a method similar to the method for producing the phthalocyanine compound (o). Production Example 4 Production of phthalocyanine compound (q) 5.0 parts of dihydroxysilicon naphthalocyanine obtained in Production Example 1, 50 parts of bis(dimethylamino)phosphoryl chloride, 50 parts of tri-n-butylamine, and 300 parts of pyridine were mixed at 110°C. After heating and stirring for 2 hours, the mixture was cooled, diluted with 1000 parts of methanol, and filtered to obtain a filtrate, from which methanol was distilled off under reduced pressure under heating. The entire amount of the product thus obtained was diluted with dilute hydrochloric acid.
Add 500 parts, filter the precipitate, wash with water,
Dry at 80℃ to obtain phthalocyanine compound (q) 3.0
I got the department. Production Example 5: Production of phthalocyanine compound (s) To 50 parts of quinoline, tetra-tert-amyl-1,
Add 7.8 parts of 3-diiminobenziisoindoline and 5.0 parts of silicon tetrachloride, heat and stir at 180-200°C for 3 hours, cool, dilute with 500 parts of methanol, filter, and wash with methanol and dimethylformamide. The mixture was dried to obtain 7.0 parts of tetra-tert-amyldihydroxysilicon naphthalocyanine. 5.0 parts of the obtained tetra-tert-amyldihydroxysilicon naphthalocyanine, 50 parts of chlorodiphenylphosphine, and 50 parts of tri-n-butylamine.
After heating and stirring 300 parts of pyridine at 110° C. for 2 hours, the mixture was cooled, diluted with 1000 parts of methanol, and filtered to obtain a filtrate, from which methanol was distilled off under reduced pressure under heating. The entire amount of the product thus obtained was diluted with dilute hydrochloric acid.
Add 500 parts, filter the precipitate, wash with water,
Dry at 80℃ to remove phthalocyanine compound(s)
Got 3.0 copies. Example 1 Phthalocyanine compound (a) on a glass substrate
After dropping a solution consisting of 3.0 parts and 97.0 parts of chloroform, it was rotated for 20 seconds at a speed of 1200 rpm, and then
An optical recording medium was obtained by drying at ℃ for 20 minutes. The recording layer of the obtained optical recording medium had a thickness of 780 Å,
The maximum absorption wavelength was 815 nm, and the reflectance for light with a wavelength of 830 nm was 42%. The obtained optical recording medium was mounted on a turntable, and while the turntable was rotating at 1800 rpm, a laser beam of 830 nm focused at 1.0 μm was applied to the turntable.
Recordings were performed using irradiation at mW and 8 MHz. When the surface of the optical recording medium after recording was observed using a scanning electron microscope, the formation of clear pits was observed. In addition, 830 nm,
When 0.4 mW laser light was irradiated and the reflected light was detected, the C/N ratio was 53 dB. Example 2 A solution consisting of 2.5 parts of phthalocyanine compound (b) and 97.5 parts of methyl cellosolve was dropped onto a polycarbonate resin substrate, and then the mixture was heated at a speed of 800 rpm.
It was rotated for 30 seconds and dried at 80° C. for 15 minutes under reduced pressure to obtain an optical recording medium. The recording layer of the obtained optical recording medium had a thickness of 850 Å,
The maximum absorption wavelength was 810 nm, and the reflectance for light with a wavelength of 830 nm was 40%. Further, when recording was performed on the obtained optical recording medium in the same manner as in Example 1, clear pit formation was observed on the surface of the recording layer, and the C/N ratio was
It was 51dB. Examples 3 to 19 Phthalocyanine compound (C) on a glass substrate
~(s) was applied in the same manner as in Example 1 and dried to obtain an optical recording medium. The maximum absorption wavelength of the recording layer of the obtained optical recording medium and the reflectance for light with a wavelength of 830 nm, and the C/N ratio when the obtained optical recording medium was subjected to recording and reproduction in the same manner as in Example 1 are shown. Shown in 1.

〔Effect of the invention〕

The phthalocyanine compound used in the optical recording medium of the present invention has extremely high solubility in the above-mentioned ordinary organic solvents, so it can be dissolved in these organic solvents and applied using a coating method with good productivity and workability. Can be provided as an organic thin film layer on a substrate,
The optical recording medium of the present invention has a very large difference in reflectance before and after recording with a laser beam, so it has high sensitivity, enables highly sensitive recording and reproduction, and is chemically and physically stable.

Claims (1)

[Scope of Claims] 1. An optical recording medium comprising an organic thin film layer containing at least one phthalocyanine compound represented by the following general formula [] on a substrate. General formula [] [In the formula, rings A ¹ to ^{A 4} each independently represent a benzene ring, a naphthalene ring, or an anthracene ring. M represents Al, Ga, In, Si, Ge, or Sn. X may be the same or different from each other, and is an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic residue that may have a substituent. , phthalimidomethyl group which may have a substituent, halogen atom, nitro group, cyano group, sulfonic acid group, -OR ¹ , -SR ² , -COOR ³ , [Formula] [Formula] [Formula] [Formula] -NHCOR ¹² , -N=NR ¹³ , or -N=CHR ¹⁴
represents. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ may be the same or different from each other, and may include hydrogen atoms and substituents. represents an alkyl group, aryl group, acyl group, cycloalkyl group, or polyether group that may have
R ⁶ and R ⁷ , R ⁸ and R ⁹ , or R ¹⁰ and R ¹¹ may form a 4- to 7-membered ring, and these 4- to 7-membered rings may further contain a nitrogen atom. , an oxygen atom, or a heterocyclic ring containing a sulfur atom. R ¹² , R ¹³ and R ¹⁴ may be the same or different and represent an alkyl group, a cycloalkyl group, or an aryl group which may have a substituent. [Formula] [Formula] [Formula] or -O-Se-R ²³ . Z represents hydrogen, a halogen atom, a hydroxyl group, an alkyl group which may have a substituent, [Formula] [Formula] [Formula] or -O-Se-R ³² . R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷
and R ³² may be the same or different from each other, and may include an alkyl group that may have a substituent, an aryl group that may have a substituent, an acyl group, a cycloalkyl group, an alkoxy group, Represents an allyloxy group, a polyether group, a hydroxyl group, or a halogen atom. R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²⁸ , R ²⁹ , R ³⁰ and
R ³¹ may be the same or different from each other, and may have a substituent(s) such as an alkyl group, an aryl group, an acyl group, a cycloalkyl group, an alkoxy group, an allyloxy group, a polyether group, a hydroxyl group, Represents a halogen atom or a hydrogen atom. W represents O, S, Se or Te. k, l, m, and n each independently represent an integer of 0 to 8. p represents 0 or 1. ]