JP3045514B2 - Optical recording medium - 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 or read by a laser beam.

(Prior Art) Conventionally, various types of optical recording media for recording and reading information using a laser beam have been known. One of them is to irradiate the recording layer on the substrate with a laser beam,
In some cases, recording is performed by causing changes such as melting, evaporation, and decomposition in the irradiated portion.

As a recording layer of such an optical recording medium, As, Te, Se,
Thin film layers of metals and alloys such as Ti have been used. Optical recording media using these metal or alloy thin film layers as recording layers are generally characterized by high write sensitivity and the ability to use semiconductor lasers that can reduce the size of the recording / reproducing optical system, but have high thermal conductivity. For some reasons, there is a disadvantage that the energy of the laser beam cannot be used efficiently during recording. Further, these recording layers were chemically unstable and sometimes deteriorated.

For this reason, JP-A-57-82093, JP-A-58-56892
Japanese Patent Application Laid-Open No. 60-89842, Japanese Patent Application Laid-Open No. 60-150243, etc. use an organic thin film layer as a recording layer and write or read information with a laser beam having a relatively long wavelength, for example, 780 nm or more. Optical recording media have been proposed.
In such an optical recording medium, minute recesses (pits) can be easily formed in the organic thin film layer by melting, evaporating, decomposing, etc. by a semiconductor laser capable of downsizing the recording / reproducing optical system. There are drawbacks such as a low absorption coefficient for laser light and insufficient recording sensitivity.

(Problems to be Solved by the Invention) The present invention improves various drawbacks of the conventional optical recording medium having an organic thin film recording layer, and is chemically and physically stable, and enables recording and reproduction with high sensitivity by a laser beam. An object of the present invention is to provide an optical recording medium using a specific phthalocyanine compound.

[Configuration of the invention]

(Means for Solving the Problems) The present invention provides an optical recording material comprising a phthalocyanine compound represented by the following general formula [I], and an optical recording comprising providing a substrate with an organic thin film layer comprising the optical recording material. Medium.

General formula [I] [Wherein, rings A ^{1 to} A ⁴ are each independently a benzene ring,
Naphthalene ring, anthracene ring, Wherein at least one of the rings A ^{1 to} A ⁴ is It is.

 M represents Al, Ga, In, Si, Ge, or Sn.

X may be the same or different from each other,
An alkyl group which may have a substituent, an aryl group which may have a substituent, a heterocyclic residue which may have a substituent, a phthalimidomethyl group which may have a substituent, a halogen atom, Nitro group, cyano group, sulfonic acid group, -OR ^1- , -S
R ² −, −COOR ³ −, Represent -N = NR ¹³ or -N = CHR ^14,.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹
May be the same or different from each other, and may have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent Represents an acyl group, a cycloalkyl group optionally having substituent (s), or a polyether group optionally having substituent (s), or 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 the 4- to 7-membered ring may be a heterocyclic ring further containing a nitrogen atom, an oxygen atom and a sulfur atom.

R ¹² , R ¹³ and R ¹⁴ may be the same or different from each other and have an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent. Represents an optionally substituted aryl group.

Y is -OSR ¹⁵ , Or Represents

Z is hydrogen, a halogen atom, a hydroxyl group, an alkyl group which may have a substituent, —OSR ¹⁸ , Represents

R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ may be the same or different from each other, and may have an alkyl group which may have a substituent, or an aryl which may have a substituent. Group, an acyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxy group which may have a substituent, an allyloxy group which may have a substituent, A polyether group which may have, an amino group which may have a substituent, a hydroxyl group,
Or a halogen 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 [I] according to the present invention, representative examples of atoms and groups constituting X, Z, and R ¹ to R ²⁰ include a chlorine atom, a bromine atom and an iodine as a halogen atom. Examples of the alkyl group which may be substituted with an atom or a fluorine atom include methyl group, n-butyl group, t
ert-butyl group, stearyl group, trichloromethyl group, 2
An aryl group which may have a substituent such as -methoxyethyl group or the like; phenyl group, chlorophenyl group, toluyl group, naphthyl group, anthryl group, dimethylaminophenyl group, hydroxyphenyl group, diethylaminonaphthyl group, hydroxynaphthyl Examples of an optionally substituted alkoxy group include a methoxy group, n-butoxy group, t-butoxy group, and trichloromethoxy group; and an optionally substituted allyloxy group include phenoxy group. Groups, nitrophenoxy group, dimethylphenoxy group, chlorophenoxy group, diethylaminophenoxy group, naphthoxy group, anthroxy group, di-n-butylaminonaphthoxy group, etc. A cyclohexyl group, a cyclobutyl group, etc.
An acyl group which may have a substituent includes an acetyl group,
Examples of the polyether group which may have a substituent include a trifluoroacetyl group and the like, and diethylene glycol monoethyl group, triethylene glycol monobutyl group and the like.
Examples of the heterocyclic group which may have a substituent include a pyridyl group,
Examples of a furyl group, a thiazolyl group, a piperazinyl group, a morpholyl group and the like and a phthalimidomethyl group which may have a substituent include a phthalimidomethyl group, a nitrophthalimidomethyl group, a tert-butylphthalimidomethyl group,
Examples include a methoxyphthalimidomethyl group and a dichlorophthalimidomethyl group, but are not limited to these groups.

In the present invention, the compound represented by the general formula [I] is
For example, it can be manufactured by the following method.

That is, from the isoindolenin compound represented by the following general formula [II] and various metal salts, or by using a carboxylic anhydride, imide or nitrile as a starting material in a conventional manner, the general formula [III] The following phthalocyanine-based compound is produced.

General formula (II) [ ^Wherein A ^1-4 , X, k, l, m, n represent the same meaning as in general formula [I]. General formula [III] [ ^Wherein , rings A ^1-4 , M, X, k, l, m, n and p represent the same meaning as in general formula [I]. Next, by reacting the obtained phthalocyanine compound represented by the general formula [III] with various sulfur compounds, the phthalocyanine compound represented by the general formula [I] can be produced.

Representative examples of the phthalocyanine compounds represented by the general formula [I] used in the present invention include the following phthalocyanine compounds (i) to (p) and (r).

The substrate used in the present invention preferably has a light transmittance of at least 85% for writing and reading signals and has a small optical anisotropy. For example, heat of glass or 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 plastic resin, an epoxy resin, or an allyl resin can be used. Among these, those made of a thermoplastic resin are preferred because of their ease of molding, ease of providing guide grooves and address signals, and those made of acrylic resin or polycarbonate resin because of their optical and mechanical properties. Is particularly desirable.

In the present invention, the thickness of these transparent substrates is not particularly limited, and may be plate-like or film-like. The shape may be a circle or a card, and the size is not particularly limited.

Also, the substrate usually has guide grooves for position control during recording and reading, and irregularities for preformatting such as address signals and various marks. These irregularities are made of the thermoplastic resin as described above. It is preferable to use a stamper or the like when molding (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-based compound on a substrate include methods such as vacuum deposition, sputter link, ion plate, and LB (Langmuir-Blodgett). However, these methods are complicated in operation and low in productivity, and the phthalocyanine compounds represented by the general formula [I] are used for conventional optical recording media having an organic thin film layer. A coating method using a spin coater or the like is the most advantageous because it has a much higher solubility in an ordinary organic solvent than an organic dye. When an organic thin film layer as a recording layer is formed by a coating method, a phthalocyanine-based compound is converted into an alcohol, a ketone, an amide, a sulfoxide, an ether, an ester, an aliphatic halogenated hydrocarbon, or an aromatic hydrocarbon. It is dispersed or dissolved in a common organic solvent such as hydrogen and applied. At this time, if necessary,
A polymeric binder may be added. Examples of the polymer binder include vinyl chloride resin, acrylic resin, polyester resin, polyamide resin, polycarbonate resin, epoxy resin, methacryl resin, vinyl acetate resin, nitrocellulose, and phenol resin. When a polymer binder is used, the ratio of the polymer binder to the phthalocyanine-based compound is preferably 10% by weight or less.

In the present invention, the phthalocyanine compound is
Other dyes can be used by mixing or dispersing or mixing and dissolving. Examples of the dyes that can be used in combination include known dyes such as aromatic or unsaturated aliphatic diamine metal complexes, aromatic or unsaturated fatty acid dithiol metal complexes, phthalocyanine complexes, naphthalocyanine complexes,
Examples include a squarium dye, a naphthoquinone complex, an anthraquinone dye, and a polymethine dye.

The thickness of the recording layer containing a phthalocyanine-based compound formed on the substrate is 10 μm or less, preferably 500 ° to 2 μm.
It is. In addition, after application, the absorption wavelength of the organic thin film layer is shifted to the longer wavelength side by exposing it to the vapor of an organic solvent such as chloroform, tetrahydrofuran, and toluene, thereby significantly improving the sensitivity of the semiconductor laser to light in the oscillation wavelength range. Sometimes you can.

In order to protect these recording layers, Al ₂ O ₃ , SiO
₂ , an inorganic compound such as SiO or SnO may be deposited to form a protective layer. Further, a polymer may be applied as a protective layer.

In order to increase the reflection level of the recording layer, gold, silver, copper, platinum, aluminum, cobalt,
Metals such as tin, MgO, ZnO, metal oxides such as SnO _2, SiN _4, AlN,
A reflective film such as a nitride such as TiN or a chalcogen compound containing Te, Se, S or the like may be provided.

The recording on the recording medium obtained as described above is performed by irradiating the recording layer provided on the substrate with a laser beam, preferably a semiconductor laser beam, focused to about 1 μm. The portion of the recording layer irradiated with laser light undergoes a thermal state change such as decomposition, evaporation, and melting due to absorption of laser energy. Reproduction is performed by reading a difference in reflectance between a portion where a thermal change has occurred and a portion where no thermal change has occurred. The phthalocyanine-based compound represented by the general formula [I] is extremely advantageous because the difference in reflectance before and after recording is extremely large as compared with an organic dye used in an optical recording medium having a conventional organic thin film layer.

As the laser, various lasers such as a He-Ne laser, an Ar laser, and a semiconductor laser can be used, but a semiconductor laser is particularly preferable in terms of price and size. As a semiconductor laser, center wavelength 830nm, 780n
m and shorter wavelength lasers can be used.

EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples. In the examples, parts mean parts by weight.

Production Example: Production of phthalocyanine compounds (i) and (m) In 50 parts of quinoline, 7.8 parts of an isoindolenin compound represented by the general formula [II] shown in Table 1 and 5.0 parts of silicon tetrachloride were added.
After stirring for 3 hours at 180-200 ° C, the mixture was filtered, washed with methanol and dimethylformamide,
After drying, dihydroxysilicon phthalocyanine was obtained. The obtained dihydroxy silicon phthalocyanine 5.0
Part, cyclohexanesulfenyl chloride 50 parts, tri-
After heating and stirring 50 parts of n-butylamine and 300 parts of pyridine at 115 ° C. for 2 hours, the mixture is cooled, diluted with 1000 parts of 5% hydrochloric acid, filtered and washed with water to obtain a precipitate. Dilute with 1000 parts, filter, wash with methanol, 80 ℃
To obtain a phthalocyanine-based compound (i).

The phthalocyanine compound (m) is the same as the silicon tetrachloride used in the production of the phthalocyanine compound (a), the isoindolenin compound represented by the general formula [II] shown in Table 1, and cyclohexanesulfenyl chloride in Table 1. And obtained by a method according to the method for producing the phthalocyanine compound (i).

Production Example 2: Production of phthalocyanine compounds (j) and (I) In 50 parts of quinoline, 7.8 parts of an isoindolenin compound represented by the general formula [II] shown in Table 2 and 5.0 parts of silicon tetrachloride were added.
After stirring for 3 hours at 180-200 ° C, the mixture was filtered, washed with methanol and dimethylformamide,
After drying, dihydroxysilicon phthalocyanine was obtained.

The obtained dihydroxy silicon phthalocyanine 5.0
Part, diethyleneglycoxyethanesulfinyl chloride
50 parts, 50 parts of tri-n-butylamine, and 30 parts of pyridine
After heating and stirring at 0 ° C for 2 hours at 115 ° C, the mixture was cooled and 10%
The mixture was diluted with 00 parts, filtered, and washed with water to obtain a precipitate. The obtained precipitate was diluted with 1000 parts of methanol, filtered, washed with methanol, and dried at 80 ° C to obtain a phthalocyanine compound (j). .

The phthalocyanine compound (I) includes silicon tetrachloride used for producing the phthalocyanine compound (j), an isoindolenin compound represented by the general formula [II] shown in Table 2, and diethyleneglycoxyethanesulfenyl chloride. And obtained by a method according to the production method of the phthalocyanine compound (j).

Production Example 3: Phthalocyanine compound (k), (n)-
Preparation of (p) and (r) To 50 parts of quinoline, 7.8 parts of an isoindolenin compound represented by the general formula [II] shown in Table 3 and 5.0 parts of silicon tetrachloride were added.
After stirring for 3 hours at 180-200 ° C, the mixture was filtered, washed with methanol and dimethylformamide,
Drying yielded dihydroxy reconphthalocyanine.

The obtained dihydroxy silicon phthalocyanine 5.0
Part, chlorosulfonic acid 50 parts, tri-n-butylamine 50
And 300 parts of pyridine were heated and stirred at 115 ° C for 2 hours, cooled, diluted with 1000 parts of 5% hydrochloric acid, filtered, washed with water to obtain a precipitate, and the obtained precipitate was diluted with 1000 parts of methanol. ,
After filtration, washing with methanol and drying at 80 ° C., a phthalocyanine compound (k) was obtained.

The phthalocyanine compounds (n) to (p) and (r)
Silicon tetrachloride used in the production of the phthalocyanine compound (k), the isoindolenin compound represented by the general formula [II] shown in Table 3, and chlorosulfonic acid are substituted as shown in Table 3, and the phthalocyanine compound Obtained by a method according to the production method.

Example 1 A phthalocyanine compound (m) was placed on a glass substrate.
After dropping a solution consisting of 0 parts and 97.0 parts of chloroform,
It was rotated at 1200 rpm for 20 seconds and dried at 80 ° C. for 20 minutes to obtain an optical recording medium.

The recording layer of the obtained optical recording medium has a thickness of 780 mm, a maximum absorption wavelength of 745 nm, and a reflectance of 43% for light having a wavelength of 780 nm.
Met.

Place the obtained optical recording medium on a turntable, and rotate the turntable at 1800 rpm to 1.0 μm.
Recording was performed by irradiating a 780 nm laser beam focused at m at 5 mW and 8 MHz.

When the surface of the optical recording medium after recording was observed with a scanning electron microscope, clear pit formation was observed. When the obtained optical recording medium was irradiated with a laser beam of 780 nm and 0.4 mW and the reflected light was detected, the C / N ratio was 45 db.
Met.

Examples 2 and 3 A phthalocyanine compound (n),
(P) was applied and dried in the same manner as in Example 1 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 having a wavelength of 780 nm, and the C / C of the obtained optical recording medium when recording and reproduction were performed in the same manner as in Example 1.
Table 4 shows the N ratio.

[Effects of the Invention] Since the phthalocyanine-based compound used in the optical recording medium of the present invention has a very high solubility in ordinary organic solvents as described above, it is dissolved in these organic solvents to improve productivity and workability. It can be provided as an organic thin film layer on a substrate by a good coating method. The optical recording medium of the present invention has high sensitivity due to a very large difference in reflectance before and after recording by a laser beam, and enables high-sensitivity recording / reproduction. Yes, and
It is chemically and physically stable.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) B41M 5/26

Claims (3)

(57) [Claims] 1. An optical recording material comprising a phthalocyanine compound represented by the following general formula [I]. General formula [I] [Wherein, rings A ^{1 to} A ⁴ each independently represent a benzene ring, a naphthalene ring, an anthracene ring, Wherein at least one of the rings A ^{1 to} A ⁴ is It is. M represents Al, Ga, In, Si, Ge, or Sn. X may be the same or different from each other, an alkyl group which may have a substituent, an aryl group which may have a substituent, a heterocyclic residue which 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 , -CO
^{OR 3, -NR 4 R 5,} -SO 2 NR 6 R 7, -CONR 8 R 9, -CH 2 NHCOCH 2 N
R ¹⁰ R ^11, -NHCOR ^12, represent -N = NR ¹³ or -N = CHR ^14. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R
¹¹ may be the same or different, and each may be a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an acyl group which may have a substituent ,
Represents a cycloalkyl group which may have a substituent, or a polyether group which may have a substituent, or R ⁶
R ⁷ and 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 further include a nitrogen atom, oxygen It may be a heterocyclic ring containing atoms or sulfur atoms. R ¹² , R ¹³ and R ¹⁴ may be the same or different from each other and have an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, and a substituent Represents an optionally substituted aryl group. Y represents an ^{-O-S-R 15, -O} -S (= W) -R 16 or _{-O-S (= W) 2} -R 17. Z is hydrogen, a halogen atom, a hydroxyl group, an alkyl group which may have a substituent, -OSR ¹⁸ , -OS (= W) -R
Represent ¹⁹ or _{-O-S (= W) 2} -R 20. R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ may be the same or different from each other, and may have an alkyl group which may have a substituent, or an aryl which may have a substituent. Group, an acyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxy group which may have a substituent, an allyloxy group which may have a substituent, Represents an optionally substituted polyether group, an optionally substituted amino group, a hydroxyl group, or a halogen 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. ] (2) all of the rings A ^{1 to} A ⁴ are The optical recording material according to claim 1, wherein 3. An optical recording medium comprising an organic thin film layer comprising the optical recording material according to claim 1 provided on a substrate.