JPH048584A - Optical information recording medium, manufacture thereof and device using the medium - Google Patents

Abstract

PURPOSE:To improve an information recording medium layer in durability and reflectance by a method wherein the information recording medium layer contains a mixture of a naphthalocyanine derivative having a predetermined value or less of a thermal decomposition initiating temperature and a crystalline dye having a predetermined value or more of a thermal decomposition initiating temperature. CONSTITUTION:An optical information recording medium is produced by forming an information recording layer on a substrate. The information recording medium layer contains a mixture of a naphthalocyanine derivative having a thermal decomposition initiating temperature of 300 deg.C or lower and a crystalline dye having a thermal decomposition initiating temperature of 350 deg.C or higher and can be read out by a 0.5-3.0mW laser light. By using such a series as a mixture of the naphthalocyanine derivative and the heat quencher, the optical information recording medium can be provided with the film on the substrate by a spin coating method or a dip coating method. The obtained film exhibits a good read-out optical stability of 10<6> times or more per 1mW to a light in a semiconductor laser oscillating wavelength region. The medium can be favorably used as an additionally-writable optical information recording medium.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an optical information recording medium capable of recording and reproducing information using a laser beam, a method for manufacturing the same, and uses of the recording medium.

[Conventional technology]

In recent years, compact discs and video discs.

2. Description of the Related Art Optical recording media that utilize semiconductor laser light are in practical use as means for writing or reading information in photoreceptors for laser beam printers, optical character readers, and the like.

To achieve this, a recording medium that absorbs semiconductor laser light, that is, near-infrared light, is required. The recording medium includes a recording medium having an inorganic recording layer made of tellurium, tellurium alloy, bismuth alloy, etc., and a phthalocyanine dye (US Pat. No. 4,298,975).

Naphthalocyanine dye (Unexamined Japanese Patent Publication No. 1-198391)
Methods of using organic dyes such as these as recording media are being considered.

[Problem to be solved by the invention]

However, with the optical recording medium having the above-mentioned inorganic recording medium layer, it is difficult to improve productivity because the means for forming a thin film on the substrate is a process in a vacuum such as vacuum evaporation or sputtering. There are limits to improving the recording density due to the high thermal conductivity of the layer, and there are health and safety issues that need to be resolved when dealing with toxic substances such as tellurium and selenium.

On the other hand, when an organic dye is used as a recording medium, it has not been possible to obtain the same characteristics as an optical recording medium having an inorganic recording medium layer in terms of durability and reflectance. Furthermore, the reality is that organic recording media have not yet achieved both durability and solubility in solvents. However, since organic recording media are thought to have the potential to overcome the problems of inorganic recording media, various studies have been made to overcome the problems. That is, a search is being made for an organic recording medium that has durability equivalent to that of inorganic recording media and is also capable of spinner coating and dip coating, which are disadvantages of inorganic recording media. For example, one example is A fl + G a + in the central metal of a naphthalocyanine compound.
I n + T e HS lp G e r S
An optical recording medium comprising an organic thin film containing various derivatives such as n Hpb (Japanese Patent Laid-Open No. 198391/1999) has been proposed.

However, the recording medium can also be read out with a readout power of 1mW of semiconductor laser light! It is not an organic recording medium that can be used more than i10' times. For this reason, currently, when using an organic recording medium, systems are being created with a readout power of 0.5 mW or less, which causes less damage to the organic recording medium layer. However, when a reproducing laser beam of 0.5 mW or less is used, there are many problems such as easy pickup of external noise and lack of compatibility with conventional devices using 1 mW.

As a means for improving the readout optical stability of organic optical recording media, it has been proposed to add a singlet oxygen quencher to cyanine dyes (Japanese Patent Publication No. 1-21798). However, although this is effective in preventing the cyanine dye from being degraded by light, it is not effective against a 1 mW laser beam.

The present invention has been made in view of this situation.

The purpose of the present invention is to improve the durability of the information recording medium layer by spin coating, spray coating, or dip coating an organic recording medium on a substrate.

An object of the present invention is to provide an optical information recording medium with excellent reflectance, a method for manufacturing the same, and uses of the recording medium.

[Means to solve the problem]

As a result of various studies to solve the above-mentioned problems with organic recording media, the inventors of the present invention have found that it is possible to read more than 10 times more times with a laser beam reproduction readout power of 0.5 to 3.0 mW. We have discovered an organic optical recording medium. Furthermore, spray coating, spinner coating, and dip coating, which were previously difficult to apply, became possible as a coating method for substrate organic recording media, and high reflectance could also be achieved.

To summarize the present invention, the first invention provides an optical information recording medium comprising an information recording layer provided on a substrate, wherein the information recording medium layer has a thermal decomposition initiation temperature of 300°C.
Contains a mixture of a naphthalocyanine derivative with a temperature of 0.5 to 3 °C and a crystalline dye with a thermal decomposition onset temperature of 350 °C or higher.
．． An optical information recording medium characterized by being readable with a 0 mW laser beam is provided.

Further, a second invention provides an optical information recording medium comprising an information recording layer provided on a substrate, wherein the information recording medium has the following general formula (I) [wherein Ml is one of Si, Ge, and Sn]. Expressed as
X is an alkyl group or alkenyl group having 1 to 20 carbon atoms,
Alkylthio group, aromatic hydrocarbon group.

represents either an acyl group or a trisubstituted silyl group, Y
, and Y2 is -OR, -0Ar, -05i(R),
-08i(OR)3. -08i(OAr)3 and -〇
C(C, H, L (wherein, R is a linear or branched alkyl group of C□ to C2o, and Ar is a group selected from the group consisting of a phenyl group, a substituted phenyl group, a benzyl group, and a substituted benzyl group). ), which may be the same or different from each other.] and a naphthalocyanine derivative represented by
Containing a mixture of heat quenchers having an effect of preventing thermal deterioration of the naphthalocyanine derivative represented by the general formula (I),
It is possible to provide an optical information recording medium characterized in that it can be read with a laser beam of 0.5 to 3.0 mW.

Further, as the heat quencher, a crystalline dye represented by the general formula (II) or a dye capable of having a relaxation process of the molecular excited state of a naphthalocyanine derivative represented by the general formula (I) is used. An optical information recording medium containing the mixture can be provided.

The present invention also provides devices such as compact discs, video discs, optical recording cards, photoreceptors for laser beam printers, and optical character readers that use the above optical information recording medium.

In addition, in the present invention, it is possible to form a film on a substrate by spinner coating, two spray coatings, and dip coating using a solution in which 0.1 to 5% by weight of an organic recording medium made of the above mixture is dissolved in a solvent, which has been difficult in the past. Provided is a method for producing an optical information recording medium, which comprises forming an optical information recording medium and then removing a solvent. As a result, not only has durability (readout optical stability) equal to or higher than that of optical information recording media with an inorganic recording medium layer been obtained, but also new optical It became possible to provide information recording media.

In the present invention, a naphthalocyanine derivative having a thermal decomposition initiation temperature of 300° C. or lower, and a lekenyl group, an alkylthio group, or an aromatic hydrocarbon group represented by the general formula (I).

represents either an acyl group or a trisubstituted silyl group, Y
l and Y2 are -OR, OA r , OS 1 (R)
, , -○S i (OR),, -OS i (○A
r), and -QC(C,H,), (where R is C0 to C
2o is a straight chain or branched alkyl group, and Ar is a group selected from the group consisting of phenyl, substituted phenyl, benzyl, and substituted benzyl. ), and
They may be the same or different. ] Examples of the naphthalocyanine derivatives include the following.

[In the formula, M is represented by either Si, Ge, or Sn,
X is an alkyl group having 1 to 20 carbon atoms, a051 (C
2H5)3 In the present invention, general formula (II) O5i(n-C4Hs)3 [wherein 1M2 represents a transition metal]. X has 1 to 20 carbon atoms
represents any one of an alkyl group, an alkenyl group, an alkylthio group, an aromatic hydrocarbon group, an acyl group, or a trisubstituted silyl group. ] Examples of the phthalocyanine derivatives represented by the above include the following.

t-C4H.

t-L,, ■.

t-C4) 1゜ t-L, 41t.

and.

In the present invention, examples of mixtures particularly excellent in readout light stability (durability), reflectance, and solubility in solvents include a combination of the following. With this combination, even if the upper limit of the reproduction readout power is 1.5 mW or more and 3.0 mW, it is possible to achieve 106 times or more.

In the present invention, the ratio of the mixture of the naphthalocyanine derivative represented by the general formula (I) and the compound having a heat quencher action is 1 to 1 to 0.01 to 0.01 to 1 for the former.
A range of 1.0 is preferred.

The substrate used in the present invention includes vinyl chloride resin, acrylic resin, and polyolefin resin.

Thermoplastic resins and thermosetting resins such as polycarbonate resin, polyvinyl acetal resin, unsaturated polyester resin, vinyl ester resin, polystyrene resin, polyether sulfone resin, polyether ether ketone resin, epoxy resin, allyl resin polyimide, polyamide resin, Or inorganic polymers such as silicone resin and phosphazene resin, glass HS 10z y S 13N4
1 Using metal etc., film, sheet, plate 1 Cylinder, 3
It is used by forming it into a columnar object, etc. that is square or larger. The substrate is
Light transmittance is 85 for writing and reading signals.
% or more, and the optical anisotropy is preferably small. Using these materials, a thin film can be formed on the mirror surface of a molded substrate or on a surface with a guide groove pattern (pre-group) in the following manner. Alternatively, the substrate may have a structure in which a photocurable resin is laminated on a flat plate molded from the above material, and the guide groove pattern is transferred onto the surface of the photocurable resin layer.

The thickness of the recording layer formed on these substrates is 20 to 500 nm.
It may be in the range of m, preferably in the range of 30 to 1100n. Furthermore, a reflective layer, a protective film layer, etc. are provided to constitute a disc-shaped or sheet-shaped optical information recording medium, but the present invention does not care about these configurations.

In the present invention, the mixture constituting the organic recording medium can be formed into a thin film on a substrate using a conventional spin cord, spray coating, or dip coating device. The coating method involves using a mixture of the naphthalocyanine derivative represented by the general formula (I) of the present invention and a compound having a heat quencher effect, or dissolving or dispersing the compound together with a binder in a solvent. Can be applied in any condition.

As a binder, polyimide and polyamide are used.

polystyrene, polyacrylic, silicone, epoxy,
Polymers such as phenol can be used.

Further, in the present invention, aromatic, halogen-based, ketone-based, ether-based, hydrocarbon-based solvents, or a mixture thereof are used as the solvent for dissolving the organic recording medium. Among these, carbon tetrachloride and a mixed system of methylcyclohexane and toluene are preferred.

[Effect]

When an optical information recording medium using a naphthalocyanine derivative represented by the general formula (I) is irradiated with a reproduction laser beam power of 1 mW, the number of reproduction readings is 103.
This is on the order of ~104 times, which is significantly inferior to the order of 106 times when an inorganic recording medium is used.

In the present invention, as a result of measuring the thermal decomposition initiation temperature of the naphthalocyanine derivative represented by the general formula (I), both
It was found that thermal decomposition begins at temperatures below 00°C. On the other hand, 1m
It was found that when a film is irradiated with a semiconductor laser beam of W or more, the temperature of the irradiated surface becomes 300°C or more in the case of a film formed only from the naphthalocyanine derivative represented by the general formula (I). . For this reason, a recording medium using a naphthalocyanine derivative represented by general formula (I) has a
It cannot withstand laser light (780nm) of mW or more,
This is thought to be the cause of poor durability.

Based on this fact, the present invention has found that the following is effective as a means for alleviating the damage caused by laser light to the naphthalocyanine derivative represented by the general formula (I). That is, (I) a crystalline dye having a thermal decomposition initiation temperature of 350° C. or higher, (ii) a thermal quencher having an effect of preventing thermal deterioration of the naphthalocyanine derivative represented by general formula (I), and (iii) general formula (I) At least one of the dyes that can undergo a relaxation process of the molecular excited state of a naphthalocyanine derivative represented by (iv) a dye compound with a large heat capacity, and (v) a dye compound with a large thermal conductivity, is combined with the general formula ( It has been discovered that by mixing it with the naphthalocyanine derivative represented by I), it is possible to stably reproduce more than 10 times with a reproduction readout power of 1.0 mW or more, which is unimaginable with conventional organic recording media, and the present invention This is what we were able to achieve.

Also, by making the recording medium a mixed type.

It has become possible to impart solubility in solvents, and it has become possible to form coatings on substrates by spin cording, dip coating, and spray coating, which was thought to be a feature of organic recording media.

Example 1 Bis(tributylsiloxy)germanium-tetra(ofthyroxycarbonyl)naphthalocyanine and copper tetra-t-butylnaphthalocyanine were coated on a polycarbonate substrate with a thickness of 1.2 rm at a weight ratio of 1:0.8 with carbon tetrachloride. A 0.5% by weight solution was prepared, and the solution was coated on a substrate using a spinner and dried to form a recording layer with a thickness of 45 nm, which was used as a recording medium. The reflectance of the recording layer of the obtained recording medium from the substrate side at a wavelength of 830 nm was 28%.

Further, the output light of a semiconductor laser with a wavelength of 830 nm was focused on the recording medium to a spot diameter of 1.2 μm, and the recording frequency I
After writing a MHz signal, 1.0 mW
When reading with the reproduction light of , the reproduction C/N ratio was 46d.
It was B.

Further, FIG. 1 shows the number of readings when 1.0 mW of reproduction light was continuously irradiated.

Example 2 Bis(triethylsiloxy)germanium-tetra(ofthyroxycarbonyl)naphthalocyanine and copper tetra-t-butylnaphthalocyanine were placed on a 1.2-thick polycarbonate substrate in a weight ratio of 4 as in Example 1. :3
Dissolved in carbon tetrachloride to create a 0.5% by weight solution,
This was coated onto a substrate using a spinner and dried to form a recording layer with a thickness of 43 nm, which was used as a recording medium. The reflectance of the recording layer of the obtained recording medium from the substrate side at a wavelength of 830 nm was 32%. Output light from a semiconductor laser with a wavelength of 830 nm was focused onto the recording medium to a spot diameter of 1.2 μm at a linear velocity of 8.0 m/s.

After writing an I MHz signal from the board side with an output of 9 mW, reading was performed with a 1.0 mW reproduction light, and the reproduction C/N ratio was 50 dB.

Furthermore, FIG. 2 shows the number of readings when 1.0 mW of reproduction light was continuously irradiated.

Comparative Example 1 Bis(tributylsiloxy)germanium-tetra(ofthyroxycarbonyl)naphthalocyanine was dissolved in carbon tetrachloride to create a 1.0% by weight solution on a polycarbonate substrate with a thickness of 1.2+ m, and the substrate was coated with a spinner. A recording layer having a thickness of 53 nm was formed by coating and drying on top of the coating, thereby preparing a recording medium.

The reflectance of the recording layer of the obtained recording medium from the substrate side at a wavelength of 830 nm was 38%.

Further, the output light of a semiconductor laser with a wavelength of 830 nm was focused on the recording medium to a spot diameter of 1.2 μm, and the recording frequency I
After writing a MHz signal, I read it with a 1.0mW reproduction light, and the reproduction C/N ratio was 42dB.
Met.

Furthermore, FIG. 3 shows the readout light stability when the power of the readout light is changed. With only the recording medium, the reproduction light is 1.0
The recording medium deteriorates due to rnW.

Example 3 Bis(tributylsiloxy)silicon-tetra(cyclohexylthio)naphthalocyanine and zinc tetra-t-butylnaphthalocyanine were prepared in a weight ratio of 1:0.8 on a polycarbonate substrate with a thickness of 1.2 mm. Dissolved in carbon to create a 1.0% by weight solution, coated on the substrate with a spinner and dried to form a recording layer with a thickness of 55 nm,
It was used as a recording medium. Wavelength 83 of the recording layer of the obtained recording medium
The reflectance from the substrate side at 0 nm was 37%.

The output light of a semiconductor laser with a wavelength of 830 nm is focused onto the recording medium to a spot diameter of 1.2 μm, and the linear velocity is 8.
After writing an IMHz signal from the board side at 0 m/s and an output of 9 mW, reading was performed using a 1.0 mW reproduction light, and the reproduction C/N ratio was 49 dB.

Furthermore, the number of times of reading when 1.0 mW of reproduction light was continuously irradiated was 106 times or more.

Example 4 Bis(tripropylsiloxy)silicon-tetra(cyclohexylthio)naphthalocyanine and vanadyltetra-t-butylnaphthalocyanine were deposited on a 1.2 m+ thick polycarbonate substrate in a weight ratio of 5:4 with carbon tetrachloride. to create a 0.8% by weight solution and apply it onto the substrate using a spinner.

A dry recording layer with a thickness of 49 nm was formed to provide a recording medium. The reflectance of the recording layer of the obtained recording medium from the substrate side at a wavelength of 830 nm was 35%. The output light of a semiconductor laser with a wavelength of 830 nm is applied onto the recording medium with a diameter of 1.
After condensing the light to a spot diameter of 2 μm, writing an I MHz signal from the substrate side at a linear velocity of 8.0 m/s and an output of 9 mW, and then reading it with a 1.0 mW reproduction light, the reproduced C/ The N ratio was 51 dB.

Furthermore, the number of times of reading when 1.0 mW of reproduction light was continuously irradiated was 106 times or more.

Example 5 Bis(tripropylsiloxy)silicon-tetra(cyclohexylthio)naphthalocyanine and zinc tetra-t-butylnaphthalocyanine were used on a polycarbonate substrate with a thickness of 1.2 m, and the compounds shown in Table 1 were used. A 1.0% by weight solution was prepared by dissolving this in carbon tetrachloride, and the solution was applied onto a substrate using a spinner and dried to form a film recording layer.

This table also lists the dye mixing ratio, film thickness, reflectance reproduction C/N ratio at a wavelength of 830 nm, and the number of readouts at 1 mW. For each of the prepared media, output light from a semiconductor laser with a wavelength of 830 nm was focused to a spot diameter of 1.2 μm, and a linear velocity of 8. A signal with a recording frequency of IMHz was written from the substrate side at Om/s and an output of 9 mW. Furthermore, 1m
The number of readings when W reproducing light was continuously irradiated was measured.

These results are shown in Table 1. Good regeneration ratio C at each mixing ratio
/N ratio and readout optical stability. Mixing ratio is 1:1
．． 5 or more, the reflectance was less than 20% and could not be detected.

Table 1 Example 6 Bis(tributylsiloxy)silicon-tetra(n-butylthio) on a polycarbonate substrate with a thickness of 1.2 μm
Naphthalocyanine and palladium tetra-t-butylnaphthalocyanine were dissolved in carbon tetrachloride at a weight ratio of 5:4 to create a 1.2% by weight solution, and the solution was applied onto the substrate using a spinner and dried. A recording layer having a film thickness of 52 nm was formed using this method to prepare a recording medium. The reflectance of the recording layer of the obtained recording medium from the substrate side at a wavelength of 830 nm was 33%. The output light of a semiconductor laser with a wavelength of 830 nm is focused onto the recording medium to a spot diameter of 1.2 μm, and the linear velocity is 8. om/S l output 9mW from the board side
After writing a Hz signal, reading was performed using a 1.0 mW reproduction light, and the reproduction C/N ratio was 46 dB.

Furthermore, the number of readings when 1.0 mW of reproduction light was continuously irradiated was 10' higher than the number of readings.

Example 7 Screws (
Tributylsiloxy) germanium-tetra(t-butyl)phthalocyanine and palladium tetra-t-butylphthalocyanine were dissolved in carbon tetrachloride at a weight ratio of 1:0.8 to create a 1.0% by weight solution, and then the substrate The solution was applied on top using a spinner and dried to a film thickness of 46 nm.
A recording layer was formed to prepare a recording medium. The reflectance of the recording layer of the obtained recording medium from the substrate side at a wavelength of 690 nm was 31%. Output light from a semiconductor laser with a wavelength of 690 nm was focused on the recording medium to a spot diameter of 1.2 μm, and an I MHz signal was written from the substrate side at a linear velocity of 8.0 m/s and an output of 6 mW. After, 1.0mW
When reading with the reproduction light of , the reproduction C/N ratio was 43d.
It was B.

Furthermore, the number of times of reading when 1.0 mW of reproduction light was continuously irradiated was 106 times or more.

Example 8 Screws (
(triethylsiloxy)germanium-tetra(t-butyl)phthalocyanine and copper tetra(t-butyl)phthalocyanine were dissolved in carbon tetrachloride at a weight ratio of 1:0.8 to create a 1.0% by weight solution, and the solution was disposed on the substrate. The solution was applied using a spinner and dried to form a recording layer with a thickness of 45 nm, which was used as a recording medium. The reflectance of the recording layer of the obtained recording medium from the substrate side at a wavelength of 690 nm is 2
It was 9%. The output light of a semiconductor laser with a wavelength of 690 nm is focused onto the recording medium to a spot diameter of 1.2 μm, and an I.D.
After writing a MHz signal, reading was performed using a 1.0 mW reproduction light, and the reproduction C/N ratio was 44 dB.

Furthermore, the number of times of reading when 1.0 mW of reproduction light was continuously irradiated was 106 times or more.

Example 9 Bis(triethylsiloxy)germanium-tetra(t-butyl) on a 1.2 mm thick polycarbonate substrate
Phthalocyanine and zinc tetra-butyl phthalocyanine were dissolved in carbon tetrachloride in the proportions shown in Table 2 to create a 1.0% by weight solution, and the solution was placed on the substrate. It was applied using a spinner and dried to form a recording layer.

This table also lists the dye mixing ratio, film thickness, reflectance reproduction C/N ratio at a wavelength of 690 nm, and the number of readings. For each of the prepared media, output light from a semiconductor laser with a wavelength of 690 nm was focused to a spot diameter of 1.2 μm, and a linear velocity of 8.
Recording frequency I M from the board side at 0 m/s and 9 mW output.
A Hz signal was written. Furthermore, the number of readings when 1.0 mW of reproduction light was continuously irradiated was measured. These results are shown in Table 2. Good reproduction C/N ratio and read optical stability were exhibited at each mixing ratio. When the mixing ratio was 1:1.5 or more, the reflectance was less than 20% and could not be detected.

Table 2 Example 10 Using the optical system shown in FIG. 4, the laser output of the readout light shown in FIG. 5 was performed, and the readout light stability was evaluated using the recording medium shown in Example 1. As a result, there were 106 or more readings when 1.0 mW of reproduction light was continuously irradiated.

Example 11 Using the same optical system as in Example 10, the laser output of the read light shown in FIG. 6 was performed, and the read light stability was evaluated using the recording medium shown in Example 1. As a result, there were 106 or more readings when 1.0 mW of reproduction light was continuously irradiated.

Example 12 Using the same optical system as in Example 10, the laser output of the read light shown in FIG. 6 was performed, and the read light stability was evaluated using the recording medium shown in Example 1. As a result, there were 106 or more readings when 1.0 mW of reproduction light was continuously irradiated.

Example 13 Bis(tripropylsiloxy)silicone-tetra(cyclohexylthio)naphthalocyanine and copper tetrat-
Butylnaphthalocyanine and the former/latter weight ratio: 110
．． 8, and carbon tetrachloride was added to the mixture to make 1.0
A weight percent solution was made. The solution was heated at 2000 r, p, m
It was dropped onto a polycarbonate substrate with a thickness of 1.2 mm that was rotated at a speed of 1.2 mm, and the mixture was rotated for about 20 seconds to perform spinner coating.

Thereafter, it was heated at 90°C for 1 hour. The thickness of the recording layer of the obtained recording medium was 40 to 60 nm.

Also, the reflectance from the substrate side at 830 nm is 32%.
Met. Furthermore, the number of times of reading when 3.0 mW of reproduction light was continuously irradiated was 106 times or more.

Example 14 Bis(tributylsiloxy)germanium-tetra(ofthyroxycarbonyl)naphthalocyanine and copper tetra-t-butylnaphthalocyanine were blended at a weight ratio of 110.8 for the former/latter, and carbon tetrachloride was added to the blend. In addition, a 1.0% by weight solution was prepared. In the solution, a thickness of 1.2
Immerse a polycarbonate substrate of mn, then 1μ/l
Pulled at a pulling rate of 11n, then heated at 90°C for 1
Carbon tetrachloride was removed by heating for a period of time. The thickness of the recording layer of the obtained recording medium was 48 nm.

This optical information recording medium has good film quality and is easy to focus and track.

Example 15 Bis(tributylsiloxy)germanium-tetra(ofthyroxycarbonyl)naphthalocyanine and copper tetra-t-butylnaphthalocyanine were blended at a weight ratio of the former/latter of 110.8, and carbon tetrachloride was added to the blend. In addition, a 1.0% by weight solution was created. After coating the solution on a polycarbonate sheet with a thickness of 550-70 nm,
'C, heated for 1 hour to remove carbon tetrachloride.

Next, the recording layer-coated sheet was cut into a disk shape or a square shape to form an optical information recording medium.

Furthermore, in order to obtain tracking, a guide groove was formed using a laser beam.

The film quality of this optical information recording medium is good, and it is easy to perform forashing and tracking.

Example 16 Bis(tributylsiloxy)silicon-tetra(cyclohexylthio)naphthalocyanine and copper tetra-t-butylnaphthalocyanine at a former/latter weight ratio of 110.4
A 9/1 mixed solvent of methylcyclohexane and toluene was added to the mixture to prepare a 1.0% by weight solution. Drop the solution onto the roll and leave it under the roll to a thickness of 1
．． A recording medium was formed on the substrate by passing it through a 2 mm polycarbonate substrate. The gap between the roll and the board is 2
0μm. The moving speed of the substrate is 2700 m/min. Next, heating was performed at 90° C. for 1 hour to obtain an optical information recording medium. The film quality of the recording medium is good, and focusing and tracking are easy to achieve.

Example 17 As a charge generation layer of an organic photoconductor (○pc), bis(tributylsiloxy)silicon-tetra(cyclohexylthio)naphthalocyanine and copper tetra-t-butylnaphthalocyanine were mixed in silicone resin. It was formed by dispersing a compound blended at a weight ratio of 110.8 and immersing a photosensitive drum (manufactured by AQ) in the dispersion solution. The pulling speed is 1 cm/Bib.

An electric field of 35 V/μm was applied to the photosensitive drum, and a wavelength of 7
As a result of irradiation with an 80 nm semiconductor laser, good charge generation was confirmed.

〔Effect of the invention〕

As described above, in the optical information recording medium of the present invention, a thin film can be formed on a substrate by a dip coating method such as a spin coating method by using a system in which a naphthalocyanine derivative and a heat quencher are mixed.

Furthermore, the obtained thin film exhibits suitable readout light stability for light in the semiconductor laser oscillation wavelength region of 106 times or more at 1 mW, and can be suitably used as a write-once optical information recording medium.

[Brief explanation of the drawing]

Figure 1 shows bis(tributylsiloxy)germanium-
A graph showing the readout photostability of tetra(ofthyrooxy)naphthalocyanine and copper tetra-t-butylnaphthalocyanine (weight ratio 1:0.8), Figure 2 shows bis(triethylsiloxy)germanium-tetra(ofthyrooxy)naphthalocyanine. A graph showing the readout photostability of copper tetra-t-butylnaphthalocyanine (weight ratio 1:0.75), Figure 3 shows the case of bis(tributylsiloxy)germanium-tetra(ofthyroxycarbonyl)naphthalocyanine alone. 3 is a graph showing the readout optical stability of . Fig. 4 shows the optical system of the recording/reproducing device, and Figs. 5 and 6 show the readout beam.・Laser light source, 2... Diffraction grating, 3... Magnifying lens, 4... Beam splitter, 5... Fixed mirror, 6... 1/4 wavelength plate, 7... Tangential mirror , 8... Tiger's knocking mirror, 9... Objective lens, 10... Disc (information recording medium), 11...
Cylindrical lens, 12...light receiving means. 0.5 1,○ 1.5 Reproduction light (mW)

Claims (1)

[Claims] 1. An optical information recording medium comprising an information recording layer provided on a substrate, wherein the information recording medium layer has a thermal decomposition initiation temperature of 30
An optical information recording medium comprising a mixture of a naphthalocyanine derivative having a temperature of 0°C or lower and a crystalline dye having a thermal decomposition initiation temperature of 350°C or higher. 2. In an optical information recording medium comprising an information recording medium layer provided on a substrate, the information recording medium layer has the following general formula (I
) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [However, in the formula, M_1 represents a metal atom, and Si, Ge, S
Represents a group IV metal selected from n. X has 1 to 20 carbon atoms
represents any one of an alkyl group, an alkenyl group, an alkylthio group, an aromatic hydrocarbon group, an acyl group, or a trisubstituted silyl group. Y^1 and Y^2 are the same or different, -OR
, -OAr, -OSi(R)_3, -OSi(OR)_
3,...OSi(OAr)_3 and -OC(C_6H
_5) A group selected from the group consisting of _3 (where R is C1-
C20 straight chain or branched alkyl group, Ar is a group selected from the group consisting of phenyl group, substituted phenyl group, benzyl group and substituted benzyl group). ] containing a mixture of a naphthalocyanine derivative represented by the formula (I) and a thermal quencher having a thermal decomposition initiation temperature of 350°C or higher and having an effect of preventing thermal deterioration of the naphthalocyanine derivative represented by the general formula (I). An optical information recording medium characterized in that it is readable with a laser beam. 3. In an optical information recording medium comprising an information recording layer provided on a substrate, the optical information recording medium layer is made of a naphthalocyanine derivative having a thermal decomposition onset temperature of 300°C or lower and a naphthalocyanine derivative having a thermal decomposition onset temperature of 350°C or higher. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) [However, M_2 in the formula represents a transition metal. X represents any one of an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkylthio group, an aromatic hydrocarbon group, an acyl group, or a trisubstituted silyl group. An optical information recording medium comprising a mixture of crystalline dyes represented by 4. In an optical information recording medium having an information recording medium layer provided on a substrate, the optical information recording medium has the following general formula (
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [However, in the formula, M_1 represents a metal atom, and Si, Ge, S
Represents a group IV metal selected from n. X has 1 to 20 carbon atoms
represents any one of an alkyl group, an alkenyl group, an alkylthio group, an aromatic hydrocarbon group, an alkyloxycarbonyl group, an acyl group, or a trisubstituted silyl group. Y^1 and Y^2 are the same or different, -OR, -OAr
, -OSi(R)_3, -OSi(OR)_3,...
OSi(OAr)_3 and -OC(C_6H_5)_3
(wherein R is a C1-C20 linear or branched alkyl group, and Ar is a group selected from the group consisting of a phenyl group, a substituted phenyl group, a benzyl group, and a substituted benzyl group). ] An optical information recording medium comprising a mixture of a naphthalocyanine derivative represented by the formula (I) and a dye capable of undergoing a relaxation process of the molecular excited state of the naphthalocyanine derivative represented by the general formula (I). . 5. An apparatus using the optical information recording medium according to claims 1 to 4. 6. A method for producing an optical information recording medium comprising an information recording layer provided on a substrate, wherein the information recording medium comprises a naphthalocyanine derivative having a thermal decomposition onset temperature of 300°C or lower and a crystalline dye having a thermal decomposition onset temperature of 350°C or higher. was dissolved in a solvent and 0.
1. A method for producing an optical information recording medium, which comprises preparing a 1 to 5% by weight solution, dipping a substrate in the solution, and then pulling up and removing the solvent. 7. In a method for manufacturing an optical information recording medium in which an information recording layer is provided on a substrate, the information recording medium contains a naphthalocyanine derivative having a thermal decomposition onset temperature of 300°C or lower and a crystalline dye having a thermal decomposition onset temperature of 350°C or higher. Dissolved in a solvent and 0.
A 1 to 5% by weight solution is prepared, and the solution is 1000 to 50% by weight.
00r. p. 1. A method for manufacturing an optical information recording medium, which comprises: forming a film on a substrate rotated at m, and then removing the solvent to form a recording medium layer having a thickness of 10 to 200 nm. 8. In the manufacturing method of an optical information recording medium in which an information recording medium layer is provided on a substrate, the information recording medium layer has the following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [in the formula , M_1 is represented by Si, Ge, or Sn, and X is an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkylthio group, an aromatic hydrocarbon group, an acyl group, or a trisubstituted silyl group. Representation, Y_1 and Y_2
is -OR, -OAr, -OSi(R)_3, -OSi(
OR)_3, -OSi(OAr)_3 and -OC(C_
6H_5)_3 (wherein, R is a linear or branched alkyl group of C_1 to C_2_0, and Ar is a group selected from the group consisting of a phenyl group, a substituted phenyl group, a benzyl group, and a substituted benzyl group). , may be the same or different from each other. ] A naphthalocyanine derivative represented by the above general formula [
A heat quencher having an effect of preventing thermal deterioration of a naphthalocyanine derivative represented by
A method for manufacturing an optical information recording medium, which comprises preparing a ~5% by weight solution, flowing the solution over a substrate while rotating the substrate, and then removing the solvent by heating. 9. Optical information characterized in that it is recorded and reproduced on the optical information recording medium according to claims 1 to 4 using semiconductor laser light with a wavelength of 640 to 720 nm, 780 nm, or 830 nm at a power of 0.5 to 3.0 mW. How to use recording media.