JPH03281387A - Optical recording medium - Google Patents

Abstract

PURPOSE:To perform the highly sensitive recording and reproduction due to laser beam by forming an optical recording medium by providing an org. membrane recording layer containing one or more kind of a phthalocyanine compound represented by a specific general formula on a substrate. CONSTITUTION:One or more kind of a phthalocyanine compound represented by formula I [wherein R<1> - R<4> are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a nitro group, an alkoxy group or a carboxylic acid group, M is A, Ca, In, Si, Ge or Sn and Y is a group represented by formula II (wherein R<9> - R<11> are a hydrogen atom or an aliphatic hydrocarbon group)] is dispersed or dissolved in an org. solvent such as alcohol to prepare a coating solution. This coating solution is applied to a substrate composed of glass or plastic and dried to form an org. membrane recording layer to obtain an optical recording medium. This optical recording medium is chemically and physically stable and can be subjected to recording and reproduction with high sensitivity by laser beam.

Description

[Detailed Description of the Invention] [Object of the Invention] (Industrial Application Field) The present invention provides a method for writing information using a laser beam,
The present invention relates to optical recording media that can be read and read.

(Prior Art) Conventionally, there are various types of media that record information using laser beams. One of them is a method that locally heats the irradiated area by irradiating a recording layer on a substrate with a laser beam. , there are some that record information by causing physical changes such as melting, evaporation, or decomposition.

Until now, As, TexSe, T
Thin film layers of metals and alloys such as i have been used. An optical recording medium having such a recording layer.

In general, it can be applied to semiconductor lasers, which have relatively high writing sensitivity and can have compact recording and reproducing optical systems, but because of their low thermal conductivity and high reflectance, it is difficult to reduce the energy of the laser beam during recording. They cannot be used efficiently, and high-power laser beams may be required to record in high-speed scans. Furthermore, these recording layers are chemically unstable and may deteriorate in the air.

For this reason, in recent years relatively long wavelengths (e.g. 780n) have been
Research has been carried out on optical recording media in which information is written to and read from an organic thin film layer on a substrate using a laser beam with a wavelength of 2.0 m or more.

Such an organic thin film layer is melted using a semiconductor laser.
Small recesses (bits) easily caused by evaporation or decomposition etc.
It has the advantage of being able to form

Unexamined Japanese Patent Publication No. 1983-1987 is an optical disc in which an organic thin film layer is formed on a substrate and information is recorded and reproduced using a laser beam.
82093, JP 58-56892, JP 60-89842, JP 60-15024
Publications such as Publication No. 3 are already publicly known. However, the reality is that a completely satisfactory optical recording medium with high recording sensitivity and a large absorption coefficient for semiconductor laser beams has not been developed.

(Purpose B to be Solved by the Invention) The present invention provides (1) an optical recording medium using a specific phthalocyanine compound that is chemically and physically stable and capable of recording and reproducing information with high sensitivity using a laser beam and is inexpensive.

[Structure of the invention]

(Means for Solving the Problem) As a result of intensive research, the present inventors have found that an optical recording medium having a recording layer containing a phthalocyanine compound having a specific structure on a substrate has various excellent properties. This discovery led to the completion of the present invention.

That is, the present invention is an optical recording medium characterized by having an organic thin film layer containing at least one phthalocyanine compound represented by the following general formula [1] on a substrate.

General formula (1) (wherein R1 to R11 are each independently a hydrogen atom, a halogen atom, an alkyl group, a l:substituted or unsubstituted aryl group, a nitro group, an alkoxy group, a carboxylic acid group,
Carboxylic acid ester group, or R1 and RzR3 and R'
, R8 and R6, R'' and R'' represent a cyclic organic residue in the lLf, tL-form.

M represents AI, Ga-, In, St, Ge or Sn.

1 Y represents 10-3i-R'', where l R' l R
"? 11 RI + each independently represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or Q RI t , provided that at least one of R9, Rlb, and R11 is 0R12.

RIz is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

\RI + p represents an integer of 1 or 2) To further explain the substituents in general formula [1)
R1 to R8 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a nitro group, an alkoxy group, a carboxylic acid group, or a carboxylic acid ester group, and the halogen atom is a chlorine atom.

Bromine atoms, iodine atoms, etc., and as alkyl groups,
Methyl group, ethyl group, n-butyl group, t-butyl group, stearyl group, etc., and aryl groups include phenyl group,
Naphthyl group, anthryl group, etc.

Examples of the alkoxy group include methoxy group, ethoxy group, n-butoxy group, stearyloxy group, and phenoxy group.

Naphthyloxy group, etc., and carboxylic acid ester groups include methyl carboxylic acid ester group, ethyl carboxylic acid ester group, n-butyl carboxylic acid ester group, etc., but are not limited to these substituents. Also,
For aryl groups, hydroxyl groups.

It may have a substituent such as a halogen atom, an alkyl group, an amino group, a dialkylamino group, a monoalkoxy group, a nitro group, a cyano group, an aralkyl group, or an aryl group.

In addition, in the general formula CI), R1 and R2, R2 and R'
, R' and R&, and R'l and R1 may be cyclic organic residues that can form an integrated planar structure.

Preferably, the cyclic organic residue is.

It has a basic skeleton selected from or. At any position of the above cyclic organic residue, i1! Substituents may be present, and these substituents include halogen atoms, alkyl groups,
Examples include substituted or unsubstituted aryl groups, nitro groups, alkoxy groups, carboxylic acid groups, and carboxylic acid ester groups.

The phthalocyanine compound represented by General 2 above has large absorption in the visible to near infrared region, and is suitable for recording and reproducing using a laser beam.

The phthalocyanine compound represented by the above general formula (1) used in the present invention is generally produced by heating the indolenine compound represented by the following general formula (II) and various metal salts, preferably in an organic solvent. can do.

General formula [I[) l-1 8M Various phthalocyanine compounds can also be obtained by mixing and reacting indolenine compounds having different substituents represented by general formula (II).

Further, the phthalocyanine compound of general formula C1) is.

It can also be produced using nitriles, phthalic acids, and phthalimides as starting materials.

Alcohols, glycols, xylene, and quinoline are used to manufacture these phthalocyanine compounds.

α-Chlornaphthalene, nitrobenzene, sulfolane,
A wide range of general organic solvents such as N,N-dimethylformamide can be used, but it can also be obtained without a solvent.

Further, it may be preferable to use an alkali or an organic amine such as diazabicycloundecene (DBU) or cyclohexylamine as a catalyst.

In the present invention, various materials such as glass, plastic, paper, and metal plates can be used as the substrate material on which the recording layer is provided.

Plastics include vinyl chloride resin, acrylic acid resin, polyester resin, and polyethylene resin.

Examples include polyamide resin, polycarbonate resin, epoxy resin, methacrylic acid resin, vinyl acetate resin, nitrocellulose, polypropylene resin, polyethylene terephthalate resin, phenol resin, and copolymers thereof.

Further, the form of the optical recording medium in the present invention is not particularly limited, and may be either disc-shaped or card-shaped.

Methods for forming a recording layer containing the specific phthalocyanine compound of the present invention on a substrate include vacuum evaporation method, sputtering method 1, ion plate method, casting method, spinner method, spray coating method, blade coating method,
There are chemical and mechanical methods such as LB method.

In the present invention, the spinner method is most preferred. It can also be mixed with a polymer binder if necessary.

As the polymer binder, the plastics used for the above-mentioned substrate materials can be used.

When coating with a spinner method, phthalocyanine compounds can be applied to general organic compounds such as alcohols, ketones, amides, sulfoxides, ethers, esters, aliphatic halogenated hydrocarbons, and aromatic hydrocarbons. Apply by dispersing or dissolving in a solvent. At this time, a polymer binder may be added depending on the case. The recording layer containing phthalocyanine formed on the substrate has a thickness of 10 μm or less, preferably 500 μm to 2 μm.
It is less than μm.

After application, chloroform, tetrahydrofuran.

By exposure to vapors of organic solvents such as toluene.

TW! In some cases, the absorption wavelength of the film can be shifted to longer wavelengths to significantly improve its sensitivity to laser light.

In some cases, AI or Au may be formed on the recording layer.

A reflective layer made of a metal thin film such as Cu may be provided.

In addition, to protect these recording layers, Al203
A protective layer may be provided by vapor-depositing an inorganic compound such as SiQz, SiO, SnQ, or the like, or a polymer used for the substrate material may be applied as the protective layer.

The optical recording medium obtained by the present invention can be written to, read from, and recorded/reproduced using various laser beams such as not only He--Ne laser beam but also ruby, Ar, and semiconductor laser beams.

Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to the following examples. Examples 0 and 9 indicate parts by weight.

(Example) [Synthesis Example Part 1: Synthesis of Compound (a)] 2.0 parts of an indolenine compound in which R1 and R1 are represented by the above general formula (II) and 2.0 parts of tetrachlorosilane were added to 20 parts of quinoline. , 180-200℃ under Nt flow
After heating and stirring for 2 hours, the mixture was cooled to room temperature.

After diluting with 300 parts of methanol, the product was filtered, washed with methanol and acetone, and then dried. After melting 1.0 parts of the obtained compound in 200 parts of concentrated sulfuric acid at 5 to 10°C,
The mixture was poured into 2000 parts of ice water, the precipitate was filtered and washed with water, and the water cake was reslurried in 300 parts of ammonia water, boiled for 1 hour, filtered, washed with water, washed with methanol, and dried.

Next, 0.5 parts of the compound thus obtained was added to 50 parts of pyridine and 10 parts of tri-n-butylamine, and heated to reflux. At this time, 20 parts of pyridine was recovered using a Dean-Stark cooling tube, and the system Removed moisture inside. The reaction solution was cooled, 5.0 parts of dichlorodimethylsilane was added, and after stirring at room temperature for 15 hours, excess dichlorodimethylsilane was distilled off and the mixture was cooled.

After cooling the reaction solution, 10 parts of ethylene glycol was added and heated under reflux for 6 hours, filtered, the residue was washed with pyridine and dimethylformamide (DMF), and the filtrate was diluted with 1000 parts of diluted hydrochloric acid.
The product was filtered and washed with water.

After drying, 0.2 parts of compound (a) was obtained.

[Synthesis Example 2 Part 2 Synthesis of Compound (b)] 2.0 parts of an indolenine compound in which R1 and R1 are represented by the above general formula (n) and 2.0 parts of aluminum trichloride were reacted in the same manner as in Synthesis Example 1. , filtration and purification.

Next, 0.5 parts of the compound thus obtained was added to 50 parts of pyridine and 10 parts of tri-n-butylamine, and heated to reflux, at which time 20 parts of pyridine was recovered using a Dean-Stark cooling tube or the like. Water in the system was removed.

The reaction solution was cooled, 5.0 parts of triethoxychlorosilane was added, and the mixture was stirred at room temperature for 2 hours, then heated under reflux for 3 hours, and then filtered. The residue was washed with pyridine and DMF, the filtrate was poured into 1000 parts of diluted hydrochloric acid, and the product was separated by filtration, washed with water,
After drying, 0.3 parts of compound (b) was obtained.

[Synthesis Example 3 Part 3 Synthesis of Compound (c)] 2.0 parts of an indolenine compound in which R1 and R1 are represented by the above general formula (n) and 2.0 parts of tetrachlorosilane were reacted in the same manner as in Synthesis Example 1, Perform filtration and purification.

Next, 0.5 parts of the compound thus obtained was added to 50 parts of pyridine and 10 parts of tri-n-butylamine, and heated to reflux, at which time 20 parts of pyridine was recovered using a Dean-Stark cooling tube or the like. Water in the system was removed.

The reaction solution is cooled, 6.0 parts of tributoxychlorosilane is added, and the mixture is stirred at room temperature for 2 hours, then heated under reflux for 3 hours, and then filtered. The residue was washed with pyridine and DMF, the filtrate was poured into 1000 parts of diluted hydrochloric acid, and the product was separated by filtration, washed with water,
After drying, 0.25 part of compound (c) was obtained.

[Synthesis Example 4 Part 4 Synthesis of Compound (d)] 2.0 parts of an indolenine compound in the general formula (If) where R1 and Rffi are and 2.0 parts of indium trichloride were reacted in the same manner as in Synthesis Example 1. , filtration.

Perform purification.

Next, 0.5 parts of the compound thus obtained was added to 50 parts of pyridine and 10 parts of tri-n-butylamine, and heated to reflux, at which time 20 parts of pyridine was recovered using a Dean-Stark cooling tube or the like. Water in the system was removed.

The reaction solution was cooled, 5.0 parts of dichlorodimethylsilane was added, and after stirring at room temperature for 15 hours, excess dichlorodimethylsilane was distilled off, the mixture was cooled, and 15 parts of hexadecanol was added to the reaction solution. Heat under reflux for 6 hours and then pass.

The residue was washed with pyridine and DMF, and the filtrate was diluted with diluted hydrochloric acid (10%).
The product was filtered, washed with water, and dried to obtain 0.17 parts of compound (d).

[Synthesis Example 5: Synthesis of Compound (e)] 2.0 parts of an indolenine compound and 2.0 parts of tetrachlorogermane in which R' and R'' are represented by the above general formula (II) in the same manner as in Synthesis Example 1. Reacts by.

Perform filtration and purification.

Next, 1.0 part of the compound thus obtained was added to chlorsulfone fI! Add to 100 parts, heat and stir at 100 to 105°C for 4 hours, and cool. Furthermore, 20 parts of thionyl chloride was added to the second reaction solution, and the mixture was heated and stirred at 80 to 85°C for 1 hour, and then poured into 1000 parts of ice water, and the precipitate was filtered.

Wash with water. All of the obtained water cake and 10 parts of di-n-butylamine were added to 50 parts of methanol, and the mixture was heated and stirred at room temperature for 2 hours and then at 70 to 75°C for 3 hours.

Cooling.

The reaction solution was poured into 500 parts of diluted hydrochloric acid and the product was filtered.

Wash with water and methanol, then dry.

Next, 50 parts of pyridine and 10 parts of tri-n-butylamine were added to 0.5 parts of the compound thus obtained, and jM
The mixture was heated under reflux, and at that time, 20 parts of pyridine was recovered using a Dean-Stark condenser or the like, and water in the system was removed.

The reaction solution was cooled, 5.0 parts of dichlorodimethylsilane was added, and the mixture was stirred at room temperature for 15 hours. Excess dichlorodimethylsilane was distilled off, the mixture was cooled, and 15 parts of hexanol was added to the reaction solution.
The mixture was heated under reflux for 6 hours, and then filtered.

The residue was washed with pyridine and DMF, and the filtrate was diluted with diluted hydrochloric acid (10%).
The product was filtered, washed with water, and dried to obtain 0.24 parts of compound (e).

Practical Example 1 2.0 parts of compound (a) was dissolved in 98.0 parts of methyl cellosolve, and this solution was coated on a polycarbonate resin disk substrate by a 70 Orpm spinner coating method, and then dried for 1 minute at 80°C under reduced pressure. Approximately 600 people recorded the event.

The maximum absorption wavelength of the obtained recording medium was 750 nm,
The reflectance for light with a wavelength of 780 nm was 30%.

The optical recording medium produced in this way was attached to a turntable, and a linear velocity of 9 was recorded using a 780 nm semiconductor laser beam.
．． Signal recording was carried out at 4 m/s, frequency IMHz, .:c energy 8 mW.

After that, the linear velocity was 9.4 m/s using the semiconductor laser beam.
The recorded signal was read at a frequency of 1 MHz and an energy of 0.68 mW, and the C/N ratio was 48 dB.

Practical example 2 2.0 parts of compound (b) was dissolved in 98.0 parts of dichloroethane, and this solution was spread on a glass disk substrate at 70Qrp.
After applying using m-spinner coating method, 80℃ under reduced pressure.
After drying for 1 minute, a recording layer of about 700 people was obtained.

The maximum absorption wavelength of the obtained recording medium was 745 nm, +
The reflectance for light with a wavelength of 780 nm was 28%.

The optical recording medium thus produced was mounted on a turntable, and signals were recorded in the same manner as in Example 1. The recorded signals were read and the C/N ratio was 45 dB.

Examples 3 to 5 Compounds (c) to (e) were coated on a glass disk substrate in the same manner as in Example 2 to obtain a recording medium.

Maximum absorption wavelength of the recording layer of the obtained recording medium, 780 nm
The results shown in Table 1 were obtained by recording and reading signals on these recording media in the same manner as in Example 1.

〔Effect of the invention〕

The present invention has the above-mentioned structure, and has the characteristics of being chemically and physically stable and capable of recording and replaying with high sensitivity using a laser beam.

Claims (1)

[Claims] 1. An optical recording medium characterized by having an organic thin film layer containing at least one phthalocyanine compound represented by the following general formula [I] on a substrate. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. , alkoxy group, carboxylic acid group,
Carboxylic acid ester group, or R^1 and R^2, R^3
and R^4, R^5 and R^6, and R^7 and R^8 each represent a cyclic organic residue. M represents Al, Ga, In, Si, Ge or Sn. Y represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where R^9, R^1^0, R^1^1 are each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group , a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or OR^1^2, provided that among R^9, R^1^0, R^1^1 At least one is OR^1^2. R^1^2 is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or ▲mathematical formula, chemical formula, table, etc. There is ▼. p represents an integer of 1 or 2. 2. The optical recording medium according to claim 1, wherein the cyclic organic residue has a basic skeleton selected from: ▲ has a mathematical formula, a chemical formula, a table, etc. ▼ or ▲ has a mathematical formula, a chemical formula, a table, etc. ▼ .