JPH03202395A - Optical recording medium - Google Patents

Abstract

PURPOSE:To obtain an optical recording medium which is chemically and physically stable and allows recording and regeneration with high sensitivity using a laser beam by providing an organic thin layer containing at least, more than one kind of specific phthalocyanine compound on a substrate. CONSTITUTION:An organic thin layer containing at least, more than one kind of phthalocyanine compound shown by formula [I] is provided on a substrate. In the formula, rings A<1> to A<4> are expressed by a benzene ring, a naphthalene ring or an anthracene ring. M is Al, Ga, In, Si, Ge or Sn. X is an alkyl group, an aryl group, a heterocyclic residual group, a phthalimidemethyl group, a halogen atom, a nitro group, a cyano group, a sulfonic acid group, -OR<1>, -SR<2>, -COOR<3>, -NR<4>R<5>, -SO2NR<6>R<7>, -CONR<8>R<9>, -CH2NHCOCH2NR<10>R<11>, -NHCOR<12>, -N=NR<13>, or -N=CHR<14>. Y is -O-P=W, -R<15>R<16>, -O-P=W, -NR<17>R<18>, -NR<19>R<20>, -O-P-R<21>R<22>, or -O-SE-R<23>.

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, two types of optical recording media are known for recording and reading information using laser beams. One such method is to perform recording 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.

As the recording layer of such an optical recording medium, As is used.

Thin film layers of metals and alloys such as Te, Se, and Ti could be used. Optical recording media whose recording layer is a thin film layer of these metals or alloys generally have high writing sensitivity.

Although it has the advantage of being able to use a semiconductor laser, which allows the recording and reproducing optical system to be miniaturized, it has the disadvantage that the energy of the laser beam cannot be used efficiently during recording due to reasons such as high thermal conductivity.

Additionally, these recording layers are chemically unstable.

Sometimes it deteriorated.

For this reason, Japanese Patent Application Laid-open No. 57-82093, Japanese Patent Application Laid-open No. 58
-56892 publication, Japanese Patent Application Laid-open No. 60-89842,
According to Japanese Unexamined Patent Publication No. 60-150243, an organic thin film layer is used as a recording layer, and a relatively long wavelength, e.g. 780 nm, is used as a recording layer.
Optical recording media have been proposed in which information is written and read using laser beams of m or more. In such optical recording media, minute recesses (bits) can be easily formed in the organic thin film layer by melting with a semiconductor laser, evaporation and decomposition, etc., which can reduce the size of the recording and reproducing optical system.

It had drawbacks such as a small extinction coefficient for semiconductor laser beams (and insufficient recording sensitivity).

(Problems to be Solved by the Invention) The present invention improves various drawbacks of the conventional optical recording medium having a 474-meter film recording layer, and provides a chemically and physically stable optical recording medium that can be recorded with high sensitivity by laser beams. Can be played. An optical recording medium using a specific phthalocyanine compound is provided.

[Structure of the invention]

(Means for Solving the Problems) The present invention is an optical recording medium in which an organic thin film layer containing at least one phthalocyanine compound represented by the following formula (1) is provided on a substrate.

[In the formula, rings A I and 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, and is an alkyl group that may have a substituent, an aryl group that may have a substituent, a heterocyclic residue that may have a substituent, Phthalite ξ tomethyl group which may have a substituent, halogen atom,
Nitro group, cyano group, sulfonic acid group, -〇R', -
3R2, -COOR'NR' Rs, -3Oz NR'
R'-CONR” R2OHz N HCOCHz
N R" represents the Rth, -NHCOR"N=NR13, or -N=CHR".

R1, R''+ R3, R4, R5R,'6 R8R9
RIO and R1+ may be the same or different and represent a hydrogen atom, an alkyl group that may have a substituent, an aryl group, an acyl group, a cycloalkyl group, or a polyether group, or With R6 and R7, with R11 and R9, or with R" and R", 4 to 7
A membered ring may be formed, and these 4- to 7-membered rings may be a heterocycle containing a heteroatom such as a nitrogen atom.

R+Z, R13 and R'' may be the same or different, and represent an alkyl group, a cycloalkyl group, or an aryl group having a substituent.

o p-RZIR2! , or -〇-3e-R''.

Z represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group which may have a substituent o p pZ4RZs or 10-3e-R''.

R15, R16, R21, Rat, R23, R24
R2S RZ6R27 and R3Z may be the same or different from each other, and are an alkyl group, an aryl group, an aryl group, an acyl group, a cycloalkyl group, which may have a substituent,
Represents an alkoxy group, allyloxy group, polyether group, hydroxyl group, or halogen atom.

R”l R”l R”l R”l R”I
R291R" and R3+ may be the same or different from each other, and are an alkyl group that may have a substituent,
Oryl group, acyl group, cycloalkyl group, alkoxy group, allyloxy group, polyether group, hydroxyl group, halogen atom.

Or represents a hydrogen atom.

W represents -0-, -3-, -3e- or -Te.

k, 7! , m, and n each independently represent an integer of 0 to 8.

p represents 10 or l. ] In the compound represented by the general formula (1) according to the present invention, as representative examples of atoms and groups constituting X, Z, and R1 to R'3z, halogen atoms include chlorine atom, 5 bromine atoms, iodine atom, Examples of alkyl groups that may have substituents include methyl groups, n-butyl groups, tert-butyl groups, stearyl groups, trichloromethyl groups, 2-methoxyethyl groups, etc. Examples of the aryl group that may be present include phenyl group, chlorophenyl group, tolyl group, naphthyl group, anthryl group, dimethylaminophenyl group, hydroxyphenyl group, diethylaminonaphthyl group, hydroxynaphthyl group, etc., and cycloalkyl group includes: Examples of cyclohexyl group, cyclobutyl group, etc., acyl group which may have a substituent such as acetyl group, trifluoroacetyl group, etc. 5 Polyether group include diethylene glycol monoethyl group, triethylene glycol monobutyl group, etc. ,? j [As the bare ring group, pyridyl group, furyl group, thiazolyl group, piperazinyl group, 1 morpholyl group, etc., and as the phthalimidomethyl group which may have a substituent, phthalimidomethyl group, nitrophthaligotomethyl group, tert-butylphthalimidomethyl group,
Examples include a methoxyphthalimidomethyl group, a dichlorophthalimidomethyl group, and the like, but the present invention is not limited to these groups.

In the present invention, the compound represented by formula (r) can be produced, for example, by the following method.

That is, from the isoindolenine compound represented by the following formula [■] and various metal salts, or by a conventional method using carboxylic acid anhydrides, imides, or nitriles as starting materials, - formula (I[[ ) is produced.

-Math [■] H I H [In the formula A1~' I X+ kr It + m
, n represent the same meaning as in formula (1). ]General formula I [[) and p represent the same meaning as in -formula CI). ] Next, by reacting the obtained phthalocyanine compound represented by general formula (I) with two various phosphorus compounds or selenium compounds, a phthalocyanine compound represented by formula CI) 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 (a) to (S).

[In the formula, ring A1~', M, X, k, 1.
m, n and (ε) The substrate used in the present invention has a light transmittance for writing and reading signals.

Preferably it is 85% or more, and it is desirable that the optical anisotropy is small. For example, heat treatment of glass, alkyl resin, polycarbonate resin, polyester resin, polyamide resin, heptavinyl chloride resin, vinyl acetate resin, polystyrene resin, polyolefin resin (such as poly-4-methylpentene), polyether sulfone resin, etc. Plastic resin or epoxy resin.

Examples include substrates made of thermosetting resins such as 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 particularly desirable.

In the present invention, the thickness of these transparent substrates is.

There is no particular restriction, and the shape may be a plate or a film. Also,
The shape may be a two-circle shape or a card shape, and there is no particular restriction on its size.

In addition, substrates usually have unevenness for preformatting, such as guide grooves for position control during recording and reading, address signals, and various marks. It is preferable to use a stamper or the like to apply the plastic resin when forming the bottom (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 vacuum evaporation, sputtering, ion plate method, and LB method (Langmuir-Blodgett method). There are these methods.

Operation is complicated and productivity is low. - Formula (I)
The phthalocyanine compound represented by i! ! Since the solubility in common organic solvents is much higher, 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 are mixed with alcohols,
Ketones 7 amides.

It is applied by dispersing or dissolving it in ordinary organic solvents such as sulfoxides, ethers, esters, aliphatic halogenated hydrocarbons, and aromatic hydrocarbons. At this time, a polymer binder may be added if necessary. The polymer binder is vinyl chloride resin.

Acrylic resin, polyester resin, polyamide resin.

Polycarbonate resin, epoxy resin, methacrylic! Examples include oils, vinyl acetate resins, nitrocellulose, and phenolic resins. When using a polymer binder, the ratio of the polymer binder to the phthalocyanine compound is preferably 10% by weight or less.

Further, in the present invention, other dyes 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, and phthalocyanine complexes.

Examples include naphthalocyanine complexes, squalium 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 μm to 2 μm.
It is μm. 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 improving the sensitivity to light in the oscillation wavelength range of semiconductor lasers. In some cases it is possible.

In addition, in order to protect these recording layers, Al.

An inorganic compound such as Off+s i Oz+S io or SnO may be deposited as a protective layer. Also as a protective layer.

A polymer may also be applied.

Recording on the recording medium obtained as above.

This is carried out by irradiating the recording layer provided on the substrate with laser light focused to about 1 μm, preferably semiconductor laser light. The part of the recording layer that is irradiated with the laser beam is
Thermal state changes such as decomposition, evaporation, and melting occur due to absorption of laser energy. As for playback.

This is done by reading the difference in reflectance between areas that have undergone thermal changes and areas that have not. - Formula (I)
The phthalocyanine compound represented by is extremely advantageous compared to organic dyes used in conventional optical recording media having organic thin film layers because the difference in reflectance before and after recording is extremely large.

Further, various lasers such as a He--Ne laser, an Ar laser, and a semiconductor laser can be used as the laser, but a semiconductor laser is particularly preferable in terms of cost and size. As a semiconductor laser.

Center wavelength 830nI1. Lasers with wavelengths of 780 parts m and shorter 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. Note that 9 parts in one example represents parts by weight.

Production example 1: 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.

After heating and stirring at 180 to 200°C for 3 hours, the mixture was cooled.

Dilute with 500 parts of methanol, filter, wash with methanol and dimethylformamide, and dry.

7.0 parts of dihydroxysilicon naphthalocyanine was obtained.

Obtained dihydroxy silicone naphthalocyanine 5.0
50 parts of chlorodiphenylphosphine, 50 parts of tri-n-butylamine, and 300 parts of pyridine were heated and stirred at 110°C for 2 hours, cooled, diluted with 1000 parts of methanol, and filtered to obtain a filtrate. Methanol was distilled off from the liquid by heating under reduced pressure.

The total amount of the product thus obtained was added to 5.0 parts of diluted hydrochloric acid, and the precipitate precipitated was filtered, washed with water, and dried at 80°C to obtain 3.0 parts of phthalocyanine compound (a).

Phthalocyanine compounds (b) to (k) and (r) were obtained by a method similar to the method for producing phthalocyanine compound (a).

Production example 2: Phthalocyanine compounds (1) to (n
) 5.0 parts of dihydroxysilicon naphthalocyanine obtained in Production Example 1, 50 parts of benzene selenenyl chloride
1 part, 50 parts of tri-n-butylamine, and 300 parts of pyridine were heated and stirred at 110° C. for 2 hours.

Cool, dilute with 1000 parts of methanol, and filter.

A filtrate was obtained, and methanol was distilled off under reduced pressure by heating from the obtained filtrate.

The total amount of the product thus obtained was diluted with dilute salt eII500.
The precipitate precipitated was filtered, washed with water, and dried at 80°C to obtain 2.5 parts of a phthalocyanine compound (]).

Phthalocyanine compounds (m) and (n) were obtained by a method similar to the method for producing phthalocyanine compound (1).

Production Example 3: Production of phthalocyanine compounds (0) and (p) 5.0 parts of dihydroxysilicon naphthalocyanine obtained in Production Example 1, 50 parts of diphenyl phosphate,
50 parts of tri-n-butylamine, 300 parts of pyridine in 1
After heating and stirring at 10°C for 2 hours, cool and add methanol 1
000 parts and filtered to obtain a filtrate, and methanol was distilled off under reduced pressure under heating from the obtained filtrate.

The total amount of the product thus obtained was added to 500 parts of diluted hydrochloric acid, and the precipitate deposited was filtered, washed with water, and dried at 80°C to obtain 2.8 parts of phthalocyanine compound (o).

Phthalocyanine compound (p) was obtained by a method similar to the method for producing phthalocyanine compound (0).

Production Example 4: Production of phthalocyanine compound (q) 5.0 parts of dihydroxysilicon naphthalocyanine obtained in Example 1, 50 parts of bis(dimethylamino)phosphoryl chloride, 50 parts of tri-n-butylaquinone, 300 parts of pyridine After heating and stirring 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 heat.

The total amount of the product thus obtained was added to 500 parts of diluted hydrochloric acid, and the precipitate deposited was filtered, washed with water, and dried at 80°C to obtain 3.0 parts of phthalocyanine compound (q).

Production Example 5: Production of phthalocyanine compound (s) To 50 parts of quinoline, tetra-tert-amyl-1,
7.8 parts of 3-diiminohenzoisoindoline and 5.0 parts of silicon tetrachloride were added, heated and stirred at 80 to 200°C for 3 hours, cooled, diluted with 500 parts of methanol, filtered, and diluted with methanol and It was washed with dimethylformamide and 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, 50 parts of tri-n-butylamine, and 300 parts of pyridine were heated and stirred at 110°C for 2 hours, and then cooled.
The mixture was diluted with 1000 parts of methanol and filtered to obtain a filtrate, and methanol was distilled off under reduced pressure under heating from the obtained filtrate.

The total amount of the product thus obtained was added to 500 parts of dilute hydrochloric acid, and the precipitate deposited was filtered, washed with water, and dried at 80° C. to obtain 3.0 parts of phthalocyanine compound (s).

Example 1 Phthalocyanine compound (a) 3. on a glass substrate.
After dropping a solution consisting of 0 parts and 97.0 parts of chloroform, it was rotated for 20 seconds at a speed of 1200 rpm+g.

An optical recording medium was obtained by drying at 80° C. for 20 minutes.

The recording layer of the obtained optical recording medium had a thickness of 780 nm, a maximum absorption wavelength of 815 parts m, and a reflectance of 42% for light at a wavelength of 830 nm.

Mount the obtained optical recording medium on a turntable,
While rotating the turntable at 1800 rpm,
．． 5mW of 830 partsm laser light focused at 0μm,
Recording was performed with irradiation at 8 MHz.

When the surface of the optical recording medium after recording was observed using a scanning electron microscope, the formation of clear bits was observed. Also,
When the obtained optical recording medium was irradiated with a laser beam of 830 parts m and 0.4 mW and one 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, rotated at a speed of 800 rpm for 30 seconds, and heated at 80° C. under reduced pressure. An optical recording medium was obtained by drying for 15 minutes.

The recording layer of the obtained optical recording medium had a thickness of 850 mm.

The maximum absorption wavelength was 810 parts m, 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 I, clear focus formation was observed on the surface of the recording layer, and the C/N ratio was 51 dB.

Examples 3 to 19 Phthalocyanine compounds (c) to (
s) was applied in the same manner as in Example 1 and dried to obtain an optical recording medium.

Table 1 shows the maximum absorption wavelength of the recording layer of the obtained optical recording medium, the reflectance for light with a wavelength of 830nI11, 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. Shown below.

(The following is a blank space) Table 1 [Effects of the Invention] The phthalocyanine compounds used in the optical recording medium of the present invention have extremely high solubility in ordinary organic solvents such as those mentioned above. 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 and high efficiency. Sensitive recording and reproduction are possible, and it 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 [I] on a substrate. General Formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [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, and is an alkyl group that may have a substituent, an aryl group that may have a substituent, 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, -S
R^2, -COOR^3, -NR^4R^5, -SO_
2NR^6R^7, -CONR^8R^9, -CH_2
NHCOCH_2NR^1^0R^1^1, -NHCO
R^1^2, -N=NR^1^3, or -N=CHR
Represents ^1^4. R^1, R^2, R^3, R^4, R^5, R^6, R
^8, R^9, R^1^0 and R^1^1 may be the same or different from each other, and represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group, represents an acyl group, cycloalkyl group, or polyether group,
Alternatively, R^6 and R^7, R^8 and R^9, or R^1^0 and R^1^1 may form a 4- to 7-membered ring, These 4- to 7-membered rings may be heterocycles containing a hetero atom such as a nitrogen atom. R^1^2, R^1^3 and R^1^4 may be the same or different and represent an alkyl group, a cycloalkyl group, or an aryl group having a substituent. Y is ▲Mathematical formula, chemical formula, table, etc.▼, -O-P-R^2^1R^2^2, or -O-Se-
Represents R^2^3. Z is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group which may have a substituent, -O-P-R^2^4R^2^5
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or -O-Se-R^3^2. R^1^5, R^1^6, R^2^1, R^2^2, R
^2^3, R^2^4, R^2^5, R^2^6, R^
2^7 and R^3^2 may be the same or different from each other, and are an alkyl group, an aryl group, an acyl group, a cycloalkyl group, an alkoxy group, an allyloxy group, which may have a substituent, Represents a polyether group, hydroxyl group, or halogen atom. R^1^7, R^1^8, R^1^9, R^2^0, R
^2^8, R^2^9, R^3^0 and R^3^1 may be the same or different from each other, and are an alkyl group, an aryl group, which may have a substituent, Represents an acyl group, cycloalkyl group, alkoxy group, allyloxy group, polyether group, hydroxyl group, halogen atom, or 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. ]