JPH01198391A - Optical recording medium - Google Patents

Abstract

PURPOSE:To obtain an optical recording medium chemically and physically stable and capable of performing recording and reproduction with high sensitivity by laser beam, by forming a membrane layer containing a specific phthalocyanine compound on a substrate. CONSTITUTION:A membrane composed of phthalocyanine represented by formula I[wherein a ring A1-4 is a benzene ring, a naphthalene ring or an anthracene ring, H is Si, Ge or the like, Z is H, alkyl, aryl or the like, Y is H, halogen, (substituted) alkyl, OSi(CH3)3 or the like, p=0-1 and l, m and n=0-8], for example, a compound represented by formula II is formed on a Pyrex substrate. When this recording medium irradiated with laser beam to perform recording, a sharp bit is formed.

Description

[Detailed Description of the Invention] [Object of the Invention] (Industrial Application Field) The present invention relates to an optical recording medium on which additional recording can be performed using a focused beam of a semiconductor laser. external memory.

The present invention relates to optical recording media used to record various types of information such as images and audio.

(Conventional technology) The above-mentioned recordable optical recording medium is tellurium.

Recording media having inorganic recording layers made of thin films of low-melting metals such as tellurium alloys and bismuth alloys are beginning to be put into practical use. However, these recording media have low productivity because they are based on thin film formats in vacuum, such as vacuum evaporation or sputtering, and are limited in terms of recording density due to the heat of recording (z = high conductivity). Since toxic substances such as tellurium are used, there is a problem in terms of hygiene.

In order to solve these problems, in recent years, methods of using organic dyes as recording media have been studied.
, Naphthoquinone (Japanese Unexamined Patent Publication No. Sho Qs-1x2793), Phthalocyanine dye (U.S. Pat. No. 4,298,975), Naphthalocyanine dye (U.S. Pat. No. 4,492,750) and other organic dyes that have absorption in the semiconductor laser oscillation wavelength region. medium is proposed. however,
The recording media using organic dyes that have been proposed so far have poor durability.

In terms of reflectance, they have disadvantages in that sufficient characteristics cannot be obtained, their solubility in solvents is poor, and thin film formation methods using economically advantageous coating methods cannot be applied.

(Means for Solving the Problems) In order to improve the problems of recording media using organic dyes, the present inventors have made extensive studies and found that the present invention has excellent practical characteristics and is also economically advantageous. This led to the invention of a new optical recording medium.

□In other words, 9 The present invention provides an information recording medium in which ``layer changes are caused and recording is performed by high-density energy irradiation such as a laser beam, in which a compound represented by the following general formula (''I'') is provided on a transparent substrate. It is an optical recording medium having a recording layer containing.

In the formula, rings A I'=A 4 are each independently a benzene ring or a naphthalene ring. represents an idlercene ring.

M is Aj! , Ga, In, T1. -3t, represents Ge, Sn or Pb. Z represents a hydrogen atom, an alkyl group which may have a substituent, a Schiffer alkyl group which may have a substituent, or an aryl group which may have a substituent.

Y is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, and a tertyl group which may have a substituent.

-OR,, -3R+, SeR, -TeR, or -
O3i R2R3R4, where R1 is an alkyl group, an aryl group, an acyl group, a cycloalkyl group, or a polyether, and RzRsRa may be the same or different and are an alkyl group or an aryl group, respectively.

It is a cycloalkyl group, a siloxy group or an alkoxy group. The substituents X may be the same or different, and each may be a halogen atom, a hydroxyl group, an alkyl group that may have a substituent, or an aryl group that may have a substituent.

Heterocyclic group which may have a substituent, -OR,, -3R5+
NHCORs, C0R5, N=CHR5゜N=NRs, NR6R7, S i R2R3R4
゜O3i R5R6R7,5OtNR@Rq.

-CONR,R9, -CH2NHCOCH2NR,R9
゜-COOR, -No□, -3O3H or =CH. Here, RS is the same as R.

Rh and R7 may be the same or different (Each is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or Rh and R'r together are a 4- to 7-membered group containing the nitrogen atom. It may form a heterocyclic ring. Re represents a hydrogen atom or an alkyl group.

R7 is a hydrogen atom or an alkyl group which may have a substituent.

Represents an aryl group that may have a substituent, a heterocyclic group that may have a substituent, or -R,, -NRr, R, □; where R1° is an alkyl group having 1 to 4 carbon atoms, Rrl,
R82 may be the same or different. An alkyl group which may each have a substituent or R++, R+□ taken together represents a heterocycle containing nitrogen, oxygen or sulfur atoms.

In addition, an alkyl group that may have a substituent of Z and Y,
The cycloalkyl group which may have a substituent and the aryl group which may have a substituent are halogen atoms.

It may have various substituents such as an alkyl group, an alkoxy group, a hydroxyl group, an alkylamino group, a trialkylsilyl group, and a trialkylsiloxy group.

p is either O or 1 and represents the number of substituents Y.

k, 42. m and n each independently represent an integer of 0 to 8, and represent the number of W substituents X.

The compound represented by the general formula [■] is 2, for example, the following - general formula (
I[) General formula (It) 1(N 呵H [Wherein, ring A represents a benzene ring, a naphthalene ring, or an anthracene ring.

The substituents X may be the same or different, and each may be a halogen atom, a glacial acid group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. Also good heterocyclic groups, 'ORs, SRs.

-NHCOR,,-,COR,,-N=C! (R,,-
N thousand N R5,, N RaRy, OS i
R2R3R4゜-O5i RsRhR-r, -3Oz
NRaRq, -CON Rs Rq, -CHz N
HCOCHz N Rs Rq.

=GOOR,, -N, O□, -SO, H or 10N. Here R5 is the same as R+.

Rh and R'r may be the same or different, and each represents a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, or an aryl group that may have a substituent. Alternatively, Rh and R'r may be taken together to form a 4- to 7-membered heterocycle containing the nitrogen atom. Re represents a hydrogen atom or an alkyl group. R represents a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent.

Heterocyclic group which may have a substituent or -RIO-NR1
1R1□; Here, R1° is an alkyl group having 1 to 4 carbon atoms + R11+ LZ may be the same or different.

An alkyl group which may each have a substituent or R11+R12 taken together represents a heterocycle containing nitrogen, oxygen or sulfur atoms.

k, I! , m, and n each independently represent an integer of 0 to 8, and represent the number of substituents X. ] It is synthesized according to a known method from the isoindoline compound represented by the following and typically an alkyl metal halide, a cycloalkyl metal halide, or an aryl metal halide. [For example, J.

N., Esposito, J., E., LIoyd, M.
E,,Kenney+ Inorg, Che#I.

5, 1979. (1966)] In addition, various compounds other than halides having an alkyl group, cycloalkyl group, or aryl group can also be used as the metal salt to be reacted. Furthermore, in place of the isoindoline of the general formula [■], it may be preferable to use a similar nitrile.

The transparent substrate used in the present invention preferably has a transmittance of light for writing and reading signals of preferably 85% or more and has small optical anisotropy. For example, glass or thermoplastic resins such as alkyl resins, polycarbonate resins, polyester resins, polyamide resins, vinyl chloride resins, polyvinyl ester resins, polystyrene resins, polyolefin resins (poly-4-methylpentene, etc.), and polyethersulfone resins. Examples include substrates using thermosetting resins such as epoxy resins, allyl resins, etc. Among these, the above-mentioned thermoplastic resins are preferred from the viewpoint of ease of molding and ease of providing guide grooves, address signals, etc., and acrylic resins and polycarbonate resins are particularly preferred from the viewpoint of optical properties and mechanical properties.

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

There is no particular restriction, and it may be in the form of a plate or a film. Also,
The shape may be circular or card-like, and there is no particular restriction on its size.

Further, the transparent substrate of the present invention usually has unevenness for preformatting, such as guide grooves for position control during recording and reading, address signals, and various marks, as described above. Molding (injection,
It is preferable to apply it using a stamper or the like during compression (compression, etc.).

In the optical recording medium of the present invention, a recording layer containing a phthalocyanine compound can be fixed on a transparent substrate by methods such as vacuum evaporation, sputtering, ion plate method, and LB method (Langmuir-Blodgett method). However, since these methods require complicated operations and are inferior in productivity, so-called coating methods are most preferred. When forming a recording layer by a coating method, the porphyrazine dinuclear compound may be alcohols, ketones, amides, sulfoxides, ethers, or esters.

It is applied by dispersing or dissolving it in a general organic solvent such as aliphatic halogenated hydrocarbons or aromatic hydrocarbons.

At this time, if the phthalocyanine compound has an amino group, by forming a salt with an organic acid,
In order to increase solubility, organic acids such as acetic acid, propionic acid, butyric acid, oleic acid, stearic acid, etc. can be mixed with the above organic solvent. Further, at this time, a polymer binder may be added depending on the case. As a polymer binder.

Vinyl chloride resin, acrylic acid resin, polyester resin,
Polyethylene resin, polyamide resin, polycarbonate resin, epoxy resin, methacrylic acid resin.

Examples include vinyl acetate resin, nitrocellulose, polypropylene resin, polyethylene terephthalate resin, phenol resin, and copolymers thereof.

At that time, the ratio of resin to phthalocyanine compound is 1
It is preferably 0 ivt% or less.

Further, it is also possible to use the phthalocyanine compound of the present invention by mixing and dispersing or mixing and dissolving other dyes.

Examples of dyes that can be used in combination include already known aromatic or unsaturated aliphatic diamine metal complexes, aromatic or unsaturated aliphatic dithiol metal complexes, phthalocyanine complexes, naphthalocyanine complexes, and squalium dyes. , naphthoquinone complexes, anthraquinone dyes, and polymethine dyes.

The recording layer containing the porphyrazine di-nuclear compound formed on the transparent substrate has a thickness of 10 μm or less, preferably 500 layers/2 μm. Furthermore, by exposing it to the vapor of an organic solvent such as chloroform, tetrahydrofuran, or toluene after coating, the absorption wavelength of the 'ii4 film shifts to longer wavelengths, significantly improving the sensitivity to light in the oscillation wavelength range of semiconductor lasers. In some cases it is possible.

Also, in order to protect these recording layers, Af.

A protective layer may be provided by depositing an inorganic compound such as o3,5ioZ, sto, SnO, or the like. Also as a protective layer.

A polymer may also be applied.

Recording on the recording medium obtained as described above is carried out by irradiating the recording layer provided on the substrate with a laser beam, preferably a semiconductor laser beam, focused to about 1 μm. This is determined by reading the difference in reflectance between the areas irradiated with the laser beam and the areas where the thermal state of the recording layer has changed, such as decomposition, evaporation, or melting due to absorption of laser energy, and the area where no changes have occurred.

As the light source, 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 cost and size.

As a semiconductor laser, the center wavelength is 830 parts m, 7
Lasers with wavelengths of 80 parts m and shorter can be used.

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples.

In the example, the middle part is the part by weight.

[Synthesis Example 1 Synthesis of Compound (a)] 1.8 parts of 2,3-dicyanonaphthalene and 2.0 parts of dimethyldichlorosilane were added to 20 parts of Kino 9F to give 180 to 20 parts of dimethyldichlorosilane.
After heating and stirring at 0°C for 3 hours, cool to room temperature.

After dilution with 300 parts of methanol, the product is filtered off, washed with methanol and acetone/water (volume ratio 1:1), and then dried to obtain 1.2 parts of a composition of the compound. concentrated sulfuric acid 300
After dissolving 1.0 part of the above composition in 2.0 parts of ice water. The precipitate was filtered and washed with water, the water cake was reslurried in 300 parts of aqueous ammonia, and after boiling for 1 hour, filtered, washed with water, washed with methanol, and dried to obtain a purified product of compound (a) with 0. 7 parts were obtained.

[Synthesis Example 2 Synthesis of compound (g))] 9230 parts of kino, 2.4 parts of 6-broboxy-2,3-dicyanonaphthalene, 5 parts of propylmethyldichlorosilane
．． 0 part was added, and the reaction was carried out in the same manner as in Synthesis Example 1.

After purification, 0.6 part of purified compound (b) was obtained.

[Synthesis Example 3 Synthesis of Compound (C)] 1.8 parts of 2,3-dicyanonaphthalene and 3.0 parts of trichloromethylsilane were added to 40 parts of 1-chloronaphthalene, and the reaction and production were carried out in the same manner as in Synthesis Example 1. , when dried, purified hydroxy-methyl-silicon naphthalocyanine 0
．． 6 parts are obtained. Add 0.5 part of the above purified product to 80% pyridine.
The mixture was heated and refluxed, at which time 30 parts of pyridine was recovered using a Dean-Stark condenser or the like, and water in the system was removed. After cooling the reaction solution, 10 ml of bis-trimethylsilylacetamide (BSA) was added, heated under reflux for 6 hours, cooled, and filtered.

The residue was washed and extracted with 50 ml of lysine, the filtrate was poured into 500 parts of diluted hydrochloric acid, and the product was filtered and washed with water.

After washing with a methanol/water (1:1) solution and drying under reduced pressure, 0.2 part of compound (C) is obtained.

[Synthesis Example 4 Synthesis of Compound (d)] 0.5 part of hydroxy-methyl-silicon naphthalocyanine synthesized in the same manner as Synthesis Example 3 was added to 50 parts of pyridine.

Add to 10 parts of tri-n-butylamine, heat and reflux,
At this time, pyridine 2 is
0 parts were collected 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 and the mixture was cooled. After adding 10 parts of diethylene glycol and heating and refluxing for 6 hours, it was filtered, the residue was washed with pyridine and DMF, and the filtrate was diluted with 1.0 parts of diluted hydrochloric acid. The product was poured into O2, filtered, washed with water, and dried to obtain 0.2 part of compound (d).

Cku) (J,) cd) (entJl>cf>(1n1.') (a)2
．． After dropping a solution consisting of 8 parts of chloroform and 97.2 parts of chloroform, the substrate was rotated at a speed of 150 rpm for 15 seconds.

Next, this substrate was dried at 80° C. for 20 minutes to obtain a recording medium.

The thickness of this recording layer was 760. The maximum absorption wavelength of this thin film was 805 nm, and the reflectance for light at a wavelength of 830 nm was 32%.

Mount this optical recording medium on the turntable.

While rotating the turntable at 180 rpm.

830 nm laser 5 mW focused at 1.0 μm, 8
Recordings were made with irradiation at MHz.

When the surface of the optical recording medium on which this recording was performed was observed using a scanning electron microscope, the formation of clear bits was observed. In addition, this optical recording medium has 830nm, 0.4n
When W laser light was irradiated and two reflected lights were detected, the C/N ratio was 51 dB.

Example 2 Phthalocyanine metal compound (
b) After dropping a solution consisting of 2.1 parts and 97.9 parts of methyl cellosolve, the substrate was rotated at a speed of 1100 Orp for 20 seconds.

Next, this substrate was dried at 80° C. for 30 minutes under reduced pressure to obtain a recording medium.

The thickness of this recording layer was 600. The maximum absorption wavelength of this thin film was 802 nm, and the reflectance for light with a light length of 830 nm was 30%.

Further, when recording was performed on this recording medium in the same manner as in Example 1, clear bit formation was observed on the surface of the recording layer, and the C/N ratio was 50 dB.

Examples 3 to 13 Phthalocyanine compound (c) on Pyrex substrate
(2) was applied in the same manner as in Example 1 to obtain a recording medium.

Table 1 shows the maximum absorption wavelength of this thin film, the reflectance for light with a wavelength of 830 nIIl, and the results of recording and reproducing the same recording and reproducing operations as in Example 1 on this recording medium.

Table I 3c 806nm 31% 51dB4
d 810 34 52 5 e 812 32 50 6 f 835 29 49 7 g 862 25 42 8 h 809 32 52 9 i 800 30 50 10 j 801 28 48 11 k 806 30 51 12 I! , 790 29 46 13 m 812 31 51 [Effects of the Invention] The present invention has the above-described structure and is chemical.

It is physically stable and can be recorded and reproduced with high sensitivity using laser beams.

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] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, rings A_1 to A_4 are each independently a benzene ring,
Represents a naphthalene ring or anthracene ring, M is Al,
Represents Ga, In, Tl, Si, Ge, Sn or Pb. Z is a hydrogen atom or an alkyl group that may have a substituent,
Represents a cycloalkyl group that may have a substituent or an aryl group that may have a substituent. Y is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, -OR_1,
-SR_1, SeR_1, -TeR_1, or -OS
iR_2R_3R_4, where R_1 is an alkyl group, aryl group, acyl group, cycloalkyl group or polyether, and R_2R_3R_4 may be the same or different, and each represents an alkyl group, aryl group, cycloalkyl group, siloxy group or alkoxy It is the basis. The substituents X may be the same or different, and each may be a halogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a hetero group that may have a substituent. cyclic group, -OR_5, -SR_5, -NHCOR_5,
-COR_5, -N=CHR_5, -N=NR_5, -
NR_6R_7, -SiR_5R_6R_7, OSiR
_5R_6R_7, -SO_2NR_8R_9, -CO
NR_8R_9, -CH_2NHCOCH_2NR_8
Represents R_9, -COOR_9, -NO_2, -SO_3H or -CN. Here, R_5 is the same as R_1. R_6 and R_7 may be the same or different, and each is a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, or R_6 and R_4 together form a 4- to 7-membered heterocyclic ring containing the nitrogen atom. It may form a ring. R
_8 represents a hydrogen atom or an alkyl group. R_9 is a hydrogen atom, an alkyl group that may have a substituent,
Aryl group which may have a substituent, heterocyclic group which may have a substituent or -R_1_0-NR_1_1R_1_
2; here, R_1_0 is an alkyl group having 1 to 4 carbon atoms, and R_1_1 and R_1_2 may be the same or different. An alkyl group which may each have a substituent or R_1_1, R_1_2 taken together represents a heterocycle containing nitrogen, oxygen or sulfur atom. p is either 0 or 1 and represents the number of substituents Y. k, l, m, n each independently represent an integer from 0 to 8,
Represents the number of substituents X.